JPH01170665A - Water-soluble dye mixture - Google Patents

Abstract

PURPOSE:To obtain the title red-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 red reactive dyes. CONSTITUTION:The aimed mixture obtained by blending (A) a red reactive dye shown by formula I [D is group shown by formula II or III; X is halogen or group shown by formula IV (R<3> is H or lower alkyl; R<4> is H, lower alkyl or halogen); R<1> is H or lower alkyl; R<2> is H, lower alkyl, halogen, -SO2CH=CH2 or -SO2CH2CH2W (W is group eliminable by action of alkali)] in the form of a free acid with (B) 0.2-2 pts.wt. based on 1 pt.wt. component A of a red reactive dye shown by formula V (Q is -CH=CH2 or -C2H4W; R<5> is lower alkyl) in the form of a free acid.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a water-soluble dye mixture, and more specifically, it is a water-soluble dye mixture that exhibits excellent color fastness when used for dyeing cellulose fibers or plain fibers. In addition, the present invention relates to a red reactive dye mixture that has well-balanced and excellent dyeing properties such as level dyeing properties, build-up properties, wash-off properties, 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 - 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, sunlight fastness, 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 JP-A Sho S Dart No. 1933) also has excellent chlorine fastness and sweat/sunlight fastness, as well as excellent salt concentration dependence, but it has poor level dyeing properties and wash/wash resistance. Poor off property.

As a method to improve this level dyeing property and wash-off property, we used a reactive dye represented by the forefoot structural formula (+).
Originally, it is possible to incorporate another reactive dye that has excellent level dyeing properties and wash-off properties. However, the uniformity of dyeing
Reactive dyes with excellent wash-off properties, on the other hand, have poor salt concentration dependence and good fastness properties. Therefore, when such two types of reactive dyes are used in combination, the physical property values of each are averaged, so
For example, although the level dyeing property is improved to some extent, the chlorine fastness becomes unsatisfactory. 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 present inventors have determined that the red 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 methods 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 that in the form of the free acid the following formula - where R
3 represents a hydrogen atom or a lower alkyl group, and R4 represents a hydrogen atom, a lower alkyl group or a halogen atom)
, R'' represents a hydrogen atom or a lower alkyl group, R2 represents a hydrogen atom, a lower alkyl group, a halogen atom,
-8o□CH=CH2 group or -8O2C2H4w group
(Herein, W represents a group that is eliminated by the action of an alkali. [
B] [In the formula, Q is -CH=CH2 group or -C2H, W group (W
is the same as defined above, and R5 is a lower alkyl group.

The present invention will be explained in detail below.

In the forefoot general formula [A] and CB) in the present invention,
The groups represented by W that are eliminated by the action of alkali are usually -0SO8H group, -8SO1H group, -0PO
Examples include acid ester groups such as 3H group and -0COCH3 group, and halogen atoms, with -08O,H group being particularly representative.

The lower alkyl group represented by R1, R2, R3, R4 and R5 usually includes C1-C2 alkyl groups such as methyl group, ethyl group, n-propyl group and n-butyl group. Moreover, X% chlorine atom and fluorine atom are preferable, and R2 and R4 are preferably chlorine atom and bromine atom.

In the front leg general formula CA), R2 is 18O2CH=CH
, group or -8o, C2H, W group, the position thereof is preferably the para position or meta position with respect to the amine 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 usually the salts include alkali metal salts such as lithium salts, sodium salts, potassium salts, calcium salts, or alkaline earth salts. Similar metal salts are preferred.

Further, the water-soluble reactive dyes represented by the general formulas (A) and (B) 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 general formula CB) of the front paw be blended with the reactive dye of the general formula [A] of the paw; however, the amount of the reactive dye of the general formula CB) is equal to
of reactive dye, 0.2 to 2 times by weight, preferably 0
．． The weight is doubled from 6 to 8. Even if the amount of the reactive dye of general formula [B] is too small or too large, it is not possible to obtain a dye that is excellent in a well-balanced manner in various fastnesses and dyeing properties targeted by the present invention. In the present invention, both reactive dyes may be mixed in advance or may be mixed during dyeing.

In the present invention, for color matching, a dye as a third component may be blended, for example, under the IO weight, within a range that does not impair the effects of the present invention.

Fibers that can be dyed with the dye mixture of the present invention include cellulosic fibers such as cotton, viscose rayon, Kiepra ammonium rayon, and linen, as well as esters, triacetates, and polyesters containing polyamide, wool, silk, etc. It may also be used as a mixed fiber of acrylonitrile or 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 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 7
It is 0-30g. The amount of inorganic salt to be used is, for example, 30 to 1/l in the dyeing bath. And the dyeing temperature is usually lIO~gθ℃, preferably 50~60℃
It is.

〔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/ Dye mixture O, which is a mixture of 50 parts by weight of a reactive dye represented by the following structural formula Ca) in the form of a free acid and 50 parts by weight of a reactive dye represented by the following structural formula [b] in the form of a free acid. Dissolve 200ml of water and add 10fl of Glauber's salt to this.
Dye bath prepared by adding and dissolving mirabilite concentration s o i/l
), soak unmercerized cotton stockinette 1011 in
It took several minutes to raise the temperature to Aθ℃, and then 3g of soda carbonate.
was added and exhaust dyeing was carried out at the same temperature for 7 hours. After dyeing, the dyed fabric was washed with water, saw pink, and dried in a conventional manner to obtain a red dyed fabric with good level dyeing properties.

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 /09
/ L and carried out similar staining, and based on this result, the dyeing concentration result when the degree of Glauber's salt * degree is soy/l is set as pace<ioθ), and the concentration of Glauber's salt for this is 7ofl.
The same result at /L was obtained as a relative value.

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

(2) Wash-off property test After the dyed fabric was squeezed, it was treated as described below, and the degree of coloring of the washing liquid was judged according to the following criteria. In addition, as a soaping agent, the product name is Diamond Server SCC'
rto (manufactured by Mitsubishi Chemical Industries, Ltd.) was used.

Water washing 25°C x 10 minutes Hot water washing SoCxio 1st soaping 60°C x 10 minutes 1st trick - Pink 60°C x 10 minutes Bath ratio l:20 Soaping agent 2g/l [Judgment criteria] ◎・・・・・・Coloring Almost none.

○...The coloring is slightly faded.

×...The coloring is large.

Me: There is significant discoloration.

■ Level dyeing test A dye bath was prepared by dissolving 0.2 g of the reactive dye mixture in 200 g of water, and adding and dissolving 10 g of Glauber's salt (Salt concentration: SO).
i/t), unmercerized cotton knitted iog is immersed and subjected to exhaustion treatment at 60°C for 3θ minutes using a shaking dyeing machine, and the exhausted cloth is collected at a wringing rate of IOO%. . Then, this exhaustion cloth (hereinafter referred to as A cloth) si and 5 g of the same kind of white cloth (hereinafter referred to as B cloth) were mixed with 200 yards of water.
After immersion in an aqueous solution of mirabilite iog and immersion treatment at 60° C. for 30 minutes, 3.9 g of soda ash was added and allowed to react at this temperature for 60 minutes. Thereafter, both fabrics A and B are washed in a conventional manner, washed with water and dried to obtain a red dyed fabric.

The surface reflectance of the fabrics A and B obtained here was measured using a color difference meter (manufactured by Nippon Heavy Industries Ltd.) 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.

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

×・・・・・・ I Kana is dark.

Valley... I j It's extremely dark.

■ Chlorine fastness JISL-Oggll (chlorine concentration -20ppm)
Measured according to.

■ Sweat and sunlight fastness Measured according to JIS L-Oggg (7-h).

Example λ and Comparative Example/~λ In the method of Example/, the blending ratio of the dye mixture is shown in the table below.
A test was conducted in exactly the same manner as in Example 7, with the changes as described in Section 7.

The results are shown in Table-/.

Example 3 In the method of Example/, the reactive dyes represented by the structural formulas [a and l were changed to the reactive dyes represented by the structural formula in Table 2,
Other than that, the test was conducted in exactly the same manner as in the example/example.
", the level dyeing rating was "O", and the chlorine fastness was "D", giving it a well-balanced overall quality.

Example 4 In the method of Example 1, the reactive dye represented by structural formula [b] was changed to the reactive dye represented by the following structural formula, and a test was conducted in exactly the same manner as in Example 1 except for the following. It was overall excellent with a well-balanced concentration dependence of 70%, wash-off property rating of "0", level dyeing property rating of "Q", and chlorine fastness of class C.

〔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.

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, D represents a ▲ mathematical formula, chemical formula, table, etc. ▼ group or ▲ a mathematical formula, chemical formula, table, etc. ▼ group, and X represents a halogen atom or ▲ a mathematical formula, chemical formula, table, etc. ▼ represents a group (where R^3 represents a hydrogen atom or a lower alkyl group, R^4 represents a hydrogen atom, a lower alkyl group, or a halogen atom), R^1 represents a hydrogen atom or a lower alkyl group, R^2 represents a hydrogen atom, a lower alkyl group, a halogen atom, a -SO_2CH=CH_2 group or a -SO_2C_2H_4W group (where W represents a group that is eliminated by the action of an alkali)] A red reactive dye represented by and the following general formula [B] in the form of a free acid of 0.2 to 2 times the weight of the dye: ▲ There are mathematical formulas, chemical formulas, tables, etc. =CH_2 group or -C_2H_4
A water-soluble dye mixture characterized in that it contains a red reactive dye represented by a W group (W is the same as defined above) and R^5 is a lower alkyl group.