JPH01103668A - Water-soluble dye mixture - Google Patents

Abstract

PURPOSE:To make it possible to improve the temperature dependency of an anthraquinone reactive dye without detriment to its excellent build-up property and to perform good dyeing even in a low salt concentration, by mixing a specified anthraquinone reactive dye with a specified formazan reactive dye at a specified ratio. CONSTITUTION:This water-soluble dye mixture comprises a blue anthraquinone reactive dye (A) represented, in the form of a free acid, by formula I (wherein X is a -CH=CH- group or a -C2H4W group, W is a group which can be eliminated by the action of an alkali) and 0.2-5pts.wt., per pt.wt. component A, blue formazan reactive dye (B) represented, in the form of a free acid, by formula II (wherein R is a hydrogen atom or a 1-4C alkyl group, Y is a halogen atom, an -NHC2H4SO3H group or a formula III, X is a -CH=CH2 group or a -C2H4W group, and W is a group which can be eliminated by the action of an alkali).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to water-soluble dye mixtures, in particular:
Good dyeing is possible even with low salt concentration, and
This invention relates to a reactive dye mixture having a bright blue color with excellent build-up properties.

(Prior Art) Water-soluble reactive dyes for dyeing cellulose-containing fibers are required to have excellent various properties, and in the case of blue dyes, those with brightness and excellent build-up properties are - Anthraquinone dyes are known for boat fishing.

However, when dyeing with anthraquinone dyes, it is necessary to increase the concentration of salt present in the dyeing bath to some extent, and there are also problems in that the dyeing properties vary depending on the dyeing temperature.

Therefore, in order to alleviate the problems of such anthraquinone dyes, it may be considered to mix and use other types of dyes that have excellent temperature dependence during dyeing and can be dyed well with a small salt concentration.

However, when other types of dyes are mixed with the anthraquinone dye, the above problems are alleviated, but the sharpness and build-up properties, which are characteristics of the anthraquinone dye itself, are deteriorated. From a practical point of view, it may be possible to sacrifice some sharpness, but it is not a good idea to sacrifice build-up performance as well, as this would diminish the value of using anthraquinone dyes.

(Problems to be Solved by the Invention) In view of the above circumstances, the present inventors have sought to improve the temperature dependence of anthraquinone dyes without impairing their excellent build-up properties, and to dye well with a low salt concentration. As a result of extensive research aimed at obtaining a dye mixture capable of achieving The present invention has been completed.

(Means for Solving the Problems) The gist of the present invention is to form a free acid with the following general formula (wherein -X
represents 100=CH2 group or -C2H4W group. however,
W represents a group that is eliminated by the action of an alkali). T-! ; In the form of the free acid twice the weight, the following general formula C
B) (wherein R represents a hydrogen atom or a C□-C4 alkyl group, Y is a halogen atom, -NHC2H4SO3H
group or -NH-C>SO,H group, and X represents 10H=CH2 group or -C2H4W group. However, W represents a group that is eliminated by the action of an alkali. ) is a water-soluble dye mixture characterized by containing a blue formazan-based reactive dye.

The present invention will be explained in detail below.

In the forward running general formulas [A] and [B] in the present invention,
The group represented by the -02H4W group that is eliminated by the action of an alkali is usually -0503H group, -8803H group.
group, -0PO3H2 group, -0COCH3 group, or a halogen atom, with -0803H group being particularly representative.

The C1-C4 alkyl group represented by R includes methyl group, ethyl group, n-propyl group, i-propyl group, n-propyl group,
-butyl group and the like.

Y is a halogen atom, -NHC2H4S03H group, and
The -502X group in the preceding general formulas (A) and [B] is usually preferably at the para- or meta-position with respect to the amino group. Alternatively, a mixture of -5O2X groups in the para position and those in the meta position may be used; in this case, the one in the meta position usually has a weight ratio of 65 to 10θ and the one in the para position has a weight coefficient of 35
Mixtures having a weight ratio of ˜0 are preferred.

In the present invention, the halogen atom specifically represents a chlorine atom, a fluorine atom, a bromine atom, etc.

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 CAI and [B] can be produced according to known methods, and the production method is not particularly limited.

The present invention requires that the formazan reactive dye of the foreleg general formula [B] be blended with the anthraquinone reactive dye of the foreleg general formula (All). For dyes,
0.2 to 5 times by weight, preferably 0.2 to 5 times by weight. It is twice as heavy as the original. Even if the amount of the formazan-based reactive dye blended is less than 9 or more, the desired effect of the present invention cannot be obtained. In the present invention, both reactive dyes may be mixed in advance or may be mixed during dyeing.

As mentioned above, in the present invention, a mixture of the forepaw general formulas [A] and [B] is used as a blue component, but in actual dyeing, in order to obtain the desired hue, yellow is added as necessary. as component and/or yellow component, in the form of the free acid,
The following general formula % formula % (wherein, Z is -CH=CH2 group or -C2H40sO
3H group) ......CI[) (In the formula, ■ represents -NHCONH2 group or -NHCOCH
3 groups, Z is -CH=CH2 group or -C2H4
A reactive dye represented by the following general formula (where U represents a hydrogen atom, methyl group or ethyl group, T
represents a hydrogen atom, a chlorine atom or a bromine atom, and Z is -
It is particularly desirable to use a reactive dye represented by CH═CH2 group or -C2H40S03H group, since the dyeing speeds of each dye are matched and the reproducibility of dyeing is good.

Examples of fibers that can be dyed with the dye mixture of the present invention include cellulose fibers such as cotton, viscose rayon, cufurammonium rayon, and hemp, as well as nitrogen-containing fibers such as polyamide, wool, and silk. , cellulose fibers are particularly desirable. In addition, these fibers, for example,
It may also be used as a mixed fiber of polyester, triacetate, polyacrylonitrile, etc.

The dye mixture of the present invention can be applied to various known dyeing methods, and although it is usually preferable to use the exhaust dyeing method, it is also effective to apply it to the cold pad patch method or the 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
It is O~3011. Just in case, the amount of inorganic salt used depends on the dye bath i.
Even if it is as large as D, soi or more, it can be dyed sufficiently with a small amount of 5 to 7 tons. The dyeing temperature is usually tio-g.

℃, preferably 0°C.

(Examples) 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 as long as it does not exceed the gist thereof.

Example/ Dye mixture 0 containing 90 parts by weight of an anthraquinone reactive dye represented by the following structural formula in the form of a free acid and a formazan reactive dye AO electrolytic corrosion part represented by the following general formula in the form of a free acid. A dye bath prepared by dissolving .2I in 200 d of water, adding and dissolving mirabilite iog (mirabilite concentration so
Unmercerized cotton knitted fabric/Ill was immersed in y7t), the temperature was raised to 60°C over 30 minutes, and then 3 g of soda carbonate was added and exhaust dyeing was carried out at the same temperature for 1 hour.

After dyeing, the dyed fabric was washed with water, soaped, and dried in a conventional manner to obtain a blue dyed fabric.

The brightness of this dyed fabric was determined, and the surface reflectance of the dyed fabric was measured using a color difference meter (manufactured by Nippon Denshoku Kogyo Co., Ltd.) to determine the dyeing rate, and the results shown in Table 7 were obtained.

In addition, in order to investigate the salt concentration dependence, temperature dependence, and build-up property during dyeing of the dye mixture used in this example, in the above dyeing method,
Similar dyeing was carried out by changing i/Ls (i) dyeing temperature to 50° C. and (i) changing the amount of dye mixture used to Olza I.

Based on this result, regarding the dependence on salt concentration, the concentration of mirabilite is 10% relative to the dyeing concentration at roy7t.
Indicate the dyeing concentration in fi/l as a percentage.

Regarding temperature dependence, we determined the dyeing concentration in SO3 with respect to the dyeing density at a dyeing temperature of 60°C, and in the case of a formazan-based reactive dye alone (comparative example), which is naturally strong in temperature dependence. ) is expressed as a percentage of the equivalent value. Furthermore, regarding the build-up property, the dye mixture has 0.2,!
Dye mixture o0g for dyeing density when using i+
The dyeing density when using i was determined and expressed as a percentage of the same value in the case of using anthraquinone reactive dye alone (comparative example/), which originally has excellent build-up properties.

These results are summarized in Table-7.

Example 1 and Comparative Example 1-2 In the method of Example 1, the blending ratio of the dye mixture is shown in the table 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 formazan-based reactive dye was changed to one shown by the structural formula below, and a test was conducted in the same manner as in Example 3, except for the same method.The sharpness was extremely good.
Dyeing rate is 75%, salt concentration dependence is 1/2, temperature dependence is 1
00. The build up property was /10.

Example G In the method of Example/, anthraquinone reactive dye qo
When the composition of parts by weight was changed to the mixture shown by , and the test was conducted in the same manner as in the above except for that, the test result was 103.

Example S In the method of Example/, the formazan reaction materials are listed in Table 1 (all are expressed in the form of free acids, the clarity is extremely good, and the salt concentration dependence, temperature dependence, and build-up property are all n.
was also good.

Example 6 A dye mixture containing 50 parts by weight of an anthraquinone-based reactive dye represented by the following structural formula in free acid form and 50 parts by weight of formazan-based reactive dye represented by the following general formula in free acid form as a blue component. 0.29. Monoazo reactive dyes o, si represented by the following structural formula in the form of a free acid as a yellow component, and monoazo reactive dyes o, t, i represented by the following structural formula in the form of a free acid as a red component in water - and prepared by adding and dissolving mirabilite ioi (mirabilite concentration sog/
Unmercerized cotton knitted Ioy was immersed in l), the temperature was raised to 60°C for 30 minutes, and then 3g of soda carbonate was added,
Exhaustion staining was carried out at the same temperature for 10 minutes, -0 minutes, μO minutes, and 0 minutes, respectively.

After dyeing, the dyed fabric was washed with water, soaped, and dried in a conventional manner to obtain a brown dyed fabric.

The resulting nine brown dyed fabrics all have similar hues, and the dyeing speeds of the yellow reactive dye, red reactive dye, and blue reactive dye are all the same, making this a combination with particularly excellent reproducibility. It turned out to be.

Examples In Example B, a dye is prepared by blending 50 parts by weight of an anthraquinone-based reactive dye whose yellow component is represented in the form of a free acid with 50 parts by weight of a formazan-based reactive dye represented by the following general formula in the form of a free acid. In the mixture, the yellow component was changed into a monoazo reactive dye represented by the following structural formula in free form, the red component was changed into a monoazo reactive dye represented by the following structural formula in free acid form, and Example 6
The same staining was carried out.

As a result, the dyeing speed of each color reactive dye was uniform.

(Effects of the Invention) According to the present invention, by blending a specific anthraquinone-based reactive dye and a specific formazan-based reactive dye in a specific ratio, it is possible to achieve brightness and good build-up properties at a low salt concentration and at a dyeing temperature of , and a blue reactive dye with little salt concentration dependence can be obtained.

Claims (1)

[Claims] (1) In the form of free acid, the following general formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...[A] (wherein, X is -CH=CH_2 group or -C_2H_4W
represents a group. However, W represents a group that is eliminated by the action of an alkali. B] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼
・・・・・・・・・・・・[B] (In the formula, R represents a hydrogen atom or an alkyl group of C_1 to C_4, Y is a halogen atom, -NHC_2H_4SO
Represents a _3H group or a ▼ group with mathematical formulas, chemical formulas, tables, etc., and X is -CH=CH_2 group or -C_2H_4
Represents W group. However, W represents a group that is eliminated by the action of an alkali)
A water-soluble dye mixture characterized by containing a blue formazan-based reactive dye represented by: