JPH0848903A - Blue reactive dye composition - Google Patents

Abstract

PURPOSE:To obtain a water-soluble dye composition that is clear, excellent in buildup properties and water solubility, and reduced in dependency on dyeing temperature by mixing a specified reactive anthraquinone dye with a specified reactive formazan dye. CONSTITUTION:This dye composition is prepared by mixing a blue reactive anthraquinone dye which, in the form of a free acid, is represented by formula I (wherein X is CH=CH2, C2H4OSO3H or C2H4Cl) with 0.2-5 pts.wt., per pts.wt. this dye, blue reactive formazan dye which, in the form of a free acid, is represented by formula II [wherein Y is NR (wherein R is H, a 1-4C alkyl, phenyl or A<1>-SO2X); A<1> is a 2 or 3 C slkylane, 2 or 3 C alkyleneoxy2 or 3 C alkylene, SO2X, CH2SO2X-substituted phenylene or the like; and Z is a halogeno or the like] and/or a blue reactive formazam dye which, in the form of a free acid, is represented by formula III (wherein A<2> is A<1> or phenylene; and (m) is 0 or 1).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a water-soluble dye composition. Specifically, it relates to a clear blue reactive dye composition having excellent build-up properties. Furthermore, the present invention relates to an excellent reactive dye composition which makes the best use of the characteristics of each of the incorporated dyes. In particular, the present invention relates to a dye composition having good reproducibility in which the dyeing speed of the compounded dye is the same.

[0002]

2. Description of the Related Art A water-soluble reactive dye for dyeing a cellulose-containing fiber is required to have various excellent properties, and a blue dye is clear and has excellent build-up properties. Anthraquinone dyes are generally known. However, in the case of dyeing with an anthraquinone dye, there is a problem that the dyeability varies depending on the dyeing temperature.

Therefore, in order to alleviate the problems of such anthraquinone dyes, it is conceivable to mix and use other types of dyes having excellent temperature dependence during dyeing.
However, when the anthraquinone dye is mixed with another type of dye, the above problems tend to be alleviated, while the sharpness and build-up properties, which are characteristics of the anthraquinone dye itself, are deteriorated. . Further, when a dye having a remarkably different dyeing speed is mixed, the leveling property and reproducibility become problems.

[0004]

In view of the above situation, the present inventors have improved temperature dependency without impairing the excellent build-up properties of anthraquinone dyes, and have a good dyeing speed of the compounded dye. Consistent, as a result of extensive studies aimed at obtaining a dye composition having a large solubility in water, an anthraquinone dye having a specific structure,
The present invention has been completed by finding that the object of the present invention can be achieved by incorporating a predetermined amount of formazan dye having a specific structure.

[0005]

The present invention provides the following general formula [I] in the form of a free acid.

[0006]

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(In the formula, X is a -CH = CH ₂ group, -C ₂ H
₄ OSO ₃ H group or —C ₂ H ₄ Cl group, respectively. ) To the blue anthraquinone-based reactive dye represented by the following general formula [II] in the form of a free acid in an amount of 0.2 to 5 times the weight of the dye.

[0008]

[Chemical 6]

A blue formazan-based reactive dye represented by and / or a general formula [III]

[0010]

[Chemical 7]

[Wherein A ² represents a phenylene group or A ¹ , and Y, A ¹ , Z and X have the same meanings as described above,
m represents 0 or 1. ] The water-soluble dye mixture formed by mixing the blue formazan-based reactive dye represented by

The present invention will be described in detail below. In the general formulas [II] and [III], C ₁ to C represented by R
_Examples of the alkyl group of ₄ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group and an n-butyl group. In addition, specific examples of the C _{2 to} C ₃ alkylene group or C _{2 to} C ₃ alkyleneoxy C _{2 to} C ₃ alkylene group represented by A ¹ include —C ₂ H ₄ — group and —C ₃ H ₆ — group.
_{Group, -C 2 H 4 OC 2 H} 4 - _{group, -C 3 H 6 OC 3 H} 6
Groups.

Specific examples of the -A ¹ -SO ₂ X group include β
-(Β-sulfatoethylsulfonyl) ethyl group, β
-(Β-chloroethylsulfonyl) ethyl group, γ- (β
-Chloroethylsulfonyl) propyl group, γ- (β-sulfatoethylsulfonyl) propyl group, β- (vinylsulfonyl) ethyl group, β- [β- (β-chloroethylsulfonyl) ethoxy] ethyl group, γ- [ γ- (β-
Sulfatoethylsulfonyl) propoxy] propyl group, β- [β- (vinylsulfonyl) ethoxy] ethyl group, β- [β- (β-sulfatoethylsulfonyl)
An ethoxy] ethyl group etc. are mentioned.

In particular, -C ₂ H ₄ SO ₂ C ₂ H ₄ OSO
_{3 H, -C 3 H 6 SO} 2 C 2 H 4 OSO 3 H, -C 2 H
_{4 OC 2 H 4 SO 2 C} 2 H 4 OSO 3 H and the like as preferred. A ¹ is a phenylene group substituted by the above-mentioned --SO ₂ X group or --CH ₂ SO ₂ X group, or

[0015]

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The fluorine atom as the halogen atom represented by Z, a chlorine atom, or bromine atom, A ¹
When A ² represents an alkylene group or an alkyleneoxyalkylene group, a fluorine atom is particularly preferable, and when A ² represents a phenylene group, a chlorine atom is particularly preferable in view of matching the dyeing speed. Further, in the general formula [I] shown above, -SO
_It is usually desirable that the ₂ X group is in the para or meta position with respect to the —NH— group. Further, a mixture of the -SO ₂ X group having a para-position and a meta-position may be used, and in this case, the meta-position is usually 65 to 95% by weight and the para-position is 35 to 35% by weight. A mixture which is 5% by weight is particularly preferred.

In the present invention, all water-soluble reactive dyes are present in the form of a free acid or a salt thereof. Usually, as the salt, lithium salt, sodium salt, potassium salt,
Alkali metal salts such as calcium salts or alkaline earth metal salts are preferred. A lithium salt is particularly preferable for improving the solubility in water. In addition, the general formulas [I] and [I
The water-soluble reactive dyes represented by I] and [III] can be produced by a known method, and the production method is not particularly limited.

The present invention requires that the anthraquinone-based reactive dye represented by the general formula [I] is blended with the formazan-based reactive dye represented by the general formula [II] and / or [III]. However, the compounding amount of this formazan-based reactive dye is 0.2 with respect to the anthraquinone-based dye.
˜5 times by weight, preferably 0.3 to 3 times by weight, particularly preferably 0.4 to 1.5 times by weight. Even if the amount of the formazan-based reactive dye compounded is too small or too large, the desired effect of the present invention cannot be obtained. In the present invention, both reactive dyes may be mixed in advance,
Further, it may be mixed at the time of dyeing.

As described above, in the present invention, a mixture of the dyes represented by the general formulas [I] and [II] and / or [III] shown above is used as the blue component. In order to obtain a desired hue, it is optionally mixed with a yellow component and / or a red component. In this case, the yellow component and the red component are not particularly limited, but for example, as the yellow component, in the form of free acid,
The following general formula [A] or [B]

[0020]

[Chemical 9]

(In the formula, V is -NHCONH ₂ group or-
Represents a NHCOCH ₃ group, and X has the same meaning as described above. ) Is used as the red component in the form of the free acid, the following general formula [C]

[0022]

[Chemical 10]

(Wherein U represents a hydrogen atom, a methyl group or an ethyl group, T represents a hydrogen atom, a chlorine atom or a bromine atom, and X has the same meaning as described above) and /
Or in the form of free acid, the following general formula [D]

[0024]

[Chemical 11]

(In the formula, Y represents a hydroxyl group or X, W represents a hydrogen atom, a carboxyl group, a sulfonic acid group or --SO ₂
Represents a group X, and m, U or X has the same meaning as described above. The use of the reactive dyes shown in (1) is particularly desirable because the dyeing speeds of the dyes are the same and the reproducibility of dyeing is good.

Fibers which can be dyed with the dye mixture of the present invention include cellulosic fibers such as cotton, viscose rayon, cupraammonium rayon and hemp, and nitrogen-containing fibers such as polyamide, wool and silk. , Cellulose fibers are particularly desirable. Further, these fibers may be used as a mixed fiber with, for example, polyester, triacetate, polyacrylonitrile, or the like.

The dye mixture of the present invention can be applied to various known dyeing methods, and it is usually desirable to apply it to the exhaust dyeing method, but it is also applicable to the cold pad batch method or the pad steam method. It is effective. For exhaustion dyeing of cellulose-containing fibers using the water-soluble dye mixture of the present invention, for example, sodium bicarbonate, sodium carbonate, lithium carbonate, alkali such as sodium hydroxide, and, for example, the presence of an inorganic salt such as mirabilite and salt. , Can be dyed. The amount of alkali used at this time is usually 3 per liter of the dyeing bath.
It is 0 to 60 g. And the dyeing temperature is usually 40 to 8
The temperature is 0 ° C, preferably 40 to 60 ° C.

[0028]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the description of the examples as long as the gist thereof is not exceeded. Example 1

[0029]

[Chemical 12]

Anthraquinone type reactive dye 40 represented by
Parts by weight and the following structural formula

[0031]

[Chemical 13]

In a dye bath prepared by dissolving 0.2 g of a dye mixture containing 60 parts by weight of the formazan-based reactive dye represented by the above, in 200 ml of water, and adding 10 g of Glauber's salt to the solution, and dissolving.
10 g of unmercerized cotton knitted fabric is dipped and shaken for 25 minutes with a shaking dyeing machine, then 100 g of soda ash aqueous solution.
Add 30 ml of 1/1 and shake for 5 minutes at the same temperature, then 1 ℃
The temperature was raised to 60 ° C. at a rate of / minute for 30 minutes.

Six pots of the same dyeing bath were prepared, and when the dyeing temperature reached the following temperature, the cotton cloth was taken out from each dyeing pot, washed with water, neutralized with an aqueous solution of acetic acid 2 g / 1, and washed with water. After washing with hot water, Hostapal CT made by Hoechst Japan
-40 (registered trademark) 100 in a 2g / 1 soaping bath
Soaping for 10 minutes at ℃, washed with water, dried to obtain a blue dyed fabric.

... 35 ° C, ... 40 ° C, ... 50 ° C, ... 60 ° C, ... 60 ° C x 10 minutes, ... 60 ° C x 60 minutes, the sharpness is determined and the surface reflectance of the dyed cloth is determined. Was measured with a color difference meter [manufactured by Nippon Denshoku Industries Co., Ltd.] to obtain the dyeing rate, and the results shown in Table 1 were obtained.

In order to examine the temperature dependence and build-up property during dyeing of the dye mixture used in this example, in the above dyeing method, (i) dyeing temperature is 50 ° C., or (ii) dye mixture The amount used was changed to 0.8 g, and dyeing was carried out at 50 ° C. × 60 minutes for (i) and 60 ° C. × 60 minutes for (ii).

Based on this result, the temperature dependence is
The dyeing density at 50 ° C. was calculated with respect to the dyeing density at a dyeing temperature of 60 ° C., and expressed as a percentage of the same value as in the case of a formazan-based reactive dye alone which originally has excellent temperature dependence (Comparative Example 2 below). . Further, regarding the build-up property, the dyeing concentration when using 0.8 g of the dye mixture is calculated with respect to the dyeing concentration when using 0.2 g of the dye mixture, and in the case of the anthraquinone-based reactive dye alone which originally has excellent build-up property It is expressed as a percentage with respect to the same value as in Comparative Example 1 below.

As a method for evaluating whether or not the dyeing rates of the anthraquinone-based reactive dye and the formazan-based reactive dye in the dye mixture are the same, a blue dyed fabric dyed at 60 ° C. for 60 minutes is used as a reference to each dyed fabric. The hues were compared. These results are summarized in Table-1.

Example 2 and Comparative Examples 1-2 In the method of Example 1, the mixing ratio of the dye mixture is shown in the table.
The same test as in Example 1 was carried out, changing as described in Example 1. The results are shown in Table 1.

[0039]

[Table 1]

Example 3 In the method of Example 1, a formazan-based reactive dye is represented by the following structural formula:

[0041]

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When the same test as in Example 1 was carried out except that the content was changed to that shown in, the sharpness was remarkably good, the dyeing rate was 78%, the temperature dependence was 100, and the buildup property was 100%. Was 105, and the dyeing speed was also the same.

Example 4 The method of Example 1 was repeated except that the anthraquinone-based reactive dye 4 was used.
0 parts by weight of composition

[0044]

[Chemical 15]

The same test as in Example 1 was carried out except that the mixture was changed to the mixture represented by, and the sharpness was remarkably good, the dyeing rate was 79%, the temperature dependence was 99, and the build-up property was It was 106.

Example 5 In the method of Example 4, formazan reactive dyes are listed in Table 2.
The same test as in Example 1 was carried out except that the formazan reactive dyes described in -A and Table 2-B were used, and other than that, the sharpness was remarkably good, and the temperature dependence and build-up property were Was also good.

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

[Table 6]

Example 6 As a blue component, the following structural formula

[0053]

Embedded image

Anthraquinone type reactive dye 50 represented by
Parts by weight and the following structural formula

[0055]

[Chemical 17]

0.2 g of a dye mixture containing 50 parts by weight of a formazan-based reactive dye represented by the following formula as a yellow component

[0057]

Embedded image

Monoazo reactive dye 0.08 represented by
g, the following structural formula

[0059]

[Chemical 19]

1.2 g of the monoazo reactive dye represented by

[0061]

Embedded image

0.2 g of the monoazo reactive dye represented by the above is dissolved in 200 ml of water, and 10 g of sodium sulfate is added and dissolved in the dye bath, and 10 g of unmercured cotton knitted fabric is immersed in the dyeing bath for 25 minutes with a shaking dyeing machine. After shaking, 30 ml of 100 g / 1 soda ash aqueous solution was added, and the mixture was shaken at the same temperature for 5 minutes and then heated to 60 ° C. over 30 minutes at a rate of 1 ° C./minute.

Six pots of the same dyeing bath were prepared, and when the dyeing temperature reached the following temperature, the cotton knit fabric was taken out from each dyeing pot, washed with water, neutralized with an aqueous solution of 2 g / L of acetic acid, and washed with water. After washing with hot water, Hostapa made by Hoechst Japan
lCT-40 (registered trademark) was soaped and dried in a soaping bath of 2 g / 1 at 100 ° C for 10 minutes to obtain a brown dyed fabric. ... 35 ° C, ... 40 ° C, ... 50 ° C, ... 60 ° C, ... 60 ° C x 10 minutes, ... 60 ° C x 60 minutes

The obtained 6-point brown dyeing cloths all have similar hues, and the yellow reactive dye, red reactive dye, and blue reactive dye have the same dyeing speed, and reproducibility is particularly high. It turned out to be an excellent combination.

Example 7 In Example 6, the blue component was

[0066]

[Chemical 21]

Anthraquinone type reactive dye 50 represented by
Parts by weight and the following structural formula

[0068]

[Chemical formula 22]

The yellow component was added to the dye mixture prepared by mixing 50 parts by weight of the formazan-based reactive dye represented by

[0070]

[Chemical formula 23]

A red component was added to the monoazo reactive dye represented by

[0072]

[Chemical formula 24]

Dyeing was performed in exactly the same manner as in Example 6 except that the monoazo reactive dyes represented by the formulas (6) and (6) were respectively changed. As a result, the dyeing speed of each color reactive dye was uniform.

[0074]

The blue reactive dye of the present invention obtained by blending a specific anthraquinone-based reactive dye and a specific formazan-based reactive dye in a specific ratio is vivid and has excellent build-up properties and good dyeing temperature dependency. In addition, the dyeing speeds of both dyes are the same, and it is possible to perform dyeing with high reproducibility. Further, this dye composition has a high solubility in water.

Claims (3)

[Claims] 1. The following general formula [I] in the form of a free acid: (Wherein, X is -CH = CH ₂ group, -C ₂ H ₄ OSO ₃ H
Represents a group or a —C ₂ H ₄ Cl group. ) To the blue anthraquinone reactive dye represented by the following general formula [II] A blue formazan-based reactive dye represented by and / or a general formula [III] [Wherein A ² represents A ¹ or a phenylene group, and Y,
A ¹ , Z and X have the same meanings as described above, and m represents 0 or 1. ] A water-soluble dye composition comprising a blue formazan-based reactive dye represented by 2. The reactive dye represented by the general formula [I] is represented by the following general formulas [IA] and [IB]. (In the formula, X has the same meaning as in the above formula [I].) A mixture of reactive dyes represented by the formula [I], wherein the mixing ratio of the two is 35 to 5:65 to 95 by weight. Item 2. A water-soluble dye composition according to item 1. 3. A method for dyeing cellulose or fibers using the water-soluble dye composition according to claim 1.