JP3115187B2 - Method for dyeing or printing water-soluble dye mixtures and cellulose fiber materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble reactive dye mixture. And a method for dyeing or printing a cellulose fiber material using the same.

[0002]

2. Description of the Related Art A water-soluble reactive dye mixture for dyeing a cellulose-containing fiber in black has good build-up properties, can be uniformly dyed, and can easily remove unfixed dye from the fiber. It is required to have good wash-off properties and to have good fastness (particularly wet fastness) of a dyed product dyed black. Also,
With the adoption of automatic weighing systems in dyeing factories, it is also required that high-concentration liquid products can be prepared.

However, at present, no black reactive dye mixture has been found which can satisfy all of these points. For example, Korean Patent Publication No. 86-594 exemplifies a black mixture comprising the reactive dyes represented by the following structural formulas (1) and (2).

[0004]

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[0005]

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However, in the case of this mixed dye, the build-up property is remarkably excellent, but the leveling property and the wet fastness are insufficient, and the solubility of the reactive dye (2) in water is low, so that a high concentration is required. There is a problem that it is difficult to prepare a liquid product. Further, there is a problem that the stability with time in an aqueous solution is poor. On the other hand, a mixture for black color comprising a reactive dye represented by the following structural formulas (3) and (4) is known.

[0007]

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[0008]

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In the case of this mixed dye, there is a problem that the build-up property and the wash-off property are inferior.

[0010]

In view of the above circumstances, the present inventors have improved leveling properties, wash-off properties and wet fastness without impairing the build-up properties of the above mixed dyes, As a result of intensive studies for the purpose of obtaining a black dye mixture capable of preparing a liquid product, the objective of the present invention is to formulate a predetermined amount of a specific monoazo orange dye with respect to the mixed dye. Have been achieved, and the present invention has been completed.

[0011]

The gist of the present invention is to provide the following general formula [A] in the form of a free acid.

[0012]

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(Wherein X is a —CH ＝ CH ₂ group or —C ₂
Represents an H ₄ W group. Here, W represents a group which is eliminated by the action of an alkali. 95) to 55% by weight of a disazo type reactive dye represented by the formula (B):

[0014]

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A dye mixture containing 5 to 45% by weight of a monoazo dye and a method for dyeing or printing a cellulose fiber material using the same.

Hereinafter, the present invention will be described in detail. In the general formulas [A] and [B] of the present invention, -C ₂ H
₄ W As group capable of leaving by the action of an alkali represented by W in the group, usually, -OSO ₃ H group, -sso ₃ H group,
-OPO ₃ H ₂ group, ₃ group or a halogen atom such as -OCOCH. In particular, -OSO ₃ H groups are representative.
In the above general formula [B], a lower alkyl group represented by R and

[0017]

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Examples of the lower alkyl group as the substituent include a methyl group, an ethyl group, a straight-chain and side-chain propyl group and a butyl group, and a methyl group and an ethyl group are particularly preferable. In the general formula [B],

[0019]

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Examples of the lower alkoxy group as the substituent include a methoxy group, an ethoxy group, a linear or side chain propoxy group, and a butoxy group. Particularly preferred structures of the general formula [B] include the following [BI], [B-II] and [B
-III].

[0021]

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(In the formula, X, Z and R have the same meanings as described above.) In the present invention, any of the water-soluble reactive dyes represented by the general formulas [A] and [B] is free acid or Although it exists in the form of its salt, usually, the salt is preferably an alkali metal salt such as a lithium salt, a sodium salt, a potassium salt, a calcium salt or an alkaline earth metal salt.

The water-soluble reactive dyes represented by the general formulas [A] and [B] can be produced according to a known method, and the production method is not particularly limited. Specifically, the dye represented by the general formula [A] is C.I. I. According to the manufacturing method of Reactive Black 5,
The dyes represented by the above general formula [B] are described, for example, in JP-B-39
It can be manufactured according to the description in JP-A-18184.

The reactive dye mixture of the present invention comprises 95 to 55% by weight of the dye represented by the general formula [A] and 5 to 45% by weight of the dye represented by the general formula [B], particularly preferably represented by the general formula [A]. Of the dye represented by the general formula [B] and 30 to 10% by weight of the dye. The reactive dyes of the general formulas [A] and [B] may be mixed in advance, or may be mixed at the time of dyeing. If necessary, inorganic salts such as anhydrous sodium sulfate, dispersant,
It may contain a pH buffer, a dust scattering inhibitor, and other dyeing auxiliaries.

In order to adjust the hue, other reactive dyes of yellow, red, and blue may be mixed in a range of 20% by weight or less based on the mixture. Fibers that can be dyed with the dye mixture of the present invention include cellulose fibers such as cotton, viscose rayon, cupra ammonium rayon, and hemp. These fibers may be used as a mixed fiber of, for example, polyester, triacetate, polyacrylonitrile, and the like.

The dye mixture of the present invention can be applied to various known dyeing methods. Generally, it is desirable to apply the dye mixture to an exhaustion dyeing method. It is effective. To exhaust dye the cellulose-containing fiber using the water-soluble dye mixture of the present invention, for example, sodium bicarbonate, sodium carbonate, lithium carbonate, alkali such as caustic soda, and, for example, in the presence of inorganic salts such as sodium sulfate and salt, Can be dyed. The amount of alkali used at this time is usually 10 per liter of dyeing bath.
３０30 g. The amount of the inorganic salt used is suitably 50 to 80 g per liter of the dyeing bath. The dyeing temperature is usually 40 to 80C, preferably 50 to 60C.

[0027]

Next, the present invention will be described 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. Example 1 The following structural formula [a-1]

[0028]

Embedded image And 75 parts by weight of a disazo dye represented by the following structural formula [b-
1]

[0029]

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0.2 g and 0.8 g of a dye mixture containing 25 parts by weight of a monoazo reactive dye represented by
10 g of mercerized cotton knitted fabric was immersed in a dyeing bath (concentration of sodium sulfate: 50 g / l) prepared by dissolving 10 g of Glauber's salt and dissolving each, and the temperature was raised to 60 ° C. for 30 minutes.
Next, 3 g of sodium carbonate was added, and exhaust dyeing was performed at the same temperature for 1 hour. After dyeing, the dyed cloth is washed with water and a detergent [Hostapearl CT-4 (trade name, manufactured by Hoechst Japan KK)]
0] in a soaping bath with a bath ratio of 1:20 containing 2 g / l, 1
The soaping was performed at 00 ° C. for 10 minutes to obtain a black dyed cloth. This dyed fabric was evaluated for build-up properties, leveling properties, wash-off properties, wet fastness, and solubility in water. The results are shown in Table 1.

The evaluation methods are described below. <Build-up property> Both dyed fabrics dyed using 0.2 g of the dye mixture and 0.8 g of the dye mixture were visually evaluated, and the build-up property was evaluated. The results are shown as relative evaluations based on the evaluation results. (The dye mixture of Comparative Example 1 is known as having excellent build-up properties.)

<Leveling property> A dyed cloth dyed using 0.2 g of the dye mixture was visually evaluated. …: Excellent (uniformly dyed) Δ: slightly poor ×: not uniformly dyed, the density is clearly visible.

<Wet fastness> The washing fastness of a dyed fabric dyed with 0.8 g of the dye mixture was determined according to JIS L08.
84 (A-4), and the degree of contamination on cotton cloth and silk was evaluated.

<Solubility in Water> To 20 g of the dye mixture was added 100 cc of water, and the mixture was stirred at room temperature of 20 ° C. for 1 hour to evaluate the solubility. ○… Dissolved ×… Insoluble (The orange dye was not dissolved)

<Wash-off property> 0.8 g of dye mixture
After squeezing the dyed fabric using squeezing rate to 100%, the following treatment was performed, and the coloring degree of the second soaping solution was measured based on the following criteria. As the soaping agent, Hostapearl CT40 (trade name, manufactured by Hoechst Japan K.K.) was used.

[0036]

[Table 1] Water washing 30 ° C x 5 minutes Bath ratio 1:20 ↓ Hot water washing 60 ° C x 10 minutes Bath ratio 1:20 ↓ First soaping 60 ° C x 10 minutes Bath ratio 1:20 Soaping agent 2g / l ↓ 2 soaping 60 ° C x 10 minutes Bath ratio 1:20 Soaping agent 2g / l

(Criteria) ◎: Almost no coloring. ○: Some coloring. ×: fairly large coloring. XX: markedly colored.

Example 2 In the method of Example 1, the mixing ratio of the dye mixture is shown in Table 1.
The same test as in Example 1 was performed with the modification as described in Example 1. Table 1 shows the results.

Comparative Examples 1-2 The procedure of Example 1 was repeated, except that the monoazo reactive dyes [b-1] were replaced by the following reactive dyes.
The same test was performed. Table 1 shows the results. Monoazo reactive dye used in Comparative Example 1

[0040]

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Monoazo reactive dye used in Comparative Example 2

[0042]

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[0043]

[Table 2]

Examples 3-1 to 3-21 The procedure of Example 1 was repeated, except that the structural formula [b-1] was changed to the monoazo dyes described in Table 2, and otherwise the same as in Example 1. A good test showed that the build-up properties were slightly better than Comparative Example 1, the leveling properties were remarkably good as ○, the wash-off properties were remarkably excellent as ◎, the solubility in water was ○, Both cotton contamination and silk contamination were 5 ^- grade or higher.

[0045]

[Table 3]

[0046]

[Table 4]

[0047]

[Table 5]

[0048]

[Table 6]

[0049]

The dye mixture of the present invention is a dye mixture having excellent build-up properties, leveling properties and wash-off properties, and can dye a cellulose fiber material in black with good wet fastness. Further, this dye mixture has excellent solubility in water, and it is possible to prepare a stable high-concentration aqueous liquid product.

Continuation of front page (56) References JP-A-2-202295 (JP, A) JP-A-63-202667 (JP, A) JP-A-56-103249 (JP, A) European Patent Application Publication 545219 (EP, A1) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09B 67/22 C09B 62/00-62/84 D06P 3/66

Claims (2)

(57) [Claims] 1. A compound of the following general formula [A] in the form of a free acid: (Wherein, X represents -CH = CH ₂ group or -C ₂ H ₄ W group. However, W represents. A group capable of leaving by the action of an alkali) disazo reactive dyes 95-55 weight represented by % And the free acid in the form of the general formula [B] A dye mixture containing 5 to 45% by weight of a monoazo dye represented by the formula: 2. The following general formula [A] in the form of a free acid: (Wherein, X represents -CH = CH ₂ group or -C ₂ H ₄ W group. However, W represents. A group capable of leaving by the action of an alkali) disazo reactive dyes 95-55 weight represented by % And the free acid in the form of the general formula [B] A method for dyeing or printing a cellulose fiber material using a mixture comprising 5 to 45% by weight of a monoazo dye represented by the following formula: