JPH07324172A - Water-soluble dye mixture and method for dyeing or printing cellulose fiber material - Google Patents

Abstract

PURPOSE:To obtain a reactive black dye which has good build-up properties, leveling properties, wash-off properties, and wet fastness and can give a high- concn. fluid by compounding a specific reactive disazo dye with a monoazo dye. CONSTITUTION:The objective dye mixture comprises 95-55wt.% reactive disazo dye having a free acid form represented by formula I [wherein X is-CH=CH2 or-C2H4W (wherein W is a group separable by the action of an alkali)] and 5-45wt.% monoazo dye having a free acid form represented by formula II (wherein X is the same as in formula I; Z is halogen or a pyridinio group optionally substd. by a carboxyl or aminocarbonyl group; and R is H or 1-4C alkyl).

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 more specifically, it has good build-up property, level dyeing property, wash-off property (Wash-off) and wet fastness, and high concentration. The present invention relates to a reactive dye mixture for black capable of preparing a liquid product and a method for dyeing or printing a cellulose fiber material using the same.

[0002]

2. Description of the Related Art As a water-soluble reactive dye mixture for dyeing cellulose-containing fibers black, the following performances are required because the amount of dye used is 3 to 5 times as large as that of ordinary medium-practical colors. To be done. 1. The dyeing rate should not decrease even if the amount of dye used increases.
(Excellent build-up property) 2. Unfixed dye remaining inside the fiber in an amount of 3 to 5 times the normal amount can be easily removed from the fiber with a small amount of washing water.
(Good wash-off property) 3. Good fastness, especially wet fastness, of dyed black.

4. Be able to dye uniformly. Further, as the regulation of the degree of coloring of wastewater in dyeing plants becomes severe, the demand for dyes having a higher dyeing rate is increasing. Further, with the adoption of an automatic weighing system in a dyeing factory, it is required to be able to prepare a liquid product having a high concentration.

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

[0005]

[Chemical 3]

[0006]

[Chemical 4]

However, in the case of this mixed dye, although the build-up property is remarkably excellent, the level dyeing property and the wet fastness are insufficient, and the reactive dye represented by the structural formula (2) with respect to water. There is a problem that it is difficult to prepare a high-concentration liquid product because of its low solubility. Further, there is a problem that the dichlorotriazinyl group is hydrolyzed in an aqueous solution and the stability with time is deteriorated. On the other hand, a black mixture composed of reactive dyes represented by the following structural formulas (3) and (4) is known.

[0008]

[Chemical 5]

[0009]

[Chemical 6]

In the case of this mixed dye, in particular, due to the orange dye represented by the structural formula (4), the dyeing ratio is only about 50% in the dark color, and about 25% of the unfixed dye is on the fiber. To remain. Unfixed dye has a high affinity with fibers,
It needs to be washed, soaped and treated with sufficient water at high temperature. (Remarkably inferior wash-off property.) In addition, the extremely dark color has a problem that stain on silk is inferior in washing fastness, and improvement is desired.

[0011]

In view of the above situation, the present inventors have improved level dyeability, wash-off property and wet fastness without impairing the build-up property of the mixed dye,
Moreover, as a result of intensive studies aimed at obtaining a black dye mixture capable of preparing a high-concentration liquid product, as a result of further mixing a predetermined amount of a specific monoazo orange dye with the mixed dye, It was found that the object of the invention was achieved and the present invention was completed.

[0012]

The gist of the present invention is in the form of a free acid, which is represented by the following general formula [A]:

[0013]

[Chemical 7]

(In the formula, X is a -CH = CH ₂ group or -C ₂
Represents a H ₄ W group. However, W represents a group capable of leaving by the action of an alkali. ) 95 to 55% by weight of a disazo reactive dye represented by

[0015]

[Chemical 8]

(In the formula, X has the same meaning as described above, and Z
Is a halogen atom, or a pyridinio group which may be substituted with a carboxyl group or an aminocarbonyl group.

[0017]

[Chemical 9]

R is a hydrogen atom, or C ₁ -C ₄
Represents an alkyl group. ) Monoazo dye 5
A dye mixture containing 45% by weight and an exhaust dyeing method, a textile printing method and a continuous dyeing method for a cellulose fiber material using the same. Hereinafter, the present invention will be described in detail. In the general formulas [A] and [B] shown above in the present invention, the group which is eliminated by the action of the alkali represented by W of the —C ₂ H ₄ W group represented by X is usually a —OSO ₃ H group. , -SSO
Examples thereof include acid ester groups such as ₃ H groups, —OPO ₃ H ₂ groups, and —OCOCH ₃ groups, halogen atoms, and the like.
The SO ₃ H group is typical. In the general formula [B] shown above, examples of the C ₁ -C ₄ alkyl group represented by R include a methyl group, an ethyl group, a linear and side chain propyl group and a butyl group, but particularly a methyl group, an ethyl group. Is preferred.

In the general formula [B], the halogen atom represented by Z includes a bromine atom, a chlorine atom or a fluorine atom, preferably a chlorine atom or a fluorine atom, particularly preferably a fluorine atom. As the pyridinio group represented by Z, 3-carboxypyridinio group, 4-carboxypyridinio group, 3-aminocarbonylpyridinio group, 4-aminocarbonylpyridinio group,
Examples thereof include a pyridinio group, but a 3-carboxypyridinio group is particularly preferable. Preferred structures of the dye represented by the general formula [B] include the following.

[0020]

[Chemical 10]

[0021]

[Chemical 11]

(In the formula, Z and R have the same meanings as described above.) In order to further improve the dyeing ratio and the dye solubility, [B-
Particularly preferred is a mixture of the dye represented by I]: the dye represented by [B-II] in a weight ratio of 30 to 70:70 to 30. Here, R is a hydrogen atom, a methyl group, or an ethyl group, and Z is a chlorine atom, a fluorine atom, or a 3-carboxypyridinio group. ) Here, when Z is a fluorine atom or a 3-carboxypyridinio group, the dyeing ratio is 85% as compared with the case of a chlorine atom.
And 10% higher, thus further improving wash-off and wet fastness.

On the other hand, in the orange dye represented by the formula [B] of the present invention, when the —SO ₂ C ₂ H ₄ OSO ₃ H group is in the ortho position or the meta position with respect to the azo group, the dyeing rate and the solubility are respectively. Inferior to the dyes of the present invention in terms of fastness and light fastness.
In the present invention, the water-soluble reactive dyes represented by the general formulas [A] and [B] are both present in the form of a free acid or a salt thereof. Usually, as the salt, lithium salt, sodium salt, Alkali metal salts or alkaline earth metal salts such as potassium salts and calcium salts are preferred. A lithium salt is particularly preferable for improving the solubility.

The water-soluble reactive dyes represented by the above general formulas [A] and [B] can be produced by 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,
Further, the dye represented by the general formula [B] shown above is, for example, JP-B-39.
It can be manufactured according to the description of 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]. It is obtained by blending 85 to 65% by weight of the dye represented by the formula and 15 to 35% by weight of the dye represented by the general formula [B]. 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, an inorganic salt such as anhydrous sodium sulfate, a tamol dispersant, a pH buffering agent such as citric acid and acetic acid, a dust scattering inhibitor, a dye dissolving agent such as ε-caprolactam, and a dyeing auxiliary agent can be contained.

In order to adjust the hue, other reactive dyes of yellow, red and blue may be mixed within the range of 20 wt% or less with respect to the mixture. Fibers that can be dyed with the dye mixture of the present invention generally include cellulosic fibers such as cotton, viscose rayon, cupra ammonium rayon, and hemp. Further, these fibers may be used as a mixed fiber of polyester, polyacetate, polyacrylonitrile, or the like.

The dye mixture of the present invention can be applied to various known dyeing methods and printing methods. That is, it is effective for a usual exhaust dyeing method, various printing methods, and a continuous dyeing method such as a cold pad batch method or a pad steam method.
In order 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, the staining can be performed in the presence of an inorganic salt such as Glauber's salt and salt. The amount of alkali used at this time is usually 1
It is 10 to 30 g per liter. The amount of the inorganic salt used is appropriately 50 to 100 g per liter of the dyeing bath. The dyeing temperature is usually 40 to 80 ° C, preferably 50 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 The following structural formula [a-1]

[0029]

[Chemical 12]

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

[0031]

[Chemical 13]

0.2 g and 1.2 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 dye bath (Glauber's salt concentration 80 g / l) prepared by dissolving and dissolving 16 g of Glauber's salt in 30 ml each, and the temperature was raised to 60 ° C. for 30 minutes.
Then, 3 g of sodium carbonate was added, and exhaust dyeing was carried out at the same temperature for 1 hour. After dyeing, the dyed cloth is washed with water and a cleaning agent [Hostal Pearl CT-40, trade name, manufactured by Hoechst Japan KK]
100 in a soaping bath with a bath ratio of 1:20 containing 2 g / l
Soaping was carried out at 10 ° C. for 10 minutes to obtain a black dyed cloth.
With respect to this dyed cloth, build-up property, level dyeing property, wash-off property, wet fastness, and water solubility were evaluated, and the results are shown in Table 1. The evaluation methods are shown below.

<Build-up property> Both dyed fabrics dyed with 0.2 g of the dye mixture and 1.2 g of the dye mixture were visually evaluated to evaluate the build-up property, and the result was evaluated as the build-up of Comparative Example 1 described later. It was shown as a relative evaluation based on the result of sex evaluation. (The dye mixture of Comparative Example 1 is known to have excellent build-up properties.)

<Leveling property> A dyed cloth dyed with 0.2 g of the dye mixture was visually evaluated. ◯: Excellent (uniformly dyed) Δ: Slightly inferior ×: Not uniformly dyed and the shade is clearly visible.

<Wet fastness> With respect to the dyed fabric dyed with 1.2 g of the dye mixture, the fastness to washing is JIS L08.
It measured according to 84 (A-4) and evaluated the contamination degree to cotton cloth and silk. <Solubility in water> 100 g of water in 20 g of the dye mixture
Was added and stirred at room temperature of 20 ° C. for 1 hour to evaluate the solubility. ○: soluble ×: insoluble (orange dye does not dissolve)

<Wash-off property> 1.2 g of dye mixture
After squeezing the dyed fabric dyed with the squeezing agent to a squeezing ratio of 100%, the dyeing cloth was treated as follows, and the coloring degree of the second soaping liquid was judged according to the following criteria. As the soaping agent, Hostapearl CT40 (trade name, manufactured by Hoechst Japan Ltd.) was used.

[0037]

[Table 1] Washing with water 30 ° C x 5 minutes, bath ratio 1:20 ↓ Washing with water 60 ° C x 10 minutes, bath ratio 1:20 ↓ 1st soaping 60 ° C x 10 minutes, bath ratio 1:20, soaping agent 2g / L ↓ 2nd soaping 60 ° C x 10 minutes, bath ratio 1:20, soaping agent 2g / l

(Judgment Criteria) A: Almost no coloring. ○: There is some coloring. ×: Coloring is quite large. XX: Remarkably colored.

Example 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 1. The results are shown in Table-1.

Comparative Examples 1 to 3 Example 1 except that the monoazo reactive dyes of [b-1] were replaced by the following reactive dyes in the method of Example 1, respectively.
Tested exactly the same as. The results are shown in Table-1. Monoazo reactive dye used in Comparative Example 1

[0041]

[Chemical 14]

Monoazo reactive dye used in Comparative Example 2

[0043]

[Chemical 15]

Monoazo type reactive dye used in Comparative Example 3

[0045]

[Chemical 16]

[0046]

[Table 2]

Example 3 The monoazo reactive dye represented by the structural formula (b-1) in Example 1 was prepared by the following structural formula.

[0048]

[Chemical 17]

[0049]

[Chemical 18]

The same test as in Example 1 was carried out except that the dye represented by the formula (3) was used. As a result, the build-up property was slightly better than the standard, the level dyeing property was ○, the wash-off property test was ⊚, and the wash fastness was cotton contamination of grade 4 and silk contamination of grade 4-5. It was Regarding the solubility in water, 100 cc of water was added to 30 g of the dye mixture, and the solubility was evaluated by stirring at room temperature of 20 ° C. for 1 hour, but it was found to be dissolved. The size of this solubility is especially due to the printing method,
This is a very important feature in obtaining a deep black dyed product in the continuous dyeing method.

Examples 4-1 to 4-20 In the method of Example 1, the dye represented by the structural formula [b-1] is changed to the monoazo dye described in Table-2,
Except for this, the same tests as in Example 1 were carried out. As a result, the build-up property was superior to that in Comparative Example 1, the level dyeing property was markedly good, and the wash-off property was markedly excellent, and the solubility in water was excellent. Is good, and the washing fastness was excellent in that cotton stain and silk stain were 4 or higher and 4-5, respectively.

[0052]

[Table 3]

[0053]

[Table 4]

[0054]

[Table 5]

[0055]

[Table 6]

[0056]

The dye mixture of the present invention is a dye mixture having excellent build-up properties, level dyeing properties and wash-off properties, and can dye cellulose fiber materials in black with good wet fastness. Further, this dye mixture has excellent solubility in water, and a stable highly concentrated aqueous liquid product can be prepared.

Claims (4)

[Claims] 1. A compound represented by 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 general formula [B] (In the formula, X has the same meaning as described above, Z represents a halogen atom, or a pyridinio group which may be substituted with a carboxyl group or an aminocarbonyl group, and R represents a hydrogen atom or a C _{1 to} C _{4 group} . A dye mixture containing 5 to 45% by weight of a monoazo dye represented by (which represents an alkyl group). 2. X in the general formulas [A] and [B] is-
The dye mixture according to claim 1, which is a C ₂ H ₄ OSO ₃ H group. 3. The dye mixture according to claim 1, wherein Z in the general formula [B] is a pyridinio group substituted with a fluorine atom or a carboxyl group. 4. A method for dyeing or printing a cellulose fiber material using the dye mixture according to any one of claims 1 to 3.