JPH0768672B2 - Dyeing method for cellulose-containing fibers - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for dyeing cellulose-containing fibers, and more specifically, it uses a specific water-soluble reactive dye as a red component and a specific blue component. And / or a method of exhaust dyeing cellulose-containing fibers by using a water-soluble reactive dye composed of a yellow component in combination.

[Conventional technology]

The reactive dye has a clear color tone and good wet fastness,
Since it can be fixed to cellulose fibers by various dyeing methods, it is widely used for dip dyeing and printing of cellulose fibers.

However, when a dense dyed product is obtained by the dip dyeing method, as a means for improving the dyeing property, at the time of dyeing, for example, an inorganic salt such as Glauber's salt or salt is added in an amount of 50 to 10 per dye bath.
Although it is necessary to add 0 g, if the addition amount increases, the cost of dyeing will increase and a problem will occur from the viewpoint of the treatment of dyeing wastewater. Therefore, it has been desired to develop a reactive dye capable of excellent dyeing even in the presence of a small amount of an inorganic salt.

From such a viewpoint, as a result of diligent studies by the present inventors,
First, in the form of the free acid, the following general formula [I] (In the formula, R ¹ and R ² each represent a hydrogen principle or a lower alkyl group which may have a substituent, R ³ represents a hydrogen atom, a lower alkyl group or a halogen atom, X 1
Represents a -CH = CH ₂ or -C ₂ H ₄ OSO ₃ H), and a red vinylsulfone-type water-soluble reactive dye represented by In comparison, it was found that sufficient dyeing property can be obtained even when the amount of inorganic salt to be added is reduced to about 1/5 to 1/10.

However, there is no problem when the water-soluble reactive dye represented by the general formula [I] shown above is used alone, but when it is used in combination with the blue component and / or the yellow component, the mixed dye is used. As for the above, unless the dye can be satisfactorily dyed with a small amount of an inorganic salt, the characteristics of the above dye cannot be sufficiently exhibited. Therefore, a blue component and a yellow component which can be favorably dyed with a small amount of an inorganic salt when used in combination with the water-soluble reactive dye represented by the above general formula [I] are desired.

[Problems to be Solved by the Invention]

The present invention has been made in view of such circumstances, and an object thereof is to mix a red component and a blue component and / or a yellow component, which enables good dyeing even in the presence of a small amount of an inorganic salt. An object of the present invention is to provide a method for dyeing a cellulose-containing fiber using a dye.

The present inventors have found that blue-based and yellow-based reactions capable of good dyeing even in the presence of a small amount of an inorganic salt, even when used in combination with a red reactive dye represented by the general formula [I] shown above. As a result of various studies to obtain a reactive dye, it was found that the above object of the present invention can be achieved by selecting a specific reactive dye, and the present invention has been completed.

[Means for Solving the Problems]

The gist of the present invention is the following formula [I] in the form of a free acid. (In the formula, R ¹ and R ² each represent a hydrogen atom or a lower alkyl group which may have a substituent, R ³ represents a hydrogen atom, a lower alkyl group or a halogen atom, X 1
Mixing the water-soluble reactive dye represented by showing a -CH = CH ₂ or -C ₂ H ₄ OSO ₃ H) as a red component, by blending a water-soluble reactive dye of the blue component and / or yellow components to In the method of exhaust dyeing a cellulose-containing fiber in the presence of an inorganic salt and an alkali using a dye, a yellow component in the form of a free acid represented by the following general formula [II] (Wherein, R ⁴ is -NHCOCH ₃ group, -NHCOC ₂ H ₅ group, -NHCONH ₂
A group or —NHCOSO ₂ CH ₃ group, and R ¹ and X have the same meaning as in the above-mentioned general formula [I]. ) Is a water-soluble reactive dye represented by the general formula [III] in the form of the free acid in the blue component. (Wherein R ⁵ represents a lower alkyl group and X has the same meaning as in the above-mentioned general formula [I]), a water-soluble reactive dye represented by the general formula [IV] in the form of a free acid. (Wherein, Y is -CH = CH ₂ group, -C ₂ H ₄ OSO ₃ H group or -O
H group, Z is chlorine atom or fluorine atom, W
Is an -OR ⁵ group or R ⁵ and X have the same meanings as in the general formulas [I] and [III] shown above. ) In the form of a water-soluble reactive dye or a free acid represented by the following general formula [V] (In the formula, R ¹ and X have the same meaning as in the above-mentioned general formula [I].) A dyeing method for cellulose-containing fibers, which is a water-soluble reactive dye.

Hereinafter, the present invention will be described in detail.

In the present invention, it is premised that the water-soluble reactive dye represented by the above-mentioned general formula [I] is used as the red component. In the general formula [I], R ¹ and R ² are used. Examples of the lower alkyl group which may have a substituent include a C _{1 to} C ₄ linear or branched unsubstituted alkyl group, 2-hydroxyethyl, 2-cyanoethyl,
Examples thereof include a hydroxyl group such as cyanomethyl, 2-chloroethyl and 3-ethoxypropyl, a cyano group, a C _{1 to} C ₄ lower alkyl group substituted with a halogen atom or an alkoxy group. Further, as the lower alkyl group represented by R ³ ,
Examples of the C _{1 to} C ₄ linear or branched unsubstituted alkyl group, and examples of the halogen atom include a bromine atom and a chlorine atom.

In the present invention, in contrast to the specific red component represented by the general formula [I] shown above, the water-soluble reactive dye represented by the general formula [II] shown above is used as a yellow component, and the red component represented by the general formula The essential requirement is to use the water-soluble reactive dyes represented by the formulas [III] to [V].

In the general formulas [II] and [V] shown above, R ¹ represents the same group as R ¹ in the general formula [I] shown above, but is a hydrogen atom or a linear or branched C _{1 to} C ₄ chain. Unsubstituted alkyl groups are preferred.

In the general formulas [III] and [IV] shown above, examples of the lower alkyl group represented by R ⁵ include C _{1 to} C ₄ linear or branched unsubstituted alkyl groups.

In the dyeing method of the present invention, the yellow component reactive dye represented by the general formula [II] and / or the general formula [III] represented by the general formula [II] to be blended with the red component reactive dye represented by the general formula [I].
The amount of each of the blue component reactive dyes represented by
The amount is 0.05 to 50 times by weight, preferably 0.1 to 10 times by weight, the amount of the red component reactive dye represented by the general formula [I] shown above. According to the present invention, various desired color tone dyes can be prepared based on the red component dye, but in any case, a good dye can be prepared in the presence of a small amount of an inorganic salt.

In the present invention, any of the water-soluble reactive dyes is present in the form of a free acid or a salt thereof.
Alkali metal salts or alkaline earth metal salts such as lithium salts, sodium salts, potassium salts and calcium salts are preferred.

The water-soluble reactive dyes represented by the general formulas [I] to [V] shown above can be produced according to known methods, and the production method is not particularly limited.

As the cellulose-containing fiber to be dyed in the present invention, cotton, viscose rayon, cupra ammonium rayon, in addition to cellulose fibers such as hemp, these cellulose fibers and polyester, cellulose triacetate, cellulose diacetate, polyacrylonitrile,
Examples include mixed fibers such as polyamide, wool and silk.

For exhaustion dyeing of cellulose-containing fibers using the reactive dye of the present invention, for example, sodium bicarbonate, sodium carbonate, lithium carbonate, caustic soda, alkali such as triethylamine, and the presence of an inorganic salt such as mirabilite and salt. under,
Preferably, it can be dyed in the presence of Glauber's salt. The amount of alkali used at this time is usually 10 to 30 g per dye bath.
Is.

On the other hand, the amount of the inorganic salt used may be as large as 50 g or more per dyeing bath, but the present invention uses a mixture of the specific reactive dyes, for example, a small amount of 5-40 g /. It is possible to sufficiently stain with. Further, the amount of the inorganic salt used varies depending on the dyeing density of the dyed cloth to be obtained, and specifically, the dyeing density is, for example, 5 to 15 g / about in the case of a light color, and 15 to 15 in the case of a medium color. About 30g / about 30 ~ 40g / in case of dark color. The dyeing temperature is 40 to 80 ° C, preferably 50 to 60 ° C. The dyed product after dyeing is subjected to soaping and washing with water, then dried and collected.

〔Example〕

Hereinafter, the method of the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

Example 1 The following structural formula [a] in the form of a free acid as a red component 0.1 g of the reactive dye represented by the formula below and the following structural formula [b] in the form of a free acid as a yellow component. 0.1 g of a reactive dye represented by the following formula and the following structural formula [c] in the form of a free acid as a blue component. A reactive mixture of 0.1 g of reactive dye represented by
Dissolve in l, add 5 g of sodium sulfate, add 10 g of cotton cloth, raise the temperature from room temperature (25 ° C) to 60 ° C over 30 minutes, and add 4 g of anhydrous sodium carbonate to 60 Staining was carried out at 0 ° C for 1 hour. Thereafter, the product was washed with water, soaped, washed with water and dried in a conventional manner to obtain a brown dyed product.

In this dyeing, the reaction fixation of each color component dye to the fiber was very good. In the above dyeing method,
When the amount of Glauber's salt used was increased from 5 g (that is, 25 g /) to 10 g (50 g /) and dyeing was performed, and the concentrations and hues of the obtained dyed products were compared, the results were almost the same.

Examples 2 to 4 In Example 1, when the compounding amounts of the reactive dyes [a] to [c] were changed to the ratios shown in Table 1 below and the same dyeing was performed, the color tone shown in Table 1 below was obtained. The dyed product of
In each case, the reaction fixing property to the fiber of each color component dyeing was very good.

Comparative Example 1 In Example 1, the reactive dye [c], which is a blue component, is a known blue dye having the following structural formula (represented in the form of free acid): When the same dyeing was carried out using 5 g of Glauber's salt, the color tone of the resulting dyeing product was orange instead of brown. This is due to the extremely poor dyeing property of the blue dye, and in fact,
This dyebath residual liquid had a very strong blue tint.

For reference, in Comparative Example 1 above, the amount of Glauber's salt used was increased from 5 g (25 g /) to 10 g (50 g /) for dyeing. It became a brown color almost the same as.

Examples 5 to 8 In Example 1, the reactive dye [b], which is a yellow component, was changed to each structural formula (shown in the form of free acid) shown in Table 2 and the reactive dye [c] which was a blue component was used. Was dyed according to the method described in Example 1 except that each of the structural formulas (shown in the form of free acid) shown in Table 2 was changed. As a result, the reaction sticking property was very good in all cases.

The hue of each dyed fabric is shown in Table-2.

Example 12 The method of Example 1 except that the reactive dye [a], which is the red component, was changed to one of the structural formulas (represented in the form of free acid) shown in Table 3 below. Dyeing was carried out according to the above-mentioned method. In each case, the reaction fixation of the dye of each color component to the fiber was good, and a deep brown dyeing product was obtained.

[Effects of the Invention] As described in detail above, in the present invention, in dyeing the cellulose-containing fiber, the desired red color tone is obtained by adding a specific red component and a specific blue component to the specific red component in appropriate amounts. Mixed dyes can be prepared and good dyeing can be carried out even in the presence of small amounts of inorganic salts. That is, good dyeing can be achieved even if the amount of the inorganic salt used is reduced by about 1/3 to 1/10 as compared with the conventional method. Therefore,
INDUSTRIAL APPLICABILITY The present invention is a dyeing method capable of industrially saving resources, reducing the cost of dyeing, and the like, and is an excellent dyeing method for cellulose-containing fibers.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location D06P 1/384 (56) References JP 62-212467 (JP, A) JP 60- 226561 (JP, A) JP 63-112781 (JP, A) JP 60-260654 (JP, A)

Claims (1)

[Claims] 1. The following general formula [I] in the form of a free acid. (In the formula, R ¹ and R ² each represent a hydrogen atom or a lower alkyl group which may have a substituent, R ³ represents a hydrogen atom, a lower alkyl group or a halogen atom, X 1
Represents a -CH = CH ₂ or -C ₂ H ₄ OSO ₃ H) mixture containing a water-soluble reactive dye of red component and a blue component and / or a yellow component of water-soluble reactive dye. In the method of exhaust dyeing a cellulose-containing fiber in the presence of an inorganic salt and an alkali using a dye, a yellow component in the form of a free acid represented by the following general formula [II] (Wherein, R ⁴ is -NHCOCH ₃ group, -NHCOC ₂ H ₅ group, -NHCONH ₂
A group or —NHCOSO ₂ CH ₃ group, and R ¹ and X have the same meaning as in the above-mentioned general formula [I]. ) Is a water-soluble reactive dye represented by the general formula [III] in which the blue component is in the form of a free acid. (In the formula, R ⁵ represents a lower alkyl group, and X has the same meaning as in the general formula [I] shown above.) A water-soluble reactive dye represented by the general formula [IV] in the form of a free acid. (Wherein, Y is -CH = CH ₂ group, -C ₂ H ₄ OSO ₃ H group or -O
H group, Z is chlorine atom or fluorine atom, W
Is an OR ⁵ group or R ⁵ and X are represented by the general formulas [I] and [III] shown above.
Has the same meaning as in. ) In the form of a water-soluble reactive dye or a free acid represented by the following general formula [V] (In the formula, R ¹ and X have the same meaning as in the general formula [I] shown above.) A dyeing method for cellulose-containing fibers, which is a water-soluble reactive dye.