JPH048551B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for dyeing cellulose-containing fibers, and more specifically, it dyes cellulose-containing fibers by an exhaustion method using a red component in combination with a yellow component and/or a blue component. In this method, by blending and using each specific water-soluble reactive dye having a vinylsulfone type, monochloro- or monofluoro-triazine type reactive group as each color component, the amount of inorganic salt used in the dye bath can be reduced compared to the conventional method. This invention relates to an industrially extremely advantageous dyeing method that can perform good exhaust dyeing even when the amount is reduced to a large extent. Water-soluble reactive dyes have vivid color tones and good wet fastness, and can be reactively fixed to cellulose-containing fibers using various dyeing methods.
It is widely used for exhaust dyeing and printing of cellulose-containing fibers. (Prior art) Conventionally, in the exhaust dyeing method using water-soluble reactive dyes,
In order to obtain a richly dyed product, it is necessary to add 50 to 100 g of inorganic salt, such as mirabilite or common salt, per dye bath during dyeing as a means to improve dyeing properties.
If the amount added is large, especially in dyeing factories, not only will dyeing costs increase, but also troublesome problems will arise in terms of dyeing wastewater treatment. Therefore, there has been a demand for water-soluble reactive dyes that can perform good exhaust dyeing even in the presence of small amounts of inorganic salts. (Problems to be Solved by the Invention) However, for example, when the water-soluble reactive dye represented by the general formula [ ] of the red component in the present invention is used alone, good dyeing can be achieved even with a small amount of inorganic salt. is possible and satisfies the above-mentioned conventional demands, and there is no problem. However, when using it in combination with a yellow component and/or blue component reactive dye, the yellow and/or blue component to be blended Regarding each component, there was a problem in that unless the components could be satisfactorily exhaust dyed with a small amount of inorganic salt, the desired good characteristics of the red component dye could not be fully exhibited. The present invention, in the form of a free acid, has the general formula [] (In the formula, R ¹ and R ² represent a hydrogen atom or a lower alkyl group that may be substituted with a hydroxyl group, R ³ represents a hydrogen atom, a lower alkyl group, or a halogen atom, and X represents a -CH=CH ₂ group. or −C ₂ H ₄ OSO ₃ H group.) When used in combination with a red water-soluble monoazo reactive dye represented by Novel water-soluble reactive dyes of three primary colors that make it possible to solve the above-mentioned conventional problems by obtaining reactive dyes of the vinyl sulfone type or of the monochloro- or monofluoro-triazine type in the blue and blue colors. The purpose is to provide an exhaust dyeing method using a suitable combination. (Means for Solving the Problems) The present inventors have conducted various studies to achieve the above object, and as a result, have arrived at the present invention. That is, the present invention provides, in the form of a free acid, the general formula [] (In the formula, R ¹ and R ² represent a hydrogen atom or a lower alkyl group that may be substituted with a hydroxyl group, R ³ represents a hydrogen atom, a lower alkyl group, or a halogen atom, and X represents a -CH=CH ₂ group. or -C ₂ H ₄ OSO ₃ H group) is used as a red component, and a mixed dye is used in which a yellow component and/or a blue component water-soluble reactive dye is blended. In the method of exhaust dyeing cellulose-containing fibers in the presence of inorganic salts and alkalis, the yellow component is in the form of a free acid of the general formula [] (In the formula, Z represents a chlorine atom or a fluorine atom, and
has the same meaning as in the general formula [] shown above. ) using the water-soluble monoazo reactive dye represented by the general formula [ ] as the blue component in the free acid form. (In the formula, Y ¹ and Y ² are −CH=CH ₂ group, −
C ₂ H ₄ OSO ₃ H group or -OH group, R ⁴ is -
Indicates a COOH group or a chlorine atom, and also m and n
represents the number 0 or 1, but m and n are never 0 at the same time, and Z has the same meaning as in the above general formula []. The gist of this paper is a method for dyeing cellulose-containing fibers, which is characterized by using a water-soluble disazo-based reactive dye represented by: The present invention will be explained in detail below. The dyeing method of the present invention is based on the premise of using a water-soluble reactive dye represented by the above general formula [] in the form of a free acid as a red component, and in the general formula [], R ¹ , The lower alkyl group represented by R ² and R ³ includes a straight or branched unsubstituted alkyl group having 1 to 4 carbon atoms,
Examples of the lower alkyl group substituted with a hydroxyl group represented by R ¹ and R ² include a 2-hydroxyethyl group, and examples of the halogen atom represented by R ³ include a bromine atom and a chlorine atom. . In the dyeing method of the present invention, the yellow component reactive dye represented by the general formula [] to be blended with the red component reactive dye represented by the general formula [] and/or the yellow component reactive dye represented by the general formula [] The amount of each blue component reactive dye used is 0.05 to 50 times, preferably 0.1 to 10 times by weight, the amount of the red component reactive dye represented by the general formula []. According to the invention,
Dyes of various desired shades can be prepared based on red component dyes, but in all cases good dyeing can be achieved in the presence of small amounts of inorganic salts. All of the water-soluble reactive dyes used in the dyeing method of the present invention exist in the form of free acids or their salts, and the salts are usually alkali metals such as lithium salts, sodium salts, potassium salts, and calcium salts. Salts or alkaline earth, metal salts are preferred.
In addition, the general formula [ ] ~ used in the present invention is
The water-soluble reactive dye represented by [ ] can be produced according to a known method. The cellulose-containing fibers to which the dyeing method of the present invention is applied are usually cellulose fibers such as cotton, viscose rayon, cuprammonium rayon, and hemp, or combinations of these cellulose fibers with polyester, triacetate, diacetate, and polyacrylonitrile. Examples include fibers mixed with polyamide, wool, silk, etc. In order to perform exhaust dyeing of cellulose-containing fibers by the dyeing method using the water-soluble reactive dyes of the three primary colors of the present invention, for example, sodium bicarbonate, sodium carbonate,
Dyeing can be carried out in the presence of an alkali such as lithium carbonate, caustic soda, or triethylamine, and an inorganic salt such as mirabilite or common salt. The amount of alkali used in this case is usually 10 to 30 per dye bath.
It is g. Further, the amount of inorganic salt used may be as large as 50 g or more per dye bath, but in the case of the dyeing method of the present invention, a small amount of 5 to 40 g is sufficient. More specifically, even within the range of the above-mentioned usage amount of inorganic salt in the case of the present invention, it varies depending on the density of the dyed fabric to be obtained. in case of
15~30g/about, 30~40g/for dark colors
That's about it. Moreover, the dyeing temperature is 40 to 80°C, preferably 50 to 60°C. After dyeing, the dyed product is soaped, washed with water, and then dried. (Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples. Example 1 The following structural formula [a] in the form of free acid as a red component 0.1 g of a reactive dye represented by 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 and the following structural formula [c] in the form of a free acid as a blue component. A dye mixture consisting of 0.1g of the reactive dye represented by is dissolved in 200ml of water, 5g of Glauber's salt is added to this, 10g of cotton cloth is added, and the temperature is raised from room temperature (25°C) to 60°C over 30 minutes. Then, 4 g of anhydrous sodium carbonate was further added and dyeing was carried out at 60° C. for 1 hour. Thereafter, the dyed product was washed with water, soaped, washed with water and dried according to a conventional method to obtain a red brown dyed product. In this dyeing, the reaction fixation of each color component dye to the fibers was very good. In addition, in the above dyeing method, the amount of Glauber's salt used was 5g (i.e. 25g/
) to 10 g (50 g/) and compared the density and hue of the dyed products, the results were almost the same. Examples 2 to 4 In Example 1, the blending amounts of reactive dyes [a] to [c] were changed to the proportions shown in Table 1 below, and similar dyeing was carried out, resulting in the color tones shown in Table 1 below. A dyed product was obtained, and in all cases, the reaction fixation of each color component dye to the fiber was very good.

[Table] Comparative Example 1 In Example 3, the blue component, reactive dye [c], was a known blue dye with the following structural formula (represented in free acid form): When similar dyeing was carried out using 0.2 g of the reactive dye represented by , the color tone of the dyed product obtained was not engine but yellowish rubin. This is due to the extremely poor dyeability of the blue dye, and in fact, the dye bath residue had a very strong blue tint. For reference, in Comparative Example 1 above,
Change the amount of Glauber's salt used from 5g (25g/) to 10g (50g/).
When dyeing was carried out by increasing the amount to 1.9 g/), the color tone of the dyed product obtained was almost the same as in Example 3, a dark red color. Example 5 The method of Example 1 was repeated, except that the red component, reactive dye [a], was changed to each structural formula (represented in free acid form) shown in Table 2 below. When dyeing was carried out according to the method, in all cases, the reactive fixity of each color component dye to the fibers was good, and a dyed product of a deep red brown color was obtained.

【table】

[Table] Example 6 Example 1 except that the blue component, reactive dye [c], was changed to each structural formula (represented in free acid form) shown in Table 3 below. Dyeing was carried out according to method 1. In all cases, the reaction fixation of each color component dye to the fibers was good, and a dyed product of a deep red brown color was obtained.

【table】

[Table] Example 7 Example 1 except that the yellow component, reactive dye [b], was changed to each structural formula (represented in free acid form) shown in Table 4 below. Dyeing was carried out according to method 1. In all cases, the reaction fixation of each color component dye to the fibers was good, and a dyed product of a deep red brown color was obtained.

【table】

[Table] Example 8 0.2 g of a dye mixture containing 0.1 g of the reactive dye [a], which is the red component of the present invention in Example 1, and 0.1 g of the reactive dye [b], which is the yellow component of the present invention, was added to water.
200 ml of sodium sulfate, and 10 g of Glauber's salt was dissolved therein to prepare a dye bath (mirabilite concentration: 50 g/1). 10g of unmercered cotton stockinette was soaked in this, and it took 30 minutes to
The temperature was raised to .degree. C., 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, washed with water, and dried in a conventional manner to obtain an orange dyed fabric. The surface reflectance of this dyed fabric was measured using a color difference meter (manufactured by Nippon Denshoku Kogyo Co., Ltd.). In addition, in order to investigate the salt concentration dependence during dyeing of the dye mixture used in this example, dyeing was carried out in the same manner as described above except that the concentration of Glauber's salt in the dye bath was changed to 25 g/1. The surface reflectance of the dyed fabric obtained was measured. Based on the above measurement results, the concentration of mirabilite is 50g/1
The surface reflectance of the dyed fabric and the concentration of mirabilite in 25g/1
The dependence on salt concentration was determined by the difference in surface reflectance (hue difference ΔE) of dyed fabrics. These results are summarized and shown in Table 5 below for comparison. Comparative Examples 2 to 3 In Example 8, the yellow component of the present invention, the reactive dye [b], was replaced with the following formula [b-1] (Comparative Example 2) or [b-2], which is a known yellow reactive dye. (Comparative Example 3) (All expressed in free acid form.) The staining test was conducted in exactly the same manner except that the dye was changed to In this way, Example 8 was prepared for the dyed fabrics obtained in Comparative Examples 2 and 3, in which the concentration of Glauber's salt in the dye bath was 50 g/1 and 25 g/1.
The surface reflectance was measured in the same manner as above, and then, based on these results, the salt concentration dependence of Comparative Examples 2 and 3 was determined in the same manner. The salt concentration dependencies obtained above are summarized and shown in Table 5 below.

[Table] Regarding salt concentration dependence, it can be said that a value of 2 or less is at an excellent level.
Example 9 In Example 8, the reactive dye [b] which is the yellow component of the present invention in Example 1 was not used, but instead No. The following formula corresponds to .6-7 Dyeing was carried out in exactly the same manner as in Example 8 except that 0.1 g of the reactive dye represented by was used to obtain a purple dyed cloth. The concentration of Glauber's salt in the dye bath thus obtained was 50g/1.
The surface reflectance was measured in the same manner as in Example 8 for the dyed fabrics with 25g/1 and 25g/1,
Based on the results, salt concentration dependence was determined. Comparative Examples 4 to 6 In Example 9, the reactive dye that is the blue component of the present invention was not used, and instead, the following formula [C-1]
(Comparative Example 4), the following formula [C-2] (Comparative Example 5), or the following formula [C-3] (Comparative Example 6) A dyeing test was carried out in exactly the same manner as in Example 9 above, except that a known blue reactive dye expressed in the form of a free acid was used in each case. In this way, for the dyed fabrics obtained in each of Comparative Examples 4 to 6, in which the concentration of Glauber's salt in the dye bath was 50 g/1 and 25 g/1, Example 9
The surface reflectance was measured in the same manner as above, and then, based on these results, the salt concentration dependence of Comparative Examples 4 to 6 was determined in the same manner. The salt concentration dependencies obtained above are summarized and shown in Table 6 below.

[Table] is at an excellent level.
Examples 10 and 11 In Example 8, the reactive dye [a], which is the red component of the present invention in Example 1, was not used, and instead, the red component of the present invention, in the form of free acid, was used in Table 2 above. The following formula corresponds to No. 5-10 of 2. Use 0.1 g of a red reactive dye represented by (Example 10), or use the following formula corresponding to No. 5-5 in 1 of Table 2 above in the form of a free acid among the red components of the present invention. Dyeing was carried out in exactly the same manner as in Example 8, except that 0.1 g of the red reactive dye represented by (Example 11) was used to obtain an orange dyed fabric. In each of Examples 10 and 11 thus obtained,
When the concentration of Glauber's salt in the dye bath is 50g/1 and 25g/1
The surface reflectance of the dyed fabric was measured in the same manner as in Example 9, and based on the results,
The salt concentration dependence during dyeing of each dye mixture used in 10 and 11 was determined. Example 12 In Example 9, as the blue component, Example 1
Reactive dye [C] which is the blue component of the present invention in
Dyeing was carried out in exactly the same manner as in Example 9, except that 0.1 g was used, to obtain a purple dyed cloth. Next, in the same manner as in Example 9, the salt concentration dependence of the dye mixture of Example 12 during dyeing was determined. The salt concentration dependence of the reactive dye mixtures of the present invention in Examples 10 to 12 obtained above is summarized in Table 7 below.

[Table] is at an excellent level.
(Effects of the Invention) As is clear from the above results, the dyeing method for cellulose-containing fibers of the present invention is a vinyl sulfone type or monochloro- or monofluoro-triazine type reaction of the three primary colors of red, yellow, and blue. It is a combination exhaust dyeing method that combines specific water-soluble reactive dyes having a group of 1, 2, 3, and 3. Because it can dye with good density, it is very advantageous not only for dyeing work in dyeing factories but also for dyeing wastewater treatment, etc., and it is an industrial method that enables resource saving and cost reduction of dyeing costs. It has a significant and valuable effect. In addition, according to the present invention, as is clear from the results of Example 1, the hue of the dyed product obtained is the same regardless of whether the amount of Glauber's salt used is 25g/50g/. This shows that in the dyeing method of the present invention, even if the concentration of the inorganic salt changes from 50 to 25 g/region, the dyeing result does not change. Therefore, in the present invention, for example, about 50
When dyeing is carried out at an inorganic salt concentration of 0/1, a remarkable effect is that even if the actual inorganic salt concentration changes slightly from the target setting value, a dyed product with a constant hue can be stably obtained. can also be played.

Claims (1)

[Claims] 1 In the form of a free acid, the general formula [] (In the formula, R ¹ and R ² represent a hydrogen atom or a lower alkyl group that may be substituted with a hydroxyl group, R ³ represents a hydrogen atom, a lower alkyl group, or a halogen atom, and X represents a -CH=CH ₂ group. or -C ₂ H ₄ OSO ₃ H group) is used as a red component, and a mixed dye is used in which a yellow component and/or a blue component water-soluble reactive dye is blended. In the method of exhaust dyeing cellulose-containing fibers in the presence of inorganic salts and alkalis, the yellow component is in the form of a free acid of the general formula [] (In the formula, Z represents a chlorine atom or a fluorine atom, and
has the same meaning as in the general formula [] shown above. ) using the water-soluble monoazo reactive dye represented by the general formula [ ] as the blue component in the free acid form. (In the formula, Y ¹ and Y ² are −CH=CH ₂ group, −
C ₂ H ₄ OSO ₃ H group or -OH group, R ⁴ is -
Indicates a COOH group or a chlorine atom, and also m and n
represents the number 0 or 1, but m and n are never 0 at the same time, and Z has the same meaning as in the above general formula []. ) A dyeing method for cellulose-containing fibers characterized by using a water-soluble disazo-based reactive dye represented by: 2. The dyeing method according to claim 1, wherein the inorganic salt is Glauber's salt. 3. The dyeing method according to claim 1 or 2, characterized in that the amount of inorganic salt used is 5 to 40 g per dye bath. 4. The dyeing method according to claim 1, wherein the dyeing temperature is 40 to 80°C. 5. The amount of the water-soluble reactive dye represented by the general formula [] or [] used is 0.05 to 50 times the weight of the water-soluble reactive dye represented by the general formula []. A dyeing method according to claim 1.