JPH0438780B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water-soluble dye suitable for dyeing composite fibers containing, for example, acrylic fibers. Specifically, a water-soluble dye having at least one reactive halogenotriazinyl group and a cationic group in the dye structure is suitable for simultaneously dyeing acrylic fibers and composite fibers made of wool, synthetic polyamide, or cellulose. It concerns soluble dyes. Conventionally, acrylic fibers have been dyed with cationic dyes that have cationic groups, and wool, synthetic polyamide, and cellulose fibers have been dyed with acid dyes, metal-containing dyes, and direct dyes that have anionic groups such as -SO ₃ Na groups and -COONa groups. , or dyed with reactive dyes. Therefore, when dyeing these composite fibers, it is carried out using a blended dye system of both, but in general dyeing where cationic dyes and anionic dyes coexist, the dyes form complexes due to the difference in charge. , there are many problems that make dyeing impossible. In view of this, the present inventors have conducted extensive research and found that if a cationic water-soluble dye having at least one reactive halogenotriazinyl group is used, acrylic fibers (dyed by ionic bonds) and wool can be dyed. We have discovered that mixed fibers with synthetic polyamide or cellulose fibers (dyed by covalent bonds) can be dyed in one step, and have arrived at the present invention. That is, the dye according to the present invention has a -SO ₃ H group or a -
The following general formula does not have a COOH group [] [In the formula, D is a dye matrix residue, R ¹ is a hydrogen atom or a methyl group, R ² , R ³ and R ⁴ are a methyl group or an ethyl group, X is a halogen atom, -Y- is -O - group, -S- group or

[Formula] represents a group (R ⁵ represents a hydrogen atom, methyl group or ethyl group), -Z- represents a methylene group, ethylene group or trimethylene group, A represents an anionic group, n is a positive integer It is. ] It is a water-soluble dye shown by. The dye represented by the general formula [] is represented by the general formula below. [In the formula, D, R ¹ , R ² , R ³ , X, Y, Z and n are the same as defined above. ] and an alkylating agent represented by the general formula [] R ³ -A...[] (R ³ and A are the same as defined above). The parent structure D represented by the general formula [ ] of the present invention includes monoazo, disazo, anthraquinone, nitro, stilbene, methyl, azamethine, polymethine, perinone, quinophthalone, and naphthoimine. can give. In particular, monoazo-based, disazo-based, and anthraquinone-based ones are preferably used. These dye matrices may contain heavy metals if necessary. Specifically, dye matrices described in JP-A-54-73988, JP-A-55-86839, JP-A-55-92769, JP-A-55-133456, JP-A-55-164250, JP-A-55-151064, etc. can be used. The halogen atom represented by X in the general formula [] includes a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom is particularly preferred because of its high reactivity. Alkylating agent R ³ -A represented by the general formula []
Specific examples include dimethyl sulfate, diethyl sulfate,
Examples include methyl bromide, ethyl bromide, methyl iodide, ethyl iodide, p-toluenesulfonic acid methyl ester, and phosphate triethyl ester. To produce the dye represented by the general formula [] of the present invention, a compound represented by the general formula [] is mixed in an organic solvent such as acetone, methyl ethyl ketone, dioxane tetrahydrofuran, toluene, chlorobenzene, dichlorobenzene, or nitrobenzene. The alkylating agent represented by the general formula [] was added in an amount of n x (1.0 to 1.1) times the mole of the compound at room temperature to 90°C.
Just heat it for about 0.5 to 5 hours. It can be obtained by cooling the resulting reaction product system and filtering the resulting precipitate. Fibers dyed with the dye represented by the general formula [] include mixed, woven, and knitted products of acrylic fibers and wool, synthetic polyamide, and/or cellulose fibers. Examples of cellulose fibers include natural fibers such as cotton and hemp, and semi-synthetic fibers such as viscose rayon and copper ammonia rayon. When carrying out dyeing, the aqueous solution of the general formula [] shown above can be used as it is as a dye bath in the dip dyeing method, as a padding bath in the padding dyeing method, and as a printing dyeing paste in combination with a sizing agent in the textile printing method. . When padding or printing mixed fibers of acrylic fibers, wool, synthetic polyamides, or cellulose fibers, use urea or an average molecular weight of 200.
Use of polyhydric alcohols that do not react with dyes whose hydroxyl groups at both ends are dimethylated or diacetylated, such as ~500 polyethylene glycols and polypropylene glycols, and also to promote the reaction between dyes and hydroxyl groups or amino groups. The use of acid binders is preferred. These acid binders are preferably alkali precursor compounds that generate alkali when heated in the presence of water, such as sodium trichloroacetate. The amount of urea or polyhydric alcohol used is about 3 to 8% by weight based on the padding bath or printing dyeing paste, and the amount of sodium trichloroacetate used is 0.3 to 0.5% by weight when X is a fluorine atom in the general formula []. 1.0 to 1.5 for chlorine or bromine atoms
Approximately % by weight is desirable. It is a method of fixing dyes, but in dip dyeing method,
About 30 to 60 minutes at 95°C to 105°C, for padding dyeing or printing, after drying, use saturated steam at 100 to 130°C for 5 to 10 minutes, and hot air or superheated steam at 160° to 220°C for 30 seconds to 10 minutes. It can be heat treated. Subsequently, by washing with hot water containing a common surfactant, a vivid and uniformly dyed product with good wet fastness can be obtained. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, "parts" in the examples indicate "parts by weight." Example 1 Above structural dye 1 part 4% sodium alginate aqueous solution 55 parts Tetraethylene glycol dimethyl ether
5 parts Sodium trichloroacetate 0.5 parts Water 38.5 parts 100 parts A printing dyeing paste with the above composition was prepared, and an acrylic/cotton (mixing ratio 50/50) blended fabric was printed using a screen printing machine, and then incubated at 80°C for 3 minutes. After drying, it was treated with superheated steam at 170°C for 7 minutes. After washing the product with water, it was soaped at 90° C. for 20 minutes at a bath ratio of 1:30 using a cleaning solution containing 2 g of nonionic surfactant (Kao Soap Co., Ltd. (trademark) Score Roll #400). In this way, a uniform yellow dyeing with excellent wet fastness properties was obtained. The dye used in this example was the following structural dye: 4.67g
and 1.3g of dimethyl sulfate in 100ml of dioxane at 50℃
The reaction was allowed to proceed for 3 hours, and after cooling, the precipitated crystals were filtered out (yield: 5.1 g). λmax of this product (80
% methanol water) was 409 nm. Example 2 The above structural dye 2 parts Diethylene glycol thioether 6 parts Sodium trichloroacetate 0.3 parts Water 91.7 parts 100 parts A padding bath with the above composition was prepared, and acrylic/
6-Impregnated nylon (mixing ratio 80/20) blended fabric,
After reducing the squeezing ratio to 50%, it was fixed by steaming at 100°C for 7 minutes. When this product was treated according to the method described in Example 1, a uniform, bright blue dyed product with excellent wet fastness was obtained. The dye used in this example was synthesized according to the method described in Example 1. The λmax (80% methanol water) of this product was 581 nm. Example 3 Acrylic / with 1wt% aqueous solution (PH7.5) of the above dye
A wool blend (mixing ratio 50/50) was treated at 98°C for 1 hour and then washed with hot water to obtain a uniform red dyed product with no irritation. The dye used in this example was synthesized according to the method described in Example 1. The λmax (80% methanol water) of this product was 552 nm. Example 4 Dyeing was carried out in exactly the same manner as in Example 1 except that the fibers used in Example 1 were changed to an acrylic/wool (mixing ratio 50/50) blended fabric, resulting in a uniform yellow dyeing with excellent wet fastness. I got something. Examples 5 to 14 Dyeing was carried out in exactly the same manner as in Example 1 except that the dyes used in Example 1 were changed to the dyes shown in Table 1. Printed fabrics with excellent wet fastness of the hues shown in Table 1 were obtained. Obtained. Table 1 shows the λmax (80% methanol water) of the dyes used. However, in Table 1, the Cy group is

【formula】 Indicates the group.

【table】

[Table] Examples 15 to 20 Dyeing was carried out in the same manner as in Example 2 except that the dyes used in Example 2 were changed to the dyes shown in Table 2. The results showed that the hues shown in Table 2 had excellent wet fastness. A dyed product was obtained. Table 2 shows the λmax (80% methanol water) of the dyes used. However, in Table 2, the Cy group is

【formula】 Indicates the group.

【table】

【table】

Claims (1)

[Claims] 1 General formula having no -SO ₃ H group or -COOH group [In the formula, D is a dye matrix residue, R ¹ is a hydrogen atom or a methyl group, R ² , R ³ and R ⁴ are a methyl group or an ethyl group, X is a halogen atom, -Y- is - O- group, -S- group or [Formula] group (R ⁵ represents a hydrogen atom, methyl group or ethyl group), -Z- represents a methylene group, ethylene group or trimethylene group, and A is an anion represents a sexual group, and n is a positive integer. ] A water-soluble dye indicated by .