JPH0437103B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to anthraquinone dyes for fibers containing hydroxyl groups, amino groups or anionic groups. For details, see cellulose fibers, wool fibers, synthetic polyamide fibers, urethane fibers, acrylic fibers, cationically dyeable polyesters, especially cellulose fibers and acrylic fibers, wool fibers (or synthetic polyamide fibers) and acrylic fibers, cellulose fibers and synthetic polyamide fibers and acrylic fibers. The present invention relates to a water-soluble anthraquinone dye that dyes mixed fibers consisting of the following in a strong bluish red to blue color. The present invention will be explained in detail below. The dye according to the present invention has the following general formula [I] General formula [In the formula, R ¹ represents an amino group or a hydroxyl group, and R ² represents a hydrogen atom, a chlorine atom, a bromine atom,
halogen atom, cyano group, ethylcarbamoyl group, or _-SO2R group (R represents an alkyl group such as a methyl group or an ethyl group, or a phenyl group).
, R ³ and R ⁴ are a hydrogen atom, an amino group, a hydroxyl group, a nitro group, or a chlorine atom,
Represents a halogen atom such as a bromine atom, -Y- is -
Represents a linking group O- or -S-, one of X ¹ and X ² is a hydrogen atom, and the other is a

[Formula] Group {-R ⁵ is a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as an ethoxy group,
Represents a halogen atom such as a chlorine atom, -Z- is -
Represents a linking group O- or -S-, -W represents a halogen atom such as a fluorine atom, chlorine atom or bromine atom, and -Q represents a linking group such as O- or -S-.

[Formula] Group or

[Formula] Group (R ⁶ represents a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, R ⁷ represents an alkylene group such as an ethylene group or a trimethylene group, and R ⁸ represents a methyl group or an alkyl group such as an ethyl group) , and A represents an anion such as a halogen anion, a methyl sulfate anion, an ethyl sulfate anion, etc.). }, and n represents 0 or 1. However, X ²
When is a hydrogen atom, n is 0. ]. In particular, dyes according to the present invention are preferably those represented by the following formula. In the formula, W and Q have the same meanings as above, R ² ' represents a halogen atom, a cyano group or -SO ₂ R'(R' represents a methyl group or an ethyl group),
R ² ″ represents a halogen atom, and R ³ ′ and R ⁴ ′ represent a hydrogen atom, a hydroxyl group, an amino group, or a nitro group. The dye represented by the above general formula [I] is represented by the following general formula [] [In the formula, R ¹ , R ² , R ³ , R ⁴ , Y and n are the same as defined above, and one of X ³ and X ⁴ is a hydrogen atom and the other is

[Formula] (R ⁵ is the same as defined above, -ZH represents a hydroxyl group or a methylcapto group). however
When X ⁴ is a hydrogen atom, n is 0. ] The anthraquinone compound represented by the following general formula [] [In the formula, W is the same as the above definition, and Q' is

[expression] or

[Formula] (R ⁶ , R ⁷ , R ⁸ are the same as defined above)] The following general formula [] is produced by reacting with an -S-triazine compound represented by [In the formula, R ¹ , R ² , R ³ , R ⁴ , Y and n are the same as above, and one of X ⁵ and X ⁶ is a hydrogen atom and the other is

[Formula] (R ⁵ , Z, -W, Q' are the same as above) Furthermore, general formula [] is changed to general formula [V] R ⁸ -An [V] (R ⁸ , An are the same as above definition) It can be easily produced by reacting with an alkylating agent represented by the formula [V]. Specific examples of the alkylating agent represented by the general formula [V] include dimethyl sulfate, diethyl sulfate, methyl bromide, Ethyl, methyl iodide, ethyl iodide, p-
Examples include toluenesulfonic acid methyl ester and phosphoric acid triethyl ester. To produce the anthraquinone dye represented by the general formula [I] of the present invention, the anthraquinone dye represented by the general formula [] is prepared in an organic solvent such as acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, toluene, chlorobenzene, dichlorobenzene, or nitrobenzene. An anthraquinone compound and an alkylating agent represented by the general formula [V] in an amount of 1.0 to 1.1 times the mole of the anthraquinone compound at room temperature to 90°C.
It is sufficient to 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. Hydroxyl group-containing fibers dyed with the dye represented by formula [I] include woven and knitted fabrics such as natural fibers such as cotton and linen, and semi-synthetic fibers such as viscose rayon and copper ammonia rayon. Examples of amino group-containing fibers include woven and knitted fabrics such as wool, silk, synthetic polyamide and polyurethane fibers. Furthermore, examples of the anionic group-containing fibers include woven and knitted fabrics of acrylic fibers and cationically dyeable polyester fibers. In particular, blended products, mixed woven products, and mixed knitted products of the above-mentioned anionic group-containing fibers and hydroxyl group-containing fibers and/or amino group-containing fibers are mentioned. When carrying out dyeing, the aqueous solution of the general formula [I] 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, or as a textile dyeing paste in combination with a sizing agent in the textile printing method. Can be used. When padding or printing mixed fibers of acrylic fibers and hydroxyl group-containing fibers and/or amino group-containing fibers, hydroxyl groups at both ends of urea, polyethylene glycol, polypropylene glycol, etc. with an average molecular weight of about 200 to 500 are used. It is desirable to use polyhydric alcohols that do not react with dimethylated or diacetylated dyes, and further to use an acid binder for the purpose of promoting the reaction between the dye and the hydroxyl group or amino group. 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 high when W is a fluorine atom in general formula [I]. Therefore, 0.3 to 0.5% by weight, and 1.0 to 1.5% by weight for chlorine atoms or bromine atoms 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 textile 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. All you need to do is heat treat for a minute. 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 at 80°C for 3 minutes. After intermediate drying, it was treated with superheated steam at 170°C for 7 minutes.
After washing this product with water, 2 g/nonionic surfactant (Kao Soap Co., Ltd. (trademark) Score Roll #400)
20 at 90°C in a bath ratio of 1:30 using a cleaning solution containing
I soaped for a minute. In this way, a uniform bluish-red dyeing with excellent wet fastness was obtained. The dye used in this example is the following structural dye 5.42.
g and 1.3 g of dimethyl sulfate in 100 ml of dioxane.
The reaction was carried out at 50° C. for 3 hours, and after cooling, the precipitated crystals were filtered out (yield: 6.4 g). The λmax (80% methanol water) of this product was 516 nm. Example 2 2 parts of the above structural dye 6 parts of diethylene glycol thioether 0.3 parts of sodium trichloroacetate 91.7 parts of water 100 parts A padding bath having 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 reddish-blue dyed product was obtained which was uniform, clear, and had excellent wet fastness. 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 557 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 blue 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 625 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 bluish red color with uniform wet fastness. A dyed product was obtained. Example 5 Dyeing was carried out in exactly the same manner as in Example 1, except that the fibers used in Example 1 were replaced with cotton cloth, and a bluish-red dyed product with excellent wet fastness was obtained. Example 6 Dyeing was carried out in exactly the same manner as in Example 1 except that the fibers used in Example 3 were changed to a cationically dyeable polyester/wool (mixing ratio 50/50) blended fabric, resulting in a uniform blue color with excellent wet fastness. A dyed product was obtained. Example 7 Printing was carried out according to the method described in Example 1 using the anthraquinone dyes listed in Tables 1, 2, 3 and 4 below. The color tone of the obtained dyed product and the λmax (80% methanol water) of the anthraquinone dye used are shown in Tables 1 and 2.
Shown in Tables 3 and 4.

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【table】

Claims (1)

[Claims] 1. General formula [In the formula, R ¹ represents an amino group or a hydroxyl group, and R ² represents a hydrogen atom, a halogen atom, a cyano group, an ethylcarbamoyl group, or a -SO ₂ R group (R represents an alkyl group or a phenyl group)] where R ³ and R ⁴ are hydrogen atoms or amino groups,
It represents a hydroxyl group, a nitro group or a halogen atom, -Y- represents a linking group of -O- or -S-, one of X ¹ and X ² is a hydrogen atom, and the other is a hydrogen atom. The group {-R ⁵ represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, -Z- represents a linking group of -O- or -S-, -W represents a halogen atom, and -Q represents a [ [Formula] group or [Formula] group (R ⁶ represents a hydrogen atom, an alkyl group, R ⁷ represents an alkylene group, R ⁸ represents an alkyl group, and A represents an anion). }, and n represents 0 or 1. However, when X ² is a hydrogen atom, n is 0. ] Anthraquinone dye for textiles.