JPH0335433B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for dyeing cellulose fibers deep blue. More specifically, the present invention provides the following general formula () in the form of a free acid: (wherein, X is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl,
β-chloroethyl or vinyl; R represents a hydrogen atom, a chlorine atom, or a sulfonic acid group; Y represents a hydrogen atom or a methyl group; Z ₁ , Z ₂ , and Z ₃ represent a hydrogen atom, a chlorine atom, and a methyl group, respectively. , represents a methoxy group, a sulfonic acid group or a carboxylic acid group. ) This is a method for dyeing cellulose fibers, which is characterized by using the dye shown in the following. It is already known that by coupling 2 moles of a benzene or naphthalene-based diazonium compound with 1 mole of 1-amino-8-naphtholsulfonic acids, a water-soluble dye that imparts a green to blue hue on textile materials can be obtained. There is. Among these dyes, dyes having a monohalogenotriazinyl group are well known as reactive dyes. However, these reactive dyes generally require high dyeing temperatures and lack suitability for exhaust dyeing, so they are only used for textile printing.Furthermore, they have the disadvantage of low acid stability of the dyed products obtained. Therefore, it could never be said to be sufficient for practical purposes. On the other hand, it is known that dyes having a β-sulfatoethyl sulfone group can be applied to dyeing textile materials as so-called vinyl sulfone type reactive dyes. However, dyed products using azo deep blue reactive dyes having a β-sulfatoethyl sulfone group generally have low chlorine fastness, and fading due to chlorine contained in tap water is often a problem. For these reasons, the present inventors have found that the chlorine fastness is particularly excellent, and furthermore, the light fastness is sufficient.
As a result of extensive research in search of a deep blue vinyl sulfone type reactive dye that has sweat and sunlight fastness, we found that the dye represented by the above general formula (), that is, the β-sulfatoethyl sulfone group as the reactive group, , β-thiosulfatoethylsulfone group,
It has been found that disazo dyes having a β-sulfatoethylsulfone group, a β-chloroethylsulfone group or a vinylsulfone group and a monochlorotriazinyl group give deep blue dyeings that meet these conditions. It has also been found that the dye of the present invention can overcome the drawbacks of reactive dyes having a monochlorotriazinyl group as described above. In the present invention, examples of cellulose fibers include natural or regenerated cellulose fibers such as cotton, linen, viscose human silk, and viscose cotton. In the case of the exhaust method, the dyeing of the present invention uses soda carbonate,
It is carried out at relatively low temperatures in a dye bath containing mirabilite or common salt in the presence of an acid binder such as tribasic sodium phosphate or caustic soda. In the case of printing, pastes such as, for example, sodium alginate, starch ethers or emulsifying pastes and soda carbonate, bicarbonate soda, caustic soda, tribasic sodium phosphate, sodium trichloroacetate or corresponding potassium or alkaline earth compounds can also be used. along with an alkaline or alkali-releasing agent such as, optionally with the addition of customary printing aids or dispersants such as urea, drying and especially in the presence of water vapor. It can be dyed by subjecting it to heat treatment. The dye of the present invention can be produced, for example, as follows. General formula () (In the formula, Z ₁ , Z ₂ and Z ₃ have the above-mentioned meanings.) The aniline compound represented by
Diazotized with sodium nitrite at ℃ to give 1-amino-
It is coupled with 8-hydroxynaphthalene-3,6-disulfonic acid under the conditions of pH 0.5 to 3.5 and 0 to 10°C to form a free acid with the general formula () A monoazo dye represented by is obtained. On the other hand, in the free acid form the general formula () (In the formula, Y has the above meaning) and a phenylenediamine sulfonic acid compound represented by the general formula () (wherein, X and R have the above-mentioned meanings) is condensed with cyanuric chloride to form a free acid of the general formula () (In the formula, X, Y and R have the above-mentioned meanings.) This amino compound was diazotized with sodium nitrite at 0 to 5°C under hydrochloric acid acidity, and this and the previously obtained The dye represented by the general formula () can be obtained by coupling the monoazo dye () in an alkali bicarbonate solution at 0 to 10°C. In the present invention, examples of the aniline compound () that can be used include aniline, aniline-
2, 3, or 4-sulfonic acid, anthranilic acid,
Examples include para-toluidine sulfonic acid, 3-amino-6-chlorotoluene-4-sulfonic acid, 2-chloro-para-toluidine-5-sulfonic acid, para-anisidine orthosulfonic acid, and 2-, 3-, or 4-chloroaniline. Examples of the diamine component (2) include metaphenylenediaminesulfonic acid and metatolylenediaminesulfonic acid. Examples of the amine component () include aniline-2-β-sulfatoethylsulfone, 5-
Chloraniline-2-β-sulfatoethylsulfone, 5-sulfoaniline-2-β-sulfatoethylsulfone, aniline-2-β-thiosulfatoethylsulfone, 5-chloroaniline-2 -β-thiosulfatoethylsulfone, 5-sulfoaniline-2-β-thiosulfatoethylsulfone, aniline-2-β-phosphateethylsulfone, 5-chloroaniline-
2-β-phosphatoethylsulfone, 5-sulfoaniline-2-β-phosphatoethylsulfone, aniline-2-vinylsulfon, 5-
Chloraniline-2-vinylsulfone, 5-sulfoaniline-2-vinylsulfone, aniline-
2-β-Chlorethylsulfon, 5-chloroaniline-2-β-chloroethylsulfon, 5-
Examples include sulfoaniline-2-β-chloroethylsulfon. The thus obtained dye of the present invention has particularly high chlorine fastness, light fastness, sweat and sunlight fastness, compared to conventional azo deep blue reactive dyes having a β-sulfatoethyl sulfone group. Excellent.
Especially considering that the use of chlorine bleach in household laundry has recently become widespread, the value of the dye of the present invention, which has excellent chlorine fastness, is high. Furthermore, the excellent light fastness, sweat fastness and sunlight fastness are suitable for dyeing external wear such as sportswear. Furthermore, since the dye of the present invention exhibits a high exhaustion rate,
Not only can dyed products with high density be obtained, but also a small amount of dye remains in the dye bath, which is advantageous in terms of waste water treatment. Furthermore, the dye of the present invention is not easily affected by dyeing temperature, so it has excellent reproducibility, and also has excellent characteristics in level dyeing property and fastness when washed. Among the dyes of the present invention, those in which the sulfonic acid group is located at the P-position with respect to the amino group in the general formula () are particularly preferable in terms of hue, and also have good chlorine fastness. It is as good as or better than what we have. As a dye similar to the present invention, for example,
Publication No. 39-11779 A monochlorotriazinyl type reactive dye represented by is described. However, the acid stability of dyed products obtained using this dye (the test method is to immerse the dyed fabric in 1% acetic acid for 30 minutes,
at a temperature of 37 ± 2 °C using a bar spirometer.
(processed at 125 g/cm ² for 6 hours) is inferior to the dyed product of the present invention, and has the disadvantages of requiring a high dyeing temperature and lacking in exhaustion dyeing suitability. It can never be said to be sufficient in practical terms. Next, the method of the present invention will be explained with reference to examples. In the text, parts represent parts by weight. Example 1 Formula (1) (λmax = 600 nm, however, in an aqueous solvent, hereinafter measured under the same conditions) Dissolve 0.3 parts of the dye shown in 200 parts of water to obtain 20 parts of mirabilite.
Add 10 parts of cotton and raise the temperature to 40℃. After 30 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were performed to obtain a deep blue dyed product with excellent chlorine light fastness and sweat/sunlight fastness. Reference Example 1 [Synthesizing agent for dye (1) of Example 1] Add 4.33 parts of aniline-4-sulfonic acid and 3.7 parts of concentrated hydrochloric acid to 25 parts of ice water, and prepare 5.1 parts of 35% sodium nitrite solution at 0 to 5°C. Diazotization is carried out by injecting After eliminating excess nitrous acid, 7.81 parts of a neutral solution of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid monosodium salt was injected over a period of about 1 hour at 0 to 10°C, and the pH was 0.5. Perform cupping at ~1.5. After stirring this mixture for several hours, it is neutralized with a caustic soda solution to a pH of 7, and salted out with sodium chloride at 30 to 35°C to obtain a monoazo dye. On the other hand, 4.61 parts of cyanuric chloride and 4.70 parts of m-phenylenediaminesulfonic acid were brought to pH 6-7 in 50 parts of an aqueous surfactant solution and kept at 0-5°C for 1-2 hours to carry out the first condensation, and then Aniline-2-β-
Added 6.95 parts of sulfate ethyl sulfone, 9%
25 while keeping the pH between 5 and 5.5 with a bicarbonate of soda solution.
The second condensation is carried out by stirring overnight at ~30°C. Then, after adding 50 parts of ice and 7.1 parts of concentrated hydrochloric acid,
Diazotization is carried out by adding 5.3 parts of % sodium nitrite solution. The diazotized solution from which excess nitrous acid has been removed is poured into a monoazo dye suspension made alkaline with sodium bicarbonate at 5 to 10°C, and the suspension is stirred for 1 to 2 hours to perform coupling. After adjusting the pH to 5.5 to 6.0 with dilute sulfuric acid and the temperature to 50 to 55°C, add sodium chloride to the solution for salting out, filter, wash, and dry at 60°C. 35.4 parts of dye (1) were obtained. Examples 2-19 In Example 1, instead of dye (1), the following (2)-
Dyeing was carried out in the same manner except that the dye (21) was used. A deep blue, intense dyeing with excellent fastness properties was obtained. The following dyes are azo component: A column, diazo component of monoazo dye [compound of the above general formula ()]: B
Column, diazo component of disazo dye Aniline compound [compound of the above general formula ()] column C, and λmax of the disazo dye solution
(Column D).

【table】

[Table] Example 22 The obtained formula (22) was synthesized in the same manner as in Example 1 except that meta-tolylene diamine sulfonic acid was used instead of meta-phenylene diamine sulfonic acid in dye (1). Dissolve 0.3 parts of the dye shown in 200 parts of water and add 20 parts of mirabilite.
1 part, add 10 parts of cotton, and raise the temperature to 50℃. Then, after 20 minutes, 3 parts of tribasic sodium phosphate is added. Dye for 1 hour at that temperature. After dyeing, washing with water and soaping were performed to obtain a deep blue dyed product with excellent fastness to chlorine, light, sweat, and sunlight. In dye (22), aniline-2-β-sulfatoethylsulfone was replaced with aniline-2-β-sulfatoethylsulfone.
2-β-phosphate, chloro or vinylsulfone, 5-sulfo or chloroaniline-2-β-sulfatoethylsulfone, or aniline-2, or 3-sulfonic acid or 3-sulfonic acid instead of aniline-4-sulfonic acid. Alternatively, dyes obtained using 4-chloroaniline also give dyeings with similar performance. Comparative Example 1 Formula (23) obtained by synthesizing in the same manner as in Example 1 using paraphenylenediaminesulfonic acid instead of metaphenylenediaminesulfonic acid in dye (1) It was dyed in the same manner using the dye shown in (λmax=630 nm). It gave a bluish-green dyeing, and no blue tones were obtained as with the dyes of the invention.

Claims (1)

[Claims] 1 The following general formula in the form of a free acid: (wherein, X is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl,
β-chloroethyl or vinyl; R represents a hydrogen atom, a chlorine atom, or a sulfonic acid group; Y represents a hydrogen atom or a methyl group; Z ₁ , Z ₂ , and Z ₃ represent a hydrogen atom, a chlorine atom, and a methyl group, respectively. , represents a methoxy group, a sulfonic acid group or a carboxylic acid group. ) A dyeing method for cellulose fibers characterized by using the dye shown in the following.