KR840000324B1 - Process for preparing reatine dye - Google Patents

Abstract

Chemical compound (I) is prepared through consecutive reactions among 1-amino-8-hydroxy naphthalene-3,6-disulfonic acid, diazo compound (II), diazo aniline compound (III), 2,4,6-trichloro-S-triazine, and amino compound (IV) at random order; where X1, X2 = H, methyl, methoxy, Cl, carboxylic acid or sulfonic acid group; Y = H, methyl or sulfonic acid group; Z= -CH2CH2OSO3H, -CH2CH2OPO3H2, -CH2CH2Cl or -CH=CH2; Z1, Z2 and Z3 = H,Cl, methyl, methoxy, sulfonic or carboxylic acid; and Y1= amino, acetyl amino or nitro radical. I is suitable to the reactive dye for blue-dyeing of cellulose fiber.

Description

Preparation of Reactive Dye

The present invention relates to a process for the preparation of reactive dyes suitable for dyeing cellulose fiber materials in dark blue.

Conventionally, it has been known that water-soluble dyes obtained by reacting 2 moles of benzene or naphthalene-based diazonium compounds with 1 mole of 1-amino-8-naphthalenesulfonic acid can dye fiber materials in green to blue. Among these dyes, dyes having a mono halogeno triazinyl group have been known as reactive dyes, but in general, their reactive dyes have been used only for printing because they require high temperatures in dyeing operations and lack of suitability in adsorption consumption dyeing. In addition, products dyed with these dyes were not satisfactory in practical terms because of their lack of acid stability in addition to the aforementioned drawbacks. For example, a monochloro triazinyl-type reactive dye represented by the following general formula is described in British Patent Publication No. 916,078. However, products dyed with this dye have insufficient acid stability, and require high temperature during dyeing operation. Due to the lack of suitability for adsorption and consumption dyeing, it was not possible to obtain a product having a desired color concentration when used for dyeing.

In addition, dyes having β-sulphatoethylsulfonyl groups and so-called vinylsulfonyl-type reactive dyes have been known for dyeing textile materials, but generally dyes as dark blue azo-based reactive dyes having β-sulphatoethyl sulfonyl groups. Because of its very low chlorine fastness, products dyed with this dye have often been discolored by chlorine in tap water.

The present inventors have conducted extensive research to solve the above-mentioned drawbacks, in particular, to develop a dark blue reactive dye having excellent chlorine fastness, high acid stability, and good light fastness and sweat-light fastness. Diazo-based dyes having both vinylsulfonyl and monochlorotriazinyl groups have been found to yield dark blue dyes that can meet all of the above requirements.

According to this invention, the compound represented by the free acid of following General formula (I), and the 1-amino-8-hydroxy naphthalene-3,6- disulfonic acid represented by the following General formula (II), Reacting (1) with the diazoaniline compound represented by general formula (III), 2,4,6-trichloro-S-triazine, and the amino compound represented by the following general formula (IV) in arbitrary order, or Or 1-amino-8-hydroxyniphthalene-3,6-disulfonic acid is reacted with the diazotized compound represented by the general formula (II) and the aniline compound represented by the general formula (II), and then The disazoated compound intermediate represented by the following general formula (V) produced by the reduction or hydrolysis operation according to the present invention is optionally selected from 2,4,6-trichloro-S-triazine and the amino compound of general formula (IV). to the reaction (2) in this order, or a compound having an amino group Y ₁ in the formula (ⅱ) Condensation reaction of 2,4,6-trichloro-S-triazine with diazotization compound, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and general formula (III) The triazinyldisazo compound represented by the following general formula (VII) produced by reacting a diazotized aniline compound with an monoazo compound represented by the following general formula (VI) is produced by reacting with an acidic condition: (3) or a compound having an amino group as a Y ₁ group in formula (II), an amino compound of formula (IV) and 2,4,6-trichloro-S -Reacting triazine with any order and then diazotizing and reacting (4) the diazotized compound represented by the following general formula (VII) with the monoazo compound represented by the general formula (VI). Provided is a method for preparing a compound of Formula (I).

Wherein X ₁ and X ₂ are each hydrogen atom, methyl, methoxy group, chlorine atom, carboxylic acid or sulfonic acid group, Y is hydrogen atom, methyl or sulfonic acid group, and Z is -CH ₂ CH ₂ OSO ₃ H, -CH ₂ CH ₂ OPO ₃ H ₂ , -CH ₂ CH ₂ Cl or -Ch = CH ₂ group and Z ₁ , Z ₂ and Z ₃ are each hydrogen atom, chlorine atom, methyl, methoxy, sulfonic acid or carbox Acid groups)

Wherein Y ₁ is an amino, acetylamino or nitro group, and Y is as defined above.

(Wherein Z ₁ , Z ₂ and Z ₃ are as defined above).

Wherein X ₁ , X ₂ and Z are as defined above.

Wherein Y, Z ₁ , Z ₂ and Z ₃ are as defined above.

(Wherein Z ₁ , Z ₂ and Z ₃ are as defined above).

Wherein Y, Z ₁ , Z ₂ and Z ₃ are as defined above.

Wherein X ₁ , X ₂ , Y and Z are as defined above.

Among the compounds of the general formula (I), compounds having a —CH ₂ CH ₂ OSO ₃ H group or a —CH═CH ₂ group, especially a —CH ₂ CH ₂ OSO ₃ H group as the Z group of the general formula (I), and general As the aniline compound of formula (III), compounds which can be obtained using aniline monosulfonic acid, in particular aniline-4-sulfonic acid, in consideration of color, reinforcement and chlorine fastness are preferable.

Examples of compound (II) that can be used in the present method in carrying out the present invention include 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonic acid, 2, 4-diaminotoluene-5-sulfonic acid, 5-acetylaminoaniline-2-sulfonic acid, 5-nitroaniline-2-sulfonic acid and the like can be enumerated, among which 1,3-diaminobenzene-4-sulfonic acid is preferred. Do.

Examples of the aniline compound (III) that can be used in the present invention include aniline, aniline-2, -3 or -4-sulfonic acid, p-toluidine-O-sulfonic acid, 3-amino-6-chlorotoluene-4- Sulfonic acid, 2-chloro-p-toluidine-5-sulfonic acid, p-anisidine-O-sulfonic acid and 2,3 or 4-chloroaniline, and the like, and among them, aniline-2, -3 or -4- Sulfoic acid is preferred.

Moreover, when amino compound (IV) is exemplified, 1-aminobenzene-3 or -4-β-sulfatoethylsulfone, 1-amino-2-methoxybenzene-5-β-sulfatoethylsulfone, 1- Amino-4-methoxybenzene-3-β-sulfatoethylsulfone, 1-amino-2-methoxy-5-methylbenzene-4-β-sulfatoethylsulfone, 1-amino-2-sulfobenzene-4 -β-sulfatoethylsulfone, 1-amino-2-sulfobenzene-5-β-sulfatoethylsulfone, 1-amino-2-carboxybenzene-4-β-sulfatoethylsulfone, 1-amino-2- Chlorobenzene-4-β-sulfatoethylsulfone, 1-aminobenzene-3 or -4-β-vinylsulfone, 1-aminobenzene-3 or -4-β-phosphatoethylsulfone, 1-aminobenzene-3 Or 4-β-chloroethylsulfone and 1-amino-2-sulfobenzene-4 or 5-β-vinylsulfone, and the like, among which 1-aminobenzene-3 or -4-β-sulfone Fatoethylsulfone is preferred.

The dye according to the present invention can be produced by various methods. For example, 1-amino-8 hydroxynaphthalene-3,6-disulfonic acid is converted into a diazotized compound of general formula (II), a diazotized aniline compound of general formula (III), 2,4,6-trichloro-S- It can be manufactured by reacting triazine and the amino compound of general formula (IV) in arbitrary order.

In the first stage of operation, 1-amino-8-hydroxy naphthalene-3,6-disulfonic acid and the diazotized aniline compound of general formula (III) are more specifically -5 ° to 30 ° C in an aqueous acidic medium. The monoazo compound of general formula (VI) was obtained by carrying out a coupling reaction by adding a coupling accelerator and / or a surfactant as necessary under stirring at a pH of 0 to 3 for 1 to 10 hours. It is preferable to isolate by salting out and filtration before performing.

The monochlorotriazinyl group and / or vinylsulfone type group as the reactive group can be introduced into the dye intermediate at the beginning of the reaction or at the end of the reaction, and when introduced at the end of the reaction, The monoazo compound and the diazotized compound of the general formula (II) are subjected to a coupling reaction with stirring in an aqueous medium at 0 to 30 ° C., especially under a pH range of 3 to 10, for 1 to 5 hours, followed by general formula (II) When a nitro group-containing compound is used as the compound of the compound, it is reduced to an amino group with sodium sulfide or sodium hydrogen sulfide at 20 to 80 ° C, or 60 ° when using an acetylamino group-containing compound as the compound of formula (II). A disazo intermediate compound of the general formula (V) obtained by performing a hydrolysis reaction with an amino group in a 1 to 10% sodium hydroxide solution at 100 ° C was prepared using 2,4,6- A -S- triazine and amino compound of general formula (Ⅳ) in Recliner can be obtained by a dye according to the invention by carrying out the reaction in any order. In this case, the first condensation reaction may be performed by adjusting the pH of the solution to 1 to 9 using an acid binder such as sodium hydroxide, sodium carbonate or sodium hydrogen carbonate at a temperature of −10 ° to 30 ° C., and second condensation. The reaction can be carried out while adjusting the pH of the solution to 2-9 at a temperature of 0 ° to 40 ° C. In the case of introducing at the first stage of the reaction, 2,4,6-trichloro-S-triazine is subjected to condensation reaction with a compound in which the Y ₁ group of the general formula (II) is an amino group under the same conditions as described above. The mixture was reacted with the monoazo compound of formula (VI) for 1 to 5 hours at a pH in the range of 3 to 10 at a temperature of 0 ° to 30 ° C, and finally the amino compound of formula (VI) with 0 The dye according to the invention is obtained by carrying out the condensation reaction for 1 to 10 hours in a pH range of 2 to 9 at a temperature of -40 ° C.

According to another method, 2,4,6-trichloro-S-triazine is condensed with an amino compound of formula (IV) and a compound of formula (II), and then optionally There is also a method of obtaining a compound of the general formula (IV) by carrying out reduction or hydrolysis reaction in order. In this method, first, 2,4,6, -trichloro-S-triazine and a compound whose Y ₁ group of the general formula (II) is an amino group are adjusted to a pH of 1 to 9 at a temperature of -10 ° to 30 ° C. The diazotized compound of the general formula (VII) obtained by condensation reaction while condensation reaction was carried out while adjusting the pH of the amino compound of general formula (IV) to 2 to 9 at a temperature of 0 ° to 40 ° C. It is preferred to obtain a dye according to the invention by carrying out the coupling reaction at a pH of 3 to 10 with a monoazo compound of) at a temperature of 0 ° to 30 ° C.

The dye thus prepared can be used for dyeing cellulose fiber material to dark blue color by conventionally employed dyeing methods such as adsorption consumption dyeing, printing and cold batch dyeing.

As cellulose fiber which can be dyed by this invention, natural or regenerated cellulose fiber, such as cotton, flax, biscose rayon, and a biscose short fiber, can be illustrated. Absorption dyeing can be carried out at a relatively low temperature in the presence of an acid binder such as sodium carbonate, trisodium phosphate, sodium hydroxide and the like using a salt bath containing sodium sulfate or sodium chloride.

The dye according to the present invention can be uniformly salted, can be dyed under a wide range of temperatures, and the color reproducibility is also good because the effects of the dyeing temperature, the type of acid binder used, the amount of inorganic salt used and the bath ratio are minimized. . In addition, when the printing method is carried out using the dye according to the present invention, the dye according to the present invention is a thickener or emulsifier such as sodium alginate, starch ether, etc., sodium carbonate, sodium bicarbonate, sodium hydroxide, phosphoric acid 3 Alkali or alkali release agents such as sodium, sodium trichloroacetate, corresponding potassium or alkaline earth metal compounds and, if necessary, ordinary fiber printing or dispersing agents such as urea, followed by drying and heat treatment, especially in the presence of water vapor. Perform

The dye according to the present invention can obtain a dyeing product which is particularly excellent in chlorine fastness, light fastness and sweat-fastness as compared with the conventional dark blue azo-based reactive dye having a β-sulfatoethylsulfonyl group. In particular, in view of the recent trend that the chlorine bleach is widely used in home washing, the dye according to the present invention is undoubtedly important because of the excellent chlorine fastness. In addition, the dye according to the present invention, which has excellent light fastness and sweat-light fastness, is suitable for dyeing of outdoor clothes such as sports clothes, and according to the present invention, the dye has high adsorption consumption and fixation rate in adsorption consumption dyeing. Dyestuffs of concentration can also be obtained.

In addition, the dye according to the present invention also has advantages in terms of wastewater treatment because of its excellent washing ability and ease of removal of unfixed dyes. In addition, the dye according to the present invention also has good wall color invention. Fabrics dyed as conventional reactive dyes having mono or dichlorotriazinyl groups have had problems of lowering chlorine fastness over time due to the influence of acidic gases or other substances in the air, but these problems are associated with the dye according to the present invention. Was also completely solved.

The present invention will be described in more detail with reference to the following Examples, which are not intended to limit the scope of the present invention. In addition, all the "parts" in an Example mean a weight part and acid stability was measured as follows. That is, the dyed clothing was impregnated in a 1% aqueous acetic acid solution for 30 minutes, and then treated using a sweat meter at a temperature of 37 ± 2 ° C. and a pressure of 125 g / cm ² .

Example 1

4.33 parts of aniline-4-sulfonic acid and 3.7 parts of concentrated hydrochloric acid were added to 25 parts of ice water, and 5.1 parts of 35% sodium nitrite aqueous solution was added at 0 ° C to 5 ° C for diazotization. After removing the excess sodium nitrite salt, 7.81 parts of 1-amino-8-hydroxy naphthalene-3,6-disulfonic acid monosodium salt was added to the diazo solution for about 1 hour at 0 ° C to 10 ° C. At the same time the pH of the liquid was maintained at 0.5 to 1.5. The reaction mixture was stirred for several hours, and an aqueous sodium hydroxide solution was added thereto to neutralize the pH of the reaction mixture to 7, followed by salting with sodium chloride to obtain a monoazo dye.

Apart from the above operation, 4.61 parts of cyanuric chloride and 4.70 parts of m-phenylenediaminesulfonic acid were condensed in a surfactant solution at 0 ° to 5 ° C. for 1 to 2 hours and the pH of the solution was changed to 6 to 7. Next, 6.95 parts of 1-amino benzene-3-β-sulfatoethylsulfone were added to the reaction solution to carry out the second condensation reaction, and the stirring was continued at 25 ° to 30 ° C. overnight. 9% aqueous sodium bicarbonate solution was added to maintain the pH of this solution between 5 and 5.5.

Next, 50 parts of ice water and 7.1 parts of concentrated hydrochloric acid were added to the reaction solution, and 5.3 parts of 35% sodium nitrite aqueous solution was added thereto to perform diazotization. After the excess nitrite was removed, this diazo solution was added to the alkaline suspension of monoazo dye prepared above and sodium hydrogencarbonate at a temperature of 5 ° to 10 ° C.

After the mixture was stirred for 1 to 2 hours to terminate the coupling reaction, diluted sulfuric acid was added to the reaction solution to adjust the pH to 5.5 to 6.0, heated to 50 ° to 55 ° C., followed by salting out with sodium chloride. The precipitate was obtained to obtain a precipitate, followed by filtration and washing and drying at 60 ° C to obtain 35.4 parts of dye (1).

[λ max = 600 nm (measured in aqueous medium); for max, measured under the same conditions below]

[Examples 2 to 6]

Each dye was prepared in a similar manner to Example 1 using the reactants described in Table 1 below.

A is; Azo ingredient.

B column; Diazo component (a compound of general formula (III)) of a mono azo dye.

C column; Aniline compound (compound of general formula (IV).) That forms the diazo component of the disazo dye.

D is; Λ max of the disazo dye solution.

[Table 1]

Example 7

61 parts of cyanuric chloride and 4.70 parts of m-phenylenediaminesulfonic acid were condensed in a surfactant solution at 0 ° to 5 ° C., and the pH of the solution was maintained at 1.5 to 3.5.

50 parts of ice water and 7.1 parts of concentrated hydrochloric acid were added to the reaction solution, and then 5.3 parts of 35% aqueous sodium nitrite solution was added thereto to perform diazotization. 1-amino-8-hydroxy-2- (p-sulfophenyl) synthesized in the same manner as in Example 1 except that excess nitrite was removed, followed by addition of urea as a coupling promoter in Example 1. Azo) naphthalene-3,6-disulfonic acid was added to the diazo solution at 5 ° to 10 ° C. The resulting mixture was stirred for 1 to 2 hours to terminate the coupling reaction and at the same time maintaining the pH of the liquid at 6-7. Next, 6.95 g of 1-aminobenzene-3-β-sulfatoethylsulfone was added to the reaction solution to carry out a second condensation reaction, and the stirring was continued at a temperature of 5 ° to 30 ° C for 20%. Aqueous sodium carbonate solution was added to maintain a pH of 4-7. Next, diluted sulfuric acid was added to the reaction solution to adjust the pH to 4.0 to 4.5, heated to 55 ° to 60 ° C., and then precipitated with sodium chloride to obtain a precipitate, followed by filtration, washing and drying at 60 ° C. Was carried out to obtain 38.2 parts of the dye (1).

[Examples 8 to 13]

Except for using the aniline compound of the general formula (IV) shown in Table 2 instead of 1-aminobenzene-3-β-sulfatoethylsulfone in Example 7 The following dyes described in Table 2 were synthesized.

[Table 2]

Example 14

5.75 parts of 5-acetylaminoaniline-2-sulfonic acid and 3.7 parts of concentrated hydrochloric acid were added to 25 parts of ice water, and 5.1 parts of 35% aqueous sodium nitrite solution was added at 0 ° to 5 ° C. for diazotization. After removing excess nitrite, 1 ° amino-8-hydroxy-2- (m-sulfophenylazo) naphthalene-3,6-disulfonic acid 3 sodium salt synthesized in the same manner as in Example 1 was 0 ° to 10 °. The diazo solution was added to the diazo solution at about 1 hour over about 1 hour, and the pH of the solution was maintained at 6-7 while performing coupling. The mixture obtained by adding sodium hydroxide to the reaction mixture in an amount of 5% of the reaction mixture volume was heated to a temperature of 90 ° to 95 ° C. for 5 to 10 hours to undergo hydrolysis, and then the liquidity was adjusted to pH 5-6. Then, the mixture was salted out with sodium chloride at 50 ° to 60 ° C. to obtain a precipitate, followed by filtration and washing to obtain a dye intermediate.

Cyanuric chloride The condensation reaction with the dye intermediate was carried out in an aqueous surfactant solution at 5 ° to 30 ° C. for 2 to 5 hours, and the pH of the solution was maintained at 5 to 7. Next, 23.6 g of dye (3) was obtained by performing a second condensation reaction with 1-aminobenzene-3-β-sulfatoethylsulfone in the same manner as in Example 7.

[Examples 15 to 37]

Each dye was prepared in the same manner as in Example 14 using the reactants described in Table 3 below. The properties of these dyes are described in Table 3 in the A, B and C columns, and λ max in the D columns, respectively.

A is; Azo ingredient.

B column; Diazo component (compound of general formula (III)) of a mono azo dye.

C column; Aniline compound (compound of general formula (IV)) forming diazo component of disazo dye

D is; Λ max of the disazo dye solution.

[Table 3]

Example 28

33.9 parts of dyes of the following general formula (28) in the same manner as in Example 1 were synthesized except that 5.05 parts of m-toluenediaminesulfonic acid was used instead of 4.70 parts of m-phenylenediamine sulfonic acid in Example 1.

Example 29

0.3 part of the dye of the following general formula (1) was dissolved in 200 parts of water, and 20 parts of sodium sulfate and 10 parts of cotton were added to the dye solution, followed by heating to 40 ° C.

After 30 minutes had elapsed, 4 parts of sodium carbonate was added and stained for 1 hour at the same temperature. After the dyeing operation was completed, the dyed cotton was washed and soaped to obtain a dark blue dye having excellent chlorine fastness, light fastness, sweat-light fastness and white dyeing property in addition to printing.

Example 30

The dyeing operation was carried out as in Example 29 except that the above-mentioned dyes (2) to (27) were used instead of the dye (1) in Example 29 to obtain a dark blue dye having excellent fastnesses.

Example 31

0.3 part of the dye represented by the following general formula (28) was dissolved in 200 parts of water and stained at 50 ° C. for 1 hour. After the dyeing operation was completed, the dyed cotton was washed and soaped to obtain a dark blue dye having excellent chlorine fastness, light fastness and sweat fastness.

In the method of synthesizing the dye 28, the components of the dye were changed as follows. : 1-aminobenzene-4-β-sulfatoethylsulfone, 1-amino-2-methoxybenzene-5-β-sulfatoethylsulfone, and 1 instead of 1-aminobenzene-3-β-sulfatoethylsulfone With amino-4-methoxy-3-β-sulfatoethylsulfone; Aniline-2- or -3-sulfonic acid and -3 or -4-chloroaniline in place of aniline-4-sulfonic acid; The dyes obtained by replacing each with 1,3-diaminobenzene-4,6-disulfonic acid instead of m-toluenediaminesulfonic acid also obtained dyeings having the same performance as described above.

Comparative Example 1

The dyeing fabric dyed with the dye according to the present invention shows high acid stability (grade 4 to 5, measured by the above-described measuring method), but the product dyed with the dye represented by the following general formula is insufficient acid stability. (Grades 2-3).

Claims (1)

1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, a diazotized compound represented by the following general formula (II), a diazotized aniline compound represented by the following general formula (III), 2,4,6- A method for producing a compound represented by the free acid of Formula (I), which is reacted with trichloro-S-triazine and an amino compound represented by Formula (IV) below in any order.

Wherein X ₁ and X ₂ are each hydrogen atom, methyl, methoxy group, chlorine atom, carboxylic acid or sulfonic acid group, Y is hydrogen atom, methyl or sulfonic acid group, and Z is -CH ₂ CH ₂ OSO ₃ H, -CH ₂ CH ₂ OPO ₃ H ₂ , -CH ₂ CH ₂ Cl or -CH = CH ₂ group, Z ₁ , Z ₂ and Z ₃ are each a hydrogen atom, a chlorine atom, methyl, methoxy, sulfonic acid or Carboxylic acid group).

(Wherein Y ₁ is an amino, acetylamino or nitro group, and Y is as defined above).

(Wherein Z ₁ , Z ₂ and Z ₃ are as defined above).

Wherein X ₁ , X ₂ and Z are as defined above.