KR830001731B1 - Method for preparing water insoluble monoazo dye - Google Patents

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Description

Method for preparing water insoluble monoazo dye

The present invention relates to a novel series of water-insoluble monoazo dyes without hydrogen dissolving, to a process for producing the same, and to a method for producing intermediates corresponding to the use for fabrics.

More specifically, the present invention relates to a method for producing a novel monoazo dye having the following general formula.

Wherein Y is H; Cl; Br

X is H; Cl; Br; C ₁ -C ₄ alkyl: C ₁ -C ₄ alkoxyl: CN: CF ₃ : NO ₂ C ₁ -C ₄ SO ₂

Alkyl C ₁ -C ₄ COO alkyl, n is 2 or 3,

R is C ₁ -C ₄ alkyl.

The dye of general formula (I) is

The amine of formula (II) is diazotized in an acid medium, and the diazo produced at pH = 4-5 is suitable for use in an aqueous medium.

And a coupling compound of formula (X, Y, n and R have the same meaning as described above).

The novel intermediates of formula (III) are prepared by the process described in the Examples under the conditions of Bucherer reaction to 1.5-dihydroxy-naphthalin alkoxy C ₁ -C ₄ alkylene-C ₁ -C ₃ amines. Obtained by reaction with

Typically, the dye of general formula (I) is obtained in high purity and does not require purification.

The monoazo dyes of the present invention are particularly suitable for dyeing and printing synthetic polymeric materials, for example esters of polyesters, polyamides, polyacrylonitriles and celluloses in any form.

When used in a conventional dyeing method, for example, when the padding is steamed in an aqueous solution bath or thermosol under pressure at 130 ° C., or the padding heat treatment or printing is used, the above-mentioned dyes are strong and bright with these materials. Dyeing is provided, and the prints exhibit moderate to cyan shades, which show good affinity and stability to sunlight, washing, and sublimation.

Because of the excellent stability exhibited by changing the pH value of the salt bath, the monoazo dyes of formula (I) are particularly suitable for dyeing polyesters at high temperatures.

Azo dyes having a reddish blue to cyan color tone and having a structure similar to one of the dyes of the present invention, such as the dyes described in the following patents, for example the azo dyes described in German Patents 659,147 and 658,124 6-chloro-2,4-dinatroaniline or 6-bromo-2,4-dinitroaniline is diazotized in a compound of the structure

US Pat. No. 2,434,150 diazotizes 2-alkylsulfonyl-4-nitro-aniline and combines it with a compound of the structure:

In German Patent 639,727 2-benzothiazole is diazotized and combined with a compound of the structure

It is also possible to diazotize from 2-amino-5-nitrothiazole or 2-amino-benzothiazole, e.g.

Other blue azo dyes or 6-bromo- or 6-chloro-2,4-dinitroaniline derived by binding to a substituted N, N-dialkylaniline phase represented by the following structural formula

The dye derived by combining the substituted N, N-dialkylaniline phase represented by is known.

However, all of these dyes have the drawback that they are less stable to pH changes during dyeing, fade during dyeing or have low fixation in the sun.

The inventors have found that the dyes of general formula (I) obtained by the present invention have improved stability, in particular in sunlight and sublimation, and are significantly improved in colorability compared to those known in the art, particularly against pH changes in salt baths. The stability is high, and practically no real difference in color was found in staining at pH values between 7 and 3.

In the above use examples, the dry or aggregated dye was ground to a particle size of 0.5-1 mu in the presence of a suitable dispersant, for example in the presence of ligninsulfonate sodium salt, and used for the fibers by the above-described method.

Features of the present invention will be described in detail with reference to the following examples, which are not limitative of the present invention and parts are parts by weight unless otherwise indicated in these examples.

Example 1

1.52 parts of 2-methyl-4-nitro-aniline were warmed by adding a volume of HCl 4.0 of d = 1.18 and 30 parts of water. After cooling this solution to 5-10 degreeC, 0.69 part of sodium nitrite in 10 volume parts of water was gradually added.

The diazo solution was then fractionated and dissolved in 20 parts of acetic acid and 50 parts of water at 5-10 ° C., and the stock was added to a solution of 2.31 parts of the following binder compound.

During binding, the pH was maintained at 4-5 by adding crystalline sodium acetate. After stirring for 30 minutes the precipitate was washed with water and dried.

The structural formula

3.8 parts of a dye can be obtained, which gives an intense and bright red-blue hue with good fixation against sunlight, moisture and sublimation in artificial fibers, in particular polyester fibers, and also with the change of dye at pH3-7. The stability was excellent. The binder compound used in the Example mentioned above was synthesize | combined as follows.

2.0 parts of 3-methoxy-propylamine were treated with 27.4 vol NaHSO ₃ and 100 vol water. After stirring this solution for 10 minutes at room temperature, it was filled with 20.3 parts of 1,5-dihydroxy-naphthalin and 14.7 parts of 3-methoxy-propylamine, and the temperature was raised to 106 ° C, and for 27 hours at this degree. Maintained. Finally, the solution was cooled to 20 ° and the pH value was maintained at 14 by adding hydrate sodium salt of d = 1.18.

It was stirred for 1 hour and then filtered to separate 1.5-bis- (3-methoxy-propylamino) -naphthalin.

The solution was acidified with d = 1.09 HCl at pH = 1, treated with activated carbon and stirred for about 1 hour, then filtered to remove unreacted 1,5-dihydroxy-naphthalin.

The filtrate was again treated with NaOH of d = 1.18 to maintain pH = 7, and 1- (3-methoxy-propylamino) -5-hydroxy-naphthalin was initially precipitated in the form of a thick oil, followed by crystalline form. The solids were separated by filtration. After washing and drying the cake, 17.7 parts (yield = 58.8%) of product having a melting point of 78-80 ° C. were obtained, which showed the following analysis.

Calculated% 72.73 7.36 6.06

C H N

Found% 72.15 7.29 6.13

Example 2

1.38 parts of P-nitro-aniline were dissolved in a volume of HCI 4.0 and 20 water in d = 1.18. The solution was diazotized by gradually adding a solution of 0.69 parts of sodium nitrite dissolved in 10 parts by volume of water at 5-10 ° C. After clarification, the diazo solution was added to a solution of 2.31 parts of the binder compound of Example 1 which was dissolved in 20 vol parts of acetic acid and 50 vol parts of water at 5-10 ° C.

Subsequent treatment as described in Example 1 yields the following structural formula,

3.65 parts of a dye were obtained, which showed a suitable color tone with good stability to the above-mentioned fibers and excellent stability to pH.

Example 3

2.17 parts of 2-bromo-4-nitro-aniline were diazotized by the method described in Example 1 and bound onto 2.31 parts of the binder compound of Example 1 according to the method illustrated in Example 1.

The structural formula

4.4 parts of a dye were obtained, which showed a cyan color tone with good stability to the fibers described above and excellent stability to pH.

Example 4

1.73 parts of 2-chloro-4-nitro-aniline were diazotized by the method described in Example 1 and bound to the binder compound 2.31 injury of Example 1.

The structural formula

3.9 parts of a dye were obtained, which exhibited a green-dark blue color with good stability to the fibers described above and excellent stability to pH.

Example 5

1.68 parts of 2-methoxy-4-nitro-aniline were diazotized by the method described in Example 1, and the following structural formula was found in 20 vol.

Binder compound was bound on 2.17 parts.

Subsequently treated by the method described in Example 1, the structural formula

3.75 parts of a dye were obtained, which stained the fiber with reddish blue with reddish blue with good stability and excellent stability at pH. The binder compound was synthesized in a similar manner to that described in Example 1.

Example 6

2-methylsulfonyl-4-nitroaniline was added to a solution of 2.16 parts of d = 1.84 for H ₂ SO ₄ 20 0.69 volume parts of sodium nitrite dissolved in bujung at 0-5 ℃ in less than an hour.

After 30 minutes of further stirring, the diazo solution was dissolved in 15 vol. Acetate and 40 vol. Water at 5-10 ° C.,

Was added to a solution of 2.45 parts of a binder compound. During the binding, the pH was maintained at 4-5 by adding crystalline sodium acetate. After stirring for 1 hour, it was filtered and the precipitate was washed with water. By drying the cake, the structural formula

4.4 parts of a dye were obtained, which showed a cyan color tone with good stability to the fibers described above and excellent stability to pH.

Binder compounds were synthesized in the same manner as described in Example 1.

Example 7

1.8 parts of 2, -dinitro-aniline were diazotized by the method described in Example 6 to be dissolved in 20 parts of acetic acid and 40 parts of water,

Was bound on 2.59 parts of a binder compound.

Subsequent treatment was carried out similarly to that described in Example 6,

4.35 parts of a dye can be obtained, which stained the fibers described above with cyan with good stability and excellent stability to pH.

Binder compounds were synthesized in a similar manner to that known in Example 1.

Example 8

A solution of 1.63 parts of 2-cyano-4-nitroaniline dissolved in 20 parts of acetic acid, 4 parts of propionic acid and 2 parts by volume of water was cooled to 5-10 ° C, and then 10 volumes of 1N nitrosyl sulfate were slowly added thereto.

After stirring at 5-10 ° C. for about 1 hour, the diazo solution was dissolved in 20 parts of acetic acid and 40 parts of water by the following structural formula:

Was gradually added to a solution of 2.73 parts of a binder compound. Then, by the method similar to that described in Example 6,

4.2 parts of dye were obtained, which dye the fibers described above in cyan with good stability and excellent stability to pH. This binder compound was synthesized in a similar manner to that described in Example 1.

Example 9

d = a solution of H ₂ SO ₄ 10 volume parts of sodium nitrite dissolved in 0.69 parts of 1.84 d = 1.84 to a solution of H ₂ SO ₄ 10 parts by volume was dissolved 2-amino-5-nitro-benzoic acid methyl ester 1.96 parts of the 1 It was added within hours and it was cooled to 0-5 ° C.

After stirring for 1 hour, the diazo solution was dissolved in 20 parts of acetic acid and 50 parts of water by the following structural formula,

Was added to a solution of 2.31 parts of a binder compound at 5-10 ° C.

Treated by the same method as described in Example 6, the structural formula

4.1 parts of dye were obtained, which stained the fibers described above with cyan with good stability and excellent stability to pH.

The binder compound was synthesized in a similar manner to that described in Example 1.

Example 10

2.18 parts of 2,4-dinitro-6-chloro-aniline were diazotized by the method described in Example 9 and bound onto 2.31 parts of the binder compound of Example 1 by the method described in Example 1.

The structural formula

4.35 parts of a dye were obtained, which stained the fibers described above in cyan with good stability and excellent stability to pH.

Example 11

2.62 parts of 2,4nitro-6-bromo-aniline were diazotized and bound onto 2.17 parts of the binder compound of Example 5 by the method described in Example 9. The structural formula

4.8 parts of a dye were obtained, which stained the fibers described above with cyan with good stability and excellent stability to pH.

Example 12

2.06 parts of 2-nitrofluoro-methyl-4-nitroaniline were diazotized and bound onto 2.31 parts of the binder compound of Example 1 by the method and description in Example 1. The structural formula

4.25 parts of a dye were obtained, which stained the fibers described above with cyan with good stability and excellent stability to pH.

Example 13

0.6 part of dye of Example 1 previously refine | purified was added to the salt bath containing 100 parts of polyester spinning at 40 degreeC.

After adding acetic acid to adjust the pH value to 5, treatment was carried out at a ratio of 1: 15, the bath was slowly heated to 130-135 ° C, and dyeing was carried out at this temperature for 1 hour.

After cooling, the contents of this bath were emptied and the dyeing material was subjected to a normal alkali reduction washing process.

An intense, bright blue-blue dye with good stability to sunlight, moisture and sublimation was obtained, and good stability to dyeing changes was obtained at pH7-3, which color tone was not particularly changed at pH 7 to pH3.

The following mono azo dye of general formula (I) was obtained by processing with what was described in the said Example.

Claims (1)

The amine of the following general formula (II) is diazotized in an acid medium and the diazo produced in the aqueous medium pH 4-5 is combined with the binder compound of the following general formula (III). Process for preparing a water insoluble monoazo dye.

In the above formula Y is H, Cl, Br and X is H, Cl, C ₁ -C ₄ alkoxyl, Br, CN, CF ₃ , NO ₂ , C ₁ -C ₄ SO ₂ alkyl, C ₁ -C ₄ COOalkyl, n is 2, 3 and R is C ₁ -C ₄ alkyl.