DE3007547A1 - ACID ACID DYES, METHOD FOR THE PRODUCTION AND USE THEREOF - Google Patents

Description

300754?

Our no. 22 810 Ka / kp

Montedison S.p.A. Milan / Italy

Acid azo dyes, processes for their production and their use

The present invention relates to a new class of water-soluble azo dyes containing at least contain a sulfonic acid residue, the general Formula I.

-N = NA -4- ^SO n ^H ) _n (I)

^ HCOR

wherein X is a halogen atom, preferably a chlorine atom or a bromine atom,

R is a methyl radical, a radical of the formula -COOH, a phenyl radical ,. a substituted Pher.yi radical or a radical of the formula NH-R ', in which R ^{1 is} a hydrogen atom,

010037/0738

BATH ORIGINAL

300754?

-kl-alkyl radical, a rhenyl radical or a substituted one Represents phenyl radical,

A one of a coupling compound of the benzene, naphthalene or pyrazole series, the at least one Contains sulfonic acid radical, derived radical and η 1 or 2 mean.

The dyes according to the invention have shades which vary from yellow to bluish-red, and are for dyeing and printing polyamide fibers, both natural (wool and silk) and artificial (Nylon), applicable. They have an excellent affinity both in the acidic bath and in the neutral one Bad and an excellent coloring power.

The dyes obtained have a remarkable color both in the dark shades and in the light shades Luminosity, good stability to sunlight and washing and good coverage for the so-called stripes or lines on nylon.

The class of dyes of the formula I according to the invention has not yet been described as far as is known to the applicant and represents a new class of water-soluble azo dyes.

The present invention also relates to a process for the preparation of these dyes which have high coloring properties in the aforementioned fields of application. The water-soluble according to the invention, at least Azo dyes of the formula I containing a sulfonic acid radical are prepared by following conventional methods Techniques an amine of formula II

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BATH ORIGINAL

300754?

NHCOR

wherein X and R have the meaning given above, diazotized at a temperature of about 0 to 5 ° C and the diazo derivative thus obtained according to conventional techniques at a temperature of about 5 to 20 C and a pH of about 2 to 7 with a compound of the benzene, naphthalene or pyrazole series.

Coupling compounds which can be used are, in particular, N-ethyl-N-benzyl-aniline-sulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 1- ( ¹ I'-sulfophenyl) -3-methyl 1-5-pyrazolone, 1- ( 2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-5-pyrazolone.

The coupling reaction is generally in the aqueous phase, depending on the dye, with an acidic or neutral pH, e.g. between pH 2 and pH 7.

The dyes thus obtained can easily be isolated by filtering the reaction mass. In some In cases it is necessary to promote the precipitation by salting out with sodium chloride.

In any case, conventional, well-known ones are used and techniques described.

The dyes according to the invention have good solubility in water and are under the usual dyeing conditions Easily applicable for polyamide fibers.

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The following examples serve to illustrate the present invention.

Unless otherwise specified, all parts and percentages are by weight.

example 1

18 parts of 2-chloro-5-acetylamino-aniline were concentrated with stirring in 200 parts of water and ^ iO parts Dissolved hydrochloric acid. It was cooled to 0 to 5 ° C and then with a solution containing 7 parts of sodium nitrite contained in 20 parts of water, added. The reaction mixture was held at about 0-5 ° C for about 30 minutes, whereupon the excess nitrous acid was removed by adding 1.5 parts of sulfamic acid. The resulting diazo compound was complete in about 30 minutes at about 5 to 10 ° C of a suspension of 27 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid in 300 parts Water (pH about 3.5) added.

At the end of the addition, a 50 # solution of sodium acetate was added dropwise to the suspension to bring the pH to about k. After two hours of stirring at 5 to 10 ⁰ C, the dye was filtered off, washed with a 10 £ sodium chloride solution and then dried in an oven at 60 ° C. There were 43 parts of a dye of the formula III

(III)

030037/0735

obtained in the form of a reddish-brown powder. This dye dyed nylon a bright red shade with good stabilities to sunlight and washing.

Example 2

24.7 parts of 2-chloro-5-benzoylamino-aniline were in the usual manner with an aqueous solution of 7 parts Sodium nitrite diazotized.

Then at about 5 to 10 ⁰ C with a solution of 33 parts of 1- (2 ^f , 5'-dichloro-4'-sulfophenyl) -3-methyl-5-pyrazolone in 300 parts of water and 15 parts of 30% sodium hydroxide coupled.

It was buffered to a pH of about 4 with sodium acetate, and the mixture was then ^{stirred at about 5 to 10 °} C. for 6 hours.

Sodium chloride was added to precipitate the reaction product. The reaction product was under vacuum filtered, washed with 10% saline and then dried. There were 75 parts of a yellowish powder, the dye of the formula V

Cl

CH_

O) - ^{n = ij} -

NHCO

(V)

Cl

03QQ37 / 0736

300754?

corresponded, received. This dye dyed nylon a bright yellow shade with good stabilities to sunlight and washing.

Example 3

In the same way as in the preceding examples, 26.2 parts of 3-amino-4-chlorocarbanilide with 7 Share sodium nitrite diazotized.

The obtained diazo compound was at pH of about 4 with 20 parts of 1- (4'-sulfophenyl) -3-methy1-5-pyrazolone coupled.

After 3 hours it was precipitated with common salt. The received Precipitate was filtered off under vacuum, washed with 10% sodium chloride solution and then dried. There were 42 parts of a yellow powder, the dye of the formula VI

(VI)

corresponded, received. This dye dyed nylon a bright yellow shade that was opposite to washing and sunlight was very stable.

I30037 / 073S

Examples M - 12.

The procedure described in the previous examples was followed, but instead of the starting materials used there, the starting materials mentioned in the table below were used the corresponding dyes produced with the shades given in the table.

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Tabel Example!

-Arnin

Coupling connection

hue

Cl

NHCOCH

Cl

Cl

KHCOCH

Cl

- / q)

Cl

CH.

CH

.Cl

NH.

SO H

SO H

• I0037 / 073S

yellow

yellow

yellow

Red

reddish yellow

Table (continued) 7547

example

Amine coupling compound

hue

Cl

NHCO- (O

Cl

'OV-NH,

HCONH- (O)

Cl

NHCONH- (O;

Cl

NH

NHCONH- (O) CH,

1

^H0A y

NH,

ηΛ /

CH.

Cl

SO H
3

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yellow

Red

yellow

yellow

Example 13

0.5 parts of the dye prepared in Example 1 were dissolved at 6O ⁰ C into 1000 parts of water. One part ammonia and one part acetic acid were added. 50 parts of nylon were placed in the dye bath. The temperature was then gradually increased to 100 ^° C. and the bath was kept boiling for 30 minutes. After addition of a portion of acetic acid, the temperature for another 30 minutes at 100 ⁰ C was maintained, and then C was cooled to 6O ^0, then washed and dried.

A bright red and perfectly uniform coloration was obtained, which can be compared with sunlight, washing and perspiration had excellent stability.

For Montedison S.ρ.Α. » Milan / Italy

/ j

Dr. H. J. Wolff Attorney at Law

• 10037/0738

Claims (3)

Γ A *, MAiN 80 '-? Fri:. TO claims 1. Water-soluble acidic azo dyes with at least one sulfonic acid radical of the general formula I. K = N-A _4_ SO H) (I) KHCOR wherein X is an halogen atom, preferably a chlorine atom or a bromine atom, R a methyl radical, a radical of the formula -COOH, a phenyl radical, a substituted phenyl radical or a radical of the formula NHR ', wherein R' is a hydrogen atom, a Is an alkyl radical, a phenyl radical or a substituted Pher.yl radical, A is one of one Coupling compound of the benzene, naphthalene or pyrazole series, which has at least one sulfonic acid residue contains, derived radical and η 1 or 2 mean. 2. Process for the preparation of the acidic azo dyes according to Claim 1, characterized in that one an amine of formula II (II) XKCOR 0I0037 / 073S BATH ORIGINAL wherein X and R are as defined in claim 1, at a temperature in the range of about 0 to 5 C diazotized and the resulting diazo compound at a temperature of about 5 to 20 ° C and a pH between about 2 and 7 with a compound the benzene, naphthalene or pyrazole series. 3. A method for dyeing and printing natural and artificial fibers, characterized in that one the water-soluble acidic azo dyes according to claim 1 are used. 030037/0735