CH628363A5 - METHOD FOR PRODUCING ANIONIC DISAZO COMPOUNDS. - Google Patents

Description

The invention relates to a process for the preparation of new compounds of the formula I,

Oh

<o.

c (ch3) 3

where the S03M group is in the m or p position to the azo group,

M is hydrogen or an equivalent of a colorless cation and

Rj and R2 independently of one another denote hydrogen, (1--4C) -alkyl or (1-4C) alkoxy, and also of mixtures of the compounds of the formula I, the compounds prepared by the process and their use.

The compounds of the formula I are obtained by preparing the diazo compound from an amine of the formula II,

N =

so3m ii

50

wherein the S03M group is in the m or p position to the azo group, or mixtures thereof on p-tert. Butylphe-nol couples.

R [resp. R2 in the meaning of alkyl preferably represents methyl or ethyl, in particular methyl.

Ri resp. R2 in the meaning of alkoxy preferably represents methoxy or ethoxy, in particular methoxy.

Rj is preferably r \ in the meaning of hydrogen or methoxy, in particular hydrogen. Preferably r2 is r'2 meaning hydrogen, methyl or methoxy, especially hydrogen.

Preferred compounds of the formula I are those in which Rj is r \ and r2 is r'2; Compounds of the formula I in which ri and r2 are hydrogen are particularly preferred.

The nature of the cation M of the sulfo group in compounds of the formula I is not a critical factor, but can be any cation customary in the chemistry of anionic azo dyes, for example an alkali metal ion or an unsubstituted or substituted

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tes ammonium ion according to the formula N (R3) 4, wherein each R3 is independently hydrogen, (1-3C) alkyl or 2-, 3- or 4-hydroxy- (2-4C) alkyl; It is known that unstable cations such as tetraalkanolammonium ions must be excluded.

Examples of suitable cations are lithium, sodium, potassium, ammonium, triethylammonium, mono-, di-, tri- and 65-tetramethylammonium, mono-, di- and triethanolammonium and mono-, di- and triisopropanolammonium. Preferred as cations are the alkali metal ions, in particular sodium, and also ammonium.

60

3rd

628 363

The diazo compounds of the formula I are prepared in a manner known per se, advantageously in an alkaline medium.

The compounds of formula I obtained can be isolated from the reaction mixture by methods known per se. The compounds of the formula I are usually obtained in the form of their salts, depending on the reaction conditions. If desired, a conversion to the free acid or a salting-out can be carried out; the conversion into another salt form can also be carried out in a manner known per se.

A - Ì; = N - B

where u.a.

A optionally substituted sulfophenyl,

B optionally substituted 1,4-phenylene,

R, hydrogen or (1-5C) alkyl and

R (1-5C) alkyl, known. The compounds obtained according to the present invention represent a specific selection from this general class of compounds, and as such are not disclosed in the US patent. Due to the specifically selected coupling component p-tert. With these dyes, butyl-phenol dyeings on polyamide of remarkable fastness properties, in particular wet fastness properties, are achieved.

The compounds of the formula I are anionic dyes and can be used for dyeing, padding and printing any substrates which can be dyed with anionic dyes. Suitable substrates are, for example, natural and synthetic polyamides, polyurethanes or base-modified polyolefins and also leather.

However, the dyes are used with particular advantage for dyeing, padding and printing fiber material which consists of or contains natural polyamides such as wool or silk and in particular synthetic polyamides, preferably nylon, with yellow to red shades of different nuances being achieved.

In particular, the dyes according to the invention can be used because of their good properties in carpet dyeing, in conventional printing and carpet printing processes. They are also well suited for the space dye process.

The compounds of the formula I or mixtures thereof can be used as such or in the form of liquid or solid preparations. The processing into stable liquid, for example concentrated aqueous or solid coloring preparations can be carried out in a generally known manner, for. B. by dissolving in suitable solvents such as water, optionally with the addition of a conventional auxiliary, for example a solubilizer such as urea, or then also by grinding or granulating. Such preparations can be obtained, for example, according to the information in French patents 1,572,030 or 1,581,900.

It is also possible to use the compounds in the form of cold-dispersible preparations. For this purpose, the dyes are subjected to mechanical comminution in the presence of one or more customary anionic dispersants and, if appropriate, further auxiliaries by dry or wet grinding with the dispersion medium water and, if appropriate, subsequently dried by atomization. Distribute the preparations made in this way

The monoazoamino compounds def formula II used as starting material are either known or they can be prepared analogously to a method known per se. The diazotization of an amine of the formula II is also carried out in a manner known per se.

US Pat. No. 3,676,050 describes a special dyeing process (so-called differential dyeing) for certain, in particular synthetic, polyamide fiber types using diazo dyes of the general formula III,

R

back into finely dispersed form when placed in cold water and are therefore easy to handle.

In order to achieve the same goal as with a cold-dispersible preparation, the addition of the dispersant can also be dispensed with in some cases, since the dye itself (only mixed with conventional couping agent) is cold-water soluble or at least cold-water dispersible.

The fiber material can be dyed with the dyes of the formula I or preparations thereof by any suitable methods, in particular by the padding process or exhaust process, the latter of which is preferred since the compounds of the formula I are neutral.

The usual methods can be used for printing and in particular carpet printing.

The dyes of the formula I are notable for good solubility and good build-up. The dyeings and prints obtained with the dyes of the formula I or mixtures thereof show good general fastness properties, in particular high light fastness, rub fastness and good wet fastness properties such as fastness to washing, water or sweat.

In addition, streak-coloring nylon covering colorations can be achieved with the dyes of the formula I.

These good properties combined with the same dyeing fastness level are particularly important in carpet printing.

The dyes of the formula I according to the invention also have the significant advantage that they can be easily combined with dyes which are similar on account of their coloring properties, in particular in trichromes; the high-quality dyeings of the individual dyes are also retained for the combination dyeings, in particular these do not show any catalytic tading.

In the following examples, parts are parts by weight, percentages are percentages by weight; the temperatures are given in degrees Celsius.

example 1

27.7 parts of 4-amino-l, l'-azobenzene-4'sulfonic acid are dissolved at 35-40 ° in 200 parts of water with the addition of 30% aqueous sodium hydroxide solution at a pH of 9-10, with 6, 9 parts of sodium nitrite dissolved in 25 parts of water and added dropwise over a period of 15 minutes at a temperature of 0-5 ° to an initial charge of 35 parts of 30% hydrochloric acid, 50 parts of water and 100 parts of ice.

15.2 parts p-tert. Butylphenol are dissolved in 100 parts of acetone and 200 parts of water with 30% sodium hydroxide solution and cooled to 0-4 °. The diazo suspension prepared according to the above instructions is added dropwise over a period of 30 minutes, the pH being kept at 8.5-9.0 by adding 10% sodium hydroxide solution. It will be 1st

5

10th

20th

25th

30th

35

40

45

50

55

60

65

628 363

Stirred for an hour, then acidified the reaction mass and salted out with sodium chloride. The separated dye is filtered, washed with ICK / iiger saline and dried; it corresponds to the formula

Na03S

= S

and dyes wool and synthetic polyamides in pure yellow tones with good light fastness and good wet fastness properties.

Analogously to Example 1, further dyes of the formula I can be prepared, which are obtained in the form of the sodium salt and for which the variables Rx and R2 and the position of the sulfo group and in the last column J the nuance of the coloration on polyamide are given in the following table . The dyeings obtained with these dyes show good light fastness and good wet fastness.

table

Example No.

ri r2

Position of the S03Na group

J

2nd

h h

3rd

yellow

3rd

och3

H

3rd

do.

4th

do.

H

4th

do.

5

do.

ch3

4th

orange-brown

6

do.

do.

3rd

do.

7

do.

och3

4th

brownish red

8th

do.

do.

3rd

do.

Dyeing Instructions In a dyebath consisting of 4000 parts of water, 10 parts of anhydrous sodium sulfate and 2 parts of the dye from Example 1, 100 parts of pre-wetted nylon cloth (nylon 66) are introduced at 40 °.

The dyeing liquor is heated to boiling temperature over the course of 30 minutes, kept at this temperature for 1 hour, 4 parts of glacial acetic acid are added and the dyeing is ended

25th

30th

35

40

OH

<o>

= N

c (ce3) 3

by heating to boiling temperature for a further 30 minutes. The evaporated water is constantly replaced during dyeing. Then you take the yellow colored nylon cloth from the fleet, rinse it with water and dry it. 15 Wool can also be dyed using the same procedure.

The dyeings have good lightfastness and good wet fastness.

In an analogous manner, the dyes from the Bel-20 games can be used to dye 2-8.

Printing instruction Polyamide is printed with a printing paste of the following composition:

30 parts of dye according to Example 1

50 parts of urea

50 parts of a solubilizer

(e.g. thiodiethylene glycol)

300 parts of water

500 parts of a suitable thickener (e.g. based on locust bean gum)

60 parts of an acid donor (e.g. Ammontartrate) 60 parts of thiourea.

The printed textile is steamed for 40 minutes at 102 ° (saturated steam), then rinsed cold, then washed for 5 minutes at 60 ° with a dilute solution of a commercially available detergent and rinsed again cold. A reddish-yellow print of good wet and light fastness results.

Printing pastes which contain a dye from Examples 2-8 as a constituent can be printed in an analogous manner.

s

Claims (3)

628 363 PATENT CLAIMS 1. Process for the preparation of new compounds of formula I, / SO.M where the S03M group is in the m or p position to the azo group, M is hydrogen or an equivalent of a colorless cation and c (ch3) 3 Rx and R2 independently of one another denote hydrogen, (1-4C) -alkyl or (1-4C) alkoxy, and also of mixtures of the compounds of the formula I, characterized in that the diazo compound is obtained from an amine of the formula II, n = • 11 S03M / wherein the S03M group is in the m or p position to the azo group, or mixtures thereof on p-tert. Butylphe-nol couples. 2. The in accordance with the method according to claim 1 25 holding compounds of formula I or mixtures thereof. 3. Process for dyeing or printing leather, characterized in that one uses a compound of formula I, defined in claim 1, or mixtures thereof.