DE1236461B - Process for dyeing fibers and threads made of hydrophobic plastics - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

D 06 ρ

German class: 8 m - 1/01

Number: 1236 461

File number: S 76839 IVc / 8m

Filing date: November 25, 1961

Open date: March 16, 1967

Water-insoluble compounds obtained by coupling diazotized amines with 5-pyrazolone-3-carboxylic acid esters or S-pyrazolone-S-carboxamides are known. They have been used as intermediates for the manufacture of Served dyes. In doing so, their quaternary ammonium compounds were produced to make them water-soluble close. The quaternary ammonium compounds were used to color polyacrylonitrile recommended.

It has now been found that fibers and threads made of hydrophobic plastics and in particular fibers or threads made of linear aromatic polyesters, optionally processed into textile materials very good with aqueous dispersions of water-insoluble monoazo dyes of general formula

/H

A-N = N-HO

■ CO - N:

dyed, padded or printed.

In this formula, A denotes a benzene radical which, in the ortho position to the azo group, is replaced by halogen, Alkoxy or cyano and otherwise can be substituted as desired, B is a hydrogen atom or a optionally substituted hydrocarbon radical and Y is a hydrogen atom or an alkyl, Cycloalkyl, aralkyl or aryl radical.

Dyes of the formula (I) in which A and B are phenyl radicals are preferred. However, B can also for other aromatic radicals, for alkyl, aralkyl or cycloalkyl radicals. As a substituent for the hydrocarbon radical B comes, for example, one or more halogen atoms, especially chlorine, Bromine or fluorine, as well as nitro, alkyl, alkoxy, acylamino, alkylsulfonyl, carboxylic acid alkyl ester and sulfonic acid amide groups and their N-substitution products.

Suitable diazo components are all aminobenzenes free from water-solubilizing groups, ie from carboxyl and sulfonic acid groups, provided they are unsubstituted in the ortho position to the diazotizable amino group or contain a halogen atom or an alkoxy or cyano group. Aminobenzene derivatives with a negative substituent in the para position to the diazotizable amino group are particularly preferred. Suitable methods for dyeing fibers and threads
made of hydrophobic plastics

Applicant:

Sandoz A. G., Basel (Switzerland)

Representative:

Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys,

Frankfurt / M., Große Eschenheimer Str. 39

Named as inventor:

Dr. Ernest Merian, Bottmingen;

Dr. Otto Senn, Ariesheim (Switzerland)

Claimed priority:

Switzerland of November 29, 1960 (13 373),

of February 15, 1961 (1773),

dated July 14, 1961 (8267)

negative substituents are especially halogen atoms, preferably chlorine or bromine, or the nitro group, an alkyloxycarbonyl group, a sulfonamide group optionally substituted by alkyl groups, the nitrile group, an alkylsulfonyl group or an optionally substituted by alkyl groups substituted carboxamide group, the alkyl radicals in particular from 1 to 4 carbon atoms contain. These dyes are new.

Dyes which have a carboxylic ester group in place of the carboxamide group in the 3-position of the pyrazolone nucleus are included, e.g. B. from the Belgian patent 570 417 known. These dyes however, they are so poor that they practically do not work on polyester fibers under normal dyeing conditions wind up.

. The dyes of the formula (I) which can be used according to the invention are prepared in a customary manner Way. It is particularly useful, the diazotized amine in the pH range between 3 and 9 with the To couple pyrazolone derivative. The so. obtained dyes serve according to the invention as disperse dyes, especially for dyeing, padding or printing fibers and threads made of linear aromatic Polyesters and textile products of all kinds made from these fibers or threads. To this

709 519/480

The purpose is to use a dye of the formula (I) or a mixture of such dyes in the usual way into a dye preparation. For this purpose, the dye is used together with in disperse dye preparations common aids finely ground. As aids come z. B. dispersants, in particular anion-active dispersants, or wetting agents or emulsifiers, are also suitable neutral inorganic salts. The preparations obtained in this way are finely dispersed in water.

When dyeing, liquors are preferably used which contain approximately 0.1 to 8% of dye, based on Fiber weight, included. The liquor ratio can vary between 1: 5 and 1:60. Foulard baths contain about 1 to 200 g per liter, especially 20 to 60 g per liter, and also in more common Printing pastes prepared with the aid of thickeners usually contain about the same Amounts of dye per kilogram of paste like dye baths per liter. Suitable thickeners are z. B. alginates, tragacanth, crystal gum or locust bean gum. Particularly suitable dispersion, Wetting and emulsifying agents are z. B. the alkali salts of condensation products from aryl sulfonic acids and formaldehyde, e.g. B. dinaphthylmethandisulfonsaures sodium, alkylarylsulfonate or fatty alcohol sulfonates or fatty alcohol sulfates.

The dyeing temperatures are approximately between 80 and 140 ⁰ C and especially between 90 and 13O ⁰ C. The addition of carriers is often useful. Suitable carriers are e.g. B. phenols, such as phenol itself or o-phenyl-phenol, oxycarboxylic acid esters, e.g. B. salicylic acid esters, or chlorinated hydrocarbons, e.g. B. chlorinated benzenes.

After the dye is applied to the fiber, it is generally fixed. For this purpose, heated, optionally after drying, either in the presence of water vapor, that is generally at about 100 to 12O ⁰ C, or dry, in which case the temperatures are often chosen to be higher, eg. As to about 180 to 22O ⁰ C. Thereafter, as can be rinsed usual and optionally washed with soap and rinsed again.

The sparingly water-soluble azo dyes pull in suspension z. B. on fibers and threads made of synthetic polyamides, z. B. from poly-e-caprolactam or polycondensates from dicarboxylic acids and diamines, such as adipic or sebacic acid and hexamethylenediamine, or from aminocarboxylic acids, such as ω-aminoundecanoic acid, also from cellulose esters, e.g. B. cellulose 2 ^x / 2 acetate or cellulose triacetate, poly vinyl compounds, polyethylene or polypropylene, optionally modified polyacrylonitrile or polymers of more than 80% acrylonitrile and about 1 to 20% with acrylonitrile copolymerizable monomers, and in particular linear aromatic polyesters, z . B. Polyterephthalic acid glycol esters and especially Polyterephthalic acid ethylene glycol esters, in yellow and orange tones. The dyeings or prints are characterized by very good light, smoke, washing, perspiration, water and sea water, pleating, sublimation and thermosetting fastness. They are etchable. Viscose, cotton and wool are reserved, especially if an aftertreatment with hydrosulphites is added. The dyes are also valuable basic dyes for lightfast and pleated green, brown and gray tones.

Some of these dyes give particularly valuable combination colors with the blue component the formula

H ₂ N

NH ₂

HO

OH

The parts mentioned in the following examples are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius.

example 1

7 parts of the dye of the formula
20th

OH

O ₂ N

N = N

NH ₂

4 parts of sodium dinaphthylmethanedisulfonic acid, 4 parts of sodium cetyl sulfate and 5 parts of anhydrous Sodium sulfate is ground to a fine powder in a ball mill for 48 hours.

0.3 parts of the dye preparation obtained are made into a paste with a little water. The suspension obtained is added through a sieve to a dyebath containing 0.5 g / l lauryl alcohol sulfonate. That The liquor ratio is 1:40, but it can be varied within wide limits. One goes with now 100 parts of cleaned polyester fiber material at 40 to 50 ° in the bath, heated it slowly and colors after the addition of 50 ccm / l of an emulsion of a chlorinated benzene in water for 1 to 2 hours 90 to 100 °.

The yellow-colored fiber material obtained in this way is then rinsed, soaped, rinsed again and dried. The colors are light, overdyeing, washing, water, sea water, sweat, smoke gas, Sublime, heat-set and pleated right. They can also be white-etched.

But you can also dye in the following way: 10 parts of the dye, 10 parts of sulfite cellulose liquor powder and 80 parts of water are wet-milled in a ball mill for 48 hours. The received Paste is dried by spraying. In 1000 parts of water from 40 to 50 °, the 1 part of the obtained Containing dye preparation, 100 parts of purified polyester fiber material are added. The dye liquor is slowly warmed up. It is dyed for about 30 minutes under static pressure at 120 to 130 ° and obtained after rinsing, soapy, renewed rinsing and drying, yellow dyeings with good fastness properties.

The dye used in the present invention can be prepared, for example, as follows:

13.8 parts of 4-nitro-l-aminobenzene are with 25 parts of 30% hydrochloric acid and 6.9 parts of sodium nitrite are diazotized. The resulting solution will if necessary clarified by filtration. They are poured with vigorous stirring at 0 ° while simultaneously Addition of 20 parts of 25% ammonia to a solution of 20.3 parts of l-phenyl-S-pyrazolone-S-car-

bonsäureamid in 200 parts of water and 10 parts of 30% sodium hydroxide solution. The failed dye is filtered and washed neutral. It has a melting point of 274 to 275 °. In the following table further dyes are listed which are after that described in Example 1 Procedures can be used. The meaning of D and B can be seen from the formula.

Diazo compound

Melting points
in ⁰ C

Color shade on polyester

2 ethyl 4-aminobenzoate

3 l-amino-2-chloro-4-nitrobenzene

4 l-amino ^ o-dichlorom-nitrobenzene

5 l-amino-4-nitrobenzene

6 l-amino-4-nitrobenzene

7 l-amino-2-chloro-4-nitrobenzene

8 l-amino-2-chlorobenzene-4-sulfonic acid

methylamide

9 l-amino-2-cyano-4-nitrobenzene

10 l-amino-2-chloro-4-nitrobenzene

11 1 -Amino ^ -chlorbenzoM-sulfonic acid-

dimethylamide

12 l-amino-4-nitrobenzene

13 l-amino-2-chloro-4-nitrobenzene

14 l-amino-2-chloro-4-nitrobenzene

15 l-amino-4-nitrobenzene

16 l-amino-2-chloro-4-nitrobenzene

17 l-amino-4-nitrobenzene

18 l-amino-2-chloro-4-nitrobenzene

19 l-Amino-2-chloro-4-nitrobenzene.:

20 l-amino-4-nitrobenzene

Example 21

10 parts of the dye according to Example 10 are mixed in the form of the non-dried filter press cake, 10 parts of Turkish red oil and enough water to give a total of 200 parts. After 2 hours, 4 parts of the paste obtained are mixed with 5 parts of 2-hydroxy-l, l'-diphenyl and 2000 parts Water mixed. 100 parts of polyester fiber material are brought into the dye liquor obtained at 40 to 50 °, colors 1 hour at the boil and finally rinses. Reddish-tinged yellow colorations with excellent results are obtained Authenticity properties. The fiber material is well colored.

Example 22

10 parts of the dye obtained from diazotized 1-amino-4-nitrobenzene and 1-phenyl-S-pyrazolone-S-carboxamide, 38 parts of sodium dinaphthylmethanedisulphonic acid and 530 parts of water are ground in a ball mill for 48 hours. The colloidal solution obtained is mixed with 25 parts of butyl carbitol (dioxethylated n-butanol) and 400 parts of 6% carboxymethyl cellulose. ■ Η

H
■ Η

-C ₄ H ₉
- C ₂ H ₄ OH

CH ₃

-H

-H

-H

■ Η
H

-H
CH ₃
CH ₃

Phenyl
Phenyl
Phenyl
Phenyl
Phenyl
Phenyl

Phenyl
Phenyl

Phenyl

Phenyl

CH ₃

H
H

Phenyl
Phenyl

to 204
to 274

282

to 191
to 235
to 253

260
288

170

174

to 289

over 300

until 193

288

297

285

205

to 190
to 189

yellow

Reddish yellow

Reddish yellow

Reddish yellow

Reddish yellow

Reddish yellow

Reddish yellow orange

Reddish yellow

Reddish yellow

Greenish yellow

yellow

Reddish yellow

Reddish yellow

yellow

Greenish yellow yellow

Red-tinged yellow Red-tinged yellow

This printing paste is very suitable for Vigoureux printing on polyester fiber sliver. Of the Printing takes place by means of two rollers (coverage 78%), whereupon without intermediate drying at 115 to 120 ° is dampened. Yellow prints with good fastness properties are obtained.

Example 23

An aqueous, finely dispersed suspension of 15 parts of the dye according to Examples, 35 parts of dinaphthylmethandisulfonsaurem Sodium and 2 parts of alginate are mixed with 1000 parts of water. A polyester fabric is padded with the resulting liquor in the usual way at temperatures of 20 to 70 °, dried with air from 60 to 100 °, then with hot, dry air from 180 to 220 ° during Treated for up to 90 seconds and finally rinsed and soaped. Yellow level dyeings are obtained with good fastness properties.

Claims (2)

Patent claims: 1. Process for dyeing fibers and threads made of hydrophobic plastics, in particular of Fibers or threads made of linear aromatic materials optionally processed into textile materials Polyesters with aqueous dispersions of monoazo dyes, characterized in that; that one with a dye of the general formula A-N = N-HO CO-N (I) rest means that in the ortho position to the azo group can be substituted by halogen, alkoxy or cyano and otherwise arbitrarily, and in which B is represents a hydrogen atom or an optionally substituted hydrocarbon radical and Y represents represents a hydrogen atom or an alkyl, cycloalkyl, aralkyl or aryl radical. 2. The method according to claim 1, characterized in that the benzene radical A is in the para position to the azo group is substituted by a negative substituent. Considered publications:
Belgian patent specification No. 570 417. colors, blocks or prints, in which A is a benzene When the application was announced, a coloring table with an explanation was displayed.