DE1644643A1 - Process for the production of basic dyes - Google Patents

Description

PATENT LAWYERS

dr.w. Schalk dipl.-inc. p. Wirth diploma in Dannenberg DR. V. SCHMIED-KOWARZIK · DR. P. WEINHOLD

6 FRANKFURT AM MAIN

OH. EfCHENIlIlME * ST *. »9

Case 1778 / a / T

Sandoz AG,
Basel

Process for the production of basic dyes

The invention relates to a process for the division of basic dyes of the anthraquinone series free of carboxylic acid and sulfonic acid groups of the formula (i). These dyes are preferably used for dyeing, padding or printing acrylonitrile polymerization products, but also for coloring, padding or printing polyesters or polyolefins modified by acid groups.

In the formula (i)

NH -A.

CH ₂ -K ₁

mean

A. hydrogen or an optionally substituted alkyl, cyclohexyl or phenyl radical,

B ₁ hydrogen, chlorine, bromine or an optionally substituted alkyl or alkoxy radical,

Z _{1 is} a methyl radical,

Z _n a methyl radical, "" 2 CH ₃

K _{1 is} the grouping -N-NH ₃ and X is an anion.

t:

109887 / U42

COPY

The alkyl radicals or alkoxy radicals are preferably low molecular weight Alkyl or alkoxy radicals with 1 to 4 carbon atoms. Optionally substituted alkyl or alkoxy radicals are for example substituted by halogen atoms (chlorine, bromine or fluorine), or by hydroxyl or cyano groups. Optionally substituted phenyl, Phenoxy or cyclohexyl radicals are, for example, by alkyl or alkoxy groups or substituted by halogen atoms such as chlorine, bromine or fluorine.

Anion X ^ includes both organic and inorganic ions understand, such as methyl sulphate, sulphate, disulphate, perchlorate, phosphate, chloride, bromide, iodide, »phosphorus molybdate, phosphorus molybdate, benzenesulphonate, 4-chloro-benzenesulphonate, Oxalate or ifaleinate ions.

A process for the preparation of the new dyes is thereby characterized in that a compound of the formula, preferably 1 Hol of a compound of the formula,

(H)

109887 / U42

where E is the acid residue of an ester with the dimethylhydrazine of the formula, preferably with 1 mole of dimethylhydrazine of the formula

V \

H-KH ₂ ^: (III)

H, 0 ^

implements.

The new dyes of the formula (i) can, however, also be prepared by one of the processes given in Belgian patent specification No. 630,895. \

Examples of acid radicals E are those of sulfuric acid (E stands for SO.H), a sulfonic acid (E stands for SO ₂ R, where R is an optionally substituted hydrocarbon radical), hydrogen sulfide (E stands for SH), but preferably those of the hydrohalic acids (E stands for Cl, Br, etc.).

The reaction of a compound of the formula (III) with the dimethylhydrazine of the formula (III) is preferably carried out in an organic one Solvent and at temperatures from -50 ° to + 25O ° C. Man "

however, the reaction can also be carried out in an aqueous medium, if appropriate with the addition of an organic solvent, or completely Carry out without solvents at the above-mentioned temperatures.

The dyes obtained can be isolated, for example, by filtration, optionally after evaporation or precipitation.

109887/1442

They are used primarily for parting and printing moldings, in particular fibers and threads, from polymerization products made of more than 80 $ acrylonitrile, for example from polyacrylonitrile, e.g. (Acrilan "," Crylor "," Courtelle "," Orion ", "Dralon" (registered trademarks), or mixed polymers, so-called "modified acrylics", e.g. "Dynel" (registered trademark).

These fibers can be colored in a mixture with others. You get strong, level dyeings with good light and wet fastness and particularly good washing, welding, subliming, pleating, Ironing, water, seawater, bleaching, dry cleaning, over-dyeing and solvent fastness. Furthermore, the dyes for dyeing or printing are modified by acidic groups Polyester or polyolefin fibers are suitable.

At Koch, dyeing is usually done in an aqueous, neutral or acidic medium temperature under atmospheric pressure or in a closed vessel at elevated temperature under elevated pressure. Commercially available Retarders do not interfere, but are not required. The dyes are also suitable for coloring acrylonitrile polymerization products and other possibly dissolved plastics in the mass in lightfast and wetfast shades, for coloring oils or lacquers or for dyeing cotton, especially tannic Cotton, wool, silk, cellulose, regenerated cellulose,

109887/1442

synthetic polyamides and paper at every stage of manufacture. It has been shown that mixtures can also be beneficial can be used from two or more dyes of the formula (i). ·

In the following examples, parts are parts by weight and percentages are percentages by weight. You temperatures are in Celsius degrees indicated *

109887/1442

example 1

One leaves at 60 10 parts of asymmetric dimethylhydrazine in a suspension of 40.5 parts of 1-methylamino-4- (2 ', 4'-dimethyl-

5'-chloromethyl) phenylaminoanthraquinone in 150 parts of water drop in and stir the mass at 60 until most of the dye is dissolved. The undissolved one is then filtered off Residue and isolate the pure dye by adding salt to the filtrate »

The new dye »a blue powder, its aqueous solution is pure blue, "Orion" (registered trademark) colors in clear, level blue tones. The colorations are very good General fastnesses on.

Example 2

81 parts of 1-imino-2-methyl-4- (2 ', 6 "-dimethyl-3" -chlorine thyl) -phenylaminoantraquinone are dissolved in 250 parts of dimethylformamide and 13.5 parts of asymmetric dimethylhydrazine are added dropwise at 50. After a short time, the dye with the quaternary group begins to precipitate. Filtration gives it pure form of fine crystals. These dissolve in water with a reddish blue color, in concentrated sulfuric acid with a purple color. The new dye colors "Orion" (registered trademark) in · violet- blue tones.

109887/1442

164A643

Other valuable dyes of the anthraquinone series, which according to the process according to the invention, e.g. according to the information in Example 1 are described in the following table. ■ *

They correspond to the formula

where the symbols R., R ₂ , R- and R- have the meanings given in the table. As the anion X ^ those listed in the description come into question.

The symbol K ₁ stands for

for the dimethylhydrazine group -N (CH,) ₂

109887 / U42

ff

TABEL

-JB-

example
No.

R,

R,

R, R,

Nuance of coloring on Dralon

CH

CH ₂ -K ₁

^ ₅

OH

CH ₀ -K ₁

CH

NH-> y ^

CH ₂ -K ₁

CH ₂ -K ₁

NHCH

CH

Br

.

OCH

.H

NH-Q

NHCH ₂ CH ₂ OH

NH-Q NO,

greenish blue

blue

blue

reddish blue

reddish blue

Red

green

greenish blue

green

reddish blue

0.988 7 / U42

Staining example

20 parts of the dye obtained according to Example 1 are initially with 80 parts of dextrin in a ball mill for 48 Intimately mixed for hours.

Then 1 part of the preparation obtained in this way is added with 1 part of acetic acid 40%, the pulp with constant shaking Pour over 400 parts of distilled water at 60 ° and boil the whole thing briefly. It is diluted again with 7600 parts of distillier- ™ tem water, adds 2 parts of glacial acetic acid and goes into the dyebath at 60 with 100 parts of "Dralon" (registered trademark). 7) the material was soaked in a bath of 60 for 10 to 15 minutes 8000 parts of water and 2 parts of glacial acetic acid pretreated. One warms up now within 50 minutes to 100 »cooks for 1 hour and rinses. A level blue dyeing of excellent light fastness and very good wet fastness properties is obtained.

Example of the foulard dyeing λ

To produce 1000 parts of block paste mani 50 parts dye preparation

3 parts sodium alginate

5 parts of concentrated acetic acid, 20 parts of sodium sulfate

Polyacrylonitrile fiber material is cold padded on a 2- or 3-roll pad. The squeeze effect is 80 #. After an intermediate drying at 90 ° in the spinning frame, hot flue or with

109887/1442

With the help of an infrared heater, it is ^{fixed with dry air in the nozzle frame at 170-190 0} for 1-3 minutes, then rinsed, soaped and rinsed again. A blue dyeing with excellent lightfastness properties is obtained.

Print example

With a printing paste that made

75 parts of dye preparation
10 parts concentrated acetic acid 450 parts sodium alginate thickener

25 parts of a cationic plasticizer, for example a condensation product of 1 mol of stearic acid and 1 mol of triethanolamine
25 parts of sodium sulfate
415 parts of water

1000 parts

consists,

polyacrylonitrile fiber material is printed using the hand printing process, the fiber material is then dried in the air, steamed in a star steamer with saturated steam for 20-30 minutes, then rinsed, soaped and rinsed again. A blue print with very good solidity properties is obtained.

109887 / U42

Claims (2)

Claims ( 1.1 Process for the preparation of anthraquinone dyes of the formula (D wherein A _{1 is} hydrogen or an optionally substituted one Alkyl, cyclohexyl or phenyl radical, B _{1 is} hydrogen, chlorine, bromine or an optionally substituted alkyl or alkoxy radical, Z _{1 is} a methyl radical, Z _{n is} a methyl radical, "" 2 CH ₃ · K ₁ the grouping -N-NH ₂ and OH, X mean an anion,
characterized in that a compound of the formula CH ₂ -E (II) 109887/1442 where E is the acid residue of an ester with the dimethyl hydrazine of the formula ' H, C. \ - HH ₂ i (III) implements. 2. The method according to claim 1, characterized in that that the anthraquinone dyes of the formula (i) are free from carboxylic acid and sulfonic acid groups. The patent attorney !
ι 109887 / UA2