DE2029314A1 - Stable, concentrated solutions of basic azo dyes - Google Patents

Description

FARBWEFKE H0ECH3T AG formerly Master Lucius & Brüning

File number: - HOE 70 / F 101

*. · ■ Date: June 10, 1970 - Dr.CZ/lA «« «^ ^.

Stable, concentrated solutions of "basic azo dyes"

The present invention relates to stable, concentrated Solutions of basic azo dyes.

Basic dyes are used extensively in the textile, paper and leather industries. You get there in general in the form of powders, which are still auxiliary or adjusting agents included, for application. Such dyestuff powders can partially or completely bake together if improperly stored, thereby reducing their solubility and quality. In addition, such dyes generate dust when decanting and weighing.

It is already known to produce concentrated solutions of basic dyes. Dyes are mainly used here the di- or triarylmethane, methine, diazamethine, oxazine and xanthene series as well as anthraquinone or azo dyes with external basic groups are used. Such dyes generally have a in organic solvents good solubility, so that the preparation of concentrated solutions does not cause any difficulties. In contrast, have azo dyes with quaternary groups which are ankonden- 'siert to the dye or are bound by a single bond, a reduced solubility, so that the production of concentrated, stable solutions has hitherto caused difficulties.

New, stable, concentrated solutions now became more basic Found azo dyes which are characterized in that they a) one or more dyes of the general formula I.

UHH- 'KJ Χ ^θ

(I)

109852/1599

ORIGINAL INSPECTED

20293U

where D is the residue of a diazo component of the general formulas II, III or IV

(II) (© A fen} - (III) («C ¥ af (IV)

lower

in which R is an optionally substituted alkyl radical, A an imidazolium, triazolium, thiazolium or "pyrazolium" radical and C denotes a cyclammonium radical and the benzene nuclei yes can contain further, non-ionic substituents, K is the rust of a coupling component -ind X is an anion,

b) one or more lower aliphatic carboxylic acids,

c) water and optionally one or more polyhydric alcohols or contain their ether «,

The preparation of the solutions can be such that the powdered batschen azo dyes in a mixture of an aliphatic carboxylic acid and water, optionally containing a polyhydric alcohol or its Xther, at ordinary or elevated temperature _o advantageously solves however, to use in the production of Dyes accumulating moist press cake »

If necessary, the solutions obtained in this way are added small amounts of an anti-foaming agent to «,

Suitable basic azo dyes dyes come into consideration, such as those described in French Patents 1322331, 1380628, 1391676, 1 420 692 ₉ 1 471 064, 1484099, 1484503, 1505141, 1520989 , 1 530 909 and 1 541 566, in German patents 87 257 ·. S? 584, 8? 585 and 643 244 _$ in the American patent publication 3 100 759 «in the Belgian patent specification 737 732 and in d ©! ³ Swiss patent 481 983 are described »

109852/1 6 9-9

Water-soluble mono- and dicarboxylic acids come into consideration as lower aliphatic carboxylic acids, for example formic acid, Acetic acid, propionic acid, maleic acid, acrylic acid or lactic acid, or mixtures thereof. . - "

Polyhydric alcohols or their ethers which may optionally be contained in the solutions include, for example, divalent and trivalent alcohols and their low molecular weight ethers, for example ethylene glycol, ethylene glycol monomethyl, ethyl, butyl or phenyl ether , Propylene glycol, diethylene glycol monomethyl, ethyl or butyl ether, triethylene glycol monobutyl ether or water-soluble polyethers of alkylene oxides, for example polyethylene glycols with molecular weights of 200-20,000. I

The solutions according to the invention contain the dyes in high concentrations, for example 15 to 50 percent by weight, and have the character of real solutions despite their high dye content. They stay at temperatures below of the freezing point liquid and the dissolved dyes do not crystallize out. The solutions are in every proportion miscible with water or with suitable organic solvents. The solutions diluted with water react weakly acidic.

The solutions according to the invention are suitable after dilution with water and K. if necessary addition of dyeing and / or f Printing auxiliaries, especially for coloring polymers or copolymers of acrylonitrile or vinylidene dicyanide as well as anionically modified polymer fibers, for example polyacrylonitrile, polyamide or polyester fibers.

In the examples below, the preparation of the Dye solutions according to the invention described.

1098 52/1599

Example 1 _s '

18.5 parts by weight of dye of the formula

Cl ⁰

H _X CN © N-CH

be in a mixed breed of 20 parts by weight of 85% formic acid, 17 weight bodies 99% pure ^he added acetic acid 41.5 parts by weight of water and 3 parts by weight of polyethylene glycol (molecular weight 1000) and stirred for 1 hour at 25 ° C. ' A stable solution is obtained which remains stable ^{even when it is cooled to 0 ° C.}

Instead of 3 parts by weight of polyethylene glycol (molecular weight 1000), 3 parts by weight of ethylene glycol can also be used. phenyl ether or 3 parts by weight of ethylene glycol monobutyl ether use.

Example 2 .

20 parts by weight of dye of the formula

85% formic acid, 17 parts by weight are added 99% acetic acid, 40.0 parts by weight of water and 3 parts by weight A'thylenglykolmonoäthyläther and briefly heated to 60 ⁰ C in a mixture of 20 parts by weight. A stable solution is obtained.

109852/1599

ti

In sp iel

17.5 parts by weight of dye of the formula

N- ^ Vn ei * ^ cH ₀ -CH ₀ -OH

H _X CN & N-GH, dd

are introduced with stirring into a mixture of 23 parts by weight of 85% formic acid, 19 parts by weight of 99% acetic acid, 4- weight steep propanediol <1.2) and 36.5 parts by weight of water and briefly warmed to 5O ⁰ O. A stable solution is obtained.

Example 4-

20 parts by weight of dye of the formula

N-

■ \ = sJ \

GH ₀ -CH ₀ -CN

Η, σ-Ν "® · N-CH, dd

are stirred into a mixture of 20 parts by weight of 85% formic acid, 10 parts by weight of 99% ige->? Was added acetic acid, 5 parts by weight of acrylic acid, 42 parts by weight of water and 3 parts by weight of glycol monomethyl ether and briefly warmed to 50 ⁰ C .. a stable solution is obtained.

Example 5 ,

20 parts by weight of dye of the formula

.Cl ^ ^ -N = Nf ^X > -N Cl "=

CH,

* 109852/1599

with stirring in a mixture of 20 parts by weight of 85% formic acid, 19 parts by weight are added 99% acetic acid, 4 parts by weight of propanediol CL.2) and 37 parts by weight of water and briefly warmed to 5O ⁰ C a stable solution "is obtained.

Example 6

30 parts by weight of dye of the formula

N = N

are added 99% acetic acid, 4 parts by weight · Glykolmonophenyläther and 52 parts by weight of water and briefly warmed to 50 ⁰ C with stirring in a mixture of 19 parts by weight of 85% formic acid, 15 parts by weight. A stable solution is obtained.

Example 7

38 parts by weight of dye of the formula

/ ° 2 ^H 5

^ CH ₉ -CH ₃ -OCOCH

are stirred into a mixture of 35-7 parts by weight 85% formic acid, 1 part by weight of polyethylene glycol 1000 and 25 »3 parts by weight of water and briefly heated to 50.degree warmed up. A stable solution is obtained

⁺ on the molecular weight

ο Example 8 dye the formula CO "C H OO
O ^ 40 parts by weight Vn - N- / ¹ cl N-CH _x ^GE l
■ 3/7 S. /
3 <ΐ> ηι

egg ©

with stirring in a mixture of 35 _t 7 parts by weight of 85% formic acid, 1 part by weight of polyethylene glycol 10000 ⁺ and 23.3 parts by weight of water was added and shortly warmed to 5O ⁰ C * are obtained, a stable solution.

* above molecular weight example 9

■ 26 parts by weight of dye of the formula

with stirring in a mixture of 26 parts by weight of 85% formic acid, 4 parts by weight of 99% acetic acid, 4 parts by weight acrylic acid, 4 parts by weight polyethylene glycol 1Ö00 and 36 parts by weight of water are added and heated briefly to 50 ⁰ C. A stable solution is obtained. ⁺ on the molecular weight

Example 10
ί 20 parts by weight of dye of the formula

Cl

H, C-K © If-CH,

^{5 1} V ³

are added 99% acetic acid, 6 parts by weight Glykolmonobutylather and 46 parts by weight of water and briefly warmed to 50 ⁰ C with stirring in a mixture of 20 parts by weight of 85% formic acid, 8 parts by weight. You get a stable solution. . '

10 9-8 62/1699

Example 11 j ' .

20 parts by weight of dye of the formula.

Cl ^€

with stirring in a mixture of 20 parts by weight of 85% formic acid, 10 parts by weight of 99% acetic acid, 5 parts by weight acrylic acid, 3 parts by weight of glycol monomethyl ether and 42 parts by weight of water was added and briefly warmed to 50 ⁰ C. A stable solution is obtained.

Example 12 . .

18 parts by weight of dye of the formula

H, C -

Η, σοοσ - c

are added 99% acetic acid, 4 parts by weight Glykolmonobutylather and 36 parts by weight of water and briefly warmed to 50 ⁰ G under Eühren in a mixture of 30 parts by weight of 85% Aueisensäure, 12 parts by weight. A stable solution is obtained. _ - —.-

Example 13 .

18 parts by weight of dye of the formula

are stirred into a mixture of 22 parts by weight cn.

κ »85% formic acid, 8 parts by weight of 99% acetic acid, ' Il 4 parts by weight of acrylic acid, 4 parts by weight of polyethylene ^ glycol 10000 and 44 parts by weight of water and

* Heated to 50 ° short ^0C. A stable solution is obtained. ⁺ on the molecular weight

Example 14 *

. . - α

20 parts by weight of dye of the formula

ZnCl

ΘΘ

with stirring in a mixture of 35 parts by weight of 85% formic acid, 5 parts by weight of 99% acetic acid, 5 weight steep propanediol CL.2) and 35 parts by weight of water are added and briefly warmed to 5O ⁰ C. A stable solution is obtained.

Example 15 .

18 parts by weight of dye of the formula

ZnCl

ΘΘ

with stirring in a mixture of 25 parts by weight of 85% formic acid, 10 parts by weight to 99%: r acetic acid, 4 parts by weight of propionic acid, 1 part by weight polyethylene glycol 4000 and 42 weight parts of water was added and Kürz heated to 50 ⁰ C. A stable solution is obtained.

⁺ on the molecular weight
Example 16

19 parts by weight of dye of the formula

> .CHr \ "* CHo

/ r 2 2 \

= /> 0Ho-

ZnCl,

_x C ^{7 Χ} ΟΊΓ CH, ·

under Hühren in a mixture of 31 parts by weight of 85% Ameiaensäure, 5 parts by weight of 99% igö37 acetic acid, 5 GewichtsteilenGlykolmonophenyläther and 40 weight parts of water are added and heated briefly to 50 ⁰ C. You get a stable solution «

Example 17

18 parts by weight of dye of the formula

HG N - CH, Il & Ii 3

HC CH

CF,

are added 99% acetic acid, 4 parts by weight of glycol monobutyl ether and 46 parts by weight of water and briefly warmed to 50 ⁰ C with stirring in a mixture of 32 parts by weight of 85% formic acid, 10 parts by weight. A stable solution is obtained.

Example 18

20 parts by weight of dye of the formula

\ Vl 'ZnCl ,, ⁰⁹

with stirring in a mixture of 35 parts by weight of 85% formic acid, 5 parts by weight of 99% acetic acid, 2 parts by weight of propionic acid, 4 parts by weight of glycol mono ethyl ether, and 3 ^ be - parts by weight of water was added and kruz at 50 ⁰ C heated, "A stable Iiösung .

Claims (1)

2020314 Fat ent; to sprue Ix Stable, concentrated solutions of basic azo dyes, characterized in that they a) one or more Dyes of the general formula I D - H »N - K (I) whereinD is the remainder of a diazo component of the general Formulas II, III or IV, (II) (III) (IV) wherein R is an optionally substituted lower alkyl radical, A is an imidazolium, triazolium, thiazolium or pyrazolium radical and C mean a cyclammonium radical and the benzene nuclei a_ may contain further, non-ionic substituents, K den The remainder of a coupling component and X is an anion, b) one or more lower aliphatic ^ carboxylic acids, c) water and optionally contain one or more polyhydric alcohols or their ethers. 109852/1599