DE1469772C - Process for coloring fiber materials made of polymer and copolymer acrylonitrile - Google Patents

Description

In the main patent is a process for dyeing, particularly for continuous dyeing, of polymeric and copolymeric acrylonitrile with basic dyes claimed, which is characterized is that the fiber material is basic with an optionally thickened, aqueous acidic solution Dye, the water-soluble salts of saturated, aliphatic, 8 to 14 carbon atoms containing monocarboxylic acids and may contain other auxiliaries customary in dyeing, especially poly-> o glycol ethers of fatty alcohols or fatty acids with 8 to 14 carbon atoms and 4 to 12 ether oxygen atoms and / or amides of saturated, aliphatic,. Monocarboxylic acids having 8 to 14 carbon atoms with primary or secondary alkanolamines at temperatures below the absorption temperature of these dyes, impregnated and the impregnated product steams. . ....

In further processing this subject it has now been found that the advantageous effect of any surface-active polyglycol ethers containing lipophilic radicals is not limited to condensation products of ethylene oxide with fatty alcohols and fatty acids with 8 to 14 carbon atoms; With a suitable selection of the constituents of such dye preparations, it extends to a much broader class of such surface-active polyglycol ethers. It can more generally lipophilic groups, ie higher aliphatic hydrocarbon radicals having polyglycol ethers and mixtures of such polyglycol ethers are used, the number of which is selected to ether groups so that: - ensure the compounds hydrophilic properties, ie that these polyglycol ethers, at least readily dispersible in water and preferably are soluble in it. It is often advantageous to use mixtures of these substances, the water-soluble constituents acting as dispersants for the dispersible constituents. In particular, it is also possible to use polyglycol ethers containing basic nitrogen, for example also polyglycol ethers of aliphatic, more highly alkylated or acylated di- and polyamines.

Accordingly, the present invention relates to a method for dyeing, in particular for continuous dyeing, of fiber material made of polymeric and copolymeric acrylonitrile using a dye preparation according to the main patent, which is characterized in that here as lipophilic residues, surface-active, hydrophilic to water-soluble polyglycol ethers, ethylene oxide condensation products, which also individual substituted epoxides, such as styrene oxide and / or propylene oxide, may contain built-in,

a) of alkylphenols together with one or more alkyl substituents having at least 8 carbon atoms,

b) of primary or secondary, monobasic or polybasic aliphatic and cycloaliphatic amines containing at least one higher alkyl or alkenyl residue of at least 8 carbon atoms or of such lipophilic alkyl or aralkyl radicals containing alkanolamines and ^6s

c) of alkanolamides aminoalkylamides and Aminfxilkylestern of higher aliphatic, in particular saturated, carboxylic acids and higher alkylated alkylaryloxycarboxylic acids,
or mixtures of two or more of the condensation products mentioned under a) to c) can be used.

Suitable as salts of saturated, 8 to 14 carbon atoms, aliphatic carboxylic acids contains the impregnating liquor which can be used according to the invention, for example, alkali salts, such as lithium, sodium or potassium salts, ammonium or N-substituted ammonium salts of the caprylic, pelargon, Capric, lauric or myristic acid, or those summarized under the collective term 'coconut oil fatty acids Acid mixtures. The preferred N-substituted ammonium salts contain as substituents in particular lower alkyl groups, such as the methyl, ethyl or propyl group, lower hydroxyalkyl groups, like the / i-hydroxyethyl or y-hydroxypropyl group, or lower alkoxyalkyl groups, such as the j3-methoxy or / f-ethoxyethyl or the y-methoxy or γ-ethoxypropyl group. Here, two N-substituents can be used together with the nitrogen atom also a ring, e.g. B. form the piperidine or morpholine ring.

The alkali, lower alkylammonium or lower hydroxyalkylammonium salts, especially the mono- and bis- (/ i-hydroxyethyl) - or bis- (γ-hydroxypropyl) -ammonium-, the N-methyl-N have proven particularly good - (/ f-hydroxyäthyI) -ammonium-, N-Methyl - N, N - bis - (ß - hydroxyäthyl) - ammonium- or N-Methyl-N - (/ i, y-hydroxypropyl) -ammoniumsaIzeder coconut oil fatty acids proven.

Basic nitrogen containing nitrogen has proven particularly valuable in the process according to the invention Polyglycol ethers, e.g. B. polyglycol ethers aliphatic, especially higher alkylated or acylated di- and polyamines, where one long or several shorter polyglycol ether chains are bonded via nitrogen can be, such as B. Ethylene oxide condensation products of higher monoalkyl or monoalkenyl ethylenediamine, -diethylenetriamine, -triethylenetetramine with at least 16 carbon atoms in the Alkyl or alkenyl radical, for example from lauroyl, Myristoyl-, oleoyl-, palmitoyl-, stearoyl-aminoethylamine, -äthylenediamine, -diethylenetriamine and preferably with at least 15 or more ethyleneoxy groups. The number of ethyleneoxy groups in these polyglycol ethers depends on the type and composition of the lipophilic constituent of these compounds in total at least 4, preferably more than 8 to about 100 ethyleneoxy radicals arranged in a single chain or in different chains can be and their ethyleneoxy groups to reinforce the lipophilic character also isolated alkyl (especially methyl-substituted) or phenyl-substituted. Particularly cheap connections of this type are addition products of 15 to 20 moles of ethylene oxide with 1 mole of N-monoalkyldiethylenetriamine, the alkyl radical of which has at least 16 carbon atoms, e.g. B. stearyl diethylenetriamine, or addition products of 1 to 3 mol of styrene oxide or propylene oxide and of at least 50 moles of ethylene oxide to an N-monoalkyl-diethylenetriamine, whose alkyl radical has 16 to 18 carbon atoms.

The number of alkyleneoxy groups in these polyglycol ethers should ensure hydrophilic properties and be so large that the compounds in

Water are at least easily dispersible and preferably soluble therein. It is often cheap to use mixtures to use these compounds with low to higher contents of ethyleneoxy groups, with the higher water-soluble polyglycol ethers act as dispersants for the lower polyethers. Examples of polyglycol ethers containing lipophilic groups which can be used according to the invention are: stearyl diethylenetriamine polyglycol ethers with 17 ethyleneoxy groups, adduct of 2 moles of styrene oxide and 50 to 60 moles of ethylene oxide in 1 mole of stearyl diethylenetriamine, nonylphenol polyglycol ether with 5 ethyleneoxy groups, coconut oil fatty acid di-jS-hydroxyethylamide polyglycol ether with 15 to 17 ethyleneoxy groups, octylphenoxyacetic acid polyglycol ether with 3 to 5 ethyleneoxy groups, adduct of

2 moles of 1,2-propylene oxide and 50 to 60 moles of ethylene oxide of 1 mole of stearyl diethylenetriamine, oleylamine polyglycol ether with 7 ethyleneoxy groups, stearoyl diethylenetriarhin polyglycol ether with 17 ethyleneoxy groups, octylphenol polyglycol ether with 4 ethyleneoxy groups and coconut oil fatty acid ß-aminoethyl ester polyglycol ether with 3 ethyleneoxy groups.

It is particularly favorable if the impregnation liquor in addition to the fatty acid salts and the polyglycol ethers nor amides of saturated aliphatic monocarboxylic acids containing 8 to 14 carbon atoms contains primary or secondary alkanolamines.

The amides which can be used according to the invention are derived, for example, from those described above for Salts of discussed higher fatty acids and of monohydroxyalkylamines, e.g. B. of /? - hydroxyethylamine, y-hydroxypropylamine or / 9, y-dihydroxypropylamine, of bis (cu-hydroxyalkyl) amines, such as bis (/ 3-hydroxyethyl) - or bis (γ-hydroxypropyl) amine or bis (a-methyl) S-hydroxyethyl) amine or N-alkyl-N- (cu-hydroxyalkyl) amines, like N-methyl- or N-ethyl-N - (/? - hydroxyethyl) - or N-methyl- or N-ethyl- (γ-hydroxypropyl) -amine.

The bis (w-hydroxyalkyl) amides are preferred, especially those whose hydroxyalkyl radicals are 2 or

Contains 3 carbon atoms, such as bis (/ S-hydroxyethyl) amides or bis (γ-hydroxypropyl) amides of coconut oil fatty acids.

The quantitative proportion of auxiliary mixture per liter of dye liquor is, for example, 15 to 100 g and preferably 20 to 40 g.

The weight ratio of the water-soluble, fatty acids Salts to the polyglycol ethers should be less than 3: 1 and preferably about 2: 1 to 1: 2. If mixtures are used which contain the named salts, polyglycol ethers and amides, this is the case mutual weight ratio of the salts mentioned to the polyglycol ether-amide mixture is less than 3: 1 and is advantageously approximately 2: 1 to 1: 8.

The impregnation fluid owes the acidic reaction above all to the presence of lower organic substances Carboxylic acids, especially acetic acid, but also formic acid and tartaric acid, which are present in amounts of 30 to 300 g and in particular 40 to 60 g per liter (100%) of the impregnation liquor are added to To ensure pH values of the liquor below 4.5, preferably between 2.5 to 4.0. The high Acidity values of the impregnating liquor which can be used according to the invention are relevant for the process according to the invention recognized as essential.

The dye preparation according to the invention contains the customary salts as basic dyes and metal halides, for example zinc chloride double salts the known cationic dyes, in particular the methine or azamethine dyes, the indolinium, pyrazolium, imidazolium, triazolium, tetrazolium, oxdiazolium, thiodiazolium, Oxazqlium, thiazqlium, pyridinium, pyrimidinium, Pyrazinium ring included. The heterocycles mentioned can optionally be substituted and / or condensed with aromatic rings. There are also cationic dyes of the diphenylmethane, Triphenylmethane, oxazine and triazine series, in question as well as finally color salts of the Arylazo and anthraquinone series with external onium group. ■■ ·, ..

In the textile industry, for example, the usual open-thickened thickeners that are compatible in an acidic bath are Types of rubber, e.g. B. so-called "crystal gum", or thickeners based on cellulose, such as locust bean gum, Tragacanth, British gum, polysaccharides or cellulose derivatives such as methyl cellulose, or name soluble salts of carboxymethyl cellulose. Thickeners made from locust bean gum are preferred as well as galactomannans.

The impregnation liquor can be used as further auxiliaries customary in dyeing, for example organic Solvents, especially ethylene glycol monoethyl ether or thiodiethylene glycol and also ethylene carbonate or propylene carbonate.

As dyeable fiber materials according to the invention polymeric or copolymeric acrylonitrile are particularly those that are predominantly Share, preferably 80 to 100%, of polymer! There are acrylonitrile and the acidic copolymers, in particular Sulphonic acid and / or carboxylic acid groups contain. ,

The fiber material can be in any form, for example in the form of flakes, yarn or fabrics, but in particular as tow, sliver or piece goods, such as plush, colored according to the invention will. . · ...... ■

The fiber material is impregnated, for example by printing, coating or spraying, but preferably by padding.

The impregnation liquor according to the invention is advantageously produced by "the basic FarbsFöff with the acid used, in particular Amount of acetic acid, preferably 60 to 80% acetic acid, made into a paste, poured hot water over it, with thickener and finally with the salts and polyglycol ethers and optionally others in the usual auxiliaries used in dyeing.

The polyacrylonitrile fiber material is advantageously impregnated at 30 to 40 ° C and then on the desired content of impregnation liquor of approximately 60 to 140% of the fiber weight squeezed off.

The impregnated fiber material is steamed using conventional methods with saturated, advantageous with neutral, slightly superheated steam.

The dyed and steamed goods are expediently rinsed, advantageously with cold or warm water, which may contain additives customary in dyeing, for example formic acid or acetic acid or substances or lubricants that make antistatic.

With the method according to the invention, especially when continuously dyeing fiber material made of polymer and copolymer acrylonitrile, very deep shades achieved without a gray haze,

which are characterized by an excellent uniformity of coloration. Especially with the preferred continuous dyeing with a mixture of different basic dyes does not become selective obtained dyed fiber sites. The impregnation liquors which can be used according to the invention are also used easy to manufacture, stable, i.e. practically indefinitely durable, and, since the action of salts and Acids whose stability does not affect, ideally suited for the continuous dyeing process.

The following examples serve to illustrate the invention. In it are the temperatures given in degrees Celsius. Unless expressly stated otherwise, the parts are parts by weight. Parts by weight are related to parts by volume as grams to cubic centimeters.

20 g of dye of the formula

CH

example 1

C-N = N-

-NO,

CH,

Cl ^e

ig will ^he made into a paste in 150 g of 80% acetic acid in the cold and dissolved with 600 ml of hot water. 4 g of MEYPROGUM KN (Meyhall, Kreuzungen, Switzerland), which are made into a paste with 20 ml of ethanol and mixed with cold water, are added to this solution with stirring. 30 g of a mixture of 1 part coconut oil fatty acid di - ^ - hydroxyethylamine salt and 1 part of an adduct of 2 mol of styrene oxide and 50 to 60 mol of ethylene oxide and 1 mol of stearyl diethylenetriamine are then added and the whole is made up to 1000 ml with water and brings it up the finished impregnation liquor to 30 to 40 °. The pH of this liquor is around 3 to 4.

This liquor is used to impregnate plush made of polyacrylonitrile, and the material is squeezed to a liquor content from 100% and steams it for 20 minutes with slightly superheated steam at 103 to 104 °.

The dyed goods are then rinsed several times with warm water at 45 °, then with a Solution which contains 4 g per liter of an antistatic and 2 g per liter of a lubricant treated and dried.

An excellent, uniformly yellow-colored material is obtained.

If the above mixture of coconut oil fatty acid di-jS-hydroxyethylamine salt and an addition product of styrene oxide and ethylene oxide with stearyl diethylenetriamine in mutual Weight ratio of 1: 3 instead of 1: 1 and otherwise proceeds as noted in the example similar results are obtained.

Similar results are obtained using from 40 to 50 g of acetic acid, formic acid or tartaric acid instead of 150 g of 80% acetic acid, otherwise the same way of working as indicated in the example.

Be i s ρ i e 1 2

20 g of the dye used in Example 1 are made into a paste in 150 g of 80% acetic acid in the cold and dissolved with 600 ml of hot water. 4 g of Solvitose OFA (W. A. Schelten, Foxhal, Holland), which are made into a paste with 20 ml of ethanol and mixed with cold water Stirring added. This is followed by 30 g of a mixture of 1 part of coconut oil fatty acid di-ß-hydroxyethylamine salt, 1 part of an adduct of 2 moles of styrene oxide and 50 to 60 moles of ethylene oxide of 1 mole of stearyl diethylenetriamine and 1 part of coconut oil fatty acid di-j3-hydroxyethylamide add, fill the whole thing up to 1000 ml with water and bring the finished impregnation liquor to 30 to 40 °. The pH of this liquor is around 3 to 4.

This liquor is used to impregnate tow made of polyacrylonitrile and treat the material continue as indicated in example 1.

An excellent uniform yellow color is obtained. Material.

Similar results are obtained using 30 grams of a mixture of 1 part of the above mentioned salt, 2 parts of the above stearyl diethylenetriamine polyglycol ether and 1 part coconut oil fatty acid di- / 3-hydroxyethylamide with otherwise the same Way of working.

If, instead of the specified dye, 33.5 g of a dye mixture consisting of 27 g of dye of the formula

CH ₃ O

C-N = N

ZnCl ₃ ⁰

3.5 g of dye of the formula

CH, O— "

Cl®

and 3.0 g of dye of the formula

HC

N (C ₂ H ₅ ), ZnCl ₃ Q

and if the rest of the procedure is as indicated in the example, an excellent, uniformly navy blue color is obtained Fibers. .

example

20 g of dye of the formula

ZnCL®

are made into a paste in 60 g 80% acetic acid in the cold and dissolved with 600 ml of hot water. This solution contains 4 g of MEYPROGUM KN, which are supplied with 20 ml of ethanol are made into a paste and mixed with cold water, added with stirring. On that 30 g of a mixture of 1 part of N-methyl-N - (/? - hydroxyethyl) ammonium salt are used of coconut oil fatty acid, 1 part of stearyl diethyfen triamine polyglycol ether with 17 ethyleneoxy groups and 1 part coconut oil fatty acid di - /? - hydroxyethylamide add, fill the whole thing up to 1000 ml with water and bring the finished impregnation liquor to 30 to 40 °. The pH of this Fleet is approximately 3 to 4.

This liquor is used to impregnate tow or sliver of polyacrylonitrile and treat it the material further, as indicated in Example 1.

An excellent, uniformly red-colored material is obtained.

You get similar results if you do this in the Example mentioned mixture of fatty acid amine, polyglycol ether and fatty acid amide by the same Replaced quantities of one of the auxiliary mixtures mentioned below:

1 part bis (/ 3-hydroxyethyl) ammonium salt of coconut oil fatty acids

1 part stearyl diethylenetriamine polyglycol ether with 17 ethyleneoxy groups

1 part sodium or potassium salt of coconut oil fatty acids

2 parts adduct of 2 moles of styrene oxide and 50 to 60 moles of ethylene oxide with 1 mole

Stearyl diethylenetriamine

1 part of N-methyl-N - (/ 3-hydroxyethyl) ammonium salt of lauric acid 1 part nonylphenol polyglycol ether with 5 ethyleneoxy groups

1 part tris (/? - hydroxyethyl) ammonium salt of coconut oil fatty acids

2 parts of stearyl diethylenetriamine polyglycol ether with 17 ethyleneoxy groups

1 part bis (/ S-hydroxyethyl) ammonium salt of coconut oil fatty acids

1 part coconut oil fatty acid di - ^ - hydroxyethylamide polyglycol ether with 15 to 17 ethyleneoxy groups

1 part dimethylammonium salt of coconut oil fatty acids 1 part octylphenoxyacetic acid polyglycol ether with 3 to 5 ethyleneoxy groups 1 part morpholinium salt of coconut oil fatty acids

1 part adduct of 2 mol of 1,2-propylene oxide and 50 to 60 mol of ethylene oxide with 1 mol Stearyl diethyl alcohol

009 526/265

ίο

11th

12th

13th
14th

15th
16

17th

18 '
19th

20th
21

22nd

1 part bis (/ I-hydroxyethyl) ammonium salt of lauric acid

1 part adduct of 2 moles of styrene oxide and 50 to 60 moles of ethylene oxide with 1 mole Stearyl diethylenetriamine

1 part bis (/ S-hydroxyethyl) ammonium salt of coconut oil fatty acid

1 part adduct of 2 moles of styrene oxide and 50 to 60 moles of ethylene oxide with 1 mole of stearyl diethylenetriamine ^:

1 part N-methyl-N - (/ S-hydroxyethyl) ammonium salt of coconut oil fatty acids Part 1. Oleylamine polyglycol ether with 7 ethyleneoxy groups

1 part N-methyl-N- (ß-hydroxyethyl) ammonium salt of coconut oil fatty acids 1 part adduct of 1 mole of styrene oxide and 50 to 60 moles of ethylene oxide with 1 mole Stearyl diethylenetriamine

1 part bis (/ S-hydroxyethyl) ammonium salt of lauric acid 1 part of coconut oil fatty acid ß-aminoethyl ester polyglycol ether with 3 ethyleneoxy groups 1 part bis (/ 3-hydroxyethyl) ammonium salt of pelargonic acid 1 part stearyl diethylenetriamine polyglycol ether with 17 ethyleneoxy groups 1 part ethylammonium salt of coconut oil fatty acids

1 part adduct of 2 moles of styrene oxide and 50 to 60 moles of ethylene oxide with 1 mole

. . . Stearyl diethylenetriamine

1 part sodium or potassium salt of coconut oil fatty acids ^: ' ^{: i} "'' ^: ""^;' ^{: iif} " ^::

1 part octylphenol polyglycol ether with 4 ethyleneoxy groups 1 part N-methyl-N, N-bis - ((9-hydroxyethyl) ammonium salt of lauric or myristic acid 3 parts of adduct of 2 moles of styrene oxide and 50 to 60 moles of ethylene oxide with 1 mole

Stearyl diethylenetriamine. j

1 part of lauric acid or myristic acid-N, N-bis - (/ S-hydroxyethyl) -amide 1 part N-methyl-N, N _: bis - (^, y-dihydroxypropyl) ammonium salt of coconut oil fatty acids 1 part stearyl diethylenetriamine polyglycol ether with 17 ethyleneoxy groups 1 part coconut oil fatty acid-N, N-bis - (/ S-hydroxyethyl) -amide

1 part sodium or potassium salt of coconut oil fatty acids 1 part adduct of 2 moles of styrene oxide and 50 to 60 moles of ethylene oxide with 1 mole

Stearyl diethylenetriamine
1 part of lauric or myristic acid-N, N-bis - (/? - hydroxyethyl) amide

35 parts of bis (5-hydroxyethyl) ammonium salt of lauric acid 35 parts of stearyl diethylenetriamine polyglycol ether with 11 ethyleneoxy groups

30 parts of coconut oil fatty acid-N, N-bis (^ - hydroxyethyl) -amide

20 g of dye of the formula

CH, O

Example 23

CH,

ZnCl, ©

^u / ^e oig made into a paste in 100 g of 80 r acetic acid in the cold and dissolved with 600 ml of hot water. This solution will be. 4 g MEYPROGUM KN, which are made into a paste with 20 ml of ethanol and mixed with cold water, are added while stirring. 30 g of a mixture of 3 parts of an adduct of 2 moles of styrene oxide and 50 to 60 moles of ethylene oxide with 1 mole of stearyl diethylenetriamine and 1 part of coconut oil fatty acid di-ß-hydroxyethylamine salt are added, the whole is made up to 1000 ml with water and the finished impregnation liquor to 30 to 40 °. The pH of this liquor is around 3 to 4.

With this liquor, piece goods made of polyacrylonitrile are impregnated and the goods are further treated as given in example 1.

An excellent, uniformly blue-colored material is obtained.

Is used in place of the example cited dye one of the specified in the table below dyes and verfahrt the rest, as indicated in the example, we obtain likewise ⁶ S if perfectly evenly dyed material in amounts shown in column 3 of Table shades.

11th

12th

Dye shade on polyacrylonitrile fibers

H, C

HCl

OH

CH, O

HCl

N = N- <TV CH ₃

CH,

OCH ₃

C - CH = CH - NH - \ ~~ V ~ OCH ₃ Cl ^e

CH, O

ι
CH

£ -N = NN-CH ₃

-NO,

CH ₃
C CH ₃

C-CH = CH-NH- / '

I.
CH,

C-CH,

Cl ©

(CH ₃ J ₃ N ₀ -CH ₂ OC

N = N-C-

II H ₃ CC

yellow

yellow

yellow

yellow

Reddish yellow

yellow

Reddish yellow

13th

Continued 14

Dye color on polyacrylic tri! Fibers

C (CH ₃ J ₂

C-CH = CH-C

X = / \ _N.

CH ₃ Cl ©

CH,

C (CH ₃ ),

C-CH = CH-C H ₃ CC

\ _N H

CH ₃ -N = C- / Vn- ^ ^- V-OC ₂ H ₅

CH,

CH ₃ SO ₄ Q

Cl ^e

CH ₂ CH ₂ Cl Cl®

HC N-CH ₃

It It

N C-N = N-f

CH ₃

N (C ₂ H ₅ ) ₂ ZnCl ₃ Q

0 NH,

0 NH- / V-OCH ₂ -CH ₁ - ⁰ N CH ₂

CH ₂ CH ₃ SO ₄ ⁰

Reddish orange

orange

violet

Red

Red

Bluish red

blue

15th

continuation

16

Dye shade on polyacrylonitrile fibers

-C (CH ₃ ), C - CH = CH - ^ , CH ₂ CH ₂ Cl

CH,

CH, Cl®

(C ₂ H ₅ ) ₂ N

N (C ₂ H ₅ ),

Cl ⁰

Cl

NHC ₂ H ₅

H, C

© NHC ₂ H ₅

Cl®

Cl ©

C-N = N-

CH ₃

CH,

N ^

y Θ

CH ₃

_ _{N = N.}

CH ₃

. _N _y \

CH ₃ ZnCl, ⁹

ZnCl ₃ Q

⁰ N (C ₂ H ₅ ), HSO ^

Red-violet

Greenish blue

Greenish blue

Greenish blue

Reddish blue

blue

green

009 520/265

17th

continuation

18th

Dye shade on polyacrylonitrile fibers

CH ₃ O

N = N-

CH, ZnCl ₃ ®

CH ₃ CO-N
H

N = N

N

CH, Ζη € 1 ₃ ^Θ

N = N

..N

© CH ₃

Ν® CH ₃

NH, ZnCl ₃ ^e

ZnCl, ®

-N = N

N-CH,

CH ₃ ZnCl ₃ ®

O, N

N-CH ₃

NH-CO-CH ₃

CH ₃ ZnCl ₃ ^e

blue

blue

violet

Red

orange

ruby

Bluish red

J 469 772

Continued 20

Dye shade on polyacrylonitrile fibers

0, N

0, N

0, N

NH,

NH-CO-CH ₃

CH,

ZnCl ₃ Q

Bluish red

N = N-C = N-N = C

I I -

N-CH ₃ CH ₃ CH ₃ -N

NO,

CH,

CH ₃

ZnCl ₁ Q

green

N = NC = NN = C N-CH ₃ CH ₃ CH ₃ -N

CH,

CH ₃

NO,

ZnCl ₃ ^e

blue

ZnCl ₃ ⁰

.Blue

ZnCl, ®

Red

N = N

-CH ₃

CH ₃ Cl®

orange

H, N

N-CH ₃

Cl®

orange

21

Γ 469

continuation

22nd

Dye shade on polyacrylonitrile fibers

O NH ₇

CO

CCK

N- (CH ₂ J ₃

-N-CH ₃

O NH, CH, OSO, Q

C ₂ H ₅ O

N,

© IC ₂ H ₅

, CH ₃

^ CH ₃ Cl®

NH,

H, C—

ZnCk®

C, H, O

N® CH ₂ CH ₂ CO-NH ₂

H ₃ C / CH ₃ C

N CH ₃ ZnCl ₃ ®

CH ₃ OOC

[Y C-CH = CH- / Vn- / VoCH ₂ CH ₃ «CH ₃

CH,

O NH ₂ Cl ^e

/ CH ₃

S-CH ₂ -CH ₂ -N-CH ₃ Cl ^e

blue

blue

Scarlet fever

blue

violet

blue

Claims (2)

Patent claims: 1. Formation of the process for dyeing fiber material from polymer! and-copolymer Acrylonitrile according to patent 1,290,914, by treating the material with a thickened, aqueous solution with a pH value below 4.5, in addition to at least one basic dye, polyglycol ether of fatty alcohols or fatty acids with 8 to 14 carbon atoms, the 4 to 12 ethereal acid atoms have, and / or amides of saturated, aliphatic, 8 to 14 carbon atoms Monocarboxylic acids that differ from primary or secondary, at least one lower hydroxyalkyl group containing amines, and soluble salts of saturated, aliphatic, 8 to 14 carbon atoms containing monocarboxylic acids and optionally common in dyeing Contains auxiliary, impregnated at temperatures below the absorption temperature of these dyes and steams the treated goods according to customary methods, characterized in that that here as lipophilic residues, surface-active, hydrophilic to water-soluble Polyglycol ethers, ethylene oxide condensation products, which also contain individual substituted epoxides, such as styrene oxide and / or propylene oxide, may contain built-in, a) of alkylphenols with one or more together at least 8 carbon atoms having alkyl substituents, ' b) of primary or secondary, monobasic or polybasic aliphatic and cycloaliphatic tables, at least one higher alkyl or alkenyl radical of at least 8 carbon atoms containing amines or containing such lipophilic alkyl or aralkyl radicals Alkanolamines and c) of alkanolamides, aminoalkylamides and aminoalkyl esters of higher aliphatic, in particular saturated, carboxylic acids and higher alkylated alkylaryloxycarboxylic acids, or mixtures of two or more of the condensation products mentioned under a) to c) Instead of the polyglycol ethers containing 8 to 14 carbon atoms fatty alcohols or fatty acids are used will. 2. Suitable for dyeing fiber material made of polymer and copolymer acrylonitrile, aqueous, optionally thickened, acidic impregnation liquor, which is characterized in that they are water-soluble as constituents other than water in addition to at least one basic dye Salts of saturated aliphatic carboxylic acids having 8 to 14 carbon atoms and surface-active, hydrophilic to water-soluble polyglycol ethers containing lipophilic residues With the exception of polyglycol ethers, which have 8 to 14 carbon atoms, fatty alcohols and fatty acids with 4 to 12 ether atoms and so much of a water-soluble, organic carboxylic acid contains that the pH of the preparation is 2 to a maximum of 4.5, and optionally also amides -saturated, aliphatic, 8 to 14 carbon atoms having monocarboxylic acids with primary or secondary alkanolamines and / or organic solvents. 009 526/265