DE1469772A1 - Process for dyeing fiber material made of polymeric and copolymeric acrylonitrile - Google Patents

Description

Dr. F. Zumttcin - Mr. E. A ^ monn

Of. R. Kooni-nbero.er
Dipl. Ι hys. R. Holzhauer

Fa sr.tanwclfe 2O9R *

Munich's brewery transformer »4 / H! Addition to ZU 1833 *

Process for dyeing fiber material made of polymer unc

copolymer acrylonitrile Addition to patent .... ... (patent application G 40 816 IVc / 8 m)

In the priority-giving Swiss patent application application No. 7 282/63, a process for dyeing, especially for continuous dyeing, of polymeric and copolymeric acrylonitrile with basic dyes is claimed, which is characterized in that the fiber material is treated with an optionally thickened, aqueous acidic solution basic dye which contains water-soluble salts of saturated, aliphatic monocarboxylic acids having 8 to 14 carbon atoms and may contain other auxiliaries customary in dyeing, especially polyglycol ethers of fatty alcohols or fatty acids with 8 to 14 carbon atoms and 4 to 12 ether oxygen atoms and / or saturated amides , aliphatic, 8 to 14 carbon atoms having · / monocarboxylic acids with primary or secondary alkanolamines at temperatures ¹ , which are below the absorption temperature of these dyes, -impregnated and the impregnated goods

In the further processing of this subject was now found that the advantageous effect of any surface-active polyglycol ethers containing lipophilic residues not on condensation products of ethylene oxide

809813/1210 _{0RIQINAL 1NSPE} cted

is restricted with fatty alcohols and fatty acids with 8 to 14 carbon atoms; it extends when appropriate Selection of the constituents of such dye preparations based on a much broader class of such surface-active polyglycol ethers. Very generally lipophilic radicals, that is to say containing higher aliphatic hydrocarbon radicals, can be used Polyglycol ethers and mixtures of such polyglycol ethers are used whose number of ether groups is chosen so that the compounds ensure hydrophilic properties, i.e. that these polyglycol ethers are at least easily dispersible in water and are preferably soluble therein. It is often advantageous to use mixtures of these substances, with the water-soluble constituents as dispersants for the dispersible ones Components work. In particular, polyglycol ethers containing basic nitrogen can also be used, for example also polyglycol ethers aliphatic, highly alkylated or acylated di- and poly-amines can be used.

Accordingly, the present invention relates to a 'method for dyeing, in particular for the continuous dyeing of fiber material made of polymeric and copolymeric acrylonitrile "-' using a dye preparation according to the main ^: - patent, which consists of aqueous, optionally thickened, 'acidic' ^j - ° solution of basic dye, water-soluble salts gösättiguer ^, 8 to 14 carbon atoms having, aliphatic carboxylic acids and lipophilic residues, surface-active ⁴ , ws hydrophilic to water-soluble ' ^{polyglycol ethers} and' as much * ~ ^{m Ar:}

_{0R (G1NAL | NSpECTED}

a water-soluble organic carboxylic acid is that the pH of the preparation is 2 to at most 4.5, the Polyglycol ethers containing 8 to 14 carbon atoms in fatty alcohols and fatty acids with 4 to 12 ether atoms are excluded, and the other auxiliaries, especially amides of saturated, aliphatic monocarboxylic acids having 8 to 14 carbon atoms with primary or secondary alkanolamines. The goods come with these preparations Temperatures which are below the absorption temperature of the dyes, impregnated and then according to customary methods of Subject to the action of moist heat.

The impregnating liquor which can be used according to the invention contains, for example, alkali metal salts, such as lithium, sodium or potassium salts, ammonium or N-substituted ammonium salts of caprylic, pelargonic, capric, lauric or myristic acid, as salts of suitable saturated aliphatic carboxylic acids having 8 to 14 carbon atoms the acid mixtures summarized under the collective term coconut oil fatty acids. The preferred N-substituted ammonium salts contain, as substituents, in particular lower alkyl groups such as methyl, ethyl or propyl groups, lower hydroxyalkyl groups such as β-hydroxyethyl or γ-hydroxypropyl groups or lower alkoxyalkyl groups such as β-methoxy or β-ethoxyethyl - or the γ-methoxy or γ-ethoxy-propyl group. Here, two N-substituents can also form a ring together with the nitrogen atom, for example the piperidine or morpholine ring.

809813/1210

The alkali, the lower * alkylammonium or lower hydroxyalkyl-ammonium salts, especially the mono- and bis- (ß-hydroxyethyl) -. or bis- (γ-hydroxypropyl) '- ammonium, the N-Methyl-N-Cß-hydroxyäthyD-ammonlum-, N-Methyl-N, N-bis- (β-hydroxyäthyl) -ammonium- or N-methyl-N- (β, γ-hydroxypropyl) ammonium salts of coconut oil fatty acids.

As lipophilic residues which can be used according to the invention, The dye preparation contains surface-active, hydrophilic to water-soluble polyglycol ethers. especially ethylene oxide condensation products, which also contain individual substituted epoxides, such as styrene oxide and /> propylene oxide, may contain built-in,

(A) of alkylphenols having one or more alkyl substituents which together have at least 8 carbon atoms; Cb) of primary or secondary, monobasic or polybasic aliphatic and cycloaliphatic, at least one higher alkyl or alkenyl radical of at least 8 carbon atoms containing amines or of such lipophilic alkyl or alkanolamines containing aralkyl radicals ^ and Cc) of alkanolamides, aminoalkylamides and aminoalkyl esters higher aliphatic, especially saturated, carboxylic acids and higher alkylated alkylaryloxycarbofic acids, or mixtures of two or more of the condensation products mentioned under Ca) to (c).

Prove particularly valuable in the inventive method basic nitrogen containing polyglycol ethers,

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for example polyglycol ethers aliphatic in particular higher alkylated or acylated di- and poly-amines, with one long or several shorter polyglycol ether chains over nitrogen can be bound, such as 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 of lauroyl, myristoyl, oleoyl, palmitoyl, stearoylaminoethyl amine, ethylenediamine, diethylenetriamine and preferably with at least 15 or more ethyleneoxy groups. the The number of ethyleneoxy groups in these polyglycol ethers depends on the type and composition of the lipophilic component of these compounds in total · at least 4, preferably more than 8, to about 100 ethyleneoxy radicals, which in a single or can be arranged in different chains, and their ethyleneoxy groups to reinforce the lipophilic character also occasionally can be alkyl (especially methyl-substituted) or phenyl-substituted. Particularly cheap connections of this type are adducts of 15 to 20 moles of ethylene oxide with one mole of N-monoalkyl-diethylenetriamine, its alkyl radical

has at least 16 carbon atoms, e.g. on stearyl diethylenetriamine, or addition products of 1 to 3 mol of styrene oxide or propylene oxide and of at least 50 mol of ethylene oxide to an N-monoalkyl-diethylenetriamine, the alkyl radical of which has 16 to 18 carbon atoms.

809813/1210

The number of alkyleneoxy groups in these polyglycol ethers should ensure hydrophilic properties and be so large that the compounds are at least easily dispersible in water and preferably soluble therein. Often it is advantageous to use mixtures of these ^r! JfexMnduixgeji.jn.it _n.iedrißeja, .b.is ..höjier..6ji_ contents of ethyleneoxy groups to use, with the higher water-soluble polyglycol ethers act as dispersants for the lower polyether .... Examples of polyglycol ethers containing lipophilic groups which can be used according to the invention are:

Steapyl diethylenetriamine polyglycol ether with 17 ethyleneoxy groups, Adduct of 2 moles of styrene oxide and 50-60 moles of ethylene oxide with 1 mole of stearyl diethylenetriamine, nonylphenol polyglycol ether with 5 ethyleneoxy groups, coconut oil fatty acid di-ß-hydroxyethylamide polyglycal ether with 15-17 ethyleneoxy groups, octylphenoxyacetic acid polyglycol ether with 3-5 ethyleneoxy groups, adduct of 2 moles of 1,2-propylene oxide and 50-60 moles of ethylene oxide on 1st mole of stearyl diethylenetriamine, oleylamine polyglycol ether with 7 ethyleneoxy groups, Stearoyl diethylenetriamine polyglycol ether with 17 ethyleneoxy groups, Oc tylphenol 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 is used in addition to the fatty acid salts and the polyglycol ethers Amides, more saturated, aliphatic, 8 to 14 carbon atoms

809813/1210

containing monocarboxylic acids with primary or secondary. Contains alkanolamines.

The amides which can be used according to the invention are derived, for example, from the higher fatty acids discussed above for the salts and from monohydroxyalkylamines, for example from β-hydroxyethylamine, γ-hydroxypropylamine or β, γ-dihydroxypropylamine, from bis (cj -hydroxyalkyl ) amines, such as Bis (β-hydroxyethyl) -. or bis (Y-hydroxypropyl) amine or bis (a-methyl-ßhydroxyäthyl) amine or N-alkyl-N- (co-hydroxyalkyl) amines, such as N-methyl- or N-ethyl-N- ( ß-hydroxyethyl) - or N-methyl- or N-ethyl-Cy-hydroxypropyD-amine.

The bis (^ - hydroxyalkyl) amides are preferred, especially those whose hydroxyalkyl radicals have two or three carbon atoms contain, such as bis (ß-hydroxyethyl) amides or bis (γ-hydroxypropyl) amides of coconut oil fatty acids.

The quantitative proportion of aids mixture per liter 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 said salts, polyglycol ethers and amides, the mutual weight ratio of the said salts is to the polyglycol ether / amide mixture is less than 3: 1 and is advantageously about 2: 1 to 1: 8.

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The impregnation liquor is responsible for the acidic reaction especially the presence of lower organic carboxylic acids, in particular Acetic acid, but also formic acid and tartaric acid, in amounts of 30 to 300 g and in particular 40 to 60 g per liter ($ 100) of the impregnation liquor to be 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 liquors which can be used according to the invention are recognized as essential for the method according to the invention.

The dye preparation according to the invention contains the common salts and metal halide, for example zinc chloride double salts of the known cationic dyes, in particular the methine or azamethine dyes, the indolinium, pyrazolium, imidazolium. Triazolium, tetrazolium, oxdiazolium, thiodiazolium, oxazolium, Contain thiazolium, pyridinium, pyrimidinium, pyrazinium rinr. The heterocycles mentioned can optionally 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 color salts of the arylazo and anthraquinone series with external onium group.

As thickeners that are compatible in acidic baths, for example, the common open rubber types in the textile industry, e.g. so-called "crystal rubber", or thickener based on cellulose, such as locust bean gum, tragacanth, British gum, poly

809813/1210

saccharides or cellulose derivatives, such as methyl cellulose or soluble salts of carboxymethyl cellulose. Preferred are thickeners made from locust bean gum, as well as galactomannans.

The impregnation liquor can be used as further auxiliaries customary in dyeing, for example organic solvents, in particular Ethylene glycol monoethyl ether or thiol diethylene glycol as well as ethylene carbonate or propylene carbonate.

As inventive dyeable fiber materials made of polymer or copolymeric acrylonitrile, in particular, those which make up the predominant proportion, preferably at $ 80-100, are suitable consist of polymeric acrylonitrile and contain acidic copolymers, in particular sulfonic acid and / or carboxylic acid groups.

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

The fiber material is impregnated, for example, by printing, coating or spraying, but preferably by foulard!

The impregnation liquor according to the invention is expediently provided by the fact that the basic dye with the amount of acid used, in particular acetic acid, is preferably 60-80 # acetic acid, dough, pour hot water over it, with thickener ·! and finally with the salts and polyglycol ethers and, if necessary, others in the dye works usual tools.

809813/1210

- ίο -

The Polyacrylnitrilfasermaterial is impregnated and advantageously at 30 to 40 ⁰ C afterwards on the desired content of the impregnating liquor squeezed vm about 60 to 140 $ of the fiber weight.

The impregnated fiber material is steamed according to the usual methods with saturated, advantageously with neutral, slightly superheated steam.

The dyed and steamed goods are appropriately rinsed, advantageously with cold or warm water, the additives customary in dyeing, for example formic acid or acetic acid or can also contain antistatic substances or lubricants.

With the method according to the invention, in particular when continuously dyeing fiber material made of polymeric and copolymeric acrylonitrile, very deep shades without a gray haze achieved, which are characterized by an excellent uniformity of coloring. Especially with the preferred Continuous dyeing with a mixture of different basic dyes does not result in selectively colored fiber sites obtain. Furthermore, the impregnating liquors which can be used according to the invention are easy to produce, stable, i.e. practical Unlimited shelf life, and, since the action of salts and acids does not affect their stability, for the continuous Dyeing process ideally suited.

8098 13/1210

The following examples are provided for illustrative purposes the invention. The temperatures are given in degrees Celsius. The parts are, unless otherwise expressly is noted, parts by weight. Parts by weight are related to parts by volume as grams are to cm.

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I ■.: '■

example 1

20 g of dye of the formula

ClV

are placed in 150 g of θObiger acetic acid in the cold and dissolved with 600 ml of hot water. This solution is 4 g MEYPROGUM KN (Meyhall, Kreuzungen, Switzerland), which are made into a paste with 20 ml of ethanol and mixed with cold water, added with stirring. This is followed by 30 g of a mixture of 1 part of coconut oil fatty acid di-ß-hydroxyethylamine salt and 1 part of an adduct of 2 moles of styrene oxide and 50-60 moles of ethylene oxide with 1 mole of st§aryl-diethylenetriamine " to and fills the whole thing up to 1000 mil with water and brings the finished impregnation liquor to 30 to 40 ° * The pH value of this liquor is around 3-4. · _. '

This liquor is used to impregnate plush made of polyacrylonitrile, squeeze the material to a liquor content of 100% and steam it for 20 minutes over heated " fPampf ~ beT ~ lÖ3 'to ~ ίÖT ° ~. """"""~~ ■: ';

The dyed goods are then washed with water at 45 ° rinsed several times, then with a solution containing 4g Contains 1 liter of an antistatic and 2 g to 1 liter of a malting agent, treated and dried.

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An excellent uniformly yellow colored material is obtained.

Used, one of the mixture given above

one

Coconut oil fatty acid di-ß-hydrojcyäthylamine salt and / adduct of styrene oxide and ethylene oxide with stearyl diethylenetriamine in a mutual weight ratio of 1: 3 instead of ItI and the rest of the procedure, as noted in the example, similar results are obtained. .

• -, Similar results are obtained using from 00 to 50 g of acetic acid, formic acid or tartaric acid instead of 150 g of 80 g acetic acid, otherwise the same Operation as indicated in the example.

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Example 2

20 g of the dye used in Example 1 become made into a paste in 150 g of 80% acetic acid in the cold and dissolved with 600 ml of hot water. This solution will be 4 g of Solvitose OFA (W.A. Schelten, Foxhal, Holland), the made into a paste with 20 ml of ethanol and mixed with cold water, added with stirring. 30 g are placed on top a mixture of 1 part coconut oil fatty acid di-ß-hydroxyethylamine salt, 1 Part of an investment product from. 2 moles of styrene oxide and 50 to 60 moles of ethylene oxide in 1 mole of stearyl diethylenetriamine and 1 part of coconut oil fatty acid di-ß-hydroxyethylamide, fill the whole thing up to 1000 ml with water and brings the finished impregnation liquor to 30 to 40 °.

The pH of this liquor is around 3 to 4.

With this liquor, Jnan impregnates tow

made of polyacrylonitrile and treats the material further, as indicated in Example 1.

An excellent, uniformly yellow color is obtained

Material.

Similar results are obtained using '

30 g of a mixture of 1 part of the above Salt, 2 parts of the above stearyl diethylenetriamine polyglycol ether and 1 part of coconut oil fatty acid di-ß-hydroxyethylamide otherwise the same / working method.

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

CH ₂ CH ₂ OH

3—

ZnCL

3.5g "dye of the formula

CH ₃ O

CH-

^ C - N = N - N - // V-NO,

CH.

Cl

and 3.0 g of dye of the formula

HC N-CH.

N = N

ZnCl.

CH ₃

.and proceeds as indicated in the example, so receives you get excellent evenly navy blue colored fibers,

809813/1210

Example 3

20 g of dye of the formula
G)

- CH.

N = N

■ ZnCl.

• j

are made into a paste in 60 g of 80% acetic acid in the cold and dissolved with 600 ml of hot water. 4 g of MEYPROGUM KN, which are made into a paste with 20 ml of ethanol and mixed with cold water, are added to this solution while stirring. Then it sets 3'0'-g a "mixture of 1 part N-methyl-N- (ß-hydroxyethyl) ammonium salt of Cocosölfettsäure, 1 part stearyl 'diäthylentriaininpolyglykoläther 17 ethyleneoxy

·· "-.- · and 1 part coconut oleic acid-di-ß-

add hydroxyethylamide, make the whole thing up to 1000 ml with water and brings the finished impregnation liquor to 30-40 °. The pH of this liquor is around 3-4.

This liquor is used to impregnate tow, or Combed top made of polyacrylonitrile and treated the material further as indicated in Example 1. ·

Excellent g-light red colored products are obtained

Material.

809813/1210

ORIGINAL INSPECTED

Similar results are obtained if the mixture of fatty acid amine salt and polyglycol ether mentioned in the example is used and fatty acid amide replaced by equal amounts of one of the following auxiliary mixtures:

1 part bis (ß-hydroxyethyl) ammonium salt of coconut

oil fatty acids

Part of stearyl diethylenetriamine polyglycol ether with

17 ethyleneoxy groups,

1 part sodium or potassium salt of coconut oil fat

acids

Parts adduct νο "ή '2 moles of styrene oxide and

50-60 mol of ethylene oxide in 1 mol of stearyl diethylenetriamine

1 part of N-methyl-N- (ß-hydroxyethyl) ammonium salt of

Lauric acid

Part of nonylphenol polyglycol ether with 5 ethyleneoxy

groups

7 1 part tris (ß-hydroxyethyl) ammonium salt of coconut oil fatty acids

Parts of stearyl diethylenetriamine polyglycol ether

with 17 ethyleneoxy groups

1 part bis (ß-hydroxyethyl) ammonium salt of coconut

oil fatty acids

Part of coconut oil fatty acid di-ß-hydroxyethylamide polyglycol ether with 15-17 ethyleneoxy groups

1 part dimethylammonium salt of coconut oil fatty acids Part Oetylphenoxyessigsäurepolyglykoläther with

3-5 ethyleneoxy groups

1 part morpholinium salt of coconut oil fatty acids Part adduct of 2 moles of 1,2-propylene oxide and 50-60 mol of ethylene oxide on 1 mol of stearyl diethylenetriamine

1 part bis (ß-hydroxyethyl) ammonium salt of lauric acid
Part of the addition product of 2 moles of styrene oxide and

50-60 mol of ethylene oxide in 1 mol of stearyl diethylenetriamine

1st part bis (β-hydroxyethyl) ammonium salt of coconut oil fatty acid
Part of the addition product of 2 moles of styrene oxide and

50-60 mol of ethylene oxide in 1 mol of stearyl diethylenetriamine

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1 part of N-methyl-N- (ß-hydroxyethyl) ammonium salt of coconut oil fatty acids

1 part oleylamine polyglycol ether with 7 ethyleneoxy groups

1 part of N-methyl-N - ({3-hydroxyethyl) ammonium salt of Coconut oil fatty acids'

1 part adduct of 1 mol of styrene oxide and 50-60 mol of ethylene oxide, 1 mol of stearyl diethylenetriamine

1 part bis (ß-hydroxyethyl) ammonium salt of laurine.

acid. . "

1 part coconut oil fatty acid ß-aminoethyl ester polyglycol ether with 3 ethyleneoxy groups

1 part bis-Cß-hydroxyethyl) ammonium salt of pelargon

acid
1 part stearyl diethylenetriamine polyglycol ether with 17 ethyleneoxy groups

. 1 part ethyl ammonium salt of coconut oil fatty acids 1 part of the adduct of 2 moles of styrene oxide and 50-60 Mol Aethylenoxydεη 1 mol stearyl diethylenetriamine

1 part sodium or potassium salt of coconut oil fatty acids 1 part octylphenol polyglycol ether with 4 ethyleneoxy groups

1 part N-methyl-N, N-bis (ß-hydroxyethyl) ammonium salt

of lauric or myristic acid 3 parts adduct of 2 moles of styrene oxide and 50-60

Mole of ethylene oxide to 1 mole of stearyl diethylenetriamine 1 part of lauric acid or myristic acid-N, N-bis- (ß-

hydroxyethyl) amide

1 part N-methyl-N, N-bis- (ß, γ-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 (ß-hydroxyethyl) amide

1 part sodium or potassium salt of coconut oil fatty acids 1 part adduct of 2 moles of styrene oxide and 50-60

Mole of ethylene oxide in 1 mole of stearyl diethylenetriamine 1 part of lauric or myristic acid-N, N-bis- (ß-hydroxyethyl) -amid

Parts bis (ß-hydroxyethyl) ammonium salt of lauric acid parts stearyl diethylenetriamine polyglycol ether with 11 ethyleneoxy groups
Parts of coconut oil fatty acid N, N-bis (ß-hydroxyethyl) amide

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Example 23 dye the formula CH ₂ -CH ₂ OH
■ N
CH ₃ 20 g .. ti N = CH ₃ O,

ZnCl,

are made into a paste in 100 g of 80% acetic acid in the cold and dissolved with 600 ml of hot water. This solution is 4 g of MEYPROGUM KN, which are made into a paste with 20 ml of ethanol and with cold water are mixed, added with stirring. This is followed by 3.0 g of a mixture of 3 parts Addition product of 2 moles of styrene oxide and 50 to 60 moles of ethylene oxide with 1 mole of stearyl diethylenetriamine and 1 part coconut oil fatty acid di-ß-hydroxyethylamine salt added, 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.

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

An excellent, uniformly blue colored material is obtained.

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If one uses one of the dyestuffs given in the table below instead of the dyestuff given in the example Dyes and if the rest of the procedure is as indicated in the example, one also obtains excellent uniformity Dyed goods in the shades given in column 3 of the table.

TABEL

dye

Color on polyacrylonitrile fibers

OH

N-N

H ₂ N. "NH ₂ OH

H ₃ O

nV AX

H ₂ U ^a NH ₂

C-N-N-N

-C- , Ji -

CH ₃

CBL

CH ⁵ - CH -

HCl

HCl

3> - NO,

Cl

OCH ₃

right"

yellow

do

Cl

yellow

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ORIGINAL INSRECTE *

Dye shade on polyacrylonitrile fibers

DL · ⁰ - ■ - H - H - <£> - NO, .Cl

CH ₅
?

C - CH - CH - KH -f *

H ₅ C

Il

H ₅

CH «CH
, C

H.

CH- - N »C -Ο" Ν - <

^ 1 I I

CH ₅ , ·>

IH ₅ - N »C -ζ ^> - Ν -ζ ^ - OC ₂ H ₅

red-tinged yellow

yellow

reddish yellow

reddish orange

orange

violet

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Dye shade on polyacrylonitrile fibers

NH (C ₂ H ₅ )

CH, COOC ₀ H

CH ₂ CH ₂ Cl

- oh - oh Cl

HC-NC IJ Il

NC - N V © CH ₃

0 NH.

N -CJ ZnCl.

_> - 0CH "red

Red

bluish red

blue

CH ₃ SO ₄

- CH - CH - € => - N

CH ₃

H.

Cl

red-violet

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Dye hue on

Polyacrylic

nitrile fibers

I 2

Cl

Cl

C - <^> - NHO ₂ H ₅

he

(C ₂ H ₅ )

Cl

Θ;

CH ₃

^CH 3 ZnCl,

CH ₃ O

"Υ®

OH ₃

greenish blue

do

do

reddish blue

ZnCl

blue

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Dye shade on polyacrylonitrile fibers

HSO,

CH, ³

CH ₃ ZnCl,

ZnCl.

CH,

^{: H} 3

ZnCl.

<κν

CH. ZnCl,

S ₁ J ^ N = N - <£ => _A , ^ ₂ green

blue

blue

violet

Red

orange

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Dye shade on polyacrylonitrile fibers

/ CH ₃ H

H,

CH,

ZnCl,

O ₂ N

N - <_> - NH.

■ ^CH 3 CH ₃ . ^

NH-CO-CH,

' ^W 2

N = N - <C3-NH

OH,

CH.

NH-CO-CEL

ZnCl.

N = N-C-N-N

EL ⁵

H- ⁵ ■ NO,

rub in

bluish red

ZnCl.

O ₁

N = N-C = N-N = C

H ₃

H-

^{! H} 3

OH, ZnOl;

N- Z-y- N

ZnCl

do

green

blue

blue

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dye

Color shade on polyacrylic fibers

H ₃

ZnCl,

^{! H} 3

he

CH.

H ₉ NI " CH,

* N CH,

ti S

Cl

Γ Ο NH,

he

CH,

O NH

-N = N - ^ V N

O ₂ H ₅

Red

orange

do

blue

blue

80 9 8 13/1210

r .27.-

Dye shade on polyacrylonitrile fibers

N = N

^H 3

Scarlet fever

O ₂ H ₅ O

CH ₂ CH ₂ C (HSTIL ZnCl

.G

"blue

CH, OOC C Il

C-CH = CI

^3Η 3 Cl °

3 - CH ₂ -

H ₂

CH ₂ - N - CH ₃

NH violet

egg ©

blue

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Claims (1)

Claims 1. A method for dyeing fiber material made of polymeric and copolymeric acrylonitrile, characterized in that one the material with an aqueous, optionally thickened, acidic solution of basic dye, the water-soluble salts more saturated, 8 to 14 carbon atoms, more aliphatic Carboxylic acids and lipophilic residues, surface-active, hydrophilic to water-soluble polyglycol ethers and contains as much of a water-soluble organic carboxylic acid as that the pH of the preparation is 2 to at most 4.5, the polyglycol ethers having 8 to 14 carbon atoms Fatty alcohols and fatty acids with 4 to 12 ether atoms are excluded, and the other auxiliaries, especially amides saturated, aliphatic monocarboxylic acids containing 8 to 14 carbon atoms with primary or secondary alkanolamines may contain, at temperatures below the absorption temperature of these dyes, impregnated and the treated goods are subjected to the action of moist heat using customary methods. 2. The method according to claim 1, characterized in that the lipophilic radicals having surface-active, hydrophilic to water-soluble polyglycol ethers containing basic nitrogen polyglycol ethers aliphatic, higher alkylated or acylated di- and poly-amines are used. 809813/1210 3. Process according to Claims 1 and 2, characterized in that amides of saturated, aliphatic, Monocarboxylic acids having 8 to 14 carbon atoms used with primary or secondary alkanolamines. 4. Process according to Claims 1 to 3, characterized in that the water-soluble organic acid used is acetic acid, Formic acid or tartaric acid is used. 5. For dyeing fiber material made of polymer and copolymer em acrylonitrile by impregnating the same at temperatures below the absorption temperature of the basic dyes, and subjecting the treated goods to the action of moist heat according to customary methods, suitable, aqueous, if necessary thickened, acidic impregnation liquor, which is characterized in that it is in addition to at least one basic dye water soluble. Salts of saturated, 8 to 14 carbon atoms containing, aliphatic carboxylic acids and lipophilic residues containing, surface-active, hydrophilic to water-soluble Polyglycol ether and enough water-soluble, organic carboxylic acid that the pH of the preparation 2 to at most 4.5, the polyglycol ethers having fatty alcohols and fatty acids containing 8 to carbon atoms 4 to 12 ether atoms are excluded, and the other auxiliaries, especially amides of saturated, aliphatic, 8 to 14 May contain carbon atoms having monocarboxylic acids with primary or secondary alkanolamines. 809813/1210 6. According to claims 1 to 4 using the Impregnation liquor according to claim 5 colored fiber material made of polymer! and copolymer acrylonitrile. 11/22/65
Ju / sh 8098 13/12 10