DE1469771A1 - Process for dyeing fiber material made of polymeric and copolymeric acrylonitrile - Google Patents

Description

Dr. F. Zurnsfein - Dr. E Assmann '469771

Dr. R. Koenigsberger Dipl. Fhys. R. Holzbauer

Paint attorney. 2097 *

Munich 2, Bräuhausstraffe 4 / lli

Dt- T ⁷ Tri-

Process for dyeing fiber material made of polymer! and · copolymeric acrylonitrile

In the priority-giving Swiss patent application application No. 7282/63, 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, the soluble salts of saturated, aliphatic, 8 to 14 carbon atoms containing monocarboxylic acids and polyglycol ethers of fatty alcohols and fatty acids with 8 to 14 carbon atoms and 4 to 12 ether oxygen atoms and / or alkanolamides 8 to 14 carbon atoms containing fatty acids, at temperatures are below the absorption temperature of the dyestuffs, impregnated and the treated goods steamed, f I During further processing of this object, it has now been found that the pH value to be set with a water-soluble strong organic carboxylic acid is recognized as essential t from 2.5 to 4.5 of the impregnation liquor

soluble salts of saturated fatty acids as a component of this j liquor can then be dispensed with if the impregnation liquor

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in amounts of $ 1 to $ 10, especially $ 2 to $ 5, based on the total weight of the preparation, hydrophilic to water-soluble, surface-active aliphatic hydrocarbon radicals of a total of at least 8 carbon atoms containing polyglycol ethers of organic hydroxyl, carboxyl, amino or Contains amido compounds.

Accordingly, the present invention relates to a method for dyeing, especially for continuous dyeing, of fiber material made of polymeric and copolymeric acrylonitrile, which is characterized in that the material is made more basic with an optionally thickened aqueous acidic solution Dyes in content = :! from 1 to 10 and preferably 2 to 5 percent by weight of the preparation hydrophilic to water-soluble, surface-active aliphatic solver water residues of a total of at least 8 carbon atoms and at least Polyglycol ethers containing ether groups of organic hydroxyl, carboxyl, amino or amido compounds or mixtures thereof Contains substances, and those with a water-soluble, strong organic carboxylic acid to a pH value of at most 4.5 is set, and the other aids, especially alkanolamides and alkanolaminoalkyl esters of fatty acids having 8 to 14 carbon atoms, at temperatures below the absorption temperature of the dyes, impregnated and the treated goods by customary methods of action subject to moist heat.

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146977t

The polymeric and copolymeric acrylonitrile which can be dyed according to the invention contains at least 80 # acrylonitrile; it can be used in the form of fibers of the most varied of textile processing stages, for example as sliver, yarn, woven, knitted or piece goods such as plush.

As basic dyes, the dye preparation according to the invention contains the customary salts and metal halides, for example zinc chloride double salts, the known cationic dyes, in particular the methine or azamethine dyes, which include the indolinium, pyrazolium, imidazolium, triazolium, tetrazolium , Oxdiazolium, thiodiazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium ring. The heterocycles mentioned can optionally be substituted and / or condensed with aromatic rings . Furthermore, cationic aromatic substances of the diphenyl methane, triphenyl methane, oxazine and thiazine series are also possible, as well as color salts of the arylazo and anthraquinone series with an external onium group.

As hydrophilic to water-soluble, surface-active polyglycol ethers, the dye preparation contains polyglycol ethers, especially ethylene oxide condensation products, which can also contain individual substituted epoxides, such as styrene oxide and propylene oxide, incorporated,

(A) of preferably saturated fatty alcohols, ie alkanols and alkenols having 8 to 20 carbon atoms;

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_ 4 - ■

(b) of preferably saturated fatty acids having 8 to 20 carbon atoms;

(c) of alkylphenols with one or more together at least 8-carbon alkyl substituents j

(d) 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 and aralkyl radicals containing alkanolamines, and

(e) of alkanolamides, aminoalkylamides and aminoalkyl esters higher aliphatic, especially saturated carboxylic acids and higher alkylated alkylaryloxycarboxylic acids,

or mixtures of two or more of the condensation products mentioned under (a) to (e).

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 in it. Depending on the type and composition of the lipophilic constituent of these compounds, the number of alkyleneoxy groups can be 4 and preferably 8 to about 100. It is often advantageous to use mixtures of these substances with low to higher contents of ethyleneoxy groups, the higher water-soluble polyglycol ethers acting as dispersants for the lower polyglycol ethers.

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

ORIQtNAL INSPECTED

809813/1209

tables, especially higher alkylated or acylated di- and polyamines, such as the polyglycol ethers of N-monoalkyl or N-monoalkenyl-mono- or -di- or -tri- or -tetraniederalkylen-di-, or -tri- or -tetra- or -pentamines with at least 16 carbon atoms in the alkyl or alkenyl radical and with at least 15 and preferably more than 25 to about 100 ethyleneoxy radicals, of which isolated C-methylated and / or Can be C-phenyl-substituted. Particularly favorable connections of this type are addition products of 15 to 20 mol of ethylene oxide with an N-monoalkyl-diethylenetriamine, whose Alkyl radical has at least 16 carbon atoms, e.g. Stearyl diethylene triamine, or addition products of 1 to 3 mol of styrene oxide or propylene oxide and of at least 50 mol Ethylene oxide to an N-monoalkyl-diethylenetriamine, its Alkyl has 16 to 18 carbon atoms.

Another valuable group of polyglycol ethers according to the definition are those of alkanols, alkenols and alkylphenols which contain hydrophobic hydrocarbon radicals of at least 8 carbon atoms and at least 5 ethyleneoxy radicals. Particularly favorable such compounds are addition products of 4 to 20 mol of ethylene oxide with an alkanol with 8 to 18 carbon atoms, such as hexadecanol or with a fatty alcohol mixture known under the collective term "Gocosöl fatty alcohol" or an alkylphenol which contains alkyl radicals with a total of at least 8 carbon atoms , for example on octylphenol or nonylphenol or di-tert-butylphenol.

ORIGINAL INSPECTED

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1 * 69771

Other polyglycol ethers according to the definition are, for example called: acylaminoalkyl mono- or polyamines, the hydrophobic hydrocarbon radicals of at least 8 carbon atoms and at least 10 ethyleneoxy radicals, preferably more than 25, of which isolated C-alkyl or C-aryl-substituted may be included. Examples of such compounds are addition products of at least 10 moles of ethylene oxide Lauroyl-, myristoyl-, oleoyl-, palmitoyl- or stearoyl-aminoethylamine, ethylenediamine or diethylenetriamine.

The quantitative proportion of defined hydrophilic, Surface-active compounds per liter of dye liquor is, for example, 15 to 100 g and preferably 20 to 40 g.

As further auxiliaries in the dye liquor according to the invention Usable alkanolamides and alkanolaminoalkyl esters are derived from a fatty acid having 8 to 14 carbon atoms from, for example, from caprylic, pelargonic, capric, lauric or myristic acid and in particular from that under the collective term "Coconut oil fatty acids" combined acid mixture and of monohydroxyalkylamines, e.g. of ß-hydroxyethylamine, γ-hydroxypropylamine or β, γ-dihydroxyprc'pylamine, of bis (cj hydroxyalkyl) amines, such as bis (ß-hydroxyethyl) - or bis (γ-hydroxypropyD-amine or bis (a-methyl-ß-hydroxyethyl) amine, or N-alkyl-N - («3 -hydroxyalkyl) amines, such as N-methyl or N-ethyl-M- (ß-hydroxyethyl) - or N-methyl- or N-ethyl- (yhydroxypropyl) amine. The bis (ω-hydroxyalkyl) - · amides, especially those whose hydroxyalkyl radicals are 2 or 3

ORIGINAL INSPECTED

809813/1209

Contain carbon atoms, such as bis (ß-hydroxyethyl) amides or Bis-Cy-hydroxypropyD-amide of coconut oil fatty acids.

The impregnation liquor owes the acidic reaction above all to the presence of lower organic carboxylic acids, in particular Acetic acid, but also formic acid or tartaric acid, in amounts of 30 to 300 g and in particular 40 to 60 g per Liter (100 #) of the impregnation liquor are added to pH values of the liquor below 4.5, preferably between 2.5 and 4.0 to ensure. These high acid contents of the impregnation liquor are essential for the process according to the invention recognized.

As a thickener that is compatible in an acid bath, for example, common open rubber types are used in the textile industry, e.g. so-called "crystal gum", or cellulose-based thickeners such as locust bean gum, tragacanth, British Gums, polysaccharides or cellulose derivatives such as methyl cellulose or soluble salts of carboxymethyl cellulose to name. Thickeners made from locust bean gum and galactomannan are preferred.

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

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

809813/1209

The impregnation liquor according to the invention is expediently provided in that the basic dye is preferably mixed with the amount of acid used, in particular acetic acid with 60-80 $ acetic acid, made into a paste, poured with hot water and with thickeners and finally with the polyglycol ether according to the definition and other auxiliaries customary in dyeing. ■

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 or sliver.

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

The impregnated fiber material is steamed according to conventional methods, advantageously with neutral, slightly overheated Steam.

The dyed and steamed goods are expediently rinsed, preferably with cold or warm water that is used in the dyeing works Usual additives, for example formic acid or acetic acid and also antistatic substances or lubricants may contain.

With the process according to the invention, particularly in the continuous dyeing of fiber material made of polymeric and copolymeric acrylonitrile, very deep shades of color are obtained without a gray haze

809813/1209

achieved, which are characterized by an excellent uniformity of coloration. Especially with the preferred continuous Dyeing with a mixture of different basic dyes does not result in selectively colored fiber sites. Furthermore, the impregnation liquors according to the invention are easy to manufacture, stable, i.e. can be kept practically indefinitely, and, since the action of salts and acids does not affect their stability, for continuous dyeing best for.

Particularly surprising is the fact that e.g. polyglycol ethers, which are obtained by condensation of compounds of the aforementioned type (e) with ethylene oxide and which is known to be used as a retarding agent in the exhaust dyeing process for polyamide, such as wool, now in the continuous Dyeing acrylic fiber material act as a dyeing aid, as they contribute to a fixation of the dye on the fiber in optimal yields in a short time To achieve steaming, especially with slightly superheated steam.

The following examples serve to illustrate the invention. The temperatures are given in degrees Celsius. Unless expressly stated otherwise, the parts are parts by weight. Parts by weight are related to Divide by volume like grams to cm. CI. means COLOR INDEX, • Second Edition, 1956, published by The Society of Dyers and Colourists, Bradford, England, and The American Association of Textile Chemists and Colorists, Lowell, Mass., USA, as well as the supplements published so far.

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example 1

A mixture consisting of. 10 g, of the dye of the formula CH.

CH ₃

5 g of the dye of the formula HC-N-CH

Cl

N = N - // V ^N ( ^c o ^H J

CH

ZnCl.

and 8 g of the dye of the formula

C-N =

CH ₂ CH ₂ OH

ZnCl.

Vffd "made into a paste in 60 ml of 80 # acetic acid in the cold and dissolved with 600 ml of hot water. This solution is 4 g of MEYPROGUMKN (from Meyhall Chemical., Kreuzungen, Switzerland), the made into a paste with 20 ml of ethanol and mixed with cold water, added with stirring. This is followed by 30 g of stearyl diethylenetriamine polyglycol ether, containing about 17 ethyleneoxy groups, make up the whole 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, tow made of polyacrylonitrile is impregnated and the fibers are squeezed to a liquor content of

ORIGINAL INSPECTED.

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10056 and steams it for 20 minutes with slightly superheaters Steam at 102-104 ° under slight excess pressure. Then the dyed goods are rinsed several times with 45 ° warm water, then with an aqueous solution containing 4 g per liter of an antistatic and 2 g per liter of a lubricant contains, treated and dried.

Excellent, uniformly deep red-brown colored fibers are obtained.

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1489771

Example 2

20 g of the dye of the formula

HC - N ^ CH-

N = N

ZnCl.

N C

7th
CH ₃

are made into a paste in 60 ml of 80 # acetic acid in the cold and dissolved with 600 ml of hot water. This solution will be

10 g Solvitose OFA (W.A. Schölten, Foxhol / HoHand) with 20 ml of ethanol are made into a paste and mixed with cold water, added with stirring. This is followed by 30 g of nonylphenol polyglycol ethers, containing 15 ethyleneoxy groups, make up the whole to 1000 ml with water and bring the finished impregnation liquor to 30 to 40 °. The pH of this liquor is around 3-4.

This liquor is used to treat cabin pulls made of polyacrylonitrile, as indicated in example 1.

This gives very uniformly red colored fibers.

Similar results are obtained when using appropriate amounts of formic acid or tartaric acid instead of acetic acid.

. If, instead of the nonylphenol polyglycol ether mentioned, octadecanol polyglycol ether with 3 to 5 ethyleneoxy groups is used, the same red-colored fibers are obtained with otherwise the same procedure, as indicated.

809813/1209

ORIGINAL INSPECTED

20 g of the dye of the formula

egg

are made into a paste in 150 ml of 80 # acetic acid in the cold and dissolved with 600 ml of hot water. This solution is 4 g of MEYPROGUM KN, which is made into a paste with 20 ml of ethanol and cold Water, mixed, added with stirring. 30 g of an adduct of 2 moles of styrene oxide and approx. 50-60 mol of ethylene oxide of stearyl diethylenetriamine are added and the procedure is continued as indicated in Example 1, using of polyacrylonitrile plush instead of tow.

Uniformly yellow colored plush is obtained.

If the dye is used instead of the dye mentioned the formula

HSO.

N (C ₂ H ₅ ) ₂

If you otherwise proceed as indicated in the example, you will get plush that is evenly colored in green.

t is used instead of said addition product, equal amounts of a mixture of 1 part by weight of this addition product and 1 part by weight Cocosölfettsäure-di-ß-hydroxyäthylamid or 1 part by weight of said addition product and 1 part by weight of 'the addition product of 10 mol of ethylene oxide with Cocosölfettsäure-ß-aminoäthylester, so one obtains similar results with otherwise the same procedure as indicated.

8 0 9 8 13/1209

Example 4

20 g of the "dye of the" formula-.

CH ₂ CH ₂ OH

C-N = N

ZnCl.

are made into a paste in 100 ml of 80 # acetic acid in the cold and dissolved with 600 ml of hot water. 10 g of Solvitose OFA (W.A. Schölten, Foxhol / Holland), containing "20 ml Ethanol can be made into a paste and mixed with cold water, added with stirring. 15 g of stearyl diethylenetriamine polyglyco are then added Lather containing about 17 ethyl enoxy groups added and 15 g Coconut fatty acid-N, N-bis- (ß-hydroxyethyl) -amide, fills up the whole thing 1000 ml with water and apply the finished impregnation liquor 30 ° to 40 °. The pH of this liquor is about 3 to

This liquor is used to impregnate a sliver made of polyacrylonitrile and treated the impregnated material as indicated in Example 1. . <

Excellent uniformly colored blue ones are obtained

Top draw.

If the procedure is otherwise the same, it is used as the color carrier instead of the 30 g of the mixture mentioned in the example the same amounts of the products or mixtures given in the table below result in colorations of similar properties.

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ORIGINAL INSPECTED

Table I.

Color carriers or mixtures of color carriers

Dodecyl alcohol pentaglycol ether Decyl alcohol hexaglycol ether Tetradecyl alcohol hexaglycol ether Dodecyl alcohol decaglycol ether tetradecyl alcohol heptaglycol ether Coconut oil fatty acid pentaglycol ether 1 part coconut oil fatty alcohol pentaglycol ether 1 part coconut oil fatty acid N, N-bis (ß-hydroxyethyl) amide 1 part tetradecyl alcohol decaglycol ether 1 part lauric or myristic acid-N, N-bis (ß-hydroxyethyl) amide 1 part dodecyl alcohol pentaglycol ether 1 part coconut oil fatty acid N, N-bis (ß-hydroxyethyl) amide.

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14Θ977Ϊ

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.

TABLE II

dye

Color on polyacrylonitrile fibers

OH

N-N

HCl

yellow

CH, 0

! Η,

OH,

, N NH ₂ OH

NH ₂

0 - H - H - H

HCl

yellow

^0H 3

Cl

© I

OCH ₃
CH - NH - Cl> - OCH ₃

CH ₃

01

yellow

809813/1209

ORIGINAL INSPECTED

Dye shade on polyacrylonitrile fibers

ΟΗ, Ο.

tJ!

3H ₃

CH ₃

If - CH ₃

C - CH - CH - «Η

r ©

CH ₃

- NH ₃ C Cl

-C

reddish yellow

yellow

Cl

-CH- CH- / 7 "

Cl

-CH-CH-

CH ₃

H ₃ C

-N-C -O

N CH ₃ OC ₂ H ₅

reddish yellow

reddish orange

orange

violet

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Color on polyacrylic nitrile fibers

Λ- COOC ₅ H

2 "5

Cl

CH ₂ CE ₂ Cl

-CH-CH - <ZJ> - N

CE,

3H ₃

HC-N Ii Ii NC

N (+

-N-N - <C

CH ₃

0 NH,

0 "NH -" ^ J

- CH. - _Λ

m ₂

CH ₃

^ X- ^ C - CH - CH - <tU> - N

OH, Cl

Red

Red

bluish red

blue

red-violet

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Dye hue on

Polyacrylic

nitrile fibers

.0O ₂ H ₅

(C ₂ H ₅ )

Cl

C => - 0 -Ο "TOO ₂ H ₅

'NHC ₂ H ₅

he

(C ₂ H ₅ ),

Cl

- H - I -O- H -Gi

^3H 3 ZnCl.

H-H -C2

H,

greenish blue

do

ZnCl

do

reddish blue.

blue

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146977 *

Color on * polyacrylonitrile fibers

HSO.

CH,

ZnCl.

ZnCl,

! Η,

ZnCl,

N-N - <O

O> -NH ₂

CH.

ZnOl,

n-n - <S.

nh ₂

! Η,

Zn ( green

blue

blue

808813/1209

ORlQINAL INSPECTED

Dye hue on

Polyacrylic

nitrile fibers

CH, -ι

N- N - <Π> - Ν

! Η,

rub in

N - ^ 3- NH,

NH-CO-CH ₃ ZnCl,

bluish red

₂
²

N-N -CZ> - NH,

OH ₃

CH,

NH-CO-C ZnCl

—R? CN »IhC» NN- 9 (] Γ ^Ν0 2

! H ₃

- NNC = NN - C N Θ Λ _ττ N

/ N _n - CH,,

CH ₃

NN - <ζ ₌ > - N

ZnOl,

r / N

OH,

ZnCl,

do

green

blue

blue

809813/1209 originally inspected

Dye shade on polyacrylonitrile fibers

H ₅

ZnCl,

S ^ - N = N

H ₂ N

^JH 3

N CH,

Il 3

Cl

O N.

0 NH

OK. OSO.

C _o H _K 0 ²

Red

orange

do

blue

blue

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Dye hue on

Polyacrylic

nitrile fibers

38

N »N

L ^CH 3 CH ₃

ZnCl,

Scarlet fever

η -ο

CH ₂ ZnCi:

blue

CH ₃ OOC

OH * CH,

Cl

.? ft

S -

CH ₂

CH ₂ - H - CH ₃

0 NH Gl ^v

violet

blue

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Claims (8)

14697 ¹ Claims
\ 1 ·) Process for dyeing fiber material made of polymeric and copolymeric acrylonitrile, characterized in that the material is treated with an optionally thickened aqueous acidic solution of basic dyes containing from 1 to 10% of the preparation hydrophilic to water-soluble, surface-active aliphatic hydrocarbon residues of contains a total of at least 8 carbon atoms and at least 4 ether groups containing polyglycol ethers of organic hydroxyl, carboxyl, amino or amido compounds or mixtures of such substances, and which is adjusted to a pH of at most 4.5 with a water-soluble, strong organic carboxylic acid, and which may contain other auxiliaries, especially alkanolamides and alkanolaminoalkyl esters of fatty acids with 8 to 14 carbon atoms, impregnated at temperatures below the absorption temperature of the dyes and subject the treated goods to the action of moist heat by customary methods. 2. The method according to claim 1, characterized in that a basic nitrogen-containing polyglycol ether of aliphatic, higher alkylated or acylated di- and polyamines is used as hydrophilic to water-soluble, surface-active polyglycol ethers. 809813/1209 3., Process according to Claims 1 and 2, characterized in that that the hydrophilic to water-soluble, surface-active polyglycol ethers are those of N-monoalkyl or N-monoalkenyl mono- or -di or -tri- or -tetra-lower alkylene-di- or -tri-'or. tetra or pentamines with at least 16 carbon atoms in the alkyl or alkenyl radical and with at least 15 and preferably more than 25 to about 100 ethyleneoxy radicals used, of which isolated C-methylated and / or C-phenyl-substituted could be. 4. Process according to Claims 1 to 3, characterized in that one is used as hydrophilic to water-soluble, surface-active Polyglycol ether is an adduct of 15 to 20 mol of ethylene oxide with an N-monoalkyl-diethylene-triamine, whose Alkyl radical has at least 16 carbon atoms is used, of which isolated C-methylated and / or C-phenyl-substituted could be. 5. The method according to claim 1, characterized in that the hydrophilic to water-soluble, surface-active Ver '' bonds polyglycol ethers of alkanols, alkenols and alkyl ! , 'used phenols, the hydrophobic hydrocarbon radicals of contain a total of at least 8 carbon atoms and at least 5 ethyleneoxy radicals. 6. The method according to claim 1, characterized in that there is used as organic acid acetic acid, formic acid or tartaric acid. 809813/1209 7. For dyeing fiber material made of polymer and copolymer Acrylonitrile by impregnating it at temperatures below the absorption temperature of the basic dyes lying, and subjecting the treated goods to the action of moist heat according to customary methods suitable aqueous, optionally thickened acidic impregnation liquor, which is characterized in that it is in addition to at least one basic Dye in contents of 1 to 10 $ of the preparation is hydrophilic to water-soluble, surface-active, aliphatic hydrocarbon residues Polyglycol ethers containing a total of at least 8 carbon atoms and at least 4 ether groups of organic hydroxyl, carboxyl, amino or amido compounds or mixtures of such substances, and with a water-soluble strong organic carboxylic acid is adjusted to a pH value of not more than 4.5, and the other auxiliaries, especially alkanolamines and alkanolaminoalkyl esters of fatty acids having 8 to 14 carbon atoms. 8. Geiräss claims 1 to 6 using the Impregnation liquor according to claim 7 colored fiber material made of polymer and copolymer acrylonitrile. 809813/1209