US3706524A

US3706524A - Process for the dyeing or printing of textile fibre mixtures using simultaneously cationic and anionic dyestuff

Info

Publication number: US3706524A
Application number: US15842A
Authority: US
Inventors: Hermann Flensberg; Felix Frey
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1969-03-24
Filing date: 1970-03-02
Publication date: 1972-12-19
Anticipated expiration: 1989-12-19
Also published as: BE747843A; NL142214B; NL7004126A; CH555444A; CH438269A4; CA918855A; FR2035838B1; DE2013891A1; GB1298703A; FR2035838A1

Abstract

A PROCESS FOR THE SIMULTANEOUS DYEING OR PRINTING OF TEXTILE FIBRE MIXTURES WITH CATIONIC AND ANIONIC DYESTUFF IS DISCLOSED EHIC COMPRISES IMPREGNATING OR PRINTING THE TEXTILE FIBRE MIXTURE, AT TEMPERATURES BELOW THE ABSORPTION TEMPERATURE OF THE DYESTUFFS, WITH AN OPTIONALLY THICKENED SOLUTION CONTAINING AT LEAST ONE CATIONIC AND AT LEAST ONE ANIONIC DYESTUFF, SUFFICIENT ACID AND BUFFER SALT FOR THE PURPOSE OF MAINTAINING A PH-VALUE OF THE SOLUTION OF BETWEEN 3 AND 7, AT LEAST 0.5 G./1. OF SULPHATED OR SULPHONATED COMPOUND AS ANION-ACTIVE AUXILIARY, AND AT LEAST 0.5 G./1. OF AN AMIDE OF ALIPHATIC MONOCARBOXYLIC ACIDS CONTAINING FROM 8 TO 20 CARBON ATOMS, OR OF MIXTURES OF SUCH FATTY ACIDS WITH PRIMARY OR SECONDARY AMINES CONTAINING AT LEAST ONE LOWER HYDROXYALKYL GROUP, AND/OR OF A WATERSOLUBLE CONDENSATION PRODUCT FROM 1 EQUIVALENT OF FATTY ACIDS HAVING FROM 8 TO 20 CARBON ATOMS OF FROM MIXTURES OF SUCH FATTY ACIDS WITH FROM 1 TO 3 EQUIVALENTS OF A DIAND/OR TRIALKANOLAMINE, AND, OPTIONALLY, FURTHER AUXILIARIES, AND FINISHING THE DYEING OR PRINT BY A MOIST HEAT TREATMENT. THEREBY, THE TEXTILE FIBRE MIXTURES ARE DYED OR PRINTED VERY EVENLY, IN ONE SHADE OR IN SEVERAL SHADES, WITH GOOD FASTNESS PROPERTIES AND WITHOUT THE SO-CALLED "SANDWICH-EFFECT."

Description

United States Patent US. Cl. 8-21 A 11 Claims ABSTRACT OF THE DISCLOSURE A process for the simultaneous dyeing or printing of textile fibre mixtures with cationic and anionic dyestuif is disclosed which comprises impregnating or printing the textile fibre mixture, at temperatures below the absorption temperature of the dyestuffs, with an optionally thickened solution containing at least one cationic and at least one anionic dyestuif, sutficient acid and buffer salt for the purpose of maintaining a pH-value of the solution of between 3 and 7, at least 0.5 g./l. of sulphated or sulphonated compound as anion-active auxiliary, and at least 0.5 g./l. of an amide of aliphatic monocarboxylic acids containing from 8 to carbon atoms, or of mixtures of such fatty acids with primary or secondary amines containing at least one lower hydroxyalkyl group, and/or of' a Watersoluble condensation product from 1 equivalent of fatty acids having from 8 to 20 carbon atoms or from mixtures of such fatty acids with from 1 to 3 equivalents of a diand/or trialkanolamine, and, optionally, further auxiliaries, and finishing the dyeing or print by a moist heat treatment. Thereby, the textile fibre mixtures are dyed or printed very evenly, in one shade or in several shades, with good fastness properties, and Without the so-called sandwich-effect.

DETAIIJED DISCLOSURE The present invention concerns a process for the simultaneous dyeing or printing of textile fibre mixtures, especially in the form of carpets or furniture covering material, in which at least one type of fibre has aflinity to cationic dyestuff and at least one other type of fibre has afiinity to anionic dyestutf, as well as the textile fibre mixtures dyed or printed using the process according to the invention.

The single-bath dyeing or printing of textile material, consisting of fibre mixtures of differing dyestulf afiinity, renders necessary the selection of specific dyestuffs for each type of fibre. The selection to be made frequently represents a compromise with respect to the evenness and fastness of the dyeings therewith obtainable, to the stability of the liquor and to other properties, since the ideal dyestuff for one type of fibre is often completely unsuitable for another type. Typical fibre mixtures, the dyeing of which presents such difficulties, consist, for example, of polyacrylonitrile and synthetic polyamide fibres or of polyacrylonitrile and cotton fibres.

It has now been found that textile fibre mixtures of the above mentioned type can be very evenly dyed or printed, in one shade or in several shades, with satisfactory fastness properties and without the effect known as the sandwich effect, by impregnating or printing the fibre mixture at temperatures below the absorption temperature of the dyestuffs using an optionally thickened solution which contains at least one cationic dyestuif and at least one anionic dyestuff, sufficient acid and buffer salt for the purpose of maintaining a pH-value of the solution between 3 and 7, at least 0.5 g./litre of sulphated or sulphonated compound as anion-active auxiliary and at least 0.5 g./

Patented Dec. 19, 1972 litre of an amide of aliphatic monocarboxylic acids containing from 8 to 20 carbon atoms, or of mixtures of such fatty acids with primary or secondary amines containing at least one lower hydroxyalkyl group, and/or of a watersoluble condensation product from 1 equivalent of fatty acids having from 8 to 20 carbon atoms, or from mixtures of such fatty acids with from 1 to 3 equivalents of a diand/ or trialkanolamine, as well as optionally further auxiliaries common in dyeing, and completing the dyeing or printing by a moist heat treatment.

Suitable sulphated or sulphonated compounds, usable in the process according to the invention, are, e.g.:

(1) sulphated primary or secondary alkanols or alkenols, the alkyl chain of which contains from 8 to 20 carbon atoms, e.g. sodium lauryl sulphate, sodium-a-methyl stearyl sulphate, ammonium tridecyl sulphate, sodium oleyl sulphate, potassium steanyl sulphate or the sodium salts of the coconut oil fatty alcohol sulphates;

(2) sulphated unsaturated higher fatty acids or fatty acid esters such as oleic acid, elaidic acid or ricinoleic acid, or their lower alkyl esters, e.g. ethyl, propyl or butyl esters, and the oils containing such fatty acids, such as olive oil, castor oil, rape oil, etc.;

(3) sulphated polyglycol ethers such as sulphated addition products of from 1 to 20 moles of ethylene oxide with fatty' acid alkanolamides, mercaptans, amines or fatty acids, particularly, however, with aliphatic alcohols or alkylphenols having from 8 to 20 carbon atoms in the alkyl chain, e.g. with lauric acid-B-hydroxyethylamide, decylmercaptan, stearylamine, stearic acid, oleic acid, lauryl alcohol, myristyl alcohol, stearyl alcohol, oleyl alcohol, octyl phenol or nonyl phenol;

I (4) the sulphates of alkanolamides, e.g. the sulphated amides of caprylic, pelargonic, capric, lauric, myristic or stearic acid, or of lower fatty acids substituted by alkylphenoxyigroups, such as octylor nonylphenoxyacetic acid, with monoor bis-hydroxyalklamines such as ,3- hydroxyethylarnine, vhydroxypropylamine, 3,y-dihy-- droxypropylfirliine, bis- (B-hydroxyethyDamine, or with N- alkyl-N-hydrpxyalkylamines such as N-methylor N- ethyl-N-(B-hydroxyethyl)-amine;

(5) sulphated esterified polyoxy compounds, e.g. sulphated, partially esterified polyols such as the sodium salt of the sulphated monoglyceride of palmitic acid;

(6) primary and secondary alkyl sulphonates, of which the alkyl chain contains from 10 to 20 carbon atoms, e.g. ammonium dodecyl sulphonate, sodium hexadecane sulphonate-8, sodium stearyl sulphonate;

(7) alkylaryl sulphonates such as alkylbenzene sulphonates with a straight-chained or branched alkyl chain having at least 7 carbon atoms, e.g. sodium dodecylbenzene sulphonate, l,3,5,7-tetramethyl-octylbenzene sulphonate, sodium octadecylbenzene sulphonate, or such as alkylnaphthalene sulphonates, e.g. sodium-l-isopropylnaphthalene-Z-sulphonate, sodium dibutylnaphthalene sulphonate; or dinaphthylmethane sulphonates, e.g. the disodium salt of the di-(6-sulphonaphthyl-2)-methane;

(8) sulphonates of polycarboxylic acid esters, e.g. potassium dioctylsulphosuccinate, sodium dihexylsulphophthalate.

In the process according to the invention, as anionactive auxiliaries, preferably alkylaryl sulphonates are used, especially dinaphthylmethane sulphonates, or sulphated polyglycol ethers, particularly sulphated polyglycol ethers of aliphatic alcohols or alkylphenos containing from 8 to 20 carbon atoms in the alkyl chain, said polyglycol ethers having from 1 to 20 ethyleneoxy groups and, most particularly, sulphated lauryl alcohol polyglycol ethers having from 2 to 3 ethyleneoxy groups, or sulphated polyglycol ethers of octyl or nonyl phenol having from 2 to 3 ethyleneoxy groups.

The anion-active auxiliaries, usable according to the invention, are advantageously used in the form of their water-soluble salts, particularly in the form of their alkali metal salts, ammonium salts, lower alkylammonium salts or hydroxyalkylammonium salts.

The amides, usable in the process according to the invention of aliphatic monocarboxylic acids containing from 8 to 20 carbon atoms, or of mixtures of such fatty acids with primary or secondary amines containing at least one lower hydroxyalkyl group, are derived, e.g. from caprylic, pelargonic, capric, lauric, myristic, oleic, stearic, decyloxyacetic, lauryloxyacetic, decylthioacetic or laurylthioacetic acid and, preferably, from the mixture of acids embraced by the collective term coconut oil fatty acids, and from the following hydroxyalkylaminesz- (a) from monohydroxyalkylamines such as fi-hydroxyethylamine, 'y-hydroxypropylamine, or dihydroxyalkylamines such as ,8, 'y-dihydroxypropylamine;

(b) from bis-(w-hydroxyalkyD-amines such as bis- (fl-hydroxyethyl)-amine, bis-(' -hydroxypropyD-amine, bis- (a-methyl-fi-hydroxyethyl)-amine;

(c) from N-alkyl-N-(hydroxyalkyl)-amines such as N- methylor N-ethyl-N-(fi-hydroxyethyl)-amine, N-methylor N-ethyl-N-('y-hydroxypropyl)-amine.

The N,N-bis-(w-hydroxyalkyl)-amides are preferred, particularly those with hydroxyalkyl radicals having two or three carbon atoms such as, in particular, the N,N-bis- (fl-hydroxyethyD-amides or N,N-bis-(' -hydroxypropyl)- amides of the above described fatty acids, especially of the coconut oil fatty acids, since these promote a particularly good dye yield.

These amides are obtained by methods known per se by reacting the esters of monocarboxylic acids, as defined, with lower alkanols, e.g. by reacting the fatty acid methyl or -ethyl esters with the desired amine in the presence of sodium or potassium alcoholates, e.g. using a process described in the British Pat. 631,637.

Instead of the above mentioned amides, it is also possible to use, as defined, condensation products from 1 equivalent of fatty acids having from 8 to 20 carbon atoms, or from mixtures of such fatty acids with from 1 to 3 equivalents of a diand/or trialkanolamine. These condensation products can be produced by the process described in U.S.A. Pat. 2,089,212, by heating the fatty acids with from 1-3 equivalents of diand/or trialkanolamines, especially diethanolamine, while splitting off more than 1 mole of water. Preferred are condensation products from 1 equivalent of the stated fatty acids or from mixtures of such fatty acids, especially from the mixture of acidsembraced by the collective term coconut oily fatty acidswith 2 equivalents of dialkanolamine.

The amounts to be used, in the process according to the invention, of anion-active auxiliaries and amides or condensation products, can vary within wide limits and they depend both on the type and amount of the dyestutfs used and on the choice and composition of the substrate. They can each be used in amounts of up to 50 g./litre of dye liquor or printing paste. The anion-active auxiliaries are preferably used in amounts of from 1-10 g./litre of dye liquor or printing paste, and the amides or condensation products, in particular, in amounts of from 0.5 to 2.5 g./litre. Advantageously, the anion-active auxiliaries and the amides or condensation products are used in a reciprocal weight ratio of about 1:1 to 10:1, preferably 1:1 to 5: 1.

Suitable cationic dyestuffs, usable according to the invention, are, advantageously, the technically easily accessible salts and metal halides, e.g. zinc chloride double salts of the known basic dyestuffs. Examples of these are: thiazines, oxazines, diphenylmethanes, triphenylmethanes, rhodamines, azo and anthraquinone dyestuffs, preferably monoazo, methine and azomethine deystulfs, all containing onium groups, whereby, in the first place, ammonium groups are to 'be mentioned as onium group.

Suitable as anionic dyestuffs, usable in the process according to the invention, are both the so-called acid wool dyestuflis and reactive or substantive dyestuffs of any class, the colouring part of which is an anion such as the alkali or ammonium salts of dyestuif sulphonic acids or dyestufi carboxylic acids or of 2:1 metal complex dyestuffs, particularly metal-free or metallised sulphonated mono-, disor polyazo dyestuffs, to which also belong the formazane dyestuffs, their chromium, cobalt, nickel and copper complexes as well as sulphonated anthraquinone, nitro and phthalocyanine dyestutfs. Suitable reactive dyestuffs are those which react with the amino .groups of the wool or with the hydroxyl groups of the cellulosic fibres and which are derived, in particular, from the azo, anthraquinone or phthalocyanine dyestulfs.

For the adjustment or maintenance of the pH-value of the liquor or printing paste between 3 and 7, lower aliphatic carboxylic acids are preferably used, especially monocarboxylic acids such as formic acid or, in particular, acetic acid, and the usual butfer salts such as sodium acetate, potassium acetate or ammonium acetate, or the corresponding sulphates and phosphates.

Advantageou'sly, the dye liquor or printing paste contains thickeners stable towards acids. The products known in the textile-printing industry are used as thickeners, e.g. locust bean flour derivatives, galactomannans, tragacanth, Solvitose or British gum, cellulose derivatives such as methyl cellulose, natural gum and solubilised types of gum such as crystal gum, or synthetic thickeners such as polymerisation and copolymerisation products of acrylic acid, methacrylic acid or maleic acid.

As further auxiliaries, the dye liquor or printing paste can contain, for example, substances accelerating fixing, such as ethylene carbonate; solubilitypromoting agents such as cellosolve, bactericidal and fungicidal compounds, or also moth-proofing agents.

Dye liquors or printing pastes, usable according to the invention, are advantageously prepared by dissolving the anionic dyestutf in hot water, adding to this the mixture of auxiliaries, and optionally thickeners, and stirring into the obtained solution, after it has cooled to room temperature, the solution of the cationic dyestutf. The latter is advantageously slurried with acid and buffer salt and then dissolved in warm water and cooled.

Suitable textile fibre mixtures, which can be dyed or printed according to the invention, are, e.g. those which consist of natural and synthetic polyamide fibres, natural and regenerated cellulose fibres and polyacrylonitrile fibres-the latter including those which are basic modified. Suitable synthetic polyamide fibre materials are both those types of fibres which are dyeable with anionic dyestutfs and acid modified polyamide fibres which are known in the textile industry, e.g. under the names of Nylon 844 and 830, Perlon Type 95, Nylon T and K 825. Fibre mixtures are preferred which consist of acid and basic dyeable synthetic polyamide, of polyacrylonitrile and synthetic polyamide or of polyacrylonitrile and cellulosic fibres, especially cotton.

The fibre mixtures can be in any desired form, e.g. as tufted material, non-woven articles such as needle punch, fabrics, knitted goods, flock, twisted or plaited yarn, etc., Preferably, the textile fibre mixture, to be dyed or printedaccording to the invention, is used in the form.

of carpets such as tufted carpets, or furniture covering and decorative materials such as furniture plush and so forth.

The process, according to the invention, is suitable both for dyeing by the usual impregnation processes, e.g. by means of dipping, padding, nip-padding or knife-coating, and for printing or for combinations of the stated processes.

The finishing of the impregnated or printed fibre material is performed by usual methods suited to the type of fibre. Advantageously, it is carried out by steaming with EXAMPLE 1 1.3 g. of the blue dyestuif of theFormula,

I l 1 $0511 (G.B. 1,167,664)

NH- CH:

SOzNHCHaCHzOH 1.2 g. of the blue dyestutf of the formula and 0.14 g. of the yellow dyestuff of the formula are dissolved in 100 ml. of water which is at 80, To this solution are added 5 g. of a mixture of auxiliaries consisting of 40 parts of coconut oil fatty acid-N,N-bis-(flhydroxyethyD-amide, 40 parts of the sodium salt of lauryl alcohol triglycol ether sulphate, 12 parts of isopropanol and 8 parts of Cellosolve, an alkyl ether of ethylene glycol, whereupon the obtained solution is cooled to 30.

0.85 g. of the blue dyestuff of the formula and 0.8 g. of the yellow dyestuff of the formula CHs("3-'("3H CHzN CN=NC are separately slurried with 2 ml. of 40% acetic acid and 2 g. of sodium acetate and 100 ml. of water at 80 are poured over the dyestuff slurry. After the obtained dyestutf solution has cooled to 30, it is stirred into the dyestufi solution, which is described in the first paragraph, and the quantity is made up with water to 1000 ml.

With the obtained dye liquor, a tufted carpet consisting of a backing of jute or polypropylene, into which are tufted, as pile or nap material, polyamide fibres, one third of which consists of acid modified polyamide fibres (Nylon 844) and each of the remaining two thirds of polyamide dyeable with acid dyestuffs and possessing differing dyestuff affinity (Nylon 845 and Nylon 847), is impregnated at room temperature (pH-value of the dye liquor=5). The impregnated tufted carpet is afterwards steamed for 15 minutes, in a carpet-steaming apparatus, with saturated steam at a temperature of 98-100. The dyed carpet is then rinsed with cold water and dried. By this means is obtained a tufted carpet which is dyed, without sandwich effect, in the colours green, pale blue and dark blue.

Tufted carpets, likewise even and without sandwichetfect and dyed in the colours green, pale blue and dark blue, are obtained by using in the above example, instead of the therein mentioned mixture of auxiliaries, but with otherwise the same procedure, one of the mixtures of auxiliauies given below in the stated amounts:

2 g. of coconut oil fatty acid-N,N-bis-(fi-hydroxyethyl)- amide,

10 g. of the disodium salt of di-(6-sulphonaphthyl-2)- methane,

2 g. of the condensation product from 1 equivalent of coconut oil fatty acid and 2 equivalents of diethanol amine (according to Example 3 of the USA. Pat. 2,089,212),

10 g. of the sodium salt of lauryl alcohol triglycol ether sulphate,

1 g. of coconut oil fatty acid-N,N-bis-(fl-hydroxyethyD- amide 4 g. of sodium lauryl sulphate,

1.5 g. of coconut oil fatty acid-N,N-bis-(B-hydroxyethyl)- amide,

5 g. of sulphated ricinoleic acid,

2 g. of coconut oil fatty acid-N,N-bis-(fi-hydroxyethyD- amide,

10 g. of sulphated stearic acid-N-methyl-N-B-hydroxyethylamide,

2 g. of coconut oil fatty acid-N,N-bis-(,B-hydroxyethyl)- amide,

10 g. of ammonium dodecyl sulphonate,

1.5 g. of coconut oil fatty acid-N,N-bis-(B-hydroxyethyD- amide,

6 g. of 1,3,5,7-tetramethyloctylbenzene sulphonate, or

2 g. of coconut oil fatty acid-N,N-bis-(fl-hydroxyethyD- amide,

10 g. of sodium dioctylsulphosuccinate.

EXAMPLE 2 0.44 g. ofthe yellow dyestuff of the formula CH:C(|?H ON=NC 7 and 1.36 g. of the blue dyestuff of the formula NH-CH:

NH-Q-NHCOCH:

(G.B. 1,167,664 0.1. 62,125) 1.7 g. of the yellow dyestulf of the formula Q-NEL-QNH-QNO:

S 01H N 0 a and 0.9 g. of the yellow dyestufi of the formula SO3H in 50 ml. of water at 80. To the solution are added 2 g. of lauric acid-N,N-bis-(fl-hydroxyethyD-amide and 4 g. of the sodium salt of nonyl phenol diglycol ether sulphate. Into this solution, after it has cooled to room temperature, is then stirred the dyestuff solution described in the first paragraph of this example. The dye liquor is afterwards made up with water to 1000 ml.

Tufted carpets (backing of jute), the nap material of which consists half of synthetic polyamide dyeable with acid dyestuff and half of synthetic polyamide dyeable with basic dyestuff, are impregnated and the above dye liquor. They are then steamed, rinsed and dried in the manner described in Example 1. By this means is obtained a tufted carpet, dyed in the colours brown and yellow.

By using the above example, instead of the dyestuffs stated there, but with otherwise the same procedure, the dyestulf mixtures (a) or (b) given below, then tufted carpet is obtained which is dyed in the colours red and scarlet using the dyestuff mixture (a) and blue and violet using the dyestulf mixture (b).

Dyestutf mixture (a) Cationic dyestuffs: 0.8 g. of the yellow dyestuff of the formula CHs-C-CH 8 and 0.6 g. of the red dyestulf of the formula CHI 9 N Cl l l L 1N=N N I? \C|H|-| CHI (U.S. 2,883,373) Anionic dyestuffs: 1.4 g. of the red dyestufi of the 10 formula HQN 20. HOW

I SO|H (U.S. 2,714,103 1.9 g. of the red dyestuif of the formula Dyestutf mixture (b) SOIH Cationic dyestuffs: 0.1 g. of the red dyestulf of the and 0.05 g. of the red-brown dyestutf of the formula formula CH: Q

N {F i on. N=NN 211121.

on, (U.s. 2,883,373) 1 g. of the blue dyestutf of the formula 0 NH-CH;

Anionic dyestuffs: 0.51 g. of the blue dyestutf of the formula O NH:

| I NH-Q-NHCOGH;

1.3 g. of the blue dyestuff of the formula 0.6 g. of the green dyestuif of the formula (II) NH- CH: l l Y urn-4311.

SIOQH (0.1. 61570) EXAMPLE 3 4.0 g. of the red dyestuif of the formula S 0311 (3H1 CH:

SO3H and 1.2 g. of the red dyestuff of the formula i0, 110- l sonar are dissolved in 150 ml. of water at 70. To the obtained solution are added 15 g. of the sodium salt of lauryl alcohol triglycol ether sulphate and 3 g. of coconut oil fatty acid-N,N-bis-(fi-hydroxyethyl)-amide and the solution is cooled to room temperature.

A slurry is prepared separately of 2 g. of the yellow dyestutf of the formula 8 g. of the red dyestuff of the formula and 0.32 g. of the blue dyestuff of the formula CHQCH; @N

CHzO- backing, the nap material of which consists to the extent of of polyacrylonitrile fibres and 20% of synthetic polyamide fibres. The impregnated tufted carpet is then steamed during 15 minutes with saturated steam at a temperature of 98-100, rinsed and dried. In this manner is obtained a uniformly red dyed tufted carpet without sandwich-efiect.

. If, in the above example, instead of the therein mentioned mixture of auxiliaries, but with otherwise the same procedure, a mixture of auxiliaries consisting of 15 g. of the disodium salt of di-(6-sulphonaphthyl-2)-methane and 3 g. of the condensation product from 1 equivalent of coconut oil fatty acid and 2 equivalents of diethanolamine is used, then likewise is obtained evenly red dyed tufted carpet without sandwich-effect.

EXAMPLE 4 1 g. of the yellow dyestufl? of the formula 0.8 g. of the blue dyestutf of the formula HzC I and 0.05 g. of the red dyestuff of the formula CHgO are slurried with 2 ml. of 40% acetic acid and 2 g. of sodium acetate, then dissolved in 100 ml. of water at 75 and the solution is cooled to room temperature.

A solution is prepared separately of 1 g. of the yellow dyestuff of the formula in 100 ml. of water. To the obtained solution are then added 2 g. of the condensation product from 1 equivalent of coconut oil fatty acid and 2 equivalents of diethanolamine and 5 g. of the sodium salt of lauryl triglycol ether sulphate and the whole is cooled to room temperature. The dyestuff solution, produced according to para- 1 1 graph 1 of this example, is then stirred in and the quantity made up to 1000 ml.

With the obtained dye liquor,v tufted carpet, the pile material of which consists of 80% of polyacrylonitrile fibres and 20% of synthetic polyamide fibres, is impregnated. The impregnated tufted carpet is then steamed in the manner described in Example 3, rinsed and dried. Green dyed tufted carpet is obtained without sandwicheflect.

By using in the above example, instead of the given dyestuffs, one of the dyestulf mixtures (a) or (b) given below, tufted carpet is obtained which is dyed blue using the dye mixture (a) or gold-yellow using the dye mix- Dyestulf mixture (a) Cationic dyestuffs: 0.08 g. of the yellow dyestulf of the 0.01 g. of the red dyestufi of the formula CHaO 0.8 g. of the blue dyestuff of the formula cmo \C-N= Org-summon znch s 011,011

0.5 g. of the blue dyestutf of the formula 01H; /C:Hl

\N o/ N\ 01 cg 01H:

Anionic dyestuffs: 0.08 g. of the yellow dyestutf of the formula N=N-(|J--COH:

Itoll 1 1.2 g. of the blue dyestuif of the formula SOzH d fax-Q-mrcocm 1 2 0.06 g. of the red dyestulf of the formula HaN SOIH

(US. 2,714,103; Dyestutf mixture (b) Catonic dyestuffs: 1.25 g. of the yellow dyestulf of the formula CH; N

I OH;

(U.S. 3,055,881) 0.075 g. of the red dyestufi of the formula CH: Q

0.09 g. of the blue dyestufl. of the formula CHICK] @N (U.S. 2,864,812) Anionic dyestulfs: 0.065 g. of the yellow dyestulf of the formula S og-H 0.45 g. of the yellow dyestufi of the formula 0.045 g. of the blue dyestuif of the formula SOIH 13 tained tufted carpet evenly dyed in the colours green, blue and-gold-yellow, respectively, and without sandwicheffect.

EXAMPLE 2 g. of the yellow dyestutf of the formula 5 CHa(J(fiH C Ha-N C-N=NC- 1| I H:C-C N 01 10 1.3 g. of the red dyestuff of the formula e9 NCH; In 1 C2115 znon \N 02H: CH: (U.S. 2,883,337) and 0.4 g. of the blue dyestuff of the formula CHaO o-N=N-rr-omornon Z Che l'l omen; (EN

are slurried with 5 ml. of 80% acetic acid and afterwards dissolved in 100 ml. of water at 80. The obtained solution is then cooled to 30.

acrylonitrile fibres and the backing of cotton (reciprocal Weight ratio 1:1), is impregnated at room temperature and squeezed out to a dye liquor absorption of 100% by weight, relative to the dry weight of the material. The impregnated material is afterwards steamed during 15 minutes at a temperature of 102. After soaping With an aqueous solution containing 1 g./litre of N-octadecyldiethylene-triamine polyglycol ether, rinsing and drying, a furniture plush is obtained, the nap material and backing of which are evenly dyed red.

If, in the above example, instead of the stated mixture of auxiliaries, a mixture of auxiliaries is used consisting of 5 g. of the disodium salt of di-(6-sulphonaphthyl-2)- methane and 1 g. of the condensation product from 1 equivalent of coconut oil fatty acid and 2 equivalents of diethanolamine, then red dyeings are obtained having similar properties. 4

EXAMPLE 6 are slurried with 5 ml. of 80% acetic acid, the slurry then dissolved in 100 ml. of water at 70 and the solution cooled to room temperature. A solution is prepared separately of 0.4 g. of the red dyestuif of the formula A solution is prepared separately of 1.4 g. of the orange dyestuff of the formula sosrr NHCOCH; NHCOCH; SOaH (11.8. 2,813,855)

0.2 g. of the grey dyestufi of the formula sour OCH; 0--Tu o N=N-N=NQN=N NHCOCH:

60H: H3 HOSS OJH (U.S. 2,982,764)

and 3.4 g. of the red dyestuif of the formula H03S NHCONH fisoni (BE HO:

in 150 ml. of hot water. Into the obtained solution are 30 first stirred 5 g. of a highly viscous galactomannan ether thickener (Solvitose CPA) and then 5 g. of the sodium salt of lauryl alcohol triglycol ether sulphate and l g. of coconut oil fatty acid-N,N-bis-(fl-hydroxyethyD-amide. After the solution has cooled to room temperature, the dyestuif solution, produced according to paragraph 1 of this example, is stirred in and the solution made up with water to 1000 ml.

With the obtained dye liquor (pH 3-3.5), a furniture plush, the nap material of which is made from poly- H0 (0.1. 35780) in ml. of water at To the obtained dyestuff solution are added 5 g. of thickener (Solvitose GPA) and 5 ml. of a mixture of auxiliaries, consisting of 40 parts of the sodium salt of lauryl alcohol triglycol ether sulphate, 40 parts of coconut oil fatty acid-N,N-bis-(;8-hydroxyethyl)-arnide, 12 parts of isopropanol and 8 parts of Cellosolve, and the solution is cooled to room temperature. Into the obtained solution is stirred the dyestuff solution, obtained according to paragraph 1 of this example, 15 g. of ethylene carbonate are added and the solution is made up with Water to 1000 ml.

25 EXAMPLE 12 3.9 g. of the blue dyestutf of the formula SO H NHQCH:

OaNHCHzCHzOH 3.6 g. of the blue dyestuff of the formula and 0.42 of the yellow dyestulf of the formula and 2.4 g. of the yellow dyestulf of the formula are separately slurried with 2 ml. of 80% acetic acid and 300 ml. of 70 warm water are poured over the dyestuff slurry. After the obtained dyestutf solution has cooled to 30", it is stirred into the dyestutf solution which is described in the first paragraph of this example, and then the printing paste is made up to 1000 ml. with water.

With the obtained printing paste a tufted carpet consisting of a backing of jute or polypropylene, into which are tufted, as pile or nap material, polyamide fibres, one

third of which consists of acid modified polyamide fibres (Nylon 844) and each of the remaining two thirds of polyamide dyeable with acid dyestuffs and possessing differing dyestufi afiinity (Nylon 845 and Nylon 847) is printed and afterwards steamed for 15 minutes, in a carpetsteaming apparatus, at a temperature of -102. The printed carpet is then rinsed with cold water and dried. By this means, a tufted carpet is obtained which is printed, without sandwich-effect, in the colours green, blueish green and dark blue.

What we claim is:

1. A process for the simultaneous dyeing or printing of textile fibre mixtures selected from the group consisting of a fibre mixture consisting of a synthetic polyamide dyeable with an acid dyestufi and a synthetic polyamide dyeable with a basic dyestuff; polyacrylonitrile dyeable with basic dyestuffs and synthetic polyamide dyeable with acid dyestuffs; polyacrylonitrile dyeable with basic dyestuffs and cellulose fibres dyeable with acid dyestuffs comprising: (I) impregnating or printing this textile fibre mixture, at temperatures below the absorption temperatures of the dyestufts, with an aqueous solution containing- (a) at least one cationic dyestutf,

(b) at least one anionic dyestutf,

(c) sufiicient acid and buffer salt for the purpose of maintaining a pH-value of the solution of between 3 and 7,

(d) at least 0.5 g./l. of a sulphated or sulphonated compound as an anionic auxiliary, selected from sulphated primary or secondary alkanols and alkenols containing from 8 to 20 carbon atoms; sulphated unsaturated higher fatty acids or their lower alkyl esters and oils containing such fatty acids; sulphated polyglycol ethers; sulphated alkanolamides; sulphated partially esterified polyols; primary and secondary alkyl sulphonates the alkyl chain of which contains from 10 to 20 carbon atoms; alkylaryl sulphonates, and sulphonates of polycarboxylic acid esters, and

(e) at least 0.5 g./l. of an amide of aliphatic monocarboxylic acids containing from 8 to 20 carbon atoms, or of mixtures of such fatty acids with primary or secondary amines containing at least one lower hydroxyalkyl group, and/or of a water-soluble condensation product from 1 equivalent of fatty acids having from 8 to 20 carbon atoms or from mixtures of such fatty acids with from 1 to 3 equivalents of a diand/or trialkanolamine, and

(H) finishing the dyeing or printing by a moist heat treatment.

2. A process as claimed in claim 1, further comprising (f) thickener admixed with said solution.

3. A process as claimed in claim 1, wherein the sulphated or sulphonated compound defined under (d) is selected from sulphonated polyglycol ethers of aliphatic alcohols containing from 8 to 20 carbon atoms and having from 1 to 20 ethyleneoxy groups, or their soluble salts; sulphated polyglycol ethers of alkyl phenols containing from 8 to 20 carbon atoms in the alkyl chain and having from 1 to 20 ethyleneoxy groups, or their soluble salts; and dinaphthylmethane sulphonates.

4. A process as claimed in claim 3, wherein there is employed sulphated lauryl alcohol polyglycol ethers having from 2 to 3 ethyleneoxy groups, or of their soluble salts.

5. A process as claimed in claim 3, wherein there is employed sulphated polyglycol ethers of octyl or nonyl phenol having from 2 to 3 ethyleneoxy groups, or of their soluble salts.

6. A process as claimed in claim 1, wherein there is employed amides of coconut oil fatty acids with primary or secondary amines containing at least one lower hydroxy alkyl group as compound defined under (e).

7. A process as claimed in claim 6, wherein there is employed coconut oil fatty acid-N,N-bis-(B-hydroxyethyD- amide.

27 8. A process as claimed in claim 1, wherein there is employed condensation products from 1 equivalent of fatty acids having from 8 to 20 carbon atoms, or from mixtures of such fatty acids with 2 equivalents of dialkanolamine,

as compound defined under (e).

9. A process as claimed in claim 1, wherein there is employed a textile fibre mixture consisting of synthetic polyarnide dyeable with acid dyestuffs and synthetic polyamide dyeable with basic dyestuff.

10. A process as claimed in claim 1, wherein there is employed a textile mixture consisting of polyacrylonitrile dyeable with basic dyes and synthetic polyamide dyeable with acid dyes.

11. A process as claimed in claim 1, wherein there is employed a textile fibre mixture consisting of polyacrylonitrile dyeable with basic dyes and cellulosic fibres dyeable with acid dyes.

. 28 References Cited UNITED STATES PATENTS 1/1960 Mueller et al 8-21 R 3/1964 Webb 821 A 3/1966 Paul 8-21 A 6/1968 David 8--21 B 6/1968 Zurbuchen 8-174 X 4/1969 Zurbuchen 8173 X GEORGE F. LESMES, Primary Examiner P. C. IVES, Assistant Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE CORRECTION;

Patent No. 3 706 5Z4 Dated December 19 1-9 72 lnventol-(s) HERMANN FLENSBERG, ET AL.

it is certified that error appear-s in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 65, "alkylphenos" should read alkylphenols Column 5 lines 35 to 44, the formula should read as follows:

I V 7 H0 5 E Column 6, line 30 after ""methan'e"; the should read line 36 after "sulphate" the should read line 38, after "amide" insert cancel "4g of sodium lauryl sulphate between lines 38 and 39, insert 4g of 3 sodium lauryl sulphate; line 41 after "acid", the

should read line 45 after "ethulamide" the should read line 48, after "sulphonate", the should read line 51, after "sulphonate" the should read Column 9 lines 23 to 33, the formula should read as follows: v

FORM Po-1os0 (10-69) USCOMMDC U.S4 GOVlEINMENY PRINYING OFFICE: IQID 0-365-3JL 3,706,524 X I Page 2 Column 10, lines 50 to 59, the formula should' read as follows:

Column 10, lines -62 to 69, the formula should read as follows:

Columns 13 and 14, in the compound identified as 0.1.

should read "-"--N Columns 13 and 14, in the compound identified as disclosed in U.S. 2,813,855, shift the "NHCOCH group in column 14, as follows:

from to.

BCOCH Signed and sealed this 21st; day of May1974.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. Attesting Officer C. MARSHALL DANN Commissioner of Patents