Process for the dyeing of materials consisting of anion-modified polyacrylonitrile, polyamide and polyester fibres
United States Patent 3900283
Compositions and a process for dyeing and printing synthetic materials of polyacrylonitrile, polyamides, or polyesters which contain anionic groups which comprises using a treating composition for aforesaid materials which consists of an aqueous dispersion of a basic dyestuff salt and a polynuclear aromatic sulfonic acid whereby the fixing times are reduced and fast and level dyeings are produced.
US Patent References:
/1613228.html
Hoz - January 1927 - 1613228
Polyacrylonitriles dyed with quaternized heterocyclic azo dyes
Tsang et al. - July 1959 - 2893816
Process of dyeing acrylonitrile articles with cationic dyes
Pitts - October 1960 - 2955009
Process for the coloring of fiber blends of polyester and native or regenerated cellulose
Raff - November 1966 - 3288551
PROCESS FOR DYEING AND PRINTING ANIONIC POLYMERIC FIBERS
Clapham et al. - April 1970 - 3504997
/1613228.html
Hoz - January 1927 - 1613228
Polyacrylonitriles dyed with quaternized heterocyclic azo dyes
Tsang et al. - July 1959 - 2893816
Process of dyeing acrylonitrile articles with cationic dyes
Pitts - October 1960 - 2955009
Process for the coloring of fiber blends of polyester and native or regenerated cellulose
Raff - November 1966 - 3288551
PROCESS FOR DYEING AND PRINTING ANIONIC POLYMERIC FIBERS
Clapham et al. - April 1970 - 3504997
Inventors:
Hildebrand, Dietrich (Odenthal, DT)
Kruckenberg, Winfried (Leverkusen, DT)
Kuhnel, Werner (Leverkusen, DT)
Molls, Hans Heinz (Cologne-Flittard, DT)
Wolf, Karlheinz (Cologne-Stammheim, DT)
Kruckenberg, Winfried (Leverkusen, DT)
Kuhnel, Werner (Leverkusen, DT)
Molls, Hans Heinz (Cologne-Flittard, DT)
Wolf, Karlheinz (Cologne-Stammheim, DT)
Application Number:
04/856468
Publication Date:
08/19/1975
Filing Date:
09/09/1969
View Patent Images:
Export Citation:
Assignee:
Bayer Aktiengesellschaft (Leverkusen-Bayerwerk, DT)
Primary Class:
Other Classes:
8/933, 8/587, 8/560, 8/589, 8/904, 8/586, 8/539
International Classes:
C09B67/32; C09B69/06; D06P1/00; D06P1/62; D06P3/00; D06P3/24; D06P3/52; D06P3/76; D06P3/82; C09B67/00; C09B69/00; D06P1/44; D06P3/34; D06P3/70; D06P5/00
Field of Search:
8/178,179,177,21,173,21A,21B,21C,168A
Other References:
Chem. Abstract, July 10, 1967, Col. 10063. .
Zollinger, Amer. Dyestuff Rep., March 7, 1960, pages 142, 143, 144 & 149. .
Schmidlin, "Preparation and Dyeing of Synthetic Fibres," Pub. April 1, 1963, pages 176-180, pub. by Chapman & Hall Ltd., London, Eng. .
D. Trotman, Dyeing and Chemical Technology of Textile Fibres, 3rd Edition, Oct. 1963, pp. 329-330, pub. by Griffin, London, Eng. .
Hoffman, German Auslegeschrift 1,260,074, 2/1/68, 2 pages spec. No drawing. .
Douglas, American Dyestuff Reporter, Feb. 11, 1951, pages P122-P125, TP890A512. .
Innarone, American Dyestuff Reporter, Feb. 14, 1966, pages 52-55, TP890A512. .
Leddy, American Dyestuff Reporter, pp. 57, 58, 65-68, 4/18/60, TP890A512. .
Egli, Textil Veredlung, Vol. 2, No. 11, pages 856-864, pub 1967..
Primary Examiner:
Levy, Donald
Attorney, Agent or Firm:
Plumley & Tyner
Claims:
We claim
1. In a process for dyeing anionically modified synthetic material selected from the class consisting of polyacrylonitrile containing internal anionic groups, polyamide containing internal anionic groups, polyesters containing internal anionic groups, and mixtures of said materials with other fiber materials, wherein the internal anionic groups are strong anionic groups that are attached to the internal portion of the molecular chains and are frequently repeated along the molecular chains, the improvement which comprises padding or printing said materials with aqueous dispersions containing the salt of a basic dyestuff which is free from carboxylic acid and sulfonic acid groups and a polynuclear aromatic sulfonic acid selected from the class consisting of diphenyl sulfonic acid, naphthalene di-, tri-, or tetrasulphonic acid, and pyrene tetrasulfonic acid, and subsequently subjecting the thus treated materials to a heat treatment.
2. Process according to claim 1 wherein the salts of basic dyestuffs are of the anthraquinone series.
3. Process according to claim 1 for the treatment of mixed textiles of cellulose and polyacrylonitrile containing anionic groups, wherein the mixed textiles are treated with aqueous dispersions of the salts obtained from basic dyestuffs which are free from carboxylic acid and sulphonic acid groups with polynuclear aromatic sulphonic acids, which also contain reactive dyestuffs, and that the reactive dyestuffs are fixed in the usual way.
4. Process according to claim 1 for the treatment of mixed textiles of cellulose and polyacrylonitrile containing anionic groups, wherein the mixed textiles are treated with aqueous dispersions of the salts obtained from basic dyestuffs which are free from carboxylic acid and sulphonic acid groups with polynuclear aromatic sulphonic acids and subsequently, without intermediate rinsing, impregnated with solutions of direct dyestuffs which are fixed.
5. Process according to claim 1 wherein the salts of basic dyestuffs are on the azo series.
6. Process of claim 4 wherein the dyeings are fixed by steaming.
7. Process of claim 4 wherein the dyeings are fixed by the cold bath method.
1. In a process for dyeing anionically modified synthetic material selected from the class consisting of polyacrylonitrile containing internal anionic groups, polyamide containing internal anionic groups, polyesters containing internal anionic groups, and mixtures of said materials with other fiber materials, wherein the internal anionic groups are strong anionic groups that are attached to the internal portion of the molecular chains and are frequently repeated along the molecular chains, the improvement which comprises padding or printing said materials with aqueous dispersions containing the salt of a basic dyestuff which is free from carboxylic acid and sulfonic acid groups and a polynuclear aromatic sulfonic acid selected from the class consisting of diphenyl sulfonic acid, naphthalene di-, tri-, or tetrasulphonic acid, and pyrene tetrasulfonic acid, and subsequently subjecting the thus treated materials to a heat treatment.
2. Process according to claim 1 wherein the salts of basic dyestuffs are of the anthraquinone series.
3. Process according to claim 1 for the treatment of mixed textiles of cellulose and polyacrylonitrile containing anionic groups, wherein the mixed textiles are treated with aqueous dispersions of the salts obtained from basic dyestuffs which are free from carboxylic acid and sulphonic acid groups with polynuclear aromatic sulphonic acids, which also contain reactive dyestuffs, and that the reactive dyestuffs are fixed in the usual way.
4. Process according to claim 1 for the treatment of mixed textiles of cellulose and polyacrylonitrile containing anionic groups, wherein the mixed textiles are treated with aqueous dispersions of the salts obtained from basic dyestuffs which are free from carboxylic acid and sulphonic acid groups with polynuclear aromatic sulphonic acids and subsequently, without intermediate rinsing, impregnated with solutions of direct dyestuffs which are fixed.
5. Process according to claim 1 wherein the salts of basic dyestuffs are on the azo series.
6. Process of claim 4 wherein the dyeings are fixed by steaming.
7. Process of claim 4 wherein the dyeings are fixed by the cold bath method.
Description:
The subject-matter of the invention is a process for the dyeing or printing, especially the continuous dyeing or printing, of synthetic fibre materials of polyacrylonitrile, polyamides or polyesters which contain anionic groups, or of mixtures thereof with other fibre materials. The process is characterised by the use of aqueous dispersions of sparingly water-soluble salts obtained from basic dyestuffs which are free from carboxylic acid and sulphonic acid groups with polynuclear aromatic sulphonic acids.
The term "synthetic fibre materials containing anionic groups" refers to those materials which can be dyed with basic dyestuffs and contain anionic groups such as sulphonic acid, carboxylic acid, sulphimide or phosphonic acid groups. Suitable fibre materials are in particular, filaments, fabrics or knitted fabrics consisting of polyacrylonitrile or of copolymers of acrylonitrile with other vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl alcohol, acrylic and methacrylic acid esters and amides, such as are described, for example, in British Patent Nos. 823,345; 867,006; 902,074; 933,483 and in German Patent Nos. 1,222,056 and 1,260,074, or those consisting of acid-modified aromatic polyesters, for example, poly-condensation products obtained from terephthalic acid, sulphoterephthalic acid and ethylene glycol (type "Dacron 64" of E. I. Dupont de Nemours Co.), such as are described, for example, in Belgian Patent Specification No. 549,179 and U.S. Pat. No. 2,893,816, i.e. polyethylene glycol terephthalates containing sulphonic acid groups. Suitable fibre materials are, furthermore, those consisting of copolyether esters obtained from p-hydroxybenzoic acid, terephthalic acid and ethylene glycol, which are modified by carboxylic and/or sulphonic acid groups. Suitable fibre materials of polyamides are, for example, polyhexane-methylene-diamine adipate, polycaprolactam and poly-ω-amino-undecanic acid, modified by sulphonic acid groups.
Fibre mixtures which can be dyed or printed according to the process of the invention are, for example, those consisting of the above fibre materials which contain anionic groups, and of cotton, regenerated cellulose, wool and polyester fibres which contain no anionic groups, for example, those of terephthalic acid and 1,4-bis-hydroxymethyl-cyclohexane or ethylene glycol, and of non-acid-modified polyamide fibres, for example those of poly-caprolactam or polyamides obtained from hexamethylene-diamine and adipic acid.
The fibre material to be dyed may be a double or treble mixture, for example, in the form of mixed fabrics or mixed knitted fabrics consisting of the fibre material which contains anionic groups and of one or two of the aforesaid fibre materials which contain no anionic groups; the mixing ratio may vary within wide limits. Fibre mixtures which contain about 45 - 70 percent of fibre materials with anionic groups are especially suitable, for example.
Salts of basic dyestuffs which are suitable for the process according to the invention are the salts of basic dyestuffs which are free from carboxylic acid and sulphonic acid groups, with polynuclear aromatic mono-, di-, tri- or tetrasulphonic acids, especially those of the naphthalene series; the di-, tri- and tetrasulphonic acids should be specially mentioned because their salts are readily precipitated with the basic dyestuff, the ratio anion/cation in the salt is advantageous, and the non-fixed dyestuff particles are more easily washed out.
The following compounds are mentioned by way of example:
naphthalene-1-sulphonic acid, naphthalene-2-sulphonic acid, naphthalene-disulphonic acid-(1,4), naphthalene-disulphonic(1,5), naphthalene-disulphonic acid-(1,6), naphthalene-disulphonic acid-(2,5), naphthalene-disulphonic acid-(2,6), naphthalene-disulphonic acid-(2,7), naphthalene-trisulphonic acid-(1,3,5), naphthalene-trisulphonic acid-(1,3,6) or naphthalene-trisulphonic acid-(1,3,7), naphthalene-tetrasulphonic acid-(1,3,5,7) and pyrene-tetrasulphonic acid-(1,3,6,8).
The salts of the basic dyestuffs to be used according to the invention are prepared by reacting water-soluble basic dyestuff salts with the aforesaid organic sulphonic acids or their water-soluble salts, such as the sodium salts, in an aqueous medium; the sparingly water-soluble salts are thus precipitated and can be separated in the usual way.
Suitable water-soluble basic dyestuff salts are, for example, dyestuff bases which are quaternised on at least one aliphatically or cyclically bound nitrogen atom, for example, those of the azo, anthraquinone, phthalocyanine, methine, hydrazone, azacyanine, styryl, acridine or nitro series, as well as the carbonium salts of the di- and triphenylmethane series, the oxonium salts of the oxazine series or the sulphonium salts of the thiazine series.
The sparingly soluble dyestuff salts so obtained are formulated in the usual way, i.e. brought into the form suitable for application from an aqueous dispersion.
This conversion is carried out according to known processes, preferably by grinding with non-ionic and/or anionic dispersing agents.
Examples of non-ionic dispersing agents are the ethylene oxide products of fatty amines, fatty acids, fatty alcohols with a chain of about 12 - 20 carbon atoms; furthermore, ethylene oxide addition products of alkyl-phenols the alkyl chain of which contains 8 - 12 carbon atoms; as well as the ethylene oxide addition products of alkylaryl- or arylphenols with 7 - 50 mols ethylene oxide.
Examples of anionic dispersing agents are sodium alkylaryl sulphonates such as the sodium salts of di-n-butylnaphthalene-1-sulphonic acid, di-isobutylnaphthalene-sulphonic acid, dinaphthyl-methane-disulphonic acid; reaction products of cresol, 2-naphthol-sulphonic acid-(6) and formaldehyde; as well as products of sulphite waste liquor.
The proportion of dispersing agents to dyestuff salt depends on the dispersibility of the dyestuff salt and may vary within wide limits. The following proportions have proved particularly suitable:
100 parts of dyestuff salt
2 - 20 parts of non-ionic dispersing agent and/or
2 - 20 parts of anionic dispersing agent.
Concentrated aqueous preparations can be obtained from the dyestuff salts thus formulated by suitable mechanical comminution (colloidal mill, subsequently stirrer ball mill with grinding elements of glass with a diameter of 0.3 - 0.8 mm).
The subject-matter of the invention also comprises concentrated aqueous preparations of sparingly water-soluble salts obtained from basic dyestuffs which are free from carboxylic acid and sulphonic acid groups, with polynuclear aromatic sulphonic acids, said preparations containing about 15 - 50 percent by weight of dyestuff salt, about 0.3 - 20 percent by weight of a non-ionic dispersing agent, and about 0.3 - 5 percent by weight of an anionic dispersing agent.
In detail, the process according to the invention is carried out by padding the fibre materials on a foulard or printing them with aqueous dispersions of the sparingly soluble dyestuff salts to be used according to the invention and subsequently subjecting them, usually after an intermediate drying, to a heat treatment by means of hot air, contact heat or steam (thermosolisation) temperatures of about 180 to 230°C being applied.
The dyebaths are prepared from the sparingly soluble dyestuff salts in the usual way by stirring the dyestuff salts formulated as described above in water, optionally at an elevated temperature and optionally with the use of thickening agents, for example, those based on sodium alginate, cellulose ethers or polyacryloamide. In general, the quantity of thickening agent amounts to about 5 - 20 parts per 1000 parts of dyebath. The dyebath may moreover contain small amounts of organic or inorganic acids, such as formic acid or acetic acid, as well as sodium bisulphite or sodium dihydrogen phosphate. However, the pH value of the bath should not be below 4.
The dyestuff salts to be used according to the invention can also be applied together with anionic dyestuffs, such as acid, direct and reactive dyestuffs or non-ionic dyestuffs for dyeing mixed fabrics, for example, for the single-bath dyeing of mixed fabrics consisting of polyacrylonitrile or polyester fibres which contain anionic groups and of wool or cellulose fibres. When reactive dyestuffs are used, compounds of alkaline reaction, such as sodium bicarbonate or disodium hydrogen phosphate, may be added to the dyebaths. It is expedient to add sodium m-nitrobenzene sulphonate and butyrolactam to the baths in order to avoid overboiling.
If the sparingly soluble basic dyestuff salts and anionic dyestuffs are used simultaneously for the single-bath dyeing of mixed fabrics, fixation of the anionic dyestuffs on the fibre materials concerned is carried out previously or simultaneously, likewise by a thermal treatment, or in a second step, after passage through a second bath, for example, an alkaline padding bath, by means of steam or of an alkaline shock bath. However, fixation can also be carried out by prolonged storage at room temperature or elevated temperature. After fixation, the material is rinsed and dried. However, the process can also be carried out by applying the sparingly soluble basic dyestuff salt in a first bath and, after fixation and without intermediate rinsing, applying and fixing the anionic or non-ionic dyestuff in a second bath.
The basic dyestuff salts to be used according to the invention are generally applied in amounts of about 5 - 40 g/litre of dyebath. For the dyeing of mixed fabrics, it is recommended to adjust the amounts of acid, direct or reactive dyestuffs to be added to the proportion of the corresponding fibre component in the mixed fabric. For every part of basic dyestuff salt there should be used at the most 1 part of nonionic acid, direct or reactive dyestuff.
The acid which may be added usually amounts to about 1 - 30 g/litre of dyebath. The quantities of alkaline compounds which may also be added, for example, sodium bicarbonate or disodium hydrogen carbonate, amount to about 1 - 10 g/litre of dyebath.
With the aid of the process according to the invention it is possible to dye fibre materials containing anionic groups, and especially their mixtures with cellulose fibres, with short fixing times and, in particular, in a continuous process, with basic dyestuffs to obtain fast and level dyeings. A particular advantage of the process according to the invention over dyeing with water-soluble salts of basic dyestuffs consists in the improvement of the fixation yield and, when dyeing mixed fabrics, the improved reserve of the accompanying fibre component as well as the fact that the dyestuff particles which are not fixed and adhere to the accompanying fibre are more easily washed out. This is of particular importance when dyeing fibre mixtures of polyacrylonitrile and regenerated cellulose and must be considered as a precondition for producing continuous dyeings of equal laps on this material.
A further advantage of the process according to the invention is the improvement of the stability of the padding liquor during the single-bath dyeing with anionic dyestuffs, as well as an improvement of the fixation yield in the presence of anionic dyestuffs.
The parts given in the following Examples are parts by wieght. The dyestuff numbers refer to Colour Index, 2nd edition, Vol. III.
The terms polyacrylonitrile, polyamide and polyester materials refer to the corresponding anion-modified materials, unless otherwise stated.
EXAMPLE 1
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC1##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol o-hydroxydiphenyl with 14 mol ethylene oxide
1 part of the sodium salt of the condensation product of 2 mol naphthalene-2-sulphonic acid with 1 mol formaldehyde and
44 parts of water are mixed with
50 parts of a conventional acrylamide thickening agent and
930 parts of warm water, and the resultant padding liquor is padded on a foulard with a liquor absorption of 100 percent on to a polyacrylonitrile fabric. The fabric is subsequently dried at 120°C for 60 seconds and thermosolised on a stenter with hot air at 200°C for 90 seconds. The fabric is then rinsed first cold with overflow and then with change of baths at 70° - 100°C.
A red dyeing of good fastness properties is obtained. If the dyestuff is used in the form of the water-soluble methosulphate, a weaker and duller dyeing is obtained.
EXAMPLE 2
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC2##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of nonylphenol with 20 mols ethylene oxide
2 parts sodium lignin sulphonate and
110 parts of water are mixed with
10 parts of the reactive dyestuff of the formula ##SPC3##
60 parts urea
50 parts of an acrylamide thickening agent and
860 parts of warm water
and the resultant padding liquor is padded on a foulard with a liquor absorptiton of 100 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of staple fibre. The material is subsequently dried at 120°C for 60 seconds and thermosolised on a stenter with hot air at 200°C for 90 seconds. The fabric is then padded on a foulard with an alkali solution consisting of 50 g/litre sodium bicarbonate and 200 g/litre sodium sulphate, again with a liquor absorption of 100 percent, and steamed at 102°C for 90 seconds. The fabric is then rinsed first cold with overflow and then with change of baths at 70° - 100°C for 1 minute each time, and subsequently cold. A clear turquoise-blue dyeing is obtained.
If the basic dyestuff is used in the ionic water-soluble form, there is obtained a dyeing the staple fibre component of which is strongly soiled with basic dyestuff and very difficult to rinse clear, and which exhibits strongly unequal laps when dyed in a continuous operation.
EXAMPLE 3
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC4##
consisting of
30 parts of the dyestuff salt
2.4 parts of the condensation product of 1 mol methylstyryl-phenol with 50 mols ethylene oxide and
31.6 parts of water are mixed with
50 parts of an acrylamide thickening agent and
930 parts of warm water,
and the resultant padding liquor is padded with a liquor absorption of 100 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts polynosic rayon. The fabric is dried at 120°C for 60 seconds and thermosolised at 200°C by means of hot air for 90 seconds. The fabric is then padded on a foulard with a dyestuff solution consisting of 10 g/litre of the dyestuff of the formula ##SPC5##
and 20 g/litre sodium bicarbonate with a liquor absorption of 100 percent and, without drying, steamed at 102°C for 90 seconds; it is subsequently rinsed as described in Example 1.
A clear red dyeing of good fastness properties is obtained. If the basic dyestuff is used in the ionic water-soluble form, there is obtained a dull dyeing with a low yield; its shade changes with the washing conditions.
If the naphthalene-disulphonic acid-(2,5) is replaced with
naphthalene-disulphonic acid -(1,5)
naphthalene-disulphonic acid -(1,6)
naphthalene-disulphonic acid -(2,6)
naphthalene-disulphonic acid -(2,7)
or naphthalene-disulphonic acid -(1,4) then dyeings of the same good fastness properties are obtained.
EXAMPLE 4
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC6##
consisting of
30 parts of the dyestuff salt
3 parts of the reaction product of 1 mol oleyl alcohol with 25 mols ethylene oxide
1 parts of the reaction product of 2 mol 2-naphthol-6-sulphonic acid with 1 mol formaldehyde/bisulphite and
67 parts of water are mixed with
20 parts of the dyestuff of the formula ##SPC7##
50 parts of an acrylamide thickening and 910 parts of warm water, and the resultant padding liquor is padded on a foulard with a liquor absorption of 100 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of staple fibre. The fabric is then dried at 120°C for 90 seconds and steamed with saturated steam at 115°C for 120 seconds; subsequently it is dipped for 5 seconds into an alkali solution consisting of
200 parts sodium sulphate
50 parts sodium carbonate and
30 parts of a sodium hydroxide solution of density 1.35.
An intense blue dyeing of good fastness properties is obtained. If the basic dyestuff is used in the soluble form, there is obtained an unstable padding liquor and varying fixation results.
EXAMPLE 5
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC8##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol p-hydroxydiphenyl with 1 mol benzyl chloride and 14 mol ethylene oxide
2 parts of the condensation product of 2 mol naphthalene-2 -sulphonic acid with 1 mol formaldehyde and 56 parts of water
are mixed with
20 parts of the dyestuff of the formula ##SPC9##
and with
50 parts of a polyacrylamide thickening agent and
910 parts of warm water,
and the resultant padding liquor is padded on a foulard with a liquor absorption of 100 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of staple fibre. The fabric is then dried at 120°C for 90 seconds and thermosolised at 200°C by means of hot air for 90 seconds. The fabric is subsequently dipped for 5 seconds into an alkali solution which has been heated to 90°C and consists of
150 parts sodium sulphate
50 parts sodium carbonate and
30 parts of a sodium hydroxide solution of density 1.356.
An intense yellow dyeing of good fastness properties is obtained. If the basic dyestuff is used in its water-soluble ionic form, there is obtained an unstable padding liquor with varying fixation results.
EXAMPLE 6
10 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC10##
consisting of
30 parts of the dyestuff salt
3 parts of the reaction product of 1 mol p-hydroxydiphenyl with 1 mol benzyl chloride and 14 mol ethylene oxide and
67 parts of water are mixed with
50 parts of an acrylamide thickening agent and
940 parts of warm water,
and the resultant padding liquor is padded on a foulard with a liquor absorption of 80 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of staple fibre; the fabric is subsequently dried at 120°C for 60 seconds and thermosolised at 200°C for 90 seconds. The fabric is then padded on the foulard with a dyestuff solution consisting of
20 parts of the dyestuff No. 35,780
150 parts urea
1 part of a glycerol ether sulphate
1 part of an alginate thickening agent and
828 parts of water with a liquor absorption of 80 percent, rolled up and left to stand covered for 24 hours. It is subsequently rinsed first with overflow and then with change of baths at 60° - 80°C.
A clear red dyeing is obtained. If the basic dyestuff is used in its ionic water-soluble form, an expensive intermediate rinsing is necessary before application of the direct dyestuff, because the rinsing clear of the dyeing would otherwise encounter great difficulties.
If the dyestuff salt is formed with the use of naphthalene-trisulphone-(1,3,7), instead of naphthalene-trisulphonic acid-(1,3,6), an equally valuable dyeing is obtained.
EXAMPLE 7
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC11##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol p-hydroxydiphenyl with 1 mol benzyl chloride and 14 mol ethylene oxide
2 parts of the condensation product of 2 mol naphthalene-sulphonic acid-(1) with 1 mol formaldehyde and
56 parts of water
are mixed with
20 parts of the dyestuff of the formula ##SPC12##
and
50 parts of an acrylamide thickening agent and
910 parts of warm water,
and the resultant padding liquor is padded on a foulard with a liquor absorption of 100 percent on to a mixed fabric consisting of 55 parts polyacrylonitrile and 45 parts of wool. The impregnated fabric is dried at 90°C for 120 seconds and subsequently steamed at 102°C for 12 minutes. If steaming is carried out with saturated steam at 102° - 110°C, the steaming time can be reduced accordingly. After steaming, the fabric is soaped first cold with overflow, then with the use of an anion-active detergent at 70° - 100°C.
A clear orange dyeing is obtained.
If the basic dyestuff is used in its ionic dissolved form, staining precipitates occur in the padding bath and the dyeing obtained shows a strong soiling of the wool component.
EXAMPLE 8
15 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC13##
consisting of
30 parts of the reaction product of 1 mol oleyl alcohol with 50 mols ethylene oxide
1.5 parts sodium di-n-butylnaphthalene-1 -sulphonate and
65.5 parts of water
are mixed with
5 parts of a dispersion of the dyestuff of the formula ##SPC14##
consisting of
30 parts of the dyestuff
25 parts of a sulphite waste liquor product
25 parts of a reaction product of cresol, 2-naphthol-sulphonic acid and formaldehyde
40 parts of an acrylamide thickening agent and
940 parts of water.
The resultant padding liquor is padded on a foulard with a liquor absorption of 80 percent on to a mixed fabric consisting of 55 parts polyacrylonitrile, 37 parts of staple fibre and 8 parts of cellulose fibres. The fabric is subsequently dried at 120°C for 90 seconds and thermosolised at 180°C with hot air for 90 seconds. The fabric is subsequently padded on a foulard with a dyestuff solution consisting of
10 parts of the dyestuff of the formula ##SPC15##
20 parts urea
10 parts sodium bicarbonate
3 parts of an alginate thickening agent and
957 parts of water
with a liquor absorption of 80 percent and, without intermediate drying, steamed at 102°C for 90 seconds. After steaming, the fabric is first rinsed cold with overflow and then soaped at 60° - 90°C with change of baths and with the use of 2.5 parts of an anion-active detergent per 1000 parts of water. A clear red dyeing of good fastness properties is obtained. If the dyestuff is used in its soluble ionic form, a dull dyeing is obtained, which is difficult to wash out and the shade of which depends on the washing conditions.
EXAMPLE 9
10 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC16##
consisting of
35 parts of the dyestuff salt
3.5 parts of the reaction product of 1 mol methylstyryl-phenol and 50 mol ethylene oxide
2 parts sodium dinaphthyl-methane-disulphonic acid and
59.2 parts of water
are mixed with
10 parts of a dispersion of the dyestuff of the formula ##SPC17##
and
1 part of a dispersion of the dyestuff No. 12,790
each consisting of
15 parts of dyestuff and
85 parts of the reaction product of cresol, 2-naphthol-sulphonic acid-(6) and formaldehyde
50 parts of an acrylamide thickening agent and
929 parts of warm water.
The resultant padding liquor is padded on a foulard with a liquor absorption of 80 percent on to a mixed fabric consisting of 50 parts polyacrylonitrile and 50 parts of unmodified polyester fibre. The fabric is then dried at 120°C for 60 seconds and thermosolised at 200°C for 90 seconds. It is subsequently soaped first cold, then at 70° - 100°C with the use of nonionic or anion-active detergents. A clear blue dyeing is obtained.
If the basic dyestuff is used in its ionic water-soluble form, then a substantially weaker dyeing is obtained.
EXAMPLE 10
10 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC18##
with naphthalene-2-sulphonic acid consisting of
35 parts of the dyestuff salt
3.5 parts of the reaction product of 1 mol methylstyryl-phenol and 50 mol ethylene oxide
2 parts sodium dinaphthyl-methane-disulphonate and
59.5 parts of water are mixed with
12 parts of a sodium alginate thickening agent and
978 parts of water
and the liquid is padded on a foulard with a liquor absorption of 80 percent on to a fabric of anion-modified polyester. The fabric is then dried at 120°C for 60 seconds and thermosolised at 200°C for 90 seconds. The fabric is then rinsed first cold with overflow, then at 70° - 100°C with the use of 2 g/litre sodium alkyl-sulphonate.
A clear yellow dyeing is obtained. If the basic dyestuff is used in its soluble ionic form, then there is obtained a dyeing which is difficult to wash out.
EXAMPLE 11
15 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC19##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol o-hydroxydiphenyl with 14 mol ethylene oxide
1 part of the sodium salt of the condensation product of 2 mol naphthalene-2-sulphonic acid with 1 mol formaldehyde and
44 parts of water
are mixed with
5 parts of the dyestuff of the formula ##SPC20##
50 parts of an acrylamide thickening and
930 parts of water
and padded on a foulard with a squeezing effect of 80 percent on to a mixed fabric consisting of 70 parts of anion-modified polyester and 30 parts of cotton.
The fabric is then dried at 120°C for 60 seconds and thermosolised at 200°C for 90 seconds. It is then padded on a foulard with a solution consisting of
350 parts of calcined sodium carbonate
650 parts of water and
30 parts of a sodium hydroxide solution of density 1.35 and steamed for 5 minutes. Rinsing and soaping is carried out as described in Example 1. A level red dyeing is obtained. If the red dyestuff is used in its soluble form, the resulting dyeing is only weak by comparison.
EXAMPLE 12
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC21##
consisting of
30 parts of the dyestuff salt
2.4 parts of the condensation product of 1 mol methyl-styryl-phenol with 50 mol ethylene oxide and
31.6 parts of water
10 parts of the dyestuff of the formula ##SPC22##
40 parts urea and
1 part sodium m-nitrobenzene-sulphonate are mixed with
12 parts of a sodium alginate thickening and 917 parts of water
and the liquor is padded on the foulard with a liquor absorption of 80 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of cotton. The fabric is then dried at 120°C for 90 seconds and thermosolised at 200°C for 90 seconds. The fabric is subsequently padded on a foulard with a solution containing 70 g/litre sodium bicarbonate and 200 g/litre sodium sulphate. It is steamed at 102°C for 120 seconds, rinsed cold with overflow and subsequently soaped at 70° - 100°C with the use of 2 g/litre sodium paraffin-sulphonate. A clear red dyeing is obtained. If the basic dyestuff is used in its soluble form, then there is obtained a weaker dyeing the shade and colour strength of which depend on the washing conditions.
EXAMPLE 13
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC23##
consisting of
30 parts of the dyestuff salt
2.4 parts of the condensation product of 1 mol methyl-styryl-phenol with 50 mol ethylene oxide
31.6 parts of water
10 parts of the dyestuff of the formula ##SPC24##
40 parts urea
1 part sodium m-nitrobenzene-sulphonate are mixed with
12 parts of a sodium alginate thickening agent and
917 parts of water and padded on a foulard with a liquor absorption of 100 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of staple fibre. The fabric is then dried at 120°C for 60 seconds and steamed with pressurized steam at 115°C for 2 minutes. The fabric is subsequently padded on a foulard with a solution consisting of
350 parts of calcined sodium carbonate
30 parts of a sodium hydroxide solution of density 1.35
650 parts of water and, after an air passage of 60 seconds, allowed to stand at room temperature for 3 hours. The fabric is rinsed and soaped as described in Example 1. A clear red dyeing is obtained.
If the basic dyestuff is used in its ionic soluble form, precipitates are formed in the dyebath, which lead to blotchy dyeings.
EXAMPLE 14
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC25##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol o-hydroxydiphenyl with 14 mol ethylene oxide
1 part of the sodium salt of the condensation product of 2 mol naphthalene-2-sulphonic acid with 1 mol formaldehyde and
44 parts of water
are mixed with
10 parts of the dyestuff No. 19.935 and
970 parts of water
and padded on a foulard on to a mixed fabric consisting of 60 parts of anion-modified polyamide and 40 parts of acid-modified polyamide. The fabric is subsequently dried at 120°C for 90 seconds and then steamed with pressurized steam at 115°C for 5 minutes. It is rinsed with water at 70°C for 5 minutes. A clear bicolour dyeing is obtained.
EXAMPLE 15
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula v,135/20
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol p-hydroxydiphenyl with 14 mol ethylene oxide
1 part of the sodium salt of the condensation product of 2 mol naphthalene-2-sulphonic acid with 1 mol formaldehyde and
44 parts of water
are mixed with
10 parts of the dyestuff of the formula ##SPC26##
5 parts sodium bicarbonate
50 parts urea
5 parts butyrolactam and
910 parts of water and padded on a foulard on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of cotton. The fabric is dried at 120°C for 2 minutes and then thermosolised at 200°C for 90 seconds. The material is rinsed and soaped as described in Example 1. A level red dyeing is obtained.
If the basic dyestuff is used in the water-soluble ionic form, then a substantially weaker dyeing is obtained.
EXAMPLE 16
25 Parts of the dispersion of dyestuff salt described in Example 5, part 1 are stirred into
975 parts of a thickening agent consisting of
300 parts of a 10% starch ether thickening
300 parts of a 40% British gum thickening
20 parts of 30% acetic acid
20 parts thio-diethylene glycol
10 parts N,N-bis-(p-cyanoethyl)-formamide
5 parts citric acid
345 parts of water 1000 parts of thickening agent
This printing paste is applied to a fabric of polyester fibres and the dyestuff is fixed by a thermosol process (at 190°C for 4 seconds); the fabric is subsequently rinsed and soaped. A yellow print is obtained which is substantially clearer and stronger than the print obtained when the dyestuff is used in its ionic water-soluble form.
EXAMPLE 17
25 parts of a 1:1 mixture of the dispersion of dyestuff salt described in Example 5, part 1, and the dyestuff dispersion described in Example 9
are stirred into
975 parts of the thickening agent described in Example 6.
The printing pastes so obtained are applied to a
fabric of polyacrylonitrile fibres in the usual way by screen or rouleaux printing, and the dyestuffs are fixed by a thermosol process (190°C for 40 seconds); the fabric is subsequently rinsed and soaped. An intense green print is obtained the yield of which is appreciably better as in the case where the dyestuffs are used in their ionic water-soluble form.
EXAMPLE 18
The printing pastes according to Example 17 are printed on to a polyester fabric and the dyestuff fixed by thermosolisation (190°C for 40 seconds), the fabric is subsequently rinsed and soaped. The print obtained is appreciably clearer and deeper as in the case where the dyestuffs are used in their ionic water-soluble form.
EXAMPLE 19
35 Parts of the dyestuff dispersion described in Example 1 are stirred into
965 parts of the thickening agent described in Example 16.
The printing paste is applied to a fabric of polyacrylonitrile fibres and the dyestuff is fixed by steaming under 0.4 atm. excess pressure for 20 minutes; the fabric is subsequently rinsed and soaped. A level and smooth print is obtained, whereas the print obtained with the use of the dyestuff in its ionic water-soluble form is uneven and blotchy.
EXAMPLE 20
Preparation of the dyestuff salts
75 Parts of the dyestuff of the formula ##SPC27##
are dissolved in
750 parts of water at 70°C. A solution of
100 parts of the sodium salt of naphthalene-1-sulphonic acid in
1000 parts of water, likewise at 70°C, is added thereto with good stirring within 15 minutes until precipitation no longer occurs. Stirring is continued for one-half hour and the mixture is then cooled to 20°C. The precipitated red dyestuff salt is filtered off with suction, washed with water until free from electrolyte, and dried.
Yield: 100 parts of the dyestuff salt of the formula ##SPC28##
All the sparingly soluble basic dyestuff salts to be used according to the invention can be obtained in an analogous manner with the use of the corresponding water-soluble basic dyestuff salts and the corresponding aromatic sulphonic acids or their salts.
EXAMPLE 21
1.2 Parts of an aqueous dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC29##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol o-hydroxydiphenyl with 14 mol ethylene oxide
1 part of the sodium salt of the condensation product of 2 mol naphthalene-2-sulphonic acid with 1 mol formaldehyde and
44 parts of water
are mixed with
80 parts of water at 50°C
and combined with a solution of
0.8 parts of the dyestuff No. 35,780
50 parts of anhydrous sodium sulphate
1 part of the reaction product of 1 mol oleyl alcohol with 50 mol ethylene oxide
2 parts of a polyphosphate giving a pH value of 4.8 in
865 parts of water at 40°C.
100 parts of a fabric consisting of
40 parts of staple fibre and
60 parts polyacrylonitrile are introduced into the above dyebath and the bath is heated with vivid circulation to boiling temperatures within 30 minutes. After dyeing at this temperature for 60 minutes, the bath is cooled to 60°C,
5 parts sodium carbonate and
15 parts sodium bicarbonate
are then added and dyeing is continued at this temperature for 60 minutes. After this period of time the fabric is rinsed, first only with an overflow of cold water, subsequently with a hot solution of 2 parts sodium alkyl sulphonate in 988 parts of water.
A clear blue-red mixed dyeing is obtained; if the basic dyestuff is used in the non-formulated form, the staple fibre is appreciably more soiled.
EXAMPLE 22
1 Part of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC30##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol p-hydroxydiphenyl with 1 mol benzyl chloride and 14 mol ethylene oxide
2 parts of the condensation product of 2 mol naphthalene-2-sulphonic acid with 1 mol formaldehyde and
56 parts of water are mixed with
80 parts of water at 50°C and then with a solution of
1 part of the copper complex of the dyestuff of the formula ##SPC31##
2 parts of a sodium polyphosphate which yields a pH value of 5.5
1 part of the reaction product of 1 mol oleyl alcohol with 50 mol ethylene oxide and
10 parts sodium sulphate in 905 parts of water.
100 Parts of a mixed yarn consisting of
50 parts polyacrylonitrile and
50 parts of cotton
are introduced into the resultant dyebath and the bath is heated with vivid circulation to 90°C within 30 minutes. After dyeing at this temperature for 90 minutes, the bath is cooled to 40°C and the fabric is rinsed with a hot solution of 2 parts sodium alkylsulphate in 988 parts of water.
A differentiated red-yellow mixed yarn is obtained. If the dyestuff is used in the non-formulated form, precipitations occur and the cotton yarn is dyed with red dyestuff.
The term "synthetic fibre materials containing anionic groups" refers to those materials which can be dyed with basic dyestuffs and contain anionic groups such as sulphonic acid, carboxylic acid, sulphimide or phosphonic acid groups. Suitable fibre materials are in particular, filaments, fabrics or knitted fabrics consisting of polyacrylonitrile or of copolymers of acrylonitrile with other vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl alcohol, acrylic and methacrylic acid esters and amides, such as are described, for example, in British Patent Nos. 823,345; 867,006; 902,074; 933,483 and in German Patent Nos. 1,222,056 and 1,260,074, or those consisting of acid-modified aromatic polyesters, for example, poly-condensation products obtained from terephthalic acid, sulphoterephthalic acid and ethylene glycol (type "Dacron 64" of E. I. Dupont de Nemours Co.), such as are described, for example, in Belgian Patent Specification No. 549,179 and U.S. Pat. No. 2,893,816, i.e. polyethylene glycol terephthalates containing sulphonic acid groups. Suitable fibre materials are, furthermore, those consisting of copolyether esters obtained from p-hydroxybenzoic acid, terephthalic acid and ethylene glycol, which are modified by carboxylic and/or sulphonic acid groups. Suitable fibre materials of polyamides are, for example, polyhexane-methylene-diamine adipate, polycaprolactam and poly-ω-amino-undecanic acid, modified by sulphonic acid groups.
Fibre mixtures which can be dyed or printed according to the process of the invention are, for example, those consisting of the above fibre materials which contain anionic groups, and of cotton, regenerated cellulose, wool and polyester fibres which contain no anionic groups, for example, those of terephthalic acid and 1,4-bis-hydroxymethyl-cyclohexane or ethylene glycol, and of non-acid-modified polyamide fibres, for example those of poly-caprolactam or polyamides obtained from hexamethylene-diamine and adipic acid.
The fibre material to be dyed may be a double or treble mixture, for example, in the form of mixed fabrics or mixed knitted fabrics consisting of the fibre material which contains anionic groups and of one or two of the aforesaid fibre materials which contain no anionic groups; the mixing ratio may vary within wide limits. Fibre mixtures which contain about 45 - 70 percent of fibre materials with anionic groups are especially suitable, for example.
Salts of basic dyestuffs which are suitable for the process according to the invention are the salts of basic dyestuffs which are free from carboxylic acid and sulphonic acid groups, with polynuclear aromatic mono-, di-, tri- or tetrasulphonic acids, especially those of the naphthalene series; the di-, tri- and tetrasulphonic acids should be specially mentioned because their salts are readily precipitated with the basic dyestuff, the ratio anion/cation in the salt is advantageous, and the non-fixed dyestuff particles are more easily washed out.
The following compounds are mentioned by way of example:
naphthalene-1-sulphonic acid, naphthalene-2-sulphonic acid, naphthalene-disulphonic acid-(1,4), naphthalene-disulphonic(1,5), naphthalene-disulphonic acid-(1,6), naphthalene-disulphonic acid-(2,5), naphthalene-disulphonic acid-(2,6), naphthalene-disulphonic acid-(2,7), naphthalene-trisulphonic acid-(1,3,5), naphthalene-trisulphonic acid-(1,3,6) or naphthalene-trisulphonic acid-(1,3,7), naphthalene-tetrasulphonic acid-(1,3,5,7) and pyrene-tetrasulphonic acid-(1,3,6,8).
The salts of the basic dyestuffs to be used according to the invention are prepared by reacting water-soluble basic dyestuff salts with the aforesaid organic sulphonic acids or their water-soluble salts, such as the sodium salts, in an aqueous medium; the sparingly water-soluble salts are thus precipitated and can be separated in the usual way.
Suitable water-soluble basic dyestuff salts are, for example, dyestuff bases which are quaternised on at least one aliphatically or cyclically bound nitrogen atom, for example, those of the azo, anthraquinone, phthalocyanine, methine, hydrazone, azacyanine, styryl, acridine or nitro series, as well as the carbonium salts of the di- and triphenylmethane series, the oxonium salts of the oxazine series or the sulphonium salts of the thiazine series.
The sparingly soluble dyestuff salts so obtained are formulated in the usual way, i.e. brought into the form suitable for application from an aqueous dispersion.
This conversion is carried out according to known processes, preferably by grinding with non-ionic and/or anionic dispersing agents.
Examples of non-ionic dispersing agents are the ethylene oxide products of fatty amines, fatty acids, fatty alcohols with a chain of about 12 - 20 carbon atoms; furthermore, ethylene oxide addition products of alkyl-phenols the alkyl chain of which contains 8 - 12 carbon atoms; as well as the ethylene oxide addition products of alkylaryl- or arylphenols with 7 - 50 mols ethylene oxide.
Examples of anionic dispersing agents are sodium alkylaryl sulphonates such as the sodium salts of di-n-butylnaphthalene-1-sulphonic acid, di-isobutylnaphthalene-sulphonic acid, dinaphthyl-methane-disulphonic acid; reaction products of cresol, 2-naphthol-sulphonic acid-(6) and formaldehyde; as well as products of sulphite waste liquor.
The proportion of dispersing agents to dyestuff salt depends on the dispersibility of the dyestuff salt and may vary within wide limits. The following proportions have proved particularly suitable:
100 parts of dyestuff salt
2 - 20 parts of non-ionic dispersing agent and/or
2 - 20 parts of anionic dispersing agent.
Concentrated aqueous preparations can be obtained from the dyestuff salts thus formulated by suitable mechanical comminution (colloidal mill, subsequently stirrer ball mill with grinding elements of glass with a diameter of 0.3 - 0.8 mm).
The subject-matter of the invention also comprises concentrated aqueous preparations of sparingly water-soluble salts obtained from basic dyestuffs which are free from carboxylic acid and sulphonic acid groups, with polynuclear aromatic sulphonic acids, said preparations containing about 15 - 50 percent by weight of dyestuff salt, about 0.3 - 20 percent by weight of a non-ionic dispersing agent, and about 0.3 - 5 percent by weight of an anionic dispersing agent.
In detail, the process according to the invention is carried out by padding the fibre materials on a foulard or printing them with aqueous dispersions of the sparingly soluble dyestuff salts to be used according to the invention and subsequently subjecting them, usually after an intermediate drying, to a heat treatment by means of hot air, contact heat or steam (thermosolisation) temperatures of about 180 to 230°C being applied.
The dyebaths are prepared from the sparingly soluble dyestuff salts in the usual way by stirring the dyestuff salts formulated as described above in water, optionally at an elevated temperature and optionally with the use of thickening agents, for example, those based on sodium alginate, cellulose ethers or polyacryloamide. In general, the quantity of thickening agent amounts to about 5 - 20 parts per 1000 parts of dyebath. The dyebath may moreover contain small amounts of organic or inorganic acids, such as formic acid or acetic acid, as well as sodium bisulphite or sodium dihydrogen phosphate. However, the pH value of the bath should not be below 4.
The dyestuff salts to be used according to the invention can also be applied together with anionic dyestuffs, such as acid, direct and reactive dyestuffs or non-ionic dyestuffs for dyeing mixed fabrics, for example, for the single-bath dyeing of mixed fabrics consisting of polyacrylonitrile or polyester fibres which contain anionic groups and of wool or cellulose fibres. When reactive dyestuffs are used, compounds of alkaline reaction, such as sodium bicarbonate or disodium hydrogen phosphate, may be added to the dyebaths. It is expedient to add sodium m-nitrobenzene sulphonate and butyrolactam to the baths in order to avoid overboiling.
If the sparingly soluble basic dyestuff salts and anionic dyestuffs are used simultaneously for the single-bath dyeing of mixed fabrics, fixation of the anionic dyestuffs on the fibre materials concerned is carried out previously or simultaneously, likewise by a thermal treatment, or in a second step, after passage through a second bath, for example, an alkaline padding bath, by means of steam or of an alkaline shock bath. However, fixation can also be carried out by prolonged storage at room temperature or elevated temperature. After fixation, the material is rinsed and dried. However, the process can also be carried out by applying the sparingly soluble basic dyestuff salt in a first bath and, after fixation and without intermediate rinsing, applying and fixing the anionic or non-ionic dyestuff in a second bath.
The basic dyestuff salts to be used according to the invention are generally applied in amounts of about 5 - 40 g/litre of dyebath. For the dyeing of mixed fabrics, it is recommended to adjust the amounts of acid, direct or reactive dyestuffs to be added to the proportion of the corresponding fibre component in the mixed fabric. For every part of basic dyestuff salt there should be used at the most 1 part of nonionic acid, direct or reactive dyestuff.
The acid which may be added usually amounts to about 1 - 30 g/litre of dyebath. The quantities of alkaline compounds which may also be added, for example, sodium bicarbonate or disodium hydrogen carbonate, amount to about 1 - 10 g/litre of dyebath.
With the aid of the process according to the invention it is possible to dye fibre materials containing anionic groups, and especially their mixtures with cellulose fibres, with short fixing times and, in particular, in a continuous process, with basic dyestuffs to obtain fast and level dyeings. A particular advantage of the process according to the invention over dyeing with water-soluble salts of basic dyestuffs consists in the improvement of the fixation yield and, when dyeing mixed fabrics, the improved reserve of the accompanying fibre component as well as the fact that the dyestuff particles which are not fixed and adhere to the accompanying fibre are more easily washed out. This is of particular importance when dyeing fibre mixtures of polyacrylonitrile and regenerated cellulose and must be considered as a precondition for producing continuous dyeings of equal laps on this material.
A further advantage of the process according to the invention is the improvement of the stability of the padding liquor during the single-bath dyeing with anionic dyestuffs, as well as an improvement of the fixation yield in the presence of anionic dyestuffs.
The parts given in the following Examples are parts by wieght. The dyestuff numbers refer to Colour Index, 2nd edition, Vol. III.
The terms polyacrylonitrile, polyamide and polyester materials refer to the corresponding anion-modified materials, unless otherwise stated.
EXAMPLE 1
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC1##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol o-hydroxydiphenyl with 14 mol ethylene oxide
1 part of the sodium salt of the condensation product of 2 mol naphthalene-2-sulphonic acid with 1 mol formaldehyde and
44 parts of water are mixed with
50 parts of a conventional acrylamide thickening agent and
930 parts of warm water, and the resultant padding liquor is padded on a foulard with a liquor absorption of 100 percent on to a polyacrylonitrile fabric. The fabric is subsequently dried at 120°C for 60 seconds and thermosolised on a stenter with hot air at 200°C for 90 seconds. The fabric is then rinsed first cold with overflow and then with change of baths at 70° - 100°C.
A red dyeing of good fastness properties is obtained. If the dyestuff is used in the form of the water-soluble methosulphate, a weaker and duller dyeing is obtained.
EXAMPLE 2
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC2##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of nonylphenol with 20 mols ethylene oxide
2 parts sodium lignin sulphonate and
110 parts of water are mixed with
10 parts of the reactive dyestuff of the formula ##SPC3##
60 parts urea
50 parts of an acrylamide thickening agent and
860 parts of warm water
and the resultant padding liquor is padded on a foulard with a liquor absorptiton of 100 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of staple fibre. The material is subsequently dried at 120°C for 60 seconds and thermosolised on a stenter with hot air at 200°C for 90 seconds. The fabric is then padded on a foulard with an alkali solution consisting of 50 g/litre sodium bicarbonate and 200 g/litre sodium sulphate, again with a liquor absorption of 100 percent, and steamed at 102°C for 90 seconds. The fabric is then rinsed first cold with overflow and then with change of baths at 70° - 100°C for 1 minute each time, and subsequently cold. A clear turquoise-blue dyeing is obtained.
If the basic dyestuff is used in the ionic water-soluble form, there is obtained a dyeing the staple fibre component of which is strongly soiled with basic dyestuff and very difficult to rinse clear, and which exhibits strongly unequal laps when dyed in a continuous operation.
EXAMPLE 3
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC4##
consisting of
30 parts of the dyestuff salt
2.4 parts of the condensation product of 1 mol methylstyryl-phenol with 50 mols ethylene oxide and
31.6 parts of water are mixed with
50 parts of an acrylamide thickening agent and
930 parts of warm water,
and the resultant padding liquor is padded with a liquor absorption of 100 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts polynosic rayon. The fabric is dried at 120°C for 60 seconds and thermosolised at 200°C by means of hot air for 90 seconds. The fabric is then padded on a foulard with a dyestuff solution consisting of 10 g/litre of the dyestuff of the formula ##SPC5##
and 20 g/litre sodium bicarbonate with a liquor absorption of 100 percent and, without drying, steamed at 102°C for 90 seconds; it is subsequently rinsed as described in Example 1.
A clear red dyeing of good fastness properties is obtained. If the basic dyestuff is used in the ionic water-soluble form, there is obtained a dull dyeing with a low yield; its shade changes with the washing conditions.
If the naphthalene-disulphonic acid-(2,5) is replaced with
naphthalene-disulphonic acid -(1,5)
naphthalene-disulphonic acid -(1,6)
naphthalene-disulphonic acid -(2,6)
naphthalene-disulphonic acid -(2,7)
or naphthalene-disulphonic acid -(1,4) then dyeings of the same good fastness properties are obtained.
EXAMPLE 4
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC6##
consisting of
30 parts of the dyestuff salt
3 parts of the reaction product of 1 mol oleyl alcohol with 25 mols ethylene oxide
1 parts of the reaction product of 2 mol 2-naphthol-6-sulphonic acid with 1 mol formaldehyde/bisulphite and
67 parts of water are mixed with
20 parts of the dyestuff of the formula ##SPC7##
50 parts of an acrylamide thickening and 910 parts of warm water, and the resultant padding liquor is padded on a foulard with a liquor absorption of 100 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of staple fibre. The fabric is then dried at 120°C for 90 seconds and steamed with saturated steam at 115°C for 120 seconds; subsequently it is dipped for 5 seconds into an alkali solution consisting of
200 parts sodium sulphate
50 parts sodium carbonate and
30 parts of a sodium hydroxide solution of density 1.35.
An intense blue dyeing of good fastness properties is obtained. If the basic dyestuff is used in the soluble form, there is obtained an unstable padding liquor and varying fixation results.
EXAMPLE 5
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC8##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol p-hydroxydiphenyl with 1 mol benzyl chloride and 14 mol ethylene oxide
2 parts of the condensation product of 2 mol naphthalene-2 -sulphonic acid with 1 mol formaldehyde and 56 parts of water
are mixed with
20 parts of the dyestuff of the formula ##SPC9##
and with
50 parts of a polyacrylamide thickening agent and
910 parts of warm water,
and the resultant padding liquor is padded on a foulard with a liquor absorption of 100 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of staple fibre. The fabric is then dried at 120°C for 90 seconds and thermosolised at 200°C by means of hot air for 90 seconds. The fabric is subsequently dipped for 5 seconds into an alkali solution which has been heated to 90°C and consists of
150 parts sodium sulphate
50 parts sodium carbonate and
30 parts of a sodium hydroxide solution of density 1.356.
An intense yellow dyeing of good fastness properties is obtained. If the basic dyestuff is used in its water-soluble ionic form, there is obtained an unstable padding liquor with varying fixation results.
EXAMPLE 6
10 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC10##
consisting of
30 parts of the dyestuff salt
3 parts of the reaction product of 1 mol p-hydroxydiphenyl with 1 mol benzyl chloride and 14 mol ethylene oxide and
67 parts of water are mixed with
50 parts of an acrylamide thickening agent and
940 parts of warm water,
and the resultant padding liquor is padded on a foulard with a liquor absorption of 80 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of staple fibre; the fabric is subsequently dried at 120°C for 60 seconds and thermosolised at 200°C for 90 seconds. The fabric is then padded on the foulard with a dyestuff solution consisting of
20 parts of the dyestuff No. 35,780
150 parts urea
1 part of a glycerol ether sulphate
1 part of an alginate thickening agent and
828 parts of water with a liquor absorption of 80 percent, rolled up and left to stand covered for 24 hours. It is subsequently rinsed first with overflow and then with change of baths at 60° - 80°C.
A clear red dyeing is obtained. If the basic dyestuff is used in its ionic water-soluble form, an expensive intermediate rinsing is necessary before application of the direct dyestuff, because the rinsing clear of the dyeing would otherwise encounter great difficulties.
If the dyestuff salt is formed with the use of naphthalene-trisulphone-(1,3,7), instead of naphthalene-trisulphonic acid-(1,3,6), an equally valuable dyeing is obtained.
EXAMPLE 7
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC11##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol p-hydroxydiphenyl with 1 mol benzyl chloride and 14 mol ethylene oxide
2 parts of the condensation product of 2 mol naphthalene-sulphonic acid-(1) with 1 mol formaldehyde and
56 parts of water
are mixed with
20 parts of the dyestuff of the formula ##SPC12##
and
50 parts of an acrylamide thickening agent and
910 parts of warm water,
and the resultant padding liquor is padded on a foulard with a liquor absorption of 100 percent on to a mixed fabric consisting of 55 parts polyacrylonitrile and 45 parts of wool. The impregnated fabric is dried at 90°C for 120 seconds and subsequently steamed at 102°C for 12 minutes. If steaming is carried out with saturated steam at 102° - 110°C, the steaming time can be reduced accordingly. After steaming, the fabric is soaped first cold with overflow, then with the use of an anion-active detergent at 70° - 100°C.
A clear orange dyeing is obtained.
If the basic dyestuff is used in its ionic dissolved form, staining precipitates occur in the padding bath and the dyeing obtained shows a strong soiling of the wool component.
EXAMPLE 8
15 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC13##
consisting of
30 parts of the reaction product of 1 mol oleyl alcohol with 50 mols ethylene oxide
1.5 parts sodium di-n-butylnaphthalene-1 -sulphonate and
65.5 parts of water
are mixed with
5 parts of a dispersion of the dyestuff of the formula ##SPC14##
consisting of
30 parts of the dyestuff
25 parts of a sulphite waste liquor product
25 parts of a reaction product of cresol, 2-naphthol-sulphonic acid and formaldehyde
40 parts of an acrylamide thickening agent and
940 parts of water.
The resultant padding liquor is padded on a foulard with a liquor absorption of 80 percent on to a mixed fabric consisting of 55 parts polyacrylonitrile, 37 parts of staple fibre and 8 parts of cellulose fibres. The fabric is subsequently dried at 120°C for 90 seconds and thermosolised at 180°C with hot air for 90 seconds. The fabric is subsequently padded on a foulard with a dyestuff solution consisting of
10 parts of the dyestuff of the formula ##SPC15##
20 parts urea
10 parts sodium bicarbonate
3 parts of an alginate thickening agent and
957 parts of water
with a liquor absorption of 80 percent and, without intermediate drying, steamed at 102°C for 90 seconds. After steaming, the fabric is first rinsed cold with overflow and then soaped at 60° - 90°C with change of baths and with the use of 2.5 parts of an anion-active detergent per 1000 parts of water. A clear red dyeing of good fastness properties is obtained. If the dyestuff is used in its soluble ionic form, a dull dyeing is obtained, which is difficult to wash out and the shade of which depends on the washing conditions.
EXAMPLE 9
10 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC16##
consisting of
35 parts of the dyestuff salt
3.5 parts of the reaction product of 1 mol methylstyryl-phenol and 50 mol ethylene oxide
2 parts sodium dinaphthyl-methane-disulphonic acid and
59.2 parts of water
are mixed with
10 parts of a dispersion of the dyestuff of the formula ##SPC17##
and
1 part of a dispersion of the dyestuff No. 12,790
each consisting of
15 parts of dyestuff and
85 parts of the reaction product of cresol, 2-naphthol-sulphonic acid-(6) and formaldehyde
50 parts of an acrylamide thickening agent and
929 parts of warm water.
The resultant padding liquor is padded on a foulard with a liquor absorption of 80 percent on to a mixed fabric consisting of 50 parts polyacrylonitrile and 50 parts of unmodified polyester fibre. The fabric is then dried at 120°C for 60 seconds and thermosolised at 200°C for 90 seconds. It is subsequently soaped first cold, then at 70° - 100°C with the use of nonionic or anion-active detergents. A clear blue dyeing is obtained.
If the basic dyestuff is used in its ionic water-soluble form, then a substantially weaker dyeing is obtained.
EXAMPLE 10
10 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC18##
with naphthalene-2-sulphonic acid consisting of
35 parts of the dyestuff salt
3.5 parts of the reaction product of 1 mol methylstyryl-phenol and 50 mol ethylene oxide
2 parts sodium dinaphthyl-methane-disulphonate and
59.5 parts of water are mixed with
12 parts of a sodium alginate thickening agent and
978 parts of water
and the liquid is padded on a foulard with a liquor absorption of 80 percent on to a fabric of anion-modified polyester. The fabric is then dried at 120°C for 60 seconds and thermosolised at 200°C for 90 seconds. The fabric is then rinsed first cold with overflow, then at 70° - 100°C with the use of 2 g/litre sodium alkyl-sulphonate.
A clear yellow dyeing is obtained. If the basic dyestuff is used in its soluble ionic form, then there is obtained a dyeing which is difficult to wash out.
EXAMPLE 11
15 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC19##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol o-hydroxydiphenyl with 14 mol ethylene oxide
1 part of the sodium salt of the condensation product of 2 mol naphthalene-2-sulphonic acid with 1 mol formaldehyde and
44 parts of water
are mixed with
5 parts of the dyestuff of the formula ##SPC20##
50 parts of an acrylamide thickening and
930 parts of water
and padded on a foulard with a squeezing effect of 80 percent on to a mixed fabric consisting of 70 parts of anion-modified polyester and 30 parts of cotton.
The fabric is then dried at 120°C for 60 seconds and thermosolised at 200°C for 90 seconds. It is then padded on a foulard with a solution consisting of
350 parts of calcined sodium carbonate
650 parts of water and
30 parts of a sodium hydroxide solution of density 1.35 and steamed for 5 minutes. Rinsing and soaping is carried out as described in Example 1. A level red dyeing is obtained. If the red dyestuff is used in its soluble form, the resulting dyeing is only weak by comparison.
EXAMPLE 12
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC21##
consisting of
30 parts of the dyestuff salt
2.4 parts of the condensation product of 1 mol methyl-styryl-phenol with 50 mol ethylene oxide and
31.6 parts of water
10 parts of the dyestuff of the formula ##SPC22##
40 parts urea and
1 part sodium m-nitrobenzene-sulphonate are mixed with
12 parts of a sodium alginate thickening and 917 parts of water
and the liquor is padded on the foulard with a liquor absorption of 80 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of cotton. The fabric is then dried at 120°C for 90 seconds and thermosolised at 200°C for 90 seconds. The fabric is subsequently padded on a foulard with a solution containing 70 g/litre sodium bicarbonate and 200 g/litre sodium sulphate. It is steamed at 102°C for 120 seconds, rinsed cold with overflow and subsequently soaped at 70° - 100°C with the use of 2 g/litre sodium paraffin-sulphonate. A clear red dyeing is obtained. If the basic dyestuff is used in its soluble form, then there is obtained a weaker dyeing the shade and colour strength of which depend on the washing conditions.
EXAMPLE 13
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC23##
consisting of
30 parts of the dyestuff salt
2.4 parts of the condensation product of 1 mol methyl-styryl-phenol with 50 mol ethylene oxide
31.6 parts of water
10 parts of the dyestuff of the formula ##SPC24##
40 parts urea
1 part sodium m-nitrobenzene-sulphonate are mixed with
12 parts of a sodium alginate thickening agent and
917 parts of water and padded on a foulard with a liquor absorption of 100 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of staple fibre. The fabric is then dried at 120°C for 60 seconds and steamed with pressurized steam at 115°C for 2 minutes. The fabric is subsequently padded on a foulard with a solution consisting of
350 parts of calcined sodium carbonate
30 parts of a sodium hydroxide solution of density 1.35
650 parts of water and, after an air passage of 60 seconds, allowed to stand at room temperature for 3 hours. The fabric is rinsed and soaped as described in Example 1. A clear red dyeing is obtained.
If the basic dyestuff is used in its ionic soluble form, precipitates are formed in the dyebath, which lead to blotchy dyeings.
EXAMPLE 14
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC25##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol o-hydroxydiphenyl with 14 mol ethylene oxide
1 part of the sodium salt of the condensation product of 2 mol naphthalene-2-sulphonic acid with 1 mol formaldehyde and
44 parts of water
are mixed with
10 parts of the dyestuff No. 19.935 and
970 parts of water
and padded on a foulard on to a mixed fabric consisting of 60 parts of anion-modified polyamide and 40 parts of acid-modified polyamide. The fabric is subsequently dried at 120°C for 90 seconds and then steamed with pressurized steam at 115°C for 5 minutes. It is rinsed with water at 70°C for 5 minutes. A clear bicolour dyeing is obtained.
EXAMPLE 15
20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula v,135/20
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol p-hydroxydiphenyl with 14 mol ethylene oxide
1 part of the sodium salt of the condensation product of 2 mol naphthalene-2-sulphonic acid with 1 mol formaldehyde and
44 parts of water
are mixed with
10 parts of the dyestuff of the formula ##SPC26##
5 parts sodium bicarbonate
50 parts urea
5 parts butyrolactam and
910 parts of water and padded on a foulard on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of cotton. The fabric is dried at 120°C for 2 minutes and then thermosolised at 200°C for 90 seconds. The material is rinsed and soaped as described in Example 1. A level red dyeing is obtained.
If the basic dyestuff is used in the water-soluble ionic form, then a substantially weaker dyeing is obtained.
EXAMPLE 16
25 Parts of the dispersion of dyestuff salt described in Example 5, part 1 are stirred into
975 parts of a thickening agent consisting of
300 parts of a 10% starch ether thickening
300 parts of a 40% British gum thickening
20 parts of 30% acetic acid
20 parts thio-diethylene glycol
10 parts N,N-bis-(p-cyanoethyl)-formamide
5 parts citric acid
345 parts of water 1000 parts of thickening agent
This printing paste is applied to a fabric of polyester fibres and the dyestuff is fixed by a thermosol process (at 190°C for 4 seconds); the fabric is subsequently rinsed and soaped. A yellow print is obtained which is substantially clearer and stronger than the print obtained when the dyestuff is used in its ionic water-soluble form.
EXAMPLE 17
25 parts of a 1:1 mixture of the dispersion of dyestuff salt described in Example 5, part 1, and the dyestuff dispersion described in Example 9
are stirred into
975 parts of the thickening agent described in Example 6.
The printing pastes so obtained are applied to a
fabric of polyacrylonitrile fibres in the usual way by screen or rouleaux printing, and the dyestuffs are fixed by a thermosol process (190°C for 40 seconds); the fabric is subsequently rinsed and soaped. An intense green print is obtained the yield of which is appreciably better as in the case where the dyestuffs are used in their ionic water-soluble form.
EXAMPLE 18
The printing pastes according to Example 17 are printed on to a polyester fabric and the dyestuff fixed by thermosolisation (190°C for 40 seconds), the fabric is subsequently rinsed and soaped. The print obtained is appreciably clearer and deeper as in the case where the dyestuffs are used in their ionic water-soluble form.
EXAMPLE 19
35 Parts of the dyestuff dispersion described in Example 1 are stirred into
965 parts of the thickening agent described in Example 16.
The printing paste is applied to a fabric of polyacrylonitrile fibres and the dyestuff is fixed by steaming under 0.4 atm. excess pressure for 20 minutes; the fabric is subsequently rinsed and soaped. A level and smooth print is obtained, whereas the print obtained with the use of the dyestuff in its ionic water-soluble form is uneven and blotchy.
EXAMPLE 20
Preparation of the dyestuff salts
75 Parts of the dyestuff of the formula ##SPC27##
are dissolved in
750 parts of water at 70°C. A solution of
100 parts of the sodium salt of naphthalene-1-sulphonic acid in
1000 parts of water, likewise at 70°C, is added thereto with good stirring within 15 minutes until precipitation no longer occurs. Stirring is continued for one-half hour and the mixture is then cooled to 20°C. The precipitated red dyestuff salt is filtered off with suction, washed with water until free from electrolyte, and dried.
Yield: 100 parts of the dyestuff salt of the formula ##SPC28##
All the sparingly soluble basic dyestuff salts to be used according to the invention can be obtained in an analogous manner with the use of the corresponding water-soluble basic dyestuff salts and the corresponding aromatic sulphonic acids or their salts.
EXAMPLE 21
1.2 Parts of an aqueous dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC29##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol o-hydroxydiphenyl with 14 mol ethylene oxide
1 part of the sodium salt of the condensation product of 2 mol naphthalene-2-sulphonic acid with 1 mol formaldehyde and
44 parts of water
are mixed with
80 parts of water at 50°C
and combined with a solution of
0.8 parts of the dyestuff No. 35,780
50 parts of anhydrous sodium sulphate
1 part of the reaction product of 1 mol oleyl alcohol with 50 mol ethylene oxide
2 parts of a polyphosphate giving a pH value of 4.8 in
865 parts of water at 40°C.
100 parts of a fabric consisting of
40 parts of staple fibre and
60 parts polyacrylonitrile are introduced into the above dyebath and the bath is heated with vivid circulation to boiling temperatures within 30 minutes. After dyeing at this temperature for 60 minutes, the bath is cooled to 60°C,
5 parts sodium carbonate and
15 parts sodium bicarbonate
are then added and dyeing is continued at this temperature for 60 minutes. After this period of time the fabric is rinsed, first only with an overflow of cold water, subsequently with a hot solution of 2 parts sodium alkyl sulphonate in 988 parts of water.
A clear blue-red mixed dyeing is obtained; if the basic dyestuff is used in the non-formulated form, the staple fibre is appreciably more soiled.
EXAMPLE 22
1 Part of a dispersion of the sparingly water-soluble dyestuff salt of the formula ##SPC30##
consisting of
20 parts of the dyestuff salt
2 parts of the reaction product of 1 mol p-hydroxydiphenyl with 1 mol benzyl chloride and 14 mol ethylene oxide
2 parts of the condensation product of 2 mol naphthalene-2-sulphonic acid with 1 mol formaldehyde and
56 parts of water are mixed with
80 parts of water at 50°C and then with a solution of
1 part of the copper complex of the dyestuff of the formula ##SPC31##
2 parts of a sodium polyphosphate which yields a pH value of 5.5
1 part of the reaction product of 1 mol oleyl alcohol with 50 mol ethylene oxide and
10 parts sodium sulphate in 905 parts of water.
100 Parts of a mixed yarn consisting of
50 parts polyacrylonitrile and
50 parts of cotton
are introduced into the resultant dyebath and the bath is heated with vivid circulation to 90°C within 30 minutes. After dyeing at this temperature for 90 minutes, the bath is cooled to 40°C and the fabric is rinsed with a hot solution of 2 parts sodium alkylsulphate in 988 parts of water.
A differentiated red-yellow mixed yarn is obtained. If the dyestuff is used in the non-formulated form, precipitations occur and the cotton yarn is dyed with red dyestuff.