US3764262A - Process for the dyeing and printing of textile materials - Google Patents
Process for the dyeing and printing of textile materials Download PDFInfo
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- US3764262A US3764262A US00070514A US3764262DA US3764262A US 3764262 A US3764262 A US 3764262A US 00070514 A US00070514 A US 00070514A US 3764262D A US3764262D A US 3764262DA US 3764262 A US3764262 A US 3764262A
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- dyestuffs
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- perchloroethylene
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/90—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof
- D06P1/92—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents
- D06P1/922—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents hydrocarbons
- D06P1/924—Halogenated hydrocarbons
Definitions
- the invention relates to the dyeing and printing of textile materials with chlorinated hydrocarbon/ water dyestuff emulsions, the aqueous phase of which contains a solution of water-soluble dyestuffs and the chlorinated hydrocarbon phase of which may be a solution of dyestuffs soluble in chlorinated hydrocarbons, and to an after-treatment in chlorinated hydrocarbon solutions containing compounds which are interface-active in chlorinated hydrocarbons.
- the invention relates to a process for the dyeing and printing of textile materials with chlorinated hydrocarbon/Water dyestuff emulsions; the process is characterised in that the textile materials are dyed or printed with chlorinated hydrocarbon/water dyestutf emulsions the aqueous phase of which is a solution of water-soluble dyestuffs and the chlorinated hydrocarbon phase of which may be a solution of dyestuffs soluble in chlorinated hydrocarbons; and that the materials are sub sequently, possibly after a heat treatment, subjected to an after-treatment in chlorinated hydrocarbon solutions containing compounds which are interface-active in chlorinated hydrocarbons and convert the dyestuffs used into a form soluble or dispersible in chlorinated hydrocarbons.
- the compounds are expediently used in an amount of 0.02-2 percent by weight, referred to the weight of the chlorinated hydrocarbons.
- the compounds which are used in the chlorinated hydrocarbon baths for after-treatment according to the invention, in order to convert the dyestuffs used into a form soluble or dispersible in chlorinated hydrocarbons, can be divided into two groups, on account of their behaviour towards the various dyestuffs.
- Group (A) This group comprises the compounds which convert basic dyestuffs as Well as acidic dyestuffs, anionic metal complex dyestuffs which are free from sulpho groups, or reactive dyestuffs which contain sulpho groups, into a form soluble or dispersible in chlorinated hydrocarbons.
- the compounds of this group are preferably used in the after-treatment baths of the process according to the invention.
- Group (B) This group comprises the compounds which convert only basic dyestuffs into a form soluble or dispersible in chlorinated hydrocarbons.
- the compounds belonging to group (A) are the following:
- R stands for an alkyl, alkenyl or aralkyl radical which carries 12-18 carbon atoms and may be interrupted by hetero atoms such as oxygen, sulphur and/or nitrogen atoms;
- R and R independently of one another, denote an alkyl, alkenyl or aralkyl radical which carries 1-28 carbon atoms and may be interrupted by hetero atoms such as oxygen, sulphur and/or nitrogen atoms; and may 'be substituted;
- R means an optionally substituted C 'C -alkyl
- R stands for hydrogen or R where R, has the same meaning as in Formula I, or together with R forms a 5- or 6-membered non-aromatic heterocycle, with the proviso that the sum total of the carbon atoms contained in R R and R amounts to at least 20 and at most 60.
- R Suitable alkyl, alkenyl or aralkyl radicals which contain 12-28 carbon atoms and may be interrupted by hetero atoms such as oxygen, sulphur and/or nitrogen atoms are the following, for example:
- C C -alkyl radicals such as the dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, 3,6,9-trirnethylhexadecyl, l-octyl-dodecyl and l-undecyl-dodecyl radicals;
- Saturated radicals with a carbon chain interrupted by hetero atoms such as 3-oXa-nonadecyl-( 1), 3-oxa-heneicosyl-(l), 4-oxa-docosyl-(1), 3,6-dioxa-docosyl-(1), 3- thia-heneicosyl-(l), dodecyl aminoethyl, hexadecylaminopropyl, octadecyl-arninoethyl, octadecyl-aminopropyl, octadecyl-aminobutyl, eicosyl-aminopropyl, docosylaminopropyl radical and especially the dodecanoyl-amind ethyl, tetradecanoyl-aminoethyl, hexadecanoyl-aminobutyl, octadecanoyl-amin
- C -c -alkenyl radicals such as the oleyl, linolyl, linolenyl, eicosenyl, docosenyl and 2-ethyl-octadecen-9,l0- yl-( 1)-radicals;
- Unsaturated radicals with a carbon chain interrupted by hetero atoms such as 3-oxa-nonadecen-l0,ll-yl-(l), 4-oxadocosen 13,14-yl-(l), hexadecen-7,-8-yl-aminoethyl, octadecen 9,10 yl aminoethyl, docosen 13,14 ylaminopropyl and especially the oleoyl-aminoethyl, linoleuoyl-aminopropyl, linolenoyl aminoethyl, eicosenoylaminopentyl and docosenoyl-aminoethyl radicals;
- Aralkyl radicals with a carbon chain interrupted by hetero atoms such as the (4-nonyl-phenyl)-ethyl-carboxyethyl radical.
- R and R Suitable alkyl, alkenyl or aralkyl radicals which contain l28 carbon atoms and may be interrupted by hetero atoms and/or may be substituted, are the following, for example:
- C -C -alkyl radicals such as the methyl, ethyl, isopropyl, dodecyl, hexadecyl, octadecyl, eicosyl and docosyl radicals;
- C C -alkenyl radicals such as the buten-3,4-yl-(l)- and undecen-10,l1-yl-(l) radicals;
- Substituted alkyl and alkenyl radicals such as the 2- hydroxyethyl, 3-hydroxypropyl, 3-hydroxybutyl, 13-hydroxy-octadecen-9,l-yl-(1), 2 chloroethyl, 3 chlor0 propyl, 1 l-bromoundecyl, 13-chloroctadecen-9,l0-yl-( l l3,l4 dichlorodocosyl, Z-cyanoethyl, 3-cyanopropyl, llcyano-undecyl, 3-aminopropyl, 3-(N-methyl-amino)-butyl, ll-amino-undecyl, l3-(N-methylamino)-docosyl and the carbethoxy-ethyl radicals;
- Alkyl and alkenyl radicals with a carbon chain interrupted by hetero atoms such as the methoxy-ethyl, ethoxy-butyl, 3-oxa-dodecyl-(1), S-OXa-heneicosyl- 1 3,6-dioxa-docosyl-( l 4-thia-hexenyll 3-thia-pentadecyl-(l), N-methyl-Z-aminoethyl, N-ethyl 3 aminopropyl, N-propyl 3 aminopropyl, N-dodecyl-Z-aminoethyl, N octadecyl-B-aminopropyl, N-heneicosyl-4-aminobutyl and the N-docosyl-6-aminobutyl radicals;
- Aralkyl radicals such as the bcnzyl, 4-chlorobenzyl, 3- methyl-benzyl and 4-nonylphenyl-ethyl-carboxyethyl radicals.
- Suitable, optionally substituted C C -alkyl, C C -alkenyl, cycloalkyl or aralkyl radicals are the follow ing, for example:
- C C -alkyl radicals such as the methyl, ethyl, isopropyl, sec.-butyl, Z-ethylhexyl, dodecyl, 2-hydroxyethyl, 3-hydroxy-propyl, Z-methoxyethyl, 2,3-epoxypropyl, chloromethyl, 2-bromoethyl, chloropropyl, 2-hydroxy-3-chlo ropropyl, 2,3-epoxy-propyl, carbethoxymethyl, carboxamidomethyl, Z-cyanoethyl, acetoxyethyl and S-trimethylammonium-propyl radicals.
- C C -alkenyl radicals such as the buten-3,4-yl-(1)- undecen-l0,l1-yl-(1) radicals;
- Cycloalkyl radicals such as the cyclohexyl, 4-methylcyclohexyl, 3-octylcyclohexyl and 4-chlor0cycl0hexyl radicals;
- Aralkyl radicals such as the benzyl, 3-methylbenzyl, 4- cyclohexyl-benzyl, 4-methoxybenzyl and 3-chlorobenzyl radicals.
- Suitable 5- or 6-membered heterocycles which may be formed by R together with R are primarily the morpholine and piperidine rings.
- Suitable anions X- are anions of organic acids, such as the chloride, bromide, iodide and sulphate ions; the anions of acidic esters of inorganic acids, such as the methyl-sulphate, ethyl-sulphate and toluene-sulphate ions; and the anions of or organic acids, such as the acetate, propionate, ethyl-caproate, oleate, behenate, benzoate and salicylate ions.
- organic acids such as the chloride, bromide, iodide and sulphate ions
- the anions of acidic esters of inorganic acids such as the methyl-sulphate, ethyl-sulphate and toluene-sulphate ions
- the anions of or organic acids such as the acetate, propionate, ethyl-caproate, oleate, behenate, benzoate and salicylate ions.
- Suitable alkylene radicals which contain 1-8 carbon atoms and may be interrupted by hetero atoms are the following, for example:
- Alkylene radicals such as 'the methylene, ethylene, propylene-1,2, propylene-1,3, butylene and hexylene radicals;
- Alkylene radicals interrupted by hetero atoms such as the 3-oxa-hexylene-L6 and 3,6-dioxa-octylene-L8 radicals.
- onium compounds of the Formula II are the following sulphonium compounds, for example:
- quaternary ammonium compounds of the Formula 111 are the following, for example:
- the compounds belonging to the group (B) are the following:
- Sulphates of monoand polyhydric alcohols containing at least 16 carbon atoms such as cetylsulphate, stearyl sulphate, oleyl sulphate, behenyl sulphate, 2-heXyl-decanol-l-sulphate, 2,4,6-triethyl-decanol-l-sulphate, 3,10-diethyl-tridecanol-7-sulphate, 1,Z-diundecyl-ethylene-glycol monosulphate, glycerol-monostearate monosulphate;
- sulphates obtainable by sulphonation of unsaturated fatty acids, fatty acid esters and fatty acid ester amides, such as oleic acid sulphate, oleic acid butyl ester sulphate, ricinoleic acid ethyl ester sulphate, oleic acid ethylamide sulphate, oleic acid ethanolamide sulphate, oleic acid diisobutylamide sulphate, oleic acid anilide sulphate,
- cfia-O-C O(CH2) 10-0 -13 sulphates of acylated or alkylated polyglycol ethers containing not more than 30 ethylene oxide and/or propylene oxide units in the molecule, such as CH (CH CH CH(CH CONH (C2H4O)1BSO3NK polypropylene glycol ether monosulphate (mol.
- acylated or alkylated alkanolamines such as N-acetyl-oleylamine sulphate Sulphates of monohydroxy-polycarboxylic acid esters, such as Acidic phosphoric acid esters, such as dioctadecyl phosphate and CH (CHa)mC ONHC2H4O-P
- Acidic phosphoric acid esters such as dioctadecyl phosphate and CH (CHa)mC ONHC2H4O-P
- Alkyl-sulphonic acids such as Araliphatic sulphonic acids, such as CH: CH:
- Aromatic sulphonic acids such as alkylbenzene-sulphonic acids, e.g.
- n-decylbenzene-sulphonic acid n-dodecylbenzene-sulphonic acid n-tetradecylbenzene-sulphonic acid n-hexadecylbenzene-sulphonic acid n-octadecylbenzene-sulphonic acid [2-(propyl)-heptyl]benzene-sulphonic acid [Z-(butyl)-octyl]-benzene-sulphonic acid [2- (amy1)-nonyl] -benzene-sulphonic acid Substituted benzene-sulphonic acids, e.g.
- acylated aminocarboxylic acids e.g.
- the chlorinated hydrocarbon after-treatment baths should contain, in addition to the compounds which are interfaceactive in chlorinated hydrocarbons and convert the dyestuffs used into a .form soluble or dispersible in chlorinated hydrocarbons, small amounts of water, e.g. 0.01-4 percent by weight, referred to the weight of the chlorinated hydrocarbons, and possibly also 0.00 1-2 percent by weight of anon-ionic emulsifier, referred to the weight of the chlorinated hydrocarbons.
- non-ionic emulsifiers there may be used the commercial non-ionic emulsifiers; for example, reaction prodducts of 1 mol of fatty alcohols, fatty acids, fatty amines, fatty acid amides, fatty acid alkanolamides, fatty acid glycerides, alkyl-phenols, alkyl-benzyl-phenols, alkyl-arylbenzyl-phenols, aryl-styryl-phenols or abietic acid, with 5-100 mol ethylene oxide; and also fatty acid esters of aliphatic polyhydroxy compounds and fatty acid alkanolamides.
- the chlorinated hydrocarbon after-treatment baths should also contain 0.001-8 percent by weight, referred to the weight of the chlorinated hydrocarbons, of water-miscible organic solvents, such as isopropanol, benzyl alcohol, phenoxy-ethanol, acetonitrile, hydroxypropionitrile, dimethyl sulphoxide, dimethyl formamide or methyl glycol acetate; and to add to the chlorinated hydrocarbon aftertreatment baths 0.0l-0.5 percent by weight, referred to the weight of the chlorinated hydrocarbons, of acetic acid when after-treating dyeings and prints obtained with cationic dyestuffs, and 0.0l-0.5 percent by weight, referred to the Weight of the chlorinated hydrocarbons, of mono-, dior triethanolamine and/or 0.01-1 percent by weight, referred to the weight of the chlorinated hydrocarbons, of acetic acid when after treating dyeings or prints obtained with acidic dyestuffs, ani
- the process according to the invention is suitable for the dyeing with cationic dyestuffs as well as for the dyeing with acid dyestuffs, anionic, sulpho group-free metal complex dyestuffs and sulpho group-containing reactive dyestuffs.
- Suitable cationic dyestuffs are methine, azomethine, hydrazone, azacyanine, triarylmethane, xanthene, thioxanthene, acridine, oxazine, thiazine and phenazine dyestuffs; furthermore, the basic dyestuffs of the azo, anthraquinone or phthalocyanine series, such as are described e.g. in Colour Index, vol. 1, 2nd Edition (1956), pages 1617- 1654, and in the Supplement of 1963, and also in French patent specification No. 1,480,930.
- Suitable acid dyestuffs are all water-soluble dyestuffs of the azo, anthraquinone, triphenyl-methane and phthalocyanine series which contain up to four sulpho groups;
- examples of anionic sulpho group-free metal complex dyestuffs are the sulpho group-free 1:2 metal complex dyestuffs of the azo and triphenylmethane series which contain at least two groups capable of dissociation; and the sulpho group-containing reactive dyestuffs comprise e.g.
- water-soluble dyestuffs of the azo, anthraquinone and phthalocyanine series which contain at least one fibrereactive group, for example, a monochloro-triazinyl, dichlorotriazinyl, dichloro-quinoxalinyl, trichloro-pyrimidinyl, difluoro-chloro-pyrimidinyl, u-bromoacrylamide group or the fl-hydroxyethyl-sulphuric acid semi ester group.
- thickening agents are required for preparing the dyestutf emulsions, thickening agents poor in body are preferred for the process according to the invention.
- the process according to the invention is suitable for the dyeing and printing of all textile materials which can be dyed or printed with the aforesaid dyestuffs.
- these include, for example, the textile materials of polyacrylonitrile, polyester, cellulose 2 /2-acetate, cellulose triacetate, synthetic polyamides and silk, which can be dyed with basic dyestuffs; the textile materials of natural or regenerated cellulose such as cotton, staple fibre and rayon, cellulose 2 /2-acetate, cellulose triacetate, of natural polyamides such as wool and silk, and of synthetic polyamides such as polyhexamethylenediamine adipate, polycaprolactam or poly-a-aminoundecanoic acid, which can be dyed with acid, metal complex and reactive dyestuffs.
- the present process has proved particularly satisfactory for the dyeing and printing of mixtures of these types of fibres, e.g. mixtures of polyacrylonitrile/ staple fibre, polyester/ cotton, polyester/staple fibre, polyamide/ staple fibre, polyamide/cotton, cellulose 2 /z-acetate/staple fibre, cellulose triacetate/staple fibre or polyacr'ylonitrile/polyester.
- these types of fibres e.g. mixtures of polyacrylonitrile/ staple fibre, polyester/ cotton, polyester/staple fibre, polyamide/ staple fibre, polyamide/cotton, cellulose 2 /z-acetate/staple fibre, cellulose triacetate/staple fibre or polyacr'ylonitrile/polyester.
- the textile materials may be present in various stages of processing, e.g. as threads, ribbons, combed material, yarn, fabrics, knitted fabrics or ready-made goods.
- chlorinated hydrocarbons expediently used in the after-treatment baths of the process according to the invention are aliphatic chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride,
- the process according to the invention is carried out by applying the dyestuffs to the textile materials by means of the dyestuff emulsions according to the exhaust, spray, padding or printing process at temperatures from 20 to 120 C. Subsequently, possibly after a conventional heat treatment such as drying, steaming or thermosolising, the textile materials are subjected in a continuous or discontinuous operation to an after-treatment in chlorinated hydrocarbon solutions containing interface-active compounds which convert the dyestuffs used into a form soluble or dispersible in chlorinated hydrocarbons. Optionally, this after-treatment is followed by rinsing in pure chlorinated hydrocarbon.
- any nonfixed dyestuifs or dyeing auxiliaries are so completely removed from the textile materials that, after separation of the wash liquor and removal of the last solvent residues by blowing out with air or steam, the materials can be stored without any further after-treatment.
- the emulsions to be used as dyebaths or printing pastes may either contain water as a continuous phase and the chlorinated hydrocarbons as a discontinuous phase, or they may contain the chlorinated hydrocarbons as a continuous phase and water as a discontinuous phase.
- the aqueous phase is a solution of water-soluble dyestuffs
- the chlorinated hydrocarbon phase may be a solution of a dyestuif soluble in chlorinated hydrocarbons, but it may also be formed by chlorinated hydrocarbons free from dyestuff.
- the amounts of dyestuff dissolved in the respective phases depend upon the desired depth of colour of the dyeings or prints, upon the solubility of the dyestuffs, and upon whether the exhaust, spray, padding or printing process is applied. In general, amounts of 0.2 to 50 g. of dyestuff per litre of dyestulf emulsion have proved satisfactory.
- emulsifiers for preparing the dyestulf emulsions there may be used the compounds which usually serve for preparing oil-in-water and water-in-oil emulsions.
- Nonionic emulsifiers have proved especially satisfactory for the process according to the invention.
- Suitable non-ionic emulsifiers are the commercial non-ionic emulsifiers, for example, reaction products of 1 mol of fatty alcohols, fatty acids, fatty amines, fatty acid amides, fatty acid alkanolamides, fatty acid glycerides, alkyl-phenols, alkyl-benzyl-phenols, alkyl-aryl-benzyl-phenols, aryl-styryl-phenols or abietic acid, with lmol ethylene oxide; furthermore, fatty acid esters of aliphatic polyhydroxy compounds and fatty acid alkanolamides.
- the amounts of emulsifier required for preparing and stabilising the emulsions should not exceed 10 percent by weight, referred to the weight of the emulsions, and should preferably amount to 0.2 to 5 percent by Weight.
- the dyestuif emulsions may contain the usual dyeing auxiliaries, e.g. urea.
- the amounts of these auxiliaries depend on the dyestuffs used and on the dyeing process. In general, they amount to about 10 to 500 percent by weight, referred to the weight of the dyestuffs.
- the emulsions can be prepared in the usual way. It has proved expedient to prepare the solutions forming the two phases separately and to emulsify, after the addition of the emulsifiers, with the aid of rapid stirrers or turbomixers.
- Chlorinated hydrocarbons which can serve for the preparation of the dyestulf emulsions are those chlorinated hydrocarbons which are also suitable for the after-treatment baths. Tetrachloroethylene, trichloroethylene and l,1,l-trichloropropane have proved especially satisfactory also in the dyestuif emulsions.
- the process according to the invention combines the advantages of dyeing from aqueous media (use of conventional dyestuffs, good fastness properties of the resultant dyeings) with the advantages of dyeing from organic solvents (unimpaired appearance of the goods, virtually no occurrence of waste water), wthout having the disadvantages of these processes.
- a particular advantage of the process according to the invention consists in that textile materials can be dyed in the chlorinated hydrocarbon medium in a single bath with water-soluble dyestuffs and with dyestuffs soluble in chlorinated hydrocarbons.
- the process according to the invention is therefore eminently suitable for the dyeing and printing of materials of cellulose fibres and of mixtures thereof with synthetic fibres with the use of water-soluble reactive dyestuffs for the cellulose fibre component and of disperse dyestuffs soluble in chlorinated hydrocarbons for the synthetic fibre component, and well as for the dyeing and printing of polyacrylonitrile/polyester fibre mixtures with the use of cationic water-soluble dyestuffs for the polyacrylonitrile component and of disperse dyestuffs for the polyester fibre component.
- the dyeings must therefore be rinsed with aqueous liquors.
- aqueous wash liquors By using aqueous wash liquors, however, the advantages of dyeing from organic solvents (unimpaired appearance of the goods, slight occurrence of waste water) are cancelled out.
- the process according to the invention has not only the advantage of permitting dyeing with water-soluble dyestuffs and with dyestuffs soluble in chlorinated hydrocarbons from chlorinated hydrocarbon/water emulsions; it has primarily the advantage that, due to the after treatment with the chlorinated hydrocarbon solutions containing compounds which convert the dyestuffs into a form soluble or dispersible in chlorinated hydrocarbons, dyeing with water-soluble dyestuffs, e.g. reactive dyestuffs and cationic dyestuffs, without having recourse to aqueous baths, yields dyeings of the same good fastness to wet processing as is achieved when dyeing from aqueous baths.
- water-soluble dyestuffs e.g. reactive dyestuffs and cationic dyestuffs
- EXAMPLE 1 A polyester/cotton mixed fabric (65:35) is padded with an emulsion consisting of parts of the dyestuff XVI 2 parts nonylphenol pentadecaethylene glycol ether 1 part oleic acid ethanolamide parts of the dyestuff XIII 14 60 parts urea 8 parts sodium bicarbonate 94 parts of water and 800 parts perchloroethylene (liquor absorption dried at 80 C. for 1 minute and thermosolised at C. for 30 seconds.
- the fabric then passes, with a time of residence of 1.5 minutes each time, through four successive closed washing aggregates which operate according to the counter-current principle and contain a solution at 55 C. which consists of 4 parts of the compound of the formula 1 part of water 5 parts of 30% acetic acid and 990 parts perchloroethylene and is mechanically agitated.
- the liquor ratio for this after-treatment amounts to 1:50.
- the fabric is freed from the adhering solvent residues by blowing with hot air, and stored. A clear yellow/red bicolour dyeing of good fastness properties is obtained. No waste Water occurs in the after-treatment.
- EXAMPLE 2 A polyester/polyacrylonitrile mixed fabric (50:50) is padded with an emulsion consisting of 20 parts of the dyestulf I 10 parts of the dyestufi XVI 4 parts methyl glycol acetate 4 parts glylcerol monoacetate 1 part oleic acid ethanolamide 3 parts nonylphenol decaethylene glycol ether 10 parts of 60% acetic acid 148 parts of water and 800 parts perchloroethylene (liquor absorption 80%) and thermosolised at 180 C. for 1 minute.
- the fabric web successively passes, in a liquor ratio of 1:50 and With a time of residence of 2 minutes each time, through four solutions of 5 parts sodium dodecyl-benzene sulphonate 0.5 part of 60% acetic acid and 5 parts of water in 989.5 parts perchloroethylene the invention, then the non-fixed, perchloroethylene-insoluble dyestufi is not removed from the fabric and the fastness properties of the resultant dyeing are therefore unsatisfactory.
- EXAMPLE 3 A polyacrylonitrile fabric is padded with an emulsion consisting of 20 parts of the dyestuff II 2 parts oleyl alcohol eicosaethylene glycol ether 12 parts B-cyanoethyl formamide 4 parts nonylphenol decaethylene glycol ether 10 parts of 60% acetic acid, parts of water and 852 parts perchloroethylene,
- the fabric is then treated in a liquor ratio of 1:100 in a bath consisting of 10 parts of the compound of the formula CH3-(CHz) sCI-Ig O O /P CH3-(CHB) ltl-CHgO 10 parts of water and 980 parts perchloroethylene at 55 C. for 6 minutes, subsequently rinsed twice with fresh perchloroethylene and, after separating the liquor, freed from the perchloroethylene adhering to the fibre by blowing with steam. Without the occurrence of waste water, there is obtained a red dyeing which is rinsed clear and has the same fastness properties as a dyeing rinsed with an aqueous Washing liquor.
- a polyacrylonitrile fabric is padded with an emulsion consisting of 15 parts of the dyestulf III 10 parts fi-cyanoethyl formamide 3 parts nonylphenol-decapentaethylene glycol ether 2 parts oleyl alcohol eicosaethylene glycol ether 100 parts of water and 870 parts perchloroethylene (liquor absorption 100%) and steamed at 102 C. for 20 minutes.
- the polyacrylonitrile fabric is then passed in a liquor ratio of 1:50 through four successive after-treatment baths which have been heated to 50 C. and operate according to the counter-current principle, each containing 1 part sodium dodecylbenzene sulphonate 3 parts of water and 0.05 part of glacial acetic acid in 996 parts perchloroethylene.
- the fabric is subsequently rinsed with pure perchloroethylene, the rinsing liquor is separated and the adhering solvent driven otf by blowing with steam.
- the blue dyeing obtained without the occurrence of waste water has the same fastness properties as a corresponding dyeing aftertreated in aqueous baths.
- EXAMPLE 5 A polyacrylonitrile fabric is printed with a printing paste of the composition parts of the dyestntf IV parts di-fi-cyanoethyl formamide 30 parts thiodiglycol 2 parts nonylphenol decaethylene glycol ether 30 parts of 30% acetic acid 30 parts of water and 873 parts perchloroethylene,
- the printed fabric is then mechanically moved about in a liquor ratio of 1:50 for 3 minutes in a bath which has been heated to 50 C. and consists of 5 parts of a compound of the formula a- (CH1) 16-0 o1;rcH,-cm-o o 0 H CH3 5 parts of water and 990 parts perchloroethylene and subsequently treated in a liquor ratio of 1:50 for 3 minutes in a second bath which has likewise been heated to 50 C.
- the perchloroethylene is then separated and the residues of perchloroethylene adhering to the fabric are removed by blowing with steam.
- EXAMPLE 6 A fabric of anion-modified polyester (Dacron 64) is padded with an emulsion consisting of 20 parts of the dyestuif V 60 parts ethylene-cyanohydrin 3 parts formamide 10 parts of glacial acetic acid 50 parts of water 3 parts nonylphenol-pentadecaethylene glycol ether and 854 parts perchloroethylene (liquor absorption dried at 100 C. for 1 minute and thermosolised at 200 C. for seconds.
- the dyed fabric is subsequently mechanically moved about in a liquor ratio of 1:50 to 2 minutes in an aftertreatment bath which has been heated to 55 C. and has the composition 1 part of technical oleic acid 1 part oleyl alcohol heptadecaethylene glycol ether 1 part sulphosuccinic acid dioctyl ester and 4 parts of water in 993 parts perchloroethylene,
- a polyacrylonitrile fabric is padded with an emulsion consisting of 10 parts of the dyestufi VI 11 parts of 85% formic acid 9 parts of 60% acetic acid 12 parts ethylene-cyanohydrin 8 parts glycerol monoacetate 8 parts methyl glycol acetate 4 parts nonylphenol decaethylene glycol ether 88 parts of water and 850 parts perchloroethylene (liquor absorption 100%), dried at 100 C. for 1 minute and thermosolised at 200 C. for 1 minute. 15
- the fabric then passes through 5 successive wash baths which have been heated to 50 C., each containing 5 parts of a mixture of 19.5 parts of the compound of the formula (CH (CH CO-NH-CH CH NH 1 part stearic acid 2 parts of the compound of the formula CH; 0.5 parts oleyl alcohol heptadecaethylene glycol ether 3 parts of glacial acetic acid 19.5 parts isopropanol and (2) When 5 parts of the mixture are replaced with 5 parts of one of the following compounds of the Formulae a-g:
- the fabric is then treated in a liquor ratio of 1:50 for 3 minutes in an after-treatment bath at 50 C. consisting of 5 parts of the N,N-di-octadecyl-N,N-dimethyl ammonium salt of sulphated rapeseed oil 5 parts of water and 990 parts perchloroethylene and subsequently in an after-treatment bath consisting of 1 part of the N,N-di-octadecyl-N,N-dimethyl ammonium salt of sulphated rapeseed oil 1 part of water and 998 parts perchloroethylene.
- rapeseed oil are replaced with 5 parts and 1 part, respeci tively, of a mixture of 3 parts of the compound of the formula c CH CH CH s( 2)l!16 ⁇ 2@/ a 9 parts isopropanol,
- EXAMPLE 10 A mixed fabric (50:50) of a polyamide which can be dyed with basic dyestuffs and a polyamide which can be dyed with acidic dyestuffs is padded with an emulsion consisting of 10 parts of the dyestulf I 10 parts of the dyestuif IX 4 parts of the reaction product of 1 mol oleyl alcohol with 50 mol ethylene oxide 4 parts nonylphenol decaethylene glycol ether 3 parts of a mixture consisting of 20 parts of a compound of the formula CgHs 40 parts oleyl alcohol eicosaethylene glycol ether and 40 parts ethyl hexanol 5 parts of 60% acetic acid 80 parts of water and 884 parts perchloroethylene with a liquor absorption of 70%, dried at 80 C. for 1 minute and steamed at 105 C. for 3 minutes.
- the fabric web then successively passes in a liquor ratio of 1:30 with a time of residence of 2 minutes each time through two after-treatment baths which are mechanically agitated and have been heated to 50 C. and which consist of 0.75 part of the N,N-di-octadecyl-N,N-dimethyl ammonium salt of sulphated rapeseed oil 0,75 parts of a compound of the formula CHs-CONH-SOP(CH2)M-CH
- EXAMPLE 1 A Turkish towelling fabric of cotton is padded with an emulsion consisting of 40 parts of the dyestufl? X parts urea 98 parts of water 10 parts sodium bicarbonate 5 parts nonylphenol decaethylene glycol ether and 767 parts perchloroethylene,
- the fabric is subsequently after-treated in a liquor ratio of 1:40 for 3 minutes each time in two successive baths which have been heated to 50 C. and consists of 5 parts of a compound of the formula 5 parts of 60% acetic acid 10 parts of water and 980 parts perchloroethylene and subsequently rinsed at the same temperature for 2 minutes with fresh perchloroethylene.
- the solvent residues are removed by blowing with steam. Without the occurrence of waste water, there is obtained a yellow dyeing which has been rinsed clear and has faultless fastness properties.
- EXAMPLE 12 A polyacrylonitrile/cotton mixed fabric (50:50) is padded with an emulsion consisting of 9 parts of the dyestuff XI 26 parts of ethylene-'cyanohydrin 15 parts formamide 2 parts nonylphenol decaethylene glycol ether 1 part oleic acid ethanolamide 60 parts urea parts of water and 804 parts perchloroethylene (liquor absorption dried at 80 C. for 90 seconds and thermosolised at 202 C. for 1 minute.
- the fabric subsequently passes with a time of residence of 90 seconds each time through 6 successive aftertreatment baths which have been heated to 50 C. and consist of 5 parts of the compound of the formula CH3(CH2)16 C0 NH (CH2)3 N (CH3)2 15 parts of water and 980 parts perchloroethylene.
- EXAMPLE 13 A staple fibre fabric is padded with an emulsion consisting of 30 parts of the dyestuif XII 4 parts nonylphenol pentadecethylene glycol ether 80 parts urea parts sodium bicarbonate 90 parts of water and 786 parts perchloroethylene (liquor absorption 80%), dried at 80 C. for 1 minute 54 parts of a mixture consisting of 0.6 parts sodium carbonate 10.4 parts of water 5 parts urea 32 parts perchloroethylene and 6 parts of a mixture consisting of 30 parts sodium paraflin sulphonate 2.5 parts sodium dodecyl-benzene sulphonate 17.5 parts of the sulphuric acid ester of a sperm oil alcohol 12.
- the fabric is subsequently after-treated in a liquor ratio of 1:50 for 2 minutes each time in 5 successive baths which have been heated to 55 C. and consisting of
- the fabric is then after-treated in a liquor ratio of 1:20 with a time of residence of 10 minutes with a bath which has been heated to 50 C. and consists of 5 parts of the compound of the formula 5 parts of a compound of the formula CH CH 0CH NCH s( 92 2 H a 019 2 5 parts isopropanol 5 parts of water 5 parts of 60% acetic acid and 985 parts perchloroethylene CHa-(CHz) 0CH:NCH1
- EXAMPLE 14 100 parts of a polyester/cotton mixed fabric (67:33) are printed in a pressure Winding frame at C. for 30 minutes with an emulsion consisting of 5 parts of water 2 parts of 60% acetic acid and 988 parts perchloroethylene The fabric is subsequently rinsed with pure perchloroethylene at C. for 2 minutes. After separating the rinsing liquor, the fabric is freed from the adhering solvent by blowing with steam. There is obtained a red/ blue bicolour dyeing which has the same fastness properties as a dyeing washed with aqueous wash baths.
- EXAMPLE 15 A cotton fabric is padded with an emulsion consisting of 40 parts of the dyestutf XIV 3 parts nonylphenol decaethylene glycol ether parts urea 10 parts sodium carbonate 100 parts of water and 787 parts perchloroethylene (liquor absorption dried at 80 C. for 1 minute and steamed at 102 C. for 5 minutes.
- the fabric is subsequently after-treated in a liquor ratio of 1:50 with a time of residence of 2 minutes each time in 3 successive baths which have been heated to 55 C and consist of 5 parts of the aminoxide of the formula 10 parts of water and 985 parts perchloroethylene.
- the fabric is then rinsed with pure perchloroethylene at 55 C., for 2 minutes. After separating the rinsing liquor,
- the fabric is freed from the adhering perchloroethylene residues in an air current.
- a clear yellow dyeing is obtained without the occurrence of Waste water.
- EXAMPLE 16 A polyester/cotton mixed fabric (65:35) is padded with an emulsion consisting of 12 parts of the dyestuff XVI 2 parts nonylphenol decaethylene glycol ether 1 part oleic acid ethanol amide 20 parts of the dyestulf VII 60 parts urea 8 parts sodium bicarbonate 97 parts of water and 800 parts perchloroethylene (liquor absorption 80% dried at 120 C. for 60 seconds and thermosolised at 18.0 for 60 seconds.
- the fabric then passes through 5 successive washing aggregates which operate according to the counter-current principle and contains a solution at 55 C. consisting of 5 parts of the compound of the formula 5 parts of water and 990 parts perchloroethylene.
- the liquor ratio for the after-treatment amounts to 1:100.
- the fabric is subsequently rinsed with a mixture at 55 C. consisting of 990 parts perchloroethylene 5 parts of 60% acetic acid and 5 parts of water.
- the fabric After separating the rinsing liquor, the fabric is freed from the adhering solvent residues by blowing with air. Without the occurrence of waste water there is obtained a clear dyeing with a red/yellow pattern which has the same fastness properties as a dyeing after-treated with aqueous liquors.
- EXAMPLE 17 A polyester/ staple fibre mixed fabric (70:30) is padded with an emulsion consisting of 20 parts of the dyestutf XVI 15 parts of the dyestutf XIV 50 parts urea 70 parts nonylphenol hexaethylene glycol ether 5 parts sodium bicarbonate 60 parts of water and 780 parts perchloroethylene (liquor absorption 80% dried at 120 C. for 90 seconds and thermosolised at 180 C. for 90 seconds.
- the fabric is subsequently after-treated in a liquor ratio of 1:50 for 5 minutes in bath at 55 C. consisting of 5 parts of the compound of the formula I [CH -(CH2)16 CO-NH-CHn-CHg]g/IgT-CHg-CHg-CHn-SOa 10 partsof 30% acetic acid and 985 parts perchloroethylene are replaced with (a) 5 parts of a mixture o f equal parts of the compound of the formula and oleic acid or (b) 5 parts of a mixture of equal parts of the compound of the formula and the compound of the formula (c) 5 parts of a mixture of equal parts of the compound of the formula and the compound of the formula or (d) 5 parts of the N,N-dioctadecyl-N,N-dimethyl ammonium salt of sulphated rapeseed oil or (e) 5 parts of a mixture of 18.5 parts of the compounds of the formula CH3 e [GH3 (CH2)10 CHB] 2 ⁇ N/ :
- the fabric then passes in a liquor ratio of 1:50 and with a time of residence of 2 minutes each time through 4 successive after-treatment baths which have been heated to 55 C. and consist of 6 parts N,N-di-eicosyl-N,N-dimethyl ammonium bromide 6 parts of water 1 part octadecyl alcohol heptadecaethylene glycol ether and 987 parts perchloroethylene.
- the fabric web then passes with a time of residence of 1 minute through a rinsing bath of pure perchloroethylene which has been heated to 50 C. After separating the rinsing liquor, the fabric is freed from the adhering perchloroethylene residues by blowing with hot air. The resultant red dyeing is rinsed clear without the occurrence of waste water and has the same fastness properites as a dyeing rinsed with water.
- EXAMPLE 19 A cellulose/poly-e-caprolactam mixed fabric (50:50) is padded with an emulsion consisting of 20 parts of the dyestufi VII 20 parts of the 1:2 chromium complex of the dyestufi XVHI 3 parts nonylphenol decaethylene glycol ether 6 parts sodium bicarbonate 80 parts urea 100 parts of water and 771 parts perchloroethylene (liquor absorption 40%), dried at 100 C. for 1 minute and thermosolised at 192 C. for 60 seconds.
- the fabric web then successively passes in a liquor ratio of 1:50 and with a time of residence of 2 minutes each time through 4 after-treatment baths which are mechanically agitated and have been heated to C. and consist of 4 parts of the compound of the formula ooz- 1 part of the compound of the formula CHz-CHg-OH e CHg-(CHz)mCHqNHCOOCHgCHz-N 01 CHn-CHa-OH 1 part of the compound of the formula 7 parts of 30% acetic acid and 987 parts perchloroethylene CONSTITUTIONS OF THE DYESTUFFS I-XVIII USED IN THE EXAMPLES Number Constitution II (32H:
- R is an alkyl, alkenyl or aralkyl radical of 12-28 carbon atoms or one of the aforesaid radicals containing oxygen, sulfur or nitrogen;
- R and R independently of one another, are unsubstituted or substituted alkyl, alkenyl, or aralkyl radicals which contain 1-28 carbon atoms or one of the aforesaid radicals containing oxygen, sulfur or nitrogen;
- R is substituted or unsubstituted C C -alkyl, C -C alkenyl, cycloalkyl or aralkyl or together with R forms a non-aromatic 5- or 6-membered heterocycle; with the proviso that the sum of carbon atoms in R R R and R is 20 to 60; and
- X- is an anion
- the interface-active compound is a quaternary ammonium compound of the formula in which R; is an alkyl, alkenyl or aralkyl radical of 12-28 carbons, or one of the aforesaid radicals containing oxygen, sulfur or nitrogen;
- R is an unsubstituted or substituted alkyl, alkenyl or aralkyl radical of 1-28 carbon atoms or one of the aforesaid radicals containing oxygen, sulfur or nitrogen;
- R is unsubstituted or substituted C C -alkyl, C C
- Z is an alkylene radical which contains l8 carbon atoms, a C C -alkylene which contains oxygen atoms or 1,4- bis-methylene-benzene radical; with the proviso that the sum of carbon atoms in R R R and R and Z is 20 to 60; and
- the interface-active compound is an amine of the formula in which R; is an alkyl, alkenyl or aralkyl radical of 12-28 carbon atoms or one of the aforesaid radicals containing oxygen, sulfur or nitrogen;
- R is an unsubstituted or substituted C C -alkyl, C C
- alkenyl, cycloalkyl or aralkyl radical alkenyl, cycloalkyl or aralkyl radical
- R is hydrogen, an unsubstituted or substituted alkyl, alkenyl or aralkyl radical of 1-28 carbon atoms or one of the aforesaid radicals containing oxygen, sulfur or nitrogen, or R together with R forms a 5- or G-membered non-aromatic heterocycle; with the proviso that the sum or carbon in R R and R is 20 to 60.
- the interface-active compound is an aminoxide of the formula in which R is an alkyl, alkenyl or aralkyl radical of 12-28 carbon atoms or one of the aforesaid radicals containing oxygen, sulfur or nitrogen;
- R is an unsubstituted or substituted alkyl, alkenyl or aralkyl radical of 1-28 carbon atoms or one of the aforesaid radicals containing oxygen, sulfur or nitrogen;
- R is an unsubstituted or substituted C -C -alky1, or C -c -alkenyl, cycloalkyl or aralkyl radical or together with R forms a non-aromatic 5- or 6-membered heterocycle; with proviso that the sum of carbon atoms in R R and R is 20 to 60.
- the aliphatic chlorinated hydrocarbon solution contains a compound selected from the group consisting of 0.01% to 1.0% by weight of acetic acid, 0.01% to 0.5% by weight of monoethanolamine 0.01% to 0.5% by weight of diethanolamine and 0.01% to 0.5% by weight of triethanolamine.
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Abstract
THE INVENTION RELATES TO THE DYEING AND PRINTING OF TEXTILE MATERIALS WITH CHLORINATED HYDROCARBON/WATER DYESTUFF EMULSIONS, THE AQUEOUS PHASE OF WHICH CONTAINS A SOLUTION OF WATER-SOLUBLE DYESTUFFS AND THE CHLORINATED HYDROCARBON PHASE OF WHICH MAY BE A SOLUTION OF DYESTUFFS SOLUBLE IN CHLORINATED HYDROCARBONS, AND TO AN AFTER-TREATMENT IN CHLORINATED HYDROCARON SOLUTIONS CONTAINING COMPOUNDS WHICH ARE INTERFACE-ACTIVE IN CHLORINATED HYDROCARBONS.
Description
United States Patent Ofice US. Cl. 884 12 Claims ABSTRACT OF THE DISCLOSURE The invention relates to the dyeing and printing of textile materials with chlorinated hydrocarbon/ water dyestuff emulsions, the aqueous phase of which contains a solution of water-soluble dyestuffs and the chlorinated hydrocarbon phase of which may be a solution of dyestuffs soluble in chlorinated hydrocarbons, and to an after-treatment in chlorinated hydrocarbon solutions containing compounds which are interface-active in chlorinated hydrocarbons.
The invention relates to a process for the dyeing and printing of textile materials with chlorinated hydrocarbon/Water dyestuff emulsions; the process is characterised in that the textile materials are dyed or printed with chlorinated hydrocarbon/water dyestutf emulsions the aqueous phase of which is a solution of water-soluble dyestuffs and the chlorinated hydrocarbon phase of which may be a solution of dyestuffs soluble in chlorinated hydrocarbons; and that the materials are sub sequently, possibly after a heat treatment, subjected to an after-treatment in chlorinated hydrocarbon solutions containing compounds which are interface-active in chlorinated hydrocarbons and convert the dyestuffs used into a form soluble or dispersible in chlorinated hydrocarbons.
The compounds are expediently used in an amount of 0.02-2 percent by weight, referred to the weight of the chlorinated hydrocarbons.
The compounds which are used in the chlorinated hydrocarbon baths for after-treatment according to the invention, in order to convert the dyestuffs used into a form soluble or dispersible in chlorinated hydrocarbons, can be divided into two groups, on account of their behaviour towards the various dyestuffs.
Group (A): This group comprises the compounds which convert basic dyestuffs as Well as acidic dyestuffs, anionic metal complex dyestuffs which are free from sulpho groups, or reactive dyestuffs which contain sulpho groups, into a form soluble or dispersible in chlorinated hydrocarbons.
Because of their universal applicability, the compounds of this group are preferably used in the after-treatment baths of the process according to the invention.
Group (B): This group comprises the compounds which convert only basic dyestuffs into a form soluble or dispersible in chlorinated hydrocarbons.
It is a precondition for the usability of the compounds of both groups that they should be soluble in the chlorinated hydrocarbons in the concentrations in which they are used at temperatures below 50 C.
The compounds belonging to group (A) are the following:
(1) Onium compounds of the formulae (I) (II) 3,764,262 Patented Oct. 9, 1973 in which A denotes a nitrogen or phosphorus atom;
R stands for an alkyl, alkenyl or aralkyl radical which carries 12-18 carbon atoms and may be interrupted by hetero atoms such as oxygen, sulphur and/or nitrogen atoms;
R and R independently of one another, denote an alkyl, alkenyl or aralkyl radical which carries 1-28 carbon atoms and may be interrupted by hetero atoms such as oxygen, sulphur and/or nitrogen atoms; and may 'be substituted;
R means an optionally substituted C 'C -alkyl,
C C -alkenyl, cycloalkyl or aralkyl radical, or together with R forms a non-aromatic 5- or 6-membered heterocycle, with the proviso that the sum total of the carbon atoms contained in R R R and R, amounts to at least 20 and at most and X denotes on anion.
(2) Quaternary ammonium compounds of the formula R1 R3 R4 Z-Y- (III) in which (3) Amines of the formula /NR5 R4 I in which R and R have the same meaning as in the Formulae 1 and II; and
R stands for hydrogen or R where R, has the same meaning as in Formula I, or together with R forms a 5- or 6-membered non-aromatic heterocycle, with the proviso that the sum total of the carbon atoms contained in R R and R amounts to at least 20 and at most 60.
(4) Aminoxides of the formula 1 1 R4 in which R R and R have the same meaning as in the Formulae I and II, with the proviso that the sum total of the carbon atoms contained in R R and R amounts to at least 20 and at most 60.
R Suitable alkyl, alkenyl or aralkyl radicals which contain 12-28 carbon atoms and may be interrupted by hetero atoms such as oxygen, sulphur and/or nitrogen atoms are the following, for example:
C C -alkyl radicals, such as the dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, 3,6,9-trirnethylhexadecyl, l-octyl-dodecyl and l-undecyl-dodecyl radicals;
Saturated radicals with a carbon chain interrupted by hetero atoms, such as 3-oXa-nonadecyl-( 1), 3-oxa-heneicosyl-(l), 4-oxa-docosyl-(1), 3,6-dioxa-docosyl-(1), 3- thia-heneicosyl-(l), dodecyl aminoethyl, hexadecylaminopropyl, octadecyl-arninoethyl, octadecyl-aminopropyl, octadecyl-aminobutyl, eicosyl-aminopropyl, docosylaminopropyl radical and especially the dodecanoyl-amind ethyl, tetradecanoyl-aminoethyl, hexadecanoyl-aminobutyl, octadecanoyl-aminopropyl, eicosanoyl-amimopropyl and docosanoyl-aminoethyl radicals;
C -c -alkenyl radicals such as the oleyl, linolyl, linolenyl, eicosenyl, docosenyl and 2-ethyl-octadecen-9,l0- yl-( 1)-radicals;
Unsaturated radicals with a carbon chain interrupted by hetero atoms, such as 3-oxa-nonadecen-l0,ll-yl-(l), 4-oxadocosen 13,14-yl-(l), hexadecen-7,-8-yl-aminoethyl, octadecen 9,10 yl aminoethyl, docosen 13,14 ylaminopropyl and especially the oleoyl-aminoethyl, linoleuoyl-aminopropyl, linolenoyl aminoethyl, eicosenoylaminopentyl and docosenoyl-aminoethyl radicals;
Aralkyl radicals with a carbon chain interrupted by hetero atoms such as the (4-nonyl-phenyl)-ethyl-carboxyethyl radical.
R and R Suitable alkyl, alkenyl or aralkyl radicals which contain l28 carbon atoms and may be interrupted by hetero atoms and/or may be substituted, are the following, for example:
C -C -alkyl radicals such as the methyl, ethyl, isopropyl, dodecyl, hexadecyl, octadecyl, eicosyl and docosyl radicals;
C C -alkenyl radicals such as the buten-3,4-yl-(l)- and undecen-10,l1-yl-(l) radicals;
Substituted alkyl and alkenyl radicals such as the 2- hydroxyethyl, 3-hydroxypropyl, 3-hydroxybutyl, 13-hydroxy-octadecen-9,l-yl-(1), 2 chloroethyl, 3 chlor0 propyl, 1 l-bromoundecyl, 13-chloroctadecen-9,l0-yl-( l l3,l4 dichlorodocosyl, Z-cyanoethyl, 3-cyanopropyl, llcyano-undecyl, 3-aminopropyl, 3-(N-methyl-amino)-butyl, ll-amino-undecyl, l3-(N-methylamino)-docosyl and the carbethoxy-ethyl radicals;
Alkyl and alkenyl radicals with a carbon chain interrupted by hetero atoms, such as the methoxy-ethyl, ethoxy-butyl, 3-oxa-dodecyl-(1), S-OXa-heneicosyl- 1 3,6-dioxa-docosyl-( l 4-thia-hexenyll 3-thia-pentadecyl-(l), N-methyl-Z-aminoethyl, N-ethyl 3 aminopropyl, N-propyl 3 aminopropyl, N-dodecyl-Z-aminoethyl, N octadecyl-B-aminopropyl, N-heneicosyl-4-aminobutyl and the N-docosyl-6-aminobutyl radicals;
Aralkyl radicals such as the bcnzyl, 4-chlorobenzyl, 3- methyl-benzyl and 4-nonylphenyl-ethyl-carboxyethyl radicals.
R Suitable, optionally substituted C C -alkyl, C C -alkenyl, cycloalkyl or aralkyl radicals are the follow ing, for example:
C C -alkyl radicals such as the methyl, ethyl, isopropyl, sec.-butyl, Z-ethylhexyl, dodecyl, 2-hydroxyethyl, 3-hydroxy-propyl, Z-methoxyethyl, 2,3-epoxypropyl, chloromethyl, 2-bromoethyl, chloropropyl, 2-hydroxy-3-chlo ropropyl, 2,3-epoxy-propyl, carbethoxymethyl, carboxamidomethyl, Z-cyanoethyl, acetoxyethyl and S-trimethylammonium-propyl radicals.
C C -alkenyl radicals such as the buten-3,4-yl-(1)- undecen-l0,l1-yl-(1) radicals;
Cycloalkyl radicals such as the cyclohexyl, 4-methylcyclohexyl, 3-octylcyclohexyl and 4-chlor0cycl0hexyl radicals;
Aralkyl radicals such as the benzyl, 3-methylbenzyl, 4- cyclohexyl-benzyl, 4-methoxybenzyl and 3-chlorobenzyl radicals.
Suitable 5- or 6-membered heterocycles which may be formed by R together with R are primarily the morpholine and piperidine rings.
Suitable anions X-, are anions of organic acids, such as the chloride, bromide, iodide and sulphate ions; the anions of acidic esters of inorganic acids, such as the methyl-sulphate, ethyl-sulphate and toluene-sulphate ions; and the anions of or organic acids, such as the acetate, propionate, ethyl-caproate, oleate, behenate, benzoate and salicylate ions.
Z: Suitable alkylene radicals which contain 1-8 carbon atoms and may be interrupted by hetero atoms are the following, for example:
Alkylene radicals, such as 'the methylene, ethylene, propylene-1,2, propylene-1,3, butylene and hexylene radicals;
Alkylene radicals interrupted by hetero atoms, such as the 3-oxa-hexylene-L6 and 3,6-dioxa-octylene-L8 radicals.
Representatives of the onium compounds of the Formula I are the following, for example:
(a) Ammonium compounds, such as,
and the compounds of the formula CHa Representatives of the onium compounds of the Formula II are the following sulphonium compounds, for example:
bis-dodecyl-methyl sulphonium methylsulphate behenyl-dimethyl sulphonium chloride oleyl-methyl-benzyl sulphonium chloride.
Representatives of the quaternary ammonium compounds of the Formula 111 are the following, for example:
cm-omoroa Representatives of the amines of the Formula IV are the following, for example:
N-methyl-N-Z-hydroxyethyl-N- ['yoctadecanoyl amino -propyl] -amine N,N-dimethyl-4-dodecyl-aniline N-octadecyl-piperidine 1- (B-hydroxyethyl -2-octadecyl-imidazoline 1- fi-octadecanoylaminoethyl -2-octadecyl-imidazoline N-oleyl-N',N-diethyl-ethylene-diamine N-oleyl-N',N-dimethyl-propy1ene-diamine-( 1,3
N-oleyl-N',N'-diethyl-propylene-diamine-( 1,3)
N- 1- (undecyl dodecyl] -N,N-dimethy1amine 1 CH: (CH2) 7CH=C H-(CHQ) 7- C O NH (CH3) a-N-CHg-CHg- 0 H [CHs-(CH3)1S-CH C O N III-(CH2) alz/N-CH; Representatives of the aminoxides of the Formula V are the following, for example:
N,N-dibutyl-N-dodecyl-aminoxide N,N-dimethyl-N- 3-octadecanoylamino-propyl) aminoxide N,N-dimethyl-N- 3- N-octadecyl-carbaminyl -aminopropyl] -aminoxide N,N-dimethyl-N- (3-octadecylsulphonylamino-propyl aminoxide N,N-dimethyl-N-( 3 -oleoylamino-propyl) -aminoxide N-methyl-N,N-bis- [3- (octadecanoylamino -propyl]- aminoxicle N-methyl-N,N-bis- 3- dodecanoylamino -propyl] aminoxide N-methyl-N,N-bis- [3 oleoylamino -propyl] -aminoxide N-methyl-N-fi-cyanoethyl-N- 3- (octadecanoylamino pro pyl] -aminoxide N-methyl-N-fi-hydroxyethyl-N- [3 -oleoylamino -propyl] aminoxide N-methyl-N- [3- (octadecanoylamino) propyl] -N- [B- (octadecanoyloxy -ethyl] -aminoxide N ,N-dimethyl-N- fi-(N'-octadecylcarbaminyl)- hydroxyethyl] -aminoxide N-methyl-N-benzyl-N-dodecylaminoxide N,N-dimethyl-N- (4-dodecyl-phenyl -arninoxide N- lfi-hydroxyethyl -2-octadecyl-imidazoline-N-oxide 1- fl-octadecanoylamino-ethyl -2-octadecyl-imidazoline- N-oxide N,N-diethyl-N'-methyl-N'-octadecyl-ethylene-diamine- N,N'-dioxide N,N,N'-tris-(fi-hydroxyethyl)-N'-octadecyl-1,3-propylenediamine-N,N'-dioxide N,N,N',N-tetramethyl-aminomethyl-stearylamine-N,N'-
dioxide N,N-dimethyl-N-3 ,6,9-trioxa-heneicosyl-aminoxide N,N-dimethyl-N-4,7,10,13,16-penta-oxa-l9-thiahentriaconyl-arninoxide N-Inonoxides of the reaction products of 3-3 mol ethylene oxide on 1 mol eicosylamine, furthermore N-methyl-N-octadecyl-N- [3- di-p-chloroethylamino propyl] -aminoxide N-methyl-N-octadecyl-N- (3 -dimethylarnino -propylaminoxide N-methyl-N-octadecyl-N- [3 -aminopropylamino propyl] -aminoxide.
The compounds belonging to the group (B) are the following:
(1) Acidic sulphuric acid and phosphoric acid esters or their alkali metal, alkaline earth metal or ammonium salts containing at least one hydrocarbon radical which carries 16 carbon atoms, e.g.
Sulphates of monoand polyhydric alcohols containing at least 16 carbon atoms, such as cetylsulphate, stearyl sulphate, oleyl sulphate, behenyl sulphate, 2-heXyl-decanol-l-sulphate, 2,4,6-triethyl-decanol-l-sulphate, 3,10-diethyl-tridecanol-7-sulphate, 1,Z-diundecyl-ethylene-glycol monosulphate, glycerol-monostearate monosulphate;
The sulphates obtainable by sulphonation of unsaturated fatty acids, fatty acid esters and fatty acid ester amides, such as oleic acid sulphate, oleic acid butyl ester sulphate, ricinoleic acid ethyl ester sulphate, oleic acid ethylamide sulphate, oleic acid ethanolamide sulphate, oleic acid diisobutylamide sulphate, oleic acid anilide sulphate,
SOaH
CH;OCO(CH;)1
HO-CO--(CH)15CH;
cfia-O-C O(CH2) 10-0 -13 sulphates of acylated or alkylated polyglycol ethers containing not more than 30 ethylene oxide and/or propylene oxide units in the molecule, such as CH (CH CH=CH(CH CONH (C2H4O)1BSO3NK polypropylene glycol ether monosulphate (mol. weight sulphates of acylated or alkylated alkanolamines, such as N-acetyl-oleylamine sulphate Sulphates of monohydroxy-polycarboxylic acid esters, such as Acidic phosphoric acid esters, such as dioctadecyl phosphate and CH (CHa)mC ONHC2H4O-P (2) Aliphatic, araliphatic and aromatic sulphonic acids or their alkali metal, alkaline earth metal or ammonium salts containing at least one hydrocarbon radical which carries 16 carbon atoms, e.g.
Alkyl-sulphonic acids, such as Araliphatic sulphonic acids, such as CH: CH:
Aromatic sulphonic acids, such as alkylbenzene-sulphonic acids, e.g.
n-decylbenzene-sulphonic acid n-dodecylbenzene-sulphonic acid n-tetradecylbenzene-sulphonic acid n-hexadecylbenzene-sulphonic acid n-octadecylbenzene-sulphonic acid [2-(propyl)-heptyl]benzene-sulphonic acid [Z-(butyl)-octyl]-benzene-sulphonic acid [2- (amy1)-nonyl] -benzene-sulphonic acid Substituted benzene-sulphonic acids, e.g.
And acylated aminocarboxylic acids, e.g.
3-sulpho-phthalic acid-di-dodecyl ester heptadecyl-benzimidazole-sulphonic acid Alkyl-naphthalene-sulphonic acids, e.g. diisopropyl-naphthalene-sulphonic acid diisobdutyl-naphthalene-sulphonic acid diisobutyl-naphthylmethane-disulphonic acid (3) Amidosulphonic acids or their alkali metal, alkaline earth metal or ammonium salts containing at least one hydrocarbon radical which carries 16 carbon atoms, e.g.
(4) Sulphinic acids or their alkali metal, alkaline earth metal or ammonium salts containing at least one hydrocarbon radical which carries 16 carbon atoms, e.g. hexadecyl-sulphinic acid.
(5) Acidic sulphurous acid esters or their alkali metal, alkaline earth metal or ammonium salts containing at least one hydrocarbon radical which carries 16 carbon atoms, e.g. oleyl sulphite.
(6) Acidic thiosulphuric acid esters or their alkali metal or ammonium salts containing at least one hydrocarbon radical which carries 16 carbon atoms, e.g.
It has proved expedient in many cases that the chlorinated hydrocarbon after-treatment baths should contain, in addition to the compounds which are interfaceactive in chlorinated hydrocarbons and convert the dyestuffs used into a .form soluble or dispersible in chlorinated hydrocarbons, small amounts of water, e.g. 0.01-4 percent by weight, referred to the weight of the chlorinated hydrocarbons, and possibly also 0.00 1-2 percent by weight of anon-ionic emulsifier, referred to the weight of the chlorinated hydrocarbons.
As non-ionic emulsifiers there may be used the commercial non-ionic emulsifiers; for example, reaction prodducts of 1 mol of fatty alcohols, fatty acids, fatty amines, fatty acid amides, fatty acid alkanolamides, fatty acid glycerides, alkyl-phenols, alkyl-benzyl-phenols, alkyl-arylbenzyl-phenols, aryl-styryl-phenols or abietic acid, with 5-100 mol ethylene oxide; and also fatty acid esters of aliphatic polyhydroxy compounds and fatty acid alkanolamides.
Furthermore, it has frequently proved advantageous that the chlorinated hydrocarbon after-treatment baths should also contain 0.001-8 percent by weight, referred to the weight of the chlorinated hydrocarbons, of water-miscible organic solvents, such as isopropanol, benzyl alcohol, phenoxy-ethanol, acetonitrile, hydroxypropionitrile, dimethyl sulphoxide, dimethyl formamide or methyl glycol acetate; and to add to the chlorinated hydrocarbon aftertreatment baths 0.0l-0.5 percent by weight, referred to the weight of the chlorinated hydrocarbons, of acetic acid when after-treating dyeings and prints obtained with cationic dyestuffs, and 0.0l-0.5 percent by weight, referred to the Weight of the chlorinated hydrocarbons, of mono-, dior triethanolamine and/or 0.01-1 percent by weight, referred to the weight of the chlorinated hydrocarbons, of acetic acid when after treating dyeings or prints obtained with acidic dyestuffs, anionic sulpho group-free metal complex dyestuffs or with sulpho group-containing reactive dyestuffs.
The process according to the invention is suitable for the dyeing with cationic dyestuffs as well as for the dyeing with acid dyestuffs, anionic, sulpho group-free metal complex dyestuffs and sulpho group-containing reactive dyestuffs.
Suitable cationic dyestuffs are methine, azomethine, hydrazone, azacyanine, triarylmethane, xanthene, thioxanthene, acridine, oxazine, thiazine and phenazine dyestuffs; furthermore, the basic dyestuffs of the azo, anthraquinone or phthalocyanine series, such as are described e.g. in Colour Index, vol. 1, 2nd Edition (1956), pages 1617- 1654, and in the Supplement of 1963, and also in French patent specification No. 1,480,930.
Suitable acid dyestuffs are all water-soluble dyestuffs of the azo, anthraquinone, triphenyl-methane and phthalocyanine series which contain up to four sulpho groups; examples of anionic sulpho group-free metal complex dyestuffs are the sulpho group-free 1:2 metal complex dyestuffs of the azo and triphenylmethane series which contain at least two groups capable of dissociation; and the sulpho group-containing reactive dyestuffs comprise e.g. water-soluble dyestuffs of the azo, anthraquinone and phthalocyanine series, which contain at least one fibrereactive group, for example, a monochloro-triazinyl, dichlorotriazinyl, dichloro-quinoxalinyl, trichloro-pyrimidinyl, difluoro-chloro-pyrimidinyl, u-bromoacrylamide group or the fl-hydroxyethyl-sulphuric acid semi ester group.
Insofar as thickening agents are required for preparing the dyestutf emulsions, thickening agents poor in body are preferred for the process according to the invention.
The process according to the invention is suitable for the dyeing and printing of all textile materials which can be dyed or printed with the aforesaid dyestuffs. These include, for example, the textile materials of polyacrylonitrile, polyester, cellulose 2 /2-acetate, cellulose triacetate, synthetic polyamides and silk, which can be dyed with basic dyestuffs; the textile materials of natural or regenerated cellulose such as cotton, staple fibre and rayon, cellulose 2 /2-acetate, cellulose triacetate, of natural polyamides such as wool and silk, and of synthetic polyamides such as polyhexamethylenediamine adipate, polycaprolactam or poly-a-aminoundecanoic acid, which can be dyed with acid, metal complex and reactive dyestuffs. The present process has proved particularly satisfactory for the dyeing and printing of mixtures of these types of fibres, e.g. mixtures of polyacrylonitrile/ staple fibre, polyester/ cotton, polyester/staple fibre, polyamide/ staple fibre, polyamide/cotton, cellulose 2 /z-acetate/staple fibre, cellulose triacetate/staple fibre or polyacr'ylonitrile/polyester.
The textile materials may be present in various stages of processing, e.g. as threads, ribbons, combed material, yarn, fabrics, knitted fabrics or ready-made goods.
The chlorinated hydrocarbons expediently used in the after-treatment baths of the process according to the invention are aliphatic chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride,
1,1 dichloroethane, 1,2 dichloroethane, 1,1,1-trichloroethane, 1,1,2 trichloroethane, 1,l,1,2 tetrachloroethane, 1,1,2,2 tetrachloroethane, pentachloroethane, l-chloropropane, 1,2 dichloropropane, l-chlorobutane, Z-chlorobutane, 1,4 dichlorobutane, 1 chloro 2 methyl-propane, 2 chloro 2 methyl propane or 4 chloro-2- methyl-propane. Tetrachloroethylene, trichloroethylene and 1,1,1 trichloropropane have proved particularly satisfactory.
The process according to the invention is carried out by applying the dyestuffs to the textile materials by means of the dyestuff emulsions according to the exhaust, spray, padding or printing process at temperatures from 20 to 120 C. Subsequently, possibly after a conventional heat treatment such as drying, steaming or thermosolising, the textile materials are subjected in a continuous or discontinuous operation to an after-treatment in chlorinated hydrocarbon solutions containing interface-active compounds which convert the dyestuffs used into a form soluble or dispersible in chlorinated hydrocarbons. Optionally, this after-treatment is followed by rinsing in pure chlorinated hydrocarbon. By this after-treatment any nonfixed dyestuifs or dyeing auxiliaries are so completely removed from the textile materials that, after separation of the wash liquor and removal of the last solvent residues by blowing out with air or steam, the materials can be stored without any further after-treatment.
The emulsions to be used as dyebaths or printing pastes may either contain water as a continuous phase and the chlorinated hydrocarbons as a discontinuous phase, or they may contain the chlorinated hydrocarbons as a continuous phase and water as a discontinuous phase. In any case the aqueous phase is a solution of water-soluble dyestuffs; the chlorinated hydrocarbon phase may be a solution of a dyestuif soluble in chlorinated hydrocarbons, but it may also be formed by chlorinated hydrocarbons free from dyestuff.
The amounts of dyestuff dissolved in the respective phases depend upon the desired depth of colour of the dyeings or prints, upon the solubility of the dyestuffs, and upon whether the exhaust, spray, padding or printing process is applied. In general, amounts of 0.2 to 50 g. of dyestuff per litre of dyestulf emulsion have proved satisfactory.
As emulsifiers for preparing the dyestulf emulsions, there may be used the compounds which usually serve for preparing oil-in-water and water-in-oil emulsions. Nonionic emulsifiers have proved especially satisfactory for the process according to the invention.
Suitable non-ionic emulsifiers are the commercial non-ionic emulsifiers, for example, reaction products of 1 mol of fatty alcohols, fatty acids, fatty amines, fatty acid amides, fatty acid alkanolamides, fatty acid glycerides, alkyl-phenols, alkyl-benzyl-phenols, alkyl-aryl-benzyl-phenols, aryl-styryl-phenols or abietic acid, with lmol ethylene oxide; furthermore, fatty acid esters of aliphatic polyhydroxy compounds and fatty acid alkanolamides.
The amounts of emulsifier required for preparing and stabilising the emulsions should not exceed 10 percent by weight, referred to the weight of the emulsions, and should preferably amount to 0.2 to 5 percent by Weight.
Besides the dyestuffs and emulsifiers, the dyestuif emulsions may contain the usual dyeing auxiliaries, e.g. urea. The amounts of these auxiliaries depend on the dyestuffs used and on the dyeing process. In general, they amount to about 10 to 500 percent by weight, referred to the weight of the dyestuffs.
The emulsions can be prepared in the usual way. It has proved expedient to prepare the solutions forming the two phases separately and to emulsify, after the addition of the emulsifiers, with the aid of rapid stirrers or turbomixers.
Chlorinated hydrocarbons which can serve for the preparation of the dyestulf emulsions are those chlorinated hydrocarbons which are also suitable for the after-treatment baths. Tetrachloroethylene, trichloroethylene and l,1,l-trichloropropane have proved especially satisfactory also in the dyestuif emulsions.
With the aid of the process according to the invention it is possible to dye textile materials of various kinds with the conventional fastness properties in a gentle and practical way without the occurrence of waste Water. The process according to the invention combines the advantages of dyeing from aqueous media (use of conventional dyestuffs, good fastness properties of the resultant dyeings) with the advantages of dyeing from organic solvents (unimpaired appearance of the goods, virtually no occurrence of waste water), wthout having the disadvantages of these processes.
A particular advantage of the process according to the invention consists in that textile materials can be dyed in the chlorinated hydrocarbon medium in a single bath with water-soluble dyestuffs and with dyestuffs soluble in chlorinated hydrocarbons.
The process according to the invention is therefore eminently suitable for the dyeing and printing of materials of cellulose fibres and of mixtures thereof with synthetic fibres with the use of water-soluble reactive dyestuffs for the cellulose fibre component and of disperse dyestuffs soluble in chlorinated hydrocarbons for the synthetic fibre component, and well as for the dyeing and printing of polyacrylonitrile/polyester fibre mixtures with the use of cationic water-soluble dyestuffs for the polyacrylonitrile component and of disperse dyestuffs for the polyester fibre component.
From Belgian patent specification No. 707,187 there is known a process for the dyeing of textile materials from chlorinated hydrocarbons, in which the textile materials are dyed in chlorinated hydrocarbon/Water emulsions containing water-soluble or water-dispersible dyestuffs in the aqueous phase. If this process is used for dyeing With water-soluble dyestuffs, especially reactive dyestuffs and cationic dyestuffs, then dyeings of unsatisfactory fastness to wet processing are obtained, since the proportion of dyestuff which is not bound by the fibre is only incompletely removed by the subsequent washing of the dyeings with chlorinated hydrocarbons. To achieve satisfactory fastness to wet processing, the dyeings must therefore be rinsed with aqueous liquors. By using aqueous wash liquors, however, the advantages of dyeing from organic solvents (unimpaired appearance of the goods, slight occurrence of waste water) are cancelled out.
Compared with the process of the Belgian patent specification, the process according to the invention has not only the advantage of permitting dyeing with water-soluble dyestuffs and with dyestuffs soluble in chlorinated hydrocarbons from chlorinated hydrocarbon/water emulsions; it has primarily the advantage that, due to the after treatment with the chlorinated hydrocarbon solutions containing compounds which convert the dyestuffs into a form soluble or dispersible in chlorinated hydrocarbons, dyeing with water-soluble dyestuffs, e.g. reactive dyestuffs and cationic dyestuffs, without having recourse to aqueous baths, yields dyeings of the same good fastness to wet processing as is achieved when dyeing from aqueous baths.
The parts given in the following examples are parts by weight; the constitution of the dyestuffs market with the figures (I)(XVIII) are given in the table following the examples.
EXAMPLE 1 A polyester/cotton mixed fabric (65:35) is padded with an emulsion consisting of parts of the dyestuff XVI 2 parts nonylphenol pentadecaethylene glycol ether 1 part oleic acid ethanolamide parts of the dyestuff XIII 14 60 parts urea 8 parts sodium bicarbonate 94 parts of water and 800 parts perchloroethylene (liquor absorption dried at 80 C. for 1 minute and thermosolised at C. for 30 seconds.
The fabric then passes, with a time of residence of 1.5 minutes each time, through four successive closed washing aggregates which operate according to the counter-current principle and contain a solution at 55 C. which consists of 4 parts of the compound of the formula 1 part of water 5 parts of 30% acetic acid and 990 parts perchloroethylene and is mechanically agitated. The liquor ratio for this after-treatment amounts to 1:50. After mechanical separation of the rinsing liquor by squeezing, the fabric is freed from the adhering solvent residues by blowing with hot air, and stored. A clear yellow/red bicolour dyeing of good fastness properties is obtained. No waste Water occurs in the after-treatment.
If the after-treatment is carried out by the same method with perchloroethylene without the additives according to the invention, then the non-fixed dyestuff component which is insoluble in perchloroethylene is not removed from the fabric, and the fastness properties of the resultant dyeing are therefore unsatisfactory.
If the after-treatment according to the invention described above is retained with the difference that the dyestuffs are not applied from the chlorinated hydrocarbon/water emulsion described above but from a pure aqueous dyebath in which the dyestuif XIII is dissolved but the dyestuff XVI is present in disperse form with the aid of dispersing agents, then a less clear yellow/red bicolour dyeing is obtained.
If the 5 parts of the compound of the formula CH: 69 X CH3 CH3 c Ha -ours -orn( C H2) 10- 31 CH3 0 S 9 ea Q] or with 5 parts of a mixture of 2.5 parts of the compound of the formula and 2.5 parts isopropanol or with 5 parts of a mixture of the compounds (a)-(1), then an equally good after-treatment efiect is achieved.
EXAMPLE 2 A polyester/polyacrylonitrile mixed fabric (50:50) is padded with an emulsion consisting of 20 parts of the dyestulf I 10 parts of the dyestufi XVI 4 parts methyl glycol acetate 4 parts glylcerol monoacetate 1 part oleic acid ethanolamide 3 parts nonylphenol decaethylene glycol ether 10 parts of 60% acetic acid 148 parts of water and 800 parts perchloroethylene (liquor absorption 80%) and thermosolised at 180 C. for 1 minute.
Subsequently, the fabric web successively passes, in a liquor ratio of 1:50 and With a time of residence of 2 minutes each time, through four solutions of 5 parts sodium dodecyl-benzene sulphonate 0.5 part of 60% acetic acid and 5 parts of water in 989.5 parts perchloroethylene the invention, then the non-fixed, perchloroethylene-insoluble dyestufi is not removed from the fabric and the fastness properties of the resultant dyeing are therefore unsatisfactory.
If the 5 parts sodium dodecyl-benzene sulphonate are replaced with 5 parts dodecyl-benzene-sulphonie acid or 5 parts sodium diisobutyl-naphthalene-sulphonate or 5 parts sodium C -paraifin sulphonate or 5 parts of the compound of the formula 5 parts of a 1:1 mixture of sulphonated sperm oil and sulphonated olive oil or 5 parts of the compound of the formula or 7 parts of a mixture of 5 parts of the compound of the formula CH3(CH2)7CH=CH(CH2)7 and 2 parts oleyl alcohol heptadecaethylene glycol ether,
then an equally Well-rinsed dyeing is obtained.
An equally satisfactory dyeing is also obtained when the 989.5 parts perchloroethylene are replaced with the same amount of 1,1,1-trichloroethane.
EXAMPLE 3 A polyacrylonitrile fabric is padded with an emulsion consisting of 20 parts of the dyestuff II 2 parts oleyl alcohol eicosaethylene glycol ether 12 parts B-cyanoethyl formamide 4 parts nonylphenol decaethylene glycol ether 10 parts of 60% acetic acid, parts of water and 852 parts perchloroethylene,
(liquor absorption 100%), dried at C. for 1 minute and steamed at 102 C. for 15 minutes.
The fabric is then treated in a liquor ratio of 1:100 in a bath consisting of 10 parts of the compound of the formula CH3-(CHz) sCI-Ig O O /P CH3-(CHB) ltl-CHgO 10 parts of water and 980 parts perchloroethylene at 55 C. for 6 minutes, subsequently rinsed twice with fresh perchloroethylene and, after separating the liquor, freed from the perchloroethylene adhering to the fibre by blowing with steam. Without the occurrence of waste water, there is obtained a red dyeing which is rinsed clear and has the same fastness properties as a dyeing rinsed with an aqueous Washing liquor.
Without the additives to the perchloroethylene aftertreatment bath, a dyeing of poor fastness properties is ob tained, since the dyestuff which is not bound by the fibre is not removed from the fabric.
1 7 EXAMPLE 4 A polyacrylonitrile fabric is padded with an emulsion consisting of 15 parts of the dyestulf III 10 parts fi-cyanoethyl formamide 3 parts nonylphenol-decapentaethylene glycol ether 2 parts oleyl alcohol eicosaethylene glycol ether 100 parts of water and 870 parts perchloroethylene (liquor absorption 100%) and steamed at 102 C. for 20 minutes.
The polyacrylonitrile fabric is then passed in a liquor ratio of 1:50 through four successive after-treatment baths which have been heated to 50 C. and operate according to the counter-current principle, each containing 1 part sodium dodecylbenzene sulphonate 3 parts of water and 0.05 part of glacial acetic acid in 996 parts perchloroethylene.
The fabric is subsequently rinsed with pure perchloroethylene, the rinsing liquor is separated and the adhering solvent driven otf by blowing with steam. The blue dyeing obtained without the occurrence of waste water has the same fastness properties as a corresponding dyeing aftertreated in aqueous baths.
If the 1 part sodium dodecyl sulphonate is replaced with 1 part of the compound of the formula CH (CH2)1CH=(CHz)1C O N-CHg-CH B O Nn or 1 part of the compound of the formula 1 part of the compound of the formula CH (CH CH cm I: 2)1a \2 then an equally good washing-out efiect is obtained.
If the 1 part sodium dodecylbenziene sulphonate is replaced with 1 part of the compound of the formula CH3- H1 16-- 14 CH CH1- H3 (C C I 2 00 C GHQ-(CH2) 15-0 0 NH-( HQP? Gill-C14,
then 6 successive after-treatment baths are required, instead of four. After the passage through these 6 baths each of which contains 1 part of the above compound and 3 parts of water in 996 parts perchloroethylene,
then an equally satisfactory dyeing is obtained.
EXAMPLE 5 A polyacrylonitrile fabric is printed with a printing paste of the composition parts of the dyestntf IV parts di-fi-cyanoethyl formamide 30 parts thiodiglycol 2 parts nonylphenol decaethylene glycol ether 30 parts of 30% acetic acid 30 parts of water and 873 parts perchloroethylene,
dried at 110 C. for 1 minute and steamed at 102 C. for 25 minutes.
The printed fabric is then mechanically moved about in a liquor ratio of 1:50 for 3 minutes in a bath which has been heated to 50 C. and consists of 5 parts of a compound of the formula a- (CH1) 16-0 o1;rcH,-cm-o o 0 H CH3 5 parts of water and 990 parts perchloroethylene and subsequently treated in a liquor ratio of 1:50 for 3 minutes in a second bath which has likewise been heated to 50 C. and has the composition 1 part of a compound of the formula CHg-(CHz) 18-0 0 N-CH1CH;C 0 OH H, 0.5 parts of the reaction product of 1 mol oleic acid with 1 mol diethanolamine 3.5 parts of water and 995 parts perchloroethylene and subsequently rinsed in a liquor ratio of 1:50 for 1 minute in pure perchloroethylene. The perchloroethylene is then separated and the residues of perchloroethylene adhering to the fabric are removed by blowing with steam.
A clear blue print of good fastness properties is obtained without the occurrence of waste water.
If the compound of the formula is replaced in the first and second washing baths with the same amount of the compound of the formula CH;(CHa)1CH=CH(CH )7 C ON-CHg-C 0 ONH4 Ha then the same good washing-out eifect is achieved.
Without the above additives, the resultant print is useless because of its poor fastness properties.
EXAMPLE 6 A fabric of anion-modified polyester (Dacron 64) is padded with an emulsion consisting of 20 parts of the dyestuif V 60 parts ethylene-cyanohydrin 3 parts formamide 10 parts of glacial acetic acid 50 parts of water 3 parts nonylphenol-pentadecaethylene glycol ether and 854 parts perchloroethylene (liquor absorption dried at 100 C. for 1 minute and thermosolised at 200 C. for seconds.
The dyed fabric is subsequently mechanically moved about in a liquor ratio of 1:50 to 2 minutes in an aftertreatment bath which has been heated to 55 C. and has the composition 1 part of technical oleic acid 1 part oleyl alcohol heptadecaethylene glycol ether 1 part sulphosuccinic acid dioctyl ester and 4 parts of water in 993 parts perchloroethylene,
1 9 EXAMPLE 7 A polyacrylonitrile fabric is padded with an emulsion consisting of 10 parts of the dyestufi VI 11 parts of 85% formic acid 9 parts of 60% acetic acid 12 parts ethylene-cyanohydrin 8 parts glycerol monoacetate 8 parts methyl glycol acetate 4 parts nonylphenol decaethylene glycol ether 88 parts of water and 850 parts perchloroethylene (liquor absorption 100%), dried at 100 C. for 1 minute and thermosolised at 200 C. for 1 minute. 15
The fabric then passes through 5 successive wash baths which have been heated to 50 C., each containing 5 parts of a mixture of 19.5 parts of the compound of the formula (CH (CH CO-NH-CH CH NH 1 part stearic acid 2 parts of the compound of the formula CH; 0.5 parts oleyl alcohol heptadecaethylene glycol ether 3 parts of glacial acetic acid 19.5 parts isopropanol and (2) When 5 parts of the mixture are replaced with 5 parts of one of the following compounds of the Formulae a-g:
CH: ila- H: 63
54.5 parts of water in 995 parts perchloroethylene,
is replaced in the mixture with the same amount of the aminoxide of the formula [CH3- (CH1) 16 C o NH-CH;CH,]z llI-CH= then the resultant dyeing is equally well rinsed.
The same good washing-out effect is achieved (1) When the 19.5 parts of the compound of the formula [CH (CH C0NH--CH -CH NH are replaced in the mixture described above with 19.5 parts of one of the following aminoxides of the Formulae a-e:
ila-( H2) ill- 3 (3) When 5 parts of the mixture are replaced with 5 parts of a mixture consisting of 2.5 parts of a compound of the formula 0113 e omcmn-orkon-ronnhom-N :lcm-om-osoa 2H5 CH3 2.5 parts of a compound of the formula CHa 9 a-CHz-OS O3 (4) When 5 parts of the mixture are replaced with 5 parts of a mixture consisting of 2.5 parts of a compound of the formula 21 22 1.2 parts of a compound of the formula 5 parts of a compound of the formula 9 9 om- H, 1-oH=oH-(om)7-o0NH-omomcm N 016 (CHz-(CHzhz-CHgh/N ole 3 5 parts isopropanol 0.6 part of a compound of the formula parts f water, d
980 parts perchloroethylene 10 and subsequently treated for 1 minute in a fresh rinsing (CH=-(CH:)14CHa):/N C1 bath at 55 C., which consists of CH1 990 parts perchloroethylene, and 0.4 part of a compound of the formula 5 Parts Of lc acld.
15 After separating the rinsing liquor, the solvent adhering /CH3 ea to the fabric is removed by blowing with steam. Without the occurrence of waste water there is obtained a well- 016 l:(CH3( 2)1B 2)2/ rinsed, clear yellow/red bicolour dyeing of good fastness CH1 properties.
If the 5 parts of the compound of the formula CH: 69 [cm-(0H,)7-CH=0H(0H,)1C0NH0HcH,CH,]2/N :l (:1
CH: are replaced with 5 parts of one of the ammonium compounds of the Formulae a-d (a) 1O (ITH: G5
[Cm-(CH1) s-CH1-NH(5 OCHzCH ]zNCH:CHr-OH] CH3O S 03 Q 6 O I ll 01 CH;(CH2)15CH;NH OCH CH;-NCH;CHg-OH CHg-CH -OH and 0.3 part of a compound of the formul 40 CHFwHmPcHa cm 9 4 01 (CHa( 2)1 I)P 02 N 019 a-( 2)1o-C 2 CH;|CH CH3 CH: O and 5 parts isopropanol. (d)
EXAMPLE 8 Ii a-( z)1- CH= C H-( H2)7- ONH(CHz)a-N-( CH3) 3]] 89 (31 030 9 A polyacrylonitrile/staple fibre mixed fabric (65:35) 5 Parts Of the r ary amine of the formula is padded with an emulsion consisting of CH: 10 parts of the dyestulf I Ha( Hi)1OH=oH- cH,)1-00NH- cm 3 N-cH,-cH,-0 10 parts of the dyestulf VII Parts urea or 5 parts of the aminoxides of the Formulae a and b;
5 parts nonylphenol decaethylene glycol ether 15 parts sodium parafiin sulphonate (a) 3 parts of glacial acetic acid 55 [CHF(CH,)7 CH=OH (CHI)I C 97 parts of water, and 800 parts perchloroethylene 0 CH1 CHs(CH:)1CH=CH-(CHq) -C 0N11-om-cm-cm-1ir-cm-cm-0 H then the good washing-out effect and an equally satisfactory dyeing is achieved.
(liquor absorption 80%), dried at 120 C. for 90 seconds and thermosolised at 200 'C. for 90 seconds. The
fabric is subsequently padded with an emulsion consisting of EXAMPLE 9 20 parts sodium carbonate A fabric of a polyester which can be dyed with basic 100 Parts of Water dyestuffs is padded with an emulsion consisting of 2 parts nonylphenol decaethylene glycol ether, and
10 parts of the dyestulf VIII 878 parts perchloroethylene 1 part oleic acid ethanolamide and steamed at c. for 5 minutes 2 parts nonylphenol decaethylene glycol ether The fabric is subsequently treated in a liquor ratio of 30 Parts butyrolactone 1:50 for 5 minutes in an after-treatment bath which has 21 Parts urea been heated to 55 C. and consists of 30 parts of 60% acetic acid 23 6 parts of water and 850 parts trichloroethylene with a liquor absorption of about 104%, dried at 100 C. for 90 seconds and thermosolised at 200 C. for 90 seconds.
The fabric is then treated in a liquor ratio of 1:50 for 3 minutes in an after-treatment bath at 50 C. consisting of 5 parts of the N,N-di-octadecyl-N,N-dimethyl ammonium salt of sulphated rapeseed oil 5 parts of water and 990 parts perchloroethylene and subsequently in an after-treatment bath consisting of 1 part of the N,N-di-octadecyl-N,N-dimethyl ammonium salt of sulphated rapeseed oil 1 part of water and 998 parts perchloroethylene.
rapeseed oil are replaced with 5 parts and 1 part, respeci tively, of a mixture of 3 parts of the compound of the formula c CH CH CH s( 2)l!16 \2@/ a 9 parts isopropanol,
then the same washing-out eifect is achieved.
EXAMPLE 10 A mixed fabric (50:50) of a polyamide which can be dyed with basic dyestuffs and a polyamide which can be dyed with acidic dyestuffs is padded with an emulsion consisting of 10 parts of the dyestulf I 10 parts of the dyestuif IX 4 parts of the reaction product of 1 mol oleyl alcohol with 50 mol ethylene oxide 4 parts nonylphenol decaethylene glycol ether 3 parts of a mixture consisting of 20 parts of a compound of the formula CgHs 40 parts oleyl alcohol eicosaethylene glycol ether and 40 parts ethyl hexanol 5 parts of 60% acetic acid 80 parts of water and 884 parts perchloroethylene with a liquor absorption of 70%, dried at 80 C. for 1 minute and steamed at 105 C. for 3 minutes.
The fabric web then successively passes in a liquor ratio of 1:30 with a time of residence of 2 minutes each time through two after-treatment baths which are mechanically agitated and have been heated to 50 C. and which consist of 0.75 part of the N,N-di-octadecyl-N,N-dimethyl ammonium salt of sulphated rapeseed oil 0,75 parts of a compound of the formula CHs-CONH-SOP(CH2)M-CH| NaSOaCH-COOCHz-CH-(OHz)a-CH;
0.5 parts of a compound of the formula 3 l)16 Efl CH:
03 l CHa-(GHflm-CH: CHf-C o 0-CHa-CH; 1 part of the reaction product of 1 mol oleyl alcohol eicosaethylene glycol ether and 5 parts of water in 980 parts perchloroethylene and subsequently with a time of residence of 1 minute through a rinsing bath of pure perchloroethylene which has been heated to 50 C. After separating the rinsing liquor, the fabric is freed from the adhering perchloroethylene by blowing with steam. Without the occurrence of waste water, there is obtained a dyeing with a yellowblue pattern of excellent fastness properties.
EXAMPLE 1 1 A Turkish towelling fabric of cotton is padded with an emulsion consisting of 40 parts of the dyestufl? X parts urea 98 parts of water 10 parts sodium bicarbonate 5 parts nonylphenol decaethylene glycol ether and 767 parts perchloroethylene,
dried at 140 C. for 1 minute and condensed at 150 C. for 3 minutes.
The fabric is subsequently after-treated in a liquor ratio of 1:40 for 3 minutes each time in two successive baths which have been heated to 50 C. and consists of 5 parts of a compound of the formula 5 parts of 60% acetic acid 10 parts of water and 980 parts perchloroethylene and subsequently rinsed at the same temperature for 2 minutes with fresh perchloroethylene. After separating the rinsing liquor, the solvent residues are removed by blowing with steam. Without the occurrence of waste water, there is obtained a yellow dyeing which has been rinsed clear and has faultless fastness properties.
EXAMPLE 12 A polyacrylonitrile/cotton mixed fabric (50:50) is padded with an emulsion consisting of 9 parts of the dyestuff XI 26 parts of ethylene-'cyanohydrin 15 parts formamide 2 parts nonylphenol decaethylene glycol ether 1 part oleic acid ethanolamide 60 parts urea parts of water and 804 parts perchloroethylene (liquor absorption dried at 80 C. for 90 seconds and thermosolised at 202 C. for 1 minute.
The fabric subsequently passes with a time of residence of 90 seconds each time through 6 successive aftertreatment baths which have been heated to 50 C. and consist of 5 parts of the compound of the formula CH3(CH2)16 C0 NH (CH2)3 N (CH3)2 15 parts of water and 980 parts perchloroethylene.
25 The material is then rinsed in pure perchloroethylene at 50 C., the rinsing liquor is separated and the fabric freed from the adhering solvent by blowing with steam. Without the occurrence of waste water, there is obtained a dyeing with a yellow/white effect which has been rinsed clear and has the same fastness properties as a dyeing after-treated with aqueous baths.
If the parts of the compound of the formula 3( 2) 1s 2) 3- 3 2 are replaced with 5 parts of the compound of the formula then the resultant dyeing is rinsed equally clear.
EXAMPLE 13 A staple fibre fabric is padded with an emulsion consisting of 30 parts of the dyestuif XII 4 parts nonylphenol pentadecethylene glycol ether 80 parts urea parts sodium bicarbonate 90 parts of water and 786 parts perchloroethylene (liquor absorption 80%), dried at 80 C. for 1 minute 54 parts of a mixture consisting of 0.6 parts sodium carbonate 10.4 parts of water 5 parts urea 32 parts perchloroethylene and 6 parts of a mixture consisting of 30 parts sodium paraflin sulphonate 2.5 parts sodium dodecyl-benzene sulphonate 17.5 parts of the sulphuric acid ester of a sperm oil alcohol 12. parts of water are then added to the dyebath and the treatment is continued at 40 C. for 1 hour. The dyebath is subsequently heated to 110 C. within 20 minutes and the same temperature is maintained for 1 hour. The dyeing emulsion is then drained ofl, and the fabric rinsed with fresh and steamed with overheated steam at 150 C. and norperchloroethylene mal pressure for 1 minute.
The fabric is subsequently after-treated in a liquor ratio of 1:50 for 2 minutes each time in 5 succesive baths which have been heated to 55 C. and consisting of The fabric is then after-treated in a liquor ratio of 1:20 with a time of residence of 10 minutes with a bath which has been heated to 50 C. and consists of 5 parts of the compound of the formula 5 parts of a compound of the formula CH CH 0CH NCH s( 92 2 H a 019 2 5 parts isopropanol 5 parts of water 5 parts of 60% acetic acid and 985 parts perchloroethylene CHa-(CHz) 0CH:NCH1
2 I or is replaced with 5 parts of the compound of the formula or with 4 parts of a mixture of the two compounds, then the same good washing-out effect is achieved.
EXAMPLE 14 100 parts of a polyester/cotton mixed fabric (67:33) are printed in a pressure Winding frame at C. for 30 minutes with an emulsion consisting of 5 parts of water 2 parts of 60% acetic acid and 988 parts perchloroethylene The fabric is subsequently rinsed with pure perchloroethylene at C. for 2 minutes. After separating the rinsing liquor, the fabric is freed from the adhering solvent by blowing with steam. There is obtained a red/ blue bicolour dyeing which has the same fastness properties as a dyeing washed with aqueous wash baths.
EXAMPLE 15 A cotton fabric is padded with an emulsion consisting of 40 parts of the dyestutf XIV 3 parts nonylphenol decaethylene glycol ether parts urea 10 parts sodium carbonate 100 parts of water and 787 parts perchloroethylene (liquor absorption dried at 80 C. for 1 minute and steamed at 102 C. for 5 minutes.
The fabric is subsequently after-treated in a liquor ratio of 1:50 with a time of residence of 2 minutes each time in 3 successive baths which have been heated to 55 C and consist of 5 parts of the aminoxide of the formula 10 parts of water and 985 parts perchloroethylene.
The fabric is then rinsed with pure perchloroethylene at 55 C., for 2 minutes. After separating the rinsing liquor,
the fabric is freed from the adhering perchloroethylene residues in an air current. A clear yellow dyeing is obtained without the occurrence of Waste water.
EXAMPLE 16 A polyester/cotton mixed fabric (65:35) is padded with an emulsion consisting of 12 parts of the dyestuff XVI 2 parts nonylphenol decaethylene glycol ether 1 part oleic acid ethanol amide 20 parts of the dyestulf VII 60 parts urea 8 parts sodium bicarbonate 97 parts of water and 800 parts perchloroethylene (liquor absorption 80% dried at 120 C. for 60 seconds and thermosolised at 18.0 for 60 seconds.
The fabric then passes through 5 successive washing aggregates which operate according to the counter-current principle and contains a solution at 55 C. consisting of 5 parts of the compound of the formula 5 parts of water and 990 parts perchloroethylene.
The liquor ratio for the after-treatment amounts to 1:100. The fabric is subsequently rinsed with a mixture at 55 C. consisting of 990 parts perchloroethylene 5 parts of 60% acetic acid and 5 parts of water.
After separating the rinsing liquor, the fabric is freed from the adhering solvent residues by blowing with air. Without the occurrence of waste water there is obtained a clear dyeing with a red/yellow pattern which has the same fastness properties as a dyeing after-treated with aqueous liquors.
EXAMPLE 17 A polyester/ staple fibre mixed fabric (70:30) is padded with an emulsion consisting of 20 parts of the dyestutf XVI 15 parts of the dyestutf XIV 50 parts urea 70 parts nonylphenol hexaethylene glycol ether 5 parts sodium bicarbonate 60 parts of water and 780 parts perchloroethylene (liquor absorption 80% dried at 120 C. for 90 seconds and thermosolised at 180 C. for 90 seconds.
The fabric is subsequently after-treated in a liquor ratio of 1:50 for 5 minutes in bath at 55 C. consisting of 5 parts of the compound of the formula I [CH -(CH2)16 CO-NH-CHn-CHg]g/IgT-CHg-CHg-CHn-SOa 10 partsof 30% acetic acid and 985 parts perchloroethylene are replaced with (a) 5 parts of a mixture o f equal parts of the compound of the formula and oleic acid or (b) 5 parts of a mixture of equal parts of the compound of the formula and the compound of the formula (c) 5 parts of a mixture of equal parts of the compound of the formula and the compound of the formula or (d) 5 parts of the N,N-dioctadecyl-N,N-dimethyl ammonium salt of sulphated rapeseed oil or (e) 5 parts of a mixture of 18.5 parts of the compounds of the formula CH3 e [GH3 (CH2)10 CHB] 2\N/ :lCl
/ CHa 17.5 parts of the compound of the formula CH3(CH2)7-CH=CH(cH2)7--CH3 0(CH CH -0) 17H and 8 parts isopropanol or (f) 5 parts of a mixture of 18 parts of the compound of the formula 6 (CH (CH) CH) N C1 a z 16- a 2/ 1 17.5 parts of the compound of the formula EXAMPLE 1 8 A fabric of polyhexamethylene-diamine adipate is padded with an emulsion consisting of 20 parts of the 1:2 chromium complexes of the dyestutf XVII 3 parts nonylphenol decaethylene glycol ether parts urea 100 parts of water and 797 parts perchloroethylene (liquor absorption 80%), dried at 80 C. for seconds and thermosolised at 210 C. for 1 minute.
The fabric then passes in a liquor ratio of 1:50 and with a time of residence of 2 minutes each time through 4 successive after-treatment baths which have been heated to 55 C. and consist of 6 parts N,N-di-eicosyl-N,N-dimethyl ammonium bromide 6 parts of water 1 part octadecyl alcohol heptadecaethylene glycol ether and 987 parts perchloroethylene.
The fabric web then passes with a time of residence of 1 minute through a rinsing bath of pure perchloroethylene which has been heated to 50 C. After separating the rinsing liquor, the fabric is freed from the adhering perchloroethylene residues by blowing with hot air. The resultant red dyeing is rinsed clear without the occurrence of waste water and has the same fastness properites as a dyeing rinsed with water.
EXAMPLE 19 A cellulose/poly-e-caprolactam mixed fabric (50:50) is padded with an emulsion consisting of 20 parts of the dyestufi VII 20 parts of the 1:2 chromium complex of the dyestufi XVHI 3 parts nonylphenol decaethylene glycol ether 6 parts sodium bicarbonate 80 parts urea 100 parts of water and 771 parts perchloroethylene (liquor absorption 40%), dried at 100 C. for 1 minute and thermosolised at 192 C. for 60 seconds.
The fabric web then successively passes in a liquor ratio of 1:50 and with a time of residence of 2 minutes each time through 4 after-treatment baths which are mechanically agitated and have been heated to C. and consist of 4 parts of the compound of the formula ooz- 1 part of the compound of the formula CHz-CHg-OH e CHg-(CHz)mCHqNHCOOCHgCHz-N 01 CHn-CHa-OH 1 part of the compound of the formula 7 parts of 30% acetic acid and 987 parts perchloroethylene CONSTITUTIONS OF THE DYESTUFFS I-XVIII USED IN THE EXAMPLES Number Constitution II (32H:
\ ornosoa CH2CH2N-(C s)a 0 NH--CH2CHaCHaN( a):
omoso Y I O NH- CH;
IV 0 G3 (C2H5)2N 2Ha)2 e OHaOSOa (HE-CHr-N-(CHa): CN
VI F CH3 -o1ar,
CHzCH2-Cl 6 ea CH-CH N 01 N CH: C
CONSTITUTION OF THE DYESTUFFS I-XVIII USED IN THE EXA)IPLES.-Continuorl Number Constitution XV lTIHz/OK (|)H II I OH O NH:
XVI (I? CHaOC- N= CH 1 IF HO N XVII (|)H N=N lH-CHa N HzNOzS HO N XVIII (J11 1110 CH3SO NH S OnCzH We claim: in which tion consisting essentially of an aliphatic chlorinated hydrocarbon solvent and dissolved therein interface-active compound means for rendering the dyestutf which was not fixed in step (B) dispersible or soluble in said chlorinated hydrocarbon solvent, said interface-active compound being interface-active in said chlorinated hydrocarbon solvent.
2. The process of claim 1 in which the interface-active compound is present in amounts of 0.022% by weight, based on the weight of the aliphatic chlorinated hydrocarbon.
3. The process of claim 1 in which the aliphatic chlorinated hydrocarbon solution contains 0.02-4% by weight of water based on the weight of aliphatic chlorinated hydrocarbon.
4. The process of claim 3 in which the aliphatic chlorinated hydrocarbon solution contains 0.0012% by weight of non-ionic emulsifier based on the weight of aliphatic chlorinated hydrocarbon.
5. The process of claim 1 in which the aliphatic chlorinated hydrocarbon solution contains 0.00 l8% by weight of water-miscible organic solvent based on the weight of the aliphatic chlorinated hydrocarbon.
6. The process of claim 1 in which the interface-active compound is an onium compound of the formula A is nitrogen or phosphorus;
R is an alkyl, alkenyl or aralkyl radical of 12-28 carbon atoms or one of the aforesaid radicals containing oxygen, sulfur or nitrogen;
R and R independently of one another, are unsubstituted or substituted alkyl, alkenyl, or aralkyl radicals which contain 1-28 carbon atoms or one of the aforesaid radicals containing oxygen, sulfur or nitrogen;
R is substituted or unsubstituted C C -alkyl, C -C alkenyl, cycloalkyl or aralkyl or together with R forms a non-aromatic 5- or 6-membered heterocycle; with the proviso that the sum of carbon atoms in R R R and R is 20 to 60; and
X- is an anion.
7. The process of claim 1 in which the interface-active compound is a quaternary ammonium compound of the formula in which R; is an alkyl, alkenyl or aralkyl radical of 12-28 carbons, or one of the aforesaid radicals containing oxygen, sulfur or nitrogen;
R is an unsubstituted or substituted alkyl, alkenyl or aralkyl radical of 1-28 carbon atoms or one of the aforesaid radicals containing oxygen, sulfur or nitrogen;
R is unsubstituted or substituted C C -alkyl, C C
alkenyl, cycloalkyl or aralkyl radical, or together with R forms a non-aromatic 5- or 6-mem-bered heterocycle;
Z is an alkylene radical which contains l8 carbon atoms, a C C -alkylene which contains oxygen atoms or 1,4- bis-methylene-benzene radical; with the proviso that the sum of carbon atoms in R R R and R and Z is 20 to 60; and
8. The process of claim 1 in which the interface-active compound is an amine of the formula in which R; is an alkyl, alkenyl or aralkyl radical of 12-28 carbon atoms or one of the aforesaid radicals containing oxygen, sulfur or nitrogen;
R is an unsubstituted or substituted C C -alkyl, C C
alkenyl, cycloalkyl or aralkyl radical;
R is hydrogen, an unsubstituted or substituted alkyl, alkenyl or aralkyl radical of 1-28 carbon atoms or one of the aforesaid radicals containing oxygen, sulfur or nitrogen, or R together with R forms a 5- or G-membered non-aromatic heterocycle; with the proviso that the sum or carbon in R R and R is 20 to 60.
9. The process of claim 1 in which the interface-active compound is an aminoxide of the formula in which R is an alkyl, alkenyl or aralkyl radical of 12-28 carbon atoms or one of the aforesaid radicals containing oxygen, sulfur or nitrogen;
R is an unsubstituted or substituted alkyl, alkenyl or aralkyl radical of 1-28 carbon atoms or one of the aforesaid radicals containing oxygen, sulfur or nitrogen; and
R is an unsubstituted or substituted C -C -alky1, or C -c -alkenyl, cycloalkyl or aralkyl radical or together with R forms a non-aromatic 5- or 6-membered heterocycle; with proviso that the sum of carbon atoms in R R and R is 20 to 60.
10. The process of claim 1 in which said chlorinated 36 hydrocarbon/water emulsion contains a water-soluble dyestuff in the aqueous phase and a chlorinated hydrocarbon soluble dyestuif in the chlorinated hydrocarbon phase.
11. The process of claim 1 in which the aliphatic chlorinated hydrocarbon solution contains a compound selected from the group consisting of 0.01% to 1.0% by weight of acetic acid, 0.01% to 0.5% by weight of monoethanolamine 0.01% to 0.5% by weight of diethanolamine and 0.01% to 0.5% by weight of triethanolamine.
12. In the process of dyeing textile materials comprising the steps of (A) exhaustion dyeing a textile material with chlorinated hydrocarbon/water dyestufi emulsions, the aqueous phase of which contains a solution of watersoluble dyestufi; and (B) rinsing to remove excess dyestuff; the improvement comprising conducting the rinsing step (B) with a solution consisting essentially of aliphatic chlorinated hydrocarbon solvent and dissolved therein interface-active compound means for rendering the excess dyestutf dispersible or soluble in said chlorinated hydrocarbon solvent, said interface-active compound being interface-active in said chlorinated hydrocarbon solvent.
References Cited UNITED STATES PATENTS 3,523,749 8/1970 MacLeod et a1 8-94 X 2,828,180 3/1958 Sertorio 86Z 3,510,243 5/1970 Seuret et al. 8174 X 3,370,330 2/1968 Sieber 2619 2,274,751 3/1942 SoWter et al 8-173 3,473,175 10/1969 Sicber 8-458 OTHER REFERENCES WAS White, Amer. Dyestutf Reporter, July 31, 1967, pp. 18-24.
LEON D. ROSDOL, Primary Examiner T. J. HERBERT, JR., Assistant Examiner US. Cl. X.R.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Q PATENT NO. 3,764,262
DATED October 9, 1973 INVENTOR(S) I DIETRICH HILDEBRAWD ET AL.
it is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
COLUMN LINE ERROR 2 36 "-SO-SO should read S-SO 5 57 "CH CH CN" should read CH CH CN 5 62 "CH CH should read CH CH 5 66 "CH CH Cl" should read CH CH -Cl a 2 2 5 69 "CH CH OSO should read CH CH OSO a 5 73 "CH CH OPO should read CH -CH OPO a Signed and Scaled this ninth Day Of September 1975 [SEAL] Arrest:
RUTH C. MASON c. MARSHALL DANN Arresting Officer Commissioner oj'lalenls and Trademarks Page 2 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,764,262
DATED October 9 1973 INVENTOR(S) DIETRICH I'IILDEBRAND ET AL.
It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
COLUMN ERROR 6 55 "CH should read CH G 9 49 diisobdutyl" should read diisobutyll3 l4 "wthout" should read without 15 23 "(CH should read 15 26 "CH should read 15 33 "-CH should read 15 35 "CE-I should read CH 17 33 "CH=(CH should read 1 CH=CII-(CH Signed and Scaled this ninth Day of September 1975 [SEAL] Arrest:
RUTH C. MASON c. MARSHALL DANN Arresting Officer Commissioner ufPaIenrs and Trademarks
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19691945965 DE1945965A1 (en) | 1969-09-11 | 1969-09-11 | Process for dyeing and printing textile materials |
Publications (1)
Publication Number | Publication Date |
---|---|
US3764262A true US3764262A (en) | 1973-10-09 |
Family
ID=5745173
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00070514A Expired - Lifetime US3764262A (en) | 1969-09-11 | 1970-09-08 | Process for the dyeing and printing of textile materials |
Country Status (9)
Country | Link |
---|---|
US (1) | US3764262A (en) |
AT (1) | AT312551B (en) |
BE (1) | BE755978A (en) |
CA (1) | CA940659A (en) |
CH (2) | CH540392A (en) |
DE (1) | DE1945965A1 (en) |
FR (1) | FR2061674B1 (en) |
GB (1) | GB1273494A (en) |
NL (1) | NL7013342A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3894842A (en) * | 1972-03-10 | 1975-07-15 | Hoechst Ag | Process for preparing dyeings and prints fast to light on synthetic fibers |
US3900286A (en) * | 1971-11-19 | 1975-08-19 | Ciba Geigy Ag | Dyestuff preparations and processes for the dyeing of synthetic organic material |
US3954399A (en) * | 1972-03-28 | 1976-05-04 | Sumitomo Chemical Company, Limited | Process for dyeing nitrogen-containing fibers |
US3957433A (en) * | 1973-05-14 | 1976-05-18 | Imperial Chemical Industries Limited | Dyeing additives |
US3995996A (en) * | 1972-04-27 | 1976-12-07 | Bayer Aktiengesellschaft | Agents for improving wet fastness properties |
US4369041A (en) * | 1980-05-12 | 1983-01-18 | Vyzkumny Ustav Zuslechtovaci | Technique for dyeing and printing of textiles with quaternary ammonium compound |
US4453943A (en) * | 1982-04-02 | 1984-06-12 | Ciba-Geigy Corporation | Solid formulations of anionic dyes |
-
1969
- 1969-09-11 DE DE19691945965 patent/DE1945965A1/en active Pending
-
1970
- 1970-07-10 BE BE70@@@@@@@@A patent/BE755978A/en unknown
- 1970-08-27 AT AT778170A patent/AT312551B/en not_active IP Right Cessation
- 1970-08-28 CA CA091,844A patent/CA940659A/en not_active Expired
- 1970-09-08 US US00070514A patent/US3764262A/en not_active Expired - Lifetime
- 1970-09-09 NL NL7013342A patent/NL7013342A/xx unknown
- 1970-09-10 CH CH1349870A patent/CH540392A/en unknown
- 1970-09-10 CH CH1349870D patent/CH1349870A4/xx unknown
- 1970-09-11 GB GB43585/70A patent/GB1273494A/en not_active Expired
- 1970-09-11 FR FR7033140A patent/FR2061674B1/fr not_active Expired
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3900286A (en) * | 1971-11-19 | 1975-08-19 | Ciba Geigy Ag | Dyestuff preparations and processes for the dyeing of synthetic organic material |
US3894842A (en) * | 1972-03-10 | 1975-07-15 | Hoechst Ag | Process for preparing dyeings and prints fast to light on synthetic fibers |
US3954399A (en) * | 1972-03-28 | 1976-05-04 | Sumitomo Chemical Company, Limited | Process for dyeing nitrogen-containing fibers |
US3995996A (en) * | 1972-04-27 | 1976-12-07 | Bayer Aktiengesellschaft | Agents for improving wet fastness properties |
US3957433A (en) * | 1973-05-14 | 1976-05-18 | Imperial Chemical Industries Limited | Dyeing additives |
US4369041A (en) * | 1980-05-12 | 1983-01-18 | Vyzkumny Ustav Zuslechtovaci | Technique for dyeing and printing of textiles with quaternary ammonium compound |
US4453943A (en) * | 1982-04-02 | 1984-06-12 | Ciba-Geigy Corporation | Solid formulations of anionic dyes |
Also Published As
Publication number | Publication date |
---|---|
CA940659A (en) | 1974-01-29 |
FR2061674B1 (en) | 1974-08-23 |
CH1349870A4 (en) | 1973-02-28 |
FR2061674A1 (en) | 1971-06-25 |
CH540392A (en) | 1973-02-28 |
DE1945965A1 (en) | 1971-03-25 |
BE755978A (en) | 1971-02-15 |
GB1273494A (en) | 1972-05-10 |
AT312551B (en) | 1974-01-10 |
NL7013342A (en) | 1971-03-15 |
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