EP0074923A1 - Dyeing auxiliary and its use in dyeing or printing synthetic polyamide fibrous materials - Google Patents
Dyeing auxiliary and its use in dyeing or printing synthetic polyamide fibrous materials Download PDFInfo
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- EP0074923A1 EP0074923A1 EP82810370A EP82810370A EP0074923A1 EP 0074923 A1 EP0074923 A1 EP 0074923A1 EP 82810370 A EP82810370 A EP 82810370A EP 82810370 A EP82810370 A EP 82810370A EP 0074923 A1 EP0074923 A1 EP 0074923A1
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- Prior art keywords
- dyeing
- component
- carbon atoms
- aid according
- dyeing aid
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Classifications
-
- 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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/62—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
- D06P1/621—Compounds without nitrogen
- D06P1/622—Sulfonic acids or their salts
-
- 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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/60—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
- D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
- D06P1/6076—Nitrogen-containing polyethers or their quaternary derivatives addition products of amines and alkylene oxides or oxiranes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/924—Polyamide fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/929—Carpet dyeing
Definitions
- the present invention relates to a novel dyeing aid and its use in dyeing or printing synthetic polyamide fiber materials, preferably with a pronounced three-dimensional character (pile and pile materials) and in particular carpets, with anionic dyes.
- the object of the invention is to provide a dyeing aid which, when dyeing synthetic polyamide fiber materials, in particular carpets, at the same time acts as a leveling agent at a temperature of 50 to 85 ° C. and promotes the exhaustion of the dye bath.
- Components (A), (B), (C) and (D) can be present as individual compounds or as mixtures with one another.
- Preferred auxiliary mixtures consist of all the specified components (A), (B), (C) and (D).
- alkyl radical R examples include isopropyl, butyl, amyl, octyl, decyl, dodecyl, myristyl, hexadecyl, heptadecyl, octadecyl, arachidyl or behenyl.
- 0 preferably denotes a phenylene radical, which may optionally be further substituted by methyl, ethyl, isopropyl or butyl.
- M means, for example, alkali metal, e.g. Sodium or potassium; Alkaline earth metal such as calcium or magnesium, also ammonium or an ammonium group, which e.g. derived from aliphatic amines such as di- and triethylamine or mono-, di- and triethanolamine or heterocyclic amines such as piperidine, morpholine or pyridine.
- alkali metal e.g. Sodium or potassium
- Alkaline earth metal such as calcium or magnesium
- ammonium or an ammonium group e.g. derived from aliphatic amines such as di- and triethylamine or mono-, di- and triethanolamine or heterocyclic amines such as piperidine, morpholine or pyridine.
- Docecylsulfonic acid tetradecylsulfonic acid, octadecylsulfonic acid, eicosylsulfonic acid, paraffinsulfonic acid, nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, diisopropylnaphthalenesulfonic acid and di-n-butylnaphthalenesulfonic acid, as well as the salts of the acids mentioned with calcium, ammonium, magnesium amine, ethylamine, sodium amine, potassium amine, magnesium amine Diethylamine, dipropylamine, diisopropylamine, monoethanolamine, diethanolamine or triethanolamine.
- the quaternary ammonium compounds which can be used as component (B) in the auxiliary mixture according to the invention are likewise known per se and can be prepared in a manner known per se, e.g. appropriate by reacting aliphatic amines, the alkyl or alkenyl group having 10 to 22 carbon atoms, such as dodecylamine, hexadecylamine, heptadecylamine, octadecylamine, tallow fatty amine, arachidylamine, behenylamine or oleylamine or di- or triamines, such Dodecylpropylendiamin, Octadecyläthylendiamin or Octadecyldiäthylentriamin with 1 to 2 equivalents of Styrene oxide and with 1 to 45, preferably 1 to 35 equivalents of an alkylene oxide, for example Propylene oxide, but especially ethylene oxide or a mixture of propylene oxide and
- R 1 is preferably alkyl or alkenyl having 12 to 18 carbon atoms, especially octadecyl or octadecenyl, X 1 and X 2 are preferably hydrogen.
- the sum of p + s is preferably 5 to 20.
- m is preferably 0.
- Quaternary ammonium compounds of the formulas have proven to be particularly interesting components (b) proven.
- the amounts in which component B is present alone or as a mixture in the auxiliary mixture are advantageously from 2 to 30 percent by weight, preferably from 2 to 20 and particularly from 2 to 8 percent by weight, based on the total auxiliary mixture.
- the new dyeing aid may additionally contain a siloxane-oxyalkylene copolymer as component (C).
- component (C) acts in particular as a foam suppressant.
- the organopolysiloxanes as the starting product for such adducts, correspond in principle to commercially available silicone oils, which are described in German specification 20 31 827. Among these silicone oils, polydimethylsiloxanes are of prime interest.
- the siloxaneoxyalkylene copolymers which are suitable as optional component (C) can be obtained, for example, from halogen-substituted organopoly siloxanes, in particular polydimethylsiloxanes and alkali metal salts of polyoxyalkylene, for example polyethylene and / or polypropylene glycols.
- siloxaneoxyalkylene copolymers are polyether siloxanes, which expediently have a cloud point at about 20 to 70 ° C., preferably 25 to 50 ° C.
- the glycol content, consisting of oxyethylene groups or oxyethylene and oxypropylene groups, is advantageously from 35 to 85, preferably 40 to 75 percent by weight, based on the total weight of the polyether siloxane.
- a preferred embodiment of the optional component (C) is accordingly a block polymer of a polydimethylsiloxane and ethylene oxide or a copolymer of ethylene and propylene oxide, which has a cloud point at 20 to 70 ° C, in particular 25 to 50 ° C.
- Such block polymers or polyether siloxanes can by the likely formula in which q is 3 to 50, advantageously 3 to 25, r 2 or 3, r 2 0 to 15, t 1 to 25, x 1 3 to 10 and R 4 alkyl having 1 to 4
- Such polyether siloxanes are e.g. in German Patent Application 1,719,238 and in U.S. Patents 2,834,748, 3,389,160 and 3,505,377.
- polyether siloxanes which can be used as optional component (C) correspond to the likely formula wherein R 5 and R 6 are each alkyl having 1 to 4 carbon atoms, preferably methyl, a '1 to 20, b' 2 to 20, c '2 to 50, d' 1 or 2, preferably 1, and m '2 to 5 mean and where C m , H 2m , O d , preferably ethylene oxide groups or mixtures of ethylene oxide groups and propylene oxide groups.
- Such siloxane compounds are described in German Patent Application 1,795,557.
- the auxiliaries according to the invention can contain water as polar solvent (D) or a water-miscible organic solvent.
- water-miscible organic solvents are aliphatic C 1 -C 4 alcohols such as methanol, ethanol, the propanols or isobutanol; Alkylene glycols such as ethylene glycol or fropylene glycol; Monoalkyl ethers of glycols such as ethylene glycol monomethyl, ethyl or butyl ether and diethylene glycol monomethyl or ethyl ether; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, diacetone alcohol; Ethers and acetals such as diisopropyl ether, diphenyl oxide, dioxane, tetrahydrofuran, also tetrahydrofurfuryl alcohol, pyridine,
- auxiliary preparations according to the invention can be prepared by simply stirring the components (A), (B) and, if appropriate, (C). With the addition of component (D), especially water, and optionally also a base, e.g. Alkali metal hydroxides such as sodium or potassium hydroxide or lower alkanolamines such as monoethanolamine, diethanolamine or triethanolamine are obtained as homogeneous, preferably clear mixtures which are very stable in storage at room temperature.
- a base e.g. Alkali metal hydroxides such as sodium or potassium hydroxide or lower alkanolamines such as monoethanolamine, diethanolamine or triethanolamine are obtained as homogeneous, preferably clear mixtures which are very stable in storage at room temperature.
- the new formulations are used in particular as leveling and retarding agents in the dyeing of synthetic polyamide fiber materials. They increase the rate of diffusion of the dyes in the fibers and thereby accelerate the migration of the dyes when dyeing synthetic polyamide fiber materials. They thus allow perfect levelness and also streak-free substrate to be achieved with complete bath exhaustion.
- the present invention accordingly also relates to a process for dyeing or printing synthetic polyamide fiber materials with anionic dyes.
- the process is characterized in that this material is dyed or printed in the presence of the dyeing aid according to the invention.
- the amounts used in which the dyeing aid according to the invention is added to the dye baths are between 1 and 10 percent by weight, preferably 2 and 5 percent by weight, based on the weight of the material to be dyed.
- Synthetic polyamide fiber materials in particular textile materials and above all with a pronounced three-dimensional character (pile and pile materials), such as carpets, which can be dyed in the presence of the new mixture of dyeing auxiliaries, are, for example, those made from adipic acid and hexamethylenediamine (polyamide 6.6), from E- Caprolactam (polyamide 6), from ⁇ -aminoundecanoic acid (polyamide 11), from ⁇ -aminoonanthic acid (polyamide 7), from ⁇ -aminopelargonic acid (polyamide 8) or from sebacic acid and hexamethylenediamine (polyamide 6.10).
- the polyamide fiber materials can also be used as a blended fabric with each other or with other fibers, e.g. Mixtures of polyamide / wool or polyamide polyester can be used.
- the fiber material can be in a wide variety of processing stages. For example, the following can be considered: flake, sliver, woven fabric, knitted fabric, nonwovens, yarn or piece goods.
- floor coverings such as e.g. Carpets, or other home textiles such as upholstery fabrics, curtains or wall coverings.
- carpet materials such as velor or loop pile carpets made of synthetic polyamide is preferred.
- the anionic dyes are, for example, salts of heavy metal-containing or preferably metal-free mono-, dis- or polyazo dyes including the formazan dyes and the anthraquinone, xanthene, nitro, triphenylmethane, naphthoquinoneimine and phthalocyanine dyes.
- the anionic character of these dyes can be caused by metal complex formation alone and / or preferably by acidic, salt-forming substituents, such as carboxylic acid groups, sulfuric acid and phosphonic acid ester groups, phosphonic acid groups or sulfonic acid groups.
- These dyes can also have so-called reactive groups in the molecule, which form a covalent bond with the material to be colored.
- the so-called acidic metal-free dyes are preferred. The latter preferably contain only a single sulfonic acid group.
- the 1: 1 or 1: 2 metal complex dyes are also of interest.
- the 1: 1 metal complex dyes preferably have one or two sulfonic acid groups. As metal they contain a heavy metal atom such as Copper, nickel or especially chrome.
- the 1: 2 metal complex dyes contain a heavy metal atom such as e.g. a cobalt atom or in particular a chromium atom.
- Two complex-forming components are connected to the central atom, at least one of which is a dye molecule, but preferably both are dye molecules.
- the two dye molecules involved in the complex formation can be the same or different from one another.
- the 1: 2 metal complex dyes can e.g. contain two azomethine molecules, a disazo dye and a monoazo dye, or preferably two monoazo dye molecules.
- the azo dye molecules can have water solubilizing groups such as e.g. Acid amide, alkylsulfonyl or the above acidic groups. Preference is given to 1: 2 cobalt or 1: 2 chromium complexes of monoazo dyes which have acid amide, alkylsulfonyl or a total of a single sulfonic acid group.
- Dye mixtures of at least 2 or 3 anionic dyes are particularly preferred for the production of level dichromia or trichromatic dyes.
- the amount of dyes added to the liquor depends on the desired depth of color. In general, amounts of 0.01 to 10, in particular 0.1 to 5 g per liter of liquor have proven successful.
- the dyebaths can contain alkali metal hydroxides, alkali metal carbonates or bicarbonates; Minralic acids such as sulfuric acid or phosphoric acid; organic acids, suitably lower, aliphatic carboxylic acids, such as formic, acetic or oxalic acid and / or salts, such as ammonium acetate, ammonium sulfate, disodium phosphate, dipotassium phosphate, potassium acetate or sodium acetate.
- the alkalis and acids serve above all to adjust the pH of the liquors used according to the invention, which is generally 8 to 8.5 at the beginning and 4.5 to 6 at the end.
- the dyebaths can also contain the usual electrolytes, dispersants, antifoams and wetting agents.
- the dyeings are advantageously carried out from an aqueous liquor using the exhaust process.
- the liquor ratio can accordingly be chosen within a wide range, e.g. 1: 3 to 1: 100, preferably 1:10 to 1:50. It is convenient to dye at a temperature in the range from 40 ° C. to the boiling point. Surprisingly, the coloring can be carried out at low temperatures in a range from 50 to 85 ° C.
- the textile material is preferably added to a liquor which has a temperature of 15 to 25 ° C. and a pH of 7.5 to 8.5. Then the dyes and the auxiliary mixture according to the invention are added and the material is treated at 15 to 25 ° C. for 5 to 15 minutes. The temperature is then slowly increased to 60 ° C. and dyeing is carried out at this temperature for 30 to 60 minutes. Then the pH of the bath is reduced to 5 - 6 and dyeing is continued for 10 to 20 minutes at 60 ° C. Finally, the bath is cooled and the colored material rinsed and dried as usual.
- the dyeing process according to the invention can also be carried out by first treating the material to be dyed with the auxiliary mixture for 10 to 15 minutes at 20 to 25 ° C. and then dyeing.
- the dyeing of the synthetic polyamide fiber material can also be carried out by a printing or padding process.
- the possibly thickened printing paste or liquor, which contains dye, auxiliary preparation according to the invention, acid and possibly other additives, is printed or padded on the fiber, preferably at a temperature between 10 and 40 ° C.
- the padded or printed fiber material can be subjected to heat treatment, e.g. Steaming. However, it is preferably packed with a plastic film and stored at 50 to 60 ° C for 45 to 120 minutes.
- the method according to the invention represents a highly energy-saving dyeing system in which synthetic polyamide fiber material can be dyed at a low temperature of 50 to 85 ° C. and complete dying of the dye bath is achieved.
- the fleet can thus be used for further dyeing, so that considerable savings can be achieved in terms of water, energy, time and chemicals.
- significant ecological progress is achieved.
- the process according to the invention is not only distinguished by the economic and ecological advantages, but also by the gentle way of dyeing an improvement in the quality of the dyeing material is achieved.
- the parts are parts by weight and the percentages are percentages by weight.
- the carpet is allowed to circulate at 20 ° C for 15 minutes and the temperature is raised to 60 ° C in the course of 40 minutes.
- the dyeing is then carried out for 30 minutes at this temperature and the pH of the bath is lowered to 5 by adding sulfuric acid over 40 minutes.
- the dyeing is then continued for 15 minutes at 60 ° C. and at a pH of 5.
- the dyeing liquor is then cooled and the carpet rinsed and finished.
- a level, well-colored dyeing is obtained.
- the bathroom exhaustion is practically complete, so that the next carpet can be dyed in the same dye bath.
- the carpet is allowed to circulate at 20 ° C for 15 minutes and the temperature is raised to 60 ° C in the course of 40 minutes, then it is dyed for 30 minutes and the pH of the bath is reduced to 5 by adding sulfuric acid over 40 minutes . After that dyeing after 15 minutes at 60 ° C. and at a pH of 5. The dyeing liquor is then cooled and the carpet is rinsed and finished.
- a level, well-colored dyeing is obtained.
- the bathroom exhaustion is practically complete, so that the next carpet can be dyed in the same dye bath.
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Abstract
Färbereihilfsmittel, enthaltend mindestens (A) ein Alkylsulfonat, Alkylbenzolsulfonat oder Alkylnaphthalinsulfonat, dessen geradkettige oder verzweigte Alkylkette 3 bis 22 Kohlenstoffatome aufweist, und (B) eine quaternäre Ammoniumverbindung, welche mindestens ein basisches Stickstoffatom aufweist, an welches mindestens eine Polyglykolätherkette und mindestens ein aliphatischer Rest mit 10 bis 22 Kohlenstoffatomen gebunden sind, wobei die Polyglykolätherketter mindestens eine Gruppierung der Formel <IMAGE> aufweist, worin von Y1 und Y2 eines Wasserstoff und das andere den Phenylrest darstellt, und gegebenenfalls (C) ein Siloxan-Oxyalkylen-Copolymerisat und/oder (D) ein polares Lösungsmittel, welches insbesondere beim Färben oder Bedrucken von synthetischen Polyamidfasermaterialien mit anionischen Farbstoffen verwendet wird.Dyeing auxiliaries containing at least (A) an alkyl sulfonate, alkylbenzenesulfonate or alkylnaphthalenesulfonate, the straight-chain or branched alkyl chain of which has 3 to 22 carbon atoms, and (B) a quaternary ammonium compound which has at least one basic nitrogen atom, to which at least one polyglycol ether chain and at least one aliphatic radical are bonded with 10 to 22 carbon atoms, the polyglycol ether chain having at least one group of the formula <IMAGE>, in which one of Y1 and Y2 is hydrogen and the other is the phenyl radical, and optionally (C) a siloxane-oxyalkylene copolymer and / or ( D) a polar solvent, which is used in particular when dyeing or printing synthetic polyamide fiber materials with anionic dyes.
Description
Die vorliegende Erfindung betrifft ein neues Färbereihilfsmittel sowie seine Verwendung beim Färben oder Bedrucken von synthetischen Polyamidfasermaterialien, vorzugsweise mit ausgeprägt dreidimensionalem Charakter (Pol- und Flormaterialien) und insbesondere Teppichen, mit anionischen Farbstoffen.The present invention relates to a novel dyeing aid and its use in dyeing or printing synthetic polyamide fiber materials, preferably with a pronounced three-dimensional character (pile and pile materials) and in particular carpets, with anionic dyes.
Aufgabe der Erfindung ist die Bereitstellung eines Färbereihilfsmittels, welches beim Färben von synthetischen Polyamidfasermaterialien, insbesondere Teppichen, bei einer Temperatur von 50 bis 85°C gleichzeitig als Egalisiermittel wirkt und die Erschöpfung des Färbebades fördert.The object of the invention is to provide a dyeing aid which, when dyeing synthetic polyamide fiber materials, in particular carpets, at the same time acts as a leveling agent at a temperature of 50 to 85 ° C. and promotes the exhaustion of the dye bath.
Es wurde nun überraschenderweise ein neues Färbereihilfsmittel gefunden, welches nicht nur die angeführten Bedingungen erfüllt, sondern auch für ein gleichmässiges Eindringen des Farbstoffes in das Fasermaterial und für eine erhöhte Migration des Farbstoffes sorgt, so dass eine Verbesserung der Egalität der Färbungen samt der erwünschten Baderschöpfung erreicht wird.Surprisingly, a new dyeing aid has now been found, which not only fulfills the stated conditions, but also ensures a uniform penetration of the dye into the fiber material and increased migration of the dye, so that the levelness of the dyeings, including the desired bath exhaustion, is improved becomes.
Gegenstand der vorliegenden Erfindung ist demnach ein neues Hilfsmittelgemisch, welches dadurch gekennzeichnet ist, dass es mindestens
- (A) ein Alkylsulfonat, Alkylbenzolsulfonat oder Alkylnaphthalinsulfonat, dessen geradkettige oder verzweigte Alkylkette 3 bis 22 Kohlenstoffatome aufweist, und
- (B) eine quaternäre Ammoniumverbindung, welche mindestens ein basisches Stickstoffatom aufweist, an welches mindestens eine Polyglykolätherkette und mindestens ein aliphatischer Rest mit 10 bis 22 Kchlenstoffatomen gebunden sind, wobei die Polyglykolätherkette mindestens eine Gruppierung der Formel
enthält.
Neben den Komponenten (A) und (B) kann das erfindungsgemässe Hilfsmit-. telgemisch noch zusätzlich - (C) ein Siloxan-Oxyalkylen-Copolymerisat und/oder
- (D) ein polares Lösungsmittel
enthalten.The present invention accordingly relates to a new auxiliary mixture, which is characterized in that it at least
- (A) an alkyl sulfonate, alkylbenzenesulfonate or alkylnaphthalenesulfonate, the straight-chain or branched alkyl chain of which has 3 to 22 carbon atoms, and
- (B) a quaternary ammonium compound which has at least one basic nitrogen atom to which at least one polyglycol ether chain and at least one aliphatic radical having 10 to 22 carbon atoms are bonded, the polyglycol ether chain having at least one grouping of the formula
contains.
In addition to components (A) and (B), the auxiliary. tel mixture additionally - (C) a siloxane-oxyalkylene copolymer and / or
- (D) a polar solvent
contain.
Die Komponenten (A), (B), (C) und (D) können als Einzelverbindungen oder als Gemische untereinander vorhanden sein. Bevorzugte Hilfsmittelgemische bestehen aus allen angegebenen Komponenten (A), (B), (C) und (D).Components (A), (B), (C) and (D) can be present as individual compounds or as mixtures with one another. Preferred auxiliary mixtures consist of all the specified components (A), (B), (C) and (D).
Die als Komponente (A) in Betracht kommenden anionaktiven Sulfonate sind an sich bekannt und entsprechen vorwiegend der Formel
- R einen geradkettigen oder verzweigten Alkylrest mit 3 bis 22, vorzugsweise 8 bis 22 Kohlenstoffatomen,
- Q einen Phenylen- oder Naphthylenrest,
- M Wasserstoff oder ein salzbildendes Kation, und
- n 1 oder 2
bedeuten.The anionic sulfonates which are suitable as component (A) are known per se and predominantly correspond to the formula
- R is a straight-chain or branched alkyl radical having 3 to 22, preferably 8 to 22, carbon atoms,
- Q is a phenylene or naphthylene radical,
- M is hydrogen or a salt-forming cation, and
- n 1 or 2
mean.
Beispiele für den Alkylrest R sind Isopropyl, Butyl, Amyl, Octyl, Decyl, Dodecyl, Myristyl, Hexadecyl, Heptadecyl, Octadecyl, Arachidyl oder Behenyl. 0 bedeutet vorzugsweise einen Phenylenrest, der gegebenenfalls durch Methyl, Ethyl, Isopropyl oder Butyl weitersubstituiert sein kann.Examples of the alkyl radical R are isopropyl, butyl, amyl, octyl, decyl, dodecyl, myristyl, hexadecyl, heptadecyl, octadecyl, arachidyl or behenyl. 0 preferably denotes a phenylene radical, which may optionally be further substituted by methyl, ethyl, isopropyl or butyl.
Als salzbildendes Kation bedeutet M beispielsweise Alkalimetall, z.B. Natrium oder Kalium; Erdalkalimetall wie Calcium oder Magnesium, ferner Ammonium oder eine Ammoniumgruppe, die sich z.B. von aliphatischen Aminen wie Di- und Triäthylamin oder Mono-, Di- und Triäthanolamin oder heterocyclischen Aminen, wie Piperidin, Morpholin oder Pyridin ableitet.As the salt-forming cation, M means, for example, alkali metal, e.g. Sodium or potassium; Alkaline earth metal such as calcium or magnesium, also ammonium or an ammonium group, which e.g. derived from aliphatic amines such as di- and triethylamine or mono-, di- and triethanolamine or heterocyclic amines such as piperidine, morpholine or pyridine.
Bevorzugte anionaktive Sulfonate sind Verbindungen der Formel
- R' einen Alkylrest mit 10 bis 16 Kohlenstoffatomen bedeutet und
- M die oben angegebene Bedeutung hat, und insbesondere Natrium, Kalium oder Ammonium
darstellt. Typische Vertreter der erfindungsgemäss als Komponenten (A) zur Anwendung gelangender Sulfonate sindPreferred anionic sulfonates are compounds of the formula
- R 'represents an alkyl radical having 10 to 16 carbon atoms and
- M has the meaning given above, and in particular sodium, potassium or ammonium
represents. Typical representatives of the sulfonates used as components (A) according to the invention are
Docecylsulfonsäure, Tetradecylsulfonsäure, Octadecylsulfonsäure, Eicosylsulfonsäure, Paraffinsulfonsäure, Nonylbenzolsulfonsäure, Dodecylbenzolsulfonsäure, Diisopropylnaphthalinsulfonsäure und Di-n-butylnaphthalinsullfonsäure, sowie die Salze der genannten Säuren mit Natrium, Kalium, Magnesium, Calcium, Ammoniak, Ethylamin, Propylamin, Diethylamin, Dipropylamin, Diisopropylamin, Monoäthanolamin, Diäthanolamin oder Triäthanolamin.Docecylsulfonic acid, tetradecylsulfonic acid, octadecylsulfonic acid, eicosylsulfonic acid, paraffinsulfonic acid, nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, diisopropylnaphthalenesulfonic acid and di-n-butylnaphthalenesulfonic acid, as well as the salts of the acids mentioned with calcium, ammonium, magnesium amine, ethylamine, sodium amine, potassium amine, magnesium amine Diethylamine, dipropylamine, diisopropylamine, monoethanolamine, diethanolamine or triethanolamine.
Die im erfindungsgemässen Hilfsmittelgemisch als Komponente (B) verwendbaren, quaternären Ammoniumverbindungen sind ebenfalls an sich bekannt und können auf an sich bekannte Weise hergestellt werden, z.B. durch Umsetzung entsprechender aliphatischer Amine, deren Alkyl- oder Alkenylrest 10 bis 22 Kohlenstoffatome aufweist, wie Dodecylamin, Hexadecylamin, Heptadecylamin, Octadecylamin, Talgfettamin, Arachidylamin, Behenylamin oder Oleylamin oder Di- oder Triamine, wie Dodecylpropylendiamin, Octadecyläthylendiamin oder Octadecyldiäthylentriamin mit 1 bis 2 Aequivalenten Styroloxid und mit 1 bis 45, vorzugsweise 1 bis 35 Aequivalenten eines Alkylenoxides, z.B. Propylenoxid, vor allem aber Aethylenoxid oder ein Gemisch aus Propylenoxid und Ethylenoxid und durch anschliessende Umsetzung mit üblichen Quaternisierungsmitteln, wie z.B. Methyl-, Ethyl- oder Benzylhalogeniden, Diäthylsulfat oder vor allem Dimethylsulfat, Halogenhydrinen oder Halogencarbonsäureamiden, wie z.B. Chloracetamid.The quaternary ammonium compounds which can be used as component (B) in the auxiliary mixture according to the invention are likewise known per se and can be prepared in a manner known per se, e.g. appropriate by reacting aliphatic amines, the alkyl or alkenyl group having 10 to 22 carbon atoms, such as dodecylamine, hexadecylamine, heptadecylamine, octadecylamine, tallow fatty amine, arachidylamine, behenylamine or oleylamine or di- or triamines, such Dodecylpropylendiamin, Octadecyläthylendiamin or Octadecyldiäthylentriamin with 1 to 2 equivalents of Styrene oxide and with 1 to 45, preferably 1 to 35 equivalents of an alkylene oxide, for example Propylene oxide, but especially ethylene oxide or a mixture of propylene oxide and ethylene oxide and by subsequent reaction with conventional quaternizing agents, such as Methyl, ethyl or benzyl halides, diethyl sulfate or especially dimethyl sulfate, halohydrins or halocarboxamides, e.g. Chloroacetamide.
Bevorzugt werden quaternäre Ammoniumverbindungen der Formel
- R Alkyl oder Alkenyl jeweils mit 10 bis 22 Kohlenstoffatomen,
- R2 Alkyl mit 1 bis 4 Kohlenstoffatomen, Hydroxyalkyl mit 2 bis 4 Kohlenstoffatomen, Carbamoylmethyl oder Benzyl, vorzugsweise Methyl,
- von Y1 und Y2 eines Wasserstoff und das andere Phenyl,
- von X1 und X2 eines Wasserstoff oder Methyl und das andere Wasserstoff, An⊖ das Anion einer anorganischen oder organischen Säure, insbesondere einer starkan Mineralsäure oder einer organischen Sulfonsäure, wie z.B. das Chlorid-, Bromid-, Sulfat-, Benzolsulfonat-, p-Toluolsulfonat-, Methansulfonat-oder Aethansulfonation,
- m 0 oder 1 und p und s ganze Zahlen bedeuten, wobei die Summe von p + s 2 bis 40, vorzugsweise 2 bis 25 beträgt.
- R alkyl or alkenyl each having 10 to 22 carbon atoms,
- R 2 alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 to 4 carbon atoms, carbamoylmethyl or benzyl, preferably methyl,
- of Y 1 and Y 2 one hydrogen and the other phenyl,
- of X 1 and X 2 of a hydrogen or methyl and the other hydrogen, An⊖ the anion of an inorganic or organic acid, in particular a strong mineral acid or an organic sulfonic acid, such as eg the chloride, bromide, sulfate, benzenesulfonate, p-toluenesulfonate, methanesulfonate or ethanesulfonate ion,
- m is 0 or 1 and p and s are integers, the sum of p + s being 2 to 40, preferably 2 to 25.
In der Formel (4) bedeutet R1 vorzugsweise Alkyl oder Alkenyl mit 12 bis 18 Kohlenstoffatomen, besonders Octadecyl oder Octadecenyl, X1 und X2 sind vorzugsweise Wasserstoff. Die Summe von p + s ist vorzugsweise 5 bis 20. m ist vorzugsweise 0.In formula (4), R 1 is preferably alkyl or alkenyl having 12 to 18 carbon atoms, especially octadecyl or octadecenyl, X 1 and X 2 are preferably hydrogen. The sum of p + s is preferably 5 to 20. m is preferably 0.
Als besonders interessante Komponenten (b) haben sich quaternäre Ammoniumverbindungen der Formeln
Die Mengen, in denen die Komponente B allein oder als Gemisch im Hilfsmittelgemisch vorhanden ist, bewegen sich vorteilhafterweise von 2 bis 30 Gewichtsprozent, vorzugsweise von 2 bis 20 und besonders von 2 bis 8 Gewichtsprozent, bezogen auf die gesamte Hilfsmittelmischung.The amounts in which component B is present alone or as a mixture in the auxiliary mixture are advantageously from 2 to 30 percent by weight, preferably from 2 to 20 and particularly from 2 to 8 percent by weight, based on the total auxiliary mixture.
Bevorzugte erfindungsgemässe Hilfsmittelgemische enthalten mindestens folgende Komponenten:
- (Aa) Dodecylbenzolsulfonsäure und
- (Bb) eine quaternäre Ammoniumverbindung der Formel
- R3 Octadecyl oder Octadecenyl und
- An1⊖ das Chlorid-, Bromid-, Methansulfonat oder Ethansulfonation bedeuten und
die Summe von p1 + s1 15 bis 25 beträgt.Preferred auxiliary mixtures according to the invention contain at least the following components:
- (Aa) dodecylbenzenesulfonic acid and
- (Bb) a quaternary ammonium compound of the formula
- R3 octadecyl or octadece nyl and
- At 1 ⊖ the chloride, bromide, methanesulfonate or ethanesulfonate mean and
the sum of p 1 + s 1 is 15 to 25.
Ausser den Komponenten (A) und (B) kann das neue Färbereihilfsmittel zusätzlich als Komponente (C) ein Siloxan-Oxyalkylen-Copolymerisat enthalten. Die Komponente (C) wirkt insbesondere als Schaumdämpfungsmittel.In addition to components (A) and (B), the new dyeing aid may additionally contain a siloxane-oxyalkylene copolymer as component (C). Component (C) acts in particular as a foam suppressant.
Als fakultative Komponente (C) können handelsübliche, oberflächenaktive, hydrophile Addukte aus einem Organopolysiloxan und Ethylen- und/oder Propylonoxid in Betracht kommen.As an optional component (C), commercially available, surface-active, hydrophilic adducts of an organopolysiloxane and ethylene and / or propylon oxide can be considered.
Die Organopolysiloxane,als Ausgangsprodukt für derartige Addukte,entsprechen grundsätzlich handelsüblichen Silikonölen, welche in der deutschen Auslegeschrift 20 31 827 beschrieben sind. Unter diesen Silikonölen stehen Polydimethylsiloxane im Vordergrund des Interesses. Die als fakultative Komponente (C) in Frage kommenden Siloxanoxyalkylen-Copolymere können beispielsweise aus halogensubstituierten Organopolysiloxanen, insbesondere Polydimethylsiloxanen und Alkalimetallsalzen von Polyoxyalkylen, z.B. Polyethylen- und/oder Polypropylenglykolen hergestellt werden.The organopolysiloxanes, as the starting product for such adducts, correspond in principle to commercially available silicone oils, which are described in German specification 20 31 827. Among these silicone oils, polydimethylsiloxanes are of prime interest. The siloxaneoxyalkylene copolymers which are suitable as optional component (C) can be obtained, for example, from halogen-substituted organopoly siloxanes, in particular polydimethylsiloxanes and alkali metal salts of polyoxyalkylene, for example polyethylene and / or polypropylene glycols.
Bei diesen Siloxanoxyalkylen-Copolymeren handelt es sich um Polyäthersiloxane, welche zweckmässigerweise einen Trübungspunkt bei etwa 20 bis 70°C, vorzugsweise 25 bis 50°C aufweisen. Der Glykolgehalt, bestehend aus Oxyäthylengruppen oder Oxyäthylen- und Oxypropylengruppen, ist vorteilhafterweise von 35 bis 85, vorzugsweise 40 bis 75 Gewichtsprozent, bezogen auf das gesamte Gewicht des Polyäthersiloxans.These siloxaneoxyalkylene copolymers are polyether siloxanes, which expediently have a cloud point at about 20 to 70 ° C., preferably 25 to 50 ° C. The glycol content, consisting of oxyethylene groups or oxyethylene and oxypropylene groups, is advantageously from 35 to 85, preferably 40 to 75 percent by weight, based on the total weight of the polyether siloxane.
Eine bevorzugte Ausführungsform der fakultativen Komponente (C) ist demgemäss ein Blockpolymer aus einem Polydimethylsiloxan und Ethylenoxid oder einem Copolymer aus Ethylen- und Propylenoxid, das einen Trübungspunkt bei 20 bis 70°C, insbesondere 25 bis 50°C, aufweist. Solche Blockpolymere bzw. Polyäthersiloxane können durch die wahrscheinliche Formel
Kohlenstoffatomen, vorzugsweise Methyl, sind. Derartige Polyäthersiloxane sind z.B. in der deutschen Auslegeschrift 1 719 238 sowie in den US-Patentschriften 2 834 748, 3 389 160 und 3 505 377 beschrieben.Are carbon atoms, preferably methyl. Such polyether siloxanes are e.g. in German Patent Application 1,719,238 and in U.S. Patents 2,834,748, 3,389,160 and 3,505,377.
Weitere Polyäthersiloxane, welche als fakultative Komponente (C) verwendet werden können, entsprechen der wahrscheinlichen Formel
Als handelsübliche fakultative Komponente (C), die wahrscheinlich der Formel (16)entspricht und einen Trübungspunkt von 32°C aufweist, eignet sich z.B. SILICONSURFACTANT L 546 ® (Handelsmarke, UNIONCARBIDE). Dieses Silikonprodukt wird vorzugsweise in Kombination mit Propylenglykol eingesetzt.As a commercially available optional component (C), which probably corresponds to the formula (16) and has a cloud point of 32 ° C, e.g. SILICONSURFACTANT L 546 ® (trademark, UNIONCARBIDE). This silicone product is preferably used in combination with propylene glycol.
Zusätzlich können die erfindungsgemässen Hilfsmittel als polares Lösungsmittel (D) Wasser oder ein mit Wasser mischbares organisches Lösungsmittel enthalten. Ein solcher Zusatz dient dazu, die Löslichkeit der Präparation bei der Anwendung zu verbessern. Beispiele von mit Wasser mischbaren organischen Lösungsmitteln sind aliphatische C1-C4-Alkohole wie Methanol, Ethanol, die Propanole oder Isobutanol; Alkylenglykole wie Ethylenglykol oder Fropylenglykol; Monoalkylether von Glykolen wie Ethylenglykolmonomethyl-, -ethyl- oder -butylether und Diethylenglylkolmonomethyl- oder -ethylether; Ketone wie Aceton, Methylethylketon, Cyclohexanon, Diacetonalkohol; Ether und Acetale wie Diisopropylether, Diphenyloxid, Dioxan, Tetrahydrofuran, ferner Tetrahydrofurfurylalkohol, Pyridin, Acetonitril, γ-Butyrolacton, N,N-Dimethylformamid, N,N-Dimethylacetamid, Tetramethylharnstoff, Tetramethylensulfon u.a.. Auch Mischungen der genannter Lösungsmittel können verwendet werden. Bevorzugt sind Wasser oder Propylenglykol oder vor allem Gemische davon.In addition, the auxiliaries according to the invention can contain water as polar solvent (D) or a water-miscible organic solvent. Such an additive serves to improve the solubility of the preparation during use. Examples of water-miscible organic solvents are aliphatic C 1 -C 4 alcohols such as methanol, ethanol, the propanols or isobutanol; Alkylene glycols such as ethylene glycol or fropylene glycol; Monoalkyl ethers of glycols such as ethylene glycol monomethyl, ethyl or butyl ether and diethylene glycol monomethyl or ethyl ether; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, diacetone alcohol; Ethers and acetals such as diisopropyl ether, diphenyl oxide, dioxane, tetrahydrofuran, also tetrahydrofurfuryl alcohol, pyridine, acetonitrile, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, tetramethyl urea, tetramethylene sulfone and others. Mixtures of the solvents mentioned can also be used. Water or propylene glycol or, above all, mixtures thereof are preferred.
Die erfindungsgemässen Hilfsmittelzubereitungen können durch einfaches Verrühren der genannten Komponenten (A), (B) und gegebenenfalls (C) hergestellt werden. Unter Zugabe der Komponente (D), insbesondere Wasser, und gegebenenfalls auch einer Base, z.B. Alkalimetallhydroxide wie Natrium- oder Kaliumhydroxid oder niedere Alkanolamine, wie Monoäthanolamin, Diäthanolamin oder Triäthanolamin,werden sie als homogene, vorzugsweise klare Mischungen erhalten, die bei Raumtemperatur sehr gut lagerstabil sind.The auxiliary preparations according to the invention can be prepared by simply stirring the components (A), (B) and, if appropriate, (C). With the addition of component (D), especially water, and optionally also a base, e.g. Alkali metal hydroxides such as sodium or potassium hydroxide or lower alkanolamines such as monoethanolamine, diethanolamine or triethanolamine are obtained as homogeneous, preferably clear mixtures which are very stable in storage at room temperature.
Die erfindungsgemässen Hilfsmittelgemische enthalten mit Vorteil, jeweils bezogen auf das Gemisch,
- 15 bis 70 Gewichtsprozent der Komponente (A)
- 2 bis 30 Gewichtsprozent der Komponente (B)
- 0 bis 5, vorzugsweise 0,5 bis 2 Gewichtsprozent der Komponente (C)
- 0 bis 70, vorzugsweise 30 bis 60 Gewichtsprozent der Komponente (D)
- 0 bis 15, vorzugsweise 2 bis 10 Gewichtsprozent einer Base.
- 15 to 70 percent by weight of component (A)
- 2 to 30 percent by weight of component (B)
- 0 to 5, preferably 0.5 to 2 percent by weight of component (C)
- 0 to 70, preferably 30 to 60 percent by weight of component (D)
- 0 to 15, preferably 2 to 10 percent by weight of a base.
Die neuen Formulierungen werden insbesondere als Egalisier- und Retardiermittel beim Färben von synthetischen Polyamidfasermaterialien verwendet. Sie erhöhen die Diffusionsgeschwindigkeit der Farbstoffe in den Fasern und beschleunigen dadurch die Migration der Farbstoffe beim Färben von synthetischen Polyamidfasermaterialien. Sie erlauben somit, bei vollständiger Baderschöpfung eine einwandfreie Egalität und zudem eine Streifenfreiheit des Substrates zu erzielen.The new formulations are used in particular as leveling and retarding agents in the dyeing of synthetic polyamide fiber materials. They increase the rate of diffusion of the dyes in the fibers and thereby accelerate the migration of the dyes when dyeing synthetic polyamide fiber materials. They thus allow perfect levelness and also streak-free substrate to be achieved with complete bath exhaustion.
Gegenstand der vorliegenden Erfindung ist demnach auch ein Verfahren zum Färben oder Bedrucken von synthetischen Polyamidfasermaterialien mit anionischen Farbstoffen. Das Verfahren ist dadurch gekennzeichnet, dass man dieses Material in Gegenwart des erfindungsgemässen Färbcreihilfsmittels färbt bzw. bedruckt.The present invention accordingly also relates to a process for dyeing or printing synthetic polyamide fiber materials with anionic dyes. The process is characterized in that this material is dyed or printed in the presence of the dyeing aid according to the invention.
Die Einsatzmengen, in denen das erfindungsgemässe Färbereihilfsmittel den Färbebädern zugesetzt wird, bewegen sich zwischen 1 und 10 Gewichtsprozent, vorzugsweise 2 und 5 Gewichtsprozent, bezogen auf das Gewicht des Färbegutes. w Als synthetische Polyamidfasermaterialien, insbesondere Textilmaterialien und vor allem mit ausgeprägt dreidimensionalen Charakter (Pol- und Flormaterialien), wie Teppiche, die in Gegenwart des neuen Färbereihilfsmittelgemisches gefärbt werden können, sind z.B. solche aus Adipinsäure und Hexamethylendiamin (Polyamid 6,6), aus E-Caprolactam (Polyamid 6), aus ω-Aminoundecansäure (Polyamid 11), aus ω-Aminoönanthsäure (Polyamid 7 ), aus ω-Aminopelargonsäure (Polyamid 8) oder aus Sebazinsäure und Hexamethylendiamin (Polyamid 6,10) zu erwähnen.The amounts used in which the dyeing aid according to the invention is added to the dye baths are between 1 and 10 percent by weight, preferably 2 and 5 percent by weight, based on the weight of the material to be dyed. w Synthetic polyamide fiber materials, in particular textile materials and above all with a pronounced three-dimensional character (pile and pile materials), such as carpets, which can be dyed in the presence of the new mixture of dyeing auxiliaries, are, for example, those made from adipic acid and hexamethylenediamine (polyamide 6.6), from E- Caprolactam (polyamide 6), from ω-aminoundecanoic acid (polyamide 11), from ω-aminoonanthic acid (polyamide 7), from ω-aminopelargonic acid (polyamide 8) or from sebacic acid and hexamethylenediamine (polyamide 6.10).
Die Polyamidfasermaterialien können auch als Mischgewebe unter sich oder mit anderen Fasern, z.B. Mischungen aus Polyamid/Wolle oder Polyamide Polyester, verwendet werden.The polyamide fiber materials can also be used as a blended fabric with each other or with other fibers, e.g. Mixtures of polyamide / wool or polyamide polyester can be used.
Das Fasermaterial kann in den verschiedensten Verarbeitungsstadien vorliegen. Beispielsweise kommen in Betracht: Flocke, Kammzug, Gewebe, Gewirke, Vliesstoffe, Garn oder Stückware. Als Stückware seien insbesondere Bodenbeläge wie z.B. Teppiche, oder andere Heimtextilien wie Möbelbezugsstoffe, Vorhänge oder Wandverkleidungen, genannt. Die Färbung von Teppichmaterialien wie Velour- oder Schlingenflorteppichen aus synthetischem Polyamid ist bevorzugt.The fiber material can be in a wide variety of processing stages. For example, the following can be considered: flake, sliver, woven fabric, knitted fabric, nonwovens, yarn or piece goods. In particular, floor coverings such as e.g. Carpets, or other home textiles such as upholstery fabrics, curtains or wall coverings. The coloring of carpet materials such as velor or loop pile carpets made of synthetic polyamide is preferred.
Bei den anionischen Farbstoffen handelt es sich beispielsweise um Salze schwermetallhaltiger oder vorzugsweise metallfreier Mono-, Dis- oder Polyazofarbstoffe einschliesslich der Formazanfarbstoffe sowie der Anthrachinon-, Xanthen--, Nitro-, Triphenylmethan-, Naphthochinonimin-und Phthalocyaninfarbscoffe. Der anionische Charakter dieser Farbstoffe kann durch Metallkomplexbildung allein und/oder vorzugsweise durch saure, salzbildende Substituenten, wie Carbonsäuregruppen, Schwefelsäure- und Phosphonsäurestergruppen, Phosphonsäuregruppen oder Sulfonsäuregruppen bedingt sein. Diese Farbstoffe Könner im Molekül auch sogenannte reaktive Gruppierungen, welche mit dem zu färbenden Material eine kovalente Bindung eingehen, aufweisen. Bevorzugt sind die sogenannten sauren metallfreian Farbstoffe. Letztere enthalten vorzugsweise nur eine einzige Sulfonsäuregruppe.The anionic dyes are, for example, salts of heavy metal-containing or preferably metal-free mono-, dis- or polyazo dyes including the formazan dyes and the anthraquinone, xanthene, nitro, triphenylmethane, naphthoquinoneimine and phthalocyanine dyes. The anionic character of these dyes can be caused by metal complex formation alone and / or preferably by acidic, salt-forming substituents, such as carboxylic acid groups, sulfuric acid and phosphonic acid ester groups, phosphonic acid groups or sulfonic acid groups. These dyes can also have so-called reactive groups in the molecule, which form a covalent bond with the material to be colored. The so-called acidic metal-free dyes are preferred. The latter preferably contain only a single sulfonic acid group.
Von Interesse sind auch die 1: 1- oder 1 : 2-Metallkomplexfarbstoffe. Die 1 : 1-Metallkomplexfarbstoffe weisen vorzugsweise eine oder zwei Sulfonsäuregruppen auf. Als Metall enthalten sie ein Schwermetallatom wie z.B. Kupfer, Nickel oder insbesondere Chrom.The 1: 1 or 1: 2 metal complex dyes are also of interest. The 1: 1 metal complex dyes preferably have one or two sulfonic acid groups. As metal they contain a heavy metal atom such as Copper, nickel or especially chrome.
Die 1: 2-Metallkomplexfarbstoffe enthalten als Zentralatom ein Schwermetallatom wie z.B. ein Kobaltatom oder insbesondere ein Chromatom. Mit dem Zentralatom sind zwei komplexbildende Komponenten verbunden, von denen mindestens eine ein Farbstoffmolekül ist, vorzugsweise jedoch beide Farbstoffmoleküle sind. Dabei können die beiden an der Komplexbildung beteiligten Farbstoffmoleküle gleich oder voneinander verschieden sein. Die 1: 2-Metallkomplexfarbstoffe können z.B. zwei Azomethinmoleküle, einen Disazofarbstoff und einen Monoazofarbstoff oder vorzugsweise zwei Monoazofarbstoffmoleküle enthalten. Die Azofarbstoffmoleküle können wasserlöslichmachende Gruppen aufweisen wie z.B. Säureamid-, Alkylsulfonyl- oder die obengenannten sauren Gruppen. Bevorzugt sind 1: 2-Kobalt-oder 1: 2-Chromkomplexe von Monoazofarbstoffen, die Säureamid-, Alkylsulfonyl- oder insgesamt eine einzige Sulfonsäuregruppe aufweisen.The 1: 2 metal complex dyes contain a heavy metal atom such as e.g. a cobalt atom or in particular a chromium atom. Two complex-forming components are connected to the central atom, at least one of which is a dye molecule, but preferably both are dye molecules. The two dye molecules involved in the complex formation can be the same or different from one another. The 1: 2 metal complex dyes can e.g. contain two azomethine molecules, a disazo dye and a monoazo dye, or preferably two monoazo dye molecules. The azo dye molecules can have water solubilizing groups such as e.g. Acid amide, alkylsulfonyl or the above acidic groups. Preference is given to 1: 2 cobalt or 1: 2 chromium complexes of monoazo dyes which have acid amide, alkylsulfonyl or a total of a single sulfonic acid group.
Es können auch Mischungen der anionischen Farbstoffe eingesetzt werden. Besonders bevorzugt sind Farbstoffmischungen von mindestens 2 oder 3 anionischen Farbstoffen zur Herstellung egaler Dichromie- oder Trichromiefärbungen.Mixtures of the anionic dyes can also be used. Dye mixtures of at least 2 or 3 anionic dyes are particularly preferred for the production of level dichromia or trichromatic dyes.
Die Menge der der Flotte zugesetzten Farbstoffe richtet sich nach der gewünschten Farbtiefe. Im allgemeinen haben sich Mengen von 0,01 bis 10, insbesondere 0,1 bis 5 g je Liter Flotte bewährt.The amount of dyes added to the liquor depends on the desired depth of color. In general, amounts of 0.01 to 10, in particular 0.1 to 5 g per liter of liquor have proven successful.
Die Färbebäder können Alkalimetallhydroxide, Alkalimetallcarbonate oder -hydrogencarbonate; Mincralsäuren, wie Schwefelsäure oder Phosphorsäure; organische Säuren, zweckmässig niedere, aliphatische Carbonsäuren, wie Ameisen-, Essig- oder Oxalsäure und/oder Salze, wie Ammoniumacetat, Ammoniumsulfat, Dinatriumphosphat, Dikaliumphosphat, Kaliumacetat oder Natriumacetat enthalten. Die Alkalien und Säuren dienen vor allem der Einstellung des pH-Wertes der erfindungsgemäss verwendeten Flotten, der in der Regel am Anfang 8 bis 8,5 und am Schluss 4,5 bis 6 beträgt.The dyebaths can contain alkali metal hydroxides, alkali metal carbonates or bicarbonates; Minralic acids such as sulfuric acid or phosphoric acid; organic acids, suitably lower, aliphatic carboxylic acids, such as formic, acetic or oxalic acid and / or salts, such as ammonium acetate, ammonium sulfate, disodium phosphate, dipotassium phosphate, potassium acetate or sodium acetate. The alkalis and acids serve above all to adjust the pH of the liquors used according to the invention, which is generally 8 to 8.5 at the beginning and 4.5 to 6 at the end.
Ferner können die Färbebäder noch die üblichen Elektrolyte, Dispergier-, Antischaum- und Netzmittel enthalten.The dyebaths can also contain the usual electrolytes, dispersants, antifoams and wetting agents.
Die Färbungen erfolgen mit Vorteil aus wässeriger Flotte nach dem Ausziehverfahren. Das Flottenverhältnis kann dementsprechend innerhalb eines weiten Bereiches gewählt werden, z.B. 1:3 bis 1: 100, vorzugsweise 1 : 10 bis 1 : 50. Man färbt zweckmässig bei einer Temperatur im Bereich von 40°C bis zum Siedepunkt. Ueberraschenderweise kann man die Färbung bei niederigen Temperaturen in einem Bereich von 50 bis 85°C durchführen.The dyeings are advantageously carried out from an aqueous liquor using the exhaust process. The liquor ratio can accordingly be chosen within a wide range, e.g. 1: 3 to 1: 100, preferably 1:10 to 1:50. It is convenient to dye at a temperature in the range from 40 ° C. to the boiling point. Surprisingly, the coloring can be carried out at low temperatures in a range from 50 to 85 ° C.
Vorzugsweise geht man mit dem Textilmaterial in eine Flotte ein, die eine Temperatur von 15 bis 25°C und einen pH-Wert von 7,5 bis 8,5 aufweist. Danach gibt man die Farbstoffe und das erfindungsgemässe Hilfsmittelgemisch zu und behandelt das Material 5 bis 15 Minuten bei 15 bis 25°C. Alsdann steigert man die Temperatur langsam auf 60°C und färbt 30 bis 60 Minuten bei dieser Temperatur. Daraufhin senkt man den pH-Wert des Bades auf 5 - 6 und färbt weiter 10 bis 20 Minuten bei 60°C. Am Schluss wird das Bad abgekühlt und das gefärbte Material wie üblich gespült und getrocknet. Das erfindungsgemässe Färbeverfahren kann auch so durchgeführt werden, dass man das Färbegut zuerst mit dem Hilfsmittelgemisch 10 bis 15 Minuten bei 20 bis 25°C behandelt und anschliessend färbt.The textile material is preferably added to a liquor which has a temperature of 15 to 25 ° C. and a pH of 7.5 to 8.5. Then the dyes and the auxiliary mixture according to the invention are added and the material is treated at 15 to 25 ° C. for 5 to 15 minutes. The temperature is then slowly increased to 60 ° C. and dyeing is carried out at this temperature for 30 to 60 minutes. Then the pH of the bath is reduced to 5 - 6 and dyeing is continued for 10 to 20 minutes at 60 ° C. Finally, the bath is cooled and the colored material rinsed and dried as usual. The dyeing process according to the invention can also be carried out by first treating the material to be dyed with the auxiliary mixture for 10 to 15 minutes at 20 to 25 ° C. and then dyeing.
Das Färben des synthetischen Polyamidfasermaterials kann auch nach einem Druck- oder Klotzverfahren durchgeführt werden. Dabei wird die gegebenenfalls verdickte Druckpaste bzw. Flotte, welche Farbstoff, erfindungsgemässe Iiilfsmittelzubereitung, Säure sowie eventuell weitere Zusätze enthält, auf die Faser gedruckt oder geklotzt, vorzugsweise bei einer Temperatur zwischen 10 und 40°C. Das geklotzte oder bedruckte Fasermaterial kann einer Hitzebehandlung unterworfen werden, wie z.B. Dämpfen. Vorzugsweise wird es jedoch mit einer Plastikfclie verpackt und bei 50 bis 60°C während 45 bis 120 Minuten gelagert.The dyeing of the synthetic polyamide fiber material can also be carried out by a printing or padding process. The possibly thickened printing paste or liquor, which contains dye, auxiliary preparation according to the invention, acid and possibly other additives, is printed or padded on the fiber, preferably at a temperature between 10 and 40 ° C. The padded or printed fiber material can be subjected to heat treatment, e.g. Steaming. However, it is preferably packed with a plastic film and stored at 50 to 60 ° C for 45 to 120 minutes.
Nach dem erfindungsgemässen Verfahren erhält man auf synthetischem Polyamidfasermaterial gleichmässige und farbkräftige Ausfärbungen, die sich auch durch gute Reibechtheiten und Farbausbeuten auszeichnen. Zudem werden die anderen Echtheiten der Färbungen z.B. Lichtechtheit durch den Einsatz der erfindungsgemässen Mischung nicht negativ beeinflusst.According to the process of the invention, uniform and vivid colorations are obtained on synthetic polyamide fiber material, which are also characterized by good rub fastness and color yields. In addition, the other fastness properties of the dyeings, e.g. Light fastness is not adversely affected by the use of the mixture according to the invention.
Insbesondere stellt das erfindungsgemässe Verfahren ein stark energiesparendes Färbesystem dar, bei dem synthetisches Polyamidfasermaterial bei einer niedrigen Temperatur von 50 bis 85°C gefärbt werden kann und eine vollständige Erschöpfung des Färbebades erreicht wird.In particular, the method according to the invention represents a highly energy-saving dyeing system in which synthetic polyamide fiber material can be dyed at a low temperature of 50 to 85 ° C. and complete dying of the dye bath is achieved.
Somit kann die Flotte für weiteres Färben eingesetzt werden, so dass in Bezug auf Wasser, Energie, Zeit und Chemikalien beträchtliche Einsparungen erzielt werden. Daneben wird ein bedeutender ökologischer Fortschritt erreicht. Das erfindungsgemässe Verfahren zeichnet sich nicht nur durch die ökonomischen und ökologischen Vorteile aus, sondern es wird zudem durch die schonende Färbeweise eine Qualitätsverbesserung des Färbematerials erzielt.The fleet can thus be used for further dyeing, so that considerable savings can be achieved in terms of water, energy, time and chemicals. In addition, significant ecological progress is achieved. The process according to the invention is not only distinguished by the economic and ecological advantages, but also by the gentle way of dyeing an improvement in the quality of the dyeing material is achieved.
In den nachfolgenden Beispielen sind die Teile Gewichtsteile und die Prozente Gewichtsprozente.In the examples below, the parts are parts by weight and the percentages are percentages by weight.
10 g eines Polyamid-6,6-Teppiches mit Polypropylenrücken werden zu einer Flotte gegeben, welche
- 0,075 g Ameisensäure 85%ig,
- 0,035 g eines gelben Farbstoffes der Formel
- 0,024 g eines roten Farbstoffes der Formel
- 0,03 g eines blauen Farbstoffes der Formel
- 0,2 g einer Hilfsmittelzubereitung (1), bestehend aus
- 36% Dodecylbenzolsulfonsäure
- 2,8%der quaternären Ammoniumverbindung der Formel (6)
- 1% eines Siloxanoxyalkylen-Copolymerisates (A) mit einer Viskosität von 1200 mPas bei 20°C und einem Trübungspunkt bei 32°C,
- 10% Propylenglykol
- 7% Monoethanolamin
- 43,2% Wasser
in 400 ml Wasser enthält. Danach heizt man das Bad auf 40°C und erhöht die Temperatur im Verlaufe von 60 Minuten auf 60°C und färbt 60 Minuten bei dieser Temperatur. Alsdann wird das Bad abgekühlt und der Teppich gespült und getrocknet.10 g of a polyamide 6.6 carpet with a polypropylene back are added to a liquor which
- 0.075 g formic acid 85%,
- 0.035 g of a yellow dye of the formula
- 0.024 g of a red dye of the formula
- 0.03 g of a blue dye of the formula
- 0.2 g of an auxiliary preparation (1) consisting of
- 36% dodecylbenzenesulfonic acid
- 2.8% of the quaternary ammonium compound of the formula (6)
- 1% of a siloxaneoxyalkylene copolymer (A) with a viscosity of 1200 mPas at 20 ° C and a cloud point at 32 ° C,
- 10% propylene glycol
- 7% monoethanolamine
- 43.2% water
contains in 400 ml of water. The bath is then heated to 40 ° C. and the temperature is raised to 60 ° C. in the course of 60 minutes and dyeing is carried out at this temperature for 60 minutes. The bath is then cooled and the carpet rinsed and dried.
Man erhält eine egale, gut durchgefärbte Färbung.A level, well-colored dyeing is obtained.
Auf einer Teppichhaspelkufe mit Dosiereinrichtungen für Natronlauge und Schwefelsäure werden 100 kg Polyamid-6,6-Teppich in 3000 1 Wasser bei 20°C auf einen pH-Wert von 8 eingestellt. Danach werden der Flotte folgende Zusätze zugegeben:
- 2500 g der Hilfsmittelzubereitung (1)
- 200 g eines gelben Farbstoffes der Formel (101)
- 300 g eines roten Farbstoffes der Formel (102) und
- 100 g eines blauen Farbstoffes der Formel (103).
- 2500 g of the auxiliary preparation (1)
- 200 g of a yellow dye of the formula (101)
- 300 g of a red dye of the formula (102) and
- 100 g of a blue dye of the formula (103).
Man lässt die Teppichware 15 Minuten bei 20°C zirkulieren und steigert die Temperatur im Verlaufe von 40 Minuten auf 60°C. Alsdann färbt man 30 Minuten bei dieser Temperatur und senkt während 40 Minuten durch Zudosierung von Schwefelsäure den pH-Wert des Bades auf 5. Hierauf färbt man noch 15 Minuten bei 60°C und bei einem pH-Wert von 5. Anschliessend wird die Färbeflotte abgekühlt und der Teppich gespült und fertiggestellt.The carpet is allowed to circulate at 20 ° C for 15 minutes and the temperature is raised to 60 ° C in the course of 40 minutes. The dyeing is then carried out for 30 minutes at this temperature and the pH of the bath is lowered to 5 by adding sulfuric acid over 40 minutes. The dyeing is then continued for 15 minutes at 60 ° C. and at a pH of 5. The dyeing liquor is then cooled and the carpet rinsed and finished.
Man erhält eine egale, gut durchgefärbte Färbung. Die Baderschöpfung ist praktisch vollständig, so dass im gleichen Färbebad der nächste Teppich gefärbt werden kann.A level, well-colored dyeing is obtained. The bathroom exhaustion is practically complete, so that the next carpet can be dyed in the same dye bath.
Egale und farbstarke Färbungen erhält man auch, wenn in den Beispielen 1 und 2 anstelle der angegebenen Hilfsmittelzubereitung (1) jeweils die gleiche Menge folgender weiterer Zubereitungen (2) und (3) eingesetzt wird.Smooth and strong dyeings are also obtained if, in Examples 1 and 2, instead of the auxiliary preparation (1) indicated, the same amount of the following further preparations (2) and (3) is used.
(2) Zubereitung, bestehend aus
- 25% Dodecylbenzolsulfonsäure
- 10% der quaternären Ammoniumverbindung der Formel (6)
- 1% des Siloxanoxyalkylen-Copolymerisates (A)
- 5% Propylenglykol
- 7% Natriumhydroxidlösung 30% und
- 52% Wasser;
- 25% dodecylbenzenesulfonic acid
- 10% of the quaternary ammonium compound of the formula (6)
- 1% of the siloxaneoxyalkylene copolymer (A)
- 5% propylene glycol
- 7% sodium hydroxide solution 30% and
- 52% water;
(3) Zubereitung, bestehend aus
- 36% Dodecylbenzolsulfonsäure
- 2,8% der quaternären Ammoniumverbindung der Formel (6)
- 1% des Siloxanoxyalkylen-Copolymerisates (A)
- 10% Diethanolamin und
- 50,2% Wasser.
- 36% dodecylbenzenesulfonic acid
- 2.8% of the quaternary ammonium compound of the formula (6)
- 1% of the siloxaneoxyalkylene copolymer (A)
- 10% diethanolamine and
- 50.2% water.
Auf einer Teppichhaspelkufe mit Dosiereinrichtungen für Natronlauge und Schwefelsäure werden 100 kg Polyamid-6,6-Teppich in 3000 1 Wasser bei 20°C auf einen pH-Wert von 8 eingestellt. Hierauf werden der Flotte folgende Zusätze zugegeben:
- 2500 g einer Hilfsmittelzubereitung (4), bestehend aus
- 36 % Dodecylbenzolsulfonsäure,
- 3 % der quäternären Ammoniumverbindung der Formel (7)
- 10 % Propylenglykol und
- 51 % Wasser
- 300 g eines gelben Farbstoffes der Formel (101)
- 400 g eines roten Farbstoffes der Formel (102) und
- 150 g eines blauen Farbstoffgemisches (1:1) bestehend aus einem Farbstoff der Formel (103) und einem Farbstoff der Formel
- 2500 g of an auxiliary preparation (4) consisting of
- 36% dodecylbenzenesulfonic acid,
- 3% of the quaternary ammonium compound of the formula (7)
- 10% propylene glycol and
- 51% water
- 300 g of a yellow dye of the formula (101)
- 400 g of a red dye of the formula (102) and
- 150 g of a blue dye mixture (1: 1) consisting of a dye of the formula (103) and a dye of the formula
Man lässt die Teppichware 15 Minuten bei 20°C zirkulieren und steigert die Temperatur im Verlaufe von 40 Minuten auf 60°C, alsdann färbt man 30 Minuten bei dieser Temperatur und senkt während 40 Minuten durch Zudosierung von Schwefelsäure den pH-Wert des Bades auf 5. Danach färbt man nach 15 Minuten bei 60°C und bei einem pH-Wert von 5. Anschliessend wird die Färbeflotte abgekühlt und der Teppich gespült und fertiggestellt.The carpet is allowed to circulate at 20 ° C for 15 minutes and the temperature is raised to 60 ° C in the course of 40 minutes, then it is dyed for 30 minutes and the pH of the bath is reduced to 5 by adding sulfuric acid over 40 minutes . After that dyeing after 15 minutes at 60 ° C. and at a pH of 5. The dyeing liquor is then cooled and the carpet is rinsed and finished.
Man erhält eine egale, gut durchgefärbte Färbung. Die Baderschöpfung ist praktisch vollständig, so dass im gleichen Färbebad der nächste Teppich gefärbt werden kann.A level, well-colored dyeing is obtained. The bathroom exhaustion is practically complete, so that the next carpet can be dyed in the same dye bath.
Eine egale und farbstarke Färbung erhält man,wenn im Beispiel 3 anstelle der Hilfsmittelzubereitung (4) die gleiche Menge einer Zubereitung (5), bestehend aus
- 36 % Diisopropylnaphthalinsulfonsäure, Natriumsalz
- 18 % der quaternären Ammoniumverbindung der Formel (8)
- 10 % Propylenglykol und
- 36 % Wasser
eingesetzt wird.A level and strong coloring is obtained if in Example 3 instead of the auxiliary preparation (4) the same amount of a preparation (5) consisting of
- 36% diisopropylnaphthalenesulfonic acid, sodium salt
- 18% of the quaternary ammonium compound of the formula (8)
- 10% propylene glycol and
- 36% water
is used.
Claims (17)
enthält.1. dyeing aid, characterized in that it is at least
contains.
bedeuten.5. dyeing aid according to one of claims 1 to 4, characterized in that component (A) is an anionic compound of the formula
mean.
darstellt.6. dyeing aid according to claim 5, characterized in that component (A) is an anionic compound of the formula
represents.
sind und die Summe von p + s 5 bis 20 beträgt.9. dyeing aid according to claim 8, characterized in that in formula (4)
are and the sum of p + s is 5 to 20.
die Summe von p1+ s1 15 bis 25 beträgt.10. dyeing aid according to one of claims 1 to 4, characterized in that it is at least
the sum of p 1 + s 1 is 15 to 25.
enthält, färbt bzw. bedruckt.15. A method for dyeing or printing synthetic polyamide faserma L erial with anionic dyes, characterized in that this material in the presence of an adjuvant, at least
contains, colors or prints.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH5752/81 | 1981-09-07 | ||
CH575281 | 1981-09-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0074923A1 true EP0074923A1 (en) | 1983-03-23 |
EP0074923B1 EP0074923B1 (en) | 1985-11-06 |
Family
ID=4298751
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82810370A Expired EP0074923B1 (en) | 1981-09-07 | 1982-09-06 | Dyeing auxiliary and its use in dyeing or printing synthetic polyamide fibrous materials |
Country Status (4)
Country | Link |
---|---|
US (1) | US4444563A (en) |
EP (1) | EP0074923B1 (en) |
JP (1) | JPS58136884A (en) |
DE (1) | DE3267310D1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0102926A1 (en) * | 1982-09-03 | 1984-03-14 | Ciba-Geigy Ag | Dyeing auxiliary and its use in dyeing or printing synthetic polyamide fibres |
EP0135198A2 (en) * | 1983-09-19 | 1985-03-27 | Ciba-Geigy Ag | Process for dyeing synthetic polyamide fibrous material |
EP0197005A1 (en) * | 1985-03-26 | 1986-10-08 | Ciba-Geigy Ag | Maleic acid or phthalic acid half esters of alkoxylated fatty amines |
EP0235088A1 (en) * | 1986-02-25 | 1987-09-02 | Ciba-Geigy Ag | Halfesters of maleic acid or phthalic acid and alkoxylated fatty amines |
FR2623218A1 (en) * | 1987-11-13 | 1989-05-19 | Sandoz Sa | NEW LEATHER DYEING PROCESS |
FR2687397A1 (en) * | 1992-02-17 | 1993-08-20 | Sandoz Sa | NOVEL LOW FOAMING SURFACTANTS, THEIR PREPARATION AND THEIR USE. |
CN111793993A (en) * | 2020-07-07 | 2020-10-20 | 山东黄河三角洲纺织科技研究院有限公司 | Anti-printing process of viscose/lyocell/cotton blended fabric |
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US4920168A (en) * | 1988-04-14 | 1990-04-24 | Kimberly-Clark Corporation | Stabilized siloxane-containing melt-extrudable thermoplastic compositions |
US4859759A (en) * | 1988-04-14 | 1989-08-22 | Kimberly-Clark Corporation | Siloxane containing benzotriazolyl/tetraalkylpiperidyl substituent |
US4923914A (en) * | 1988-04-14 | 1990-05-08 | Kimberly-Clark Corporation | Surface-segregatable, melt-extrudable thermoplastic composition |
US4857251A (en) * | 1988-04-14 | 1989-08-15 | Kimberly-Clark Corporation | Method of forming a nonwoven web from a surface-segregatable thermoplastic composition |
US5120888A (en) * | 1988-04-14 | 1992-06-09 | Kimberly-Clark Corporation | Surface-segregatable, melt-extrudable thermoplastic composition |
US4976788A (en) * | 1988-06-03 | 1990-12-11 | Kimberly-Clark Corporation | Method of cleaning melt-processing equipment with a thermoplastic polyolefin and a bifunctional siloxane |
JPH0219577A (en) * | 1988-07-04 | 1990-01-23 | Nippon Saafuakutanto Kogyo Kk | Level dyeing agent composition for reactive dye |
US5114646A (en) * | 1989-09-18 | 1992-05-19 | Kimberly-Clark Corporation | Method of increasing the delay period of nonwoven webs having delayed wettability |
US5696191A (en) * | 1989-09-18 | 1997-12-09 | Kimberly-Clark Worldwide, Inc. | Surface-segregatable compositions and nonwoven webs prepared therefrom |
US5641822A (en) * | 1989-09-18 | 1997-06-24 | Kimberly-Clark Corporation | Surface-segregatable compositions and nonwoven webs prepared therefrom |
US5344862A (en) * | 1991-10-25 | 1994-09-06 | Kimberly-Clark Corporation | Thermoplastic compositions and nonwoven webs prepared therefrom |
US5427589A (en) * | 1993-03-03 | 1995-06-27 | Springs Industries, Inc. | Method for dyeing fibrous materials |
US5494855A (en) * | 1994-04-06 | 1996-02-27 | Kimberly-Clark Corporation | Thermoplastic compositions and nonwoven webs prepared therefrom |
US5437690A (en) * | 1994-05-25 | 1995-08-01 | Springs Industries, Inc. | Method for dyeing fibrous materials and dye assistant relating to the same |
CA2327034C (en) * | 1999-12-01 | 2007-07-17 | Canon Kabushiki Kaisha | Method of reforming element surface, element with reformed surface, method of manufacturing element with reformed surface, surface treatment liquid for forming reformed surface, and method of manufacturing surface treatment liquid |
US6497731B1 (en) | 2000-04-07 | 2002-12-24 | Basf Corporation | Dyed polyamide-6 articles having improved wetfastness properties and methods of making same |
EP1777337A1 (en) * | 2005-10-07 | 2007-04-25 | Clariant International Ltd. | Method of dyeing polyamide fibres |
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1982
- 1982-09-02 US US06/414,103 patent/US4444563A/en not_active Expired - Lifetime
- 1982-09-06 EP EP82810370A patent/EP0074923B1/en not_active Expired
- 1982-09-06 DE DE8282810370T patent/DE3267310D1/en not_active Expired
- 1982-09-07 JP JP57154742A patent/JPS58136884A/en active Granted
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DE1920357A1 (en) * | 1968-04-26 | 1970-02-12 | Sandoz Ag | Process for dyeing textile material with different dye affinities from synthetic polyamide fibers |
DE1919120A1 (en) * | 1969-03-24 | 1970-11-26 | Geigy Ag J R | Process for uniform, streak-free dyeing of synthetic polyamide fiber material |
DE2360632A1 (en) * | 1972-12-06 | 1974-07-04 | Soprosoie Fa | METHOD OF COLORING POLYAMIDE TEXTILE PRODUCTS |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4563190A (en) * | 1982-03-09 | 1986-01-07 | Ciba-Geigy Corporation | Dyeing assistant and use thereof for dyeing or printing synthetic polyamide fibre material |
EP0102926A1 (en) * | 1982-09-03 | 1984-03-14 | Ciba-Geigy Ag | Dyeing auxiliary and its use in dyeing or printing synthetic polyamide fibres |
EP0135198A2 (en) * | 1983-09-19 | 1985-03-27 | Ciba-Geigy Ag | Process for dyeing synthetic polyamide fibrous material |
EP0135198A3 (en) * | 1983-09-19 | 1985-06-12 | Ciba-Geigy Ag | Process for dyeing synthetic polyamide fibrous material |
EP0197005A1 (en) * | 1985-03-26 | 1986-10-08 | Ciba-Geigy Ag | Maleic acid or phthalic acid half esters of alkoxylated fatty amines |
AU581975B2 (en) * | 1985-03-26 | 1989-03-09 | Ciba-Geigy Ag | Maleic or phthalic acid half esters of alkoxylated fatty amines |
EP0235088A1 (en) * | 1986-02-25 | 1987-09-02 | Ciba-Geigy Ag | Halfesters of maleic acid or phthalic acid and alkoxylated fatty amines |
FR2623218A1 (en) * | 1987-11-13 | 1989-05-19 | Sandoz Sa | NEW LEATHER DYEING PROCESS |
FR2687397A1 (en) * | 1992-02-17 | 1993-08-20 | Sandoz Sa | NOVEL LOW FOAMING SURFACTANTS, THEIR PREPARATION AND THEIR USE. |
BE1006384A3 (en) * | 1992-02-17 | 1994-08-09 | Sandoz Sa | New low foaming surfactants, preparation and use. |
CN111793993A (en) * | 2020-07-07 | 2020-10-20 | 山东黄河三角洲纺织科技研究院有限公司 | Anti-printing process of viscose/lyocell/cotton blended fabric |
Also Published As
Publication number | Publication date |
---|---|
DE3267310D1 (en) | 1985-12-12 |
JPS58136884A (en) | 1983-08-15 |
US4444563A (en) | 1984-04-24 |
JPH0357230B2 (en) | 1991-08-30 |
EP0074923B1 (en) | 1985-11-06 |
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