EP0149116A2 - Process for dyeing fibrous materials from polyacrylonitrile or acrylonitrile copolymers and an auxiliary agent containing a retarder - Google Patents
Process for dyeing fibrous materials from polyacrylonitrile or acrylonitrile copolymers and an auxiliary agent containing a retarder Download PDFInfo
- Publication number
- EP0149116A2 EP0149116A2 EP84114978A EP84114978A EP0149116A2 EP 0149116 A2 EP0149116 A2 EP 0149116A2 EP 84114978 A EP84114978 A EP 84114978A EP 84114978 A EP84114978 A EP 84114978A EP 0149116 A2 EP0149116 A2 EP 0149116A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyacrylonitrile
- alkyl
- retarder
- acrylonitrile copolymers
- dyeing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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
- D06P1/655—Compounds containing ammonium groups
- D06P1/66—Compounds containing ammonium groups containing quaternary ammonium groups
-
- 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/70—Material containing nitrile groups
- D06P3/76—Material containing nitrile groups using basic dyes
Definitions
- the compounds (I) are prepared by known processes from unsaturated fatty acids or from mixtures of saturated and unsaturated fatty acids, for example mixtures obtained from natural fats, or from their esters or chlorides and the unsymmetrical dialkylalkylenediamines.
- the amidamines are then again quaternized by known processes using quaternizing agents such as benzyl chloride, methyl, ethyl, butyl chloride, dimethyl and diethyl sulfate and dimethyl methane phosphoric acid.
- quaternizing agents such as benzyl chloride, methyl, ethyl, butyl chloride, dimethyl and diethyl sulfate and dimethyl methane phosphoric acid.
- oleic acid, soy oleic acid Suitable for palm kernel acid, poppy oil acid, sunflower oil acid, rapeseed acid and tallow fatty acid.
- Unsymmetrical alkylated alkylenediamines for example N, N-dimethyl-ethylenediamine, NN-diethylethylenediamine, N, N-dimethyl-propylenediamine and N, N-diethyl-propylenediamine, are to be mentioned as diamines.
- Suitable cationic dyes are dyes of the most varied classes of compounds, for example diphenylmethane, triphenylmethane and rhodamine dyes, azo or anthraquinone dyes containing onium groups, furthermore thiazine, oxazine, methine and azomethine dyes, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 3 Edition 1970, supplement volume p. 225 are described.
- the required amounts of the compounds of formula (I) to be used according to the invention can easily be determined by preliminary tests. In general, amounts of about 0.25 to 2.5%, based on the weight of the dye material used, of these compounds are used.
- Suitable Acrylnitrilmischpolymerisate are for example copolymers of Acyrlnitril with vinyl chloride, vinylidene chloride, vinyl acetate, vinyl chloroacetate, vinyl alcohol, acrylic and methacrylic acid, Acyrl and methacrylic acid esters, allyl or basi - specific vinyl compounds such as vinyl imidazole, Vinylbenzimidazol, vinylpyridine, Vinylmethylpyridin, vinylpyrimidine, the proportion provided that Co-monomers is not more than 20 percent by weight.
- the dyeing of the polyacrylonitrile fiber materials can be carried out in the customary manner in the exhaust process by introducing the material to be dyed into an aqueous dye liquor heated to about 50-85 ° C. which contains the cationic dye, compounds of the formula (I), additions of salts such as sodium acetate or Sodium sulfate, also contains acids such as acetic acid or formic acid, then the temperature of the dyebath is raised to approximately 100 ° C. in the course of about 30 minutes and then the dyebath is kept at this temperature until it is exhausted.
- the material to be dyed can also be pretreated at a temperature of 40-100 ° C.
- fiber materials consisting of polyacrylonitrile or acrylonitrile-containing copolymers or containing such copolymers or copolymers, which can be present in various processing stages, for example as spun tow, sliver, flakes, threads, yarns, woven or knitted fabrics, are excellently uniform and to color in deep tones.
- DE-A-1 127 865 discloses the use of retarders of the formula (I), in which R 1 is a saturated aliphatic hydrocarbon radical when dyeing with poly fiber materials containing acrylonitrile are known.
- R 1 is a saturated aliphatic hydrocarbon radical when dyeing with poly fiber materials containing acrylonitrile are known.
- a compound with R 1 C 11 H 23 b eschrie- ben.
- ammonium compounds (I) of the present invention ß compared to the corresponding saturated derivatives have improved activity as retarder, so that one can operate with smaller amounts of auxiliaries. In general, 3-4 times the amount of saturated ammonium compound is required to achieve comparable effectiveness.
- the dyeing curve of the dyes has a uniform slope with a constant temperature increase in the drawing phase.
- the compounds prepared according to the following examples show a band at 6.1-6.25 p in the IR spectrum.
- the effectiveness against the corresponding ammonium compound from stearic acid is about 3 times.
- 250 g of palm kernel fatty acid are converted into the fatty acid amine amine using 114 g of N, N-diethylethylenediamine.
- the quaternization is carried out by mixing with excess butyl chloride by heating in an autoclave at 100 ° C. for 1 hour, at 120 ° C. for 1 hour and at 130 ° C. for 2 hours. Excess butyl chloride is then stripped off with steam. A slightly water-soluble product is obtained.
- Example 4 Of a substance produced by the process described in Example 4 from the coconut fat consisting of over 95% saturated fatty acid glycerides, three times the amount of the compound of Example 4 is required in order to achieve the same retarding effect.
- Example 4 400 g of the tallow fatty acid amidamine used in Example 4 are reacted with 100 g of butyl chloride at 110 ° C. in an autoclave for 6 hours. The pressure initially increased to 2 bar drops to 0.3 bar towards the end of the reaction.
- the quaternary compound obtained is readily soluble in water and shows an activity which is three times as great on both dry-spun and wet-spun acrylic fibers as that of the compound prepared from the correspondingly hydrogenated tallow fat.
- Yarn made of polyacrylonitrile fibers is introduced in a liquor ratio of 1:40 into a bath heated to 80 ° C., which contains 0.06 g of a cationic dye of the formula in liters
- a knitted fabric made from staple polyacrylonitrile fibers is introduced in a liquor ratio of 1:15 into a bath at 85 ° C., which contains 0.3 g of a dye of the formula
Abstract
Description
Gegenstand der Erfindung ist ein Verfahren zum Färben von Fasermaterialien aus Polyacrylnitril oder Acrylnitrilmischpolymerisaten mit kationischen Farbstoffen in Gegenwart von Verbindungen der allgemeinen Formel
- R1 einen aliphatischen Kohlenwasserstoffrest mit 11 - 21 Kohlenstoffatomen, der aus mindestens 30 Mol-% eines ungesättigten aliphatischen Kohlenwasserstoffs besteht,
- R2 und R3 Alkyl,
- R 4 Alkyl oder Aralkyl,
- n 1 - 3 und
- An(-) ein Anion bedeuten.
- R 1 is an aliphatic hydrocarbon radical with 11-21 carbon atoms, which consists of at least 30 mol% of an unsaturated aliphatic hydrocarbon,
- R 2 and R 3 alkyl,
- R 4 alkyl or aralkyl,
- n 1 - 3 and
- An (-) means an anion.
Bevorzugt stehen in Formel (I)
- Rl für einen aliphatischen Kohlenwasserstoffrest mit 11 - 17 Kohlenstoffatomen, der zu 40 - 100 Mol-% aus einem Rest mit mindestens einer Doppelbindung besteht,
- R2 und R3 für C1-C5-Alkyl, insbesondere Methyl oder Ethyl,
- R4 für C1-C5-Alkyl, insbesondere Butyl, oder für Benzyl und
- n für 2 oder 3.
- Rl for an aliphatic hydrocarbon radical with 11-17 carbon atoms, which consists of 40-100 mol% of a radical with at least one double bond,
- R 2 and R 3 are C 1 -C 5 alkyl, in particular methyl or ethyl,
- R 4 for C 1 -C 5 alkyl, especially butyl, or for benzyl and
- n for 2 or 3.
Die Herstellung der Verbindungen (I) erfolgt nach bekannten Verfahren aus ungesättigten Fettsäuren oder aus Mischungen von gesättigten und ungesättigten Fettsäuren, beispielsweise aus natürlichen Fetten erhaltenen Mischungen, oder aus deren Estern oder Chloriden und den unsymetrischen Dialkyl-alkylendiaminen. Anschließend werden die Amidamine wiederum nach bekannten Verfahren quaterniert unter Verwendung von Quaternierungsmitteln wie Benzylchlorid, Methyl-, Ethyl-, Butylchlorid, Dimethyl- und Diethylsulfat und Dimethylmethanphosphorsäure. Als ungesättigte Säuren bzw. als deren Gemisch mit gesättigten Säuren sind z.B. ölsäure, Sojaölsäure, Palmkernölsäure, Mohnölsäure, Sonnenblumenölsäure, Rapsölsäure und Talgfettsäure geeignet. Als Diamine sind vorzugsweise unsymetrische alkylierte Alkylendiamine, z.B. N,N-Dimethyl-ethylendiamin, N-N-Diethylethylendiamin, N,N-Dimethyl-propylendiamin und N,N-Diethyl-propylendiamin zu nennen.The compounds (I) are prepared by known processes from unsaturated fatty acids or from mixtures of saturated and unsaturated fatty acids, for example mixtures obtained from natural fats, or from their esters or chlorides and the unsymmetrical dialkylalkylenediamines. The amidamines are then again quaternized by known processes using quaternizing agents such as benzyl chloride, methyl, ethyl, butyl chloride, dimethyl and diethyl sulfate and dimethyl methane phosphoric acid. Examples of oleic acid, soy oleic acid, Suitable for palm kernel acid, poppy oil acid, sunflower oil acid, rapeseed acid and tallow fatty acid. Unsymmetrical alkylated alkylenediamines, for example N, N-dimethyl-ethylenediamine, NN-diethylethylenediamine, N, N-dimethyl-propylenediamine and N, N-diethyl-propylenediamine, are to be mentioned as diamines.
Als kationische Farbstoffe kommen Farbstoffe der verschiedensten Verbindungsklassen in Betracht, beispielsweise Diphenylmethan-, Triphenylmethan- und Rhodaminfarbstoffe, Oniumgruppen enthaltende Azo- oder Anthrachinonfarbstoffe, ferner Thiazin-, Oxazin-, Methin-und Azomethinfarbstoffe, wie sie beispielsweise in Ullmanns Encyclopädie der technischen Chemie, 3. Auflage 1970, Ergänzungsband S. 225 beschrieben sind.Suitable cationic dyes are dyes of the most varied classes of compounds, for example diphenylmethane, triphenylmethane and rhodamine dyes, azo or anthraquinone dyes containing onium groups, furthermore thiazine, oxazine, methine and azomethine dyes, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 3 Edition 1970, supplement volume p. 225 are described.
Die erforderlichen Mengen an den erfindungsgemäß zu verwendenden Verbindungen der Formel (I) lassen sich durch Vorversuche leicht ermitteln. Im allgemeinen werden von diesen Verbindungen Mengen von ca. 0,25 bis 2,5 %, bezogen auf das Gewicht des eingesetzten Färbeguts, angewandt.The required amounts of the compounds of formula (I) to be used according to the invention can easily be determined by preliminary tests. In general, amounts of about 0.25 to 2.5%, based on the weight of the dye material used, of these compounds are used.
Geeignete Acrylnitrilmischpolymerisate sind beispielsweise Mischpolymerisate von Acyrlnitril mit Vinylchlorid, Vinylidenchlorid, Vinylacetat, Vinylchloracetat, Vinylalkohol, Acryl- und Methacrylsäure, Acyrl-und Methacrylsäureestern, Allylchloracetat oder basi- schen Vinylverbindungen, wie Vinylimidazol, Vinylbenzimidazol, Vinylpyridin, Vinylmethylpyridin, Vinylpyrimidin, sofern der Anteil diese Co-Monomeren nicht mehr als 20 Gewichtsprozent beträgt.Suitable Acrylnitrilmischpolymerisate are for example copolymers of Acyrlnitril with vinyl chloride, vinylidene chloride, vinyl acetate, vinyl chloroacetate, vinyl alcohol, acrylic and methacrylic acid, Acyrl and methacrylic acid esters, allyl or basi - specific vinyl compounds such as vinyl imidazole, Vinylbenzimidazol, vinylpyridine, Vinylmethylpyridin, vinylpyrimidine, the proportion provided that Co-monomers is not more than 20 percent by weight.
Das Färben der Polyacrylnitrilfasermaterialien kann in üblicher Weise im Ausziehverfahren durchgeführt werden, indem man das Färbegut in eine auf etwa 50 - 85°C erwärmte wäßrige Färbeflotte einbringt, welche den kationischen Farbstoff, Verbindungen der Formel (I), Zusätze von Salzen, wie Natriumacetat oder Natri- ümsulfat, ferner Säuren, wie Essigsäure oder Ameisensäure enthält, anschließend die Temperatur des Färbebades im Verlauf von etwa 30 Minuten auf annähernd 100°C erhöht und dann das Färbebad so lange auf diese Temperatur hält, bis es erschöpft ist. Man kann das Färbegut auch bei einer Temperatur von 40 - 100°C mit einer Flotte vorbehandeln, welche die üblichen Salze und Säuren sowie Verbindungen der Formel (I), jedoch noch keinen Farbstoff enthält, dann erst den Farbstoff zusetzen und das Färben bei 100°C durchführen. Schließlich ist es auch möglich, das Färbegut unmittelbar in das auf annähernd 100°C erhitzte Färbebad einzubringen, welches Verbindungen der Formel (I) enthält.The dyeing of the polyacrylonitrile fiber materials can be carried out in the customary manner in the exhaust process by introducing the material to be dyed into an aqueous dye liquor heated to about 50-85 ° C. which contains the cationic dye, compounds of the formula (I), additions of salts such as sodium acetate or Sodium sulfate, also contains acids such as acetic acid or formic acid, then the temperature of the dyebath is raised to approximately 100 ° C. in the course of about 30 minutes and then the dyebath is kept at this temperature until it is exhausted. The material to be dyed can also be pretreated at a temperature of 40-100 ° C. using a liquor which contains the customary salts and acids and compounds of the formula (I) but does not yet contain any dye, only then add the dye and dyeing at 100 ° C carry out. Finally, it is also possible to introduce the material to be dyed directly into the dyebath which has been heated to approximately 100 ° C. and which contains compounds of the formula (I).
Mit Hilfe des erfindungsgemäßen Verfahrens gelingt es, aus Polyacrylnitril bzw. acrylnitrilhaltigen Mischpolymerisaten bestehende bzw. derartige Polymerisate oder Mischpolymerisate enthaltende Fasermaterialien, die in den verschiedensten Verarbeitungsstadien beispielsweise als Spinnkabel, Kammzüge, Flocken, Fäden, Garne, Gewebe oder Gewirke vorliegen können, hevorragend gleichmäßig und in tiefen Tönen zu färben.With the aid of the method according to the invention, fiber materials consisting of polyacrylonitrile or acrylonitrile-containing copolymers or containing such copolymers or copolymers, which can be present in various processing stages, for example as spun tow, sliver, flakes, threads, yarns, woven or knitted fabrics, are excellently uniform and to color in deep tones.
Aus der DE-A-1 127 865 ist die Verwendung von Retardern der Formel (I), worin R1 für einen gesättigten aliphatischen Kohlenwasserstoffrest beim Färben mit Polyacrylnitril enthaltenden Fasermaterialien bekannt. Als Beispiel wird eine Verbindung mit R1 = C11H23 beschrie- ben.DE-A-1 127 865 discloses the use of retarders of the formula (I), in which R 1 is a saturated aliphatic hydrocarbon radical when dyeing with poly fiber materials containing acrylonitrile are known. As an example, a compound with R 1 = C 11 H 23 b eschrie- ben.
überraschenderweise zeigte sich nun, daß die Ammoniumverbindungen (I) der vorliegenden Erfindung im Vergleich zu den entsprechenden gesättigten Derivaten eine verbesserte Wirksamkeit als Retarder aufweisen, so daß mit geringeren Hilfsmittelmengen gearbeitet werden kann. Im allgemeinen ist zur Erzielung einer vergleichbaren Wirksamkeit die 3-4 mal größere Menge an gesättigter Ammoniumverbindung erforderlich.Surprisingly, now shown as the ammonium compounds (I) of the present invention ß compared to the corresponding saturated derivatives have improved activity as retarder, so that one can operate with smaller amounts of auxiliaries. In general, 3-4 times the amount of saturated ammonium compound is required to achieve comparable effectiveness.
Die gesteigerte Wirksamkeit ist vor allem beim Färben mit hoch affinen, d.h. sehr schnell ziehenden Farbstoffen von Bedeutung, da hierbei die bekannten Retarder in großen Mengen eingesetzt werden müssen.The increased effectiveness is especially when dyeing with high affinity, i.e. very fast-drawing dyes are important because the known retarders must be used in large quantities.
Vorteilhaft ist weiterhin, daß die Aufziehkurve der Farbstoffe bei einer konstanten Temperatursteigerung in der Aufziehphase eine gleichmäßige Steilheit aufweist.It is also advantageous that the dyeing curve of the dyes has a uniform slope with a constant temperature increase in the drawing phase.
Die nach den folgenden Beispielen hergestellten Verbindungen zeigen im IR-Spektrum eine Bande bei 6,1 - 6,25 p.The compounds prepared according to the following examples show a band at 6.1-6.25 p in the IR spectrum.
275 g ölsäure werden durch Umsetzung mit 102 g N,N-Dimethylpropylendiamin-1,3 bei 175°C in das Amidamin übergeführt. Dieses wird mit 126 g Benzylchlorid in die quartäre Verbindung übergeführt:
Diese ist leicht in eine klare, wäßrige Lösung überzuführen. In wäßrigen, konzentrierten Lösungen wird ein klares Gel gebildet, und wasserfrei erhält man ein glasiges Harz. Im IR-Spektrum ist eine Absorptionsbande 6,1 µ für die Säureamidgruppe nachweisbar.This can easily be converted into a clear, aqueous solution. A clear gel is formed in aqueous, concentrated solutions, and a glassy resin is obtained when anhydrous. An absorption band of 6.1 μ for the acid amide group is detectable in the IR spectrum.
Die Umsetzung des Amidamins mit 110 g Butylchlorid innerhalb von 5 Stunden bei 110°C führt gleichfalls zu einer als Retarder gut wirksamen Ammoniumverbindung.The reaction of the amidamine with 110 g of butyl chloride within 5 hours at 110 ° C. likewise leads to an ammonium compound which is highly effective as a retarder.
Die Wirksamkeit gegenüber der entsprechenden Ammoniumverbindung aus Stearinsäure beträgt etwa das 3-fache.The effectiveness against the corresponding ammonium compound from stearic acid is about 3 times.
320 g Sojaöl werden 3 - 4 Stunden bei 150 - 165°C mit 102 g N,N-Dimethylpropylendiamin-1,3 erhitzt, bis durch Titration gegen verdünnte Säuren der vollständige Umsatz der primären Aminogruppe mit den Estergruppen des Sojaöls nachgewiesen werden kann. Dann wird nach bekannten Methoden mit 126 g Benzylchlorid quaterniert, ohne Abtrennung des entstehenden Glycerins. Letzteres begünstigt die Einstellung zu hochprozentigen wäßrigen Lösungen.320 g of soybean oil are heated for 3 - 4 hours at 150 - 165 ° C with 102 g of 1,3-N, N-dimethylpropylenediamine until the complete change by titration against dilute acids can be set of the primary amino group with the Estergruppen the S detected ojaöls. Then it is quaternized according to known methods with 126 g of benzyl chloride, without separating off the glycerol formed. The latter favors the attitude towards high-proof aqueous solutions.
250 g Palmkernfettsäure werden mit 114 g N,N-Diethyl- ethylendiamin in das Fettsäureamid-amin übergeführt. Die Quaternierung wird durch Vermischen mit überschüssigem Butylchlorid durchgeführt, in dem im Autoklaven 1 Stunde auf 100°C, 1 Stunde auf 120°C und 2 Stunden auf 130°C erhitzt wird. Anschließend wird überschüssiges Butylchlorid mit Wasserdampf abgetrieben. Es wird ein leicht wasserlösliches Produkt erhalten.250 g of palm kernel fatty acid are converted into the fatty acid amine amine using 114 g of N, N-diethylethylenediamine. The quaternization is carried out by mixing with excess butyl chloride by heating in an autoclave at 100 ° C. for 1 hour, at 120 ° C. for 1 hour and at 130 ° C. for 2 hours. Excess butyl chloride is then stripped off with steam. A slightly water-soluble product is obtained.
200 g eines Talgfettsäureamidamins, das durch Amidierung von 148,2 g Rindertalg mit 50,8 g N,N-Dimethylamino-propylendiamin-1,3 bei 160°C erhalten wurde, werden 1 Stunde bei 100°C mit 63 g Benzylchlorid umgesetzt und 2 Stunden bei 110°C nachbehandelt. Das feste, harzartige Reaktionsprodukt ist leicht löslich in Wasser.200 g of a tallow fatty acid amidamine, which was obtained by amidating 148.2 g of beef tallow with 50.8 g of N, N-dimethylamino-propylenediamine-1,3 at 160 ° C., are reacted with 63 g of benzyl chloride at 100 ° C. for 1 hour and Treated for 2 hours at 110 ° C. The solid, resinous reaction product is easily soluble in water.
Es zeigt beim Färben von Polyacrylnitrilfasern mit kationischen Farbstoffen eine ausgezeichnete Wirksamkeit als Retarder.It shows excellent effectiveness as a retarder when dyeing polyacrylonitrile fibers with cationic dyes.
Von einer nach dem im Beispiel 4 beschriebenen Verfahren aus dem Kokosfett, bestehend aus über 95 % gesättigten Fettsäureglyceriden, hergestellen Substanz ist die dreifache Menge der Verbindung des Beispiel 4 erforderlich, um eine gleiche retardierende Wirkung zu erzielen.Of a substance produced by the process described in Example 4 from the coconut fat consisting of over 95% saturated fatty acid glycerides, three times the amount of the compound of Example 4 is required in order to achieve the same retarding effect.
400 g des in Beispiel 4 verwendeten Talgfettsäureamidamins werden mit 100 g Butylchlorid bei 110°C im Autoklaven 6 Stunden zur Reaktion gebracht. Der anfangs auf 2 bar gestiegene Druck fällt gegen Ende der Reaktion auf 0,3 bar ab.400 g of the tallow fatty acid amidamine used in Example 4 are reacted with 100 g of butyl chloride at 110 ° C. in an autoclave for 6 hours. The pressure initially increased to 2 bar drops to 0.3 bar towards the end of the reaction.
Die erhaltene quartäre Verbindung ist in Wasser leicht löslich und zeigt eine Wirksamkeit, die sowohl auf trockengesponnenen als auch auf naßgesponnenen Acrylfasern 3-fach so groß ist wie die der aus dem entsprechend hydrierten Talgfett hergestellten Verbindung.The quaternary compound obtained is readily soluble in water and shows an activity which is three times as great on both dry-spun and wet-spun acrylic fibers as that of the compound prepared from the correspondingly hydrogenated tallow fat.
Garn aus Polyacrylnitrilfasern wird im Flottenverhältnis von 1 : 40 in ein auf 80°C erwärmtes Bad eingebracht, das im Liter 0,06 g eines kationischen Farbstoffs der FormelYarn made of polyacrylonitrile fibers is introduced in a liquor ratio of 1:40 into a bath heated to 80 ° C., which contains 0.06 g of a cationic dye of the formula in liters
0,25 g Natriumacetat, 0,3 g Eisessig und 0,2 g der Verbindung des Beispiels 1 enthält. Das Bad wird in 30 Minuten auf 98°C erhitzt und 45 Minuten bei dieser Temperatur gehalten. Man erhält eine gleichmäßige blaue Anfärbung des Garnes. Während des Färbevorgangs ist feststellbar, daß der Farbstoff zu Beginn retardiert wird und erst mit steigender Temperatur langsam, bis zum Ende aber vollständig auf die Faser aufzieht.Contains 0.25 g of sodium acetate, 0.3 g of glacial acetic acid and 0.2 g of the compound of Example 1. The bath is heated to 98 ° C. in 30 minutes and kept at this temperature for 45 minutes. A uniform blue dyeing of the yarn is obtained. During the dyeing process, it can be seen that the dye is retarded at the beginning and only slowly as the temperature rises, but completely on the fiber until the end.
Eine Wirkware aus Polyacrylnitril-Stapfelfasern wird im Flottenverhältnis von 1 : 15 in ein Bad von 85°C eingebracht, das 0,3 g eines Farbstoffs der Formel
0,25 g Natriumacetat, 0,3 g Eisessig und 0,25 g der Verbindung des Beispiel 1 enthält. Das Bad wird in 30 Minuten zum Kochen gebracht und 60 Minuten bei Kochtemperatur gehalten. In dieser Zeit zieht der Farbstoff langsam und gleichmäßig auf die Faser auf. Man erhält eine vollkommen egale Rotfärbung.Contains 0.25 g of sodium acetate, 0.3 g of glacial acetic acid and 0.25 g of the compound of Example 1. The bath is brought to the boil in 30 minutes and held at the cooking temperature for 60 minutes. During this time, the dye slowly and evenly spreads onto the fiber. You get a completely level red color.
Claims (3)
verwendet.1. A process for dyeing fiber materials made of polyacrylonitrile or acrylonitrile copolymers with cationic dyes in the presence of retarders, characterized in that a compound of the general formula is used as retarder
used.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833345900 DE3345900A1 (en) | 1983-12-20 | 1983-12-20 | METHOD FOR DYEING FIBER MATERIALS FROM POLYACRYLNITRILE OR ACRYLNITRILE MIXED POLYMERISATES, AND AGENTS CONTAINING RETARDERS |
| DE3345900 | 1983-12-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0149116A2 true EP0149116A2 (en) | 1985-07-24 |
| EP0149116A3 EP0149116A3 (en) | 1985-08-14 |
Family
ID=6217376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84114978A Withdrawn EP0149116A3 (en) | 1983-12-20 | 1984-12-08 | Process for dyeing fibrous materials from polyacrylonitrile or acrylonitrile copolymers and an auxiliary agent containing a retarder |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0149116A3 (en) |
| JP (1) | JPS60151390A (en) |
| DE (1) | DE3345900A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0327379A2 (en) * | 1988-02-05 | 1989-08-09 | CRODA INTERNATIONAL plc | Humectants |
| WO1993002042A1 (en) * | 1991-07-18 | 1993-02-04 | Eastman Kodak Company | Amide-containing quaternary ammonium salts |
| WO1997034041A1 (en) * | 1996-03-11 | 1997-09-18 | High Point Chemical Corporation | Biodegradable dye leveler compounds for acrylic fibers |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2963339A (en) * | 1960-12-06 | Retarding and levelling agents | ||
| GB866335A (en) * | 1956-07-31 | 1961-04-26 | Ciba Ltd | Process for the dyeing of fibres of polyacrylonitrile |
| GB969855A (en) * | 1960-01-14 | 1964-09-16 | Sandoz Ltd | Process for the level dyeing of natural or synthetic polyamide fibres |
| JPS444609Y1 (en) * | 1965-06-18 | 1969-02-19 | ||
| DE2430853A1 (en) * | 1974-06-27 | 1976-01-08 | Cassella Farbwerke Mainkur Ag | TOOLS FOR COLORING IMAGES MADE OF POLYACRYLNITRILE OR ACID-MODIFIED POLYESTERS |
| DE2548009A1 (en) * | 1974-10-29 | 1976-05-06 | Ciba Geigy Ag | PROCESS FOR LEVELING INTO COLORING OF SLOW, NORMAL AND FAST DRAWING POLYACRYLNITRILE MATERIALS |
| EP0105034A1 (en) * | 1982-09-27 | 1984-04-04 | Ciba-Geigy Ag | Dyeing aid and process for dyeing of polyacrylonitrile fibre material |
-
1983
- 1983-12-20 DE DE19833345900 patent/DE3345900A1/en not_active Withdrawn
-
1984
- 1984-12-08 EP EP84114978A patent/EP0149116A3/en not_active Withdrawn
- 1984-12-17 JP JP59264661A patent/JPS60151390A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2963339A (en) * | 1960-12-06 | Retarding and levelling agents | ||
| GB866335A (en) * | 1956-07-31 | 1961-04-26 | Ciba Ltd | Process for the dyeing of fibres of polyacrylonitrile |
| GB969855A (en) * | 1960-01-14 | 1964-09-16 | Sandoz Ltd | Process for the level dyeing of natural or synthetic polyamide fibres |
| JPS444609Y1 (en) * | 1965-06-18 | 1969-02-19 | ||
| DE2430853A1 (en) * | 1974-06-27 | 1976-01-08 | Cassella Farbwerke Mainkur Ag | TOOLS FOR COLORING IMAGES MADE OF POLYACRYLNITRILE OR ACID-MODIFIED POLYESTERS |
| DE2548009A1 (en) * | 1974-10-29 | 1976-05-06 | Ciba Geigy Ag | PROCESS FOR LEVELING INTO COLORING OF SLOW, NORMAL AND FAST DRAWING POLYACRYLNITRILE MATERIALS |
| EP0105034A1 (en) * | 1982-09-27 | 1984-04-04 | Ciba-Geigy Ag | Dyeing aid and process for dyeing of polyacrylonitrile fibre material |
Non-Patent Citations (1)
| Title |
|---|
| DERWENT JAPANESE PATENTS REPORT, Band 8, Nr. 8, 1969, Sektion 2, Seite 3; & JP-Y-44 004 609 (MORIN KAGAKU KOGYO CO., LTD.) 25.02.1969 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0327379A2 (en) * | 1988-02-05 | 1989-08-09 | CRODA INTERNATIONAL plc | Humectants |
| EP0327379A3 (en) * | 1988-02-05 | 1991-01-09 | CRODA INTERNATIONAL plc | Humectants |
| WO1993002042A1 (en) * | 1991-07-18 | 1993-02-04 | Eastman Kodak Company | Amide-containing quaternary ammonium salts |
| WO1997034041A1 (en) * | 1996-03-11 | 1997-09-18 | High Point Chemical Corporation | Biodegradable dye leveler compounds for acrylic fibers |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0149116A3 (en) | 1985-08-14 |
| JPS60151390A (en) | 1985-08-09 |
| DE3345900A1 (en) | 1985-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0074057A2 (en) | Perfluor-alkyl esters, process for their preparation and their use as dirt repulsing agents | |
| DE3626051A1 (en) | AQUEOUS DISPERSIONS FOR THE SIMULTANEOUS SOFTENING AND HYDROPHILIZING EQUIPMENT OF FIBER MATERIALS, METHOD FOR THEIR PRODUCTION AND THEIR USE | |
| DE1103284B (en) | Process for antistatic finishing and improving the dyeing properties of textile fabrics | |
| DE1469608A1 (en) | Process for the simultaneous dyeing and bleaching of proteinaceous fiber material | |
| DE2556376C2 (en) | Process for dyeing polyacrylonitrile fiber material | |
| EP0149116A2 (en) | Process for dyeing fibrous materials from polyacrylonitrile or acrylonitrile copolymers and an auxiliary agent containing a retarder | |
| DE1149687B (en) | Process for the treatment, in particular antistatic finishing, of textile materials | |
| DE2932869A1 (en) | METHOD FOR SOFT-GRIPING TEXTILE MATERIALS WITH UNSATURATED, ALIPHATIC ACID AMIDES | |
| DE2539310C2 (en) | ||
| DE1909963A1 (en) | Process for increasing the dye affinity of fiber materials made from natural polyamides | |
| DE1619476A1 (en) | Process for coloring polyacrylonitrile structures | |
| DE948237C (en) | Process for the production of washable embossments on textiles | |
| DE2409437A1 (en) | PROCESS FOR SELECTIVE DYEING OF MIXED FIBERS OR MIXED FIBERS TEXTILES | |
| DE2815511A1 (en) | Dyeing and printing of cellulose-polyester blends - using mixts. of reactive and dispersion dyes, with fixing at reduced temp. | |
| DE2214997A1 (en) | Process for generating antistatic effects in textiles | |
| DE2250352A1 (en) | METHOD OF FLAME RESISTANT OF DRAFTED POLYAMIDE FIBERS | |
| DE1054656B (en) | Process for the production of threads or fibers from polyacrylonitrile and / or its copolymers with good fiber properties | |
| DE701863C (en) | Process for dyeing cellulose fibers with iron-sensitive basic and substantive dye | |
| DE733689C (en) | Process for making textile fabrics water repellent | |
| AT208500B (en) | Process for the production of synthetic fibers from polyacrylonitrile polymers or copolymers with a predominant proportion of acrylonitrile | |
| DE2428688A1 (en) | Quaternary ammonium salts prepd from polyhydric alcohols - epihalohydrin and fatty amine, used as retarders in dyeing polyacrylo-nitrile fibres | |
| DE765123C (en) | Process for making textile fabrics waterproof and water-repellent while maintaining air permeability | |
| DE1927920A1 (en) | Process for reducing the dye affinity of fiber materials made of polyacrylonitrile | |
| DE686170C (en) | Method for sizing rayon | |
| DE1940179A1 (en) | Process for dyeing fiber materials made of polyacrylonitrile or acrylonitrile-containing copolymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| 17P | Request for examination filed |
Effective date: 19841208 |
|
| AK | Designated contracting states |
Designated state(s): DE FR GB IT |
|
| AK | Designated contracting states |
Designated state(s): DE FR GB IT |
|
| 17Q | First examination report despatched |
Effective date: 19860430 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
| 18W | Application withdrawn |
Withdrawal date: 19860729 |
|
| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: BOEHMKE, GUENTHER, DR. Inventor name: JAKOBS, KARLHANS, DIPL.-ING. |