EP0131865B1 - Esterified oxyalkylated quaternary ammonium compounds, process for their preparation and their use as treating agents for fibres - Google Patents

Esterified oxyalkylated quaternary ammonium compounds, process for their preparation and their use as treating agents for fibres Download PDF

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Publication number
EP0131865B1
EP0131865B1 EP84107892A EP84107892A EP0131865B1 EP 0131865 B1 EP0131865 B1 EP 0131865B1 EP 84107892 A EP84107892 A EP 84107892A EP 84107892 A EP84107892 A EP 84107892A EP 0131865 B1 EP0131865 B1 EP 0131865B1
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Prior art keywords
acid
anion
quaternary ammonium
ammonium compounds
formula
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German (de)
French (fr)
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EP0131865A1 (en
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Manfred Dr. Hofinger
Rolf Dr. Kleber
Lothar Jaeckel
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Hoechst AG
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Hoechst AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/372—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing etherified or esterified hydroxy groups ; Polyethers of low molecular weight

Definitions

  • the invention relates to novel quaternary ammonium compounds, a process for their preparation and their use as fiber preparation agents.
  • Quaternary ammonium compounds with only one long-chain alkyl radical as described, for example, in DE-OS 23 35 675 and recommended as fiber preparation agents, can indeed be converted into aqueous dispersions with an active substance content of up to 50% and have a good antistatic activity, but have such an effect Compounds have a significantly reduced softening and softening effect.
  • EP-A-69948 describes quaternary N-alkyl-N, N ', N'-polyoxyalkyl-a-w-diaminoalkylene fatty acid esters. From GB-A 1 567 947 diesters of quaternized amino alcohols are known. Both classes of compounds are described as fabric softeners. None is said about its use as a fiber preparation agent.
  • the compounds of the formula are prepared from the compounds of the formula II. These are obtained by known processes by oxyalkylating primary fatty amines or fatty alkylalkylenediamines, such as, for example, tallow fat propylene diamine. An overview of methods for the preparation of this well-known class of compounds is given in Schönfeldt, "Surface Active Ethylene Oxide Adducts", Erasmusliche Verlagsgesellschaft, Stuttgart, 1976, pages 70 to 73. The esterification of these compounds is carried out according to known methods with a fatty acid in higher-boiling inert solvents such as Toluene or xylene or preferably without solvent in the melt and covered with a protective gas.
  • a fatty acid in higher-boiling inert solvents such as Toluene or xylene or preferably without solvent in the melt and covered with a protective gas.
  • the reflux temperature of the reaction mixture is expediently chosen as the reaction temperature and the water of reaction formed is removed azeotropically.
  • the water of reaction is distilled off directly from the reaction mixture.
  • the reaction temperatures here are 140 to 220 ° C, preferably 150 to 180 ° C.
  • an acid catalyst such as p-toluenesulfonic acid or hypophosphorous acid, is advantageously used.
  • the completeness of the reaction is checked by determining the acid number.
  • the molar ratio of fatty acid to compounds of formula II is constant 1, so that practically exclusively the monoester results.
  • the corresponding aminoxalkylate fatty acid ester is reacted with an equivalent amount (corresponding to the number of N atoms) of one of those carboxylic acids on which the anions A defined above are based.
  • carboxylic acids forming the anion which have already been mentioned as preferred above, the following may also be mentioned: capric, lauric, myristic, palmitic, stearic acid, glycolic acid, oxalic, succinic, adipic, sebacic and malic acid.
  • the equivalent amount is to be measured accordingly.
  • the reaction is optionally carried out in a lower alkanol, such as ethanol or isopropanol, or in water.
  • the quaternization reaction is advantageously carried out with ethylene oxide or propylene oxide or mixtures thereof at a temperature of 80 to 95 ° C. in a suitable stirred autoclave, the reaction pressure generally being up to 3 bar. Ethylene oxide is preferably used. Typical reaction times are in the range of 5 to 10 hours, with degrees of quaternization of up to 85% being achieved. The degrees of quaternization are determined by two-phase titration of the quaternary product of the formula with sodium dodecyl sulfate at pH 1 to 2 or pH 10.
  • Particularly preferred amines which can be alkoxylated to give starting compounds of the formulas Ila and Ilb are the industrially available products stearyl arachidyl / behenyl amine and stearyl, arachidyl / behenyl propylene diamine.
  • the diamines are prepared in a known manner by adding acrylonitrile to primary fatty amines and then catalytically hydrogenating the propionitriles.
  • Fatty acids suitable for esterification are products on a natural or synthetic basis, which can be individual chemical individuals; however, mixtures with appropriate chain distribution are often used.
  • Such fatty acids or fatty acid mixtures are, for example, tallow fatty acid, palm oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, rapeseed oil fatty acid (hardened or not hardened), stearic acid, erucic acid, behenic acid, oleic acid, ricinoleic acid, or branched-chain compounds from oxo synthesis, such as, for example, isostearic acid.
  • the mixtures according to the invention of the esterified, oxyalkylated quaternary ammonium compounds of the formula and the corresponding amine salts are highly thermostable, highly plasticizing and antistatically effective, liquor and substance-stable preparation agents for native and synthetic fibers which, in liquid to soft-pasty state, are dispersible in water and are easily miscible with this high active ingredient content. They can be used for filament ( «endless») preparation as well as for the preparation of staple fibers and especially tear cables. These mixtures according to the invention do not cause any corrosion on the thread-carrying organs of the textile machines. They create an ideal friction behavior of the fibers thus prepared and give them a soft, voluminous, pleasant grip.
  • the fibers and threads to be prepared are primarily those made from cotton, wool, viscose, polyacrylonitrile, polyester, polyamide-6 and -6.6 and from polyolefins.
  • the mixtures according to the invention do not contain any inorganic salts. They do not have a yellowing effect on the fiber even under thermal stress. They are generally used in amounts of 0.2 to 4, preferably 0.5 to 2% by weight, based on the weight of the fiber or thread.
  • polyacrylonitrile fibers When preparing polyacrylonitrile fibers, they give the fiber softness, antistatic properties and smoothness, reduce the static fiber-fiber static friction, whereby the dynamic thread-metal sliding friction is regulated and the resolving power of the acrylonitrile fiber structure is increased so that a This results in trouble-free tearing on the tearing machine and leads to perfect running properties during the subsequent spinning.
  • the mixtures according to the invention can also be applied to the dyed fibers, especially those made from polyacrylonitrile, after dyeing in the last rinsing bath or added already in the dyebath. It is advantageous that these compounds according to the invention can also be stored down to pH 4 in acid dye baths and up to pH 9 in alkaline dye baths and fully develop their softening effect.
  • the use of an additional antistatic can be dispensed with here, since the compounds of the formula according to the invention also have a sufficiently antistatic effect in such baths.
  • the mixtures according to the invention can also be applied to the fiber as a finishing agent in front of the crimping chamber, in order to provide the cut flake with good dissolving power or good willingness to open, which is particularly important in the case of acrylic wool types for carpet manufacture.
  • the preparation pad is 0.05 to 1.5, preferably 0.15 to 0.5% by weight, based on the fiber weight.
  • such preparation and finishing agents can also contain customary additives, such as nonionic or other cationic agents, mineral or ester oils, emulsifiers, such as, for example, fatty alcohol oxalkylates.
  • customary additives such as nonionic or other cationic agents, mineral or ester oils, emulsifiers, such as, for example, fatty alcohol oxalkylates.
  • 360 g (0.6 mol) of monostearic acid ester prepared according to a) is neutralized in the presence of 43 g (2.4 mol) of water and 60 g of isopropanol with 75 g (0.6 mol) of lactic acid and with 132 g (3, 0 mol) quaternized ethylene oxide.
  • the reaction is complete in 6 hours at a temperature of 85 ° C and a maximum pressure of 3 bar.
  • the degree of quaternization of the product is determined from the ratio of the acidic or alkaline two-phase titration with sodium lauryl sulfate and is 80%.
  • PA 6 filament, dtex 220f40, as well as experimentally spun PAC filament, dtex 300f100, are treated with aqueous solutions of the following products in the immersion roller process by means of godets, a preparation layer of 0.7% active substance, based on the fiber weight, being set.
  • the prepared threads are measured analogously to DE-OS 23 35 675 for their dynamic friction and analogously to DE-PS 2518124 for their static friction (as a measure of the tape adhesion and the resolving power).
  • PA 6 flake, 1.2 dtex / 40 mm, PAC flake, 3 dtex / 60 mm and PES flake, 1.4 dtex / 40 mm, are treated according to Comparative Example A with aqueous solutions of the following products (edition 0.2 %).
  • conductivity values are determined for the dried and air-conditioned fibers using a textometer from Mahlo GmbH, Saal / Donau, measured in divisions (high values indicate high antistatic effect):
  • a PAC tear cable colored, total titer 800,000 dtex, is treated with an aqueous solution of the following products, the preparation being applied on a Lisseux by padding and adjusted to 0.5% active substance.
  • the cables are torn on a Seydel tearing machine, after which the following tearing effects are observed:
  • the cable equipped with the pasty comparison product b) does show good running behavior, but the stack diagram created from the torn fibers is uneven due to column tears and long fibers present . In some cases, pimples and nits can also be found on the fibers.
  • the cable equipped with the liquid preparation of Example 13 according to the invention shows no pimples.
  • the stack diagram is uniform. There are no column cracks. The fibers are bulky and separate well from one another.

Description

Die Erfindung betrifft neuartige quaternäre Ammoniumverbindungen, ein Verfahren zu deren Herstellung und deren Verwendung als Faserpräparationsmittel.The invention relates to novel quaternary ammonium compounds, a process for their preparation and their use as fiber preparation agents.

Es ist seit längerem bekannt, kationische quaternäre Ammoniumverbindungen als antistatisch wirksame Faserpräparationsmittel, die ein besseres Gleiten von Fasern und Filamenten über die fadenführenden Aggregate von Textilverarbeitungsmaschinen bewirken sollen, einzusetzen (vgl. K-Lindner: « Tenside - Textilhilfsmittel - Waschrohstoffe », Wissenschaftliche Verlagsgesellschaft Stuttgart, Band 11, Seite 1618). Insbesondere ist aus der DE-OS 28 43 659 die Verwendung quaternärer Etheramine als Präparationsmittel bei der Herstellung und Verarbeitung nativer und synthetischer Fasern bekanntgeworden. Diese quaternären Etheramine mit zwei langen Alkylketten vermitteln den Fasern - neben ihrer Wirksamkeit als Antistatika - auch einen Weichmachungseffekt. Diese Etheramine können teilweise als Feststoffe appliziert werden. Will man sie jedoch in die Form von stabilen, gießbaren Dispersionen in Wasser bringen, so gelingt dies nur bis zu einem Wirkstoffgehalt von etwa 25 %. Quaternäre Ammoniumverbindungen mit nur einem langkettigen Alkylrest, wie sie beispielsweise in der DE-OS 23 35 675 beschrieben und als Faserpräparationsmittel empfohlen werden, lassen sich zwar in wäßrige Dispersionen mit bis zu 50 % Wirkstoffgehalt umwandeln und besitzen eine gute Antistatik-Wirkung, jedoch weisen solche Verbindungen einen deutlich verringerten Avivier- und Weichmachungseffekt auf.It has been known for a long time to use cationic quaternary ammonium compounds as antistatic fiber preparation agents, which are supposed to improve the sliding of fibers and filaments over the thread-carrying aggregates of textile processing machines (cf.K-Lindner: "Tensides - Textile auxiliaries - Washing raw materials", Scientific Publishing House Stuttgart , Volume 11, page 1618). In particular, DE-OS 28 43 659 has disclosed the use of quaternary ether amines as preparation agents in the production and processing of native and synthetic fibers. These quaternary ether amines with two long alkyl chains impart not only their effectiveness as antistatic agents but also a softening effect. Some of these ether amines can be applied as solids. However, if you want to bring them into the form of stable, pourable dispersions in water, this is only possible up to an active ingredient content of about 25%. Quaternary ammonium compounds with only one long-chain alkyl radical, as described, for example, in DE-OS 23 35 675 and recommended as fiber preparation agents, can indeed be converted into aqueous dispersions with an active substance content of up to 50% and have a good antistatic activity, but have such an effect Compounds have a significantly reduced softening and softening effect.

In der EP-A-69948 werden quartäre N-Alkyl-N,N',N'-polyoxyalkyl-a-w-diaminoalkylenfettsäureester beschrieben. Aus der GB-A 1 567 947 sind Diester von quaternisierten Aminoalkoholen bekannt. Beide Verbindungsklassen werden als Wäscheweichspülmittel beschrieben. Über eine Verwendung als Faserpräparationsmittel ist nichts ausgesagt.EP-A-69948 describes quaternary N-alkyl-N, N ', N'-polyoxyalkyl-a-w-diaminoalkylene fatty acid esters. From GB-A 1 567 947 diesters of quaternized amino alcohols are known. Both classes of compounds are described as fabric softeners. Nothing is said about its use as a fiber preparation agent.

Es besteht ein Bedürfnis nach quaternären Ammoniumverbindungen, die als Faserpräparationsmittel sowohl einen guten Antistatik- als auch einen guten Avivageeffekt aufweisen, und die entweder in flüssigem Zustand vorliegen und in diesem leicht gehandhabt und in diesem leicht gehandhabt und appliziert werden können oder leicht in stabile, gießbare Einstellungen in Wasser bei hohem Wirkstoffgehalt überführt werden können.There is a need for quaternary ammonium compounds which, as fiber preparation agents, have both a good antistatic and a good softening effect, and which are either in the liquid state and easy to handle and easy to handle and apply in it, or easily in stable, pourable Settings in water with a high active ingredient content can be transferred.

Zur Befriedigung dieses Bedürfnisses stellt die vorliegende Erfindung Gemische bestehend aus 57 bis 85 Mol-% an veresterten, oxalkylierten quaternären Ammoniumverbindungen der Formel

Figure imgb0001
und 43 bis 15 Mol-% an Aminsalzen der Formel
Figure imgb0002
worin

  • R' einen Alkylrest oder einen Alkenylrest mit 8 bis 23 C-Atomen,
  • R2 = H oder CH3 mit der Maßgabe, daß R2 im Gesamtmolekül auch beide Bedeutungen annehman kann ;
  • R3 einen Alkylrest oder den Alkylrest einer natürlichen Fettsäure mit 8 bis 45 C-Atomen, wobei letzterer gegebenenfalls auch 1 bis 3 Mehrfachbindungen und 1 bis 3 OH-Gruppen enthalten kann ;
  • A- das Anion einer Alkancarbonsäure oder einer Monohydroxyalkancarbonsäure mit einem Alkylrest von 1 bis 23 C-Atomen, das Anion einer Dicarbonsäure mit 0 bis 8 Methylengruppen, wobei diese Methylengruppen 1 bis 2 OH-Substituenten tragen können, das Anion der Fumar-, Malein- oder Citronensäure, das Anion der Benzoesäure oder einer hydroxy- oder methylsubstituierten Benzoesäure, wobei die Basizität x dieser Carbonsäuren demgemäß die Werte 1, 2 oder 3 annehmen kann, bedeuten ;
  • a, b und c eine ganze oder gebrochene Zahl von 1 bis 3 ;
  • d und e eine ganze oder gebrochene Zahl von 1 bis 3 ;
  • m = 2 oder 3 und
  • n = 0 oder 1 sind

zur Verfügung.To meet this need, the present invention provides mixtures consisting of 57 to 85 mole percent of esterified, oxyalkylated quaternary ammonium compounds of the formula
Figure imgb0001
 and 43 to 15 mol% of amine salts of the formula
Figure imgb0002
 wherein
  • R 'is an alkyl radical or an alkenyl radical with 8 to 23 C atoms,
  • R 2 = H or CH 3 with the proviso that R 2 in the whole molecule can also assume both meanings;
  • R 3 is an alkyl radical or the alkyl radical of a natural fatty acid with 8 to 45 carbon atoms, the latter optionally also containing 1 to 3 multiple bonds and 1 to 3 OH groups;
  • A- the anion of an alkane carboxylic acid or a monohydroxyalkane carboxylic acid with an alkyl radical of 1 to 23 carbon atoms, the anion of a dicarboxylic acid with 0 to 8 methylene groups, these methylene groups can carry 1 to 2 OH substituents, the anion of fumaric, maleic or citric acid, the anion of benzoic acid or a hydroxy- or methyl-substituted benzoic acid, where the basicity x of these carboxylic acids can accordingly assume the values 1, 2 or 3;
  • a, b and c are an integer or fraction from 1 to 3;
  • d and e are an integer or fractional number from 1 to 3;
  • m = 2 or 3 and
  • n = 0 or 1

to disposal.

Vorzugsweise bedeuten in Formel und in der Formel für die entsprechenden Aminsalze

  • R' einen Alkylrest oder Alkenylrest mit 12 bis 23 C-Atomen ;
  • R2 Wasserstoff ; a, b und c die Zahl 1 ;
  • A das Anion einer Alkanmonocarbonsäure oder einer Monohydroxyalkanmonocarbonsäure mit 1 bis 6 C-Atomen, das Anion einer Dicarbonsäure mit 0 bis 4 Methylengruppen, wobei diese Methylengruppen 1 bis 2 OH-Substituenten tragen können, das Anion der Fumar-, Malein-, Citronen-, Benzoe- oder Salicylsäure. Der Index m nimmt bevorzugt den Wert 3 an. Besonders bevorzugt bedeutet A- das Anion der Essigsäure, Propionsäure, Milchsäure, Weinsäure, Citronensäure oder Maleinsäure. x ist die Basizität der diesen Anionen zugrundeliegenden Carbonsäuren und hier - entsprechend der Art der oben definierten Carbonsäuren - gleich 1, 2 oder 3. Bei Vorliegen eines Monohydrogenoder Dihydrogen-Anions einer Di- beziehungsweise Tricarbonsäure bedeutet x die tatsächlich betätigte Basizität.
Preferably in the formula and in the formula for the corresponding amine salts
  • R 'is an alkyl radical or alkenyl radical having 12 to 23 carbon atoms;
  • R 2 is hydrogen; a, b and c the number 1;
  • A is the anion of an alkane monocarboxylic acid or a monohydroxyalkane monocarboxylic acid with 1 to 6 carbon atoms, the anion of a dicarboxylic acid with 0 to 4 methylene groups, these methylene groups can carry 1 to 2 OH substituents, the anion of the fumaric, maleic, citric, Benzoic or salicylic acid. The index m preferably takes the value 3. A- is particularly preferably the anion of acetic acid, propionic acid, lactic acid, tartaric acid, citric acid or maleic acid. x is the basicity of the carboxylic acids on which these anions are based and here - depending on the type of carboxylic acids defined above - equal to 1, 2 or 3. If a monohydrogen or dihydrogen anion of a di- or tricarboxylic acid is present, x means the basicity actually actuated.

Ausgangsverbindungen für die Herstellung der Ammoniumverbindungen der Formel sind oxalkylierte Amine oder Diamine der Formel

Figure imgb0003
worin R', R2, a, b, c, m und n die in der Formel I angegebene Bedeutung haben.Starting compounds for the preparation of the ammonium compounds of the formula are oxyalkylated amines or diamines of the formula
Figure imgb0003
 wherein R ', R 2 , a, b, c, m and n have the meaning given in formula I.

Die Verbindungen der Formel für den Fall, daß n = 0 ist, werden erhalten, indem man eine Verbindung der Formel

Figure imgb0004
in der R1, R2, b und c die in Formel angegebene Bedeutungen haben, mit einer Carbonsäure der Formel R3COOH, worin R3 die in Formel angegebene Bedeutung hat, verestert und das erhaltene Reaktionsprodukt mit einer Carbonsäure und einem Alkylenoxid quaternisiert. In gleicher Weise lassen sich Verbindungen der Formel
Figure imgb0005
umsetzen zu Verbindungen der Formel in der n = 1 ist.The compounds of the formula when n = 0 are obtained by using a compound of the formula
Figure imgb0004
 in which R 1 , R 2 , b and c have the meanings given in the formula, esterified with a carboxylic acid of the formula R 3 COOH, in which R 3 has the meaning given in the formula, and the reaction product obtained is quaternized with a carboxylic acid and an alkylene oxide. In the same way, compounds of the formula
Figure imgb0005
 convert to compounds of the formula in which n = 1.

Die Herstellung der Verbindungen der Formel geht aus von den Verbindungen der Formel II. Diese werden erhalten nach bekannten Verfahren durch Oxalkylierung von primären Fettaminen oder Fettalkylalkylendiaminen, wie zum Beispiel Talgfettpropylendiamin. Eine Übersicht über Methoden zur Herstellung dieser wohlbekannten Verbindungsklasse wird gegeben in Schönfeldt, « Surface Active Ethyleneoxide Adducts », Wissenschaftliche Verlagsgesellschaft, Stuttgart, 1976, Seiten 70 bis 73. Die Veresterung dieser Verbindungen erfolgt nach bekannten Methoden mit einer Fettsäure in höhersiedenden inerten Lösungsmitteln, wie Toluol oder Xylol oder bevorzugt ohne Lösungsmittel in der Schmelze und unter Abdeckung mit einem Schutzgas. Bei Veresterung in einem Lösungsmittel wählt man als Reaktionstemperatur zweckmäßigerweise die Rückflußtemperatur des Reaktionsgemisches und entfernt das gebildete Reaktionswasser azeotrop. Bei Veresterung in Substanz wird das Reaktionswasser direkt aus der Reaktionsmischung abdestilliert. Die Reaktionstemperaturen liegen hier bei 140 bis 220 °C, bevorzugt bei 150 bis 180 °C. Zur Beschleunigung der Reaktion verwendet man mit Vorteil einen sauren Katalysator, wie zum Beispiel p-Toluolsulfonsäure oder hypophosphorige Säure. Die Vollständigkeit der Reaktion wird über die Bestimmung der Säurezahl kontrolliert. Das Molverhältnis von Fettsäure zu Verbindungen der Formel II beträgt konstant 1, so daß praktisch ausschließlich der Monoester resultiert.The compounds of the formula are prepared from the compounds of the formula II. These are obtained by known processes by oxyalkylating primary fatty amines or fatty alkylalkylenediamines, such as, for example, tallow fat propylene diamine. An overview of methods for the preparation of this well-known class of compounds is given in Schönfeldt, "Surface Active Ethylene Oxide Adducts", Wissenschaftliche Verlagsgesellschaft, Stuttgart, 1976, pages 70 to 73. The esterification of these compounds is carried out according to known methods with a fatty acid in higher-boiling inert solvents such as Toluene or xylene or preferably without solvent in the melt and covered with a protective gas. When esterifying in a solvent, the reflux temperature of the reaction mixture is expediently chosen as the reaction temperature and the water of reaction formed is removed azeotropically. In the case of esterification in bulk, the water of reaction is distilled off directly from the reaction mixture. The reaction temperatures here are 140 to 220 ° C, preferably 150 to 180 ° C. To accelerate the reaction, an acid catalyst, such as p-toluenesulfonic acid or hypophosphorous acid, is advantageously used. The completeness of the reaction is checked by determining the acid number. The molar ratio of fatty acid to compounds of formula II is constant 1, so that practically exclusively the monoester results.

Zur Salzbildung wird der entsprechende Aminoxalkylat-Fettsäureester mit einer äquivalenten Menge (entsprechend der Zahl der N-Atome) einer derjenigen Carbonsäuren umgesetzt, die den oben definierten Anionen A zugrundeliegen. Neben den oben bereits als bevorzugt genannten, das Anion bildenden Carbonsäuren seien noch genannt : Capron-, Laurin-, Myristin-, Palmitin-, Stearinsäure, Glykolsäure, Oxal-, Bernstein-, Adipin-, Sebacin-sowie Äpfelsäure.To form the salt, the corresponding aminoxalkylate fatty acid ester is reacted with an equivalent amount (corresponding to the number of N atoms) of one of those carboxylic acids on which the anions A defined above are based. In addition to the carboxylic acids forming the anion, which have already been mentioned as preferred above, the following may also be mentioned: capric, lauric, myristic, palmitic, stearic acid, glycolic acid, oxalic, succinic, adipic, sebacic and malic acid.

Wird im Falle eines sich von einer Di- oder Tricarbonsäure ableitenden Anions das Mono- bzw. Dihydrogenanion gewünscht, so ist die äquivalente Menge entsprechend zu bemessen.If the mono- or dihydrogen anion is desired in the case of an anion derived from a di- or tricarboxylic acid, the equivalent amount is to be measured accordingly.

Gegebenenfalls wird die Reaktion in einem niederen Alkanol, wie Ethanol oder Isopropanol oder auch in Wasser durchgeführt. Die Quaternisierungsreaktion wird mit Ethylen- oder Propylenoxid oder deren Gemischen zweckmäßig bei einer Temperatur von 80 bis 95 °C in einem geeigneten Rührautoklaven vorgenommen, wobei der Reaktionsdruck im allgemeinen bis zu 3 bar beträgt. Vorzugsweise wird Ethylenoxid eingesetzt. Typische Reaktionszeiten liegen im Bereich von 5 bis 10 Stunden, wobei Quaternisierungsgrade bis zu 85 % erzielt werden. Die Quaternisierungsgrade werden durch Zweiphasentitration des quaternären Produktes der Formel mit Natriumdodecylsulfat bei pH 1 bis 2 beziehungsweise pH 10 ermittelt.The reaction is optionally carried out in a lower alkanol, such as ethanol or isopropanol, or in water. The quaternization reaction is advantageously carried out with ethylene oxide or propylene oxide or mixtures thereof at a temperature of 80 to 95 ° C. in a suitable stirred autoclave, the reaction pressure generally being up to 3 bar. Ethylene oxide is preferably used. Typical reaction times are in the range of 5 to 10 hours, with degrees of quaternization of up to 85% being achieved. The degrees of quaternization are determined by two-phase titration of the quaternary product of the formula with sodium dodecyl sulfate at pH 1 to 2 or pH 10.

Besonders bevorzugte Amine, die zu Ausgangsverbindungen der Formeln Ila und Ilb oxalkyliert werden können, sind die technisch verfügbaren Produkte Stearyl- Arachidyl-/Behenylamin sowie Stearyl-, Arachidyl-/Behenyl-propylendiamin. Es ist aber gemäß der Erfindung ebensogut möglich, andere Mono-oder Diamine mit mehr oder weniger breiter Alkylkettenverteilung, wie sie sich aus der oben erläuterten Definition oder der bevorzugten Definition von R' ergeben, zu verwenden. Die Diamine werden in bekannter Weise durch Anlagerung von Acrylnitril an primäre Fettamine und anschließende katalytische Hydrierung der Propionitrile hergestellt.Particularly preferred amines which can be alkoxylated to give starting compounds of the formulas Ila and Ilb are the industrially available products stearyl arachidyl / behenyl amine and stearyl, arachidyl / behenyl propylene diamine. However, it is equally possible according to the invention to use other mono- or diamines with a more or less broad alkyl chain distribution, such as result from the definition explained above or the preferred definition of R '. The diamines are prepared in a known manner by adding acrylonitrile to primary fatty amines and then catalytically hydrogenating the propionitriles.

Zur Veresterung geeignete Fettsäuren sind Produkte auf natürlicher oder synthetischer Basis, wobei diese einzelne chemische Individuen sein können ; häufig werden aber Gemische mit entsprechender Kettenverteilung verwendet. Solche Fettsäuren oder Fettsäuregemische sind beispielsweise Talgfettsäure, Palmölfettsäure, Sojaölfettsäure, Sonnenblumenölfettsäure, Rübölfettsäure (gehärtet oder nicht gehärtet), Stearinsäure, Erucasäure, Behensäure, Ölsäure, Ricinolsäure, oder verzweigtkettige Verbindungen aus der Oxo-Synthese, wie zum Beispiel Isostearinsäure.Fatty acids suitable for esterification are products on a natural or synthetic basis, which can be individual chemical individuals; however, mixtures with appropriate chain distribution are often used. Such fatty acids or fatty acid mixtures are, for example, tallow fatty acid, palm oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, rapeseed oil fatty acid (hardened or not hardened), stearic acid, erucic acid, behenic acid, oleic acid, ricinoleic acid, or branched-chain compounds from oxo synthesis, such as, for example, isostearic acid.

Die erfindungsgemäßen Gemische aus den veresterten, oxalkylierten quaternären Ammoniumverbindungen der Formel und den entsprechenden Aminsalzen sind gut thermostabile, hochgradig weichmachende und antistatisch wirksame, flotten- und substanzstabile Präparationsmittel für native und synthetische Fasern, die, in flüssigem bis weichpastösem Aggregatzustand vorliegend, in Wasser dispergierbar und mit diesem bis zu hohen Wirkstoffgehalten problemlos mischbar sind. Sie können sowohl für die Filament (« Endlos »)-Präparation als auch für die Präparation von Stapelfasern und speziell von Reißkabeln dienen. Diese erfindungsgemäßen Gemische rufen keinerlei Korrosion auf den fadenführenden Organen der Textilmaschinen hervor. Sie bewirken ein ideales Reibungsverhalten der so präparierten Fasern und verleihen diesen einen weichen, voluminösen, angenehmen Griff. Die zu präparierenden Fasern und Fäden sind vor allem solche aus Baumwolle, Wolle, Viskose, Polyacrylnitril, Polyester, Polyamid-6 und -6,6 sowie aus Polyolefinen.The mixtures according to the invention of the esterified, oxyalkylated quaternary ammonium compounds of the formula and the corresponding amine salts are highly thermostable, highly plasticizing and antistatically effective, liquor and substance-stable preparation agents for native and synthetic fibers which, in liquid to soft-pasty state, are dispersible in water and are easily miscible with this high active ingredient content. They can be used for filament («endless») preparation as well as for the preparation of staple fibers and especially tear cables. These mixtures according to the invention do not cause any corrosion on the thread-carrying organs of the textile machines. They create an ideal friction behavior of the fibers thus prepared and give them a soft, voluminous, pleasant grip. The fibers and threads to be prepared are primarily those made from cotton, wool, viscose, polyacrylonitrile, polyester, polyamide-6 and -6.6 and from polyolefins.

Durch die strukturellen Variationsmöglichkeiten, wie sie sich aus den Definitionen der Reste der Formel 1 ergeben, ist es möglich, Verbindungen von flüssiger bis weichpastöser Konsistenz zu gewinnen. Beide Formen sind gut handhabbar, da sie in Wasser von Raumtemperatur ausgezeichnet dispergierbar sind. Bei bisher üblichen Einstellungen von quaternären Ammoniumverbindungen, die für die Faserpräparation geeignet sind, konnten lediglich Konzentrationen von bis zu 50 Gew.-% Wirkstoffgehalt erreicht werden, während die erfindungsgemäßen Gemische flüssige Einstellungen mit 50 bis zu 85 Gew.-% Wirkstoffgehalt erlauben und ein Teil dieser Verbindungen von der Herstellung her flüssig mit bis 85 % Wirkstoffgehalt anfällt.The structural variation possibilities, as they result from the definitions of the residues of formula 1, make it possible to obtain compounds with a liquid to soft-pasty consistency. Both forms are easy to handle because they are excellently dispersible in water at room temperature. With hitherto customary settings of quaternary ammonium compounds which are suitable for fiber preparation, it was only possible to achieve concentrations of up to 50% by weight of active ingredient, while the mixtures according to the invention allow liquid adjustments with 50 to 85% by weight of active ingredient and some these compounds are produced in liquid form with an active substance content of up to 85%.

Die erfindungsgemäßen Gemische enthalten keine anorganischen Salze. Sie wirken auf die Faser auch unter thermischer Belastung nicht vergilbend. Sie werden im allgemeinen in Mengen von 0,2 bis 4, vorzugsweise 0,5 bis 2 Gew: %, bezogen auf Faser- oder Fadengewicht, eingesetzt.The mixtures according to the invention do not contain any inorganic salts. They do not have a yellowing effect on the fiber even under thermal stress. They are generally used in amounts of 0.2 to 4, preferably 0.5 to 2% by weight, based on the weight of the fiber or thread.

Bei der Präparation von Polyacrylnitril-Fasern verleihen sie der Faser Weichheit, Antistatik und Glätte, setzen die statische Faser-Faser-Haftreibund herab, wobei die dynamische Faden-Metall-Gleitreibung so geregelt und das Auflösungsvermögen des Acrylnitril-Faserverbandes so erhöht wird, daß ein störungsfreies Reißen auf der Reißmaschine resultiert und beim anschließenden Verspinnen zu einwandfreien Laufeigenschaften führt. Die erfindungsgemäßen Gemische können auch auf die gefärbten Fasern, speziell solche aus Polyacrylnitril, nach dem Färben im letzten Spülbad appliziert oder bereits im Färbebad zugesetzt werden. Dabei ist es von vorteil, daß diese erfindungsgemäßen Verbindungen auch in sauren Färbebädern bis herunter zu pH 4 und in alkalischen Färbebädern bis hinauf zu pH 9 haltbar sind und ihre weichmachende Wirkung voll entfalten. Der Einsatz eines zusätzlichen Antistatikums kann hierbei entfallen, da die erfindungsgemäßen Verbindungen der Formel auch in solchen Bädern ausreichend antistatisch wirken.When preparing polyacrylonitrile fibers, they give the fiber softness, antistatic properties and smoothness, reduce the static fiber-fiber static friction, whereby the dynamic thread-metal sliding friction is regulated and the resolving power of the acrylonitrile fiber structure is increased so that a This results in trouble-free tearing on the tearing machine and leads to perfect running properties during the subsequent spinning. The mixtures according to the invention can also be applied to the dyed fibers, especially those made from polyacrylonitrile, after dyeing in the last rinsing bath or added already in the dyebath. It is advantageous that these compounds according to the invention can also be stored down to pH 4 in acid dye baths and up to pH 9 in alkaline dye baths and fully develop their softening effect. The use of an additional antistatic can be dispensed with here, since the compounds of the formula according to the invention also have a sufficiently antistatic effect in such baths.

Schließlich können die erfindungsgemäßen Gemische auch als Endavivage vor der Kräuselkammer auf die Faser aufgebracht werden, um der geschnittenen Flocke ein gutes Auflösevermögen beziehungsweise eine gute Öffnungswilligkeit zu verschaffen, was speziell bei Acryl-Woll-Typen für die Teppichfabrikation von Bedeutung ist. Hier beträgt die Präparationsauflage 0,05 bis 1,5, vorzugsweise 0,15 bis 0,5 Gew:-%, bezogen auf das Fasergewicht.Finally, the mixtures according to the invention can also be applied to the fiber as a finishing agent in front of the crimping chamber, in order to provide the cut flake with good dissolving power or good willingness to open, which is particularly important in the case of acrylic wool types for carpet manufacture. Here the preparation pad is 0.05 to 1.5, preferably 0.15 to 0.5% by weight, based on the fiber weight.

Außer den erfindungsgemäßen Gemische können solche Präparations- und Avivagemittel noch übliche Zusätze, wie nicht-ionische oder andere kationische Mittel, Mineral- oder Esteröle, Emulgatoren, wie zum Beispiel Fettalkohol-Oxalkylate, enthalten.In addition to the mixtures according to the invention, such preparation and finishing agents can also contain customary additives, such as nonionic or other cationic agents, mineral or ester oils, emulsifiers, such as, for example, fatty alcohol oxalkylates.

Folgende Beispiele sollen die Erfindung verdeutlichen :The following examples are intended to illustrate the invention:

Beispiel 1example 1 a) Herstellung von N―C16/C18-alkyl-N,N-di(2-hydroxyethyl)-amino-mono-stearinsäureestera) Preparation of N ― C 16 / C 18 alkyl-N, N-di (2-hydroxyethyl) amino monostearic acid ester

In einem 2-1-Rührkolben, versehen mit Wasserabscheider, Gaseinleitung und Heizung, werden 454 g (1,3 mol) N―C16/C16-alkyl-N,N-di(2-hydroxyethyl)-amin, 351 g (1,3 mol) Stearinsäure und 2 g 50 %ige hypophosphorige Säure vorgelegt, unter Schutzgasatmosphäre auf 160 °C gebracht und unter kontinuierlicher Wasserabscheidung die Veresterungsreaktion bei dieser Temperatur fortgesetzt. Nach 6 stündiger Reaktionszeit zeigt die Restsäurezahl von 1,4 an, daß die Veresterung abgeschlossen ist und das Produkt in die Quaternisierungsstufe eingesetzt werden kann.454 g (1.3 mol) of N ― C 16 / C 16 -alkyl-N, N-di (2-hydroxyethyl) amine, 351 g are placed in a 2-1 stirred flask equipped with a water separator, gas inlet and heating (1.3 mol) of stearic acid and 2 g of 50% hypophosphorous acid are introduced, brought to 160 ° C. under a protective gas atmosphere and the esterification reaction is continued at this temperature with continuous water separation. After a reaction time of 6 hours, the residual acid number of 1.4 indicates that the esterification is complete and the product can be used in the quaternization stage.

b) Quaternisierung von N―C16/C18-alkyl-N,N-di(2-hydroxyethyl)-amino-mono-stearinsäureester mit Carbonsäure und Alkylenoxidb) Quaternization of N ― C 16 / C 18 -alkyl-N, N-di (2-hydroxyethyl) amino-monostearic acid ester with carboxylic acid and alkylene oxide

360 g (0,6 mol) gemäß a) hergestellter Mono-stearinsäureester wird in Gegenwart von 43 g (2,4 mol) Wasser und 60 g Isopropanol mit 75 g (0,6 mol) Milchsäure neutralisiert und mit 132 g (3,0 mol) Ethylenoxid quaternisiert. Die Reaktion ist bei einer Temperatur von 85 °C und einem maximalen Druck von 3 bar in 6 Stunden beendet. Der Quaternisierungsgrad des Produktes wird aus dem Verhältnis der sauren beziehungsweise alkalischen Zweiphasentitration mit Natriumlaurylsulfat ermittelt und beträgt 80%.360 g (0.6 mol) of monostearic acid ester prepared according to a) is neutralized in the presence of 43 g (2.4 mol) of water and 60 g of isopropanol with 75 g (0.6 mol) of lactic acid and with 132 g (3, 0 mol) quaternized ethylene oxide. The reaction is complete in 6 hours at a temperature of 85 ° C and a maximum pressure of 3 bar. The degree of quaternization of the product is determined from the ratio of the acidic or alkaline two-phase titration with sodium lauryl sulfate and is 80%.

Unter den in Beispiel 1 beschriebenen Reaktionsbedingungen werden die in der folgenden Tabelle I genannten Verbindungen der Formel I mit den aufgeführten Quaternisierungsgraden im Gemisch mit den entsprechenden Ausgangs-Aminsalzen erhalten :
(Siehe Tabelle 1 Seite 6 ff.)

Figure imgb0006
Figure imgb0007
 Under the reaction conditions described in Example 1, the compounds of the formula I mentioned in Table I below with the degrees of quaternization listed are obtained in a mixture with the corresponding starting amine salts:
(See table 1 on page 6 ff.)
Figure imgb0006
Figure imgb0007

Einige der erfindungsgemäßen Verbindungen der Formel nämlich die Substanzen aus den Beispielen 1, und 13, werden in den folgenden Vergleichsversuchen kationischen Faserpräparationsmitteln des Standes der Technik gegenübergestellt, nämlich

  • a = [C20/C22-Alkyl-(CH2CH2O)2]N+(CH3)2 CH3SO4 - (beschrieben in DE-OS 28 43 659)
  • b = Talgfett-propylendiamin, quaternisiert mit Dimethylsulfat, 40 %ig in Wasser (beschrieben in DE-OS 23 35 675).
Some of the compounds of the formula according to the invention, namely the substances from Examples 1 and 13, are compared in the following comparative experiments with cationic fiber preparation agents of the prior art, namely
  • a = [C 20 / C 22 alkyl- (CH 2 CH 2 O) 2 ] N + (CH 3 ) 2 CH 3 SO 4 - (described in DE-OS 28 43 659)
  • b = tallow fat propylene diamine, quaternized with dimethyl sulfate, 40% in water (described in DE-OS 23 35 675).

Folgende Abkürzungen werden verwendet:

  • PA6 = Polyamid 6
  • PAC = Polyacrylnitril
  • ZW = Zellwolle
  • PES = Polyester (Polyethylentherephthalat).
The following abbreviations are used:
  • PA 6 = polyamide 6
  • PAC = polyacrylonitrile
  • ZW = cellulose
  • PES = polyester (polyethylene terephthalate).

Vergleichsbeispiel AComparative Example A

PAs-Flocke vom Titer 1,2 dtex/40 mm, PAC-Flocke, naßgesponnen 3 dtex/60 mm, Zellwoll-Flocke 1,4 dtex/40 mm sowie PA6-Flocke 6 dtex/100 mm, gefärbt, werden mit wäßrigen Lösungen folgender Produkte behandelt, wobei ein Präparationsauftrag von 0,2 % Wirksubstanz, bezogen auf das Fasergewicht, eingestellt wird. Nach dem Trocknen und Ausklimatisieren wird eine Griffbeurteilung der textilweichmachenden Wirkung vorgenommen, wobei Noten zwischen 1 = sehr hart, stumpf knirschend und 6 = sehr weich, sehr glatt, vergeben werden und bei den unbehandelten Standard-Flocken der Weichheitsgrad mit Note 1 festgelegt wird.PA s flake with a titer of 1.2 dtex / 40 mm, PAC flake, wet-spun 3 dtex / 60 mm, cellulose flake 1.4 dtex / 40 mm and PA 6 flake 6 dtex / 100 mm, are dyed with treated aqueous solutions of the following products, a preparation order of 0.2% active substance, based on the fiber weight, is set. After drying and conditioning, a grip assessment of the fabric softening effect is carried out, with grades between 1 = very hard, blunt grating and 6 = very soft, very smooth, and the degree of softness for the untreated standard flakes is given a grade of 1.

Es wird folgende Bewertung gefunden :

Figure imgb0008
The following evaluation is found:
Figure imgb0008

Vergleichsbeispiel BComparative Example B

PA6-Filament, dtex 220f40, sowie experimentell gesponnenes PAC-Filament, dtex 300f100 werden mit wäßrigen Lösungen folgender Produkte im Tauchwalzenverfahren über Galette behandelt, wobei eine Präparationsauflage von 0.7% Wirksubstanz, bezogen auf das Fasergewicht, eingestellt wird. Die präparierten Fäden werden analog DE-OS 23 35 675 auf ihre dynamische Reibung und analog DE-PS 2518124 auf ihre statische Reibung (als Maß für die Bandhaftung und das Auflösungsvermögen) gemessen.

Figure imgb0009
PA 6 filament, dtex 220f40, as well as experimentally spun PAC filament, dtex 300f100, are treated with aqueous solutions of the following products in the immersion roller process by means of godets, a preparation layer of 0.7% active substance, based on the fiber weight, being set. The prepared threads are measured analogously to DE-OS 23 35 675 for their dynamic friction and analogously to DE-PS 2518124 for their static friction (as a measure of the tape adhesion and the resolving power).
Figure imgb0009

Vergleichsbeispiel CComparative Example C

PA6-Flocke, 1,2 dtex/40 mm, PAC-Flocke, 3 dtex/60 mm und PES-Flocke, 1,4 dtex/40 mm, werden gemäß Vergleichsbeispiel A mit wäßrigen Lösungen folgender Produkte behandelt (Auflage 0,2 %). An den getrockneten und klimatisierten Fasern werden folgende Leitfähigkeitswerte mit einem Textometer der Firma Mahlo GmbH, Saal/Donau, gemessen in Skalenteilen, ermittelt (hohe Werte zeigen hohe antistatische Wirkung an) :

Figure imgb0010
PA 6 flake, 1.2 dtex / 40 mm, PAC flake, 3 dtex / 60 mm and PES flake, 1.4 dtex / 40 mm, are treated according to Comparative Example A with aqueous solutions of the following products (edition 0.2 %). At The following conductivity values are determined for the dried and air-conditioned fibers using a textometer from Mahlo GmbH, Saal / Donau, measured in divisions (high values indicate high antistatic effect):
Figure imgb0010

Vergleichsbeispiel DComparative Example D

Ein PAC-Reißkabel, gefärbt, Gesamttiter 800 000 dtex, wird mit einer wäßrigen Lösung folgender Produkte behandelt, wobei der Präparationsauftrag auf einer Lisseux durch Foulardieren erfolgt und auf 0,5% wirksame Substanz eingestellt wird. Die Kabel werden nach dem Trocknen auf einer Seydel-Reißmaschine gerissen, wonach folgende Reißeffekte beobachtet werden : Das mit dem pastösen Vergleichsprodukt b) ausgerüstete Kabel zeigt zwar ein gutes Laufverhalten, das aus den gerissenen Fasern erstellte Stapeldiagramm ist jedoch aufgrund von Kolonnenrissen und vorhandenen Langfasern ungleichmäßig. Vereinzelt" sind auch Noppen und Nissen an den Fasern feststellbar. Dagegen zeigt das mit dem erfindungsgemäßen flüssigen Präparationsmittel des Beispiels 13 ausgerüstete Kabel keinerlei Noppen. Das Stapeldiagramm ist gleichmäßig. Es gibt keine Kolonnenrisse. Die Fasern sind hochbauschig und lösen sich gut voneinander.A PAC tear cable, colored, total titer 800,000 dtex, is treated with an aqueous solution of the following products, the preparation being applied on a Lisseux by padding and adjusted to 0.5% active substance. After drying, the cables are torn on a Seydel tearing machine, after which the following tearing effects are observed: The cable equipped with the pasty comparison product b) does show good running behavior, but the stack diagram created from the torn fibers is uneven due to column tears and long fibers present . In some cases, pimples and nits can also be found on the fibers. In contrast, the cable equipped with the liquid preparation of Example 13 according to the invention shows no pimples. The stack diagram is uniform. There are no column cracks. The fibers are bulky and separate well from one another.

Claims (7)

1. Mixtures consisting of 57 to 85 mol-% of esterified alkoxylated quaternary ammonium compounds of the formula
Figure imgb0014
and of 43 to 15 mol-% of salts of amines of the formula
Figure imgb0015
in which
R' denotes an alkyl radical or an alkenyl radical of 8 to 23 carbon atoms,
R2 denotes H or CH3, and can also assume both meanings within the total molecule,
R3 denotes an alkyl. radical or the alkyl radical of a natural fatty acid of 8 to 45 carbon atoms whereby the latter radical may also contain 1 to 3 multiple bonds and 1 to 3 OH groups,
A― denotes the anion of an alkanoic acid or a monohydroxyalkanoic acid having an alkyl radical of 1 to 23 carbon atoms, the anion of a dicarboxylic acid of 0 to 8 methylene groups which may carry 1 to 2 OH substituents, the anion of fumaric, maleic or citric acid, the anion of benzoic acid or of a hydroxyl- or methyl-substituted benzoic acid where the basicity x of these carboxylic acids can accordingly take the values 1, 2 or 3,
a, b and c are each an integer or non-integer from 1 to 3,
d and e are each an integer or non-integer from 1 to 3,
m is 2 or 3 and
n is 0 or 1.
2. Mixtures consisting of esterified alkoxylated quaternary ammonium compounds and salts of amines as claimed in claim 1, wherein R' is an alkyl radical or alkenyl radical of 12 to 23 carbon atoms.
3. Mixtures consisting of esterified alkoxylated quaternary ammonium compounds and salts of amines as claimed in claims 1 and 2, wherein R2 is hydrogen.
4. Mixtures consisting of esterified alkoxylated quaternary ammonium compounds and salts of amines as claimed in claims 1 to 3, wherein m = 3.
5. Mixtures consisting of esterified alkoxylated quaternary ammonium compounds and salts of amines as claimed in claims 1 to 4, wherein A- is the anion of an alkanemonocarboxylic acid or of a monohydroxyalkanemonocarboxylic acid of 1 to 6 carbon atoms, the anion of a dicarboxylic acid of 0 to 4 methylene groups which may carry 1 or 2 OH substituents, or the anion of fumaric, maleic, citric, benzoic or salicylic acid.
6. A process for preparing mixtures consisting of esterified alkoxylated quaternary ammonium compounds and salts of amines as claimed in claim 1, which comprises esterifying an alkoxylated amine of the formula
Figure imgb0016
in which R1, R2, a, b, c, m and n are as defined in the formula I, with a carboxylic acid R3COOH in which R3 is as defined in the formula I, reacting the ester with a carboxylic acid which forms the A- anion defined in the formula I, to form a salt. and quaternising with at least one alkylene oxide from the group consisting of ethylene oxide and propylene oxide.
7. The use of the mixtures consisting of esterified alkoxylated quaternary ammonium compounds and salts of amines as claimed in one or more of the claims 1 to 5 as treating agents for fibres.
EP84107892A 1983-07-13 1984-07-06 Esterified oxyalkylated quaternary ammonium compounds, process for their preparation and their use as treating agents for fibres Expired EP0131865B1 (en)

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DE69121887T2 (en) * 1991-07-29 1997-04-03 Kao Corp Process for the preparation of quaternary compounds
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FR2688419B1 (en) * 1992-03-12 1994-07-08 Stepan Europe SURFACTANT BASE COMPRISING A CATIONIC QUATERNARY AMMONIUM COMPOUND AND A COMPOUND AS A SOLVENT AND SOFTENING COMPOSITION COMPRISING SUCH A BASE.
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DE4243547C2 (en) * 1992-12-22 1994-10-20 Henkel Kgaa Quaternized fatty acid triethanolamine ester salts
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