WO1993021291A1 - Low-viscosity aqueous textile-treatment agents - Google Patents

Low-viscosity aqueous textile-treatment agents Download PDF

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Publication number
WO1993021291A1
WO1993021291A1 PCT/EP1993/000794 EP9300794W WO9321291A1 WO 1993021291 A1 WO1993021291 A1 WO 1993021291A1 EP 9300794 W EP9300794 W EP 9300794W WO 9321291 A1 WO9321291 A1 WO 9321291A1
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WO
WIPO (PCT)
Prior art keywords
fatty
quaternary ammonium
ammonium compounds
treatment agent
agent according
Prior art date
Application number
PCT/EP1993/000794
Other languages
German (de)
French (fr)
Inventor
Martina Kihn-Botulinski
Theodor Völkel
Rolf Puchta
Peter Sandkühler
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO1993021291A1 publication Critical patent/WO1993021291A1/en

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Classifications

    • 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
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/50—Modified hand or grip properties; Softening compositions

Definitions

  • Quaternary ammonium compounds which due to their cationic character easily and completely absorb onto the negatively charged fiber surface, are particularly popular active ingredients. Because of their easy biodegradability, quaternary ammonium compounds which contain fatty acyloxyalkyl radicals bound to nitrogen have recently attracted interest. Such compounds have also been known for a long time, for example from DE-A-16 19 058, DE-A-19 35 499 or US Pat. No. 3,915,867. These compounds can easily be obtained, for example, by esterification of alkanolamines with fatty acid or by transesterification of fatty acid esters with alkanolamine and subsequent quaternization. Corresponding processes for manufacturing on an industrial scale have also been known for a long time.
  • the object of the present invention is therefore to provide an aqueous textile softener concentrate with low viscosity which contains the quaternary ammonium compounds which are interesting because of their easy biodegradability and which contain 1, * 2 or 3 fatty acyloxyalkyl radicals bound to the nitrogen atom, and also their viscosity does not increase or increases only slightly after long storage.
  • the proportion of fatty acyl groups which are wholly or partly derived from unsaturated fatty acids present in cis form have an influence on the viscosity and the storage behavior.
  • the invention therefore relates to aqueous fabric softener concentrates with low viscosity, containing quaternary ammonium compounds which contain 1, 2 or 3 fatty acyloxyalkyl radicals bound to the nitrogen atom and which are characterized in that the fatty acyl groups are derived in whole or in part from unsaturated fatty acids which lead to at least 30% are in cis form.
  • low viscosity means a viscosity of at most 1000 mPas.
  • a high proportion of fatty acyl groups in cis form has an extremely favorable effect on the viscosity during the production and storage of textile softener concentrates according to the invention.
  • Textile plasticizer concentrates for the purposes of the present patent application are to be understood as meaning aqueous preparations which contain quaternary ammonium compounds with 1, 2 or 3 fatty acyloxyethyl radicals in a concentration of 4 to 55% by weight, based on the total amount of the concentrate; such fabric softener concentrates are therefore preferred.
  • the textile softeners described above can in principle contain quaternary ammonium compounds as the active ingredient which contain either 1 or 2 or 3 fatty acyloxyalkyl radicals. Since such compounds can only be prepared on an industrial scale in a complex manner, textile-plasticizer concentrates are preferred which contain quaternary ammonium compounds in the form of a mixture of compounds having 1, 2 or 3 fatty acyloxyalkyl radicals, in particular having 1, 2 and 3 fatty acyloxyethyl radicals.
  • Preferred textile softener concentrates are those which contain such compounds in the mixture of the quaternary ammonium compounds, in which the proportion with 2 fatty acyloxyalkyl radicals is greater than the proportion of quaternary ammonium compounds with 1 or 3 fatty acyloxyethyl radicals.
  • the fabric softener concentrates according to the invention additionally contain auxiliaries customary in aqueous fabric softener concentrates, such as, for example, dispersants, preservatives, inorganic or organic acids, buffer substances, electrolytes, viscosity regulators, dyes, fragrances or solvents.
  • auxiliaries customary in aqueous fabric softener concentrates, such as, for example, dispersants, preservatives, inorganic or organic acids, buffer substances, electrolytes, viscosity regulators, dyes, fragrances or solvents.
  • the auxiliaries mentioned can optionally additionally be present in aqueous textile softener concentrates according to the invention.
  • the fabric softener concentrates according to the invention contain, in addition to quaternary ammonium compounds with 1, 2 or 3 fatty acyloxyethyl radicals, additionally one or more other softening active ingredients of other classes of compounds.
  • Examples include sorbitan esters, swellable layered silicates, fatty acid combination products with polyamines, quaternary ammonium compounds with fatty alkyl or alkenyl radicals, alkyl polyglycosides or fatty acids.
  • the textile softener concentrates according to the invention are expediently brought to a pH in the range from 2.5 to 7, preferably in the range from 2.5 to 5, measured at 20 ° C. after dilution with distilled water to a concentration between 0. 5 and 5 wt .-% quaternary ammonium compounds with 1, 2 or 3 fatty acyloxyethyl radicals.
  • fabric softener concentrates which have a pH in the range from 2.5 to 4.5, measured at a concentration between 0.5 and 2.0% by weight of quaternary ammonium compounds with 1 Have 2 or 3 fatty acyloxyethyl residues. Such fabric softener concentrates are therefore particularly preferred.
  • a cis / trans ratio of 30:70 at all storage temperatures with and without shear stress leads to an undesirable increase in viscosity after only a few days, whereas with a cis / trans ratio of 70:30 no irrelevant regardless of the shear stress Viscosity increases even after 12 weeks of storage.
  • This effect caused by a cis / trans ratio of over 50:50 could not be achieved by adding organic solvents (glycerol, dipropylene glycol), magnesium chloride or ammonium chloride.

Abstract

Described are textile-treatment agents containing as a softener quaternary ammonium compounds with 1, 2 or 3 acyloxyalkyl groups (in which the acyl group is derived from a fatty acid) bound to the nitrogen atom. Such compounds have a low viscosity if all or some of the acyl groups are derived from unsaturated fatty acids with at least 30 % in the cis form.

Description

"Wäßrige Textil-Behandlunos ittel mit geringer Viskosität" "Aqueous textile treatments with low viscosity"
Die vorliegende Patentanmeldung betrifft wäßrige Textilweichmacher-Kon- zentrate, die trotz hoher Konzentration an quartären Ammoniumverbindungen, die 1, 2 oder 3 Fettacyloxyalkylreste am Stickstoff gebunden enthalten, eine niedrige Viskosität haben, die sich auch bei längerer Lagerung nicht oder nur unwesentlich erhöht.The present patent application relates to aqueous fabric softener concentrates which, despite the high concentration of quaternary ammonium compounds which contain 1, 2 or 3 fatty acyloxyalkyl radicals bound to the nitrogen, have a low viscosity which does not increase or increases only insignificantly even after prolonged storage.
Mittel zum Behandeln von Textilien, die den damit behandelten Textilien eine erwünschte Weichheit verleihen, sind seit langem bekannt. Quartäre Ammoniumverbindungen, die wegen ihres kationischen Charakters leicht und vollständig auf die negativ geladene Faseroberfläche aufziehen, sind dabei besonders gern eingesetzte Wirkstoffe. Wegen ihrer leichten biologischen Abbaubarkeit haben in letzter Zeit vor allem solche quartäre Ammoniumver¬ bindungen an Interesse gewonnen, die Fettacyloxyalkylreste am Stickstoff gebunden enthalten. Derartige Verbindungen sind ebenfalls seit langem be¬ kannt, beispielsweise aus der DE-A-16 19 058, der DE-A-19 35 499 oder der US 3, 915, 867. Man kann diese Verbindungen beispielsweise leicht durch Veresterung von Alkanolaminen mit Fettsäure oder durch Umesterung von Fettsäureestern mit Alkanolamin und anschl eßender Quaternierung herstel¬ len. Entsprechende Verfahren zur Herstellung im großtechnischen Maßstab sind ebenfalls seit langem bekannt.Agents for treating textiles which impart a desired softness to the textiles treated with them have long been known. Quaternary ammonium compounds, which due to their cationic character easily and completely absorb onto the negatively charged fiber surface, are particularly popular active ingredients. Because of their easy biodegradability, quaternary ammonium compounds which contain fatty acyloxyalkyl radicals bound to nitrogen have recently attracted interest. Such compounds have also been known for a long time, for example from DE-A-16 19 058, DE-A-19 35 499 or US Pat. No. 3,915,867. These compounds can easily be obtained, for example, by esterification of alkanolamines with fatty acid or by transesterification of fatty acid esters with alkanolamine and subsequent quaternization. Corresponding processes for manufacturing on an industrial scale have also been known for a long time.
Die Behandlung von Textilien mit den genannten quartären Ammoniumverbin¬ dungen mit Fettacyloxyalkylresten erfolgt in wäßrigen Behandlungsflotten, die pro Liter etwa ein oder wenige Gramm an quartären Ammoniumverbindun¬ gen, gegebenenfalls in Kombination mit anderen weichmachenden Wirkstoffen sowie Hilfs- und Zusatzstoffen enthalten. Bei der Herstellung und der Konfektionierung strebt man gießfähige und leicht mit Wasser verdünnbare Zubereitungen an, die eine wesentlich höhere Konzentration an Wirkstoffen enthalten, als es der Anwenαungskonzentration entspricht. So sind bei¬ spielsweise Handelprodukte bekannt, wie etwa 4 Gew.-% an quartären Arnmo- m'umverDindungen des oben beschriebenen Typs enthalten. Das heißtr der Hauptbestandte l derartiger Produkte ist Wasser. Es hat daher nicht an Versuchen gefehlt, Produkte mit einem höherem Wirstoffgehalt herzustellen, die erst unmittelbar vor der Anwendung vom Verbraucher auf die gewünschte Anwendungskonzentration verdünnt werden. Es sind daher auch Handelspro¬ dukte entwickelt worden, die etwa 50 Gew.-% an weichmachenden Wirkstoffen enthalten. Derart hoch konzentrierte Produkte weisen aber auch den Nach¬ teil auf, daß ihre Viskosität sehr hoch ist und beim Lagern oft sogar noch zunimmt, bzw., daß ihre Verdünnbarkeit mit Wasser auf die Anwendungskon¬ zentration oft problematisch ist.The treatment of textiles with the quaternary ammonium compounds mentioned with fatty acyloxyalkyl radicals takes place in aqueous treatment liquors which contain about one or a few grams of quaternary ammonium compounds per liter, optionally in combination with other softening active ingredients and auxiliaries and additives. In manufacturing and packaging, the aim is to have pourable and water-dilutable preparations that have a much higher concentration of active ingredients included than it corresponds to the application concentration. To play as commercial products are bei¬ known, such as 4 wt .-% of quaternary Arnmo- m 'umverDindungen the type described above contain. That is the r l Hauptbestandte such products is water. There has been no shortage of attempts to produce products with a higher active substance content, which are only diluted to the desired application concentration by the consumer immediately before use. Commercial products have therefore also been developed which contain about 50% by weight of softening active ingredients. However, such highly concentrated products also have the disadvantage that their viscosity is very high and often even increases when stored, or that their dilutability with water to the application concentration is often problematic.
Gegenstand der vorliegenden Erfindung ist daher, ein wäßriges Textil- weichmacher-Koπzentrat mit geringer Viskosität bereitzustellen, das die wegen ihrer leichten biologischen Abbaubarkeit interessanten quartären Ammoniumverbindungen, die 1, * 2 oder 3 Fettacyloxyalkylreste am Stick¬ stoffatom gebunden enthalten, enthält und dessen Viskosität auch nach längerer Lagerung nicht oder nur unwesentlich ansteigt. Überraschender¬ weise hat sich dabei herausgestellt, daß der Anteil von Fettacylgruppen, die sich ganz oder teilweise von in cis-Form vorliegenden .ungesättigten Fettsäuren ableiten, einen Einfluß auf das Viskositäts- und das Lage¬ rungsverhalten haben.The object of the present invention is therefore to provide an aqueous textile softener concentrate with low viscosity which contains the quaternary ammonium compounds which are interesting because of their easy biodegradability and which contain 1, * 2 or 3 fatty acyloxyalkyl radicals bound to the nitrogen atom, and also their viscosity does not increase or increases only slightly after long storage. Surprisingly, it has been found that the proportion of fatty acyl groups which are wholly or partly derived from unsaturated fatty acids present in cis form have an influence on the viscosity and the storage behavior.
Die Erfindung betrifft daher wäßrige Textilweichmacher-Konzentrate mit geringer Viskosität, enthaltend quartäre Ammoniumverbindungen, die 1, 2 oder 3 Fettacyloxyalkylreste am Stickkstofatom gebunden enthalten, und die dadurch gekennzeichnet sind, daß die Fettacylgruppen sich ganz oder teil¬ weise von ungesättigten Fettsäuren ableiten, die zu wenigsten 30 % in cis-Form vorliegen. Im Rahmen dieser Patentanmeldung bedeutet "geringe Viskosität" eine Viskosität von höchstens 1000 mPas. Bei der Herstellung von quartären Ammoniumverbindungen mit 1, 2 oder 3 Fettacyloxyalkylresten ist es daher wichtig, solche Fettsäuren, bzw. Fettsäure-Derivate zu ver¬ wenden, die sich ganz oder teilweise von ungesättigten Fettsäuren ablei¬ ten, die zu wenigstens 55 % in cis-Form vorliegen. Damit lassen sich Tex¬ tilweichmacher-Konzentrate herstellen, die auch bei niedrigen Temperaturen lagerstabil sind und darüberhinaus noch eine geringe Empfindlichkeit ge¬ genüber Scherbelastung, zum Beispiel beim Pumpen oder Abfüllen aufweisen. Bevorzugt ist, daß wenigstens 50 %, insbesondere wenigstens 70 % der sich von ungesättigten Fettsäuren ableitenden Fettacylgruppen in cis-Form vor¬ liegen. Ein hoher Anteil an in cis-Form vorliegenden Fettacylgruppen wirkt sich ausgesprochen günstig auf die Viskosität bei der Herstellung und La¬ gerung von erfindungsgemäßen Textilweichmacher-Konzentraten aus. Unter Textilweichmacher-Konzentraten im Sinne der vorliegenden Patentanmeldung sind solche wäßrige Zubereitungen zu verstehen, die quartäre Ammoπiumver- bindungen mit 1, 2 oder 3 Fettacyloxyethylresten in einer Konzentration von 4 bis 55 Gew.-%, bezogen auf die Gesamtmenge des Konzentrats enthal¬ ten; derartige Textilweichmacher-Konzentrate sind daher bevorzugt. In ge¬ wissem Sinne gilt das für quartäre Ammoniumverbindungen mit Fett¬ acyloxyethylresten enthaltende Produkte Gesagte auch für solche Produkte, die quartäre Ammoniumverbindungen mit anderen Fettacyloxyalkylresten als Fettacyloxyethylreste enthalten, beispielsweise für Produkte, die quartäre Ammoniumverbindungen mit Fettacyloxypropylresten und mit Fett- acyloxyisopropylresten enthalten. Wegen ihres hohen Wirkstoffanteils sind Textilweichmacher-Konzentrate mit 15 bis 40 Gew.-% quartären Ammoniumver¬ bindungen mit 1, 2 oder 3 Fettacyloxyethylresten eine bevorzugte Ausfüh¬ rungsform der vorliegenden Erfindung. Bei der Herstellung von Konzentraten geht man zweckmäßigerweise von quartären A moniumverbindungen aus, deren Fettacylreste zu einem großen Anteil ungesättigt sind, beispielsweise Ölsäurereste sind. Neben Wasser setzt man in Konzentraten auch nennens¬ werte Mengen organischer Lösemittel ein.The invention therefore relates to aqueous fabric softener concentrates with low viscosity, containing quaternary ammonium compounds which contain 1, 2 or 3 fatty acyloxyalkyl radicals bound to the nitrogen atom and which are characterized in that the fatty acyl groups are derived in whole or in part from unsaturated fatty acids which lead to at least 30% are in cis form. In the context of this patent application, "low viscosity" means a viscosity of at most 1000 mPas. In the production of quaternary ammonium compounds with 1, 2 or 3 fatty acyloxyalkyl radicals, it is therefore important to use those fatty acids or fatty acid derivatives which are wholly or partly derived from unsaturated fatty acids which are at least 55% in cis Form. This enables textile plasticizer concentrates to be produced, even at low temperatures are stable in storage and moreover have a low sensitivity to shear stress, for example when pumping or filling. It is preferred that at least 50%, in particular at least 70%, of the fatty acyl groups derived from unsaturated fatty acids are in cis form. A high proportion of fatty acyl groups in cis form has an extremely favorable effect on the viscosity during the production and storage of textile softener concentrates according to the invention. Textile plasticizer concentrates for the purposes of the present patent application are to be understood as meaning aqueous preparations which contain quaternary ammonium compounds with 1, 2 or 3 fatty acyloxyethyl radicals in a concentration of 4 to 55% by weight, based on the total amount of the concentrate; such fabric softener concentrates are therefore preferred. In a certain sense, what is said for products containing quaternary ammonium compounds with fatty acyloxyethyl radicals also applies to products which contain quaternary ammonium compounds with fatty acyloxyalkyl radicals other than fatty acyloxyethyl radicals, for example for products which contain quaternary ammonium compounds with fatty acyloxypropyl radicals and with fatty acyloxyisopropyl radicals. Because of their high active ingredient content, fabric softener concentrates with 15 to 40% by weight of quaternary ammonium compounds with 1, 2 or 3 fatty acyloxyethyl radicals are a preferred embodiment of the present invention. In the preparation of concentrates, it is expedient to start from quaternary ammonium compounds, the fatty acyl residues of which are largely unsaturated, for example oleic acid residues. In addition to water, significant amounts of organic solvents are also used in concentrates.
Die zuvor beschriebenen TextilWeichmacher können als Wirkstoff zwar grundsätzlich quartäre Ammoniumverbindungen enthalten, die entweder 1 oder 2 oder 3 Fettacyloxyalkylreste enthalten. Da derartige Verbindungen im industriellem Maßstab aber nur aufwendig herstellbar sind, sind Textil¬ weichmacher-Konzentrate bevorzugt, die quartäre Ammoniumverbindungen in Form eines Gemischs von Verbindungen mit 1, 2 oder 3 Fettacyloxyalkyl¬ resten, insbesondere mit 1, 2 und 3 Fettacyloxyethylresten enthalten. Da¬ bei werden solche Textilweichmacher-Konzentrate bevorzugt, die in dem Ge¬ misch der quartären Ammoniumverbindungen solche Verbindungen enthalten, bei denen der Anteil mit 2 Fettacyloxyalkylresten größer ist als der An¬ teil quartärer Am oniumverbindungen mit 1 oder 3 Fettacyloxyethylresten.The textile softeners described above can in principle contain quaternary ammonium compounds as the active ingredient which contain either 1 or 2 or 3 fatty acyloxyalkyl radicals. Since such compounds can only be prepared on an industrial scale in a complex manner, textile-plasticizer concentrates are preferred which contain quaternary ammonium compounds in the form of a mixture of compounds having 1, 2 or 3 fatty acyloxyalkyl radicals, in particular having 1, 2 and 3 fatty acyloxyethyl radicals. Preferred textile softener concentrates are those which contain such compounds in the mixture of the quaternary ammonium compounds, in which the proportion with 2 fatty acyloxyalkyl radicals is greater than the proportion of quaternary ammonium compounds with 1 or 3 fatty acyloxyethyl radicals.
Die erfindungsgemäßen Textilweichmacher-Konzentrate enthalten zusätzlich in wäßrigen Textilweichmacher-Konzentraten übliche Hilfsstoffe wie bei¬ spielsweise Dispergatoren, Konservierungsmittel, anorganische oder orga¬ nische Säuren, Puffersubstanzen, Elektrolyte,, Viskositätsstellmittel , Farbstoffe, Duftstoffe oder Lösungsmittel. Die genannten Hilfsstoffe kön¬ nen fakultativ zusätzlich in erfindungsgemäßen wäßrigen Textilweichmacher- Konzentraten enthalten sein. In einer weiteren bevorzugten Ausführungsform enthalten die erfindungsgemäßen Textilweichmacher-Konzentrate neben quar¬ tären Ammoniumverbindungen mit 1, 2 oder 3 Fettacyloxyethylresten zusätz¬ lich einen oder mehrere andere weichmachende Wirkstoffe anderer Verbin¬ dungsklassen. Beispiele hierfür sind Sorbitanester, quellfähige Schicht¬ silikate, Fettsäurekoπdeπsationsprodukte mit Polyaminen, quartäre Ammoni¬ umverbindungen mit Fettalkyl- bzw. -alkenylresten, Alkylpolyglykoside oder Fettsäuren.The fabric softener concentrates according to the invention additionally contain auxiliaries customary in aqueous fabric softener concentrates, such as, for example, dispersants, preservatives, inorganic or organic acids, buffer substances, electrolytes, viscosity regulators, dyes, fragrances or solvents. The auxiliaries mentioned can optionally additionally be present in aqueous textile softener concentrates according to the invention. In a further preferred embodiment, the fabric softener concentrates according to the invention contain, in addition to quaternary ammonium compounds with 1, 2 or 3 fatty acyloxyethyl radicals, additionally one or more other softening active ingredients of other classes of compounds. Examples include sorbitan esters, swellable layered silicates, fatty acid combination products with polyamines, quaternary ammonium compounds with fatty alkyl or alkenyl radicals, alkyl polyglycosides or fatty acids.
Zweckmäßigerweise werden die erfindungsgemäßen Textilweichmacher-Konzen¬ trate auf einen pH-Wert im Bereich von 2,5 bis 7, vorzugsweise im Bereich von 2,5 bis 5, gemessen bei 20 °C nach Verdünnen mit desti liertem Wasser auf eine Konzentration zwischen 0,5 und 5 Gew.-% quartärer Ammoniumver¬ bindungen mit 1, 2 oder 3 Fettacyloxyethylresten eingestellt. Von beson¬ derer praktischer Bedeutung sind Textilweichmacher-Konzentrate, die einen pH-Wert im Bereich von 2,5 bis 4,5, gemessen bei einer Konzentration zwi¬ schen 0,5 und 2,0 Gew.-% quartären Ammoniumverbindungen mit 1, 2 oder 3 Fettacyloxyethylresten haben. Derartige Textilweichmacher-Konzentrate sind daher besonders bevorzugt.The textile softener concentrates according to the invention are expediently brought to a pH in the range from 2.5 to 7, preferably in the range from 2.5 to 5, measured at 20 ° C. after dilution with distilled water to a concentration between 0. 5 and 5 wt .-% quaternary ammonium compounds with 1, 2 or 3 fatty acyloxyethyl radicals. Of particular practical importance are fabric softener concentrates which have a pH in the range from 2.5 to 4.5, measured at a concentration between 0.5 and 2.0% by weight of quaternary ammonium compounds with 1 Have 2 or 3 fatty acyloxyethyl residues. Such fabric softener concentrates are therefore particularly preferred.
Wäßrige Textilweichmacher-Konzentrate, die quartäre Ammoniumverbindungen mit 1, 2 oder 3 Fettacyloxyalkylresten am Stickkszoff gebunden enthalten und deren Fettacylgruppen sich ganz oder teilweise von ungesättigten Fett¬ säuren ableiten, die zu wenigstens 55 Gew.- in cis-Form vorliegen und deren wäßrige Verdünnungen die obengenannte pH-Werte haben, lassen sich leicht zu lagerstabilen Produkten konfektionieren, deren Viskosität auch bei Lagerung bei niedrigen Temperaturen nicht oder nur unwesentlich ansteigt und die gegenüber Scherbelastung unempfindlich sind. Die ge¬ nannten Vorteile gehen ganz oder teilweise verloren, wenn zur Herstellung der genannten Produkte quartäre Ammoniumverbindungen verwendet werden, deren Fettacyloxyalkylgruppen sich von Fettsäuren ableiten, deren Anteil an ungesättigten Fettsäuren in cis-Form unter 30 % liegt. Aqueous fabric softener concentrates which contain quaternary ammonium compounds with 1, 2 or 3 fatty acyloxyalkyl radicals attached to the stickks and whose fatty acyl groups are wholly or partly derived from unsaturated fatty acids which are present in cis form at least 55% by weight and whose aqueous dilutions are have the above-mentioned pH values, can be easily assembled into storage-stable products, the viscosity of which, even when stored at low temperatures, is not or only insignificantly increases and are insensitive to shear stress. All or some of the advantages mentioned are lost if quaternary ammonium compounds are used to produce the products mentioned, the fatty acyloxyalkyl groups of which are derived from fatty acids and the proportion of unsaturated fatty acids in cis form is below 30%.
B e i s p i e 1 eExample: 1 e
Beispiele 1 bis 8Examples 1 to 8
Eine quartäre Ammoniumverbindung mit der idealisierten Formel Methyl- hydroxyethyldifettacyloxyethyl-ammonium-methosulfat wurde zur Herstellung eines wäßrigen Weichspülmittel-Konzentrats mit 17,2 Gew.-% quartärer Am¬ moniumverbindung verwendet. Der Fettrest leitete sich von Taigfettsäure mit einem ungesättigten Anteil ab, der in unterschiedlichem cis/trans-Verhältnis vorlag.A quaternary ammonium compound with the idealized formula methylhydroxyethyldifettacyloxyethylammonium methosulfate was used to produce an aqueous fabric softener concentrate with 17.2% by weight quaternary ammonium compound. The fat residue was derived from tallow fatty acid with an unsaturated content that was present in different cis / trans ratios.
Bei mehreren Lagertemperaturen wurden die Konzentrate mit und ohne vor¬ heriger Scherbelastung bis zu 12 Wochen lang gelagert und die Viskosi¬ tätsveränderung gemessen. Die Ergebnisse und die Versuchsbedingungen sind aus den folgenden Abbildungen 1 bis 8 ersichtlich.At several storage temperatures, the concentrates with and without prior shear stress were stored for up to 12 weeks and the change in viscosity was measured. The results and the test conditions are shown in the following Figures 1 to 8.
Wie zu sehen ist, führt ein cis/trans-Verhältnis von 30 : 70 bei allen Lagertemperaturen mit und ohne Scherbelastung zu einem unerwünschten Vis- kositätsaπstieg bereits nach wenigen Tagen, wohingegen bei einem cis/transVerhältnis von 70 : 30 unabhängig von der Scherbelastung kein nenennswerter Viskositätsanstieg auch nach 12-wöchiger Lagerung erfolgt. Dieser durch ein cis/trans-Verhältnis von über 50 : 50 bewirkte Effekt ließ sich weder durch Zusätze von organischen Lösungsmitteln (Glycerin, Dipropyenglykol) noch Magnesiumchlorid oder A moniumchlorid erzielen. As can be seen, a cis / trans ratio of 30:70 at all storage temperatures with and without shear stress leads to an undesirable increase in viscosity after only a few days, whereas with a cis / trans ratio of 70:30 no irrelevant regardless of the shear stress Viscosity increases even after 12 weeks of storage. This effect caused by a cis / trans ratio of over 50:50 could not be achieved by adding organic solvents (glycerol, dipropylene glycol), magnesium chloride or ammonium chloride.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Wäßrige Textil-Behandlungsmittel mit geringer Viskosität enthaltend quartäre Ammoniumverbindungen, die 1, 2 oder 3 Fettacyloxyalkylreste am Stickstoffatom gebunden enthalten, dadurch gekennzeichnet, daß die Fettacylgruppen sich ganz oder teilweise von ungestättigten Fettsäuren ableiten, die zu wenigstens 30 % in cis-Form vorliegen.1. Aqueous textile treatment agent with low viscosity containing quaternary ammonium compounds containing 1, 2 or 3 fatty acyloxyalkyl radicals bound to the nitrogen atom, characterized in that the fatty acyl groups are wholly or partly derived from unsaturated fatty acids, which are at least 30% in cis form .
2. Textil-Behandlungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß wenigstens 50 % und insbesondere wenigstens 70 % der sich von unge¬ sättigten Fettsäuren ableitenden Fettacylgruppen in cis-Form vor¬ liegen.2. Textile treatment agent according to claim 1, characterized in that at least 50% and in particular at least 70% of the fatty acyl groups derived from unsaturated fatty acids are present in cis form.
3. Textil-Behandlungsmittel nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß sie quartäre Ammoniumverbindungen mit 1, 2 oder 3 Fettacyloxyethylresten in einer Konzentration von 4 bis 55 Gew.-%, bezogen auf die Gesamtmenge des Konzentrats, enthalten.3. Textile treatment agent according to one of claims 1 or 2, characterized in that it contains quaternary ammonium compounds with 1, 2 or 3 fatty acyloxyethyl radicals in a concentration of 4 to 55 wt .-%, based on the total amount of the concentrate.
4. Textil-Behandlungsmittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß sie 15 bis 40 Gew.-% quartäre Ammoniumverbindungen mit 1, 2 oder 3 Fettacyloxyethylresten enthalten.4. Textile treatment agent according to one of claims 1 to 3, characterized in that it contains 15 to 40 wt .-% quaternary ammonium compounds with 1, 2 or 3 fatty acyloxyethyl radicals.
5. Textil-Behandlungsmittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die quartäre Ammoniumverbindung ein Gemisch von Verbindungen mit 1, 2 und 3 Fettacyloxyethylresten darstellt.5. Textile treatment agent according to one of claims 1 to 4, characterized in that the quaternary ammonium compound is a mixture of compounds having 1, 2 and 3 fatty acyloxyethyl radicals.
6. Textil-Behandlungsmittel nach Anspruch 5, dadurch gekennzeichnet, daß in dem Gemisch quartäre Ammoniumverbindungen mit 2 Fettacyloxyethyl¬ resten in größerer Menge enthalten sind als quartäre Ammoniumverbin¬ dungen mit 1 oder 3 Fettacyloxyethylresten. - ff -6. Textile treatment agent according to claim 5, characterized in that quaternary ammonium compounds with 2 fatty acyloxyethyl residues are contained in the mixture in a larger amount than quaternary ammonium compounds with 1 or 3 fatty acyloxyethyl residues. - ff -
7. Textil-Behandlungsmittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß sie zusätzlich in wäßrigen Textilweichmacher-Kon¬ zentraten übliche Hilfsstoffe wie Dispergatoren, Konservierungsmittel, anorganische oder organische Säuren, Puffersubstanzen, Elektrolyte, Viskositätsstellmittel, Farbstoffe, Duftstoffe und Lösungsmittel ent¬ halten.7. Textile treatment agent according to one of claims 1 to 6, characterized in that it ent ent in aqueous textile softener concentrates usual auxiliaries such as dispersants, preservatives, inorganic or organic acids, buffer substances, electrolytes, viscosity adjusters, dyes, fragrances and solvents ent ¬ hold.
8. Textil-Behandlungsmittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß sie als weichmachenden Wirkstoff neben quartären Ammoniumverbindungen mit 1, 2 oder 3 Fettacyloxyethylresten zusätzlich einen oder mehrere weichmachende Wirkstoffe anderer Verbindungsklassen enthalten.8. Textile treatment agent according to one of claims 1 to 7, characterized in that it additionally contains one or more softening active substances of other classes of compound as quaternary ammonium compounds with 1, 2 or 3 fatty acyloxyethyl radicals.
9. Textil-Behandlungsmittel nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß sie einen pH-Wert im Bereich von 2,5 bis 7, vor¬ zugsweise im Bereich von 2,5 bis 5, gemessen bei 20 °C nach Verdünnen mit destilliertem Wasser auf eine Konzentration zwischen 0,5 und 5 Gew.-% quartären Ammoniumverbindungen mit 1, 2 oder 3 Fettacyl¬ oxyethylresten, haben.9. Textile treatment agent according to one of claims 1 to 8, characterized in that it has a pH in the range from 2.5 to 7, preferably in the range from 2.5 to 5, measured at 20 ° C after dilution with distilled water to a concentration of between 0.5 and 5% by weight of quaternary ammonium compounds with 1, 2 or 3 fatty acyl oxyethyl radicals.
10. Textil-Behandlungsmittel nach Anspruch 9, dadurch gekennzeichnet, daß sie einen pH-Wert im Bereich von 2,5 bis 4,5, gemessen bei einer Konzentration zwischen 0,5 und 2,0 Gew.-% quartären Ammoniumverbin¬ dungen, haben. 10. Textile treatment agent according to claim 9, characterized in that it has a pH in the range from 2.5 to 4.5, measured at a concentration between 0.5 and 2.0% by weight of quaternary ammonium compounds, to have.
PCT/EP1993/000794 1992-04-10 1993-04-01 Low-viscosity aqueous textile-treatment agents WO1993021291A1 (en)

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WO1994014935A1 (en) * 1992-12-23 1994-07-07 Henkel Kommanditgesellschaft Auf Aktien Aqueous textile softener dispersions
WO1994020597A1 (en) * 1993-03-01 1994-09-15 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions and compounds containing intermediate iodine value unsaturated fatty acid chains
US5407589A (en) * 1991-07-05 1995-04-18 Lever Brothers Company, Division Of Conopco, Inc. Fabric softening composition
US5474690A (en) * 1994-11-14 1995-12-12 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions containing intermediate iodine value fatty acid chains
WO1998047991A1 (en) * 1997-05-19 1998-10-29 The Procter & Gamble Company Softener active derived from acylated triethanolamine
US5916863A (en) * 1996-05-03 1999-06-29 Akzo Nobel Nv High di(alkyl fatty ester) quaternary ammonium compound from triethanol amine
US5919750A (en) * 1997-07-24 1999-07-06 Akzo Nobel Nv Fabric softener composition
US6486121B2 (en) 1998-04-15 2002-11-26 The Procter & Gamble Company Softener active derived from acylated triethanolamine
US8618316B1 (en) 2004-03-05 2013-12-31 Stepan Company Low temperature ramp rate ester quat formation process

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5407589A (en) * 1991-07-05 1995-04-18 Lever Brothers Company, Division Of Conopco, Inc. Fabric softening composition
WO1994014935A1 (en) * 1992-12-23 1994-07-07 Henkel Kommanditgesellschaft Auf Aktien Aqueous textile softener dispersions
US5574179A (en) * 1993-03-01 1996-11-12 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions and compouds containing intermediate iodine value unsaturated fatty acid chains
WO1994020597A1 (en) * 1993-03-01 1994-09-15 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions and compounds containing intermediate iodine value unsaturated fatty acid chains
US5545340A (en) * 1993-03-01 1996-08-13 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions and compounds containing intermediate iodine value unsaturated fatty acid chains
US5562849A (en) * 1993-03-01 1996-10-08 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions and compounds containing intermediate iodine value unsaturated fatty acid chains
US5474690A (en) * 1994-11-14 1995-12-12 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions containing intermediate iodine value fatty acid chains
US5916863A (en) * 1996-05-03 1999-06-29 Akzo Nobel Nv High di(alkyl fatty ester) quaternary ammonium compound from triethanol amine
US6004913A (en) * 1996-05-03 1999-12-21 Akzo Nobel N.V. High di(alkyl fatty ester) quaternary ammonium compound in esteramine from triethanolamine
US6037315A (en) * 1996-05-03 2000-03-14 Akzo Nobel Nv High di(alkyl fatty ester) quaternary ammonium compounds in fabric softening and personal care compositions
US6323167B1 (en) 1996-05-03 2001-11-27 Akzo Nobel N.V. High di(alkyl fatty ester) quaternary ammonium compounds in fabric softening and personal care compositions
WO1998047991A1 (en) * 1997-05-19 1998-10-29 The Procter & Gamble Company Softener active derived from acylated triethanolamine
US5919750A (en) * 1997-07-24 1999-07-06 Akzo Nobel Nv Fabric softener composition
US6486121B2 (en) 1998-04-15 2002-11-26 The Procter & Gamble Company Softener active derived from acylated triethanolamine
US8618316B1 (en) 2004-03-05 2013-12-31 Stepan Company Low temperature ramp rate ester quat formation process

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