EP0243735A2 - Concentrated aqueous textile softener - Google Patents

Concentrated aqueous textile softener Download PDF

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Publication number
EP0243735A2
EP0243735A2 EP87105084A EP87105084A EP0243735A2 EP 0243735 A2 EP0243735 A2 EP 0243735A2 EP 87105084 A EP87105084 A EP 87105084A EP 87105084 A EP87105084 A EP 87105084A EP 0243735 A2 EP0243735 A2 EP 0243735A2
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EP
European Patent Office
Prior art keywords
carbon atoms
acid
acid ester
quaternary ammonium
derived
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.)
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EP87105084A
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German (de)
French (fr)
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EP0243735A3 (en
Inventor
Hans Dr. Nüsslein
Rolf Dr. Puchta
Theodor Völkel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0243735A2 publication Critical patent/EP0243735A2/en
Publication of EP0243735A3 publication Critical patent/EP0243735A3/en
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Classifications

    • 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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds

Definitions

  • the present invention relates to an aqueous concentrated textile softening agent with particularly good dispersibility in water and particularly good absorbency of the textiles treated with it.
  • Aqueous fabric softening agents which are usually added to the last rinsing bath of the washing process in an automatic washing machine for post-treatment of freshly washed laundry, contain about 3 to about 6% fabric softening agents. These are mostly largely water-insoluble quaternary ammonium compounds with 2 long residues in the molecule. One of the most effective compounds of this type is the widely used ditallow alkyl dimethyl ammonium chloride.
  • concentrates In addition to these textile softening agents with a relatively low active ingredient content, so-called concentrates have recently become known, which have the advantage of having a larger amount of active ingredient in the same volume. Such fabric softener concentrates contain about 10 to 15% fabric softening agents.
  • Particularly highly concentrated textile softeners even contain about 50 percent by weight of textile softening agents.
  • Examples of such highly concentrated aqueous fabric softening agents are the products of DE-OS 33 14 677.
  • the concentrates are either diluted to the usual active ingredient concentration of about 3 to about 6% with water, or correspondingly smaller amounts of the concentrated fabric softening agents are added last Rinse water added. Both the dilution of the fabric softener concentrates and the flushing of the concentrates into the rinse water place high demands on the distributability of the concentrates in the water.
  • the fabric softener concentrates therefore contain emulsifiers or dispersants or auxiliaries and viscosity regulators, which belong to a wide variety of substance classes.
  • these emulsifiers or dispersants or auxiliary substances in turn do not contribute to the softening of the textiles and are therefore to be regarded as dietary fibers. It has therefore been tried again and again to get by with a minimum of such non-softening agents in fabric softeners without the water dispersibility and the absorbency of treated textiles being impaired.
  • suitable alcohol residues in the ester are methane, ethanol, isopropanol, myristyl, lauryl, cetyl, oleyl, stearyl, behenyl, myricyl and isopalmityl alcohol, 2-octyldodecanol, ethylene glycol, propylene glycol, dipropylene glycol, glycerin, vinyl alcohol, Diglycerin, xylitol, sucrose, erythritol, pentaerythritol, sorbitol and sorbitan.
  • esters are derived from ethylene glycol, glycerol and sorbitan, and the adducts of up to 20 moles of ethylene oxide and propylene oxide or combinations thereof with the esters can likewise be used in the context of the invention.
  • esters examples include ethylene glycol stearates, mono-, di- and triglycerides of saturated and unsaturated fatty acids with the chain length C12 to C 22 and in particular sorbitan mono-, di- and triesters with the proviso that the acid esters in the sorbitan ester have the chain length C 12 to C 22 have.
  • Sorbitan monolaurate + 40 EO, sorbitan monolaurate + 20 EO, sorbitan monostearate + 4 EO, sorbitan monostearate + 20 EO and sorbitan monooleate + 20 EO may be mentioned as examples of the polyethylene glycol derivatives of sorbitan esters.
  • the active ingredient combination in agents according to the invention is particularly well suited for the production of plasticizer concentrates, i.e. of laundry aftertreatment agents with 8 to 15 percent by weight of quaternary ammonium compounds.
  • Another object of the present invention is a method for producing the agents according to the invention.
  • the quaternary ammonium compound and the carboxylic acid ester are heated to 50 to 90 ° C., the melt thus obtained is mixed with water from 60 to 70 ° C., which may contain auxiliaries and additives, with vigorous stirring, the mixture is cooled and, if appropriate, fragrances and other additives.
  • Suitable stirrers are in particular those which introduce high shear forces into the mixture.
  • the agents according to the invention contain auxiliaries and additives with which the manufacture is facilitated or the properties of the agents are improved.
  • the dispersibility of the products according to the invention in water can be increased if the products are additionally added with 0.5 to 5 percent by weight of dispersing and softening polyglycol ethers.
  • Suitable polyglycol ethers are derived from ethylene oxide and have a molecular weight in the range from 200 to 8000, preferably in the range from 200 to 1000 and in particular in the range from 400 to 600.
  • Additives with a dispersing action are also those by addition of ethylene oxide and / or propylene oxide onto fatty alcohols , Fatty acids, fatty amines, fatty acid or sulfonic acid amides, polyethylene or polypropylene glycols, epoxy glycols, alkylenediamine or aliphatic C 1 to C 8, preferably C 3 to C 6 alcohols.
  • Suitable Additives are ether amines of the formula R- (C 2 H 4 O) n -NR 1 R 2 .
  • R is an alkyl or alkenyl radical having 10 to 20 carbon atoms
  • n is a number between 2 and 10
  • R 1 and R 2 which may be the same or different, are —C 2 H 4 OH or their esters with C10 bis C 20 monocarboxylic acids or with sulfosuccinic acid or alkali metal salts of these acids.
  • Quaternary ammonium salts of the last-mentioned compounds are also very suitable, in which a further alkyl group having 1 to 18 carbon atoms is formed on the nitrogen atom with the formation of a positive charge, which is balanced by an anion which produces electroneutrality, as a rule the chloride anion.
  • Other suitable additives are esters of fatty alcohols, especially tallow alcohol with optionally hydroxyl-substituted monocarboxylic acids with 1 to 3 carbon atoms.
  • high molecular weight polyglycol ethers whose molecular weight is in the range from about 10,000 to 80,000 are also suitable in some compositions according to the invention.
  • 2-benzylalkanol polyglycol ethers with 2 to 10 moles of ethylene oxide as additives, particularly when the underlying alcohol component is 2-benzyoctanol.
  • Addition products of 2 to 10 moles of ethylene oxide with branched alcohols, such as, for example, isotridecanol and with hydroxyl-substituted fatty alcohols, can also be used successfully as additives in many cases.
  • 1,4-Alkylglycosides and 2,2-alkylglycosides with alkyl radicals which have 10 to 20 carbon atoms are also suitable additives.
  • Paraffin oil is also a suitable additive.
  • polyhydric alcohols e.g. B.
  • Suitable acids are organic or inorganic, non-surfactant acids, which are water-soluble. Examples of suitable acids are acetic acid, oxalic acid, glycolic acid, lactic acid, citric acid, tartaric acid as well as hydrochloric acid, sulfuric acid or phosphoric acid. Mixtures of the acids mentioned can also be used. Of the organic acids, glycolic acid and citric acid are preferred, while of the inorganic acids orthophosphoric acid is preferred for setting the desired pH.
  • the concentrate according to the invention can also contain further additives and auxiliaries customary in textile treatment compositions in concentrations of up to about 10 percent by weight.
  • Antimicrobial agents, optical brighteners, soluble salts for adjusting the viscosity of the agent according to the invention, and colorants and fragrances are considered to be customary ingredients.
  • Agents according to the invention with an addition of bleaching agents have a bleaching effect in addition to the properties described.
  • the plasticizer was dimethyl-di- (acyloxyisopropyJ) ammonium chloride, the acyl group being derived from rapeseed oil fatty acid, the carboxylic acid ester was glycerol monostearate.
  • the concentrate had a viscosity of 60 mPas and a pH of 4.9 at room temperature; its distributability in water was excellent. There was practically no change in consistency within 8 weeks when the concentrates were stored in the range from 0 to 40 ° C.
  • test textiles hardened Molton fabric, Krefeld control fabric
  • the Krefeld control fabric was tested for absorbency using the rising height method (DIN 53924). The values given are mm as a measure of the rise of water in the immersed tissues.
  • the table shows that the softness of the Molton fabric treated with the agents according to the invention is just as good as the softness of Molton fabric which is in the rinse water with the same concentration with a commercially available textile softener concentrate.
  • the absorbency of the test fabric treated with the agent according to the invention is twice as high as the absorbency of the test fabric treated with the commercially available product.
  • the absorbency of the test fabric treated with the agent according to the invention corresponds to the absorbency of untreated test fabric.
  • the described combination of properties of the agent according to the invention is extremely surprising, since textiles which have been softened are generally more hydrophobic than non-softened and, on the other hand, concentrated plasticizers have poorer distributability in water and storage stability than dilute plasticizers. If other quaternary ammonium compounds and / or other carboxylic acid esters are used in the context of this invention, similar results to those described above were obtained. This also applies to agents with less than 8 percent by weight quaternary ammonium compound.
  • the quaternary ammonium compound was derived from oleic acid, the carboxylic acid ester was glycerol monostearate.
  • the recipe according to the prior art was inhomogeneous and tended to phase separate, while the recipe according to the invention was stable.
  • the formulation according to the invention showed a better softening effect on all examined fabrics.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Aqueous aftertreatment agents for laundry which are based on quaternary ammonium compounds having two 2-acyloxyalkyl groups whose acyl groups are derived from saturated or unsaturated carboxylic acids, and containing carboxylic esters, are stable systems which have a good fabric conditioning action, even in concentrated form.

Description

Die vorliegende Erfindung betrifft ein wäßriges konzentriertes Textilweichmachungsmittel mit besonders guter Verteilbarkeit in Wasser und besonders guter Saugfähigkeit der damit behandelten Textilien.The present invention relates to an aqueous concentrated textile softening agent with particularly good dispersibility in water and particularly good absorbency of the textiles treated with it.

Wäßrige Textilweichmachungsmittel, die zur Nachbehandlung frisch gewaschener Wäsche in der Regel dem letzten Spülbad des Waschprozesses in einer automatischen Waschmaschine zugegeben werden, enthalten etwa 3 bis etwa 6 % textilweichmachende Wirkstoffe. Hierbei handelt es sich meist um weitgehend wasserunlösliche quartäre Ammoniumverbindungen mit 2 langen Resten im Molekül. Zu den wirksamsten Verbindungen dieses Typs gehört das in großem Umfang eingesetzte Ditalgalkyldimethylammoniumchlorid. In jüngster Zeit sind außer diesen Textilweichmachungsmitteln mit einem verhältnismäßig niedrigen Wirkstoffgehalt auch sogenannte Konzentrate bekannt geworden, die den Vorteil haben, eine größere Wirkstoffmenge im gleichen Volumen aufzuweisen. Derartige Weichspülerkonzentrate enthalten etwa 10 bis 15 % textilweichmachende Wirkstoffe. Besonders hoch konzentrierte Textilweichmacher enthalten sogar etwa 50 Gewichtsprozent an textilweichmachenden Wirkstoffen. Beispiele für derart hochkonzentrierte wäßrige Textilweichmachungsmittel sind die Produkte der DE-OS 33 14 677. Beim Gebrauch werden die Konzentrate entweder auf die übliche Wirkstoffkonzentration von ca. 3 bis ca. 6 % mit Wasser verdünnt, oder es werden entsprechend geringere Mengen der konzentrierten Textilweichmachungsmittel dem letzten Spülwasser zugesetzt. Sowohl beim Verdünnen der Textilweichmacherkonzentrate als auch beim Einspülen der Konzentrate in das Spülwasser werden an die Verteilbarkeit der Konzentrate im Wasser hohe Ansprüche gestellt. Zur Verbesserung der Verteilbarkeit in Wasser enthalten daher die Textilweichmacherkonzentrate Emulgatoren beziehungsweise Dispergatoren beziehungsweise Hilfsmittel und Viskositätsregulatoren, die unterschiedlichsten Stoffklassen angehören. Im allgemeinen tragen diese Emulgatoren beziehungsweise Dispergatoren beziehungsweise Hilfsstoffe ihrerseits nicht zur Weichmachung der Textilien bei und sind daher als Ballaststoffe anzusehen. Es ist daher immer wieder versucht worden, mit einem Minimum an derartigen nichtweichmachenden Hilfsmitteln in Weichspülmitteln auszukommen ohne daß dabei die Wasserverteilbarkeit und die Saugfähigkeit behandelter Textilien verschlechtert wird.Aqueous fabric softening agents, which are usually added to the last rinsing bath of the washing process in an automatic washing machine for post-treatment of freshly washed laundry, contain about 3 to about 6% fabric softening agents. These are mostly largely water-insoluble quaternary ammonium compounds with 2 long residues in the molecule. One of the most effective compounds of this type is the widely used ditallow alkyl dimethyl ammonium chloride. In addition to these textile softening agents with a relatively low active ingredient content, so-called concentrates have recently become known, which have the advantage of having a larger amount of active ingredient in the same volume. Such fabric softener concentrates contain about 10 to 15% fabric softening agents. Particularly highly concentrated textile softeners even contain about 50 percent by weight of textile softening agents. Examples of such highly concentrated aqueous fabric softening agents are the products of DE-OS 33 14 677. When used, the concentrates are either diluted to the usual active ingredient concentration of about 3 to about 6% with water, or correspondingly smaller amounts of the concentrated fabric softening agents are added last Rinse water added. Both the dilution of the fabric softener concentrates and the flushing of the concentrates into the rinse water place high demands on the distributability of the concentrates in the water. To improve the distributability in water, the fabric softener concentrates therefore contain emulsifiers or dispersants or auxiliaries and viscosity regulators, which belong to a wide variety of substance classes. In general, these emulsifiers or dispersants or auxiliary substances in turn do not contribute to the softening of the textiles and are therefore to be regarded as dietary fibers. It has therefore been tried again and again to get by with a minimum of such non-softening agents in fabric softeners without the water dispersibility and the absorbency of treated textiles being impaired.

Es wurde nun überraschenderweise gefunden, daß in bestimmter Weise zusammengesetzte Weichmachungsmittel, die nahezu oder vollständig frei sind von nichttextilweichmachenden Hilfsmitteln, bei ausgezeichneter weichmachender Wirkung besonders gute Verteilbarkeit in Wasser und hervorragende Saugfähigkeit gewährleisten. Diese gute Verteilbarkeit wirkt sich nicht nur bei der Anwendung der Weichmachungsmittel im Wasch- beziehungsweise Nachbehandlungsprozeß aus, sondern es wird auch eine besonders einfache Herstellung damit gewährleistet. Gegenstand der vorliegenden Erfindung ist daher ein flüssiges, wäßriges, konzentriertes Wäschenachbehandlungsmittel mit einem Gehalt an quartären Ammonium-Verbindungen mit zwei 2-Acyloxyalkylgruppen, deren Acylgruppen sich von gesättigten oder ungesättigten Carbonsäuren mit 12 bis 22 Kohlenstoffatomen ableiten, dadurch gekennzeichnet, daß das Mittel

  • a) 1 - 15 Gewichtsprozent quartäre Ammoniumverbindung
  • b) 0,5 - 5 Gewichtsprozent eines Carbonsäureesters sowie gegebenenfalls weitere in Wäschenachbehandlungsmitteln übliche Hilfs- und Zusatzstoffe enthält, wobei das Verhältnis von a) zu b) im Bereich von 10:1 bis 1:1 liegt.
It has now surprisingly been found that plasticizers composed in a certain way, which are almost or completely free of non-fabric softening auxiliaries, ensure particularly good dispersibility in water and excellent absorbency with an excellent softening effect. This good distributability not only has an effect when the plasticizers are used in the washing or aftertreatment process, but also ensures particularly simple manufacture. The present invention therefore relates to a liquid, aqueous, laundry aftertreatment agent containing quaternary ammonium compounds with two 2-acyloxyalkyl groups, the acyl groups of which are derived from saturated or unsaturated carboxylic acids having 12 to 22 carbon atoms, characterized in that the agent
  • a) 1-15 weight percent quaternary ammonium compound
  • b) 0.5-5 percent by weight of a carboxylic acid ester and, if appropriate, further auxiliaries and additives customary in laundry aftertreatment agents, the ratio of a) to b) being in the range from 10: 1 to 1: 1.

Die Acylgruppen der quartären Ammoniumverbindung leiten sich von aliphatischen, gesättigten, ein- oder mehrfach-ungesättigten, verzweigten oder unverzweigten Mono-Carbonsäuren mit 12 bis 22 Kohlenstoffatomen, insbesondere von Talgfettsäure, Olein, Kokosöl oder vor allem Rüböl ab. Typische Vertreter dieser Verbindungsklasse sind die beispielsweise aus der DE-OS 16 19 058, der DE-OS 19 35 499, der DE-AS 24 30 140 und insbesondere der DE-OS 17 94 068 bekannten Verbindungen vom Typ Dimethyl-di-2- acyloxyalkyl-ammoniummethosulfat. Statt der Methylgruppen können in dem Molekül C2- bis C4-Alkyl- oder- Hydroxyalkylgruppen, die gegebenenfalls auch alkoxyliert sein können, enthalten sein. Das Anion kann beispielsweise auch das Chlorid-, Bromid-oder Ethylsulfat-Anion sein oder sich von Phosphonsäure ableiten. Die Acylgruppen sind über Oxyalkylgruppen mit 2 bis 4 Kohlenstoffatomen an das Stickstoffatom gebunden. Im Fall von Oxyalkylgruppen mit 3 oder 4 Kohlenstoffatomen kann die Kohlenstoffkette linear oder verzweigt sein; von besonderer Bedeutung sind Verbindungen mit 3 Kohlenstoffatomen in der insbesondere verzweigten Kohlenstoffkette. Ein typischer bevorzugter Vertreter dieser Verbindungen ist Dimethyl-di-(acyloxyisopropyl-)ammonium- methosulfat. Besonders wertvolle Eigenschaften hat die zuletzt genannte Verbindung, wenn sich die Acylgruppe von Rübölfettsäure ableitet. Der Carbonsäureester leitet sich insbesondere von Mono- oder Polycarbonsäuren mit 2 bis 26 Kohlenstoffatomen und von ein- oder mehrwertigen Alkoholen mit 1 bis 28 Kohlenstoffatomen ab. Die Anzahl der Kohlenstoffatome des Esters liegt zwischen 16 und 30. Besonders wertvolle Eigenschaften haben Ester, deren Alkoholkomponente und /oder deren Säurekomponente wenigstens 12 Kohlenstoffatome enthält. Beispielsweise leiten sich besonders geeignete Carbonsäureester von den folgenden Monocarbonsäuren ab:

  • Essigsäure, Glycolsäure, Propionsäure, Sorbinsäure, Caprylsäure, Isononansäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Hydroxy-C 16/18-Fettsäuren, Stearinsäure, 12-Oxystearinsäure, Ölsäure, Ricinolsäure, Linolsäure, Behensäure und Cerotinsäure. Als Beispiel für Polycarbonsäuren dienen Bernsteinsäure, Adipinsäure, Citronensäure und Phthalsäure.
The acyl groups of the quaternary ammonium compound are derived from aliphatic, saturated, mono- or polyunsaturated, branched or unbranched monocarboxylic acids with 12 to 22 carbon atoms, in particular from tallow fatty acid, oleic acid, coconut oil or above all rapeseed oil. Typical representatives of this class of compounds are the compounds of the dimethyl-di-2- type known, for example, from DE-OS 16 19 058, DE-OS 19 35 499, DE-AS 24 30 140 and in particular DE-OS 17 94 068. acyloxyalkyl ammonium methosulfate. Instead of the methyl groups, the molecule can contain C 2 - to C 4 -alkyl or hydroxyalkyl groups, which can optionally also be alkoxylated. The anion can, for example, also be the chloride, bromide or ethyl sulfate anion or be derived from phosphonic acid. The acyl groups are bonded to the nitrogen atom via oxyalkyl groups with 2 to 4 carbon atoms. In the case of oxyalkyl groups with 3 or 4 carbon atoms, the carbon chain can be linear or branched; Compounds with 3 carbon atoms in the branched carbon chain in particular are of particular importance. A typical preferred representative of these compounds is dimethyl di (acyloxyisopropyl) ammonium methosulfate. The last-mentioned compound has particularly valuable properties if the acyl group is derived from rapeseed oil fatty acid. The carboxylic acid ester is derived in particular from mono- or polycarboxylic acids with 2 to 26 carbon atoms and from mono- or polyhydric alcohols with 1 to 28 carbon atoms. The number of carbon atoms in the ester is between 16 and 30. Esters whose alcohol component and / or whose acid component contains at least 12 carbon atoms have particularly valuable properties. For example, derive particularly suitable carboxylic acid esters from the following monocarboxylic acids:
  • Acetic acid, glycolic acid, propionic acid, sorbic acid, caprylic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, hydroxy-C 16/18 fatty acids, stearic acid, 12-oxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid and cerotic acid. Succinic acid, adipic acid, citric acid and phthalic acid serve as examples of polycarboxylic acids.

Beispiele für geeignete Alkoholreste im Ester sind Methanot, Ethanol, Isopropanol, Myristyl-, Lauryl-, Cetyl-, Oleyl-, Stearyl-, Behenyl-, Myricyl- und lsopalmitylalkohol, 2-Octyldodecanol, Ethylenglycol, Propylenglycol, Dipropylenglycol, Glycerin, Vinylalkohol, Diglycerin, Xylit, Saccharose, Erythrit, Pentaerythrit, Sorbit und Sorbitan.Examples of suitable alcohol residues in the ester are methane, ethanol, isopropanol, myristyl, lauryl, cetyl, oleyl, stearyl, behenyl, myricyl and isopalmityl alcohol, 2-octyldodecanol, ethylene glycol, propylene glycol, dipropylene glycol, glycerin, vinyl alcohol, Diglycerin, xylitol, sucrose, erythritol, pentaerythritol, sorbitol and sorbitan.

Bevorzugte Ester leiten sich von Ethylenglycol-, Glycerin- und Sorbitan ab, wobei ebenfalls die Anlagerungsprodukte von bis zu 20 Mol Ethylenoxyd und Propylenoxid beziehungsweise Kombinationen davon an die Ester im Rahmen der Erfindung Verwendung finden können.Preferred esters are derived from ethylene glycol, glycerol and sorbitan, and the adducts of up to 20 moles of ethylene oxide and propylene oxide or combinations thereof with the esters can likewise be used in the context of the invention.

Beispiele für die bevorzugten Ester sind Ethylenglycolstearate, Mono-, Di- und Triglyceride der gesättigten und ungesättigten Fettsäuren mit der Kettenlänge C12 bis C22 sowie insbesondere Sorbitanmono-, di- und triester mit der Maßgabe, daß die Säureester im Sorbitanester die Kettenlänge C12 bis C22 haben. Von den Polyethylenglykolderivaten der Sorbitanester seien als Beispiel Sorbitanmonolaurat + 40 EO, Sorbitanmonolaurat + 20 EO, Sorbitanmonostearat + 4 EO, Sorbitanmonostearat + 20 EO und Sorbitanmonooleat + 20 EO angeführt.Examples of the preferred esters are ethylene glycol stearates, mono-, di- and triglycerides of saturated and unsaturated fatty acids with the chain length C12 to C 22 and in particular sorbitan mono-, di- and triesters with the proviso that the acid esters in the sorbitan ester have the chain length C 12 to C 22 have. Sorbitan monolaurate + 40 EO, sorbitan monolaurate + 20 EO, sorbitan monostearate + 4 EO, sorbitan monostearate + 20 EO and sorbitan monooleate + 20 EO may be mentioned as examples of the polyethylene glycol derivatives of sorbitan esters.

Die Wirkstoffkombination bei erfindungsgemäßen Mitteln ist besonders gut geeignet zur Herstellung von Weichmacher-Konzentraten, d.h. von Wäschenachbehandlungsmitteln mit 8 bis 15 Gewichtsprozent quartärer Ammoniumverbindungen.The active ingredient combination in agents according to the invention is particularly well suited for the production of plasticizer concentrates, i.e. of laundry aftertreatment agents with 8 to 15 percent by weight of quaternary ammonium compounds.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung der erfindungsgemäßen Mittel. Man erhitzt die quartäre Ammoniumverbindung und den Carbonsäureester auf 50 bis 90 °C, vermischt die so erhaltene Schmelze mit Wasser von 60 bis 70 °C, das gegebenenfalls Hilfs- und Zusatzstoffe enthält, unter intensivem Rühren, kühlt das Gemisch ab und fügt gegebenenfalls Duftstoffe und weitere Zusatzstoffe hinzu. Geeignete Rührer sind insbesondere solche, die hohe Scherkräfte in die Mischung einbringen.Another object of the present invention is a method for producing the agents according to the invention. The quaternary ammonium compound and the carboxylic acid ester are heated to 50 to 90 ° C., the melt thus obtained is mixed with water from 60 to 70 ° C., which may contain auxiliaries and additives, with vigorous stirring, the mixture is cooled and, if appropriate, fragrances and other additives. Suitable stirrers are in particular those which introduce high shear forces into the mixture.

In vielen Fällen enthalten die erfindungsgemäßen Mittel Hilfs- und Zusatzstoffe, mit denen die Herstellung erleichtert beziehungsweise die Eigenschaften der Mittel verbessert werden. Die Verteilbarkeit der erfindungsgemäßen Produkte in Wasser kann gesteigert werden, wenn man den Produkten zusätzlich 0,5 bis 5 Gewichtsprozent dispergierend und weichmachend wirkende Polyglykolether zusetzt. Geeignete Polyglykolether leiten sich von Ethylenoxid ab und haben ein Molgewicht im Bereich von 200 bis 8000, vorzugsweise im Bereich von 200 bis 1 000 und insbesondere im Bereich 400 bis 600. Dispergierend wirkende Zusätze sind auch die durch Anlagerung von Ethylenoxid und/oder Propylenoxid an Fettalkohole, Fettsäuren, Fettamine, Fettsäure- oder Sulfonsäureamide, Polyethylen- oder Polypropylenglykole, Epoxyglykole, Alkylendiamin oder aliphatische C1- bis C8-, vorzugsweise C3- bis C6-Alkohole.In many cases, the agents according to the invention contain auxiliaries and additives with which the manufacture is facilitated or the properties of the agents are improved. The dispersibility of the products according to the invention in water can be increased if the products are additionally added with 0.5 to 5 percent by weight of dispersing and softening polyglycol ethers. Suitable polyglycol ethers are derived from ethylene oxide and have a molecular weight in the range from 200 to 8000, preferably in the range from 200 to 1000 and in particular in the range from 400 to 600. Additives with a dispersing action are also those by addition of ethylene oxide and / or propylene oxide onto fatty alcohols , Fatty acids, fatty amines, fatty acid or sulfonic acid amides, polyethylene or polypropylene glycols, epoxy glycols, alkylenediamine or aliphatic C 1 to C 8, preferably C 3 to C 6 alcohols.

Auch der Zusatz verschiedener Stoffe aus anderen Verbindungsklassen bewirkt in vielen Fällen eine Steigerung der Weichheitsleistung und/oder der Verteilbarkeit in Wasser. Geeignete Zusätze sind Etheramine der Formel R-(C2H4O)n-NR1R2. In dieser Formel bedeutet R einen Alkyl- oder Alkenylrest mit 10 bis 20 Kohlenstoffatomen, n eine Zahl zwischen 2 und 10, R 1 und R2, die gleich oder verschieden sein können, bedeuten -C2H4OH oder deren Ester mit C10 bis C20-Monocarbonsäuren oder mit Sulfobernsteinsäure beziehungsweise Alkalimetallsalzen dieser Säuren. Gut geeignet sind auch quartäre Ammoniumsalze der zuletzt genannten Verbindungen, bei denen an das Stickstoffatom eine weitere Alkylgruppe mit 1 bis 18 Kohlenstoffatomen unter Ausbildung einer positiven Ladung, die durch ein die Elektroneutralität herstellendes Anion, in der Regel das Chlorid-Anion, ausgeglichen wird. Andere geeignete Zusätze sind Ester von Fettalkoholen, insbesondere Talgalkohol mit gegebenenfalls hydroxylsubstituierten Monocarbonsäuren mit 1 bis 3 Kohlenstoffatomen. Außer den oben genannten niedermolekularen Polyglykolethern sind in manchen erfindungsgemäßen Zusammensetzungen auch hochmolekulare Polyglykolether, deren Molekulargewicht im Bereich von etwa 10 000 bis 80 000 liegt, geeignet. Ebenfalls sind 2-Benzylalkanolpolyglykolether mit 2 bis 10 Mol Ethylenoxid als Zusätze geeignet, insbesondere dann, wenn die zugrundeliegende Alkoholkomponente 2-Benzyoctanol ist. Auch Anlagerungsprodukte von 2 bis 10 Mol Ethylenoxid an verzweigte Alkohole, wie beispielsweise Isotridecanol sowie an hydroxylsubstituierte Fettalkohole lassen sich in vielen Fällen mit Erfolg als Zusätze verwenden. Auch 1,4-Alkylglycoside und 2,2-Alkylglycoside mit Alkylresten, die 10 bis 20 Kohlenstoffatome aufweisen, sind geeignete Zusätze. Auch Paraffinöl ist ein geeigneter Zusatzstoff. Ebenfalls geeignet sind mehrwertige Alkohole, z. B. Ethylenglykol, Propylenglykol oder Glycerin. Erfindungsgemäße Produkte mit einem pH-Wert in unverdünntem Zustand von etwa 3,5 bis etwa 5 weisen ein besonders günstiges Viskositätsverhalten auf. Geeignete Säuren sind organische oder anorganische, nichttensidische Säuren, die wasserlöslich sind. Beispiele für geeignete Säuren sind Essigsäure, Oxalsäure, Glykolsäure, Milchsäure, Citronensäure, Weinsäure sowie Salzsäure, Schwefelsäure oder Phosphorsäure. Auch Gemische der genannten Säuren sind verwendbar. Von den organischen Säuren sind Glykolsäure und Citronensäure bevorzugt, während von den anorganischen Säuren Orthophosphorsäure zur Einstellung des gewünschten pH-Wertes bevorzugt wird.In many cases, the addition of different substances from other classes of compounds also increases the softness and / or the distributability in water. Suitable Additives are ether amines of the formula R- (C 2 H 4 O) n -NR 1 R 2 . In this formula, R is an alkyl or alkenyl radical having 10 to 20 carbon atoms, n is a number between 2 and 10, R 1 and R 2 , which may be the same or different, are —C 2 H 4 OH or their esters with C10 bis C 20 monocarboxylic acids or with sulfosuccinic acid or alkali metal salts of these acids. Quaternary ammonium salts of the last-mentioned compounds are also very suitable, in which a further alkyl group having 1 to 18 carbon atoms is formed on the nitrogen atom with the formation of a positive charge, which is balanced by an anion which produces electroneutrality, as a rule the chloride anion. Other suitable additives are esters of fatty alcohols, especially tallow alcohol with optionally hydroxyl-substituted monocarboxylic acids with 1 to 3 carbon atoms. In addition to the above-mentioned low molecular weight polyglycol ethers, high molecular weight polyglycol ethers whose molecular weight is in the range from about 10,000 to 80,000 are also suitable in some compositions according to the invention. Also suitable are 2-benzylalkanol polyglycol ethers with 2 to 10 moles of ethylene oxide as additives, particularly when the underlying alcohol component is 2-benzyoctanol. Addition products of 2 to 10 moles of ethylene oxide with branched alcohols, such as, for example, isotridecanol and with hydroxyl-substituted fatty alcohols, can also be used successfully as additives in many cases. 1,4-Alkylglycosides and 2,2-alkylglycosides with alkyl radicals which have 10 to 20 carbon atoms are also suitable additives. Paraffin oil is also a suitable additive. Also suitable are polyhydric alcohols, e.g. B. ethylene glycol, propylene glycol or glycerin. Products according to the invention with a pH value in the undiluted state of approximately 3.5 to approximately 5 have a particularly favorable viscosity behavior. Suitable acids are organic or inorganic, non-surfactant acids, which are water-soluble. Examples of suitable acids are acetic acid, oxalic acid, glycolic acid, lactic acid, citric acid, tartaric acid as well as hydrochloric acid, sulfuric acid or phosphoric acid. Mixtures of the acids mentioned can also be used. Of the organic acids, glycolic acid and citric acid are preferred, while of the inorganic acids orthophosphoric acid is preferred for setting the desired pH.

Außer den genannten Bestandteilen kann das erfindungsgemäße Konzentrat noch weitere in Textilbehandlungsmittein übliche Zusatz- und Hilfsstoffe in Konzentrationen bis zu etwa 10 Gewichtsprozent enthalten. Als übliche Bestandteile gelten antimikrobielle Wirkstoffe, optische Aufheller, lösliche Salze zur Einstellung der Viskosität des erfindungsgemäßen Mittels sowie Farb- und Duftstoffe.In addition to the constituents mentioned, the concentrate according to the invention can also contain further additives and auxiliaries customary in textile treatment compositions in concentrations of up to about 10 percent by weight. Antimicrobial agents, optical brighteners, soluble salts for adjusting the viscosity of the agent according to the invention, and colorants and fragrances are considered to be customary ingredients.

Erfindungsgemäße Mittel mit einem Zusatz an bleichenden Wirkstoffen, wie zum Beispiel Wasserstoffperoxid oder sonstige Perverbindungen, haben zuätzlich zu den beschriebenen Eigenschaften bleichende Wirkung.Agents according to the invention with an addition of bleaching agents, such as hydrogen peroxide or other per compounds, have a bleaching effect in addition to the properties described.

B e i s p i e l eExample Beispiel 1example 1

Man stellt ein erfindungsgemäßes Textilweichmachungsmittel-Konzentrat her mit der folgenden Zusammensetzung:

  • 10 Gewichtsprozent quartäre Ammoniumverbindung
  • 3 Gewichtsprozent Carbonsäureester
  • 1 Gewichtsprozent Stearylamin + 25 Mol Ethylenoxid
  • 0,1 Gewichtsprozent Orthophosphorsäure
  • 0,005 Gewichtsprozent Magnesiumchlorid
  • Rest Wasser sowie Konservierungsstoff, Farbstoff und Duftstoff in geringen Mengen.
A fabric softener concentrate according to the invention is produced with the following composition:
  • 10 percent by weight quaternary ammonium compound
  • 3 percent by weight carboxylic acid ester
  • 1 percent by weight stearylamine + 25 moles of ethylene oxide
  • 0.1% by weight orthophosphoric acid
  • 0.005 percent by weight magnesium chloride
  • Rest of water as well as preservative, dye and fragrance in small quantities.

Der Weichmacher war Dimethyl-di-(acyloxyisopropyJ)ammoniumchlorid, wobei sich die Acylgruppe von Rübölfettsäure ableitete, der Carbonsäureester war Glycerinmonostearat. Das Konzentrat hatte bei Raumtemperatur eine Viskosität von 60 mPas und einen pH-Wert von 4,9; seine Verteilbarkeit in Wasser war ausgezeichnet. Innerhalb von 8 Wochen traten bei Lagerung der Konzentrate im Bereich von 0 bis 40 C praktisch keine Konsistenzänderungen auf.The plasticizer was dimethyl-di- (acyloxyisopropyJ) ammonium chloride, the acyl group being derived from rapeseed oil fatty acid, the carboxylic acid ester was glycerol monostearate. The concentrate had a viscosity of 60 mPas and a pH of 4.9 at room temperature; its distributability in water was excellent. There was practically no change in consistency within 8 weeks when the concentrates were stored in the range from 0 to 40 ° C.

Bei einem Vergleich dieses Konzentrats mit einem marktüblichen Weichmacher-Konzentrat hinsichtlich Weichheit und Saugfähigkeit von damit behandelten Testgeweben ergaben sich die in Tabelle 1 aufgeführten Werte. Die Prüftextilien (gehärtetes Moltongewebe, Krefelder Kontrollgewebe) wurden im letzten Spülgang einer automatischen Waschmaschine mit einer Menge Weichmacher-Konzentrat behandelt, die 0,7 g pro Liter Spülwasser entsprach. Nach der Behandlung wurden die Textilien hängend an der Luft getrocknet und das Moltongewebe anschließend durch 5 geübte Beurteiler auf Weichheit geprüft. Die Prüfergebnisse wurden in Noten von "0" = sehr hart bis "6" = sehr weich registriert. Das Krefelder Kontrollgewebe wurde auf Saugfähigkeit nach der Steighöhenmethode (DIN 53924) geprüft. Die angegebenen Werte sind mm als Maß für die Steighöhe von Wasser in den eingetauchten Geweben.

Figure imgb0001
A comparison of this concentrate with a commercially available plasticizer concentrate with regard to the softness and absorbency of test fabrics treated with it gave the values listed in Table 1. The test textiles (hardened Molton fabric, Krefeld control fabric) were treated in the last rinse of an automatic washing machine with an amount of softener concentrate that corresponded to 0.7 g per liter of rinse water. After the treatment, the textiles were dried in the air while hanging net and the molton fabric then checked for softness by 5 experienced assessors. The test results were registered in grades from "0" = very hard to "6" = very soft. The Krefeld control fabric was tested for absorbency using the rising height method (DIN 53924). The values given are mm as a measure of the rise of water in the immersed tissues.
Figure imgb0001

Der Tabelle ist zu entnehmen, daß die Weichheit der mit den erfindungsgemäßen Mittel behandelten Moltongewebe genau so gut ist wie die Weichheit von Moltongewebe, das mit einem handelsüblichen erfolgreichen Textilweichmacher-Konzentrat bei gleicher Konzentration im Spülwasser ist. Die Saugfähigkeit des mit dem erfindungsgemäßen Mittel behandelten Testgewebes ist doppelt so hoch wie die Saugfähigkeit des mit dem handelsüblichen Produkt behandelten Testgewebes. Wie der Vergleich mit dem unbehandelten Testgewebe zeigt, entspricht die Saugfähigkeit des mit dem erfindungsgemäßen Mittel behandelten Testgewebes der Saugfähigkeit von unbehandeltem Testgewebe. Die geschilderte Eigenschaftskombination des erfindungsgemäßen Mittels ist äußerst überraschend, da einmal weichgemachte Textilien in der Regel hydrophober sind als nichtweichgemachte und zum anderen konzentrierte Weichmachungsmittel eine schlechtere Verteilbarkeit in Wasser und schlechtere Lagerfähigkeit als verdünnte Weichmachungsmittel aufweisen. Verwendet man im Rahmen dieser Erfindung andere quartäre Ammoniumverbindungen und/oder andere Carbonsäureester, erhielt man ähnliche Ergebnisse wie die zuvor geschilderten. Dies gilt auch für Mittel mit weniger als 8. Gewichtsprozent quartärer Ammoniumverbindung.The table shows that the softness of the Molton fabric treated with the agents according to the invention is just as good as the softness of Molton fabric which is in the rinse water with the same concentration with a commercially available textile softener concentrate. The absorbency of the test fabric treated with the agent according to the invention is twice as high as the absorbency of the test fabric treated with the commercially available product. As the comparison with the untreated test fabric shows, the absorbency of the test fabric treated with the agent according to the invention corresponds to the absorbency of untreated test fabric. The described combination of properties of the agent according to the invention is extremely surprising, since textiles which have been softened are generally more hydrophobic than non-softened and, on the other hand, concentrated plasticizers have poorer distributability in water and storage stability than dilute plasticizers. If other quaternary ammonium compounds and / or other carboxylic acid esters are used in the context of this invention, similar results to those described above were obtained. This also applies to agents with less than 8 percent by weight quaternary ammonium compound.

Beispiel 2Example 2

In weiteren Versuchen wurde die Überlegenheit der erfindungsgemäßen Mittel gegenüber den Mitteln der DE-OS 17 94 068 gezeigt. Die Mittel hatten folgende Zusammensetzung:

Figure imgb0002
In further experiments, the superiority of the agents according to the invention over the agents of DE-OS 17 94 068 was shown. The composition of the funds was as follows:
Figure imgb0002

Die quartäre Ammoniumverbindung leitete sich von Ölsäure ab, der Carbonsäureester war Glycerinmonostearat.The quaternary ammonium compound was derived from oleic acid, the carboxylic acid ester was glycerol monostearate.

Die Rezeptur nach dem Stand der Technik war inhomogen und neigte zur Phasentrennung, während die erfindungsgemäße Rezeptur stabil war. Die erfindungsgemäße Rezeptur zeigte an allen untersuchten Geweben bessere weichmachende Wirkung.The recipe according to the prior art was inhomogeneous and tended to phase separate, while the recipe according to the invention was stable. The formulation according to the invention showed a better softening effect on all examined fabrics.

Claims (8)

1. Flüssiges, wäßriges Wäschenachbehandlungsmittel mit einem Gehalt an quartären Ammonium-Verbindungen mit zwei 2-Acyloxyalkylgruppen, deren Acylgruppen sich von gesättigten oder ungesättigten Carbonsäuren mit 12 bis 22 Kohlenstoffatomen ableiten, dadurch gekennzeichnet, daß das Mittel a) 1 - 15 Gewichtsprozent quartäre Ammoniumverbindung b) 0,5 - 5 Gewichtsprozent eines Carbonsäureesters sowie gegebenenfalls weitere in Wäschenachbehandlungsmitteln übliche Hilfs- und Zusatzstoffe enthält, wobei das Verhältnis von a) zu b) im Bereich von 10:1 bis 1:1 liegt. 1. Liquid, aqueous laundry treatment agent containing quaternary ammonium compounds with two 2-acyloxyalkyl groups, the acyl groups of which are derived from saturated or unsaturated carboxylic acids having 12 to 22 carbon atoms, characterized in that the agent a) 1-15 weight percent quaternary ammonium compound b) contains 0.5-5 percent by weight of a carboxylic acid ester and, if appropriate, further auxiliaries and additives customary in laundry aftertreatment agents, the ratio of a) to b) being in the range from 10: 1 to 1: 1. 2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß die Acylgruppen sich von Talgfettsäure, Olein, Kokosöl oder insbesondere Rüböl ableiten.2. Composition according to claim 1, characterized in that the acyl groups are derived from tallow fatty acid, oleic, coconut oil or in particular rapeseed oil. 3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Carbonsäureester sich von Säuren mit 2 bis 26 Kohlenstoffatomen und von Alkoholen mit 1 bis 28 Kohlenstoffatomen ableiten mit der Maßgabe, daß der Ester 16 bis 30 Kohlenstoffatome hat.3. Composition according to claim 1 or 2, characterized in that the carboxylic acid ester is derived from acids with 2 to 26 carbon atoms and from alcohols with 1 to 28 carbon atoms with the proviso that the ester has 16 to 30 carbon atoms. 4. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der dem Carbonsäureester zugrunde liegende Alkohol und/oder die zugrunde liegende Säure wenigstens 12 Kohlenstoffatome enthält.4. Composition according to one of claims 1 to 3, characterized in that the alcohol and / or the acid on which the carboxylic acid ester is based contains at least 12 carbon atoms. 5. Mittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Carbonsäureester sich von Ethylenglykol, Glycerin oder Sorbitan ableitet.5. Composition according to one of claims 1 to 4, characterized in that the carboxylic acid ester is derived from ethylene glycol, glycerol or sorbitan. 6. Mittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Ester ein Sorbitan-Fettsäureester ist, dessen Fettsäure 12 bis 22 Kohlenstoffatome enthält.6. Composition according to one of claims 1 to 5, characterized in that the ester is a sorbitan fatty acid ester, the fatty acid contains 12 to 22 carbon atoms. 7. Mittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Mittel 8 bis 15 Gewichtsprozent quartäre Ammoniumverbindungen enthält.7. Agent according to one of claims 1 to 6, characterized in that the agent contains 8 to 1 5 percent by weight of quaternary ammonium compounds. 8. Verfahren zur Herstellung eines Mittels nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man die quartäre Ammoniumverbindung und den Carbonsäureester auf 50 bis 90 °C erhitzt, die so erhaltene Schmelze mit Wasser von 60 bis 70 °C, das gegebenenfalls Hilfs- und Zusatzstoffe enthält, unter intensivem Rühren vermischt, das Gemisch abkühlt und gegebenenfalls Duftstoffe und weitere Zusatzstoffe hinzufügt.8. A process for the preparation of an agent according to any one of claims 1 to 7, characterized in that the quaternary ammonium compound and the carboxylic acid ester are heated to 50 to 90 ° C, the melt thus obtained with water of 60 to 70 ° C, which may be auxiliary - and additives, mixed with vigorous stirring, the mixture cools and optionally adds fragrances and other additives.
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EP0309052A2 (en) * 1987-09-23 1989-03-29 The Procter & Gamble Company Stable biodegradable fabric softening compositions containing linear alkoxylated alcohols
EP0293955A3 (en) * 1987-05-01 1989-07-05 The Procter & Gamble Company Quaternary isopropyl ester ammonium compounds as fiber and fabric treatment compositions
EP0334482A1 (en) * 1988-02-23 1989-09-27 The British Petroleum Company p.l.c. Fabric conditioners
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EP0293955A3 (en) * 1987-05-01 1989-07-05 The Procter & Gamble Company Quaternary isopropyl ester ammonium compounds as fiber and fabric treatment compositions
EP0309052A3 (en) * 1987-09-23 1989-07-05 The Procter & Gamble Company Stable biodegradable fabric softening compositions containing linear alkoxylated alcohols
EP0309052A2 (en) * 1987-09-23 1989-03-29 The Procter & Gamble Company Stable biodegradable fabric softening compositions containing linear alkoxylated alcohols
EP0334482A1 (en) * 1988-02-23 1989-09-27 The British Petroleum Company p.l.c. Fabric conditioners
EP0387064A2 (en) * 1989-03-10 1990-09-12 Unilever Plc Fabric conditioning
EP0387064A3 (en) * 1989-03-10 1991-11-21 Unilever Plc Fabric conditioning
WO1992018593A1 (en) * 1991-04-22 1992-10-29 The Procter & Gamble Company Granular fabric softener compositions which form aqueous emulsion concentrates
EP0530959B1 (en) * 1991-09-06 1998-10-14 Colgate-Palmolive Company Fabric softening compositions based on pentaerythritol compound and dispersant for such a compound
US5545350A (en) * 1992-05-12 1996-08-13 The Procter & Gamble Company Concentrated fabric softener compositions containing biodegradable fabric softeners
WO1994019439A1 (en) * 1993-02-25 1994-09-01 Unilever Plc Use of fabric softening composition
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
WO1995004811A1 (en) * 1993-08-06 1995-02-16 The Procter & Gamble Company Dryer-activated fabric conditioning compositions containing ethoxylated/propoxylated sugar derivatives
US5505866A (en) * 1994-10-07 1996-04-09 The Procter & Gamble Company Solid particulate fabric softener composition containing biodegradable cationic ester fabric softener active and acidic pH modifier
WO1996012002A1 (en) * 1994-10-17 1996-04-25 Henkel Kommanditgesellschaft Auf Aktien Concentrated textile softeners
US5854201A (en) * 1994-10-17 1998-12-29 Henkel Kommanditgesellschaft Auf Aktien Textile softeners concentrates based on pentaerythritol or esters thereof containing quaternary and nonionic emulsifiers
WO1996015213A1 (en) * 1994-11-14 1996-05-23 Henkel Kommanditgesellschaft Auf Aktien Textile softening agents
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
WO1997008285A1 (en) * 1995-08-31 1997-03-06 Colgate-Palmolive Company Stable fabric softener compositions
US5726144A (en) * 1995-08-31 1998-03-10 Colgate-Palmolive Company Stable fabric softener compositions
CN1087342C (en) * 1995-08-31 2002-07-10 科尔加特·帕尔莫利弗公司 Stable fabric softener compositions
US6022845A (en) * 1995-11-03 2000-02-08 The Procter & Gamble Co. Stable high perfume, low active fabric softener compositions
US6083899A (en) * 1996-09-19 2000-07-04 The Procter & Gamble Company Fabric softeners having increased performance
EP1290124B2 (en) † 2000-06-16 2007-01-03 Unilever Plc Fabric softening compositions

Also Published As

Publication number Publication date
DK182187A (en) 1987-10-15
DK182187D0 (en) 1987-04-09
DE3612479A1 (en) 1987-10-15
JPS62243877A (en) 1987-10-24
EP0243735A3 (en) 1988-07-27

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