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EP0920486B2 - Aqueous laundry softening agent with high zeta potential - Google Patents
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EP0920486B2 - Aqueous laundry softening agent with high zeta potential - Google Patents

Aqueous laundry softening agent with high zeta potential Download PDF

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Publication number
EP0920486B2
EP0920486B2 EP97927127A EP97927127A EP0920486B2 EP 0920486 B2 EP0920486 B2 EP 0920486B2 EP 97927127 A EP97927127 A EP 97927127A EP 97927127 A EP97927127 A EP 97927127A EP 0920486 B2 EP0920486 B2 EP 0920486B2
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EP
European Patent Office
Prior art keywords
fatty
weight
carbon atoms
fatty acids
fabric softeners
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.)
Expired - Lifetime
Application number
EP97927127A
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German (de)
French (fr)
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EP0920486A2 (en
EP0920486B1 (en
Inventor
Ansgar Behler
Anneliese Wilsch-Irrgang
Theodor Völkel
Bernhard Guckenbiehl
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Cognis IP Management GmbH
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Cognis Deutschland GmbH and Co KG
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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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/201—Monohydric alcohols linear
    • C11D3/2013—Monohydric alcohols linear fatty or with at least 8 carbon atoms in the alkyl chain
    • 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
    • C11D1/645—Mixtures of compounds all of which are cationic
    • 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
    • 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
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • 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
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to aqueous dispersions which contain fatty substances and emulsifiers as fabric softeners, which are characterized by a high positive zeta potential of the dispersion.
  • Textile treatment agents that have a softening effect on laundry are well known. you will be usually used in the last rinse of a machine wash and give the laundry a pleasant, soft feel, as they have a pronounced sorption capacity on a wide variety of fiber surfaces.
  • the coating of the fiber with the long-chain molecules leads to a sliding effect between the fibers and prevents the water or dry rigidity that is responsible for the hard grip of the fabric.
  • the adsorption mechanism for the drawing up of softening materials consists in the electrostatic attraction between the e.g. due to washing alkali negatively charged fiber surface and positively charged plasticizer particles.
  • Water-insoluble quaternary ammonium compounds containing two long chain alkyl or alkenyl radicals are used. Commonly used connections are Ditallow dimethyl ammonium chloride or distearyl dimethyl ammonium chloride. Because such connections but as ecological are of concern, increasingly used difatty acid trialkanolamine ester salts by reaction a trialkanolamine with technical fatty acids and subsequent quaternization can be obtained, such as Methyl-N- (2-hydroxyethyl) -N, N-di (talgacyloxyethyl) ammonium methosulfate.
  • fabric softeners are offered in the form of aqueous dispersions.
  • EP 043 622 B1 proposed an aqueous stable dispersion which contains 8 to 22% by weight of a water-insoluble cationic fabric softener, and a viscosity-regulating system containing 0.5 to 6% by weight C 10-24 hydrocarbons, C 10-24 fatty acids or C 10-24 fatty acid esters from fatty acids with short-chain alcohols or C 10-24 fatty alcohols and 0.05 to 1% by weight of a water-soluble cationic polymer.
  • the addition of polymers for viscosity control often leads to reduced performance of the fabric softener. Agents without polymeric viscosity regulators are described in DE 36 02 089 C2.
  • the compositions contain a fatty alcohol with 10 to 24 carbon atoms, the weight ratio between cationic softeners to fatty alcohols being between 3.5: 1 and 6: 1.
  • Ethoxylated amines are used as emulsifiers.
  • Solid agents are known from German patent application 42 32 448 A1 which contain quaternary difatty acid trialkanolamine ester salts and a hydroxy compound selected from the group of fatty alcohols, fatty alcohol polyglycol ethers, polyol fatty acid partial esters and carbohydrates and which are suitable for the production of liquid, aqueous plasticizer compositions (with 1 to 50% by weight). -% active substance).
  • the weight ratio between quaternary esteramine salt and hydroxy compound should be between 9: 1 and 1: 1.
  • a disadvantage of these agents is that relatively large amounts of ecologically unsatisfactory nitrogen-containing compounds are still used.
  • EP 497 769 A2 proposes acidic, aqueous fabric softeners which contain pentaerythritol esters as a softening component in amounts between 1 and 25% by weight and 0.1 to 10% by weight of a nonionic emulsifier and are therefore ecologically harmless.
  • the object of the invention was therefore to provide stable, aqueous textile plasticizer dispersions To produce the basis of largely biodegradable ingredients with advantageous ecotoxicological properties. It has now been found that combinations of biodegradable, water-insoluble fatty substances with emulsifiers in certain quantitative ratios leads to efficient means when the zeta potential of the aqueous Dispersions exceeds a certain value.
  • the invention therefore relates to fabric softeners in the form of an aqueous dispersion of an anti-aging component, wherein the finishing component, based on the weight of the fabric softener, is from 0.5 to 20 %
  • the finishing component based on the weight of the fabric softener, is from 0.5 to 20 %
  • the weight ratio between fat and emulsifiers is between 10: 1 and 0.5: 1 and the proviso that the zeta potential the aqueous dispersion at a pH of 7 and a temperature of 25 ° C at least + 30 mV is.
  • zeta potential is a common method for characterizing solid / liquid dispersions (RJ Hunter, Zeta Potential in Colloid Science, pages 150 to 162, Academic Press, New York 1981).
  • Dispersed particles can become electrically charged, for example by adsorption of ions on their surface.
  • An electrical double layer forms on the surface of these electrically charged particles, which is firmly connected to the particles and causes an apparent increase in volume.
  • This solid layer is enveloped by a movable and diffuse ion layer.
  • the potential ⁇ 0 on the particle surface now drops linearly within the solid ion layer with the thickness ⁇ to the value ⁇ ⁇ in order to decrease exponentially to the value 0 in the diffuse layer.
  • the potential difference between the inner solid ion layer ⁇ ⁇ and the point within the diffuse ion layer at which the potential has decreased to 1 / e • ⁇ ⁇ is called the zeta potential.
  • the rate of migration is measured depending on the size of the particles to be examined either by means of light microscopic observation or, especially for smaller particles, by means of laser correlation spectroscopy (W. Demtröder, laser spectroscopy: basics and techniques, 2nd edition, Springer-Verlag, Berlin 1991, chapters 12.7 to 12.7.2).
  • the high positive zeta potential of the dispersions means that the dispersed particles completely can pull up the negatively charged fibers and by completely covering the fibers with hydrophobic, long-chain alkyl residues a good softening effect is achieved.
  • Means are particularly suitable here have the highest possible zeta potential over a wide pH range, as is present in the wash liquor.
  • Dispersions according to the invention which not only have a zeta potential of not only at a pH of 7 are particularly preferred have at least + 30 mV, but also at a pH of 8, which is often in the wash liquor during reached in the rinse cycle, still show at least a zeta potential of + 25 mV (temperature in each case 25 ° C.).
  • Dispersions whose zeta potential at a temperature of 25 ° C. and a pH of are particularly preferred 7 show at least + 40 mV.
  • the dispersions according to the invention contain at least one fatty substance in amounts between 0.5 and 20 % By weight, preferably between 2 and 12% by weight and in particular between 4 and 6% by weight, based on the Total amount of the agent, and the cationic emulsifier in amounts between 0.2 and 10 wt .-%, preferably between 0.3 and 8% by weight, in particular between 0.4 and 6% by weight and optionally a nonionic Emulsifier in amounts up to 10% by weight. It is essential that the weight ratio between fat and Emulsifier is between 10: 1 and 0.5: 1 and the amounts of the ingredients are adjusted so that the zeta potential the dispersion at a pH of 7 and 25 ° C is at least + 30 mV.
  • Particularly preferred dispersions have a weight ratio between fat and emulsifiers between 1: 1 and 8: 1, and in particular between 2: 1 and 6: 1.
  • fatty substances are understood to mean solid fats, fatty alcohols, waxes and hydrocarbons at normal temperature (20 ° C.). These include, for example, hardened fats and oils of animal and vegetable origin, as well as non-cyclic, branched and unbranched hydrocarbons with 12 to 30 carbon atoms. Examples of such compounds are tetradecane, hexadecane, octadecane and octadecene.
  • the fatty substances are preferably selected from the group of the fatty acid esters of fatty acids with 12 to 22 carbon atoms with mono- or polyhydric alcohols with 1 to 22 carbon atoms, as well as fatty acids or fatty alcohols with 12 to 22 carbon atoms and mixtures of these substances.
  • monoesters or diesters of fatty acids with pentaerythritol monoesters and diesters of C 12-18 fatty acids with glycerol or monoesters of C 12-18 fatty acids with C 12-18 fatty alcohols are preferred.
  • Examples of such compounds are lauric, myristic, palmitic or stearic acid as well as methyl and Ethyl ester of these acids.
  • decanol, dodecanol, tetradecanol, pentadecanol, Hexadecanol or octadecanol and mixtures of these alcohols are used.
  • Examples of preferred uses Fat substances are technical pentaerythritol distearic acid esters or glycerol monostearic acid esters as well as technical ones Fatty alcohols.
  • Cationic emulsifiers are understood in the context of the present application to mean compounds which are selected from the group of the quaternary ammonium compounds of the formulas (I) and (II), where R is an acyclic alkyl radical having 12 to 24 carbon atoms, R 1 is a saturated C 1 -C 4 alkyl or hydroxyalkyl radical, R 2 is either R or R 1 and COR 3 is an aliphatic acyl radical having 12 to 22 carbon atoms 0, 1, 2 or 3 double bonds and R 4 is H or OH, where n is 1, 2 or 3 and X is either a halide, methosulfate, metophosphate or phosphate ion, and mixtures of these compounds. Compounds which contain alkyl radicals having 16 to 18 carbon atoms are particularly preferred.
  • Examples of cationic surfactants of the formula (I) are didecyldimethylammonium chloride and ditallow dimethylammonium chloride oderDihexadecylammoniumchlorid.
  • Examples of compounds of the formula (II) are methyl-N- (2-hydroxyethyl) -N, N-di (tallow acyl-oxyethyl) ammonium methosulfate, Bis- (palmitoyl) -ethyl hydroxyethyl methyl ammonium methosulfate or methyl-N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate.
  • connection of the Formulas (I) and (II) can also be used in short-chain, water-soluble, quaternary ammonium compounds, such as trihydroxyethyl methyl ammonium methosulfate or cetyl trimethyl ammonium chloride.
  • quaternary ammonium compounds such as trihydroxyethyl methyl ammonium methosulfate or cetyl trimethyl ammonium chloride.
  • Protonated too Alkylamine compounds that have a softening effect, and the non-quaternized, protonated Precursors of the cationic emulsifiers are suitable.
  • quaternized compounds of formula (II) which have unsaturated alkyl chains preference is given to the acly groups whose corresponding fatty acids preferably have an iodine number between 5 and 25 have between 10 and 25 and in particular between 15 and 20 and which have a cis / trans isomer ratio (in % By weight) of 30:70, preferably greater than 50:50 and in particular greater than 70:30.
  • R 7 each independently represents a C 1-4 alkyl, alkenyl or hydroxyalkyl group
  • R 8 each independently represents a C 8-28 alkyl group
  • n is a number between 0 and 5.
  • nonionic emulsifiers are understood to mean compounds which come from the group of the alkoxylated fatty acids with 12 to 22 carbon atoms, the alkoxylated fatty acid esters from fatty acids with 12 to 22 carbon atoms with alcohols with 1 to 10 carbon atoms and the alkoxylated fatty alcohols with 12 to 22 carbon atoms , where the alkoxylated compounds have HLB values between 3 and 20, and fatty acid amides and monoalkanolamides from C 12 -C 22 fatty acids with amines or alkanolamines with 1 to 9 carbon atoms, as well as alkyl glycosides or glucamides, are selected.
  • Alkoxylated compounds with an HLB value between 3 and 20, preferably between 8 and 14 are preferred.
  • nonionic emulsifiers according to the invention are C 12-18 fatty alcohols with 7 EO, cetyl / stearyl alcohol with 20 EO or fatty acid polyglycol esters.
  • the alkyl glycosides used are compounds of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol, which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • Fatty acid N-alkylglucamides such as are represented by the formula (IV) are preferably used as glucamides, where R 10 is hydrogen or an alkyl group and R 9 CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, gadoleic acid or erucic acid or its technical mixtures.
  • Fatty acid N-alkylglucamides of the formula (IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C 12/14 coconut fatty acid or a corresponding derivative are particularly preferred.
  • the agents according to the invention can also be used in textile softeners Contain common substances.
  • these include, for example, organic solvents such as ethanol or isopropyl alcohol, Fungicides, enzymes, for example cellulase, dyes, optical brighteners, lecithin, UV absorbers, Preservatives, soil repellents, pearlescent agents or fragrances.
  • the agents may also contain electrolytes, preferably sodium, magnesium or calcium chloride, as well as pH adjusting agents such as e.g. organic and inorganic Acids.
  • the dispersions according to the invention are prepared in a manner known per se by the Ingredients mixed with the necessary amount of water, then heated to a temperature of 60 ° C and Mix for 5 to 30 minutes in a high speed mixer.
  • the aqueous white rinse dispersions thus obtained have a pH between 2 and 7, preferably between 3 and 6.
  • aqueous dispersions mentioned in Examples 1 to 8 were prepared by the corresponding Fatty substances with the emulsifiers and water were introduced and heated to 80 ° C. with thorough mixing. After this the raw materials were homogeneously dispersed, the cationic emulsifier was added with thorough mixing. The dispersion was cooled to 30 ° C. with moderate stirring and then the remaining constituents, such as perfume oils.
  • the zeta potentials of the aqueous dispersions and the assessment of the gripping effect can be found in the table 1 can be removed.
  • the determination of the gripping effect was carried out on pre-washed terry towels, which with the investigating agents and then dried in the air.
  • the test fabrics were in addition in a glass drum with the agents to be examined (concentration 15 g / kg dry wash, water hardness 16 ° d, liquor ratio 1: 5) treated for 5 minutes, causing the drum to reverse has been.
  • the wipes were fingered from a test panel (5 people).
  • the zeta potential was measured using a Malvern-Zetazisers® 3 at a temperature of 25 ° C. To determine the zeta potential, the respective dispersion was mixed with 0.001 molar potassium chloride solution 1: 400 diluted and then the pH with hydrochloric acid or sodium hydroxide to the desired Value set. The values given represent mean values from 5 measurements.
  • the dispersions according to the invention with a small proportion of quaternary N-containing compounds, good grip properties that are comparable to the performance of commercially available plasticizers, which as Avivage component contain only cationic N-containing salts.
  • the missing amounts are up to 100% by weight of water and small amounts other components (electrolytes, perfume oil, auxiliaries, etc.).

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Abstract

Aqueous softening dispersions which, in relation to the weight of the dispersion, contain 0.5 to 20 wt % of at least one non-ionic fat, 0.2 to 10 wt % of a water-soluble or insoluble cationic emulsifier and possibly upon to 10 wt % of a non-ionic emulsifier, in which the weight ratios between fat and emulsifiers is between 10:1 and 0.5:1, exhibit a good soft-care effect if the zeta potential of the dispersion is at least +30 mV at 25 DEG C and a pH of 7.

Description

Die vorliegende Erfindung betrifft wäßrige Dispersionen, die Fettstoffe und Emulgatoren enthalten, als Wäscheweichspülmittel, die sich durch ein hohes positives Zeta-Potential der Dispersion auszeichnen.The present invention relates to aqueous dispersions which contain fatty substances and emulsifiers as fabric softeners, which are characterized by a high positive zeta potential of the dispersion.

Textilbehandlungsmittel, die einen weichpflegenden Effekt auf Wäsche haben sind wohlbekannt. Sie werden üblicherweise im letzten Spülgang einer maschinellen Wäsche eingesetzt und verleihen der Wäsche einen angenehmen, weichen Griff, da sie ein ausgeprägtes Sorptionsvermögen auf den unterschiedlichsten Faseroberflächen aufweisen. Die Belegung der Faser mit den langkettigen Molekülen führt zu einem Gleiteffekt zwischen den Fasern und verhindert damit die Wasser- oder Trockenstarre, die für den harten Griff des Gewebes verantwortlich ist. Ein möglicher Adsorptionsmechanismus für das Aufziehen von weichmachenden Wrkstoffen besteht in der elektrostatischen Anziehung zwischen der, z.B. durch Waschalkalie negativ geladenen Faseroberfläche und positiv geladenen Weichmacher-Partikeln. Aussagen über die Größe und das Vorzeichen der Oberflächenladung können durch Messung des sogenannten Zeta-Potentials erhalten werden, welches die Galvani-Spannung an der diffusen elektrochemischen Doppelschicht an der Phasengrenze zwischen der Oberfläche eines Feststoffs, beispielsweise eines dispergierten Weichmachers, und einer Flüssigkeit, beispielsweise der Waschflotte, beschreibt.Textile treatment agents that have a softening effect on laundry are well known. you will be usually used in the last rinse of a machine wash and give the laundry a pleasant, soft feel, as they have a pronounced sorption capacity on a wide variety of fiber surfaces. The coating of the fiber with the long-chain molecules leads to a sliding effect between the fibers and prevents the water or dry rigidity that is responsible for the hard grip of the fabric. A possible one The adsorption mechanism for the drawing up of softening materials consists in the electrostatic attraction between the e.g. due to washing alkali negatively charged fiber surface and positively charged plasticizer particles. Statements about the size and the sign of the surface charge can be made by measuring the so-called Zeta potential is obtained, which is the electroplating voltage at the diffuse electrochemical double layer at the phase boundary between the surface of a solid, for example a dispersed plasticizer, and a liquid, for example the washing liquor.

Üblicherweise werden als textilweichmachende Wirkstoffe wasserunlösliche quaternäre Ammoniumverbindungen, die zwei langkettige Alkyl- oder Alkenylreste enthalten, verwendet. Häufig eingesetzte Verbindungen sind Ditalgdimethylammmoniumchlorid oder Distearyldimethylammoniumchlorid. Da derartige Verbindungen aber als ökologisch bedenklich gelten, werden zunehmend Difettsäuretrialkanolaminestersalze eingesetzt, die durch Umsetzung eines Trialkanolamins mit technischen Fettsäuren und anschließender Quaternierung erhalten werden, wie beispielsweise Methyl-N-(2-hydroxyethyl)-N,N-di(talgacyloxyethyl)ammonium-methosulfat.Water-insoluble quaternary ammonium compounds, containing two long chain alkyl or alkenyl radicals are used. Commonly used connections are Ditallow dimethyl ammonium chloride or distearyl dimethyl ammonium chloride. Because such connections but as ecological are of concern, increasingly used difatty acid trialkanolamine ester salts by reaction a trialkanolamine with technical fatty acids and subsequent quaternization can be obtained, such as Methyl-N- (2-hydroxyethyl) -N, N-di (talgacyloxyethyl) ammonium methosulfate.

Üblicherweise werden Wäscheweichspülmittel in Form wäßriger Dispersionen angeboten. Dabei stellt sich das Problem, daß mit zunehmenden Anteil an Aktivsubstanz die Viskosität der Dispersion ansteigt, was die Handhabung durch den Verbraucher erschwert, und weiterhin die Stabilität derartiger Produkte nicht ausreicht. Um derartige Probleme zu überwinden wurde beispielsweise in der EP 043 622 B1 eine wäßrige stabile Dispersion vorgeschlagen, die 8 bis 22 Gew.-% eines wasserunlöslichen kationischen Textilweichmachers enthält, sowie ein die Viskosität regulierendes System, enthaltend 0,5 bis 6 Gew.-% C10-24-Kohlenwasserstoffe, C10-24-Fettsäuren oder C10-24-Fettsäureester aus Fettsäuren mit kurzkettigen Alkoholen oder C10-24-Fettalkohole und 0,05 bis 1 Gew.-% eines wasserlöslichen kationischen Polymers. Der Zusatz von Polymeren zur Viskositätsregelung führt aber häufig zu einer verringerten Leistung der Weichspülmittel. Mittel ohne polymere Viskositätsregler werden in der DE 36 02 089 C2 beschrieben. Die Mittel enthalten neben üblichen kationischen Textilweichmachem einen Fettalkohol mit 10 bis 24 Kohlenstoffatomen, wobei das Gewichtsverhältnis zwischen kationischen Weichmachern zu Fettalkoholen zwischen 3,5 : 1 und 6 : 1 liegt. Als Emulgatoren werden ethoxylierte Amine eingesetzt. Aus der Deutschen Patentanmeldung 42 32 448 A1 sind feste Mittel bekannt, die quartäre Difettsäuretrialkanolaminestersalze, sowie eine Hydroxyverbindung, ausgewählt aus der Gruppe der Fettalkohole, Fettalkoholpolyglykolether, Polyolfettsäurepartialester und Kohlenhydrate enthalten und die sich zur Herstellung flüssiger, wäßriger Weichmacherzusammensetzungen (mit 1 bis 50 Gew.-% Aktivsubstanz) eignen. Das Gewichtsverhältnis zwischen quartärem Esteraminsalz und Hydroxyverbindung soll zwischen 9 : 1 und 1 : 1 liegen. Nachteilig bei diesen Mittel ist aber, daß noch relativ hohe Mengen an ökologisch unbefriedigenden, stickstoffhaltigen Verbindungen eingesetzt werden. Dagegen werden in der EP 497 769 A2 saure, wäßrige Weichspülmittel vorgeschlagen, die als weichmachende Komponente Pentaerythrithester in Mengen zwischen 1 und 25 Gew.-%, sowie 0,1 bis 10 Gew.-% eines nichtionischen Emulgators enthalten und somit ökologisch unbedenklich sind. Die in dieser Schrift offenbarten Mittel können aber auch bis zu 0,5 Gew.-% quaternierte Ammoniumverbindungen enthalten. Derartige Zusammensetzungen weisen aber bei pH=7 nur Zeta-Potentiale von höchstens +27 mV auf.Usually, fabric softeners are offered in the form of aqueous dispersions. The problem arises here that the viscosity of the dispersion increases with an increasing proportion of active substance, which makes handling by the consumer more difficult, and furthermore the stability of such products is insufficient. In order to overcome such problems, for example, EP 043 622 B1 proposed an aqueous stable dispersion which contains 8 to 22% by weight of a water-insoluble cationic fabric softener, and a viscosity-regulating system containing 0.5 to 6% by weight C 10-24 hydrocarbons, C 10-24 fatty acids or C 10-24 fatty acid esters from fatty acids with short-chain alcohols or C 10-24 fatty alcohols and 0.05 to 1% by weight of a water-soluble cationic polymer. However, the addition of polymers for viscosity control often leads to reduced performance of the fabric softener. Agents without polymeric viscosity regulators are described in DE 36 02 089 C2. In addition to conventional cationic fabric softeners, the compositions contain a fatty alcohol with 10 to 24 carbon atoms, the weight ratio between cationic softeners to fatty alcohols being between 3.5: 1 and 6: 1. Ethoxylated amines are used as emulsifiers. Solid agents are known from German patent application 42 32 448 A1 which contain quaternary difatty acid trialkanolamine ester salts and a hydroxy compound selected from the group of fatty alcohols, fatty alcohol polyglycol ethers, polyol fatty acid partial esters and carbohydrates and which are suitable for the production of liquid, aqueous plasticizer compositions (with 1 to 50% by weight). -% active substance). The weight ratio between quaternary esteramine salt and hydroxy compound should be between 9: 1 and 1: 1. However, a disadvantage of these agents is that relatively large amounts of ecologically unsatisfactory nitrogen-containing compounds are still used. On the other hand, EP 497 769 A2 proposes acidic, aqueous fabric softeners which contain pentaerythritol esters as a softening component in amounts between 1 and 25% by weight and 0.1 to 10% by weight of a nonionic emulsifier and are therefore ecologically harmless. However, the agents disclosed in this document can also contain up to 0.5% by weight of quaternized ammonium compounds. Such compositions, however, only have zeta potentials of at most +27 mV at pH = 7.

Trotz dieser unterschiedlichen Ansätze, stabile, problemlos handhabbare Textilweichmacherdispersionen herzustellen, besteht nach wie vor das Bedürfnis, die bestehenden Formulierungen in der Leistung und ökologischem Verhalten zu verbessern. Aufgabe der Erfindung war es daher, stabile, wäßrige Textilweichmacherdispersionen auf Basis weitgehend biologisch abbaubarer Inhaltsstoffe mit vorteilhaften ökotoxikologischen Eigenschaften herzustellen. Es wurde nun gefunden, daß Kombinationen biologisch abbaubarer, wasserunlöslicher Fettstoffe mit Emulgatoren in bestimmten Mengenverhältnissen gerade dann zu leistungsfähigen Mitteln führt, wenn das Zeta-Potential derwäßrigen Dispersionen einen bestimmten Wert überschreitet.Despite these different approaches, stable, easy-to-use textile softener dispersions There is still a need to manufacture the existing formulations in terms of performance and ecology Improve behavior. The object of the invention was therefore to provide stable, aqueous textile plasticizer dispersions To produce the basis of largely biodegradable ingredients with advantageous ecotoxicological properties. It has now been found that combinations of biodegradable, water-insoluble fatty substances with emulsifiers in certain quantitative ratios leads to efficient means when the zeta potential of the aqueous Dispersions exceeds a certain value.

Gegenstand der Erfindung sind daher Wäscheweichspülmittel in Form einer wäßrigen Dispersion einer Avivagekomponente, wobei die Avivagekomponente, bezogen auf das Gewicht des Weichspülmittels, aus 0,5 bis 20 Gew.-% mindestens eines nichtionischen Fettstoffs und 0,2 bis 10 Gew.-% eines wasserlöslichen und/oder wasserunlöslichen kationischen Emulgators und 0 bis 10 Gew.-% eines nichtionischen Emulgators besteht, wobei das Gewichtsverhältnis zwischen Fettstoff und Emulgatoren zwischen 10 : 1 und 0,5 : 1 liegt und der Maßgabe, daß das Zeta-Potential der wäßrigen Dispersion bei einem pH-Wert von 7 und einer Temperatur von 25 °C mindestens + 30 mV beträgt.The invention therefore relates to fabric softeners in the form of an aqueous dispersion of an anti-aging component, wherein the finishing component, based on the weight of the fabric softener, is from 0.5 to 20 % By weight of at least one nonionic fatty substance and 0.2 to 10% by weight of a water-soluble and / or water-insoluble cationic emulsifier and 0 to 10 wt .-% of a nonionic emulsifier, the weight ratio between fat and emulsifiers is between 10: 1 and 0.5: 1 and the proviso that the zeta potential the aqueous dispersion at a pH of 7 and a temperature of 25 ° C at least + 30 mV is.

Um Mittel mit den gewünschten Zeta-Potentialen zu erhalten, ist es vorteilhaft zunächst den Fettstoff mit einer geeigneten Menge an nichtionischem Emulgator vollständig in Wasser zu dispergieren und dann durch Zugabe des kationischen Emulgators das Zeta-Potential einzustellen.In order to obtain agents with the desired zeta potential, it is advantageous to start with the fatty substance appropriate amount of nonionic emulsifier to completely disperse in water and then by adding the cationic emulsifier to set the zeta potential.

Die Messung des Zeta-Potentials stellt eine übliche Methode zur Charakterisierung von fest/flüssig-Dispersionen dar (R.J. Hunter, Zeta Potential in Colloid Science, Seiten 150 bis 162, Academic Press, New York 1981). Dispergierte Teilchen können sich, beispielsweise durch Adsorption von lonen auf ihrer Oberfläche, elektrisch aufladen. An der Oberfläche dieser elektrisch geladenen Teilchen bildet sich dadurch eine elektrische Doppelschicht, die fest mit den Partikeln verbunden ist und eine scheinbare Volumenzunahme bewirken. Diese feste Schicht wird von einer beweglichen und diffusen lonenschicht umhüllt. Das Potential ψ0 an der Partikeloberflächefällt nun innerhalb der festen lonenschicht mit der Dicke δ linear auf den Wert ψδ ab, um in der diffusen Schicht annähernd exponentiell bis auf den Wert 0 zurückzugehen. Die Potentialdifferenz zwischen der inneren festen lonenschicht ψδ und dem Punkt innerhalb der diffusen lonenschicht, bei der das Potential auf 1/e • ψδ zurückgegangen ist, bezeichnet man als Zeta-Potential.Measuring the zeta potential is a common method for characterizing solid / liquid dispersions (RJ Hunter, Zeta Potential in Colloid Science, pages 150 to 162, Academic Press, New York 1981). Dispersed particles can become electrically charged, for example by adsorption of ions on their surface. An electrical double layer forms on the surface of these electrically charged particles, which is firmly connected to the particles and causes an apparent increase in volume. This solid layer is enveloped by a movable and diffuse ion layer. The potential ψ 0 on the particle surface now drops linearly within the solid ion layer with the thickness δ to the value ψ δ in order to decrease exponentially to the value 0 in the diffuse layer. The potential difference between the inner solid ion layer ψ δ and the point within the diffuse ion layer at which the potential has decreased to 1 / e • ψ δ is called the zeta potential.

Das Zeta-Potential kann aus der Wanderungsrichtung und -geschwindigkeit der dispergierten Teilchen im elektrischen Feld direkt ermittelt werden (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik II, Georg Thieme Verfag, Stuttgart 1977, Seiten 260 bis 264), wobei man folgende Beziehung zugrunde legt: ζ = f·π·v·η E·ε

  • ζ = Zeta-Potential (in mV)
  • ε = Dielektrizitätskonstante des Dispersionsmittels
  • v = elektrophoretische Wanderungsgeschwindigkeit ( in cm/s)
  • η = Viskosität des Dispersionsmittels (Poise, 1 Poise = 0,1 Pa · s)
  • E = Feldstärke (in mV)
  • f = Zahlenfaktor (Reibungsfaktor), der von der Form der Teilchen, ihrer Leitfähigkeit und der Größe der Teilchen im Vergleich zur Dicke der diffusen Doppelschicht abhängt
    • The zeta potential can be determined directly from the direction and speed of migration of the dispersed particles in the electric field (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik II, Georg Thieme Verfag, Stuttgart 1977, pages 260 to 264), whereby based on the following relationship: ζ = f · Π · v · η e · ε
  • ζ = zeta potential (in mV)
  • ε = dielectric constant of the dispersant
  • v = electrophoretic migration speed (in cm / s)
  • η = viscosity of the dispersant (poise, 1 poise = 0.1 Pa · s)
  • E = field strength (in mV)
  • f = numerical factor (friction factor), which depends on the shape of the particles, their conductivity and the size of the particles compared to the thickness of the diffuse double layer

    • Die Messung der Wanderungsgeschwindigkeit erfolgt dabei, je nach Größe der zu untersuchenden Teilchen entweder mittels lichtmikroskopischer Beobachtung oder, insbesondere bei kleineren Teilchen, mittels Laser-Korrelations-Spektroskopie (W. Demtröder, Laserspektroskopie: Grundlagen und Techniken, 2. Auflage, Springer-Verlag, Berlin 1991, Kapitel 12.7 bis 12.7.2).The rate of migration is measured depending on the size of the particles to be examined either by means of light microscopic observation or, especially for smaller particles, by means of laser correlation spectroscopy (W. Demtröder, laser spectroscopy: basics and techniques, 2nd edition, Springer-Verlag, Berlin 1991, chapters 12.7 to 12.7.2).

    Das hohe positive Zeta-Potential der Dispersionen führt dazu, daß die dispergierten Teilchen vollständig auf die negativ geladenen Fasern aufziehen können und durch die vollständige Umhüllung der Fasern mit hydrophoben, langkettigen Alkylresten eine gute weichmachende Wirkung erzielt wird. Dabei sind Mittel besonders geeignet, die über einen breiten pH-Wertbereich, wie er in der Waschflotte vorliegt, ein möglichst hohes Zeta-Potential aufweisen. Besonders bevorzugt sind erfindungsgemäße Dispersionen, die nicht nur bei einem pH von 7 ein Zeta-Potential von mindestens + 30 mV aufweisen, sondern die auch bei einem pH-Wert von 8, der häufig in der Waschflotte während des Spülgangs erreicht wird, noch mindestens ein Zeta-Potential von + 25 mV zeigen (Temperatur jeweils 25 °C). Besonders bevorzugt sind Dispersionen, deren Zeta-Potential bei einer Temperatur von 25 °C und einem pH-Wert von 7 mindestens + 40 mV zeigen.The high positive zeta potential of the dispersions means that the dispersed particles completely can pull up the negatively charged fibers and by completely covering the fibers with hydrophobic, long-chain alkyl residues a good softening effect is achieved. Means are particularly suitable here have the highest possible zeta potential over a wide pH range, as is present in the wash liquor. Dispersions according to the invention which not only have a zeta potential of not only at a pH of 7 are particularly preferred have at least + 30 mV, but also at a pH of 8, which is often in the wash liquor during reached in the rinse cycle, still show at least a zeta potential of + 25 mV (temperature in each case 25 ° C.). Dispersions whose zeta potential at a temperature of 25 ° C. and a pH of are particularly preferred 7 show at least + 40 mV.

    Die erfindungsgemäßen Dispersionen enthalten mindestens einen Fettstoff in Mengen zwischen 0,5 und 20 Gew.-%, vorzugsweise zwischen 2 und 12 Gew.-% und insbesondere zwischen 4 und 6 Gew.-%, bezogen auf die Gesamtmenge des Mittels, sowie den kationischen Emulgator in Mengen zwischen 0,2 und 10 Gew.-%, vorzugsweise zwischen 0,3 und 8 Gew.-%, insbesondere zwischen 0,4 und 6 Gew.-% und gegebenenfalls einen nichtionischen Emulgator in Mengen bis zu 10 Gew.-%. Wesentlich ist dabei, daß das Gewichtsverhältnis zwischen Fettstoff und Emulgator zwischen 10 : 1 und 0,5 : 1 liegt und die Mengen der Inhaltsstoffe so abgestimmt werden, daß das Zeta-Potential der Dispersion bei einem pH-Wert von 7 und 25 °C mindestens + 30 mV beträgt. Nur dann ist es möglich, daß in ausreichender Menge weichmachende Substanzen auf die Textilfasern aufziehen, um einen guten weichmachenden Effekt zu erzielen. Besonders bevorzugte Dispersionen weisen dabei ein Gewichtsverhältnis zwischen Fettstoff und Emulgatoren zwischen 1 : 1 und 8 : 1, und insbesondere zwischen 2 : 1 und 6 : 1 auf.The dispersions according to the invention contain at least one fatty substance in amounts between 0.5 and 20 % By weight, preferably between 2 and 12% by weight and in particular between 4 and 6% by weight, based on the Total amount of the agent, and the cationic emulsifier in amounts between 0.2 and 10 wt .-%, preferably between 0.3 and 8% by weight, in particular between 0.4 and 6% by weight and optionally a nonionic Emulsifier in amounts up to 10% by weight. It is essential that the weight ratio between fat and Emulsifier is between 10: 1 and 0.5: 1 and the amounts of the ingredients are adjusted so that the zeta potential the dispersion at a pH of 7 and 25 ° C is at least + 30 mV. Only then is it possible that absorb sufficient amounts of softening substances on the textile fibers to a good softening To achieve effect. Particularly preferred dispersions have a weight ratio between fat and emulsifiers between 1: 1 and 8: 1, and in particular between 2: 1 and 6: 1.

    Unter Fettstoffen werden im Rahmen dieser Anmeldungen bei Normaltemperatur (20 °C) feste Fette, Fettalkohole, Wachse und Kohlenwasserstoffe verstanden. Dazu gehören beispielsweise gehärtete Fette und Öle tierischen und pflanzlichen Ursprungs, sowie nichtzyklische, verzweigte und unverzweigte Kohlenwasserstoffe mit 12 bis 30 Kohlenstoffatomen. Beispiele für derartige Verbindungen sind Tetradecan, Hexadecan, Octadecan und Octadecen. Vorzugsweise werden die Fettstoffe aus der Gruppe der Fettsäureester von Fettsäuren mit 12 bis 22 Kohlenstoffatomen mit ein- oder mehrwertigen Alkoholen mit 1 bis 22 Kohlenstoffatomen, sowie Fettsäuren oder Fettalkoholen mit 12 bis 22 Kohlenstoffatomen und Mischungen aus diesen Substanzen ausgewählt. Insbesondere sind Mono- oder Diester von Fettsäuren mit Pentaerythrit, Monoester und Diester von C12-18-Fettsäuren mit Glycerin oder Monoester von C12-18-Fettsäuren mit C12-18-Fettalkoholen bevorzugt. In the context of these applications, fatty substances are understood to mean solid fats, fatty alcohols, waxes and hydrocarbons at normal temperature (20 ° C.). These include, for example, hardened fats and oils of animal and vegetable origin, as well as non-cyclic, branched and unbranched hydrocarbons with 12 to 30 carbon atoms. Examples of such compounds are tetradecane, hexadecane, octadecane and octadecene. The fatty substances are preferably selected from the group of the fatty acid esters of fatty acids with 12 to 22 carbon atoms with mono- or polyhydric alcohols with 1 to 22 carbon atoms, as well as fatty acids or fatty alcohols with 12 to 22 carbon atoms and mixtures of these substances. In particular, monoesters or diesters of fatty acids with pentaerythritol, monoesters and diesters of C 12-18 fatty acids with glycerol or monoesters of C 12-18 fatty acids with C 12-18 fatty alcohols are preferred.

    Beispiele für derartige Verbindungen sind Laurin-, Myristin-, Palmitin- oder Stearinsäure sowie Methyl- und Ethylester dieser Säuren. Als Fettalkohle werden beispielsweise Decanol, Dodecanol, Tetradecanol, Pentadecanol, Hexadecanol oder Octadecanol sowie Mischungen dieser Alkohole eingesetzt. Beispiele für bevorzugt eingesetzte Fettstoffe sind technische Pentaerytrithdistearinsäureester oder Glycerinmonostearinsäureester sowie technische Fettalkohole.Examples of such compounds are lauric, myristic, palmitic or stearic acid as well as methyl and Ethyl ester of these acids. For example, decanol, dodecanol, tetradecanol, pentadecanol, Hexadecanol or octadecanol and mixtures of these alcohols are used. Examples of preferred uses Fat substances are technical pentaerythritol distearic acid esters or glycerol monostearic acid esters as well as technical ones Fatty alcohols.

    Unter kationische Emulgatoren werden im Rahmen der vorliegenden Anmeldung Verbindungen verstanden, die aus der Gruppe der quaternären Ammoniumverbindungen der Formeln (I) und (II) ausgewählt sind,

    Figure 00030001
    wobei R für einen acyclischen Alkylrest mit 12 bis 24 Kohlenstoffatomen, R1 für einen gesättigten C1-C4 Alkyl- oder Hydroxyalkylrest steht, R2 entweder gleich R oder R1 ist und COR3 für einen aliphatischen Acylrest mit 12 bis 22 Kohlenstoffatomen mit 0, 1, 2 oder 3 Doppelbindungen steht sowie R4 gleich H oder OH bedeutet, wobei n den Wert 1, 2 oder 3 hat und X entweder ein Halogenid-, Methosulfat- , Metophosphat- oder Phosphation ist, sowie Mischungen dieser Verbindungen. Besonders bevorzugt sind Verbindungen, die Alkylreste mit 16 bis 18 Kohlenstoffatomen enthalten.Cationic emulsifiers are understood in the context of the present application to mean compounds which are selected from the group of the quaternary ammonium compounds of the formulas (I) and (II),
    Figure 00030001
    where R is an acyclic alkyl radical having 12 to 24 carbon atoms, R 1 is a saturated C 1 -C 4 alkyl or hydroxyalkyl radical, R 2 is either R or R 1 and COR 3 is an aliphatic acyl radical having 12 to 22 carbon atoms 0, 1, 2 or 3 double bonds and R 4 is H or OH, where n is 1, 2 or 3 and X is either a halide, methosulfate, metophosphate or phosphate ion, and mixtures of these compounds. Compounds which contain alkyl radicals having 16 to 18 carbon atoms are particularly preferred.

    Beispiele für kationische Tenside der Formel (I) sind Didecyldimethylammoniumchlorid, Ditalgdimethylammoniumchlorid oderDihexadecylammoniumchlorid. Beispiele für Verbindungen der Formel (II) sind Methyl-N-(2-hydroxyethyl)-N,N-di(talgacyl-oxyethyl)ammonium-methosulfat, Bis-(palmitoyl)-ethyl-hydroxyethyl-methyl-ammonium-methosulfat oder Methyl-N,N-bis(acyloxyethyl)-N-(2-hydroxyethyl)ammonium-methosulfat. Neben den Verbindungen der Formeln (I) und (II) können auch kurzkettige, wasserlösliche, quatemäre Ammoniumverbindungen eingesetzt werden, wie beispielsweise Trihydroxyethyl-methyl-ammonium-methosulfat oder Cetyl-trimethylammonium-chlorid. Auch protonierte Alkylaminverbindungen, die weichmachende Wirkung aufweisen, sowie die nicht quaternierten, protonierten Vorstufen der kationischen Emulgatoren sind geeignet.Examples of cationic surfactants of the formula (I) are didecyldimethylammonium chloride and ditallow dimethylammonium chloride oderDihexadecylammoniumchlorid. Examples of compounds of the formula (II) are methyl-N- (2-hydroxyethyl) -N, N-di (tallow acyl-oxyethyl) ammonium methosulfate, Bis- (palmitoyl) -ethyl hydroxyethyl methyl ammonium methosulfate or methyl-N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. In addition to the connections of the Formulas (I) and (II) can also be used in short-chain, water-soluble, quaternary ammonium compounds, such as trihydroxyethyl methyl ammonium methosulfate or cetyl trimethyl ammonium chloride. Protonated too Alkylamine compounds that have a softening effect, and the non-quaternized, protonated Precursors of the cationic emulsifiers are suitable.

    Werden quartemierte Verbindungen der Formel (II) eingesetzt, die ungesättigte Alkylketten aufweisen, sind die Aclygruppen bevorzugt, deren korrespondierenden Fettsäuren eine Jodzahl zwischen 5 und 25, vorzugsweise zwischen 10 und 25 und insbesondere zwischen 15 und 20 aufweisen und die ein cis/trans-Isomerenverhältnis (in Gew.-%) von 30 : 70, vorzugsweise größer als 50 : 50 und insbesondere größer als 70 : 30 haben.If quaternized compounds of formula (II) are used which have unsaturated alkyl chains preference is given to the acly groups whose corresponding fatty acids preferably have an iodine number between 5 and 25 have between 10 and 25 and in particular between 15 and 20 and which have a cis / trans isomer ratio (in % By weight) of 30:70, preferably greater than 50:50 and in particular greater than 70:30.

    Neben den oben beschriebenen quarternären Verbindungen können auch andere bekannte Verbindungen eingesetzt werden, wie beispielsweise quartemäre Imidazoliniumverbindungen der Formel (III)

    Figure 00030002
    wobei R5 eine gesättigten Alkylrest mit 12 bis 18 Kohlenstoffatomen, R6 einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder H bedeutet und Z eine NH-Gruppe oder Sauerstoff bedeutet und A ein Anion ist.In addition to the quaternary compounds described above, other known compounds can also be used, such as quaternary imidazolinium compounds of the formula (III)
    Figure 00030002
    wherein R 5 is a saturated alkyl radical having 12 to 18 carbon atoms, R 6 is an alkyl radical having 1 to 4 carbon atoms or H and Z is an NH group or oxygen and A is an anion.

    Weitere geeignete quarternäre Verbindungen sind durch Formel (IV) beschrieben,

    Figure 00040001
    wobei R7 jeweils unabhängig ausgewählt für eine C1-4 Alkyl-, Alkenyl- oder Hydroxyalkylgruppe steht, R8 jeweils unabhängig ausgewählt eine C8-28 Alkylgruppe darstellt und n eine Zahl zwischen 0 und 5 ist.Further suitable quaternary compounds are described by formula (IV)
    Figure 00040001
    where R 7 each independently represents a C 1-4 alkyl, alkenyl or hydroxyalkyl group, R 8 each independently represents a C 8-28 alkyl group and n is a number between 0 and 5.

    Im Rahmen dieser Anmeldung werden unter nichtionischen Emulgatoren Verbindungen verstanden, die aus der Gruppe der alkoxylierten Fettsäuren mit 12 bis 22 Kohlenstoffatomen, der alkoxylierten Fettsäureester aus Fettsäuren mit 12 bis 22 Kohlenstoffatomen mit Alkoholen mit 1 bis 10 Kohlenstoffatomen und der alkoxylierten Fettalkohole mit 12 bis 22 Kohlenstoffatomen, wobei die alkoxylierten Verbindungen HLB-Werte zwischen 3 und 20 aufweisen, sowie Fettsäureamiden und Monoalkanolamiden aus C12-C22-Fettsäuren mit Aminen oder Alkanolaminen mit 1 bis 9 Kohlenstoffatomen, sowie Alkylglykosiden oder Glucamiden, ausgewählt sind. Bevorzugt sind alkoxylierte Verbindungen mit einem HLB-Wert zwischen 3 und 20, vorzugsweise zwischen 8 und 14. Beispiel für erfindungsgemäße nichtionische Emulgatoren sind C12-18-Fettalkohole mit 7 EO, Cetyl/Stearylalkohol mit 20 EO oder Fettsäurepolyglykolester. Als Alkylglykoside werden Verbindungen der allgemeinen Formel RO(G)x eingesetzt, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4.In the context of this application, nonionic emulsifiers are understood to mean compounds which come from the group of the alkoxylated fatty acids with 12 to 22 carbon atoms, the alkoxylated fatty acid esters from fatty acids with 12 to 22 carbon atoms with alcohols with 1 to 10 carbon atoms and the alkoxylated fatty alcohols with 12 to 22 carbon atoms , where the alkoxylated compounds have HLB values between 3 and 20, and fatty acid amides and monoalkanolamides from C 12 -C 22 fatty acids with amines or alkanolamines with 1 to 9 carbon atoms, as well as alkyl glycosides or glucamides, are selected. Alkoxylated compounds with an HLB value between 3 and 20, preferably between 8 and 14 are preferred. Examples of nonionic emulsifiers according to the invention are C 12-18 fatty alcohols with 7 EO, cetyl / stearyl alcohol with 20 EO or fatty acid polyglycol esters. The alkyl glycosides used are compounds of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol, which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

    Als Glucamide werden bevorzugt Fettsäure-N-alkylglucamide eingesetzt wie sie durch die Formel (IV) wiedergegeben werden,

    Figure 00040002
    wobei R10 für Wasserstoff oder eine Alkylgruppe steht und R9 CO für den Acylrest der Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Arachinsäure, Gadoleinsäure, Behensäure oder Erucasäure beziehungsweise derer technischer Mischungen steht. Besonders bevorzugt sind Fettsäure-N-alkylglucamide der Formel (IV), die durch reduktive Aminierung von Glucose mit Methylamin und anschließende Acylierung mit Laurinsäure oder C12/14-Kokosfettsäure beziehungsweise einem entsprechenden Derivat erhalten werden.Fatty acid N-alkylglucamides such as are represented by the formula (IV) are preferably used as glucamides,
    Figure 00040002
    where R 10 is hydrogen or an alkyl group and R 9 CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, gadoleic acid or erucic acid or its technical mixtures. Fatty acid N-alkylglucamides of the formula (IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C 12/14 coconut fatty acid or a corresponding derivative are particularly preferred.

    Neben den oben genannten Inhaltsstoffen können die erfindungsgemäßen Mittel auch weitere, in Textilweichmachern übliche Stoffe enthalten. Dazu gehören beispielsweise organische Lösungsmittel wie Ethanol oder Isopropylalkohol, Fungizide, Enzyme, beispielsweise Cellulase, Farbstoffe, optische Aufheller, Lecithin, UV-Absorbentien, Konservierungsmittel, soil-repellents, Perlglanzmittel oder Duftstoffe. Weiterhin können die Mittel Elektrolyte enthalten, vorzugsweise Natrium-, Magnesium- oder Calciumchlorid, sowie pH-Stellmittel wie z.B. organische und anorganische Säuren.In addition to the ingredients mentioned above, the agents according to the invention can also be used in textile softeners Contain common substances. These include, for example, organic solvents such as ethanol or isopropyl alcohol, Fungicides, enzymes, for example cellulase, dyes, optical brighteners, lecithin, UV absorbers, Preservatives, soil repellents, pearlescent agents or fragrances. The agents may also contain electrolytes, preferably sodium, magnesium or calcium chloride, as well as pH adjusting agents such as e.g. organic and inorganic Acids.

    Die Herstellung der erfindungsgemäßen Dispersionen erfolgt in an sich bekannter Weise, indem man die Inhaltsstoffe mit der notwendigen Menge Wasser vermischt, anschließend auf eine Temperatur von 60 °C erhitzt und 5 bis 30 Minuten in einem Hochgeschwindigkeitsmischer vermischt. Die so erhaltenen wäßrigen Weispülerdispersionen weisen einen pH-Wert zwischen 2 und 7, vorzugsweise zwischen 3 und 6 auf.The dispersions according to the invention are prepared in a manner known per se by the Ingredients mixed with the necessary amount of water, then heated to a temperature of 60 ° C and Mix for 5 to 30 minutes in a high speed mixer. The aqueous white rinse dispersions thus obtained have a pH between 2 and 7, preferably between 3 and 6.

    BeispieleExamples

    Die in den Beispielen 1 bis 8 genannten wäßrigen Dispersionen wurden hergestellt indem die entsprechenden Fettstoffe mit den Emulgatoren und Wasser vorgelegt und unter guter Durchmischung auf 80 °C erhitzt wurden. Nachdem die Rohstoffe homogen dispergiert waren erfolgte die Zugabe des kationischen Emulgators unter guter Durchmischung. Die Dispersion wurde unter mäßigem Rühren auf 30 °C abgekühlt und anschließend die restlichen Bestandteile, wie beispielsweise Parfümöle zudosiert.The aqueous dispersions mentioned in Examples 1 to 8 were prepared by the corresponding Fatty substances with the emulsifiers and water were introduced and heated to 80 ° C. with thorough mixing. After this the raw materials were homogeneously dispersed, the cationic emulsifier was added with thorough mixing. The dispersion was cooled to 30 ° C. with moderate stirring and then the remaining constituents, such as perfume oils.

    Die Zeta-Potentiale der wäßrigen Dispersionen und die Beurteilung der griffgebenden Wirkung kann derTabelle 1 entnommen werden.The zeta potentials of the aqueous dispersions and the assessment of the gripping effect can be found in the table 1 can be removed.

    Die Ermittlung der griffgebenden Wirkung erfolgte an vorgewaschenen Frottiergewebetücher, die mit den zu untersuchenden Mitteln ausgerüstet und anschließend an der Raumluft getrocknet wurden. Die Testgewebe wurden dazu in einer Glastrommel mit den zu untersuchenden Mitteln (Konzentration 15 g/kg Trockenwäsche, Wasserhärte 16 °d, Flottenverhältnis 1:5) 5 Minuten lang behandelt, wobei die Trommel in reversierende Bewegungen versetzt wurde. Die Tücherwurden von einem Testpanel (5 Personen) grifftechnisch beurteilt. Der Wäschegriff wurde als Durchschnittswert aus drei Bestimmungen in Noten angegeben (0 = hart, 6 = weich), wobei Griffnoten ab 3,8 als gut bewertet wurden.The determination of the gripping effect was carried out on pre-washed terry towels, which with the investigating agents and then dried in the air. The test fabrics were in addition in a glass drum with the agents to be examined (concentration 15 g / kg dry wash, water hardness 16 ° d, liquor ratio 1: 5) treated for 5 minutes, causing the drum to reverse has been. The wipes were fingered from a test panel (5 people). The laundry handle was given as an average out of three determinations given in grades (0 = hard, 6 = soft), with grades from 3.8 as good were.

    Die Messung des Zeta-Potential erfolgte mit Hilfe eines Malvern-Zetazisers® 3 bei einer Temperatur von 25 °C. Zur Bestimmung des Zeta-Potentials wurde die jeweilige Dispersion mit 0,001 molarer Kaliumchlorid-Lösung 1 : 400 verdünnt und anschließend der pH-Wert mit Salzsäure beziehungsweise Natriumhydroxid auf den gewünschten Wert eingestellt. Die angegebenen Werte stellen Mittelwerte aus 5 Messungen dar.The zeta potential was measured using a Malvern-Zetazisers® 3 at a temperature of 25 ° C. To determine the zeta potential, the respective dispersion was mixed with 0.001 molar potassium chloride solution 1: 400 diluted and then the pH with hydrochloric acid or sodium hydroxide to the desired Value set. The values given represent mean values from 5 measurements.

    Die erfindungsgemäßen Dispersionen wiesen, bei geringem Anteil an quaternären N-haltigen Verbindungen, gute griffgebende Eigenschaften auf, die mit der Leistung marktüblicher Weichmacher vergleichbar sind, welche als Avivagekomponente nur kationische N-haltige Salze enthalten.The dispersions according to the invention, with a small proportion of quaternary N-containing compounds, good grip properties that are comparable to the performance of commercially available plasticizers, which as Avivage component contain only cationic N-containing salts.

    Zum Vergleich wurden die beiden nichterfindungsgemäßen Beispiele 7 und 8 sowie ein handelsüblicher Weichmacher 9 auf Basis eines bekannten quaternären Esteraminsalzes untersucht. 7 weist zwar eine Kombination aus Fettstoff und kationischem und nichtionischem Emulgator auf, das Zeta-Potential bei pH = 7 liegt aber unter + 30 mV. 8 stellt eine Kombination aus einem kationischen und zwei nichtionischen Emulgatoren dar, ohne daß ein erfindungsgemäßer Fettstoff zugesetzt wurde. Das Beispiel 10 zeigt, daß die Kombination der erfindungsgemäßen Inhaltsstoffe nicht zwangsläufig zu Dispersionen mit hohem Zeta-Potential führt.For comparison, the two examples 7 and 8 not according to the invention and one commercially available Plasticizer 9 based on a known quaternary esteramine salt examined. 7 has a combination from fat and cationic and nonionic emulsifier, but the zeta potential at pH = 7 is below + 30 mV. 8 shows a combination of a cationic and two nonionic emulsifiers without an inventive one Fat was added. Example 10 shows that the combination of the ingredients according to the invention does not necessarily lead to dispersions with high zeta potential.

    Für alle Beispielzusammensetzungen gilt, daß die fehlenden Mengen bis 100 Gew.-% Wasser und geringe sonstige Bestandteile (Elektrolyte, Parfümöl, Hilfsstoffe etc.) bedeuten.For all example compositions, the missing amounts are up to 100% by weight of water and small amounts other components (electrolytes, perfume oil, auxiliaries, etc.).

    Beispiel 1example 1

  • 1,26 Gew.-% C16-18 Fettalkohol1.26% by weight of C 16-18 fatty alcohol
  • 0,70 Gew.-% Laurinsäuremethylester +12 EO0.70% by weight of methyl laurate +12 EO
  • 0,54 Gew.-% Bis-(palmytoyl)ethylhydroxyethyl-methylammonium-methosulfat0.54 wt% bis (palmytoyl) ethylhydroxyethyl methylammonium methosulfate

    • Beispiel 2Example 2

  • 5,00 Gew.-% Di-C16-18-alkyl-pentaerythritester5.00% by weight di-C 16-18 alkyl pentaerythritol ester
  • 0,36 Gew.-% Trimethyl-hexadecyl-ammoniumchlorid0.36% by weight trimethyl hexadecyl ammonium chloride
  • 0,30 Gew.-% C12-16-Fettalkohol-1,4-glykosid0.30 wt% C 12-16 fatty alcohol 1,4-glycoside

    • Beispiel 3Example 3

  • 7,70 Gew.-% Di-C16-18-alkyl-pentaerythritester7.70% by weight di-C 16-18 alkyl pentaerythritol ester
  • 0,82 Gew.-% Talgamin + 2 EO Addukt (Handelsprodukt Genamin® T 020, Fa. Hoechst)0.82% by weight tallow amine + 2 EO adduct (commercial product Genamin® T 020, Hoechst)
  • 1,25 Gew.-% Tris-(oligooxyethyl)-alkylammoniumphosphat1.25% by weight tris (oligooxyethyl) alkylammonium phosphate

    • Beispiel 4Example 4

  • 5,00 Gew.-% Di-C16-18-alkyl-pentaerythritester 5.00% by weight di-C 16-18 alkyl pentaerythritol ester
  • 1,08 Gew.-% Methyl-N-(2-hydroxyethyl)-N,N-di(talgacyloxyethyl)-ammonium-methosulfat1.08% by weight of methyl-N- (2-hydroxyethyl) -N, N-di (tallow acyloxyethyl) ammonium methosulfate
  • 0,56 Gew.-% Laurinsäuremethylester +12 EO0.56% by weight of methyl laurate +12 EO

    • Beispiel 5Example 5

  • 4,00 Gew.-% C16-18 Fettalkohol4.00% by weight of C 16-18 fatty alcohol
  • 1,35 Gew.-% Methyl-N-(2-hydroxyethyl)-N,N-di(talgacyloxyethyl)-ammonium-methosulfat1.35% by weight of methyl N- (2-hydroxyethyl) -N, N-di (tallow acyloxyethyl) ammonium methosulfate
  • 0,75 Gew.-% Laurinsäuremethylester +12 EO0.75% by weight of methyl laurate +12 EO

    • Beispiel 6Example 6

  • 4,00 Gew.-% Glycerin-mono-di-palmitat4.00% by weight glycerol mono-di-palmitate
  • 1,35 Gew.-% Methyl-N-(2-hydroxyethyl)-N,N-di(talgacyloxyethyl)-ammonium-methosulfat1.35% by weight of methyl N- (2-hydroxyethyl) -N, N-di (tallow acyloxyethyl) ammonium methosulfate
  • 0,90 Gew.-% Laurinsäuremethylester +12 EO0.90% by weight of methyl laurate +12 EO

    • Beispiel 7Example 7

  • 5,00 Gew.-% Di-C16-18-alkyl-pentaerythritester5.00% by weight di-C 16-18 alkyl pentaerythritol ester
  • 0,17 Gew.-% Methyl-N,N-bis(acyloxyethyl)-N-(2-hydroxyethyl)-ammonium-methosulfat0.17% by weight of methyl-N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate
  • 1,26 Gew.-% Laurinsäuremethylester +12 EO1.26% by weight of methyl laurate +12 EO

    • Beispiel 8Example 8

  • 2,50 Gew.-% C12-16-Fettalkohol-1,4-glykosid2.50% by weight of C 12-16 fatty alcohol 1,4-glycoside
  • 0,19 Gew.-% Methyl-N,N-bis(acyloxyethyl)-N-(2-hydroxyethyl)-ammonium-methosulfat0.19% by weight of methyl-N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate
  • 0,84 Gew.-% Laurinsäuremethylester +12 EO0.84% by weight of methyl laurate +12 EO

    • Beispiel 9Example 9

  • 4,50 Gew.-% Methyl-N-(2-hydroxyethyl)-N,N-di(talgacyloxyethyl)-ammonium-methosulfat4.50% by weight of methyl N- (2-hydroxyethyl) -N, N-di (tallow acyloxyethyl) ammonium methosulfate

    • Beispiel 10Example 10

  • 5,00 Gew.-% Di-C16-18-alkyl-pentaerythritester5.00% by weight di-C 16-18 alkyl pentaerythritol ester
  • 1,28 Gew.-% C12-18-Fettalkohol +7 EO1.28% by weight of C 12-18 fatty alcohol +7 EO
  • 0,82 Gew.-% Talgamin-2 EO-Addukt (Genamin® T 020, Fa. Hoechst)0.82% by weight of tallow amine-2 EO adduct (Genamin® T 020, Hoechst)
  • 0,50 Gew.-% Methyl-N-(2-hydroxyethyl)-N,N-di(talgacyloxyethyl)-ammonium-methosulfat0.50% by weight of methyl-N- (2-hydroxyethyl) -N, N-di (tallow acyloxyethyl) ammonium methosulfate
    • Zeta-Potential [mV]Zeta potential [mV] Zusammensetzungcomposition pH = 7pH = 7 pH = 8pH = 8 Notegrade 11 5252 5252 4,74.7 22 4141 3838 3,93.9 33 4242 3030 4,74.7 44 4545 4545 4,84.8 55 5252 4141 4,74.7 66 5252 4444 4,34.3 77 2424 2727 2,62.6 88th -35-35 -32-32 1,51.5 99 6565 6565 5,05.0 1010 2727 2323 3,53.5

    Claims (8)

    1. Fabric softeners in the form of an aqueous dispersion of a softening component, characterized in that the softening component consists of 0.5 to 20% by weight - based on the weight of the fabric softener - of at least one fat, fatty alcohol, wax or hydrocarbon solid at normal temperature (20°C) as a nonionic fatty compound and 0.2 to 10% by weight of a watersoluble and/or water-insoluble cationic emulsifier and 0 to 10% by weight of a nonionic emulsifier, the ratio by weight of fatty compound to emulsifiers being between 10:1 and 0.5:1 and the zeta potential of the aqueous dispersion at a pH value of 7 and a temperature of 25°C having to be at feast +30 mV.
    2. Fabric softeners as claimed in claim 1, characterized in that the water-insoluble nonionic fatty compound is selected from the group of fatty acid esters of C12-22 fatty acids with mono- or polyhydric C1-22 alcohols and C12-22 fatty acids and fatty alcohols and mixtures thereof.
    3. Fabric softeners as claimed in claim 1 or 2, characterized in that the fatty compound present is selected from mono- or diesters of fatty acids with pentaerythritol, monoesters and diesters of C12-18 fatty acids with glycerol or monoesters of C12-18 fatty acids with C12-18 fatty alcohols.
    4. Fabric softeners as claimed in any of claims 1 to 3, characterized in that the water-insoluble cationic emulsifiers is selected from the group of quaternary ammonium compounds corresponding to formula (I) or (II):
      Figure 00110001
      in which R is an acyclic alkyl group containing 12 to 24 carbon atoms, R1 is a saturated C1-4 alkyl or hydroxyalkyl group, R2 has the same meaning as R or R1, COR3 is an aliphatic acyl group containing 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R4 is H or OH, n has a value of 1, 2 or 3 and X is a halide, methosulfate or metophosphate ion, and mixtures of these compounds.
    5. Fabric softeners as claimed in any of claims 1 to 4, characterized in that the nonionic emulsifier is selected from the group of alkoxylated fatty acids containing 12 to 22 carbon atoms, alkoxylated fatty acid esters of fatty acids containing 12 to 22 carbon atoms with alcohols containing 1 to 10 carbon atoms, alkoxylated fatty alcohols containing 12 to 22 carbon atoms, the alkoxylated compounds having HLB values of 3 to 20, fatty acid amides and monoalkanolamides of C12-22 fatty acids with amines or alkanolamines containing 1 to 9 carbon atoms, alkyl glucosides or glucamides.
    6. Fabric softeners as claimed in any of claims 1 to 5, characterized in that the aqueous dispersion has a zeta potential of at least + 40 mV at pH 7 and at a temperature of 25°C.
    7. Fabric softeners as claimed in any of claims 1 to 6, characterized in that the aqueous dispersion has a zeta potential of at least + 25 mV at pH 8 and at a temperature of 25°C.
    8. Fabric softeners as claimed in any of claims 1 to 6, characterized in that the ratio by weight of fatty compound to emulsifier is between 1:1 and 8:1 and preferably between 2:1 and 6:1.
    EP97927127A 1996-06-14 1997-06-04 Aqueous laundry softening agent with high zeta potential Expired - Lifetime EP0920486B2 (en)

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    Cited By (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US8232239B2 (en) 2010-03-09 2012-07-31 Ecolab Usa Inc. Liquid concentrated fabric softener composition
    US8673838B2 (en) 2011-06-22 2014-03-18 Ecolab Usa Inc. Solid concentrated fabric softener composition
    US9150819B2 (en) 2007-06-15 2015-10-06 Ecolab Usa Inc. Solid fabric conditioner composition and method of use
    US9506015B2 (en) 2014-11-21 2016-11-29 Ecolab Usa Inc. Compositions to boost fabric softener performance

    Families Citing this family (16)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0919608A1 (en) * 1997-11-25 1999-06-02 The Procter & Gamble Company Use of a polyhydroxyfatty acid amide compound as a softening compound
    BR9904829A (en) * 1998-02-19 2000-05-23 Colgate Palmolive Co Fabric softener composition, dispersible in water, pourable and stable, and softening process to fabrics.
    US6057285A (en) * 1998-02-19 2000-05-02 Colgate-Palmolive Co. Stable rinse cycle fabric softener composition with GMS co-softener
    GB0014891D0 (en) * 2000-06-16 2000-08-09 Unilever Plc Fabric softening compositions
    US20020187911A1 (en) * 2001-03-05 2002-12-12 Goldschmist Chemical Company Viscosity and softening enhancement by low-solids rinse cycle fabric softeners based on quaternary ammonium compounds and amine ethoxylates
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    GB0213263D0 (en) * 2002-06-10 2002-07-17 Unilever Plc Improvements relating to fabric detergent compositions
    US8470756B2 (en) 2009-03-17 2013-06-25 S.C. Johnson & Son, Inc. Eco-friendly laundry pretreatment compositions
    US9688945B2 (en) 2014-11-21 2017-06-27 Ecolab Usa Inc. Compositions to boost fabric softener performance
    US9725679B2 (en) 2014-11-21 2017-08-08 Ecolab Usa Inc. Compositions to boost fabric softener performance
    EP3969555A1 (en) 2019-06-21 2022-03-23 Ecolab USA, Inc. Solid nonionic surfactant compositions
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    CN121712872A (en) 2023-08-21 2026-03-20 雷克特本克斯尔健康有限公司 Laundry disinfection and softening composition
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    Citations (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    GB1601359A (en) † 1977-05-30 1981-10-28 Procter & Gamble Textile treating composition
    US4320013A (en) † 1980-06-10 1982-03-16 The Procter & Gamble Company Fabric conditioning compositions
    WO1994019439A1 (en) † 1993-02-25 1994-09-01 Unilever Plc Use of fabric softening composition

    Family Cites Families (5)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE2733493C2 (en) * 1976-05-17 1986-11-13 Henkel KGaA, 4000 Düsseldorf Smoothing agent for textile fiber material
    GB1601360A (en) * 1977-07-12 1981-10-28 Procter & Gamble Textile treatment composition
    JP2688719B2 (en) * 1990-09-25 1997-12-10 ユシロ化学工業株式会社 Oil agent for fiber processing
    NO300383B1 (en) * 1991-09-06 1997-05-20 Colgate Palmolive Co softergent
    DE4437032A1 (en) * 1994-10-17 1996-04-18 Henkel Kgaa Textile softener concentrates

    Patent Citations (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    GB1601359A (en) † 1977-05-30 1981-10-28 Procter & Gamble Textile treating composition
    US4320013A (en) † 1980-06-10 1982-03-16 The Procter & Gamble Company Fabric conditioning compositions
    WO1994019439A1 (en) † 1993-02-25 1994-09-01 Unilever Plc Use of fabric softening composition

    Cited By (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US9150819B2 (en) 2007-06-15 2015-10-06 Ecolab Usa Inc. Solid fabric conditioner composition and method of use
    US8232239B2 (en) 2010-03-09 2012-07-31 Ecolab Usa Inc. Liquid concentrated fabric softener composition
    US8367601B2 (en) 2010-03-09 2013-02-05 Ecolab Usa Inc. Liquid concentrated fabric softener composition
    US8673838B2 (en) 2011-06-22 2014-03-18 Ecolab Usa Inc. Solid concentrated fabric softener composition
    US9388366B2 (en) 2011-06-22 2016-07-12 Ecolab Usa Inc. Solid concentrated fabric softener composition
    US9506015B2 (en) 2014-11-21 2016-11-29 Ecolab Usa Inc. Compositions to boost fabric softener performance

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