EP1849855A1 - thixotropic softening compositions - Google Patents

thixotropic softening compositions Download PDF

Info

Publication number
EP1849855A1
EP1849855A1 EP06113229A EP06113229A EP1849855A1 EP 1849855 A1 EP1849855 A1 EP 1849855A1 EP 06113229 A EP06113229 A EP 06113229A EP 06113229 A EP06113229 A EP 06113229A EP 1849855 A1 EP1849855 A1 EP 1849855A1
Authority
EP
European Patent Office
Prior art keywords
fabric softener
groups
viscosity
alkyl
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06113229A
Other languages
German (de)
French (fr)
Inventor
Ulrike Dr. Kottke
Michael Fender
Harald Dr. Jakob
Kurt Seidel
Ellen Reuter
Eberhard Esselborn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
Degussa GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Evonik Degussa GmbH, Degussa GmbH filed Critical Evonik Degussa GmbH
Priority to EP06113229A priority Critical patent/EP1849855A1/en
Priority to CNA2007800066882A priority patent/CN101389741A/en
Priority to EP07727773A priority patent/EP2010637A1/en
Priority to PCT/EP2007/053302 priority patent/WO2007125005A1/en
Priority to US12/226,636 priority patent/US20090124533A1/en
Publication of EP1849855A1 publication Critical patent/EP1849855A1/en
Withdrawn legal-status Critical Current

Links

Images

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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726—Polyurethanes

Definitions

  • the invention is directed to viscous aqueous fabric softeners.
  • Aqueous fabric softeners are usually added to the last rinse when washing laundry in a washing machine to give the laundry a softer feel.
  • Such fabric softeners usually contain fabric softening quaternary ammonium salts in an amount of 2 to 20% by weight as active components dispersed in an aqueous solution.
  • fabric softeners with a content of active components of up to 10% by weight generally have only a low viscosity and are therefore difficult to meter in the application.
  • consumers typically judge the effectiveness of a fabric softener by its viscosity and estimate a more highly viscous fabric softener to be more effective. Too high a viscosity, however, is undesirable because it results in the application to incomplete flushing in the washing machine. Therefore, there is a need for aqueous fabric softeners having an increased, precisely predetermined viscosity.
  • fabric softeners containing an oligomeric ester quat and a thickener selected from ethoxylated and / or propoxylated cellulose, ethoxylated and / or propoxylated C 10-15 fatty alcohol or an ethoxylated and / or propoxylated fatty alcohol polyurethane are known.
  • Suitable thickeners include the Accusol 880 TM polyurethane polymer marketed by Rohm and Haas.
  • Fabric softeners which contain a quaternary ammonium salt and a Fatty alcohol ethoxylate diurethane polymer as thickener.
  • Suitable thickeners mentioned are products of BASF with the code numbers 71495, 71496 and 71497.
  • the fabric softener during mixing and filling has a lower viscosity than the desired viscosity of the final product.
  • the viscosity of the fabric softener does not change during storage to allow quality control of the viscosity of the product produced during manufacture and to ensure that the quality of the product does not change during storage.
  • aqueous fabric softeners which contain a polyurethane thickener and have a reversibly thixotropic flow behavior.
  • the invention therefore relates to aqueous fabric softeners which comprise at least one textile softening quaternary ammonium salt and at least one polyurethane thickener and which have a reversibly thixotropic flow behavior.
  • Thixotropic flow behavior of a fabric softening agent means that the viscosity of the fabric softening agent decreases with a shear load and rises again after the end of the shear load.
  • a reversibly thixotropic flow behavior in the context of the invention is present when the viscosity of the Softener at a shear load decreases and after the end of the shear load within a short time, ie usually less than one hour, again rises to at least 90% of the initial value.
  • the fabric softeners according to the invention preferably have a quiescent viscosity in the linear viscoelastic range of more than 100 mPa.s, the viscosity being measured according to DIN 53019 in a rotary viscometer with cylinder geometry.
  • the linear-viscoelastic region is the region of small shear stresses in which the elastic component G 'of the complex shear modulus is independent of the shear stress.
  • the viscosity of these preferred fabric softeners decreases to less than 30% of the quiescent viscosity and rises again to more than 80% of the quiescent viscosity in less than 10 minutes after the end of the shear stress.
  • fabric softeners in which the viscosity at a shear stress with a shear stress of 30 Pa to less than 20% of the rest viscosity decreases and rises after the end of the shear stress in less than 10 minutes back to more than 90% of the rest viscosity.
  • the fabric softeners according to the invention preferably have a viscosity in the range from 200 to 3000 mPa ⁇ s, particularly preferably in the range from 400 to 1500 mPa ⁇ s.
  • Polyurethane thickeners in the context of the invention are thickening polymers in aqueous solution, their Polymer skeleton is obtained by polyaddition from diisocyanates and diols.
  • Such polyurethane thickeners and their preparation are known to those skilled in the art, for example from US 4,155,892 ,
  • the fabric softeners according to the invention preferably contain a polyurethane thickener, which is an addition product of a diisocyanate with a polyalkylene glycol, wherein the addition product carries at the chain ends in each case a C 14 -C 20 -alkyl radical.
  • the diisocyanate is preferably an aliphatic diisocyanate and is more preferably selected from hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethylene diisocyanate.
  • the polyalkylene glycol preferably comprises more than 80 mol% of ethylene oxide monomer units and preferably has a molecular weight of at least 3000 g / mol.
  • Quaternary ammonium salts with textile softening effect and their preparation are known to the person skilled in the art.
  • the fabric softeners according to the invention preferably contain quaternary ammonium salts of the formula (I) (I) R 2 4-m N + [(CH 2 ) n -QR 3 ] m X - wherein the groups R 2 independently of one another are C 1 -C 6 -alkyl, C 1 -C 6 -hydroxyalkyl or benzyl, the groups R 3 independently of one another are hydrogen or linear or branched C 11 -C 22 -alkyl or -alkenyl, where at least one of the radicals R 3 is not hydrogen, the groups Q are independently selected from groups of the formulas -OC (O) -, -C (O) O-, -NR 4 -C (O) -, -C (O) -NR 4 -, -OC (O ) -O-, -CHR 5 -OC (O) - or -CH (OCOR 3 ) -CH 2 -OC (O) -, wherein R
  • Chlorides, bromide, methylsulfate, ethylsulfate, sulfate and nitrate are particularly suitable anions suitable for fabric softeners.
  • R 2 is methyl
  • Q is -OC (O) - or -NH-C (O) -
  • m is 2 or 3
  • n 2 and X - chloride or methyl sulfate.
  • these compounds are used in the form of mixtures, compounds containing on average from 1.2 to 2.5 groups R 3 which are not hydrogen. More preferably, the proportion of non-hydrogen groups R 3 is on average 1.4 to 2.0, most preferably 1.6 to 1.9.
  • Preferred compounds of the formula (I) are quaternary ammonium salts of the formulas (II) to (IV) (II) R 6 N + [CH 2 CHR 8 OH] [CH 2 CHR 8 OC (O) R 7 ] 2 X - (III) R 6 2 N + [CH 2 CHR 8 OC (O) R 7 ] 2 X - (IV) R 6 N + [CH 2 CHR 8 OH] [CH 2 CH 2 NHC (O) R 7 ] 2 X - where the groups R 6 independently of one another are C 1 -C 6 -alkyl, C 1 -C 6 -hydroxyalkyl or benzyl, the groups R 7 are independently linear or branched C 11 -C 22 alkyl or alkenyl, and the groups R 8 are hydrogen or methyl.
  • the group -C (O) R 7 is preferably a fatty acid residue.
  • Suitable fatty acids are obtainable from natural triglycerides, preferably from tallow, vegetable oils, partially hydrogenated tallow or partially hydrogenated vegetable oils.
  • Suitable sources of triglycerides are, for example, soybean oil, tallow, partially hydrogenated tallow, palm oil, palm kernel oil, rapeseed oil, coconut oil, sunflower oil, corn oil, rice oil and tall oil.
  • the fatty acids from natural sources are usually mixtures of unbranched and branched, and saturated and unsaturated aliphatic fatty acids.
  • fatty acids obtained from various natural sources may be used in admixture.
  • the proportion of unsaturated fatty acid residues R 7 is preferably at least 10%, particularly preferably at least 25% and in particular 40% to 70%.
  • the proportion of polyunsaturated groups R 7 is preferably less than 10%, particularly preferably less than 5% and in particular less than 3%. If necessary, the proportion of polyunsaturated fatty acid residues can be reduced by partial hydrogenation to improve the storage stability of the product in terms of color change and odor development.
  • the proportion of unsaturated fatty acid residues is preferably in the range of an iodine value of from 5 to 150, particularly preferably 5 to 50.
  • the ratio of cis and trans isomers of the double bonds is preferably greater than 1: 1 and more preferably in the range of 4: 1 to 50: 1.
  • quaternary ammonium salts of the formulas (V) to (VII) (V) R 6 2 R 7 2 N + X - (VI) [R 7 -C (O) NHCH 2 CH 2 ] 2 N + R 6 [CH 2 CH 2 OH] X - wherein the radicals R 6 , R 7 and X have the same meaning as in the formulas (II) to (IV) and Q is -OC (O) - or -NH-C (O) -.
  • the aqueous fabric softeners according to the invention preferably contain one or more quaternary ammonium salts in a total amount of from 2 to 10% by weight, more preferably from 2 to 6% by weight, and one or more polyurethane thickeners in a total amount of from 0.001 to 2% by weight. %, more preferably 0.005 to 1 wt .-% and in particular 0.005 to 0.5 wt .-%.
  • aqueous fabric softeners according to the invention may additionally contain further additives which are known to the person skilled in the art for the formulation of fabric softeners, in particular those from US Pat US 6,737,392 Column 8, line 1 to column 14, line 6 known additives.
  • compositions of the prepared aqueous fabric softeners are shown in Table 1.
  • Table 1 Fabric Softening Compositions (The balance at 100% by weight is water, dye and perfume oil) example Rewoquat WE 18 [Wt .-%] Tego Visco Plus 3030 [Wt .-%] Accusol 880 [Wt .-%] Acrysol RM-8W [Wt .-%] Acrysol RM-825 [Wt .-%] 1 3 0.1 - - - 2 3 0.25 - - - 3 3 0.5 - - - * 4 3 - 0.17 - - 5 * 3 - 0.43 - - 6 * 3 - 0.86 - - 7 4 0.5 - - - 8th* 4 - 0.86 - - 9 * 4 - - 1.7 - 10 * 4 - - - 1.2 11 5 0.1 12 5 0.05 - - 13 5 0,025 - - - 14 * 5 - 0.
  • the thixotropic flow behavior was determined using a rotary viscometer model Stresstech from the manufacturer Reologica. The measurements were made with cylinder geometry by oscillating measurement at an oscillation frequency of 1 Hz in a measuring cup model 26.5 mm diameter EMB-Z3 using a model CC25 oscillating cylinder with 25 mm outer diameter. It was measured at 23 ° C immediately after 300 s at a shear stress of 0.2 Pa, 120 s at a shear stress of 30 Pa and 900 s at a shear stress of 0.2 Pa. Control measurements at the same frequency of oscillation at which the viscosity was determined as a function of the shear stress ensured that all samples were measured with a shear stress of 0.2 Pa in the linear viscoelastic region.
  • the viscosity was determined within 0.5 h after the preparation and after 12 weeks storage at room temperature. Viscosity was measured with a Brookfield viscometer at 20 ° C with spindle LVT # 2 at a rotational speed of 30 min -1 .
  • Table 3 Viscosity before and after 12 weeks storage example Viscosity after preparation [mPa s] Viscosity after storage [mPa s] viscosity change [%] 1 235 265 +13 2 410 420 + 2 3 510 560 +10 * 4 325 210 -35 5 * 345 280 -19 6 * 950 480 -49 11 745 880 +18 12 530 620 +17 13 375 340 - 9 14 * 760 300 -61 15 * 740 320 -57 16. * 430 265 -38 * not according to the invention
  • the fabric softeners according to the invention with a polyurethane thickener which causes a reversibly thixotropic flow behavior show a good stability of the viscosity, which changes little during storage over 12 weeks compared to the viscosity immediately after production.
  • a quality control after production it is possible with these fabric softeners to ensure that the product reaches the consumer with a predetermined viscosity.

Landscapes

  • 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)
  • Dispersion Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Aqueous soft detergent (I) comprises at least a textile softening quaternary ammonium salt and polyurethane thickener, where (I) exhibits a reversible thixotropic flow behavior.

Description

Die Erfindung richtet sich auf viskose wässrige Weichspülmittel.The invention is directed to viscous aqueous fabric softeners.

Wässrige Weichspülmittel werden üblicherweise beim Waschen von Wäsche in einer Waschmaschine dem letzten Spülgang zugesetzt, um der Wäsche einen weicheren Griff zu geben. Solche Weichspülmittel enthalten üblicherweise textilweichmachende quaternäre Ammoniumsalze in einer Menge von 2 bis 20 Gew.-% als aktive Komponenten, dispergiert in einer wässrigen Lösung. Ohne weitere Zusätze weisen Weichspülmittel mit einem Gehalt an aktive Komponenten von bis zu 10 Gew.-% meist nur eine geringe Viskosität auf und sind deshalb bei der Anwendung schlecht zu dosieren. Außerdem beurteilen Verbraucher die Wirksamkeit eines Weichspülmittels in der Regel nach dessen Viskosität und schätzen ein höher viskoses Weichspülmittel als wirksamer ein. Eine zu hohe Viskosität ist allerdings unerwünscht, da sie bei der Anwendung zu unvollständigem Einspülen in die Waschmaschine führt. Deshalb besteht ein Bedarf an wässrigen Weichspülmitteln mit einer erhöhten, genau vorherbestimmten Viskosität.Aqueous fabric softeners are usually added to the last rinse when washing laundry in a washing machine to give the laundry a softer feel. Such fabric softeners usually contain fabric softening quaternary ammonium salts in an amount of 2 to 20% by weight as active components dispersed in an aqueous solution. Without further additives, fabric softeners with a content of active components of up to 10% by weight generally have only a low viscosity and are therefore difficult to meter in the application. In addition, consumers typically judge the effectiveness of a fabric softener by its viscosity and estimate a more highly viscous fabric softener to be more effective. Too high a viscosity, however, is undesirable because it results in the application to incomplete flushing in the washing machine. Therefore, there is a need for aqueous fabric softeners having an increased, precisely predetermined viscosity.

Im Stand der Technik ist vorgeschlagen worden, die Viskosität eines wässrigen Weichspülmittels durch Zusatz von Verdickern zu erhöhen.In the prior art it has been proposed to increase the viscosity of an aqueous fabric softener by adding thickeners.

Aus EP 0 051 983 ist bekannt, die Viskosität von wässrigen Weichspülmitteln durch den Zusatz von nichtionischen oder schwach anionischen polymeren Verdickern zu erhöhen. Als geeignete Polymere sind modifizierte Cellulosen, Guar Gum und modififizierter Guar Gum, Polyacrylamide und Polyvinylacetate genannt. Mit 0,08 bis 0,3 Gew.-% Guar Gum wurden verdickte Weichspülmittel erhalten, deren Viskosität sich bei Lagerung bei 20°C nur wenig änderte. Guar Gum und modifizierte Cellulosen haben allerdings den Nachteil, dass sie vor der Herstellung des Weichspülmittels gequollen und aufgelöst werden müssen. In diesen Lösungen erfolgt leicht ein mikrobieller Abbau des Verdickers, der zu einer Abnahme der Viskosität führt. Deshalb lässt sich mit diesen Verdickern die Viskosität des fertigen Weichspülmittels nicht zuverlässig vorherbestimmen.Out EP 0 051 983 It is known to increase the viscosity of aqueous fabric softeners by the addition of nonionic or weakly anionic polymeric thickeners. When suitable polymers are modified celluloses, guar gum and modified guar gum, called polyacrylamides and polyvinyl acetates. With 0.08 to 0.3 wt .-% guar gum thickened fabric softeners were obtained whose viscosity changed only slightly when stored at 20 ° C. However, guar gum and modified celluloses have the disadvantage that they must be swollen and dissolved prior to the preparation of the fabric softener. In these solutions, microbial degradation of the thickener easily occurs, resulting in a decrease in viscosity. Therefore, the viscosity of the finished fabric softener can not be reliably predicted with these thickeners.

Aus EP 0 385 749 ist bekannt, die Viskosität von wässrigen Weichspülmitteln durch den Zusatz von hydrophob modifizierten nichtionischen Polymeren zu erhöhen, die eine hydrophile Kette aufweisen. Als geeignete Polymere sind hydrophob modifizierte Polyoxyalkylene oder Polyvinylalkohole genannt. In Beispiel 2 wird die Verdickung mit dem von Rohm und Haas vertriebenen Polyurethanpolymer Acrysol RM-825™ offenbart.Out EP 0 385 749 It is known to increase the viscosity of aqueous fabric softeners by the addition of hydrophobically modified nonionic polymers having a hydrophilic chain. Suitable polymers are hydrophobically modified polyoxyalkylenes or polyvinyl alcohols. Example 2 discloses thickening with the Acrysol RM-825 ™ polyurethane polymer marketed by Rohm and Haas.

Aus US 6,881,716 sind Weichspülmittel bekannt, die ein oligomeres Esterquat und einen Verdicker enthalten, der aus ethoxylierter und/oder propoxylierter Cellulose, ethoxyliertem und/oder propoxyliertem C10-15 Fettalkohol oder einem ethoxyliertem und/oder propoxyliertem Fettalkoholpolyurethan ausgewählt wird. Als geeigneter Verdicker wird das von Rohm und Haas vertriebene Polyurethanpolymer Accusol 880™ genannt.Out US 6,881,716 For example, fabric softeners containing an oligomeric ester quat and a thickener selected from ethoxylated and / or propoxylated cellulose, ethoxylated and / or propoxylated C 10-15 fatty alcohol or an ethoxylated and / or propoxylated fatty alcohol polyurethane are known. Suitable thickeners include the Accusol 880 ™ polyurethane polymer marketed by Rohm and Haas.

Aus WO 00/04118 sind Weichspülmittel bekannt, die ein quaternäres Ammoniumsalz und ein Fettalkoholethoxylatdiurethanpolymer als Verdicker enthalten. Als geeignete Verdicker werden Produkte von BASF mit den Codenummern 71495, 71496 und 71497 genannt.Out WO 00/04118 Fabric softeners are known which contain a quaternary ammonium salt and a Fatty alcohol ethoxylate diurethane polymer as thickener. Suitable thickeners mentioned are products of BASF with the code numbers 71495, 71496 and 71497.

Für die Herstellung der wässrigen Weichspülmittel ist es von Vorteil, wenn das Weichspülmittel während des Mischens und Abfüllens eine geringere Viskosität aufweist als die angestrebte Viskosität des Endprodukts. Außerdem ist es wünschenswert, dass sich die Viskosität des Weichspülmittels während der Lagerung nicht mehr verändert, damit bei der Herstellung eine Qualitätskontrolle der Viskosität des hergestellten Produkts erfolgen kann und sich die Qualität des Produkts während der Lagerung nicht mehr ändert.For the preparation of the aqueous fabric softeners, it is advantageous if the fabric softener during mixing and filling has a lower viscosity than the desired viscosity of the final product. In addition, it is desirable that the viscosity of the fabric softener does not change during storage to allow quality control of the viscosity of the product produced during manufacture and to ensure that the quality of the product does not change during storage.

Es wurde nun gefunden, dass sich diese Aufgaben durch wässrige Weichspülmittel lösen lassen, die einen Polyurethanverdicker enthalten und ein reversibel thixotropes Fließverhalten aufweisen.It has now been found that these objects can be achieved by aqueous fabric softeners which contain a polyurethane thickener and have a reversibly thixotropic flow behavior.

Gegenstand der Erfindung sind deshalb wässrige Weichspülmittel, die mindestens ein textilweichmachendes quaternäres Ammoniumsalz und mindestens einen Polyurethanverdicker enthalten und die ein reversibel thixotropes Fließverhalten aufweisen.The invention therefore relates to aqueous fabric softeners which comprise at least one textile softening quaternary ammonium salt and at least one polyurethane thickener and which have a reversibly thixotropic flow behavior.

Thixotropes Fließverhalten eines Weichspülmittels bedeutet, dass die Viskosität des Weichspülmittels bei einer Scherbelastung abnimmt und nach Ende der Scherbelastung wieder ansteigt. Ein reversibel thixotropes Fließverhalten im Sinne der Erfindung liegt vor, wenn die Viskosität des Weichspülmittels bei einer Scherbelastung abnimmt und nach Ende der Scherbelastung innerhalb von kurzer Zeit, d.h. in der Regel weniger als einer Stunde, wieder auf mindestens 90 % des Ausgangswerts ansteigt.Thixotropic flow behavior of a fabric softening agent means that the viscosity of the fabric softening agent decreases with a shear load and rises again after the end of the shear load. A reversibly thixotropic flow behavior in the context of the invention is present when the viscosity of the Softener at a shear load decreases and after the end of the shear load within a short time, ie usually less than one hour, again rises to at least 90% of the initial value.

Vorzugsweise weisen die erfindungsgemäßen Weichspülmittel eine Ruheviskosität im linear-viskoelastischen Bereich von mehr als 100 mPa·s auf, wobei die Viskosität nach DIN 53019 in einem Rotationsviskosimeter mit Zylindergeometrie gemessen wird. Der linear-viskoelastische Bereich ist dabei der Bereich kleiner Schubspannungen, in dem der elastische Anteil G' des komplexen Schubmoduls unabhängig von der Schubspannung ist. Bei einer Scherbelastung mit einer Schubspannung von 30 Pa nimmt die Viskosität dieser bevorzugten Weichspülmittel auf weniger als 30 % der Ruheviskosität ab und steigt nach Ende der Scherbelastung innerhalb von weniger als 10 Minuten wieder auf mehr als 80 % der Ruheviskosität an. Besonders bevorzugt sind Weichspülmittel, bei denen die Viskosität bei einer Scherbelastung mit einer Schubspannung von 30 Pa auf weniger als 20 % der Ruheviskosität abnimmt und nach Ende der Scherbelastung innerhalb von weniger als 10 Minuten wieder auf mehr als 90 % der Ruheviskosität ansteigt.The fabric softeners according to the invention preferably have a quiescent viscosity in the linear viscoelastic range of more than 100 mPa.s, the viscosity being measured according to DIN 53019 in a rotary viscometer with cylinder geometry. The linear-viscoelastic region is the region of small shear stresses in which the elastic component G 'of the complex shear modulus is independent of the shear stress. At a shear stress with a shear stress of 30 Pa, the viscosity of these preferred fabric softeners decreases to less than 30% of the quiescent viscosity and rises again to more than 80% of the quiescent viscosity in less than 10 minutes after the end of the shear stress. Particularly preferred are fabric softeners in which the viscosity at a shear stress with a shear stress of 30 Pa to less than 20% of the rest viscosity decreases and rises after the end of the shear stress in less than 10 minutes back to more than 90% of the rest viscosity.

Bei Bestimmung der Viskosität mit einem Brookfield-Viskosimeter (Spindel LVT Nr. 2, Rotationsgeschwindigkeit 30 min-1) weisen die erfindungsgemäßen Weichspülmittel vorzugsweise eine Viskosität im Bereich von 200 bis 3000 mPa·s auf, besonders bevorzugt im Bereich von 400 bis 1500 mPa·s.When determining the viscosity with a Brookfield viscometer (spindle LVT No. 2, rotational speed 30 min -1 ), the fabric softeners according to the invention preferably have a viscosity in the range from 200 to 3000 mPa · s, particularly preferably in the range from 400 to 1500 mPa · s.

Polyurethanverdicker im Sinn der Erfindung sind in wässriger Lösung verdickend wirkende Polymere, deren Polymergerüst durch Polyaddition aus Diisocyanaten und Diolen erhalten wird. Solche Polyurethanverdicker und deren Herstellung sind dem Fachmann aus dem Stand der Technik bekannt, beispielsweise aus US 4,155,892 .Polyurethane thickeners in the context of the invention are thickening polymers in aqueous solution, their Polymer skeleton is obtained by polyaddition from diisocyanates and diols. Such polyurethane thickeners and their preparation are known to those skilled in the art, for example from US 4,155,892 ,

Das Fließverhalten des Weichspülmittels wird im Wesentlichen durch die Struktur des Polyurethanverdickers bestimmt. Weitere Faktoren, die das Fließverhalten beeinflussen können, sind allerdings auch die Art und Menge der quaternären Ammoniumsalze, sowie die Art und Menge von weiteren Additiven, insbesondere von Salzen und sauren Komponenten. Falls mit einem Polyurethanverdicker bei der angestrebten Zusammensetzung des Weichspülmittels nicht das gewünschte reversibel thixotrope Fließverhalten erzielt wird, kann der Fachmann durch eine oder mehrere der folgenden Veränderungen an der Struktur des Polyurethanverdickers zu einem erfindungsgemäßen Weichspülmittel mit reversibel thixotropen Fließverhalten gelangen:

  • Einführung von zwei oder mehr Substituenten mit einem langkettigen Alkylrest in das Polyurethan.
  • Herstellung des Polyurethans aus einem sterisch weniger anspruchsvollen Diisocyanat.
  • Herstellung des Polyurethans aus einem Polyalkylenglykol mit höherem Molekulargewicht.
The flow behavior of the fabric softener is essentially determined by the structure of the polyurethane thickener. However, other factors which may influence the flow behavior are also the type and amount of the quaternary ammonium salts, as well as the type and amount of other additives, in particular of salts and acidic components. If the desired reversibly thixotropic flow behavior is not achieved with a polyurethane thickener in the desired composition of the fabric softener, the skilled person can arrive at a fabric softener according to the invention having reversibly thixotropic flow behavior by one or more of the following changes to the structure of the polyurethane thickener:
  • Introduction of two or more substituents with a long-chain alkyl radical into the polyurethane.
  • Preparation of the polyurethane from a sterically less demanding diisocyanate.
  • Production of the polyurethane from a higher molecular weight polyalkylene glycol.

Die erfindungsgemäßen Weichspülmittel enthalten vorzugsweise einen Polyurethanverdicker, der ein Additionsprodukt eines Diisocyanats mit einem Polyalkylenglykol ist, wobei das Additionsprodukt an den Kettenenden jeweils einen C14-C20-Alkylrest trägt. Das Diisocyanat ist vorzugsweise ein aliphatisches Diisocyanat und wird besonders bevorzugt ausgewählt aus Hexamethylendiisocyanat, Isophorondiisocyanat und Dicyclohexylmethylendiisocyanat. Das Polyalkylenglykol umfasst vorzugsweise mehr als 80 mol-% Ethylenoxid-Monomereinheiten und weist vorzugsweise ein Molekulargewicht von mindestens 3000 g/mol auf. Der Alkylrest ist an den Kettenenden vorzugsweise in Form einer Gruppe R1-NH-C(=O)O- verknüpft, wobei R1 der C14-C20-Alkylrest ist.The fabric softeners according to the invention preferably contain a polyurethane thickener, which is an addition product of a diisocyanate with a polyalkylene glycol, wherein the addition product carries at the chain ends in each case a C 14 -C 20 -alkyl radical. The diisocyanate is preferably an aliphatic diisocyanate and is more preferably selected from hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethylene diisocyanate. The polyalkylene glycol preferably comprises more than 80 mol% of ethylene oxide monomer units and preferably has a molecular weight of at least 3000 g / mol. The alkyl radical is preferably linked at the chain ends in the form of a group R 1 -NH-C (= O) O-, where R 1 is the C 14 -C 20 -alkyl radical.

Quaternäre Ammoniumsalze mit textilweichmachender Wirkung und deren Herstellung sind dem Fachmann aus dem Stand der Technik bekannt.Quaternary ammonium salts with textile softening effect and their preparation are known to the person skilled in the art.

Die erfindungsgemäßen Weichspülmittel enthalten vorzugsweise quaternäre Ammoniumsalze der Formel (I)

         (I)     R2 4-mN+[(CH2)n-Q-R3]m X-

worin die Gruppen R2 unabhängig voneinander C1-C6-Alkyl, C1-C6-Hydroxyalkyl oder Benzyl sind,
die Gruppen R3 unabhängig voneinander Wasserstoff oder lineares oder verzweigtes C11-C22-Alkyl oder -Alkenyl sind, wobei mindestens einer der Reste R3 nicht Wasserstoff ist,
die Gruppen Q unabhängig voneinander ausgewählt sind aus Gruppen der Formeln -O-C(O)-, -C(O)O-, -NR4-C(O)-, -C(O)-NR4-, -O-C(O)-O-, -CHR5-O-C(O)- oder -CH(OCOR3)-CH2-O-C(O)-, wobei R4 Wasserstoff, Methyl, Ethyl, Propyl oder Butyl ist und R5 Wasserstoff oder Methyl ist,
m von 1 bis 4 ist,
n von 1 bis 4 ist,
und X- ein für Weichspüler geeignetes Anion ist.The fabric softeners according to the invention preferably contain quaternary ammonium salts of the formula (I)

(I) R 2 4-m N + [(CH 2 ) n -QR 3 ] m X -

wherein the groups R 2 independently of one another are C 1 -C 6 -alkyl, C 1 -C 6 -hydroxyalkyl or benzyl,
the groups R 3 independently of one another are hydrogen or linear or branched C 11 -C 22 -alkyl or -alkenyl, where at least one of the radicals R 3 is not hydrogen,
the groups Q are independently selected from groups of the formulas -OC (O) -, -C (O) O-, -NR 4 -C (O) -, -C (O) -NR 4 -, -OC (O ) -O-, -CHR 5 -OC (O) - or -CH (OCOR 3 ) -CH 2 -OC (O) -, wherein R 4 is hydrogen, methyl, ethyl, propyl or butyl and R 5 is hydrogen or methyl is
m is from 1 to 4,
n is from 1 to 4,
and X - is an anion suitable for softener.

Für Weichspüler geeignete Anionen sind insbesondere Chlorid, Bromid, Methylsulfat, Ethylsulfat, Sulfat und Nitrat.Chlorides, bromide, methylsulfate, ethylsulfate, sulfate and nitrate are particularly suitable anions suitable for fabric softeners.

Besonders bevorzugt sind Verbindungen der Formel (I), in denen R2 Methyl ist, Q -O-C(O)- oder -NH-C(O)- ist, m = 2 oder 3 ist, n = 2 ist und X- Chlorid oder Methylsulfat ist. Vorzugsweise werden diese Verbindungen in Form von Mischungen verwendet, wobei Verbindungen im Mittel 1,2 bis 2,5 Gruppen R3 enthalten, die nicht Wasserstoff sind. Weiter bevorzugt beträgt der Anteil an Nicht-Wasserstoff-Gruppen R3 im Mittel 1,4 bis 2,0, am meisten bevorzugt 1,6 bis 1,9.Particularly preferred are compounds of formula (I) in which R 2 is methyl, Q is -OC (O) - or -NH-C (O) -, m is 2 or 3, n = 2 and X - chloride or methyl sulfate. Preferably, these compounds are used in the form of mixtures, compounds containing on average from 1.2 to 2.5 groups R 3 which are not hydrogen. More preferably, the proportion of non-hydrogen groups R 3 is on average 1.4 to 2.0, most preferably 1.6 to 1.9.

Bevorzugte Verbindungen der Formel (I) sind quaternäre Ammoniumsalze der Formeln (II) bis (IV)

         (II)     R6N+[CH2CHR8OH] [CH2CHR8OC(O)R7]2 X-

         (III)     R6 2N+[CH2CHR8OC(O)R7]2 X-

         (IV)     R6N+[CH2CHR8OH] [CH2CH2NHC(O)R7]2 X-

wobei die Gruppen R6 unabhängig voneinander C1-C6-Alkyl, C1-C6-Hydroxyalkyl oder Benzyl sind,
die Gruppen R7 unabhängig voneinander lineares oder verzweigtes C11-C22-Alkyl oder -Alkenyl sind, und
die Gruppen R8 Wasserstoff oder Methyl sind.Preferred compounds of the formula (I) are quaternary ammonium salts of the formulas (II) to (IV)

(II) R 6 N + [CH 2 CHR 8 OH] [CH 2 CHR 8 OC (O) R 7 ] 2 X -

(III) R 6 2 N + [CH 2 CHR 8 OC (O) R 7 ] 2 X -

(IV) R 6 N + [CH 2 CHR 8 OH] [CH 2 CH 2 NHC (O) R 7 ] 2 X -

where the groups R 6 independently of one another are C 1 -C 6 -alkyl, C 1 -C 6 -hydroxyalkyl or benzyl,
the groups R 7 are independently linear or branched C 11 -C 22 alkyl or alkenyl, and
the groups R 8 are hydrogen or methyl.

In diesen Formeln ist die Gruppe -C(O)R7 vorzugsweise ein Fettsäurerest. Geeignete Fettsäuren sind aus natürlichen Triglyceriden erhältlich, vorzugsweise aus Talg, Pflanzenölen, teilhydriertem Talg oder teilhydrierten Pflanzenölen. Geeignete Quellen für Triglyceride sind beispielsweise Sojaöl, Talg, teilhydrierter Talg, Palmöl, Palmkernöl, Rapsöl, Kokosnussöl, Sonnenblumenöl, Maisöl, Reisöl und Tallöl. Die Fettsäuren aus natürlichen Quellen sind in der Regel Mischungen von unverzweigten und verzweigten, sowie gesättigten und ungesättigten aliphatischen Fettsäuren. Um die Eigenschaften des Weichspülers, wie weich machende Wirkung und Rücknetzvermögen des behandelten Gewebes, einzustellen, können aus unterschiedlichen natürlichen Quellen erhaltene Fettsäuren in Mischung verwendet werden. Der Anteil an ungesättigten Fettsäureresten R7 beträgt vorzugsweise mindestens 10 %, besonders bevorzugt mindestens 25 % und insbesondere 40 % bis 70 %. Der Anteil an mehrfach ungesättigten Gruppen R7 beträgt vorzugsweise weniger als 10 %, besonders bevorzugt weniger als 5 % und insbesondere weniger als 3 %. Falls erforderlich kann der Anteil an mehrfachungesättigten Fettsäureresten durch eine Teilhydrierung verringert werden, um die Lagerstabilität des Produkts hinsichtlich Farbveränderung und Geruchsentwicklung zu verbessern. Der Anteil an ungesättigten Fettsäureresten, ausgedrückt als Iodzahl der freien Fettsäure, liegt vorzugsweise im Bereich einer Iodzahl von 5 bis 150, besonders bevorzugt 5 bis 50. In den ungesättigten Fettsäureresten ist Verhältnis von cis- und trans-Isomeren der Doppelbindungen vorzugsweise größer als 1:1 und besonders bevorzugt im Bereich von 4:1 bis 50:1.In these formulas, the group -C (O) R 7 is preferably a fatty acid residue. Suitable fatty acids are obtainable from natural triglycerides, preferably from tallow, vegetable oils, partially hydrogenated tallow or partially hydrogenated vegetable oils. Suitable sources of triglycerides are, for example, soybean oil, tallow, partially hydrogenated tallow, palm oil, palm kernel oil, rapeseed oil, coconut oil, sunflower oil, corn oil, rice oil and tall oil. The fatty acids from natural sources are usually mixtures of unbranched and branched, and saturated and unsaturated aliphatic fatty acids. In order to adjust the properties of the fabric conditioner, such as softening effect and back wetting properties of the treated fabric, fatty acids obtained from various natural sources may be used in admixture. The proportion of unsaturated fatty acid residues R 7 is preferably at least 10%, particularly preferably at least 25% and in particular 40% to 70%. The proportion of polyunsaturated groups R 7 is preferably less than 10%, particularly preferably less than 5% and in particular less than 3%. If necessary, the proportion of polyunsaturated fatty acid residues can be reduced by partial hydrogenation to improve the storage stability of the product in terms of color change and odor development. The proportion of unsaturated fatty acid residues, expressed as the iodine value of the free fatty acid, is preferably in the range of an iodine value of from 5 to 150, particularly preferably 5 to 50. In the unsaturated fatty acid residues, the ratio of cis and trans isomers of the double bonds is preferably greater than 1: 1 and more preferably in the range of 4: 1 to 50: 1.

Ebenfalls bevorzugt sind quaternäre Ammoniumsalze der Formeln (V) bis (VII)

         (V)     R6 2R7 2N+ X-

         (VI)     [R7-C(O)NHCH2CH2]2N+R6[CH2CH2OH] X-

Figure imgb0001
wobei die Reste R6, R7 and X die gleiche Bedeutung wie in den Formeln (II) bis (IV) haben und Q für -O-C(O)- oder -NH-C(O)- steht.Also preferred are quaternary ammonium salts of the formulas (V) to (VII)

(V) R 6 2 R 7 2 N + X -

(VI) [R 7 -C (O) NHCH 2 CH 2 ] 2 N + R 6 [CH 2 CH 2 OH] X -

Figure imgb0001
 wherein the radicals R 6 , R 7 and X have the same meaning as in the formulas (II) to (IV) and Q is -OC (O) - or -NH-C (O) -.

Die erfindungsgemäßen wässrigen Weichspülmittel enthalten vorzugsweise ein oder mehrere quaternäre Ammoniumsalze in einer Menge von insgesamt 2 bis 10 Gew.-%, besonders bevorzugt 2 bis 6 Gew.-%, und einen oder mehrere Polyurethanverdicker in einer Menge von insgesamt 0,001 bis 2 Gew.-%, besonders bevorzugt 0,005 bis 1 Gew.-% und insbesondere 0,005 bis 0,5 Gew.-%.The aqueous fabric softeners according to the invention preferably contain one or more quaternary ammonium salts in a total amount of from 2 to 10% by weight, more preferably from 2 to 6% by weight, and one or more polyurethane thickeners in a total amount of from 0.001 to 2% by weight. %, more preferably 0.005 to 1 wt .-% and in particular 0.005 to 0.5 wt .-%.

Die erfindungsgemäßen wässrigen Weichspülmittel können darüber hinaus noch weitere Additive enthalten, die dem Fachmann für die Formulierung von Weichspülmitteln bekannt sind, insbesondere die aus US 6,737,392 Spalte 8, Zeile 1 bis Spalte 14, Zeile 6 bekannten Additive.The aqueous fabric softeners according to the invention may additionally contain further additives which are known to the person skilled in the art for the formulation of fabric softeners, in particular those from US Pat US 6,737,392 Column 8, line 1 to column 14, line 6 known additives.

Die nachfolgenden Beispiele verdeutlichen die Erfindung, ohne jedoch deren Gegenstand zu beschränken.The following examples illustrate the invention, but without limiting its subject matter.

BeispieleExamples Herstellung der wässrigen WeichspülmittelPreparation of the aqueous fabric softeners

Bei 35°C wurde Wasser mit dem Farbstoff Sandolan Walkblau NBL 150 (Hersteller Clariant, 0,15 Gew.-% bezogen auf die Gesamtmenge an Weichspüler) vorgelegt. Unter Rühren mit 500 Umdrehungen/min wurde auf 50°C erwärmtes Rewoquat WE 18 (teilhydriertes Methyl-tris-(hydroxyethyl)-ammonium-di-talgfettsäureester-methosulfat, 90 Gew.-% in Isopropanol) in der angegebenen Menge zugegeben. Die erhaltene Dispersion wurde weitere 20 min mit 620 Umdrehungen/min gerührt. Danach wurde abgekühlt und bei 30°C 0,2 Gew.-% Parfumöl Skyline DW 10557 (Hersteller Symrise) zugegeben. Nach Abkühlen auf Raumtemperatur wurde das Verdickungsmittel zugegeben und die Dispersion 10 min bei 520 Umdrehungen/min gerührt.At 35 ° C water with the dye Sandolan Walk Blue NBL 150 (manufacturer Clariant, 0.15 wt .-% based on the total amount of fabric softener) was submitted. Rewoquat WE 18 (partially hydrogenated methyltris (hydroxyethyl) ammonium di tallow fatty acid methosulphate, 90% by weight in isopropanol) heated to 50 ° C. was added with stirring at 500 revolutions / min in the stated amount. The dispersion obtained was stirred for a further 20 minutes at 620 revolutions / min. It was then cooled and added at 30 ° C 0.2 wt .-% perfume oil Skyline DW 10557 (manufacturer Symrise). After cooling to room temperature, the thickener was added and the dispersion was stirred for 10 minutes at 520 rpm.

Folgende Verdickungsmittel wurden verwendet:

  • Tego Visco Plus 3030™ (Polyurethanverdicker, Polymergehalt 60 Gew.-%), Hersteller Degussa AG
  • Accusol 880™ (Polyurethanverdicker, Polymergehalt 35 Gew.-%), Hersteller Rohm und Haas
  • Acrysol RM-8W™, (Polyurethanverdicker, Polymergehalt 17,5 Gew.-%), Hersteller Rohm und Haas
  • Acrysol RM-825™, (Polyurethanverdicker, Polymergehalt 25 Gew.-%), Hersteller Rohm und Haas
The following thickeners were used:
  • Tego Visco Plus 3030 ™ (polyurethane thickener, polymer content 60% by weight), manufacturer Degussa AG
  • Accusol 880 ™ (polyurethane thickener, polymer content 35% by weight), manufacturer Rohm and Haas
  • Acrysol RM-8W ™ , (polyurethane thickener, polymer content 17.5% by weight), manufacturer Rohm and Haas
  • Acrysol RM-825 ™ , (polyurethane thickener, polymer content 25% by weight), manufacturer Rohm and Haas

Die Zusammensetzungen der hergestellten wässrigen Weichspülmittel sind in Tabelle 1 angeführt. Tabelle 1 Zusammensetzungen der Weichspülmittel (Der Rest zu 100 Gew.-% ist Wasser, Farbstoff und Parfumöl) Beispiel Rewoquat WE 18
[Gew.-%] Tego Visco Plus 3030
[Gew.-%] Accusol 880
[Gew.-%] Acrysol RM-8W
[Gew.-%] Acrysol RM-825
[Gew.-%] 1 3 0,1 - - - 2 3 0,25 - - - 3 3 0,5 - - - 4* 3 - 0,17 - - 5* 3 - 0,43 - - 6* 3 - 0,86 - - 7 4 0,5 - - - 8* 4 - 0,86 - - 9* 4 - - 1,7 - 10* 4 - - - 1,2 11 5 0,1 12 5 0,05 - - - 13 5 0,025 - - - 14* 5 - 0,17 - - 15* 5 - 0,085 - - 16* 5 - 0,043 - - * nicht erfindungsgemäß The compositions of the prepared aqueous fabric softeners are shown in Table 1. Table 1 Fabric Softening Compositions (The balance at 100% by weight is water, dye and perfume oil) example Rewoquat WE 18
[Wt .-%] Tego Visco Plus 3030
[Wt .-%] Accusol 880
[Wt .-%] Acrysol RM-8W
[Wt .-%] Acrysol RM-825
[Wt .-%] 1 3 0.1 - - - 2 3 0.25 - - - 3 3 0.5 - - - * 4 3 - 0.17 - - 5 * 3 - 0.43 - - 6 * 3 - 0.86 - - 7 4 0.5 - - - 8th* 4 - 0.86 - - 9 * 4 - - 1.7 - 10 * 4 - - - 1.2 11 5 0.1 12 5 0.05 - - - 13 5 0,025 - - - 14 * 5 - 0.17 - - 15 * 5 - 0.085 - - 16. * 5 - 0.043 - - * not according to the invention

Bestimmung des FließverhaltensDetermination of flow behavior

Das thixotrope Fließverhalten wurde mit einem Rotationsviskosimeter Modell Stresstech des Herstellers Reologica bestimmt. Die Messungen erfolgten mit Zylindergeometrie durch oszillierende Messung bei einer Oszillationsfrequenz von 1 Hz in einem Messbecher Modell EMB-Z3 mit 26,5 mm Inndurchmesser unter Verwendung eines oszillierenden Zylinders Modell CC25 mit 25 mm Außendurchmesser. Es wurde bei 23°C unmittelbar nacheinander 300 s bei einer Schubspannung von 0,2 Pa, 120 s bei einer Schubspannung von 30 Pa und 900 s bei einer Schubspannung von 0,2 Pa gemessen. Durch Kontrollmessungen bei der gleichen Oszillationsfrequenz, bei denen die Viskosität in Abhängigkeit von der Schubspannung bestimmt wurde, wurde sichergestellt, dass bei allen Proben die Messung mit einer Schubspannung von 0,2 Pa im linear-viskoelastischen Bereich erfolgte.The thixotropic flow behavior was determined using a rotary viscometer model Stresstech from the manufacturer Reologica. The measurements were made with cylinder geometry by oscillating measurement at an oscillation frequency of 1 Hz in a measuring cup model 26.5 mm diameter EMB-Z3 using a model CC25 oscillating cylinder with 25 mm outer diameter. It was measured at 23 ° C immediately after 300 s at a shear stress of 0.2 Pa, 120 s at a shear stress of 30 Pa and 900 s at a shear stress of 0.2 Pa. Control measurements at the same frequency of oscillation at which the viscosity was determined as a function of the shear stress ensured that all samples were measured with a shear stress of 0.2 Pa in the linear viscoelastic region.

Die Ergebnisse der Messungen sind in Tabelle 2 und Fig. 1 bis 4 wiedergegeben. Tabelle 2 Viskosität vor Scherbelastung (0-300 s), unter Scherbelastung** (300-420 s) und nach Scherbelastung (420-1200 s). Beispiel 7 Beispiel 8* Beispiel 9* Beispiel 10* t [s] Viskosität η [Pa s] 1 3,32 0,864 1,05 1,07 62 3,35 1,00 1,23 0,976 121 3,39 1,01 1,30 0,950 182 3,42 0,992 1,34 0,939 271 3,45 0,952 1,38 0,957 301** 0,211** 0,240** 0,269** 0,221** 362** 0,200** 0,236** 0,243** 0,218** 421 2,02 0,388 0,752 0,465 482 2,51 0,438 0,789 0,465 541 2,71 0,427 0,775 0,444 602 2,85 0,418 0,760 0,409 662 2,96 0,409 0,749 0,411 842 3,17 0,384 0,710 0,377 1020 3,32 0,368 0,689 0,362 1200 3,43 0,359 0,668 0,366 *nicht erfindungsgemäß

  • Fig. 1: Beispiel 7 (erfindungsgemäß)
  • Fig. 2: Beispiel 8 (nicht erfindungsgemäß)
  • Fig. 3: Beispiel 9 (nicht erfindungsgemäß)
  • Fig. 4: Beispiel 10 (nicht erfindungsgemäß)
The results of the measurements are shown in Table 2 and Figs. Table 2 Viscosity before shear stress (0-300 s), under shear ** (300-420 s) and after shear stress (420-1200 s). Example 7 Example 8 * Example 9 * Example 10 * t [s] Viscosity η [Pa s] 1 3.32 0,864 1.05 1.07 62 3.35 1.00 1.23 0,976 121 3.39 1.01 1.30 0.950 182 3.42 0.992 1.34 0.939 271 3.45 0,952 1.38 0.957 301 ** 0.211 ** 0.240 ** 0.269 ** 0.221 ** 362 ** 0.200 ** 0.236 ** 0.243 ** 0.218 ** 421 2.02 0.388 0.752 0,465 482 2.51 0.438 0.789 0,465 541 2.71 0.427 0.775 0.444 602 2.85 0.418 0,760 0.409 662 2.96 0.409 0.749 0.411 842 3.17 0.384 0,710 0.377 1020 3.32 0.368 0.689 0.362 1200 3.43 0.359 0.668 0,366 * not according to the invention
  • 1: Example 7 (according to the invention)
  • 2: Example 8 (not according to the invention)
  • 3: Example 9 (not according to the invention)
  • 4: Example 10 (not according to the invention)

Bestimmung der LagerstabilitätDetermination of storage stability

Zur Bestimmung der Lagerstabilität wurde die Viskosität innerhalb von 0,5 h nach der Herstellung und nach 12 Wochen Lagerung bei Zimmertemperatur bestimmt. Die Messung der Viskosität erfolgte mit einem Brookfield-Viskosimeter bei 20°C mit Spindel LVT Nr. 2 bei einer Rotationsgeschwindigkeit von 30 min-1.To determine the storage stability, the viscosity was determined within 0.5 h after the preparation and after 12 weeks storage at room temperature. Viscosity was measured with a Brookfield viscometer at 20 ° C with spindle LVT # 2 at a rotational speed of 30 min -1 .

Die Ergebnisse der Messungen sind in Tabelle 3 wiedergegeben. Tabelle 3 Viskosität vor und nach 12 Wochen Lagerung Beispiel Viskosität nach Herstellung
[mPa s] Viskosität nach Lagerung
[mPa s] Viskositätsänderung
[%] 1 235 265 +13 2 410 420 + 2 3 510 560 +10 4* 325 210 -35 5* 345 280 -19 6* 950 480 -49 11 745 880 +18 12 530 620 +17 13 375 340 - 9 14* 760 300 -61 15* 740 320 -57 16* 430 265 -38 *nicht erfindungsgemäß The results of the measurements are shown in Table 3. Table 3 Viscosity before and after 12 weeks storage example Viscosity after preparation
[mPa s] Viscosity after storage
[mPa s] viscosity change
[%] 1 235 265 +13 2 410 420 + 2 3 510 560 +10 * 4 325 210 -35 5 * 345 280 -19 6 * 950 480 -49 11 745 880 +18 12 530 620 +17 13 375 340 - 9 14 * 760 300 -61 15 * 740 320 -57 16. * 430 265 -38 * not according to the invention

Die erfindungsgemäßen Weichspülmittel mit einem Polyurethanverdicker, der ein reversibel thixotropes Fließverhalten bewirkt, zeigen eine gute Stabilität der Viskosität, die sich während einer Lagerung über 12 Wochen nur wenig gegenüber der Viskosität unmittelbar nach der Herstellung ändert. Durch eine Qualitätskontrolle nach der Produktion kann bei diesen Weichspülmitteln sicher gestellt werden, dass das Produkt den Verbraucher mit einer vorherbestimmten Viskosität erreicht. Die Weichspülmittel mit einem aus dem Stand der Technik bekannten Polyurethanverdicker, der kein reversibel thixotropes Fließverhalten bewirkt, zeigen während der Lagerung eine stärkere Veränderung der Viskosität. Bei ihnen kann nicht vorherbestimmt werden, mit welcher Viskosität das Produkt den Verbraucher erreicht.The fabric softeners according to the invention with a polyurethane thickener which causes a reversibly thixotropic flow behavior, show a good stability of the viscosity, which changes little during storage over 12 weeks compared to the viscosity immediately after production. By means of a quality control after production, it is possible with these fabric softeners to ensure that the product reaches the consumer with a predetermined viscosity. The fabric softeners with a known from the prior art polyurethane thickener, which does not cause reversible thixotropic flow behavior, show during storage a greater change in viscosity. They can not be predetermined with what viscosity the product reaches the consumer.

Claims (9)

Wässriges Weichspülmittel, enthaltend mindestens ein textilweichmachendes quaternäres Ammoniumsalz und mindestens einen Polyurethanverdicker,
dadurch gekennzeichnet,
dass das Weichspülmittel ein reversibel thixotropes Fließverhalten aufweist.Aqueous fabric softener, comprising at least one textile softening quaternary ammonium salt and at least one polyurethane thickener,
characterized,
that the fabric softening agent has a reversibly thixotropic flow behavior. Weichspülmittel nach Anspruch 1,
dadurch gekennzeichnet,
dass es eine Ruheviskosität im linear-viskoelastischen Bereich von mehr als 100 mPa·s aufweist, die Viskosität bei einer Schubspannung von 30 Pa auf weniger als 30 % der Ruheviskosität abnimmt und nach Ende der Scherbelastung innerhalb von weniger als 10 Minuten wieder auf mehr als 80 % der Ruheviskosität ansteigt, wobei die Viskositäten nach DIN 53019 in einem Rotationsviskosimeter mit Zylindergeometrie gemessen werden.Fabric softener according to claim 1,
characterized,
that it has a linear viscosity in the linear viscoelastic range of more than 100 mPa · s, the viscosity at a shear stress of 30 Pa to less than 30% of the quiescent viscosity decreases and after the end of the shear load in less than 10 minutes back to more than 80 % of the quiescent viscosity increases, wherein the viscosities are measured according to DIN 53019 in a rotary viscometer with cylinder geometry. Weichspülmittel nach Anspruch 1 oder 2,
dadurch gekennzeichnet,
dass das Polyurethan ein Additionsprodukt eines Diisocyanats mit einem Polyalkylenglykol ist, das an den Kettenenden jeweils einen C14-C20-Alkylrest trägt.Fabric softener according to claim 1 or 2,
characterized,
that the polyurethane is an addition product of a diisocyanate with a polyalkylene glycol, which carries 14 -C 20 alkyl group at the chain ends each have a C. Weichspülmittel nach Anspruch 3,
dadurch gekennzeichnet,
dass das Diisocyanat ausgewählt ist aus Hexamethylendiisocyanat, Isophorondiisocyanat und Dicyclohexylmethylendiisocyanat.Fabric softener according to claim 3,
characterized,
that the diisocyanate is selected from hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethylene. Weichspülmittel nach Anspruch 3 oder 4,
dadurch gekennzeichnet,
dass das Polyurethan an den Kettenenden jeweils eine Gruppe R1-NH-C(=O)O- trägt, wobei R1 ein C14-C20-Alkylrest ist.Fabric softener according to claim 3 or 4,
characterized,
that the polyurethane at the chain ends are each a group R 1 -NH-C (= O) O- carries, wherein R 1 is a C 14 -C 20 alkyl. Weichspülmittel nach einem der vorangehenden Ansprüche,
dadurch gekennzeichnet,
dass es ein quaternäres Ammoniumsalz der Formel (I)

         (I)     R2 4-mN+[(CH2)n-Q-R3]m X-

enthält,
worin die Gruppen R2 unabhängig voneinander C1-C6-Alkyl, C1-C6-Hydroxyalkyl oder Benzyl sind,
die Gruppen R3 unabhängig voneinander Wasserstoff oder lineares oder verzweigtes C11-C22-Alkyl oder -Alkenyl sind, wobei mindestens einer der Reste R3 nicht Wasserstoff ist,
die Gruppen Q unabhängig voneinander ausgewählt sind aus Gruppen der Formeln -O-C(O)-, -C(O)O-, -NR4-C(O)-, -C(O)-NR4-, -O-C(O)-O-, -CHR5-O-C(O)- oder -CH(OCOR3)-CH2-O-C(O)-, wobei R4 Wasserstoff, Methyl, Ethyl, Propyl oder Butyl ist und R5 Wasserstoff oder Methyl ist,
m von 1 bis 4 ist,
n von 1 bis 4 ist,
und X- ein für Weichspüler geeignetes Anion ist.Fabric softener according to one of the preceding claims,
characterized,
that it is a quaternary ammonium salt of the formula (I)

(I) R 2 4-m N + [(CH 2 ) n -QR 3 ] m X -

contains
wherein the groups R 2 independently of one another are C 1 -C 6 -alkyl, C 1 -C 6 -hydroxyalkyl or benzyl,
the groups R 3 independently of one another are hydrogen or linear or branched C 11 -C 22 -alkyl or -alkenyl, where at least one of the radicals R 3 is not hydrogen,
the groups Q are independently selected from groups of the formulas -OC (O) -, -C (O) O-, -NR 4 -C (O) -, -C (O) -NR 4 -, -OC (O ) -O-, -CHR 5 -OC (O) - or -CH (OCOR 3 ) -CH 2 -OC (O) -, wherein R 4 is hydrogen, methyl, ethyl, propyl or butyl and R 5 is hydrogen or methyl is
m is from 1 to 4,
n is from 1 to 4,
and X - is an anion suitable for softener. Weichspülmittel nach Anspruch 6,
dadurch gekennzeichnet,
dass in Formel (I) R2 Methyl ist, Q -O-C(O)- oder -NH-C(O)- ist, m = 2 oder 3 ist, n = 2 ist und X- Chlorid oder Methylsulfat ist.Fabric softener according to claim 6,
characterized,
that in formula (I) R 2 is methyl, Q is -OC (O) - or -NH-C (O) -, m is 2 or 3, n = 2 and X - is chloride or methyl sulfate. Weichspülmittel nach einem der Ansprüche 1 bis 5,
dadurch gekennzeichnet,
dass es ein quaternäres Ammoniumsalz ausgewählt aus Verbindungen der Formeln (II) bis (VII)

         (II)     R6N+[CH2CHR8OH] [CH2CHR8OC(O)R7]2X-

         (III)     R6 2N+[CH2CHR8OC(O)R7]2 X-

         (IV)     R6N+[CH2CHR8OH] [CH2CH2NHC(O)R7]2 X-

         (V)     R6 2R7 2N+ X-

         (VI)     [R7-C(O)NHCH2CH2]2N+R6[CH2CH2OH] X-

Figure imgb0002
 enthält,
wobei die Gruppen R6 unabhängig voneinander C1-C6-Alkyl, C1-C6-Hydroxyalkyl oder Benzyl sind,
die Gruppen R7 unabhängig voneinander lineares oder verzweigtes C11-C22-Alkyl oder -Alkenyl sind,
die Gruppen R8 Wasserstoff oder Methyl sind, Q -O-C (O) - oder -NH-C (O) - ist,
und X- ein für Weichspüler geeignetes Anion ist.Fabric softener according to one of claims 1 to 5,
characterized,
in that it is a quaternary ammonium salt selected from compounds of the formulas (II) to (VII)

(II) R 6 N + [CH 2 CHR 8 OH] [CH 2 CHR 8 OC (O) R 7 ] 2 X -

(III) R 6 2 N + [CH 2 CHR 8 OC (O) R 7 ] 2 X -

(IV) R 6 N + [CH 2 CHR 8 OH] [CH 2 CH 2 NHC (O) R 7 ] 2 X -

(V) R 6 2 R 7 2 N + X -

(VI) [R 7 -C (O) NHCH 2 CH 2 ] 2 N + R 6 [CH 2 CH 2 OH] X -

Figure imgb0002
 contains
where the groups R 6 independently of one another are C 1 -C 6 -alkyl, C 1 -C 6 -hydroxyalkyl or benzyl,
the groups R 7 independently of one another are linear or branched C 11 -C 22 -alkyl or -alkenyl,
the groups R 8 are hydrogen or methyl, Q is -OC (O) - or -NH-C (O) -,
and X - is an anion suitable for softener. Weichspülmittel nach einem der vorangehenden Ansprüche,
dadurch gekennzeichnet,
dass es quaternäre Ammoniumsalze in einer Menge von 2 bis 10 Gew.-% und Polyurethanverdicker in einer Menge von 0,001 bis 2 Gew.-% enthält.Fabric softener according to one of the preceding claims,
characterized,
that it contains quaternary ammonium salts in an amount of 2 to 10 wt .-% and polyurethane thickener in an amount of 0.001 to 2 wt .-%.
EP06113229A 2006-04-27 2006-04-27 thixotropic softening compositions Withdrawn EP1849855A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP06113229A EP1849855A1 (en) 2006-04-27 2006-04-27 thixotropic softening compositions
CNA2007800066882A CN101389741A (en) 2006-04-27 2007-04-04 Thixotropic softening compositions
EP07727773A EP2010637A1 (en) 2006-04-27 2007-04-04 Thixotropic softener
PCT/EP2007/053302 WO2007125005A1 (en) 2006-04-27 2007-04-04 Thixotropic softener
US12/226,636 US20090124533A1 (en) 2006-04-27 2007-04-04 Thixotropic Fabric Softeners

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP06113229A EP1849855A1 (en) 2006-04-27 2006-04-27 thixotropic softening compositions

Publications (1)

Publication Number Publication Date
EP1849855A1 true EP1849855A1 (en) 2007-10-31

Family

ID=37020563

Family Applications (2)

Application Number Title Priority Date Filing Date
EP06113229A Withdrawn EP1849855A1 (en) 2006-04-27 2006-04-27 thixotropic softening compositions
EP07727773A Withdrawn EP2010637A1 (en) 2006-04-27 2007-04-04 Thixotropic softener

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP07727773A Withdrawn EP2010637A1 (en) 2006-04-27 2007-04-04 Thixotropic softener

Country Status (4)

Country Link
US (1) US20090124533A1 (en)
EP (2) EP1849855A1 (en)
CN (1) CN101389741A (en)
WO (1) WO2007125005A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2746377A1 (en) * 2012-12-20 2014-06-25 The Procter & Gamble Company Improved structuring using an external structurant and a cosmotrope
WO2016009150A1 (en) * 2014-07-18 2016-01-21 Coatex Fabric softening composition comprising a heur thickener

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0512095D0 (en) * 2005-06-14 2005-07-20 Unilever Plc Fabric softening composition
US8361953B2 (en) * 2008-02-08 2013-01-29 Evonik Goldschmidt Corporation Rinse aid compositions with improved characteristics
BR112012025002B1 (en) 2010-04-01 2021-02-23 Evonik Operations Gmbh active fabric softener composition, and its preparation processes
ES2484719T3 (en) 2010-04-01 2014-08-12 Evonik Degussa Gmbh Active fabric softener composition
HUE033227T2 (en) 2010-04-28 2017-11-28 Evonik Degussa Gmbh Textile softening composition
US8507425B2 (en) 2010-06-29 2013-08-13 Evonik Degussa Gmbh Particulate fabric softener comprising ethylenediamine fatty acid amides and method of making
DE102010062156A1 (en) 2010-10-25 2012-04-26 Evonik Goldschmidt Gmbh Polysiloxanes with nitrogen-containing groups
DE102011078382A1 (en) 2011-06-30 2013-01-03 Evonik Goldschmidt Gmbh Microemulsion of quaternary ammonium group-containing polysiloxanes, their preparation and use
DE102011110100A1 (en) 2011-08-12 2013-02-14 Evonik Goldschmidt Gmbh Process for the preparation of polysiloxanes with nitrogen-containing groups
WO2013113453A1 (en) 2012-01-30 2013-08-08 Evonik Industries Ag Fabric softener active composition
BR112014027174B1 (en) 2012-05-07 2021-04-06 Evonik Degussa Gmbh ACTIVE COMPOSITION OF CLOTHING SOFTENER AND ITS MANUFACTURING METHOD
DE102013206175A1 (en) 2013-04-09 2014-10-09 Evonik Industries Ag Polysiloxane-polyether copolymers having amino and / or quaternary ammonium groups in the polyether part and process for their preparation
BR102014025172B1 (en) 2013-11-05 2020-03-03 Evonik Degussa Gmbh METHOD FOR MANUFACTURING A TRIS- (2-HYDROXYETHYL) -METHYLMETHYL ESTER OF FATTY ACID AND ACTIVE COMPOSITION OF SOFTENING CLOTHES
AU2014379659B2 (en) 2014-01-22 2017-06-22 Halliburton Energy Services, Inc. Clusters of micron-and nano-sized proppant for use in subterranean operations
FR3023845B1 (en) 2014-07-18 2018-01-05 Coatex Sas FABRIC SOFTENING COMPOSITION COMPRISING A HEAVY THICKENING.
EP2997958B1 (en) * 2014-09-22 2021-03-10 Evonik Operations GmbH Emulsion comprising liquid ester quats and polymer thickener
UA119182C2 (en) 2014-10-08 2019-05-10 Евонік Дегусса Гмбх ACTIVE FABRIC SOFTWARE
MX2019009454A (en) 2017-02-09 2019-11-05 Evonik Degussa Gmbh Polymers for hydrophobic and oelophobic textile finishing.
EP3679117B1 (en) 2017-09-06 2025-08-06 Evonik Operations GmbH Microemulsion comprising quaternary ammonium compound, especially for production of fabric softener formulations
CN111133089B (en) 2017-09-25 2021-09-28 赢创运营有限公司 Silicone-containing concentrate with improved storage stability and use thereof, preferably in textile care compositions
ES2936215T3 (en) 2018-07-05 2023-03-15 Evonik Operations Gmbh Active substances for highly viscous washing and cleaning formulations
JP2023051098A (en) * 2021-09-30 2023-04-11 ライオン株式会社 Liquid softener composition
JP2023051094A (en) * 2021-09-30 2023-04-11 ライオン株式会社 Liquid softener composition
JP2023051095A (en) * 2021-09-30 2023-04-11 ライオン株式会社 Liquid softener composition
JP2023051097A (en) * 2021-09-30 2023-04-11 ライオン株式会社 Liquid softener composition
JP2023051096A (en) * 2021-09-30 2023-04-11 ライオン株式会社 Liquid softener composition
WO2024011447A1 (en) 2022-07-13 2024-01-18 Evonik Operations Gmbh A fabric softener active composition for preparing a transparent fabric softener composition
WO2025036785A1 (en) 2023-08-17 2025-02-20 Evonik Operations Gmbh Active substances for cleaning compositions
WO2025036787A1 (en) 2023-08-17 2025-02-20 Evonik Operations Gmbh Active substances for cleaning compositions

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4155892A (en) * 1975-10-03 1979-05-22 Rohm And Haas Company Polyurethane thickeners for aqueous compositions
EP0385749A2 (en) * 1989-03-02 1990-09-05 Unilever Plc Fabric softening composition
DE9107984U1 (en) * 1991-06-28 1992-10-29 Joh. A. Benckiser Gmbh, 6700 Ludwigshafen Liquid, aqueous, viscous surfactant system
EP0799887A1 (en) * 1996-04-01 1997-10-08 The Procter & Gamble Company Fabric softener compositions
WO2000004118A1 (en) * 1998-07-20 2000-01-27 Colgate-Palmolive Fabric softening compositions containing diurethane polymer as a thickener
EP1295591A1 (en) * 2000-06-26 2003-03-26 Shiseido Company Limited Hair grooming preparation
US20040087472A1 (en) * 2002-11-01 2004-05-06 Jean-Paul Grandmaire Aqueous composition comprising oligomeric esterquats

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PH18436A (en) * 1980-11-07 1985-07-08 Unilever Nv A fabric softening composition and a process for preparing it
RU2330878C2 (en) * 2002-12-20 2008-08-10 Дегусса Аг Liquid detergent composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4155892A (en) * 1975-10-03 1979-05-22 Rohm And Haas Company Polyurethane thickeners for aqueous compositions
EP0385749A2 (en) * 1989-03-02 1990-09-05 Unilever Plc Fabric softening composition
DE9107984U1 (en) * 1991-06-28 1992-10-29 Joh. A. Benckiser Gmbh, 6700 Ludwigshafen Liquid, aqueous, viscous surfactant system
EP0799887A1 (en) * 1996-04-01 1997-10-08 The Procter & Gamble Company Fabric softener compositions
WO2000004118A1 (en) * 1998-07-20 2000-01-27 Colgate-Palmolive Fabric softening compositions containing diurethane polymer as a thickener
EP1295591A1 (en) * 2000-06-26 2003-03-26 Shiseido Company Limited Hair grooming preparation
US20040087472A1 (en) * 2002-11-01 2004-05-06 Jean-Paul Grandmaire Aqueous composition comprising oligomeric esterquats

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2746377A1 (en) * 2012-12-20 2014-06-25 The Procter & Gamble Company Improved structuring using an external structurant and a cosmotrope
WO2014099852A1 (en) * 2012-12-20 2014-06-26 The Procter & Gamble Company Improved structuring using an external structurant and a cosmotrope
WO2016009150A1 (en) * 2014-07-18 2016-01-21 Coatex Fabric softening composition comprising a heur thickener

Also Published As

Publication number Publication date
CN101389741A (en) 2009-03-18
WO2007125005A1 (en) 2007-11-08
EP2010637A1 (en) 2009-01-07
US20090124533A1 (en) 2009-05-14

Similar Documents

Publication Publication Date Title
EP1849855A1 (en) thixotropic softening compositions
EP1006176B1 (en) Low-concentrated highly viscous aqueous softener compositions
EP0675941B1 (en) Aqueous textile softener dispersions
EP2563889B1 (en) Textile softening composition
DE60316181T3 (en) Softener compositions containing a mixture of cationic polymers as thickeners
DE60012787T2 (en) Fabric softener compositions
EP1141189B1 (en) Clear softening agent formulations
DE602004008217T2 (en) Easily dispersible concentrated esterquat compositions
EP0920486A2 (en) Aqueous laundry softening agent with high zeta potential
DE69532508T2 (en) Fabric softening composition
EP0718275B1 (en) Quaternary fatty-acid triethanolamine esters
EP3818137B1 (en) Active substances for highly viscous washing and cleaning formulations
EP2582780B1 (en) Thickened fabric softener
DE60312204T3 (en) ESTERQUATED SOFT WATER CONCENTRATE WITH SPECIAL ESTER DISTRIBUTION AND ELECTROLYTE
EP0688356B1 (en) Aqueous textile softener compositions
DE3730444A1 (en) SOFTENER
DE69935337T2 (en) PLASTICISERS COMPOSITION
DE60016735T2 (en) USE OF ALKOXILY SUGAR STARTERS IN LIQUID AQUEOUS SOFTMAKER COMPOSITIONS
DE4405702A1 (en) Highly concentrated aqueous fabric softener with improved storage stability
EP2909294B1 (en) Fabric softener composition with trialkanolamine-based ester quat
DE4108025A1 (en) SOFT SOFTEN DETERGENT BASED ON QUATERNAEREN POLY (OXYALKYLEN) ALKANOLAMINE ESTERS
EP0747468A1 (en) Aqueous softeners for the treatment of textiles
EP1491617B1 (en) Aqueous pearlescent compositions
DE102022132709A1 (en) Fabric softener composition with polysaccharide
DE4242480A1 (en) Aqueous textile softener dispersions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20060427

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK DEGUSSA GMBH

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK DEGUSSA GMBH

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20080503