CA2533809C - Fabric conditioning compositions - Google Patents
Fabric conditioning compositions Download PDFInfo
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- CA2533809C CA2533809C CA2533809A CA2533809A CA2533809C CA 2533809 C CA2533809 C CA 2533809C CA 2533809 A CA2533809 A CA 2533809A CA 2533809 A CA2533809 A CA 2533809A CA 2533809 C CA2533809 C CA 2533809C
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- Prior art keywords
- phase
- composition according
- fabric softening
- composition
- cationic
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- 239000000203 mixture Substances 0.000 title claims abstract description 105
- 239000004744 fabric Substances 0.000 title claims abstract description 35
- 230000003750 conditioning effect Effects 0.000 title description 7
- 239000004902 Softening Agent Substances 0.000 claims abstract description 38
- 125000002091 cationic group Chemical group 0.000 claims abstract description 33
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 31
- 239000002562 thickening agent Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000008139 complexing agent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- -1 C22 fatty acids Chemical class 0.000 claims description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011630 iodine Substances 0.000 claims description 12
- 229910052740 iodine Inorganic materials 0.000 claims description 12
- 239000002979 fabric softener Substances 0.000 claims description 8
- 229920003086 cellulose ether Polymers 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 3
- 239000012634 fragment Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 14
- 125000003342 alkenyl group Chemical group 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- 238000009472 formulation Methods 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 8
- 239000003760 tallow Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 150000002191 fatty alcohols Chemical class 0.000 description 6
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 6
- 239000002304 perfume Substances 0.000 description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UMSVPCYSAUKCAZ-UHFFFAOYSA-N propane;hydrochloride Chemical compound Cl.CCC UMSVPCYSAUKCAZ-UHFFFAOYSA-N 0.000 description 4
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 150000003333 secondary alcohols Chemical class 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002194 fatty esters Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- OXGBCSQEKCRCHN-UHFFFAOYSA-N octadecan-2-ol Chemical compound CCCCCCCCCCCCCCCCC(C)O OXGBCSQEKCRCHN-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 150000001204 N-oxides Chemical class 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 101100020518 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) kyn-1 gene Proteins 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001153 anti-wrinkle effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229940096386 coconut alcohol Drugs 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002190 fatty acyls Chemical group 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- ACDUHTSVVVHMGU-UHFFFAOYSA-N hexadecan-3-ol Chemical compound CCCCCCCCCCCCCC(O)CC ACDUHTSVVVHMGU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- BTTMZEBIMDNSPK-UHFFFAOYSA-N icosan-4-ol Chemical compound CCCCCCCCCCCCCCCCC(O)CCC BTTMZEBIMDNSPK-UHFFFAOYSA-N 0.000 description 1
- WLIISNIPNDLIFS-UHFFFAOYSA-N icosan-5-ol Chemical compound CCCCCCCCCCCCCCCC(O)CCCC WLIISNIPNDLIFS-UHFFFAOYSA-N 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003445 sucroses Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
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
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
-
- 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
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)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Detergent Compositions (AREA)
Abstract
A liquid fabric softening composition comprising: i) an aqueous continuous phase; ii) a disperse phase comprising a cationic softening agent; iii) a nonionic surfactant; and iv) an associative thickener, wherein the disperse phase has a phase volume of 0.75 or less and the cationic softening agent comprises 5% or greater by weight of the total composition.
Description
FABRIC CONDITIONING COMPOSITIONS
Field of the Invention The present invention relates to fabric conditioning compositions. More specifically, the invention relates to thick and creamy fabric softening compositions comprising a softener of low phase volume and an associative thickener.
Background of the Invention It is well known to provide liquid fabric conditioning compositions that soften treated fabric, i.e. liquid fabric softeners. Such compositions are typically added to fabric in the rinse cycle of the wash process. Consumer preference is for liquid fabric softeners that are thick and creamy;
however, attaining this goal can lead to problems, particularly with regard to the dispensing and storage stability of the composition. It is often found that thick and creamy liquid softeners dispense poorly; this can lead to wasted product and, when used in automatic washing machines, messy residues being left the dispenser draw of the machine. A further problem associated with thick and creamy fabric softeners is poor storage stability, the desirable rheological properties of the composition being lost upon storage. A particularly common rheological problem is product thickening on storage, especially at elevated temperature or low temperature.
Field of the Invention The present invention relates to fabric conditioning compositions. More specifically, the invention relates to thick and creamy fabric softening compositions comprising a softener of low phase volume and an associative thickener.
Background of the Invention It is well known to provide liquid fabric conditioning compositions that soften treated fabric, i.e. liquid fabric softeners. Such compositions are typically added to fabric in the rinse cycle of the wash process. Consumer preference is for liquid fabric softeners that are thick and creamy;
however, attaining this goal can lead to problems, particularly with regard to the dispensing and storage stability of the composition. It is often found that thick and creamy liquid softeners dispense poorly; this can lead to wasted product and, when used in automatic washing machines, messy residues being left the dispenser draw of the machine. A further problem associated with thick and creamy fabric softeners is poor storage stability, the desirable rheological properties of the composition being lost upon storage. A particularly common rheological problem is product thickening on storage, especially at elevated temperature or low temperature.
EP 331,237 (Unilever, 1989) discloses liquid fabric softeners comprising thickening polymers that act as associative thickeners. However, this publication does not disclose compositions comprising 5% or greater of cationic softening agent having a phase structure adjusted by nonionic surfactant and having a phase volume of less than 0.75, nor does it suggest the benefits that such micro-structure can lead to in liquid softeners comprising cationic softening agent and associative thickener (vide infra).
Numerous publications disclose liquid fabric softeners comprising a cationic softening agent and a nonionic surfactant, an example being EP 523,922 B1 (Unilever, 1992).
WO 03/012019 (Unilever, 2002) also discloses associative thickener as an optional component; however, compositions comprising 5% or greater of cationic softening agent having a phase volume of less than 0.75 are not disclosed nor envisaged. WO 01/46360 (Unilever, 2000) discloses liquid fabric softeners comprising a cationic softening agent, a nonionic surfactant and an optional associative thickener;
however, this publication is also silent regarding systems comprising 5% or greater of cationic softening agent that have a phase volume of less than 0.75.
Objects of the Invention It is an object of the present invention to provide a fabric conditioning composition that appears thick and creamy and yet dispenses efficiently and gives a good degree of softness to treated fabrics. It is a further object of the present invention to provide a fabric conditioning composition having the aforementioned benefits and good storage stability.
Summary of the Invention According to a first aspect of the present invention, there is provided a liquid fabric softening composition comprising:
i). an aqueous continuous phase;
ii). a disperse phase comprising a cationic softening agent;
iii). a nonionic surfactant; and iv). an associative thickener, wherein the disperse phase has a phase volume of 0.75 or less and the cationic softening agent comprises 5% or greater by weight of the total composition.
According to a second aspect of the present invention, there is provided a method for the treatment of fabrics comprising contacting fabrics with a liquid fabric softening composition according to the first aspect of the invention or any of the particular variants thereof disclosed in the following description.
According to a third aspect of the present invention, there is provided a method for the manufacture of a liquid fabric softening composition comprising the steps of dispersing a cationic softening agent and a nonionic surfactant in an aqueous continuous phase, reducing the phase volume of the disperse phase, and using an associative thickener to thicken the composition, wherein the disperse phase is reduced to a phase volume of 0.75 or less and the cationic softening agent comprises 5% or greater of the total composition.
In the-context of the present invention, the term "comprising" means "including" and is non-exhaustive.
Detailed Description of the Invention The compositions of the invention are highly effective fabric softeners, having 5% or greater by weight of cationic softening agent present. They appear thick and creamy and yet have surprisingly good storage stability and dispensing efficiency, leaving little or no residue in the conditioner portion of the dispenser draw of a conventional automatic washing machine. It is believed that the combination of a disperse phase comprising 5% or greater cationic softening agent and a phase volume of 0.75 or less, an associative thickener, and a non-ionic surfactant leads to a product micro-structure that enables the above benefits to be attained. The product micro-structure is believed to comprise dispersed fragments of cationic softening agent, generally in lamellar phase, stabilised by nonionic surfactant and linked together, under low shear conditions (for example, at shear rates of from 2 to 20 /s), by the associative thickener.
The benefits given by the compositions of the invention relate to their rheological properties. At a shear rate relevant to the pouring of the composition from a bottle, it -is important that the composition appears thick and creamy -at such a shear rate, for example at 20 Is, the viscosity of the composition is preferably from 200 to 450 mPa.s. At lower shear rates such as 2 Is, which are believed to be 5 relevant to the dispensing of the formulation, the composition may have a viscosity as high as from 600 to 1100 mPa.s and yet still dispense efficiently. At higher shear rates, however, the composition will generally have a lower viscosity - at 106 Is it is preferred that the viscosity is from 90 to 200 mPa.s.
Throughout this specification it should be understood that all values requiring measurement, in particular viscosity values, relate to measurements made at 20 C and 1 atmosphere pressure.
By measuring the viscosity (ii) at a range of shear rates (y) it is possible to obtain a value for the infinite shear rate viscosity (71,,) of a composition by using the Sisco model:
11 = i1. + Kyn-1 where `K' is the consistency and `n' is the power law index.
The infinite shear rate viscosity may then be used to obtain a value for the phase volume (0) of a disperse phase within a composition as a whole by using a Kreigher-Dougherty equation:
'nom = 11c (l - 0/0m) -2 where plc is the viscosity of the continuous phase and 0m is the maximum volume fraction; the values of both of these terms can be equated to unity for the aqueous based liquid compositions of the present invention.
Details of the above equations and their usage may be found in basic rheology textbooks such as "Rheology for Chemists, An Introduction", by J. W. Goodwin and R. W. Hughes, published by the Royal Society of Chemists in 2000 and "Colloidal Dispersions" by W. B. Russel et al, published by Cambridge University Press in 1989.
The phase volume of the disperse phase may be thought of as the volume of the total composition occupied by the disperse phase at infinite shear rate. The compositions of the present invention have a phase volume of 0.75 or less. Only at such low phase volumes can the desired efficiency of dispensing be attained. The phase volume is preferably 0.70 or less. Fabric softening compositions comprising 5% or greater of cationic softening agent do not generally have such low phase volumes, unless induced by processing and/or the additives.
The cationic softening agent The cationic softening agent is typically a quaternary ammonium compound ("QAC"), in particular one having two C12_28 groups connected to the nitrogen head group that may independently be alkyl or alkenyl groups, preferably being connected to the nitrogen head group by at least one ester link, and more preferably by two ester links.
The average chain length of the alkyl and/or alkenyl groups is preferably at least C14 and more preferably at least C16.
It is particularly preferred that at least half of the groups have a chain length of C18. In general, the alkyl and/or alkenyl groups are predominantly linear.
A first group of QACs suitable for use in the present invention is represented by formula (I):
[(CH2)n(TR)]m R1-N+-[(CH2)n(OH)]3-m X (I) wherein each R is independently selected from a C5-35 alkyl or alkenyl group; R1 represents a C1_4 alkyl, C2_4 alkenyl or a C1_4 hydroxyalkyl group; T is generally 0-CO. (i.e. an ester group bound to R via its carbon atom), but may alternatively be C0.0 (i.e. an ester group bound to R via its oxygen atom); n is a number selected from 1 to 4; m is a number selected from 1, 2, or 3; and X is an anionic counter-ion, such as a halide or alkyl sulphate, e.g.
chloride or methylsulphate. Di-esters variants of formula I
(i.e. m = 2) are preferred and typically have mono- and tri-ester analogues associated with them. Such materials are particularly suitable for use in the present invention.
Numerous publications disclose liquid fabric softeners comprising a cationic softening agent and a nonionic surfactant, an example being EP 523,922 B1 (Unilever, 1992).
WO 03/012019 (Unilever, 2002) also discloses associative thickener as an optional component; however, compositions comprising 5% or greater of cationic softening agent having a phase volume of less than 0.75 are not disclosed nor envisaged. WO 01/46360 (Unilever, 2000) discloses liquid fabric softeners comprising a cationic softening agent, a nonionic surfactant and an optional associative thickener;
however, this publication is also silent regarding systems comprising 5% or greater of cationic softening agent that have a phase volume of less than 0.75.
Objects of the Invention It is an object of the present invention to provide a fabric conditioning composition that appears thick and creamy and yet dispenses efficiently and gives a good degree of softness to treated fabrics. It is a further object of the present invention to provide a fabric conditioning composition having the aforementioned benefits and good storage stability.
Summary of the Invention According to a first aspect of the present invention, there is provided a liquid fabric softening composition comprising:
i). an aqueous continuous phase;
ii). a disperse phase comprising a cationic softening agent;
iii). a nonionic surfactant; and iv). an associative thickener, wherein the disperse phase has a phase volume of 0.75 or less and the cationic softening agent comprises 5% or greater by weight of the total composition.
According to a second aspect of the present invention, there is provided a method for the treatment of fabrics comprising contacting fabrics with a liquid fabric softening composition according to the first aspect of the invention or any of the particular variants thereof disclosed in the following description.
According to a third aspect of the present invention, there is provided a method for the manufacture of a liquid fabric softening composition comprising the steps of dispersing a cationic softening agent and a nonionic surfactant in an aqueous continuous phase, reducing the phase volume of the disperse phase, and using an associative thickener to thicken the composition, wherein the disperse phase is reduced to a phase volume of 0.75 or less and the cationic softening agent comprises 5% or greater of the total composition.
In the-context of the present invention, the term "comprising" means "including" and is non-exhaustive.
Detailed Description of the Invention The compositions of the invention are highly effective fabric softeners, having 5% or greater by weight of cationic softening agent present. They appear thick and creamy and yet have surprisingly good storage stability and dispensing efficiency, leaving little or no residue in the conditioner portion of the dispenser draw of a conventional automatic washing machine. It is believed that the combination of a disperse phase comprising 5% or greater cationic softening agent and a phase volume of 0.75 or less, an associative thickener, and a non-ionic surfactant leads to a product micro-structure that enables the above benefits to be attained. The product micro-structure is believed to comprise dispersed fragments of cationic softening agent, generally in lamellar phase, stabilised by nonionic surfactant and linked together, under low shear conditions (for example, at shear rates of from 2 to 20 /s), by the associative thickener.
The benefits given by the compositions of the invention relate to their rheological properties. At a shear rate relevant to the pouring of the composition from a bottle, it -is important that the composition appears thick and creamy -at such a shear rate, for example at 20 Is, the viscosity of the composition is preferably from 200 to 450 mPa.s. At lower shear rates such as 2 Is, which are believed to be 5 relevant to the dispensing of the formulation, the composition may have a viscosity as high as from 600 to 1100 mPa.s and yet still dispense efficiently. At higher shear rates, however, the composition will generally have a lower viscosity - at 106 Is it is preferred that the viscosity is from 90 to 200 mPa.s.
Throughout this specification it should be understood that all values requiring measurement, in particular viscosity values, relate to measurements made at 20 C and 1 atmosphere pressure.
By measuring the viscosity (ii) at a range of shear rates (y) it is possible to obtain a value for the infinite shear rate viscosity (71,,) of a composition by using the Sisco model:
11 = i1. + Kyn-1 where `K' is the consistency and `n' is the power law index.
The infinite shear rate viscosity may then be used to obtain a value for the phase volume (0) of a disperse phase within a composition as a whole by using a Kreigher-Dougherty equation:
'nom = 11c (l - 0/0m) -2 where plc is the viscosity of the continuous phase and 0m is the maximum volume fraction; the values of both of these terms can be equated to unity for the aqueous based liquid compositions of the present invention.
Details of the above equations and their usage may be found in basic rheology textbooks such as "Rheology for Chemists, An Introduction", by J. W. Goodwin and R. W. Hughes, published by the Royal Society of Chemists in 2000 and "Colloidal Dispersions" by W. B. Russel et al, published by Cambridge University Press in 1989.
The phase volume of the disperse phase may be thought of as the volume of the total composition occupied by the disperse phase at infinite shear rate. The compositions of the present invention have a phase volume of 0.75 or less. Only at such low phase volumes can the desired efficiency of dispensing be attained. The phase volume is preferably 0.70 or less. Fabric softening compositions comprising 5% or greater of cationic softening agent do not generally have such low phase volumes, unless induced by processing and/or the additives.
The cationic softening agent The cationic softening agent is typically a quaternary ammonium compound ("QAC"), in particular one having two C12_28 groups connected to the nitrogen head group that may independently be alkyl or alkenyl groups, preferably being connected to the nitrogen head group by at least one ester link, and more preferably by two ester links.
The average chain length of the alkyl and/or alkenyl groups is preferably at least C14 and more preferably at least C16.
It is particularly preferred that at least half of the groups have a chain length of C18. In general, the alkyl and/or alkenyl groups are predominantly linear.
A first group of QACs suitable for use in the present invention is represented by formula (I):
[(CH2)n(TR)]m R1-N+-[(CH2)n(OH)]3-m X (I) wherein each R is independently selected from a C5-35 alkyl or alkenyl group; R1 represents a C1_4 alkyl, C2_4 alkenyl or a C1_4 hydroxyalkyl group; T is generally 0-CO. (i.e. an ester group bound to R via its carbon atom), but may alternatively be C0.0 (i.e. an ester group bound to R via its oxygen atom); n is a number selected from 1 to 4; m is a number selected from 1, 2, or 3; and X is an anionic counter-ion, such as a halide or alkyl sulphate, e.g.
chloride or methylsulphate. Di-esters variants of formula I
(i.e. m = 2) are preferred and typically have mono- and tri-ester analogues associated with them. Such materials are particularly suitable for use in the present invention.
Especially preferred agents are di-esters of triethanolammonium methylsulphate, otherwise referred to as "TEA ester quats.". Commercial examples include Prapagen TQL, ex Clariant, and Tetranyl AHT-l, ex Kao, (both di-[hardened tallow ester] of triethanolammonium methylsulphate), AT-7-1-(di-[tallow ester] of triethanolammonium methylsulphate), and L5/90 (di-[palm ester] of triethanolammonium methylsulphate), both ex Kao, and Rewoquat WE15 (a di-ester of triethanolammonium methylsulphate having fatty acyl residues deriving from C10-C20 and C16-C18 unsaturated fatty acids), ex Witco Corporation.
The second group of QACs suitable for use in the invention is represented by formula (II):
(R1)3N+-(CH2)n-CH-TR2 X (II) wherein each R1 group is independently selected from C1-4 alkyl, hydroxyalkyl or C2_4 alkenyl groups; and wherein each R2 group is independently selected from C8-28 alkyl or alkenyl groups; and wherein n, T, and X are as defined above.
Preferred materials of this second group include 1,2 bis[tallowoyloxy]-3-trimethylammonium propane chloride, 1,2 bis[hardened tallowoyloxy]-3-trimethylammonium propane chloride, 1,2-bis[oleoyloxy]-3-trimethylammonium propane chloride, and 1,2 bis[stearoyloxy]-3-trimethylammonium propane chloride. Such materials are described in US 4,137,180 (Lever Brothers). Preferably, these materials also comprise an amount. of the corresponding mono-ester.
A third group'of QACs suitable for use in the invention is represented by formula (III):
(R1)2-N+-[(CH2)n-T-R2]2 X (III) wherein each R1 group is independently selected from C1-4 alkyl, or C2_4 alkenyl groups; and wherein each R2 group is independently selected from C8-28 alkyl or alkenyl groups;
and n, T, and X are as defined above. Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride and hardened versions thereof.
A fourth group of QACs suitable for use in the invention is represented by formula (IV):
(R1)2-N+-(R2)2 X_ (IV) wherein each R1 group is independently selected from C1-4 alkyl, or C2_4 alkenyl groups; and wherein each R2 group is independently selected from C8_28 alkyl or alkenyl groups;
The second group of QACs suitable for use in the invention is represented by formula (II):
(R1)3N+-(CH2)n-CH-TR2 X (II) wherein each R1 group is independently selected from C1-4 alkyl, hydroxyalkyl or C2_4 alkenyl groups; and wherein each R2 group is independently selected from C8-28 alkyl or alkenyl groups; and wherein n, T, and X are as defined above.
Preferred materials of this second group include 1,2 bis[tallowoyloxy]-3-trimethylammonium propane chloride, 1,2 bis[hardened tallowoyloxy]-3-trimethylammonium propane chloride, 1,2-bis[oleoyloxy]-3-trimethylammonium propane chloride, and 1,2 bis[stearoyloxy]-3-trimethylammonium propane chloride. Such materials are described in US 4,137,180 (Lever Brothers). Preferably, these materials also comprise an amount. of the corresponding mono-ester.
A third group'of QACs suitable for use in the invention is represented by formula (III):
(R1)2-N+-[(CH2)n-T-R2]2 X (III) wherein each R1 group is independently selected from C1-4 alkyl, or C2_4 alkenyl groups; and wherein each R2 group is independently selected from C8-28 alkyl or alkenyl groups;
and n, T, and X are as defined above. Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride and hardened versions thereof.
A fourth group of QACs suitable for use in the invention is represented by formula (IV):
(R1)2-N+-(R2)2 X_ (IV) wherein each R1 group is independently selected from C1-4 alkyl, or C2_4 alkenyl groups; and wherein each R2 group is independently selected from C8_28 alkyl or alkenyl groups;
and X is as defined above. Preferred materials of this fourth group include di(hardened tallow) dimethylammonium chloride.
The iodine value of the softening agent is preferably from 0 to 20, more preferably from 0 to 4, and most preferably from 0 to 2. Essentially saturated material, i.e. having an iodine value of from 0 to 1, is used in especially high performing compositions. At low iodine values, the softening performance is excellent and the composition has improved resistance to oxidation and associated odour problems upon storage. To optimise the properties of compositions having agents of low iodine value, it is preferred that the level and nature of the nonionic surfactant are carefully selected (vide infra).
Iodine value is defined as the number of grams of iodine absorbed per 100 g of test material. NMR spectroscopy is a suitable technique for determining the iodine value of the softening agents of the present invention, using the method described in Anal. Chem., 34, 1136 (1962) by Johnson and Shoolery and in EP 593,542 (Unilever, 1993).
The softening agent is present in the compositions of the invention at a level of 5% or greater by weight of the total composition. For even greater softening effect, this level may be 8% or greater;. whilst for particularly high performance, this level may be 11% or greater. At these higher concentrations, which are also desirable for supply chain and environmental reasons, the low dispenser residues found with the compositions of the present invention is particularly relevant and unexpected.
For ease of formulation, the amount of softening agent is generally 50% or less, particularly 40% or less, and especially 30% or less by weight of the total composition.
The nonionic surfactant Suitable nonionic surfactants include alkoxylated materials, particularly addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines.
Preferred materials are of the general formula:
R-Y-(CH2CH20)zH
Where R is a hydrophobic moiety, typically being an alkyl or alkenyl group, said group being linear or branched, primary or secondary, and preferably having from 8 to 25, more preferably 10 to 20, and most preferably 10 to 18 carbon atoms; R may also be an aromatic group, such as a phenolic group, substituted by an alkyl or alkenyl group as described above; Y is a linking group, typically being 0, C0.0, or CO.N(R1), where R1 is H or a C1-4 alkyl group; and z represents the average number of ethoxylate (E0) units present, said number being 8 or more, preferably 10 or more, and most preferably 15 to 30.
The iodine value of the softening agent is preferably from 0 to 20, more preferably from 0 to 4, and most preferably from 0 to 2. Essentially saturated material, i.e. having an iodine value of from 0 to 1, is used in especially high performing compositions. At low iodine values, the softening performance is excellent and the composition has improved resistance to oxidation and associated odour problems upon storage. To optimise the properties of compositions having agents of low iodine value, it is preferred that the level and nature of the nonionic surfactant are carefully selected (vide infra).
Iodine value is defined as the number of grams of iodine absorbed per 100 g of test material. NMR spectroscopy is a suitable technique for determining the iodine value of the softening agents of the present invention, using the method described in Anal. Chem., 34, 1136 (1962) by Johnson and Shoolery and in EP 593,542 (Unilever, 1993).
The softening agent is present in the compositions of the invention at a level of 5% or greater by weight of the total composition. For even greater softening effect, this level may be 8% or greater;. whilst for particularly high performance, this level may be 11% or greater. At these higher concentrations, which are also desirable for supply chain and environmental reasons, the low dispenser residues found with the compositions of the present invention is particularly relevant and unexpected.
For ease of formulation, the amount of softening agent is generally 50% or less, particularly 40% or less, and especially 30% or less by weight of the total composition.
The nonionic surfactant Suitable nonionic surfactants include alkoxylated materials, particularly addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines.
Preferred materials are of the general formula:
R-Y-(CH2CH20)zH
Where R is a hydrophobic moiety, typically being an alkyl or alkenyl group, said group being linear or branched, primary or secondary, and preferably having from 8 to 25, more preferably 10 to 20, and most preferably 10 to 18 carbon atoms; R may also be an aromatic group, such as a phenolic group, substituted by an alkyl or alkenyl group as described above; Y is a linking group, typically being 0, C0.0, or CO.N(R1), where R1 is H or a C1-4 alkyl group; and z represents the average number of ethoxylate (E0) units present, said number being 8 or more, preferably 10 or more, and most preferably 15 to 30.
Preferably the nonionic surfactant has an HLB of from 7 to 20, more preferably from 10 to 20, and most preferably from 15 to 20.
Examples of suitable nonionic surfactants include the ethoxylates of mixed natural or synthetic alcohols in the "coco" or "tallow" chain length. Preferred materials are condensation products of coconut fatty alcohol with 15-20 moles of ethylene oxide and condensation products of tallow fatty alcohol with 10-20 moles of ethylene oxide.
The ethoxylates of secondary alcohols such as 3-hexadecanol, 2-octadecanol, 4-eicosanol, and 5-eicosanol may also be used. Exemplary ethoxylated secondary alcohols have formulae C12-EO (20) ; C14-EO (20) ; C14-EO (25) ; and C16-EO (30) .
Polyol-based nonionic surfactants may also be used, examples including sucrose esters (such as sucrose monooleate), alkyl polyglucosides (such as stearyl monoglucoside and stearyl triglucoside), and alkyl polyglycerols.
A particular nonionic surfactant may be useful in the present compositions alone or in combination with other nonionic surfactants. The preferred amounts of nonionic surfactant indicated below refer to the total amount of such materials that are present in the composition.
The nonionic surfactant is present in an amount from 0.05 to 10%, more preferably 0.1 to 5%, and most preferably 0.35 to 3.5%, based on the total weight of the composition.
Examples of suitable nonionic surfactants include the ethoxylates of mixed natural or synthetic alcohols in the "coco" or "tallow" chain length. Preferred materials are condensation products of coconut fatty alcohol with 15-20 moles of ethylene oxide and condensation products of tallow fatty alcohol with 10-20 moles of ethylene oxide.
The ethoxylates of secondary alcohols such as 3-hexadecanol, 2-octadecanol, 4-eicosanol, and 5-eicosanol may also be used. Exemplary ethoxylated secondary alcohols have formulae C12-EO (20) ; C14-EO (20) ; C14-EO (25) ; and C16-EO (30) .
Polyol-based nonionic surfactants may also be used, examples including sucrose esters (such as sucrose monooleate), alkyl polyglucosides (such as stearyl monoglucoside and stearyl triglucoside), and alkyl polyglycerols.
A particular nonionic surfactant may be useful in the present compositions alone or in combination with other nonionic surfactants. The preferred amounts of nonionic surfactant indicated below refer to the total amount of such materials that are present in the composition.
The nonionic surfactant is present in an amount from 0.05 to 10%, more preferably 0.1 to 5%, and most preferably 0.35 to 3.5%, based on the total weight of the composition.
When the softening agent has an iodine value from 0 to 20, particularly from 0 to 4 and especially from 0 to 2, it is preferred that nonionic surfactant having an HLB of 15-20 is present at a level of 0.05% or greater, more preferably 0.1%
or greater, and most preferably 0.35% or greater, based on the total weight of the composition.
The associative thickener An associative thickener is an essential component of the compositions of the invention, serving to promote the desired thick and creamy appearance. Suitable associative thickeners may be selected from hydrophobically modified cellulose ethers, as described in GB 2,043,646 (Hercules) and disclosed in fabric conditioning compositions in EP
331,237 B1 (Unilever). Such materials are typically nonionic polymers and have a sufficient degree of nonionic substitution selected from the class consisting of methyl, hydroxyethyl and hydroxypropyl to cause them to be water-soluble and which are further substituted with one or more hydrocarbon radicals having from 10 to 24 carbon atoms, in an amount from 0.2% by weight to an amount which renders the cellulose ether less than 1% by weight soluble in water.
The nonionic cellulose ether that forms the `backbone' of the hydrophobically modified derivative may be any nonionic water soluble cellulose ether substrate, such as hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose or methyl hydroxyethyl cellulose.
The preferred `backbone' is HEC.
or greater, and most preferably 0.35% or greater, based on the total weight of the composition.
The associative thickener An associative thickener is an essential component of the compositions of the invention, serving to promote the desired thick and creamy appearance. Suitable associative thickeners may be selected from hydrophobically modified cellulose ethers, as described in GB 2,043,646 (Hercules) and disclosed in fabric conditioning compositions in EP
331,237 B1 (Unilever). Such materials are typically nonionic polymers and have a sufficient degree of nonionic substitution selected from the class consisting of methyl, hydroxyethyl and hydroxypropyl to cause them to be water-soluble and which are further substituted with one or more hydrocarbon radicals having from 10 to 24 carbon atoms, in an amount from 0.2% by weight to an amount which renders the cellulose ether less than 1% by weight soluble in water.
The nonionic cellulose ether that forms the `backbone' of the hydrophobically modified derivative may be any nonionic water soluble cellulose ether substrate, such as hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose or methyl hydroxyethyl cellulose.
The preferred `backbone' is HEC.
Other suitable associative thickeners include the Collacralt range (ethoxylate urethanes) from BASF, the PureThixT"' range from Sud-Chemie, the Aquaflowtm range (HM end-capped PEGs) from Aqualon, and the Nexton''"' range (HMHEC), also from Aqualon.
Especially preferred associative thickeners are hydrophobically modified cellulose ethers sold under the trade names Natrosoll Plus 100, 250, 331, and 430, by Hercules.
The molecular weight of the associative thickener is preferably from 1,000 to 1,000,000, more preferably from 50,000 to 500,000 and most preferably from 100,000 to 400,000.
The associative thickener is typically used at a level of at least 0.0005%, in particular at from 0.0005 to 2%, and especially at from 0.001 to 0.5% by weight of the total composition.
Aqueous continuous phase The aqueous continuous phase typically comprises 80% or greater by weight of water; sometimes this figure may rise to 90% or greater, or 95% or greater. The water in the aqueous continuous phase typically comprises 40% or greater by weight of the total formulation; preferably this figure is 60% or greater, more preferably it is 70% or greater.
Especially preferred associative thickeners are hydrophobically modified cellulose ethers sold under the trade names Natrosoll Plus 100, 250, 331, and 430, by Hercules.
The molecular weight of the associative thickener is preferably from 1,000 to 1,000,000, more preferably from 50,000 to 500,000 and most preferably from 100,000 to 400,000.
The associative thickener is typically used at a level of at least 0.0005%, in particular at from 0.0005 to 2%, and especially at from 0.001 to 0.5% by weight of the total composition.
Aqueous continuous phase The aqueous continuous phase typically comprises 80% or greater by weight of water; sometimes this figure may rise to 90% or greater, or 95% or greater. The water in the aqueous continuous phase typically comprises 40% or greater by weight of the total formulation; preferably this figure is 60% or greater, more preferably it is 70% or greater.
The aqueous continuous phase may also comprise water-soluble species, such as mineral salts or short chain (C1-4) alcohols. The mineral salts may aid the attainment of the required phase volume for the composition, as may water soluble organic salts and cationic deflocculating polymers, as described in EP 41,698 A2 (Unilever). Such salts may be present at from 0.001 to 1% and preferably at from 0.005 to 0.1% by weight of the total composition. Examples of suitable mineral salts for this purpose include calcium chloride and magnesium chloride. Short chain alcohols that may be present include primary alcohols, such as ethanol, propanol, and butanol, secondary alcohols such as isopropanol, and polyhydric alcohols such as propylene glycol and glycerol. The short chain alcohol may be added with cationic softening agent during the preparation of the composition.
Fatty complexing agent A highly preferred additional component in the compositions of the present invention is a fatty complexing agent. Such agents typically have a C8 to C22 hydrocarbyl chain present as part of their molecular structure. Suitable fatty complexing agents include C8 to C22 fatty alcohols and Cg to C22 fatty acids; of these, the C8 to C22 fatty alcohols are most preferred. A fatty complexing agent is particularly valuable in compositions comprising a QAC having a single C12_28 group connected to the nitrogen head group, such as mono-ester associated with a TEA ester quat. or a softening agent of formula II.
It is thought that the complexing agent may bind to the single chain QAC described above in preference to the nonionic surfactant and thereby free the nonionic surfactant to stabilise the disperse phase and help reduce its phase volume. Complexing the single chain QAC may also aid the rheological stability of the composition in another manner;
the presence of such single chain QACs, particular when present at levels of 10 mole% or greater of the total QAC, can lead to depletion flocculation - addition of a complexing agent has the effect of reducing their free concentration, thereby reducing or eliminating this problem.
Enhanced softening performance may also result from the presence of the complex formed between the single chain QAC
and the complexing agent.
Preferred fatty acid complexing agents include hardened tallow fatty acid (available as PristereneTM, ex Unigema).
Preferred fatty alcohol complexing agents include hardened tallow alcohol (available as StenolT" and HydrenolT"', ex Cognis, and Laurext CS, ex Albright and Wilson) and behenyl alcohol, a C22 fatty alcohol, available as LanetteT" 22, ex Henkel.
The fatty complexing agent may be used at from 0.1% to 10%, particularly at from 0.5% to 5%, and especially at from 0.75 to 2% by weight, based on the total weight of the composition.
Fatty complexing agent A highly preferred additional component in the compositions of the present invention is a fatty complexing agent. Such agents typically have a C8 to C22 hydrocarbyl chain present as part of their molecular structure. Suitable fatty complexing agents include C8 to C22 fatty alcohols and Cg to C22 fatty acids; of these, the C8 to C22 fatty alcohols are most preferred. A fatty complexing agent is particularly valuable in compositions comprising a QAC having a single C12_28 group connected to the nitrogen head group, such as mono-ester associated with a TEA ester quat. or a softening agent of formula II.
It is thought that the complexing agent may bind to the single chain QAC described above in preference to the nonionic surfactant and thereby free the nonionic surfactant to stabilise the disperse phase and help reduce its phase volume. Complexing the single chain QAC may also aid the rheological stability of the composition in another manner;
the presence of such single chain QACs, particular when present at levels of 10 mole% or greater of the total QAC, can lead to depletion flocculation - addition of a complexing agent has the effect of reducing their free concentration, thereby reducing or eliminating this problem.
Enhanced softening performance may also result from the presence of the complex formed between the single chain QAC
and the complexing agent.
Preferred fatty acid complexing agents include hardened tallow fatty acid (available as PristereneTM, ex Unigema).
Preferred fatty alcohol complexing agents include hardened tallow alcohol (available as StenolT" and HydrenolT"', ex Cognis, and Laurext CS, ex Albright and Wilson) and behenyl alcohol, a C22 fatty alcohol, available as LanetteT" 22, ex Henkel.
The fatty complexing agent may be used at from 0.1% to 10%, particularly at from 0.5% to 5%, and especially at from 0.75 to 2% by weight, based on the total weight of the composition.
When a QAC having a single C12-28 group connected to the nitrogen head group is present, the mole ratio of the fatty complexing.agent to said single chain QAC is preferably from 1:3 to 3:1, more preferably 1:2 to 2:1, and most preferably 2:3 to 3:2.
Perfume The compositions of the invention typically comprise one or more perfumes. The perfume is preferably present in an amount from 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, most preferably 0.5 to 4.0% by weight, based on the total weight of the composition.
Co-softener Co-softeners may be used together with the cationic softening agent. When employed, they are typically present at from 0.1 to 20% and particularly at from 0.5 to 10%, based on the total weight of the composition. Preferred co-softeners include fatty esters, and fatty N-oxides.
Fatty esters that may be employed include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed WO 01/46361 (Unilever).
Further Optional Ingredients The compositions of the invention may contain one or more other ingredients. Such ingredients include preservatives (e.g. bactericides), pH buffering agents, perfume carriers, fluorescers, colourants, hydrotropes, antifoaming agents, anti-redeposition agents, soil-release agents, polyelectrolytes, enzymes, optical brightening agents, anti-shrinking agents, anti-wrinkle agents, anti-spotting agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids and dyes.
A particularly preferred optional'ingredient is an opacifier or pearlescer. Such ingredients can serve to augment the creamy appearance of the compositions of the invention.
Suitable materials may be selected from the Aqusol' ' OP30X
range (ex Rohm and Haas), the PuriColourl White range (ex Ciba) and the LameSoft TM range (ex Cognis). Such materials are typically used.at a level of from 0.01 to 1% by weight of'the total composition.
Product Use The compositions of the present invention are preferably rinse conditioner compositions and may be used in the rinse cycle of a domestic laundry process.
The composition is preferably used in the rinse cycle of a home textile laundering operation, where, it may be added directly in an undiluted state to a washing machine, e.g.
through a dispenser drawer or, for a top-loading washing machine, directly into the drum. Alternatively, it can be diluted prior to use. The compositions may also be used in a domestic hand-washing laundry operation.
Perfume The compositions of the invention typically comprise one or more perfumes. The perfume is preferably present in an amount from 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, most preferably 0.5 to 4.0% by weight, based on the total weight of the composition.
Co-softener Co-softeners may be used together with the cationic softening agent. When employed, they are typically present at from 0.1 to 20% and particularly at from 0.5 to 10%, based on the total weight of the composition. Preferred co-softeners include fatty esters, and fatty N-oxides.
Fatty esters that may be employed include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed WO 01/46361 (Unilever).
Further Optional Ingredients The compositions of the invention may contain one or more other ingredients. Such ingredients include preservatives (e.g. bactericides), pH buffering agents, perfume carriers, fluorescers, colourants, hydrotropes, antifoaming agents, anti-redeposition agents, soil-release agents, polyelectrolytes, enzymes, optical brightening agents, anti-shrinking agents, anti-wrinkle agents, anti-spotting agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids and dyes.
A particularly preferred optional'ingredient is an opacifier or pearlescer. Such ingredients can serve to augment the creamy appearance of the compositions of the invention.
Suitable materials may be selected from the Aqusol' ' OP30X
range (ex Rohm and Haas), the PuriColourl White range (ex Ciba) and the LameSoft TM range (ex Cognis). Such materials are typically used.at a level of from 0.01 to 1% by weight of'the total composition.
Product Use The compositions of the present invention are preferably rinse conditioner compositions and may be used in the rinse cycle of a domestic laundry process.
The composition is preferably used in the rinse cycle of a home textile laundering operation, where, it may be added directly in an undiluted state to a washing machine, e.g.
through a dispenser drawer or, for a top-loading washing machine, directly into the drum. Alternatively, it can be diluted prior to use. The compositions may also be used in a domestic hand-washing laundry operation.
It is also possible, though less desirable, for the compositions of the present invention to be used in industrial laundry operations, e.g. as a finishing agent for softening new clothes prior to sale to consumers.
Method of Manufacture Formulations according to the invention may be prepared by the method of manufacture described as the third aspect of the invention. In this method, the is should be understood that the dispersing of the cationic softening agent and nonionic surfactant in the aqueous continuous phase may involve dissolution of at least some of the nonionic surfactant in the aqueous continuous phase. The required reduction in the phase volume of the disperse phase may be brought about by any of the means known in the art. Such means may comprise the addition of an electrolyte, such as a mineral salt, and/or milling of the formulation. Milling of the formulation, when employed, is typically performed until 50% or greater, in particular 100% or greater and especially 150% or greater of the batch volume has passed through the mill.
In a typical method of manufacture, the cationic softening agent, nonionic surfactant, and any optional hydrophobic components such co-softener are heated together until a co-melt is formed. Water is heated and the co-melt is added to the water with stirring. The phase volume of the disperse phase is reduced by the addition of an electrolyte and/or by milling, preferably whilst the mixture is still hot. When the cationic softening agent is present as a lamellar phase dispersion, it is preferred that milling is carried above the La-Lp phase transition temperature. The mixture is then thickened by the addition of associative thickener, typically added as an aqueous solution of concentration from 1 to 2% by weight, and is then allowed to cool.
Examples The invention will now be illustrated by the following non-limiting examples. Further modifications will be apparent to the person skilled in the art.
Examples of the invention are represented by a number.
Comparative examples are represented by a letter.
Table 1: Base Formulation for Examples A to E and 1 Component Amount (wt. %) PrapagenTM TQL TEA ester quat., ex Clariant 12.7 Genapolt 0200 Coconut alcohol polyglycol 0.4 ether (20 EO), ex Clariant StenolTM Hardened tallow fatty alcohol, 1.0 ex Cognis Perfume 0.7 Water and To 100 minors The base formulation indicated in Table 1 was prepared by methods standard in the art. The phase volume of the core formulation was then reduced to the levels indicated in Table 2 by shearing the formulation for the number of batch volumes (BV) indicated. Phase volumes were determined by measuring the viscosity at a range of shear rates, using these data to calculate the infinite shear rate viscosity via the Sisco model and then using using the Kreigher-Dougherty equation to get a value for the phase volume from the infinite shear rate viscosity so calculated (vide supra) .
Associative thickener (Natrosol' Plus 331, ex Hercules) was added to Example E to give Example 1. The sensitivity of the dispensing efficiency to the phase volume is clear from the dispenser residue figures indicated in Table 2. These figures were obtained on use of the indicated formulation in a conventional Miele Novotronic automatic washing machine.
These figures indicate that by using a suitable formulation of low phase volume, it is possible to add the associative thickener without major detrimental effect upon the dispensing. The addition of the associative thickener gave a formulation of thick and creamy appearance (viscosity 245 mPa.s at 20 Is, in comparison with a value of 71 mPa.s, at the same shear, rate for example E).
Method of Manufacture Formulations according to the invention may be prepared by the method of manufacture described as the third aspect of the invention. In this method, the is should be understood that the dispersing of the cationic softening agent and nonionic surfactant in the aqueous continuous phase may involve dissolution of at least some of the nonionic surfactant in the aqueous continuous phase. The required reduction in the phase volume of the disperse phase may be brought about by any of the means known in the art. Such means may comprise the addition of an electrolyte, such as a mineral salt, and/or milling of the formulation. Milling of the formulation, when employed, is typically performed until 50% or greater, in particular 100% or greater and especially 150% or greater of the batch volume has passed through the mill.
In a typical method of manufacture, the cationic softening agent, nonionic surfactant, and any optional hydrophobic components such co-softener are heated together until a co-melt is formed. Water is heated and the co-melt is added to the water with stirring. The phase volume of the disperse phase is reduced by the addition of an electrolyte and/or by milling, preferably whilst the mixture is still hot. When the cationic softening agent is present as a lamellar phase dispersion, it is preferred that milling is carried above the La-Lp phase transition temperature. The mixture is then thickened by the addition of associative thickener, typically added as an aqueous solution of concentration from 1 to 2% by weight, and is then allowed to cool.
Examples The invention will now be illustrated by the following non-limiting examples. Further modifications will be apparent to the person skilled in the art.
Examples of the invention are represented by a number.
Comparative examples are represented by a letter.
Table 1: Base Formulation for Examples A to E and 1 Component Amount (wt. %) PrapagenTM TQL TEA ester quat., ex Clariant 12.7 Genapolt 0200 Coconut alcohol polyglycol 0.4 ether (20 EO), ex Clariant StenolTM Hardened tallow fatty alcohol, 1.0 ex Cognis Perfume 0.7 Water and To 100 minors The base formulation indicated in Table 1 was prepared by methods standard in the art. The phase volume of the core formulation was then reduced to the levels indicated in Table 2 by shearing the formulation for the number of batch volumes (BV) indicated. Phase volumes were determined by measuring the viscosity at a range of shear rates, using these data to calculate the infinite shear rate viscosity via the Sisco model and then using using the Kreigher-Dougherty equation to get a value for the phase volume from the infinite shear rate viscosity so calculated (vide supra) .
Associative thickener (Natrosol' Plus 331, ex Hercules) was added to Example E to give Example 1. The sensitivity of the dispensing efficiency to the phase volume is clear from the dispenser residue figures indicated in Table 2. These figures were obtained on use of the indicated formulation in a conventional Miele Novotronic automatic washing machine.
These figures indicate that by using a suitable formulation of low phase volume, it is possible to add the associative thickener without major detrimental effect upon the dispensing. The addition of the associative thickener gave a formulation of thick and creamy appearance (viscosity 245 mPa.s at 20 Is, in comparison with a value of 71 mPa.s, at the same shear, rate for example E).
Table 2 Example Polymer Milling Phase Dispenser wt.%) (BV) volume residue (wt.%) A 0 0 0.81 52.5 B 0 0.5 0.79 20.9 C 0 1 0.69 4.1 D 0 1.5 0.68 2.5 E 0 2 0.65 2.5 1 0.012 2 0.64 2.9 The phase volume may also be reduced by the addition of mineral salt. Example F (Table 3) was prepared in a similar manner to that used for examples A to E, using 13% of the TEA quat., 0.6% of the nonionic surfactant, 0.6% of the fatty alcohol, and 0.75% of perfume. Calcium chloride and associative thickener were then added to give Examples 2 and 3, as shown in Table 3. The Table also shows the phase volumes for the samples and the dispenser residues resulting from their use in a conventional Miele Novotronic automatic washing machine. Examples 2 and 3 each had a thick and creamy appearance (viscosities at 20 Is of 232 mPa.s and 197 mPa.s, respectively) and yet both gave low dispenser residues, in comparison with Example F.
Table 3 Example CaC12 Polymer Phase Dispenser (wt.%) (wt.%) volume residue (wt.%) F 0 0 0.79 25.7 2 0.01 0.001 0.70 7.8 3 0.01 0.0012 0.66 5.3 1. Natrosol- Plus 331, ex Hercules, Mw. ca. 370,000.
2. Natrosol'T' Plus 100, ex Hercules.
Examples similar to the above have also been prepared using Natrosol1'r' Plus 430 (Mw. ca. 470,000). This material also gave compositions having a thick and creamy appearance, that dispensed without leaving excessive residues; however, it was less weight effective than its lower molecular weight analogues.
In a further series of control experiments, process-thinned compositions were thickened using a continuous phase thickener: Softgel' " BDA, a cationically modified potato starch, ex Avebe. Thick products could be produced in this manner (having viscosities at 20/s of 290 mPa.s and above), but only at the expense of high dispenser residues (25 wt.%
and above), showing the inferiority of continuous phase thickeners when compared with the associative thickeners used in conjunction with the other aspects of the present invention.
2. Natrosol'T' Plus 100, ex Hercules.
Examples similar to the above have also been prepared using Natrosol1'r' Plus 430 (Mw. ca. 470,000). This material also gave compositions having a thick and creamy appearance, that dispensed without leaving excessive residues; however, it was less weight effective than its lower molecular weight analogues.
In a further series of control experiments, process-thinned compositions were thickened using a continuous phase thickener: Softgel' " BDA, a cationically modified potato starch, ex Avebe. Thick products could be produced in this manner (having viscosities at 20/s of 290 mPa.s and above), but only at the expense of high dispenser residues (25 wt.%
and above), showing the inferiority of continuous phase thickeners when compared with the associative thickeners used in conjunction with the other aspects of the present invention.
Claims (17)
1. A liquid fabric softener composition comprising:
i) an aqueous continuous phase;
ii) a disperse phase containing a cationic softening agent in an amount of at least 5% by weight of the total composition;
iii) at least 0.05% by weight of the total composition of an non-ionic surfactant;
(iv) a fatty complexing agent selected from the group consisting of C8 to C22 fatty acids and C8 to C22 fatty alcohols; and (v) an associative thickener which is a hydrophobically modified cellulose ether, wherein the disperse phase has a phase volume of 0.75 or less.
i) an aqueous continuous phase;
ii) a disperse phase containing a cationic softening agent in an amount of at least 5% by weight of the total composition;
iii) at least 0.05% by weight of the total composition of an non-ionic surfactant;
(iv) a fatty complexing agent selected from the group consisting of C8 to C22 fatty acids and C8 to C22 fatty alcohols; and (v) an associative thickener which is a hydrophobically modified cellulose ether, wherein the disperse phase has a phase volume of 0.75 or less.
2. A fabric softening composition according to claim 1, having a viscosity at 20 Is of from 200 to 450 mPa.s.
3. A fabric softening composition according to claim 1 or 2, wherein the disperse phase comprises fragments of lamellar phase cationic softening agent stabilised by non-ionic surfactant and linked by associative thickener.
4. A fabric softening composition according to any one of claims 1-3, wherein the disperse phase has a phase volume of 0.70 or less.
5. A fabric softening composition according to any one of claims 1-4, wherein the cationic softening agent has an iodine value of from 0 to 20 g iodine absorbed/100 g cationic softening agent.
6. A fabric softening composition according to any one of claims 1-5, wherein the non-ionic surfactant has an HLB
of from 7 to 20.
of from 7 to 20.
7. A fabric softening composition according to claim 6, wherein the non-ionic surfactant is present at a level of 0.35% or greater, based on the total weight of the composition.
8. A fabric softening composition as claimed in any one of claims 1-7, in which the fatty complexing agent is a C8 to C22 fatty alcohol.
9. A fabric softening composition according to any one of claims 1-8, wherein the associative thickener has a molecular weight of from 50,000 to 500,000 g/mol.
10. A fabric softening composition according to any one of claims 1-9, wherein the associative thickener is present at a level of from 0.001 to 0.5% by weight of the total composition.
11. A fabric softening composition according to any one of claims 1-10, wherein said cationic softening agent comprises a quaternary ammonium compound having a single C12-Z8 group connected to the nitrogen head group.
12. A fabric softening composition according to claim 11, wherein the mole ratio of the fatty complexing agent to the quaternary ammonium compound having a single C12-28 group connected to the nitrogen head group is from 1:3 to 3:1.
13. A method for the treatment of fabrics comprising contacting fabrics with a liquid fabric softening composition according to any one of claims 1-12.
14. A method for the manufacture of a liquid fabric softening composition as claimed in any one of claims 1-12, comprising the steps of dispersing a cationic softening agent, a non-ionic surfactant, and a fatty complexing agent in an aqueous continuous phase, reducing the phase volume of the disperse phase, and using an associative thickener to thicken the composition, wherein the disperse phase is reduced to a phase volume of 0.75 or less and the cationic softening agent comprises 5% or greater of the total composition.
15. A method according to claim 14, wherein the phase volume is reduced by the addition of an electrolyte and/or milling the composition.
16. A fabric softening composition according to claim 5, wherein the cationic softening agent has an iodine value of from 0 to 2 g iodine absorbed/100 g cationic softening agent.
17. A fabric softening composition according to claim 6, wherein the non-ionic surfactant has an HLB of from 15 to 20.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0318154.2 | 2003-08-02 | ||
GBGB0318154.2A GB0318154D0 (en) | 2003-08-02 | 2003-08-02 | Fabric conditioning compositions |
PCT/EP2004/007305 WO2005014767A1 (en) | 2003-08-02 | 2004-07-05 | Fabric conditioning compositions |
Publications (2)
Publication Number | Publication Date |
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CA2533809A1 CA2533809A1 (en) | 2005-02-17 |
CA2533809C true CA2533809C (en) | 2011-12-06 |
Family
ID=27799705
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Application Number | Title | Priority Date | Filing Date |
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CA2533809A Expired - Fee Related CA2533809C (en) | 2003-08-02 | 2004-07-05 | Fabric conditioning compositions |
Country Status (14)
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US (1) | US20050026808A1 (en) |
EP (1) | EP1654345B1 (en) |
CN (1) | CN100422298C (en) |
AR (1) | AR045171A1 (en) |
AT (1) | ATE480614T1 (en) |
BR (1) | BRPI0413138B1 (en) |
CA (1) | CA2533809C (en) |
DE (1) | DE602004029056D1 (en) |
ES (1) | ES2349638T3 (en) |
GB (1) | GB0318154D0 (en) |
MX (1) | MXPA06001261A (en) |
PL (1) | PL1654345T3 (en) |
WO (1) | WO2005014767A1 (en) |
ZA (1) | ZA200600871B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0425181D0 (en) * | 2004-11-15 | 2004-12-15 | Unilever Plc | Fabric treatment composition |
GB0504535D0 (en) * | 2005-03-04 | 2005-04-13 | Unilever Plc | Fabric softening composition |
GB0504536D0 (en) | 2005-03-04 | 2005-04-13 | Unilever Plc | Fabric softening composition |
WO2010019727A1 (en) | 2008-08-15 | 2010-02-18 | The Procter & Gamble Company | Benefit compositions comprising polyglycerol esters |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3021698C2 (en) | 1980-06-10 | 1982-06-09 | Ludwig Taprogge Reinigungsanlagen für Röhren-Wärmeaustauscher, 4000 Düsseldorf | Cleaning body for cleaning the inside of tubular heat exchangers |
GB8804818D0 (en) * | 1988-03-01 | 1988-03-30 | Unilever Plc | Fabric softening composition |
CN1077134C (en) * | 1994-04-07 | 2002-01-02 | 尤尼利弗公司 | Fabric softening composition |
GB9526182D0 (en) * | 1995-12-21 | 1996-02-21 | Unilever Plc | Fabric softening composition |
US6020304A (en) * | 1996-04-01 | 2000-02-01 | The Procter & Gamble Company | Fabric softener compositions |
US5916863A (en) * | 1996-05-03 | 1999-06-29 | Akzo Nobel Nv | High di(alkyl fatty ester) quaternary ammonium compound from triethanol amine |
GB9930430D0 (en) * | 1999-12-22 | 2000-02-16 | Unilever Plc | A method of preparing fabric softening compositions |
GB0121804D0 (en) * | 2001-09-10 | 2001-10-31 | Unilever Plc | Fabric conditioning compositions |
-
2003
- 2003-08-02 GB GBGB0318154.2A patent/GB0318154D0/en not_active Ceased
-
2004
- 2004-07-05 WO PCT/EP2004/007305 patent/WO2005014767A1/en active Application Filing
- 2004-07-05 ES ES04740643T patent/ES2349638T3/en not_active Expired - Lifetime
- 2004-07-05 MX MXPA06001261A patent/MXPA06001261A/en active IP Right Grant
- 2004-07-05 EP EP04740643A patent/EP1654345B1/en not_active Expired - Lifetime
- 2004-07-05 DE DE602004029056T patent/DE602004029056D1/en not_active Expired - Lifetime
- 2004-07-05 CN CNB2004800282125A patent/CN100422298C/en not_active Expired - Fee Related
- 2004-07-05 PL PL04740643T patent/PL1654345T3/en unknown
- 2004-07-05 BR BRPI0413138-0A patent/BRPI0413138B1/en not_active IP Right Cessation
- 2004-07-05 AT AT04740643T patent/ATE480614T1/en not_active IP Right Cessation
- 2004-07-05 ZA ZA200600871A patent/ZA200600871B/en unknown
- 2004-07-05 CA CA2533809A patent/CA2533809C/en not_active Expired - Fee Related
- 2004-07-30 AR ARP040102716A patent/AR045171A1/en not_active Application Discontinuation
- 2004-08-02 US US10/909,522 patent/US20050026808A1/en not_active Abandoned
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CN1860213A (en) | 2006-11-08 |
DE602004029056D1 (en) | 2010-10-21 |
EP1654345B1 (en) | 2010-09-08 |
GB0318154D0 (en) | 2003-09-03 |
BRPI0413138B1 (en) | 2015-06-09 |
MXPA06001261A (en) | 2006-04-11 |
ES2349638T3 (en) | 2011-01-07 |
ZA200600871B (en) | 2007-06-27 |
BRPI0413138A (en) | 2006-10-03 |
EP1654345A1 (en) | 2006-05-10 |
PL1654345T3 (en) | 2011-03-31 |
WO2005014767A1 (en) | 2005-02-17 |
US20050026808A1 (en) | 2005-02-03 |
ATE480614T1 (en) | 2010-09-15 |
AR045171A1 (en) | 2005-10-19 |
CA2533809A1 (en) | 2005-02-17 |
CN100422298C (en) | 2008-10-01 |
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