EP0094118B1 - Low phosphate laundry detergent compositions - Google Patents
Low phosphate laundry detergent compositions Download PDFInfo
- Publication number
- EP0094118B1 EP0094118B1 EP83200604A EP83200604A EP0094118B1 EP 0094118 B1 EP0094118 B1 EP 0094118B1 EP 83200604 A EP83200604 A EP 83200604A EP 83200604 A EP83200604 A EP 83200604A EP 0094118 B1 EP0094118 B1 EP 0094118B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- surfactant
- nonionic
- surfactants
- compositions
- ethylene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 239000000203 mixture Substances 0.000 title claims abstract description 99
- 239000003599 detergent Substances 0.000 title claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 title claims description 9
- 239000010452 phosphate Substances 0.000 title claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 42
- 239000003093 cationic surfactant Substances 0.000 claims description 32
- 239000002736 nonionic surfactant Substances 0.000 claims description 32
- -1 hydroxyalkylphenyl Chemical group 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 150000001720 carbohydrates Chemical class 0.000 claims description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 6
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 4
- 125000003147 glycosyl group Chemical group 0.000 claims description 4
- 125000006177 alkyl benzyl group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 22
- 125000002091 cationic group Chemical group 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 43
- 239000007859 condensation product Substances 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000004744 fabric Substances 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 16
- 230000003068 static effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 125000000129 anionic group Chemical group 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 239000002689 soil Substances 0.000 description 8
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 6
- 229940096386 coconut alcohol Drugs 0.000 description 6
- 235000001727 glucose Nutrition 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000004064 cosurfactant Substances 0.000 description 4
- 150000004676 glycans Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920001282 polysaccharide Polymers 0.000 description 4
- 239000005017 polysaccharide Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IYAQFFOKAFGDKE-UHFFFAOYSA-N 4,5-dihydro-1h-imidazol-3-ium;methyl sulfate Chemical compound C1CN=CN1.COS(O)(=O)=O IYAQFFOKAFGDKE-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- WWYHAQDAMPXWSI-UHFFFAOYSA-N dodecan-1-ol;methane Chemical compound C.CCCCCCCCCCCCO WWYHAQDAMPXWSI-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004264 Petrolatum Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920002359 Tetronic® Polymers 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical group OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical group OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229930182830 galactose Chemical group 0.000 description 2
- 150000008195 galaktosides Chemical class 0.000 description 2
- 229930182478 glucoside Natural products 0.000 description 2
- 150000008131 glucosides Chemical class 0.000 description 2
- 239000003752 hydrotrope Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 235000019271 petrolatum Nutrition 0.000 description 2
- 229940066842 petrolatum Drugs 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- FNRRHKQTVNDRSJ-UHFFFAOYSA-N 2,3-bis(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC(O)=C1CCCCCC(C)C FNRRHKQTVNDRSJ-UHFFFAOYSA-N 0.000 description 1
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- VCCWZAQTNBYODU-UHFFFAOYSA-N CC(=C)CC(C)CCC(C)=C Chemical group CC(=C)CC(C)CCC(C)=C VCCWZAQTNBYODU-UHFFFAOYSA-N 0.000 description 1
- 0 CCC/N=C(\*)/[N+] Chemical compound CCC/N=C(\*)/[N+] 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001553290 Euphorbia antisyphilitica Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- MEESPVWIOBCLJW-KTKRTIGZSA-N [(z)-octadec-9-enyl] dihydrogen phosphate Chemical class CCCCCCCC\C=C/CCCCCCCCOP(O)(O)=O MEESPVWIOBCLJW-KTKRTIGZSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
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- 239000000969 carrier Substances 0.000 description 1
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- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
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- 238000007046 ethoxylation reaction Methods 0.000 description 1
- GEHLEADVHVVTET-UHFFFAOYSA-N ethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[NH2+]C GEHLEADVHVVTET-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
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- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 125000002960 margaryl 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])[H] 0.000 description 1
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- FFJMLWSZNCJCSZ-UHFFFAOYSA-N n-methylmethanamine;hydrobromide Chemical compound Br.CNC FFJMLWSZNCJCSZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- 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 1
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- 239000000375 suspending agent Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- 125000002948 undecyl 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])[H] 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- This invention relates to laundry detergent compositions which exhibit surprisingly effective detergency as well as fabric softening and static control, even in the total absence of detergency builder materials. Specifically, completely unbuilt compositions of the present invention have demonstrated the ability to provide good detergency, fabric softening and static control.
- Other detergent compositions which utilize mixtures of selected nonionic surfactants and cationic surfactants are defined in U.S. Patents 4,259,217 and 4,222,905, as well as in European Patent Application 12 483 and in German Patent Application 2 948 921. European Patent Applications No. 75 995 and 75 996, both published 06.04.83, disclose built detergent compositions containing alkylpolysaccharides and nonionic surfactants.
- compositions of the present invention have excellent cleaning capabilities and are relatively insensitive to water hardness conditions, performing well in both hard and soft water conditions. Finally, in addition to this cleaning performance, the present invention provides, in a single detergent product, fabric softening and static control to the laundered fabrics.
- the present invention relates to low- or no- phosphate laundry detergent compositions, especially beneficial for good cleaning and the effective provision of softening and antistatic benefits, having a pH in the laundry solution of greater than about 7, and, preferably, containing no more than 15% phosphate, and no more than 10% silicate materials, which comprise from 5% to 100%, by weight, of a surfactant mixture containing:
- the weight ratio of nonionic surfactant to alkylpolysaccharide surfactant is not greater than 7:1 preferably from 3:1 to 1:3, and the weight ratio of nonionic surfactant plus alkylpolysaccharide surfactant to quaternary ammonium cationic surfactant is in the range of from 2:1 to 12:1.
- compositions of the present invention comprise, by weight, from 5 to 100%, preferably from 15 to 90%, and most preferably from 20 to 80%, of a mixture of particularly defined nonionic, alkylpolysaccharide and cationic surfactants in the ratios stated herein.
- Preferred compositions contain at least 15% of the nonionic/alkylpoly- saccharide/cationic surfactant mixture and at least 1 1/2 of the cationic component, itself, in order to assure the presence of a sufficient amount of both the cationic surfactant and the mixture to provide the desired cleaning and fabric conditioning benefits.
- compositions of the present invention contain the nonionic, alkylpolysaccharide and cationic surfactants, defined hereinafter, within ratios of nonionic and alkylpolysaccharide to cationic surfactant of from 2:1 to 12:1, preferably from 3:1 to 9:1 for cleaning; and most preferably from 4:1 to 9:1, in order to achieve the best soil removal performance.
- compositions of the present invention are formulated so as to have a pH of greater than 7 in the laundry solution, at conventional usage concentrations, in order to optimize their overall cleaning performance, to aid in their manufacturing and processing, and to minimize the possibility of washing machine corrosion.
- Alkalinity sources such as potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate and sodium bicarbonate, may be included in the compositions for this purpose.
- Some of the cationic/nonionic systems of the present invention may attain optimum removal of greasy/oily soils at higher pH's, while attaining optimum particulate soil removal at relatively lower pH's. In these systems, overall performance may be enhanced by varying the pH of the wash solution during the laundering process.
- compositions have a pH of at least about 8 in the laundry solution, in order to optimize the removal of greasy/oily and body soils.
- these preferred compositions should also have the ability to maintain a pH in the laundry solution of from about 8 to 11 throughout the washing operation (reserve alkalinity).
- a reserve alkalinity may be obtained by incorporating compounds which buffer at pH's of from about 8 to 11, such as monoethanolamine, diethanolamine or triethanolamine.
- compositions of the present invention are also essentially free of oily hydrocarbon materials and solvents, such as mineral oil, paraffin oil and kerosene, since these materials, which are themselves oily by nature, load the washing liquor with excessive oily material, thereby diminishing the cleaning effectiveness of the compositions.
- oily hydrocarbon materials and solvents such as mineral oil, paraffin oil and kerosene
- the alkylpolysaccharides are those having a hydrophobic group containing preferably from 10 to 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1,to 10, preferably from Is to 3, most preferably from 1.6 to 2.7 saccharide units.
- Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g. glucose, galactose and galactosyl moieties can substitute for the glucosyl moieties.
- hydrophobic group is attached at the 2, 3, 4 etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside).
- the intersaccharide bonds can be between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6 positions on the preceding saccharide units.
- polyalkoxide chain joining the hydrophobic moiety and the polysaccharide moiety.
- the preferred alkoxide is ethylene oxide.
- Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from 8 to 18, preferably from 10 to 16 carbon atoms.
- the alkyl group is a straight chain saturated alkyl group.
- the alkyl group can contain up to 3 hydroxy groups and/or the polyalkoxide chain can contain up to 10, preferably less than 5, most preferably 0, alkoxide moieties.
- Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses, and/or galactoses.
- Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
- the preferred alkylpolyglycosides have the formula wherein R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from 10 to 18, preferably from 12 to 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1a to 10, preferably from 12 to 3, most preferably from 1.6 to 2.7.
- the glycosyl is preferably derived from glucose. To prepare compounds the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units are attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominately the 2-position.
- the content of alkylmonoglycoside is low, preferably less than 60%, more preferably less than 50%.
- Nonionic surfactants are well known in the detergency art. They are included in the compositions of the present invention together with the, e.g. alkylpolyglycoside surfactants defined hereinbefore. They may be used singly or in combination with one or more of the preferred alcohol ethoxylate nonionic surfactants, described below, to form nonionic surfactant mixtures useful in combination with the alkylpolyglycosides. Examples of such surfactants are listed in U.S. Pat. No. 3,717,630, Booth, issued Feb 20,1973, and U.S. Pat. No. 3,332,880, Kessler et al, issued July 25, 1967.
- suitable nonionic surfactants which may be used in the present invention are as follows:
- the conventional nonionic detergent surfactants which are preferred for use in the compositions of the present invention are biodegradable and have the formula R(OC2H4)nOH, wherein R is a primary alkyl chain containing an average of from 10 to 18, preferably from 10 to 16, carbon atoms, and n is an average of from 2 to 9, preferably from 2 to 7.
- These nonionic surfactants have an HLB (hydrophilic-lipophilic balance) of from 5 to 14, preferably from 6 to 13.
- HLB hydrophilic-lipophilic balance
- HLB an indicator of a surfactants' hydrophilic or lipophilic nature, is defined in detail in Nonionic Surfactants, by M. J. Schick, Marcel Dekker, Inc., 1966, pages 607-613.
- Preferred nonionic surfactants for use in the present invention include the condensation product of coconut alcohol with 5 moles of ethylene oxide; the condensation product of coconut alcohol with 6 moles of ethylene oxide; the condensation product of C 12-15 alcohol with 7 moles of ethylene oxide; the condensation product of C 12 - 15 alcohol with 9 moles of ethylene oxide; the condensation product of C 14-15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C 14 - 15 alcohol with 7 moles of ethylene oxide; the condensation product of C 9-11 alcohol with 8 moles of ethylene oxide, which is stripped so as to remove unethoxylated and lower ethoxylate fractions; the condensation product of C 12 - 13 alcohol with 6.5 moles of ethylene oxide, and this same alcohol ethoxylate which is stripped so as to remove unethoxylated and lower ethoxylate fractions.
- a preferred class of such surfactants utilize alcohols which contain 20% 2-methyl branched isomers, and are commercially available, under the tradename Neodol@, from Shell Chemical Company.
- the condensation product of tallow alcohol with 9 moles of ethylene oxide is also a preferred nonionic surfactant for use herein.
- Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensation product of coconut alcohol with 5 moles of ethylene oxide, the condensation product of C 12 - 13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C 12 - 15 alcohol with 7 moles of ethylene oxide, the condensation product of C 14 - 15 alcohol with 7 moles of ethylene oxide, and mixtures of those surfactants.
- nonionic surfactants well known in the detergency art may be used, in combination with one or more of the required nonionic surfactants, to form useful nonionic surfactant mixtures. Examples of such surfactants are listed in U.S. Pat. No. 3,717,630, Booth, issued Feb. 20, 1973, and U.S. Pat. No. 3,332,880, Kessler et al, issued July 25, 1967.
- Nonlimiting examples of suitable nonionic surfactants which may be used in conjunction with the required nonionic surfactants, defined above, are: polyethylene oxide condensates of alkyl phenols, such as the Igepal@ surfactants, marketed by the GAF Corporation, and the Triton@ surfactants, marketed by the Rohm & Haas Company; condensation products of aliphatic alcohols with from 10 to 25 moles of ethylene oxide, where those alcohols are of a primary, branched or secondary alkyl chain structure; condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, such as Pluronic@ surfactants, marketed by Wyandotte Chemical Corporation; and condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine, such as the Tetronic@ surfactants, marketed by Wyandotte Chemical Corporation.
- polyethylene oxide condensates of alkyl phenols such as the Igepal@ surfactants, marketed
- compositions of the present invention are substantially free of fatty acid polyglycol ether di-ester compounds, such as polyethylene glycol-600-dioleate or polyethylene glycol-800- distearate.
- fatty acid polyglycol ether di-ester compounds such as polyethylene glycol-600-dioleate or polyethylene glycol-800- distearate.
- the cationic surfactants used in the compositions of the present invention are of the di-long chain quaternary ammonium type, having two chains which contain an average of from 16 to 22, preferably from 16 to 18, carbon atoms.
- the remaining groups, if any, attached to the quaternary nitrogen atom are preferably C 1 to C 4 alkyl or hydroxyalkyl groups.
- the long chains be alkyl groups, these chains can contain hydroxy groups or can contain heteroatoms or other linkages, such as double or triple carbon-carbon bonds, and ester, amide, or ether linkages as long as each chain falls within the carbon atoms ranges required given above.
- Preferred cationic surfactants are those having the formulae or wherein the R' and R groups contain an average of from 16 to 22 carbon atoms, preferably as alkyl groups, and most preferably contain an average of from 16 to 18 carbon atoms, R 3 and R 4 are C, to C 4 alkyl or hydroxyalkyl groups, and X is any compatible anion, particularly one selected from the group consisting of a halide (e.g., chloride), hydroxide, methylsulfate, or acetate anions.
- a halide e.g., chloride
- cationic surfactants can also be mixed with other types of cationic surfactants, such as sulfonium, phosphonium, and mono- or tri-long chain quaternary ammonium materials, as long as the amount of required cationic surfactant contained in the composition, falls with the nonionic:cationic ratio requirements specified herein.
- cationic surfactants which can be used together with those required herein, include those described in U.S. Pat. 4,259,217, Murphy, U.S. Pat. 4,222,905, Cockrell, U.S. Pat. 4,260,529, Letton, and U.S. Pat. 4,228,042, Letton.
- Preferred cationic surfactants include ditallow- alkyldimethyl (or diethyl or dihydroxyethyl) ammonium chloride, ditallowalkyldimethylammonium methyl sulfate, dihexadecylalkyl (C 16 ) dimethyl (or diethyl or dihydroxyethyl) ammonium chloride, dioctodecylalkyl (C, s )-dimethylammonium chloride, dieicosylalkyl-(C 20 ) dimethylammonium chloride, methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium methyl sulfate (commercially available as Varisoft@ 475 from Ashland Chemical Company), or mixtures of those surfactants.
- Particularly preferred cationic surfactants are ditallowalkyldimethylammonium methyl sulfate, methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium methyl sulfate, and mixtures of those surfactants, with ditallowalkyldimethylammonium chloride being especially preferred.
- compositions of the present invention can be formulated so as to be substantially free of ethoxylated cationic surfactants which contain more than an average of 10, and preferably free of those which contain more than an average of 7, moles of ethylene oxide per mole of surfactant. It is to be noted that polyethoxylated cationic surfactants having relatively low levels of ethoxylation, i.e., those with less than 10, and particularly less than 7, ethylene oxide groups exhibit better biodegradability characteristics.
- the detergent compositions additionally contain from 2 to 25%, preferably from 2 to 16%, and most preferably from 2 to 10% of a fatty amide surfactant, such as ammonia amides (e.g., coconut ammonia amides), diethanol amides, and ethoxylated amides.
- a fatty amide surfactant such as ammonia amides (e.g., coconut ammonia amides), diethanol amides, and ethoxylated amides.
- ammonia amides e.g., coconut ammonia amides
- diethanol amides e.g., diethanol amides
- ethoxylated amides e.g., ethoxylated amides.
- the ratio of the cationic/nonionic mixture to the amide component in the composition is in the range of from 5:1 to 50:1, preferably from 8:1 to 25:1.
- These amide components may also be added in small amounts, i.e., from 2% to 5%, to act as suds modifiers. Specifically, it is believed that they tend to boost the sudsing in an active system which exhibits relatively low sudsing, and depress the sudsing in an active system which exhibits relatively high sudsing.
- compositions of the present invention may also contain additional ingredients generally found in laundry detergent compositions, at their conventional art-established levels, as long as these ingredients are compatible with the nonionic and cationic components required herein.
- the compositions can contain up to 15%, preferably up to 5%, and most preferably from 0.001 to 2%, of a suds suppressor component.
- Typical suds suppressors useful in the compositions of the present invention include, but are not limited to, silicone-type suds suppressing additives which are described in U.S. Pat. 3,933,672, issued Jan. 20, 1976, Bartolotta et al, and the self-emulsifying silicone suds suppressors, described in U.S. Pat. 4,075,118, Gault et al.
- An example of such a compound is DB-544@, commercially available from Dow Corning, which contains a siloxane/glycol copolymer together with solid silica and a siloxane resin.
- Microcrystalline waxes having a melting point in the range from 35°C-115°C and a saponification value of less than 100 represent additional examples of a preferred suds regulating component for use in the subject compositions, and are described in detail in U.S. Pat. 4,056,481, Tate, issued Nov. 1, 1977.
- Alkyl phosphate esters represent an additional preferred suds suppressant for use herein. These preferred phosphate esters are predominantly monostearyl phosphate which, in addition thereto, can contain di- and tristearyl phosphates and monooleyl phosphates, which can contain di-and trioleyl phosphates.
- adjunct components which can be included in the compositions of the present invention, in their conventional art-established levels for use (i.e., from 0 to 40%), include semi-polar nonionic (such as trialkyl amine oxides), zwitterionic and ampholytic detergency cosurfactants; detergency builders; bleaching agents; bleach activators; soil release agents; soil suspending agents; corrosion inhibitors; dyes, fillers; optical brighteners; germicides; pH adjusting agents; alkalinity sources; hydrotropes; enzymes; enzyme-stabilizing agents; perfumes; solvents; carriers; suds modifiers; opacifiers; and the like.
- compositions of the present invention can contain less than 15% phosphate materials.
- Preferred compositions contain less than 7% phosphate, and can even be substantially, or totally free of such phosphate materials, without excessively decreasing the performance of the compositions.
- the compositions of the present invention preferably contain less than 10%, and are preferably substantially free of, silicate, materials.
- Preferred compositions of the present invention are also substantially free of carboxymethylcellulose.
- compositions of the present invention can contain very small amounts of anionic materials, such as hydrotropes (e.g., alkali metal toluene sulfonates), it is preferred that particular anionic materials be contained in amounts sufficiently small such that not more than 10%, preferably not more than 1%, of the cationic surfactant, contained in the laundry solution, is complexed by the anionic material. Such a complexing of the anionic material with the cationic surfactant, decreases the overall cleaning and fabric conditioning performance of the composition. Suitable anionic materials can be selected based on their strength of complexation with the cationic material included in the composition (as indicated by their dissociation constant).
- an anionic material when it has a dissociation constant of at least about 1x10- 3 (such as sodium toluene sulfonate), it can be contained in an amount up to 40%, by weight, of the cationic surfactant; and where the anionic material has a dissociation constant of at least 1 ⁇ 10 ⁇ °, but less than about 1x10- 3 , it can be contained in an amount up to 15%, by weight, of the cationic surfactant.
- Preferred compositions are substantially or completely free of such anionic materials.
- cosurfactants and detergency builders which can be used in the compositions of the present invention are found in U.S. Pat. 3,717,630, Booth, issued Feb. 20, 1973, and U.S. Pat. 4,259,217, Murphy.
- these components, particularly the anionic surfactants should be checked with the particular nonionic/ cationic surfactant system chosen, and used in an amount, so as to be certain that they will be compatible with the nonionic/cationic surfactant system.
- compositions of the present invention can be produced in a variety of forms, including liquid, solid, granular, paste, powder or substrate compositions.
- the compositions of the present invention are formulated as liquids and contain up to 20% of a lower alkyl (C 1 to C 4 ) alcohol, particularly ethanol. Liquid compositions containing lower levels of such alcohols (i.e., 7 to 12%) tend to exhibit less phase separation than compositions containing higher alcohol levels.
- compositions of the present invention are used in the laundering process by forming an aqueous solution containing from 0.01 (100 parts per million) to 0.3% (3,000 parts per million), preferably from 0.02 to 0.2%, and most preferably from 0.03 to 0.15%, of the nonionic/cationic detergent mixture, and agitating the soiled fabrics in that solution. The fabrics are then rinsed and dried.
- the compositions of the present invention yield exceptionally good particulate soil removal, and also provide fabric softening, static control, color fidelity, and dye transfer inhibition to the laundered fabrics, without requiring the use of any of the other conventionally-used fabric softening and/or static control laundry additives.
- compositions illustrate the advantage in softening and antistatic performance for the invention as compared to conventional compositions containing only conventional nonionic detergent surfactants.
- Softening is determined by grading with expert graders who used a grading scale of 0 to 4 in which 0 is equal; 1 is “I think this one is better.”; 2 is “I know this one is a little better.”; 3 is “This one is a lot better.”; and 4 is “This one is a whole lot better.” A difference of about 3/4 is significant.
- the softening grades for A and B as compared to the base were 1.6 to 1.9 which are significant.
- C was compared to the base and was essentially equal in cleaning and static control, but was superior in softening.
- the invention provides equal or better cleaning. With respect to static only, H is equivalent to the base with only one half of the static agent.
- nonionic surfactant in Composition A is replaced, in whole or in part, by the condensation product of C 14 - 15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C 14 - 15 alcohol with 7 moles of ethylene oxide; the condensation product of C 12-5 alcohol with 9 moles of ethylene oxide; the condensation product of C 12-13 alcohol with 6.5 moles of ethylene oxide, which is stripped so as to remove lower ethoxylate and nonethoxylated fractions; the condensation product of coconut alcohol with 5 moles of ethylene oxide; the condensation product of coconut alcohol with 6 moles of ethylene oxide; the condensation product of C 12 - 15 alcohol with 7 moles of ethylene oxide; the condensation product of tallow alcohol with 9 moles of ethylene oxide; a 1:1 by weight mixture of the condensation product of C 12 - 15 alcohol with 7 moles of ethylene oxide and the condensation product of C 14-15 alcohol with 7 moles of ethylene oxide; and other mixtures of those surfactants.
- the above composition additionally contains monoethanolamine, diethanolamine or triethanolamine, as an alkalinity source.
- compositions contain a silicone suds suppressor selected from the group consisting of trimethyl-, diethyl-, dipropyl-, dibutyl-, methylethyl-, phenylmethyl polysiloxane, and mixtures thereof; a petrolatum or oxidized petrolatum wax; a Fischer-Tropsch or oxidized Fischer-Tropsch wax; ozokerite; ceresin; montan wax; beeswax; candelilla; or carnauba wax.
- silicone suds suppressor selected from the group consisting of trimethyl-, diethyl-, dipropyl-, dibutyl-, methylethyl-, phenylmethyl polysiloxane, and mixtures thereof; a petrolatum or oxidized petrolatum wax; a Fischer-Tropsch or oxidized Fischer-Tropsch wax; ozokerite; ceresin; montan wax; beeswax; candelilla; or carnauba wax.
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Abstract
Description
- This invention relates to laundry detergent compositions which exhibit surprisingly effective detergency as well as fabric softening and static control, even in the total absence of detergency builder materials. Specifically, completely unbuilt compositions of the present invention have demonstrated the ability to provide good detergency, fabric softening and static control. Other detergent compositions which utilize mixtures of selected nonionic surfactants and cationic surfactants are defined in U.S. Patents 4,259,217 and 4,222,905, as well as in European Patent Application 12 483 and in German Patent Application 2 948 921. European Patent Applications No. 75 995 and 75 996, both published 06.04.83, disclose built detergent compositions containing alkylpolysaccharides and nonionic surfactants.
- The compositions of the present invention have excellent cleaning capabilities and are relatively insensitive to water hardness conditions, performing well in both hard and soft water conditions. Finally, in addition to this cleaning performance, the present invention provides, in a single detergent product, fabric softening and static control to the laundered fabrics.
- The present invention relates to low- or no- phosphate laundry detergent compositions, especially beneficial for good cleaning and the effective provision of softening and antistatic benefits, having a pH in the laundry solution of greater than about 7, and, preferably, containing no more than 15% phosphate, and no more than 10% silicate materials, which comprise from 5% to 100%, by weight, of a surfactant mixture containing:
- - a nonionic surfactant, preferably one having the formula R(OC2H4)rOH, wherein R is a primary alkyl chain containing an average of from 10 to 18 carbon atoms and n is an average of from 2 to 9, said nonionic surfactant having an HLB of from 5 to 14, or a mixture of such surfactants;
- - a quaternary ammonium cationic surfactant having 2 chains which contain an average of from 16 to 22 carbon atoms, or a mixture of such surfactants;
- - an alkylpolysaccharide detergent surfactant of the formula RO (R'O)Y(Z)X where R is an alkyl, hydroxyalkyl, alkylphenyl, hydroxyalkylphenyl, alkylbenzyl, or mixtures thereof, said alkyl groups containing from 8 to 18 carbon atoms; where each R' contains from 2 to 4 carbon atoms and y is from 0 to 12; and where each Z is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms, and x is a number from 1 1/2 to 10.
- The weight ratio of nonionic surfactant to alkylpolysaccharide surfactant is not greater than 7:1 preferably from 3:1 to 1:3, and the weight ratio of nonionic surfactant plus alkylpolysaccharide surfactant to quaternary ammonium cationic surfactant is in the range of from 2:1 to 12:1.
- The compositions of the present invention comprise, by weight, from 5 to 100%, preferably from 15 to 90%, and most preferably from 20 to 80%, of a mixture of particularly defined nonionic, alkylpolysaccharide and cationic surfactants in the ratios stated herein. Preferred compositions contain at least 15% of the nonionic/alkylpoly- saccharide/cationic surfactant mixture and at least 1 1/2 of the cationic component, itself, in order to assure the presence of a sufficient amount of both the cationic surfactant and the mixture to provide the desired cleaning and fabric conditioning benefits.
- The compositions of the present invention contain the nonionic, alkylpolysaccharide and cationic surfactants, defined hereinafter, within ratios of nonionic and alkylpolysaccharide to cationic surfactant of from 2:1 to 12:1, preferably from 3:1 to 9:1 for cleaning; and most preferably from 4:1 to 9:1, in order to achieve the best soil removal performance.
- In addition, using the mixtures of conventional nonionic detergent surfactants and polysaccharide detergent surfactants permits the use of considerably lower levels of the cationic surfactant to achieve a level of softening or antistatic effect that is achieved with a higher level of cationic surfactant when only the conventional nonionic detergent surfactant is used. In addition, there is no loss of cleaning when the polysaccharide detergent surfactant is used.
- The compositions of the present invention are formulated so as to have a pH of greater than 7 in the laundry solution, at conventional usage concentrations, in order to optimize their overall cleaning performance, to aid in their manufacturing and processing, and to minimize the possibility of washing machine corrosion. Alkalinity sources, such as potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate and sodium bicarbonate, may be included in the compositions for this purpose. Some of the cationic/nonionic systems of the present invention may attain optimum removal of greasy/oily soils at higher pH's, while attaining optimum particulate soil removal at relatively lower pH's. In these systems, overall performance may be enhanced by varying the pH of the wash solution during the laundering process. Particularly preferred compositions have a pH of at least about 8 in the laundry solution, in order to optimize the removal of greasy/oily and body soils. In addition to the higher pH in the laundry solution, these preferred compositions should also have the ability to maintain a pH in the laundry solution of from about 8 to 11 throughout the washing operation (reserve alkalinity). Such a reserve alkalinity may be obtained by incorporating compounds which buffer at pH's of from about 8 to 11, such as monoethanolamine, diethanolamine or triethanolamine.
- Preferred compositions of the present invention are also essentially free of oily hydrocarbon materials and solvents, such as mineral oil, paraffin oil and kerosene, since these materials, which are themselves oily by nature, load the washing liquor with excessive oily material, thereby diminishing the cleaning effectiveness of the compositions.
- It has surprisingly been found that the nonionic cosurfactant interacts with the alkylpolysaccharide surfactant of this invention to provide good laundry detergency for a wide range of fabrics. The alkylpolysaccharides are those having a hydrophobic group containing preferably from 10 to 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1,to 10, preferably from Is to 3, most preferably from 1.6 to 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g. glucose, galactose and galactosyl moieties can substitute for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2, 3, 4 etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside). The intersaccharide bonds can be between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6 positions on the preceding saccharide units.
- Optionally, and less desirably, there can be polyalkoxide chain joining the hydrophobic moiety and the polysaccharide moiety. The preferred alkoxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from 8 to 18, preferably from 10 to 16 carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to 3 hydroxy groups and/or the polyalkoxide chain can contain up to 10, preferably less than 5, most preferably 0, alkoxide moieties. Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses, and/or galactoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
- The preferred alkylpolyglycosides have the formula
- Preferably the content of alkylmonoglycoside is low, preferably less than 60%, more preferably less than 50%.
- Nonionic surfactants, are well known in the detergency art. They are included in the compositions of the present invention together with the, e.g. alkylpolyglycoside surfactants defined hereinbefore. They may be used singly or in combination with one or more of the preferred alcohol ethoxylate nonionic surfactants, described below, to form nonionic surfactant mixtures useful in combination with the alkylpolyglycosides. Examples of such surfactants are listed in U.S. Pat. No. 3,717,630, Booth, issued Feb 20,1973, and U.S. Pat. No. 3,332,880, Kessler et al, issued July 25, 1967. Nonlimiting examples of suitable nonionic surfactants which may be used in the present invention are as follows:
- (1) The polyethylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, said ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene, and the like. Examples of compounds of this type include nonyl phenol condensed with 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with 15 moles of ethylene oxide per mole of phenol; and diisooctyl phenol condensed with 15 moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include Igepal® CO-630, marketed by the GAF Corporation, and Triton@ X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company.
- (2) The condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with 10 moles of ethylene oxide per mole of alcohol; and the condensation product of 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms). Examples of commercially available nonionic surfactants in this type include Tergitol@ 15-S-9, marketed by Union Carbide Corporation, Neodol@ 45-9, Neodol@ 23-6.5, Neodol@ 45-7, and Neodol@ 45-4, marketed by Shell Chemical Company, and Kyro EOB@, marketed by The Procter & Gamble Company.
- (3) The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds has a molecular weight of from 1500 to 1800 and exhibits water insolubility. The addition of polyoxyethylene moieties of this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially available Pluronic@ surfactants, marketed by Wyandotte Chemical Corporation.
- (4) The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, said moiety having a molecular weight of from 2500 to 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from 40% to 80% by weight of polyoxyethylene and has a molecular weight of from 5,000 to 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic@ compounds, marketed by Wyandotte Chemical Corporation.
- The conventional nonionic detergent surfactants which are preferred for use in the compositions of the present invention are biodegradable and have the formula R(OC2H4)nOH, wherein R is a primary alkyl chain containing an average of from 10 to 18, preferably from 10 to 16, carbon atoms, and n is an average of from 2 to 9, preferably from 2 to 7. These nonionic surfactants have an HLB (hydrophilic-lipophilic balance) of from 5 to 14, preferably from 6 to 13. HLB, an indicator of a surfactants' hydrophilic or lipophilic nature, is defined in detail in Nonionic Surfactants, by M. J. Schick, Marcel Dekker, Inc., 1966, pages 607-613.
- Preferred nonionic surfactants for use in the present invention include the condensation product of coconut alcohol with 5 moles of ethylene oxide; the condensation product of coconut alcohol with 6 moles of ethylene oxide; the condensation product of C12-15 alcohol with 7 moles of ethylene oxide; the condensation product of C12-15 alcohol with 9 moles of ethylene oxide; the condensation product of C14-15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C14-15 alcohol with 7 moles of ethylene oxide; the condensation product of C9-11 alcohol with 8 moles of ethylene oxide, which is stripped so as to remove unethoxylated and lower ethoxylate fractions; the condensation product of C12-13 alcohol with 6.5 moles of ethylene oxide, and this same alcohol ethoxylate which is stripped so as to remove unethoxylated and lower ethoxylate fractions. A preferred class of such surfactants utilize alcohols which contain 20% 2-methyl branched isomers, and are commercially available, under the tradename Neodol@, from Shell Chemical Company. The condensation product of tallow alcohol with 9 moles of ethylene oxide is also a preferred nonionic surfactant for use herein. Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensation product of coconut alcohol with 5 moles of ethylene oxide, the condensation product of C12-13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C12-15 alcohol with 7 moles of ethylene oxide, the condensation product of C14-15 alcohol with 7 moles of ethylene oxide, and mixtures of those surfactants.
- Other nonionic surfactants well known in the detergency art may be used, in combination with one or more of the required nonionic surfactants, to form useful nonionic surfactant mixtures. Examples of such surfactants are listed in U.S. Pat. No. 3,717,630, Booth, issued Feb. 20, 1973, and U.S. Pat. No. 3,332,880, Kessler et al, issued July 25, 1967. Nonlimiting examples of suitable nonionic surfactants which may be used in conjunction with the required nonionic surfactants, defined above, are: polyethylene oxide condensates of alkyl phenols, such as the Igepal@ surfactants, marketed by the GAF Corporation, and the Triton@ surfactants, marketed by the Rohm & Haas Company; condensation products of aliphatic alcohols with from 10 to 25 moles of ethylene oxide, where those alcohols are of a primary, branched or secondary alkyl chain structure; condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, such as Pluronic@ surfactants, marketed by Wyandotte Chemical Corporation; and condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine, such as the Tetronic@ surfactants, marketed by Wyandotte Chemical Corporation.
- Preferred compositions of the present invention are substantially free of fatty acid polyglycol ether di-ester compounds, such as polyethylene glycol-600-dioleate or polyethylene glycol-800- distearate. Such additives offer no advantage, and possibly even result in a disadvantage, in terms of achieving the particulate soil removal and fabric conditioning benefits provided by the present invention.
- The cationic surfactants used in the compositions of the present invention are of the di-long chain quaternary ammonium type, having two chains which contain an average of from 16 to 22, preferably from 16 to 18, carbon atoms. The remaining groups, if any, attached to the quaternary nitrogen atom, are preferably C1 to C4 alkyl or hydroxyalkyl groups. Although it is preferred that the long chains be alkyl groups, these chains can contain hydroxy groups or can contain heteroatoms or other linkages, such as double or triple carbon-carbon bonds, and ester, amide, or ether linkages as long as each chain falls within the carbon atoms ranges required given above. Preferred cationic surfactants are those having the formulae
- Mixtures of the above surfactants are also useful in the present invention. These cationic surfactants can also be mixed with other types of cationic surfactants, such as sulfonium, phosphonium, and mono- or tri-long chain quaternary ammonium materials, as long as the amount of required cationic surfactant contained in the composition, falls with the nonionic:cationic ratio requirements specified herein.
- Examples of cationic surfactants which can be used together with those required herein, include those described in U.S. Pat. 4,259,217, Murphy, U.S. Pat. 4,222,905, Cockrell, U.S. Pat. 4,260,529, Letton, and U.S. Pat. 4,228,042, Letton.
- Preferred cationic surfactants include ditallow- alkyldimethyl (or diethyl or dihydroxyethyl) ammonium chloride, ditallowalkyldimethylammonium methyl sulfate, dihexadecylalkyl (C16) dimethyl (or diethyl or dihydroxyethyl) ammonium chloride, dioctodecylalkyl (C,s)-dimethylammonium chloride, dieicosylalkyl-(C20) dimethylammonium chloride, methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium methyl sulfate (commercially available as Varisoft@ 475 from Ashland Chemical Company), or mixtures of those surfactants. Particularly preferred cationic surfactants are ditallowalkyldimethylammonium methyl sulfate, methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium methyl sulfate, and mixtures of those surfactants, with ditallowalkyldimethylammonium chloride being especially preferred.
- The compositions of the present invention can be formulated so as to be substantially free of ethoxylated cationic surfactants which contain more than an average of 10, and preferably free of those which contain more than an average of 7, moles of ethylene oxide per mole of surfactant. It is to be noted that polyethoxylated cationic surfactants having relatively low levels of ethoxylation, i.e., those with less than 10, and particularly less than 7, ethylene oxide groups exhibit better biodegradability characteristics.
- In one embodiment of the present invention, the detergent compositions additionally contain from 2 to 25%, preferably from 2 to 16%, and most preferably from 2 to 10% of a fatty amide surfactant, such as ammonia amides (e.g., coconut ammonia amides), diethanol amides, and ethoxylated amides. In relation to the nonionic/cationic surfactant system, the ratio of the cationic/nonionic mixture to the amide component in the composition is in the range of from 5:1 to 50:1, preferably from 8:1 to 25:1. The use of amide in prior art compositions is described in greater detail in U.S. Pat. 4,228,004, Cambre. These amide components may also be added in small amounts, i.e., from 2% to 5%, to act as suds modifiers. Specifically, it is believed that they tend to boost the sudsing in an active system which exhibits relatively low sudsing, and depress the sudsing in an active system which exhibits relatively high sudsing.
- The compositions of the present invention may also contain additional ingredients generally found in laundry detergent compositions, at their conventional art-established levels, as long as these ingredients are compatible with the nonionic and cationic components required herein. For example, the compositions can contain up to 15%, preferably up to 5%, and most preferably from 0.001 to 2%, of a suds suppressor component. Typical suds suppressors useful in the compositions of the present invention include, but are not limited to, silicone-type suds suppressing additives which are described in U.S. Pat. 3,933,672, issued Jan. 20, 1976, Bartolotta et al, and the self-emulsifying silicone suds suppressors, described in U.S. Pat. 4,075,118, Gault et al. An example of such a compound is DB-544@, commercially available from Dow Corning, which contains a siloxane/glycol copolymer together with solid silica and a siloxane resin.
- Microcrystalline waxes having a melting point in the range from 35°C-115°C and a saponification value of less than 100 represent additional examples of a preferred suds regulating component for use in the subject compositions, and are described in detail in U.S. Pat. 4,056,481, Tate, issued Nov. 1, 1977.
- Alkyl phosphate esters represent an additional preferred suds suppressant for use herein. These preferred phosphate esters are predominantly monostearyl phosphate which, in addition thereto, can contain di- and tristearyl phosphates and monooleyl phosphates, which can contain di-and trioleyl phosphates.
- Other adjunct components which can be included in the compositions of the present invention, in their conventional art-established levels for use (i.e., from 0 to 40%), include semi-polar nonionic (such as trialkyl amine oxides), zwitterionic and ampholytic detergency cosurfactants; detergency builders; bleaching agents; bleach activators; soil release agents; soil suspending agents; corrosion inhibitors; dyes, fillers; optical brighteners; germicides; pH adjusting agents; alkalinity sources; hydrotropes; enzymes; enzyme-stabilizing agents; perfumes; solvents; carriers; suds modifiers; opacifiers; and the like. However, because of the numerous and diverse performance advantages of the present invention, certain conventional components, such as detergent cosurfactants and detergency builders, as well as fabric softening and static control agents, will not generally be necessary in a particular formulation, giving the compositions of the present invention a potential cost advantage over conventional detergent/softener compositions. For environmental reasons the compositions of the present invention can contain less than 15% phosphate materials. Preferred compositions contain less than 7% phosphate, and can even be substantially, or totally free of such phosphate materials, without excessively decreasing the performance of the compositions. The compositions of the present invention preferably contain less than 10%, and are preferably substantially free of, silicate, materials. Preferred compositions of the present invention are also substantially free of carboxymethylcellulose. Finally, while the compositions of the present invention can contain very small amounts of anionic materials, such as hydrotropes (e.g., alkali metal toluene sulfonates), it is preferred that particular anionic materials be contained in amounts sufficiently small such that not more than 10%, preferably not more than 1%, of the cationic surfactant, contained in the laundry solution, is complexed by the anionic material. Such a complexing of the anionic material with the cationic surfactant, decreases the overall cleaning and fabric conditioning performance of the composition. Suitable anionic materials can be selected based on their strength of complexation with the cationic material included in the composition (as indicated by their dissociation constant). Thus, when an anionic material has a dissociation constant of at least about 1x10-3 (such as sodium toluene sulfonate), it can be contained in an amount up to 40%, by weight, of the cationic surfactant; and where the anionic material has a dissociation constant of at least 1×10``°, but less than about 1x10-3, it can be contained in an amount up to 15%, by weight, of the cationic surfactant. Preferred compositions are substantially or completely free of such anionic materials.
- Examples of cosurfactants and detergency builders which can be used in the compositions of the present invention are found in U.S. Pat. 3,717,630, Booth, issued Feb. 20, 1973, and U.S. Pat. 4,259,217, Murphy. However, these components, particularly the anionic surfactants, should be checked with the particular nonionic/ cationic surfactant system chosen, and used in an amount, so as to be certain that they will be compatible with the nonionic/cationic surfactant system.
- The compositions of the present invention can be produced in a variety of forms, including liquid, solid, granular, paste, powder or substrate compositions. In a particularly preferred embodiment, the compositions of the present invention are formulated as liquids and contain up to 20% of a lower alkyl (C1 to C4) alcohol, particularly ethanol. Liquid compositions containing lower levels of such alcohols (i.e., 7 to 12%) tend to exhibit less phase separation than compositions containing higher alcohol levels.
- The compositions of the present invention are used in the laundering process by forming an aqueous solution containing from 0.01 (100 parts per million) to 0.3% (3,000 parts per million), preferably from 0.02 to 0.2%, and most preferably from 0.03 to 0.15%, of the nonionic/cationic detergent mixture, and agitating the soiled fabrics in that solution. The fabrics are then rinsed and dried. When used in this manner, the compositions of the present invention yield exceptionally good particulate soil removal, and also provide fabric softening, static control, color fidelity, and dye transfer inhibition to the laundered fabrics, without requiring the use of any of the other conventionally-used fabric softening and/or static control laundry additives.
- All percentages, parts, and ratios used herein are by weight unless otherwise specified.
- The following nonlimiting examples illustrate the compositions and the method of the present invention.
-
- The static control readings were obtained as follows:
- A load of clothing was washed in a full size washing machine, using the composition given above at a usage concentration of about 1750 parts per million in 79.6 I (17
- Softening is determined by grading with expert graders who used a grading scale of 0 to 4 in which 0 is equal; 1 is "I think this one is better."; 2 is "I know this one is a little better."; 3 is "This one is a lot better."; and 4 is "This one is a whole lot better." A difference of about 3/4 is significant.
- Cleaning was determined by grading standardly soiled and laundered swatches with expert graders using the standard grading scale previously described. A difference of about 3/4 is significant as an average for all the stained swatches.
- The softening grades for A and B as compared to the base were 1.6 to 1.9 which are significant. C was compared to the base and was essentially equal in cleaning and static control, but was superior in softening. The grades were softening=1; cleaning (average)=0.1; and static control (total volts/clings)=52/2 for base and 42/0 for C, D, E, F, and G were tested against the base for softness and cleaning at the 2 cup level. The softening results vs. base were D=0.2, E=0.2, F=0.2, and G=0 which are all nonsignificant. The cleaning averages were D=0.7, E=0.1, F=0, and G=1.0 of which only the last result is significant. The invention provides equal or better cleaning. With respect to static only, H is equivalent to the base with only one half of the static agent.
- Similar results are obtained when the cationic surfactant in Composition A is replaced, in whole or in part, by ditallowalkyldimethylammonium methyl sulfate, ditallowalkyldimethylammonium iodide, dihexadecylalkyldimethylammonium chloride, dihexadecylalkyldihydroxylethylammonium methyl sulfate, dioctadecylalkyldimethylammonium chloride, dieicosylalkyl methyl ethyl ammonium chloride, dieicosylalkyl dimethylammonium bromide, methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium methyl sulfate, or mixtures of these surfactants.
- Substantially similar results are also obtained where the nonionic surfactant in Composition A is replaced, in whole or in part, by the condensation product of C14-15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C14-15 alcohol with 7 moles of ethylene oxide; the condensation product of C12-5 alcohol with 9 moles of ethylene oxide; the condensation product of C12-13 alcohol with 6.5 moles of ethylene oxide, which is stripped so as to remove lower ethoxylate and nonethoxylated fractions; the condensation product of coconut alcohol with 5 moles of ethylene oxide; the condensation product of coconut alcohol with 6 moles of ethylene oxide; the condensation product of C12-15 alcohol with 7 moles of ethylene oxide; the condensation product of tallow alcohol with 9 moles of ethylene oxide; a 1:1 by weight mixture of the condensation product of C12-15 alcohol with 7 moles of ethylene oxide and the condensation product of C14-15 alcohol with 7 moles of ethylene oxide; and other mixtures of those surfactants.
- Excellent results are also obtained where the ratio of nonionic surfactant to cationic surfactant used in Composition A is 2:1,3:1,3.5:1,4.5:1, 5:1, 6:1 or 8:1.
- Excellent cleaning results are also obtained where the above composition additionally contains monoethanolamine, diethanolamine or triethanolamine, as an alkalinity source.
- Similar performance is also obtained where the compositions contain a silicone suds suppressor selected from the group consisting of trimethyl-, diethyl-, dipropyl-, dibutyl-, methylethyl-, phenylmethyl polysiloxane, and mixtures thereof; a petrolatum or oxidized petrolatum wax; a Fischer-Tropsch or oxidized Fischer-Tropsch wax; ozokerite; ceresin; montan wax; beeswax; candelilla; or carnauba wax.
Claims (4)
the surfactant mixture contains in addition an alkylpolysaccharide detergent surfactant of the formula RO (R'O)y(Z)x where R is an alkyl, hydroxyalkyl, alkylphenyl, hydroxyalkylphenyl, alkylbenzyl, or mixtures thereof, said alkyl groups containing from 8 to 18 carbon atoms; where each R' contains from 2 to 4 carbon atoms and y is from 0 to 12; and where each Z is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms, and x is a numberfrom 1 1/2 to 10;
Priority Applications (1)
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AT83200604T ATE21926T1 (en) | 1982-05-10 | 1983-04-28 | LOW-PHOSPHATE LAUNDRY DETERGENT COMPOSITIONS. |
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US37687782A | 1982-05-10 | 1982-05-10 | |
US376877 | 1982-05-10 |
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JP (1) | JPS5925896A (en) |
AT (1) | ATE21926T1 (en) |
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DE (1) | DE3365810D1 (en) |
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US4228042A (en) * | 1978-06-26 | 1980-10-14 | The Procter & Gamble Company | Biodegradable cationic surface-active agents containing ester or amide and polyalkoxy group |
NL7915015A (en) * | 1978-03-13 | 1980-05-30 | Procter & Gamble | DETERGENTS WITH LOW PHOSPHATE CONTENT. |
JPS54163907A (en) * | 1978-03-13 | 1979-12-27 | Procter & Gamble | Low phosphate detergent composition for washing |
US4239659A (en) * | 1978-12-15 | 1980-12-16 | The Procter & Gamble Company | Detergent compositions containing nonionic and cationic surfactants, the cationic surfactant having a long alkyl chain of from about 20 to about 30 carbon atoms |
GR76286B (en) * | 1981-09-28 | 1984-08-04 | Procter & Gamble | |
GR76287B (en) * | 1981-09-28 | 1984-08-04 | Procter & Gamble |
-
1983
- 1983-04-28 AT AT83200604T patent/ATE21926T1/en not_active IP Right Cessation
- 1983-04-28 DE DE8383200604T patent/DE3365810D1/en not_active Expired
- 1983-04-28 EP EP83200604A patent/EP0094118B2/en not_active Expired - Lifetime
- 1983-05-03 GR GR71272A patent/GR78555B/el unknown
- 1983-05-09 IE IE1062/83A patent/IE55426B1/en not_active IP Right Cessation
- 1983-05-09 CA CA000427703A patent/CA1209005A/en not_active Expired
- 1983-05-10 JP JP58081606A patent/JPS5925896A/en active Granted
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4627925A (en) * | 1984-04-19 | 1986-12-09 | Lever Brothers Company | Aqueous concentrated fabric softening composition |
US4622154A (en) * | 1984-04-19 | 1986-11-11 | Lever Brothers Company | Aqueous fabric softening composition |
EP0246246A1 (en) * | 1985-09-26 | 1987-11-25 | Henkel Kommanditgesellschaft auf Aktien | Fine fabric detergent composition |
EP0246246A4 (en) * | 1985-09-26 | 1988-01-07 | Staley Mfg Co A E | Fine fabric detergent composition. |
BE1002958A4 (en) * | 1986-01-30 | 1991-10-08 | Colgate Palmolive Co | LIQUID DETERGENT AND FABRIC SOFTENER COMPOSITION CONTAINING ALKYL-GLYCOSIDE AND METHOD FOR SIMULTANEOUS CLEANING AND SOFTENING OF TISSUES. |
FR2593516A1 (en) * | 1986-01-30 | 1987-07-31 | Colgate Palmolive Co | DETERGENT AND LIQUID SOFTENING COMPOSITION FOR FABRICS CONTAINING ALKYL GLYCOSIDE AND METHOD FOR SIMULTANEOUSLY CLEANING AND SOFTENING FABRICS |
US4780234A (en) * | 1986-05-06 | 1988-10-25 | Staley Continental, Inc. | Built liquid laundry detergent containing alkyl glycoside surfactant |
EP0377500A2 (en) * | 1989-01-05 | 1990-07-11 | Unilever Plc | Laundry treatment article |
EP0377500A3 (en) * | 1989-01-05 | 1991-11-21 | Unilever Plc | Laundry treatment article |
US5268126A (en) * | 1989-08-04 | 1993-12-07 | Huels Aktiengesellschaft | Emulsifiers for the preparation of aqueous polysiloxane emulsions and aqueous polysiloxane-paraffin oil emulsions with long shelf lives |
EP0418479A1 (en) * | 1989-08-04 | 1991-03-27 | Hüls Aktiengesellschaft | Emulsifier for shelf stable aqueous organosiloxane and/or paraffine oil emulsions |
EP0439019A1 (en) * | 1990-01-10 | 1991-07-31 | Kao Corporation | liquid detergent composition for clothes |
WO1993003130A1 (en) * | 1991-07-29 | 1993-02-18 | Henkel Kommanditgesellschaft Auf Aktien | Liquid washing agent |
US5330674A (en) * | 1992-09-09 | 1994-07-19 | Henkel Corporation | Method for increasing the efficiency of a disinfectant cleaning composition using alkyl polyglycosides |
US5627144A (en) * | 1992-09-11 | 1997-05-06 | Henkel Kommanditgesellschaft Auf Aktien | Composition for enhanced crude oil recovery operations containing hydrochloric acid or hydrofluoric acid, or mixtures thereof with ester quaternary ammonium compounds or/and alkyl quaternary ammonium compounds |
US5576284A (en) * | 1994-09-26 | 1996-11-19 | Henkel Kommanditgesellschaft Auf Aktien | Disinfecting cleanser for hard surfaces |
US5856290A (en) * | 1994-09-26 | 1999-01-05 | Henkel Kommanditgesellschaft Auf Aktien | Disinfecting cleanser for hard surfaces based on mixtures of APG and C8 -C18 alkyl ether |
EP0753567A1 (en) | 1995-07-14 | 1997-01-15 | The Procter & Gamble Company | Softening through the wash compositions |
EP0753569A1 (en) | 1995-07-14 | 1997-01-15 | The Procter & Gamble Company | Stable liquid softening through the wash compositions |
EP0773284A1 (en) | 1995-11-10 | 1997-05-14 | The Procter & Gamble Company | Microemulsion with high level of anionic surfactants, using branched fatty acids |
GB2323377A (en) * | 1997-03-20 | 1998-09-23 | Procter & Gamble | Detergent compositions |
GB2323375A (en) * | 1997-03-20 | 1998-09-23 | Procter & Gamble | Detergent compositions |
GB2323382A (en) * | 1997-03-20 | 1998-09-23 | Procter & Gamble | Detergent compositions |
GB2323391A (en) * | 1997-03-20 | 1998-09-23 | Akzo Nobel Nv | Dryer-activated fabric conditioning and antistatic compositions |
Also Published As
Publication number | Publication date |
---|---|
JPH05438B2 (en) | 1993-01-05 |
EP0094118A1 (en) | 1983-11-16 |
CA1209005A (en) | 1986-08-05 |
GR78555B (en) | 1984-09-27 |
EP0094118B2 (en) | 1993-04-21 |
IE55426B1 (en) | 1990-09-12 |
IE831062L (en) | 1983-11-10 |
ATE21926T1 (en) | 1986-09-15 |
JPS5925896A (en) | 1984-02-09 |
DE3365810D1 (en) | 1986-10-09 |
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