WO1998032821A1 - Antibacterial liquid dishwashing detergent compositions - Google Patents
Antibacterial liquid dishwashing detergent compositions Download PDFInfo
- Publication number
- WO1998032821A1 WO1998032821A1 PCT/US1998/000695 US9800695W WO9832821A1 WO 1998032821 A1 WO1998032821 A1 WO 1998032821A1 US 9800695 W US9800695 W US 9800695W WO 9832821 A1 WO9832821 A1 WO 9832821A1
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- WIPO (PCT)
- Prior art keywords
- weight
- composition
- carbon atoms
- alkyl
- composition according
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- 239000000203 mixture Substances 0.000 title claims abstract description 105
- 239000007788 liquid Substances 0.000 title claims abstract description 17
- 238000004851 dishwashing Methods 0.000 title claims abstract description 16
- 230000000844 anti-bacterial effect Effects 0.000 title abstract description 5
- 239000003599 detergent Substances 0.000 title description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 20
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003752 hydrotrope Substances 0.000 claims abstract description 9
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 35
- -1 butoxy, propoxy Chemical group 0.000 claims description 21
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 229940077388 benzenesulfonate Drugs 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 5
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical class CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 claims description 4
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical class CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 claims description 4
- ZZXDRXVIRVJQBT-UHFFFAOYSA-M Xylenesulfonate Chemical class CC1=CC=CC(S([O-])(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-M 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical class [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims description 4
- 229940071118 cumenesulfonate Drugs 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- 229940071104 xylenesulfonate Drugs 0.000 claims description 4
- 239000005792 Geraniol Substances 0.000 claims description 3
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- 229940113087 geraniol Drugs 0.000 claims description 3
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005770 Eugenol Substances 0.000 claims description 2
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000005844 Thymol Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229960002217 eugenol Drugs 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229960000790 thymol Drugs 0.000 claims description 2
- 230000003165 hydrotropic effect Effects 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 description 36
- 235000019441 ethanol Nutrition 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 14
- 150000001298 alcohols Chemical class 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 10
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 241000612703 Augusta Species 0.000 description 4
- 241000640882 Condea Species 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
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- 125000000129 anionic group Chemical group 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
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- 239000000194 fatty acid Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 description 2
- DZNVIZQPWLDQHI-UHFFFAOYSA-N Citronellyl formate Chemical compound O=COCCC(C)CCC=C(C)C DZNVIZQPWLDQHI-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 125000004450 alkenylene group Chemical group 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 2
- JOZKFWLRHCDGJA-UHFFFAOYSA-N citronellol acetate Chemical compound CC(=O)OCCC(C)CCC=C(C)C JOZKFWLRHCDGJA-UHFFFAOYSA-N 0.000 description 2
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- UWKAYLJWKGQEPM-LBPRGKRZSA-N linalyl acetate Chemical compound CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 230000001180 sulfating effect Effects 0.000 description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 2
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- 125000004958 1,4-naphthylene group Chemical group 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- VVUMWAHNKOLVSN-UHFFFAOYSA-N 2-(4-ethoxyanilino)-n-propylpropanamide Chemical compound CCCNC(=O)C(C)NC1=CC=C(OCC)C=C1 VVUMWAHNKOLVSN-UHFFFAOYSA-N 0.000 description 1
- DVCHJFSLGUNEQZ-UHFFFAOYSA-M 2-ethenyl-2,6-dimethylhept-5-enoate Chemical compound CC(C)=CCCC(C)(C=C)C([O-])=O DVCHJFSLGUNEQZ-UHFFFAOYSA-M 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- GNTQOKGIVMJHQG-UHFFFAOYSA-N 2-propan-2-yloxypyridine-3-carbaldehyde Chemical compound CC(C)OC1=NC=CC=C1C=O GNTQOKGIVMJHQG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- 102000004190 Enzymes Human genes 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- QEALYLRSRQDCRA-UHFFFAOYSA-N myristamide Chemical compound CCCCCCCCCCCCCC(N)=O QEALYLRSRQDCRA-UHFFFAOYSA-N 0.000 description 1
- FALTVGCCGMDSNZ-UHFFFAOYSA-N n-(1-phenylethyl)benzamide Chemical compound C=1C=CC=CC=1C(C)NC(=O)C1=CC=CC=C1 FALTVGCCGMDSNZ-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical class NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
-
- 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
- C11D1/75—Amino oxides
-
- 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
- C11D1/86—Mixtures of anionic, cationic, and non-ionic 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/2034—Monohydric alcohols aromatic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/2037—Terpenes
-
- 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
- C11D3/34—Organic compounds containing sulfur
- C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
-
- 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
- C11D3/50—Perfumes
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
Definitions
- the invention relates to liquid dishwashing detergent compositions.
- the compositions have antibacterial properties.
- Liquid dishwashing compositions are much desired by consumers and can be used neat or diluted.
- a composition In diluted mode, a composition is diluted in water to form a wash liquor in which the dishes to be cleaned are immersed.
- neat mode a composition is directly applied neat onto dishes, and in this mode a dish implement is often use. Specifically, the composition is applied onto the implement, usually a sponge or a dishcloth, which is in turn contacted with the dishes to be cleaned.
- dish implements are left humid most of the time, and so they provide a good medium for bacterial growth.
- the contaminated implement which is used to clean dishes will in turn contaminate those dishes.
- compositions of the present invention are liquid dishwashing compositions comprising :
- hydrotrope selected from the group consisting of salts of cumene sulfonate, toluene sulfonate, xylene sulfonate, benzene sulfonate or mixtures thereof;
- the invention further encompasses a method of washing dishes with these compositions.
- the anti bacterial efficacy of said formulations is mainly driven by a synergy between the hydrotrope(s) and the unsaturated aliphatic terpene alcohol(s) or derivative.
- compositions of the invention are aqueous liquid compositions. They typically comprise from 30% to 90% by weight of the total composition of water, preferably 40% to 85%.
- compositions herein are liquid and so they typically have a viscosity of from 5 cps to 2000 cps, preferably 5 cps to 400 cps, most preferably 5 cps to 350 cops, measured with a Brookfield Viscometer, with a No. 18 spindle, at 20°C.
- compositions of the present invention comprise, as an essential ingredient, one or several of the following surfactants.
- surfactants Suitable for use herein are amine oxides according to the formula :
- R 2 represents a straight or branched alkyl or alkenyl group having 10 to 16 carbon atoms
- R3 and R4 represent a C-
- the number of carbon atoms in R 2 is less than 10, the detergency of the composition is lowered, while if it exceeds 16, the stability of the composition at low temperatures deteriorates.
- alkyl alkoxylated sulfates of the formula R-
- alkyl alkoxylated sulfates with lower values for n, on an equal weight basis, typically when n is below 1.0, improves the performance of the composition on grease removal and sudsing due to the corresponding increase in moles of anionic but results in an increase in the total amount of unalkoxylated alkyl sulphate, and this seems to make the low temperature instability issue more acute. If different alkyl alkoxylated sulfates are used which have different n values, the resulting average n value of the alkyl alkoxylated sulfate in the composition will be the weighted molar average n value of the individual n values of the different alkyl alkoxylated sulfates used in the composition.
- the average n value is less than 0.5, the stimulus to skin increases and this is not desirable. On the other hand, if the average n value is more than 3, the detergency deteriorates.
- if the average number of carbon atoms in R-
- Suitable alkyl alkoxylated material for use herein can be straight or branched materials.
- branched material it is meant that R ⁇
- the increase in the proportion of branched material can improve the physical stability of the composition at low temperature.
- the branched alkyl alkoxylated sulfate material should not represent more than 60%, by weight, of the total alkyl alkoxylated sulfate (branched plus linear), otherwise the sudsing performance of the product deteriorates unacceptably.
- branched alkyl alkoxylated sulfates should be present in amounts of up to 60%, preferably from 10% to 55%, most preferably 10% to 50%.
- Alkyl alkoxylated sulfates are commercially available with a variety of chain lengths, degrees of alkoxylation and degrees of branching under the trade names Empicol® ESA 70 (AE1S) or Empicol® ESB 70 (AE2S) by Albright & Wilson, with C12/14 carbon chain length distribution which are derived from natural alcohols and are 100% linear, Empimin® KSL68/A - AE1S and Empimin® KSN70/LA - AE3S by Albright & Wilson with C12/13 chain length distribution and about 60% branching, Dobanol® 23 ethoxylated sulphates from Shell with C12/13 chain length distribution and about 18% branching, Lial® 123 ethoxylated sulphates from Condea Augusta with C12/13 chain length distribution and about 60% branching and Isalchem® 123 alkoxylated sulphates with C12/13 chain length distribution and about 95% branching.
- suitable alkyl alkoxylated sulfates can be prepared by alkoxylating and sulfating the appropriate alcohols, as described in "Surfactants in Consumer Products" by J.Falbe and "Fatty oxo-alcohols : Relation between their alkyl chain structure and the performance of the derived AE,AS,AES” submitted to the 4th World Surfactants, Barcelona, 3-7 VI 1996 Congress by Condea Augusta.
- Commercial oxo-alcohols are a mixture of primary alcohols containing several isomers and homologues. Industrial processes allow one to separate these isomers hence resulting in alcohols with linear isomer content ranging from 5-10% to upto 95%.
- Examples of available alcohols for alkoxylation and sulfation are Lial® alcohols by Condea Augusta (60% branched), Isalchem® alcohols by Condea Augusta (95% branched), Dobanol® alcohols by Shell (18% linear).
- Alkyl benzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, preferably 11 to 40 carbon atoms in straight chain or branched chain configuration.
- An especially preferred linear alkyl benzene sulfonate contains about 12 carbon atoms.
- Alkyl sulfates obtained by sulfating an alcohol having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms.
- the alkyl sulfates have the formula ROSO3- M + where R is the Cs- 2 alkyl group and M is a mono- and/or divalent cation.
- Paraffin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, in the alkyl moiety. These surfactants are commercially available as Hostapur SAS from Hoechst Celanese.
- Olefin sufonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms.
- U.S. Pat. No. 3,332,880 contains a description of suitable olefin sulfonates.
- Alkyl glyceryl ether sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, in the alkyl moiety.
- is straight or branched alkyl from about C ⁇ to C-
- Secondary alcohol sulfates having 6 to 18, preferably 8 to 16 carbon atoms.
- Fatty acid amide surfactants having the formula :
- R 6 is an alkyl group containing from 7 to 21 , preferably from 9 to 17, carbon atoms and each R? is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C 2 H4O) x H where x varies from 1 to about 3.
- R 1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C-j or C 2 alkyl, most preferably C-
- Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
- Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
- Z preferably will be selected from the group consisting of -CH 2 -(CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) n .
- n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof.
- R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof.
- Most preferred are glycityls wherein n is 4, particularly -CH 2 -(CHOH) -CH 2 OH.
- R1 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
- R2-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
- Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1- deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
- Betaine detergent surfactants having the general formula :
- R is a hydrophobic group selected from the group consisting of alkyl groups containing from 10 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amide or ether linkages; each R ⁇ is an alkyl group containing from 1 to about 3 carbon atoms; and R2 is an alkylene group containing from 1 to about 6 carbon atoms.
- Ethylene oxide condensates which can be broadly defined as compounds produced by the condensation of ethylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which can be aliphatic or alkyl aromatic in nature.
- the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired balance between hydrophilic and hydrophobic elements.
- ethylene oxide condensates suitable as suds stabilizers are the condensation products of aliphatic alcohols with ethylene oxide.
- the alkyl chain of the aliphatic alcohol can either be straight or branched and generally contains from about 8 to about 18, preferably from about 8 to about 14, carbon atoms for best performance as suds stabilizers, the ethylene oxide being present in amounts of from about 8 moles to about 30, preferably from about 8 to about 14 moles of ethylene oxide per mole of alcohol.
- compositions herein typically comprise from 10% to 60% by weight of the total composition of a surfactant, or mixtures thereof, preferably from 10% to 55%, most preferably from 10% to 50%.
- compositions herein comprise a hydrotrope selected from the group consisting of salts of cumene sulfonate, toluene sulfonate, xylene sulfonate, benzene sulfonate or mixtures thereof.
- Preferred salts are ammonium and sodium salts.
- compositions herein typically comprise from 1% to 15% by weight of the total composition of said hydrotropes, preferably 1% to 10%, most preferably 2% to 6%.
- the compositions herein comprise an unsaturated aliphatic terpene alcohol or derivates thereof (i.e unsaturated aliphatic terpene alcohols where the alcohol group is functionalized, e.g. into acetate, formate, propionate, or the like) or mixtures thereof.
- Suitable such alcohols or derivatives for use herein include geraniol, nerol, citronellol, linalool, citronellyl acetate, geranyl acetate, linalyl acetate, citronellyl formate, geranyl formate, linalyl formate, citronellyl propionate, geranyl propionate and linalyl propionate.
- geraniol is geraniol.
- compositions herein typically comprise from 0.1 % to 3% by weight of the total composition of said unsaturated aliphatic terpene alcohol, preferably 0.2% to 2.5%, most preferably 0.4% to 2%.
- compositions herein can comprise a number of other, optional ingredients, as follows :
- a first optional, but preferred ingredient is a phenolic compound according to the formula
- R, R1 , R2, R3, R4 are independently H, a linear or branched, saturated or unsaturated hydrocarbon chain having from 1 to 20 carbon atoms, preferably from 1 to 10, more preferably from 1 to 4, an alkoxylated hydrocarbon chain according to the formula Ra(A) n wherein Ra is a linear or branched, saturated or unsaturated hydrocarbon chain having from 1 to 20 carbon atoms, preferably from 1 to 10, more preferably from 1 to 4, wherein A is butoxy, propoxy and/or ethoxy, and n is an integer of 1 to 4, preferably from 1 to 3, or an aryl chain having from 1 to 20 carbon atoms, preferably from 1 to 10 and more preferably from 1 to 4, or mixtures thereof.
- Highly preferred from that class of ingredients are Eugenol and Thymol.
- compositions herein can comprise from 0.1 % to 4%, preferably from 0.2% to 1.5% by weight of the total composition of such a phenolic compound or mixtures thereof.
- Magnesium ions can comprise from 0.1 % to 4%, preferably from 0.2% to 1.5% by weight of the total composition of such a phenolic compound or mixtures thereof.
- compositions herein preferably comprise from 0% to 2.0%, preferably 0.1% to 1.5%, most preferably from 0.2% to 1% by weight of the composition, of magnesium ions which may be added to the liquid detergent compositions of the invention for improved product stability, as well as improved sudsing and skin mildness.
- the magnesium ions are introduced by neutalization of the acid form of alkylethoxy surfactants with a magnesium oxide or magnesium hydroxide slurry in water. Normally, this method is limited by the amount of anionic surfactants in the composition.
- An alternative method is to use MgCI2, MgSO4 or other inorganic Mg salts. These materials are less desirable because they can cause corrosivity problems (chloride salts), decrease the solubility of the formulations, or cause formulatibility/stability problems in the compositions. It is desirable for these reasons to limit the addition of inorganic salts to less than 2%, preferably less than 1 % by weight of the anionic inorganic counterion.
- Anti-qelling polymer
- compositions of the invention comprise an anti-gelling polymer which improves the compositions' resistance to gelling.
- Suitable polymers for use herein have a molecular weight of at least 500, preferably from 500 to 20000, more preferably 1000 to 5000, most preferably 1000 to 3000.
- compositions herein comprise from 0.5% to 6% by weight of the total composition of an anti-gelling polymer, or mixtures thereof, preferably 0.5% to 4%, most preferably 1.5% to 3%.
- Suitable polymers for use herein include :
- polyalkylene glycols preferably polyethylene glycol and polypropylene glycol
- polyamines Particularly suitable polyamine polymer for use herein are alkoxylated or polyalkoxylated polyamines.
- Such materials can conveniently be represented as molecules of the empirical structures with repeating units :
- R is a hydrocarbyl group, usually of 2-6 carbon atoms; R1 may be a C-
- polyethylene amines i.e., the polymerized reaction product of ethylene oxide with ethyleneimine, having the general formula :
- ethoxylated polyethylene amine in particular ethoxylated tetraethylenepentamine, and quaternized ethoxylated hexamethylene diamine.
- ethoxylated polyethylene amine in particular ethoxylated tetraethylenepentamine, and quaternized ethoxylated hexamethylene diamine.
- Suitable terephtalate polymers for use herein include polymers having the formula :
- each R 1 is a 1 ,4-phenylene moiety; the R2 are essentially 1 ,2- propylene moieties; the R3 are essentially the polyoxyethylene moiety - (CH 2 H 2 O)q-CH 2 -CH 2 -; each X is ethyl or preferably methyl; each n is from about 12 to about 45; q is from about 12 to about 90; the average value of u is from about 5 to about 20; the average value of v is from about 1 to about 10; the average value of u+v is from about 6 to about 30; the ratio u to v is from about 1 to about 6.
- Hihgly preferred polymers for use herein are polymers of the formula :
- X can be any suitable capping group, with each X being selected from the group consisting of H, and alkyl or acyl groups containing from 1 to about 4 carbon atoms, preferably 1 to 2 carbon atoms, most preferably alkyl.
- the alkyl group may contain anionic, cationic or nonionic substituents such as sulphonate, sulphato, ammonium, hydroxy etc. groups, n is selected for water solubility and is a range of values which generally averages from about 10 to about 50, preferably from about 10 to about 25.
- the R1 moieties are essentially 1 ,4-phenylene moieties.
- the term "the R1 moieties are essentially 1,4-phenylene moieties” refers to compounds where the R1 moieties consist entirely of 1,4-phenylene moieties, or are partially substituted with other arylene or alkarylene moieties, alkylene moieties, alkenylene moieties, or mixtures thereof.
- Arylene and alkarylene moieties which can be partially substituted for 1 ,4-phenylene include 1 ,3- phenylene, 1,2-phenylene, 1,8-naphthylene, 1 ,4-naphthylene, 2,2-biphenylene, 4,4'-biphenylene and mixtures thereof.
- Alkylene and alkenylene moieties which can be partially substituted include ethylene, 1 ,2-propylene, 1 ,4-butylene, 1,5- pentylene, 1 ,6-hexamethylene, 1 ,7-heptamethylene, 1,8-octamethylene, 1,4- cyclohexylene, and mixtures thereof.
- the R 1 moieties consist entirely of (i.e., comprise 100%) 1,4- phenylene moieties, i.e. each R1 moiety is 1,4-phenylene.
- suitable ethylene or substituted ethylene moieties include ethylene, 1 ,2-propylene, 1 ,2-butylene, 1 ,2-hexylene, 3-methoxy-1,2-propylene and mixtures thereof.
- the R2 moieties are essentially ethylene moieties, or, preferably, 1 ,2-propylene moieties or mixtures thereof.
- from about 75% to about 100%, more preferably from about 90% to about 100% of the R 2 moieties are 1 ,2-propylene moieties.
- n averages at least about 10, but a distribution of n values is present.
- the value of each n usually ranges from about 10 to about 50.
- the value for each n averages in the range of from about 10 to about 25.
- the most preferred polymers for use herein are polymers according to the formula :
- X is methyl, n is 16, R 1 is 1 ,4-phenylene moiety, R2 is 1 ,2-propylene moiety and u is essentially between 3 and 5.
- compositions of the invention can comprise a solvent in an effective amount so as to reach the desired viscosity.
- Suitable solvents for use herein include low molecular weight alcohols such as C -C-
- compositions herein typically comprise from 3% to 20% by weight of the total composition of an alcohol, or mixtures thereof, preferably 3% to 15%, most preferably 5% to 10%.
- compositions herein are formulated as clear liquid compositions.
- clear it is meant isotropic, stable and transparent.
- solvents and hydrotropes are well known to those familiar with the art of dishwashing formulations.
- Those clear compositions are preferably packaged in transparent containers, which can typically be made out of plastic or glass.
- compositions can contain other optional components suitable for use in liquid dishwashing compositions such as perfume, dye, opacifiers, enzymes, builders and chelants and pH buffering means so that the compositions herein generally have a pH of from 5 to 11 , preferably 6.0 to 10.0, most preferably 7 to 9 measured at a 10% solution in water.
- soiled dishes are contacted with an effective amount, typically from about 0.5 ml. to about 20 ml. (per 25 dishes being treated), preferably from about 3 ml. to about 10 ml., of the detergent composition of the present invention.
- an effective amount typically from about 0.5 ml. to about 20 ml. (per 25 dishes being treated), preferably from about 3 ml. to about 10 ml., of the detergent composition of the present invention.
- the actual amount of liquid detergent composition used will be based on the judgement of user, and will typically depend upon factors such as the particular product formulation of the composition, including the concentration of active ingredients in the compositon, the number of soiled dishes to be cleaned, the degree of soiling on the dishes, and the like.
- the particular product formulation in turn, will depend upon a number of factors, such as the intended market (i.e., U.S., Europe, Japan, etc.) for the composition product.
- the soiled dishes are preferably immersed into a water bath with or without a liquid dishwashing detergent as described herein.
- a dish implement i.e. a device suitable for absorbing a liquid dishwashing detergent such as a sponge or a dishcloth, is placed directly onto or contacted with a separate quantity of undiluted liquid dishwashing composition as described herein for a period of time typically ranging from about 3 to about 10 seconds.
- the absorbing device, and consequently the undiluted liquid dishwashing composition is then contacted individually to the surface of each of the soiled dishes to remove said soiling.
- the absorbing device is typically contacted with each dish surface for a period of time ranging from about 5 to about 30 seconds, although the actual time of application will be dependent upon factors such as the degree of soiling of the dish.
- the contacting of the absorbing device to the dish surface is preferably accompanied by concurrent scrubbing.
- the dish implement is preferably contacted, e.g. soaked with neat product and left to dry.
- contaminated dish implements i.e. dish implements contaminated by previous uses with other compositions
- the following compositions, which illustrate the invention, are made by mixing together the listed ingredients in the listed proportions.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
HU0001655A HUP0001655A3 (en) | 1997-08-14 | 1998-01-14 | Antibacterial liquid dishwashing detergent compositions |
IL13095698A IL130956A0 (en) | 1997-01-24 | 1998-01-14 | Antibacterial liquid dishwashing detergent compositions |
BR9807005-3A BR9807005A (en) | 1997-01-24 | 1998-01-14 | Detergent compositions for washing liquid antibacterial dishes |
AU59171/98A AU5917198A (en) | 1997-01-24 | 1998-01-14 | Antibacterial liquid dishwashing detergent compositions |
EP98902537A EP0971995A4 (en) | 1997-01-24 | 1998-01-14 | Antibacterial liquid dishwashing detergent compositions |
JP53202998A JP2002511110A (en) | 1997-01-24 | 1998-01-14 | Antimicrobial liquid dishwashing detergent composition |
US09/355,080 US6152152A (en) | 1997-01-24 | 1998-01-14 | Antibacterial liquid dishwashing detergent compositions |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97870006.O | 1997-01-24 | ||
EP97870006A EP0855439A1 (en) | 1997-01-24 | 1997-01-24 | Antibacterial liquid dishwashing detergent compositions |
EP97870119A EP0855440A1 (en) | 1997-01-24 | 1997-08-14 | Antibacterial liquid dishwashing detergent compositions |
EP97870119.1 | 1997-08-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998032821A1 true WO1998032821A1 (en) | 1998-07-30 |
Family
ID=26148208
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/000695 WO1998032821A1 (en) | 1997-01-24 | 1998-01-14 | Antibacterial liquid dishwashing detergent compositions |
Country Status (11)
Country | Link |
---|---|
EP (2) | EP0855440A1 (en) |
JP (1) | JP2002511110A (en) |
KR (1) | KR20000070247A (en) |
CN (1) | CN1255156A (en) |
AR (1) | AR011430A1 (en) |
AU (1) | AU5917198A (en) |
BR (1) | BR9807005A (en) |
IL (1) | IL130956A0 (en) |
PL (1) | PL336995A1 (en) |
TR (1) | TR199901727T2 (en) |
WO (1) | WO1998032821A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6451748B1 (en) | 1999-06-23 | 2002-09-17 | The Dial Corporation | Compositions containing a high percent saturation concentration of antibacterial agent |
WO2005013692A1 (en) * | 2003-08-06 | 2005-02-17 | Syngenta Limited | Agrochemical concentrate comprising an adjuvant and a hydrotrope |
US6861397B2 (en) | 1999-06-23 | 2005-03-01 | The Dial Corporation | Compositions having enhanced deposition of a topically active compound on a surface |
AU2011236046B2 (en) * | 2003-08-06 | 2012-11-15 | Syngenta Limited | Agrochemical concentrate comprising an adjuvant and a hydrotrope |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0916720A1 (en) * | 1997-11-17 | 1999-05-19 | The Procter & Gamble Company | Anti-bacterial liquid dishwashing detergent compositions |
DE19918192A1 (en) * | 1999-04-22 | 2000-10-26 | Cognis Deutschland Gmbh | Cleaning agent for hard surfaces, especially flush toilet pans, comprising a mixture of alk(en)yl oligoglycoside, alk(en)yl (ether)sulfate and/or betaine, and terpene alcohol |
MXPA01013312A (en) * | 1999-06-23 | 2003-09-04 | Dial Corp | Antibacterial compositions. |
US6605579B1 (en) * | 2001-05-11 | 2003-08-12 | Colgate- Palmolive Company | Antibacterial liquid dish cleaning compositions |
DE102011085998A1 (en) * | 2011-11-09 | 2013-05-16 | Henkel Ag & Co. Kgaa | Dishwashing detergent containing emulsifiers |
DE102016202822A1 (en) * | 2016-02-24 | 2017-08-24 | Henkel Ag & Co. Kgaa | Stabilized detergents |
DE102016204272A1 (en) * | 2016-03-15 | 2017-09-21 | Henkel Ag & Co. Kgaa | Amine oxide-containing cleaning agents |
CN111893000B (en) * | 2020-08-04 | 2022-03-08 | 韶关浪奇有限公司 | Non-phosphorus detergent for dish-washing machine and preparation process thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4767563A (en) * | 1983-04-19 | 1988-08-30 | The Procter & Gamble Company | Liquid scouring cleansers containing solvent system |
US5281354A (en) * | 1991-10-24 | 1994-01-25 | Amway Corporation | Liquid cleanser composition |
US5538664A (en) * | 1992-02-21 | 1996-07-23 | The Procter & Gamble Company | Hard surface detergent compositions |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0106266B1 (en) * | 1980-05-27 | 1988-02-24 | The Procter & Gamble Company | Terpene-solvent mixture useful for making liquid detergent compositions |
US4371461A (en) * | 1980-10-02 | 1983-02-01 | The Procter & Gamble Company | Liquid detergent compositions with tertiary alcohol skin feel additives |
GB8520548D0 (en) * | 1985-08-16 | 1985-09-25 | Unilever Plc | Detergent compositions |
US5108643A (en) * | 1987-11-12 | 1992-04-28 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
US5147456A (en) * | 1990-10-01 | 1992-09-15 | Olin Corporation | Polyglycidol sulfated surfactants having antimicrobial activity |
FR2727289B1 (en) * | 1994-11-30 | 1999-03-05 | Derives Resiniques Terpenique | DISINFECTANT COMPOSITION COMPRISING AT LEAST ONE TERPENIC ALCOHOL AND AT LEAST ONE BACTERICIDAL ACID SURFACTANT, AND USE OF SUCH SURFACTANTS |
-
1997
- 1997-08-14 EP EP97870119A patent/EP0855440A1/en not_active Withdrawn
-
1998
- 1998-01-14 IL IL13095698A patent/IL130956A0/en unknown
- 1998-01-14 BR BR9807005-3A patent/BR9807005A/en not_active IP Right Cessation
- 1998-01-14 WO PCT/US1998/000695 patent/WO1998032821A1/en not_active Application Discontinuation
- 1998-01-14 AU AU59171/98A patent/AU5917198A/en not_active Abandoned
- 1998-01-14 CN CN98801998A patent/CN1255156A/en active Pending
- 1998-01-14 JP JP53202998A patent/JP2002511110A/en active Pending
- 1998-01-14 KR KR1019997006475A patent/KR20000070247A/en active IP Right Grant
- 1998-01-14 TR TR1999/01727T patent/TR199901727T2/en unknown
- 1998-01-14 PL PL98336995A patent/PL336995A1/en unknown
- 1998-01-14 EP EP98902537A patent/EP0971995A4/en not_active Withdrawn
- 1998-01-23 AR ARP980100302A patent/AR011430A1/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4767563A (en) * | 1983-04-19 | 1988-08-30 | The Procter & Gamble Company | Liquid scouring cleansers containing solvent system |
US5281354A (en) * | 1991-10-24 | 1994-01-25 | Amway Corporation | Liquid cleanser composition |
US5538664A (en) * | 1992-02-21 | 1996-07-23 | The Procter & Gamble Company | Hard surface detergent compositions |
Non-Patent Citations (1)
Title |
---|
See also references of EP0971995A4 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6451748B1 (en) | 1999-06-23 | 2002-09-17 | The Dial Corporation | Compositions containing a high percent saturation concentration of antibacterial agent |
US6861397B2 (en) | 1999-06-23 | 2005-03-01 | The Dial Corporation | Compositions having enhanced deposition of a topically active compound on a surface |
WO2005013692A1 (en) * | 2003-08-06 | 2005-02-17 | Syngenta Limited | Agrochemical concentrate comprising an adjuvant and a hydrotrope |
AU2004262987B2 (en) * | 2003-08-06 | 2011-07-21 | Syngenta Limited | Agrochemical concentrate comprising an adjuvant and a hydrotrope |
US8211829B2 (en) | 2003-08-06 | 2012-07-03 | Syngenta Crop Protection Llc | Agrochemical concentrate comprising an adjuvant and a hydrotrope |
AU2011236046B2 (en) * | 2003-08-06 | 2012-11-15 | Syngenta Limited | Agrochemical concentrate comprising an adjuvant and a hydrotrope |
US8809235B2 (en) | 2003-08-06 | 2014-08-19 | Syngenta Limited | Formulation |
Also Published As
Publication number | Publication date |
---|---|
IL130956A0 (en) | 2001-01-28 |
CN1255156A (en) | 2000-05-31 |
EP0855440A1 (en) | 1998-07-29 |
EP0971995A1 (en) | 2000-01-19 |
TR199901727T2 (en) | 2001-05-21 |
BR9807005A (en) | 2000-03-14 |
AU5917198A (en) | 1998-08-18 |
JP2002511110A (en) | 2002-04-09 |
PL336995A1 (en) | 2000-07-31 |
AR011430A1 (en) | 2000-08-16 |
EP0971995A4 (en) | 2000-11-02 |
KR20000070247A (en) | 2000-11-25 |
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