EP0125854B1 - Liquid detergent compositions - Google Patents
Liquid detergent compositions Download PDFInfo
- Publication number
- EP0125854B1 EP0125854B1 EP84303044A EP84303044A EP0125854B1 EP 0125854 B1 EP0125854 B1 EP 0125854B1 EP 84303044 A EP84303044 A EP 84303044A EP 84303044 A EP84303044 A EP 84303044A EP 0125854 B1 EP0125854 B1 EP 0125854B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alcohol
- alkyl
- weight
- ethoxylated
- liquid detergent
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 123
- 239000007788 liquid Substances 0.000 title claims abstract description 29
- 239000003599 detergent Substances 0.000 title claims description 28
- -1 alkyl sulphate Chemical compound 0.000 claims abstract description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910021653 sulphate ion Inorganic materials 0.000 claims abstract description 38
- 150000001298 alcohols Chemical class 0.000 claims abstract description 37
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 239000002736 nonionic surfactant Substances 0.000 claims description 21
- 239000003945 anionic surfactant Substances 0.000 claims description 12
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 7
- 150000003138 primary alcohols Chemical class 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 3
- 238000004851 dishwashing Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 238000007046 ethoxylation reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 10
- 229910001425 magnesium ion Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000003752 hydrotrope Substances 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 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 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- 241000894007 species Species 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 3
- 238000009966 trimming Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- LYUCYGUJPUGIQI-UHFFFAOYSA-N 2-hydroxy-n,n-dimethyloctadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCCC(O)C[N+](C)(C)[O-] LYUCYGUJPUGIQI-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- NGMDZEFYHOTXAD-UHFFFAOYSA-N 4-phenylmethoxy-2h-triazole Chemical compound C=1C=CC=CC=1COC1=CNN=N1 NGMDZEFYHOTXAD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 description 1
- 102100021587 Embryonic testis differentiation protein homolog A Human genes 0.000 description 1
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 101000898120 Homo sapiens Embryonic testis differentiation protein homolog A Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229960003168 bronopol Drugs 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DZJFABDVWIPEIM-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)dodecan-1-amine oxide Chemical compound CCCCCCCCCCCC[N+]([O-])(CCO)CCO DZJFABDVWIPEIM-UHFFFAOYSA-N 0.000 description 1
- BACGZXMASLQEQT-UHFFFAOYSA-N n,n-diethyldecan-1-amine oxide Chemical compound CCCCCCCCCC[N+]([O-])(CC)CC BACGZXMASLQEQT-UHFFFAOYSA-N 0.000 description 1
- RSVIRMFSJVHWJV-UHFFFAOYSA-N n,n-dimethyloctan-1-amine oxide Chemical compound CCCCCCCC[N+](C)(C)[O-] RSVIRMFSJVHWJV-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- WNGXRJQKUYDBDP-UHFFFAOYSA-N n-ethyl-n-methylhexadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCC[N+](C)([O-])CC WNGXRJQKUYDBDP-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000000075 primary alcohol group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 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
- C11D1/83—Mixtures of non-ionic with anionic 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
-
- 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
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
- C11D1/02—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
- C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
Definitions
- This invention relates to aqueous liquid detergent compositions and particularly to dishwashing compositions incorporating a mixture of anionic and ethoxylated nonionic surfactants.
- Liquid detergent compositions intended for use as dishwashing products conventionally take the form of clear aqueous solutions containing a mixture of one or more sulphate and sulphonate anionic surfactants together with a suds stabilising agent.
- sulphonate surfactants may be of the olefin sulphonate, paraffin sulphonate, or most usually, alkyl benzene sulphonate type, whilst alkyl sulphates and alkyl ether sulphates form the sulphate species commonly employed.
- magnesium cations for at least part of the anionic surfactants present and the disclosures of British Patent Specifications Nos.
- Ethoxylated nonionic surfactants constitute a class of materials capable of solubilising other components in aqueous media but this capability is strongly dependent on their average degree of ethoxylation (E av ) '
- Highly ethoxylated nonionic surfactants, (i.e. E av >20) are very hydrophilic in nature and thus tend to reduce the oily soil removal capability of liquid dishwashing detergent formulations, which is undesirable where oil and grease removal is an important criterion of consumer acceptance.
- Highly ethoxylated nonionics having hydrocarbon chain lengths less than C 12 are not readily available commercially, but longer chain length materials having high levels of ethoxylation which are available in bulk (e.g.
- nonionic surfactants having low levels of ethoxylation i.e. E av ⁇ 2
- E av ⁇ 2 are relatively hydrophobic and have a limited ability to solubilise other components in the absence of other surfactant species.
- aqueous liquid detergent composition in the form of a pourable suspension comprising a C 10 -C 18 alkyl aryl sulphonate together with a C 8 -C 18 alkyl ethoxysulphate containing from one to ten ethoxy groups per mole, a solid phosphate builder and an ethoxylated nonionic surfactant.
- the nonionic surfactant may be any of the well known types such as ethoxylates of aliphatic alcohols, alkyl phenols, fatty acids or alkylolamides, or block copolymers with other alkylene oxides.
- a feature shared by all ethoxylated nonionic surfactants is the presence of a level of unethoxylated material, the magnitude of which depends on the degree of ethoxylation, but which can constitute up to 20% by weight of the nonionic surfactant.
- Unethoxylated C 6 -C 13 aliphatic primary alcohols are odorous materials having a low water solubility, and these characteristics are discernible in the ethoxylated alcohols to an extent which depends on the level of ethoxylation, the effect diminishing as Eav increases.
- ethoxylated alcohol surfactants in particulate laundry detergent formulations makes the odour characteristics of the ethoxylated alcohol of relatively minor importance in such products, particularly granular products for use in automatic washing machines.
- consumers tend to be very aware of the physical characteristics of liquid detergent compositions, particularly those used for dishwashing, because of the manual nature of the task and the greater degree of exposure of the consumer to the hot wash liquor.
- Dishwashing liquid detergent formulations are commercially available containing paraffin sulphonate as the principal anionic species, together with ethoxylated nonionic surfactants having E av in the range 2-6 so that formulations have a measure of aesthetic acceptance by consumers.
- the adverse influence of unethoxylated components in the nonionic surfactant on the phase stability characteristics of liquid dishwashing detergents has been judged to be unacceptable.
- liquid dishwashing detergent compositions containing alkyl sulphates and/or alkyl benzene sulphonates have been found to be subject to odour and storage stability problems when formulated with ethoxylated nonionic surfactants containing the normal spread of ethoxylated species, and this effect is more pronounced when the composition also contains magnesium ions.
- a physically stable liquid detergent composition comprising from 20 to 50% by weight of an anionic surfactant system consisting essentially of a C 10 -C 16 alkyl benzene sulphonate salt and/or a C 10 -C 16 primary alkyl sulphate salt together with a C 10 -C 16 primary alkyl ethoxy sulphate salt containing an average of not more than 6 ethylene oxide groups per alkyl group in the alkyl ether sulphate, and optionally including a suds stabilising agent wherein the composition also includes from 1 to 10% by weight of an ethoxylated Cs-C,3 aliphatic alcohol containing an average of from 1.5 to 25 moles of ethylene oxide per mole of alcohol, said ethoxylated alcohol containing not more than 1% by weight of unethoxylated alcohol where the ethoxylated alcohol contains an average of less than 9 moles of ethylene oxide and not more than 2% by weight of unethoxylated alcohol
- the ethoxylated aliphatic alcohol has an HLB in the range from 8.0 to 17.0, more preferably from 11.0 to 17.0, and most preferably from 11.0 to 15.0.
- the ethoxylated aliphatic alcohol is a C 9 -C 11 primary alcohol condensed with an average of from 6 to 10 moles of ethylene oxide per mole of alcohol.
- the ethoxylated alcohol contains less than 0.7% by weight, most preferably less than 0.5% by weight of unethoxylated material, and in highly preferred compositions the level of mono- ethoxylated Cg-C il alcohol is no more than 5% by weight of the nonionic surfactant.
- Preferred liquid detergent compositions incorporate an alkyl sulphate surfactant and magnesium ions in a molar amount corresponding to at least half of the molar amount of the alkyl sulphate present and contain from 1% to 5% by weight of the ethoxylated alcohol.
- compositions incorporates a three component anionic surfactant system, comprising 8-12% by weight of the composition of C 10 -C 16 primary alkyl sulphate, 9-11 % by weight of a C 10 -C 16 primary alkyl ethoxysulphate containing an average of from 1.5 to 3 ethoxy groups per alkyl group, and 13-17% by weight of a C 10 -C 16 alkyl benzene sulphonate.
- the cations in this system are a mixture of ammonium and magnesium ions, the level of magnesium corresponding to approximately one half of the molar amount of alkyl sulphate present.
- compositions employs a two component anionic surfactant system comprising from 4 to 8% by weight of a C lo -C, 6 primary alkyl sulphate and from 20 to 25% by weight of a C 10 -C 16 alkyl ethoxy sulphate containing from 0.5 to 2.0 ethoxy groups per alkyl group.
- compositions in accordance with the invention also contain 2%-8%, most preferably 3%-4%, by weight of a suds booster selected from C 10 -C 16 mono and di C 2 -C 3 alkanolamides, and C 8 -C 18 alkyl di C,-C 3 alkyl amine oxides.
- a suds booster selected from C 10 -C 16 mono and di C 2 -C 3 alkanolamides, and C 8 -C 18 alkyl di C,-C 3 alkyl amine oxides.
- Detergent compositions in accordance with the present invention comprise a mixture of anionic surfactants of defined constitution, in an amount of from 20% to 50% by weight of the composition, together with an ethoxylated nonionic surfactant having a low content of unethoxylated material.
- compositions in accordance with the invention incorporate an alkyl sulphate and/or an alkyl benzene sulphonate component in combination with an alkyl ethoxy sulphate.
- the alkyl sulphate component is a primary alkyl sulphate in which the alkyl group contains 10-16 carbon atoms, more preferably an average of 12-14 carbon atoms.
- the alkyl group may be linear or branched in configuration.
- Examples of synthetically derived materials include Dobanol 23 (RTM) sold by Shell Chemicals (UK) Ltd, Ethyl 24 sold by the Ethyl Corporation, a blend of C 13 -C 15 alcohols in the ratio 67% C 13 , 33% C, 5 sold under the trade name Lutensol by BASF GmBH and Synperonic (RTM) by ICI Ltd, and Lial 125 sold by Liquichimica Italiana.
- Examples of naturally occurring materials from which the alcohols can be derived are coconut oil and palm kernel oil and the corresponding fatty acids.
- the level of the alkyl sulphate component lies in the range of from 4% to 20% by weight of the composition, more generally from 4% to 16% by weight.
- the usage level lies in the range from 8% to 12% by weight, most preferably in the range from 8% to 11% by weight.
- the alkyl sulphate level lies in the range from 12% to 20%, more preferably from 14% to 18% by weight.
- any alkali metal, alkali earth metal, ammonium or substituted ammonium cation can be used in association with the alkyl sulphate.
- the alkyl sulphate is associated with a source of magnesium ions which, as will be described hereinafter, can either be introduced as the oxide or hydroxide to neutralise the acid, or can be added to the composition as a water soluble salt.
- the addition of appreciable levels of magnesium salts to the dishwashing compositions of the invention raises the temperature at which inorganic salt crystals form in the compositions on cooling and is therefore less preferable.
- the molar amount of magnesium ion in the compositions is controlled to correspond to 0.20-0.70X, preferably 0.45-0.55X where X is the number of moles of C lO -C l6 alkyl sulphate present.
- the magnesium ion content is adjusted to provide the stoichiometric equivalent of the alkyl sulphate present.
- the magnesium ion will be present at a level of from 0.15% to 0.70% by weight, preferably from 0.25% to 0.55% by weight of the composition.
- compositions containing only alkyl sulphate and alkyl ether sulphate as the anionic surfactants will preferably contain up to 0.90% by weight of the composition of magnesium ion, and part of the alkyl ether sulphate will also be neutralised by magnesium ion.
- Alkyl benzene sulphonates useful in compositions of the present invention are those in which the alkyl group, which is substantially linear, contains 10-16 carbon atoms, preferably 11-13 carbon atoms, a material with an average carbon chain length of 11.8 being most preferred.
- the phenyl isomer distribution i.e. the point of attachment of the alkyl chain to the benzene nucleus, is not critical but alkyl benzenes having a high 2-phenyl isomer content are preferred.
- an alkylbenzene sulphonate content of from 10% to 28% by weight of the composition is required generally from 12% to 26% by weight.
- an alkylbenzene sulphonate content of from 13% to 17% by weight is used and highly preferred compositions in accordance with this aspect of the invention have from 14% to 17% by weight of C".8 alkyl benzene sulphonate.
- the alkyl ethoxy sulphate surfactant component comprises a primary alkyl ethoxy sulphate derived from the condensation product of a C 10 -C 16 alcohol with an average of up to 6 ethylene oxide groups.
- the C 10 -C 16 alcohol itself can be obtained from any of the sources previously described for the alkyl sulphate component. It has, however, been found preferable to use alkyl sulphate and alkyl ether sulphate in which the carbon chain length distributions are the same.
- C 12 -C 13 alkyl ether sulphates are preferred and the level of alkyl ethoxy sulphate in the composition lies between 8% and 25% by weight of the compositions, generally in the range from 10% to 25% by weight.
- the level lies in the range from 9% to 15% by weight, most preferably in the range from 9% to 11% by weight.
- Blends can be made of material having different degrees of ethoxylation and/or different ethoxylate distributions arising from the specific ethoxylation techniques employed and subsequent processing steps such as distillation. For example, it has been found that equivalent sudsing and grease removal performance to that given by a blend of alkyl sulphate and alkyl triethoxy ether sulphate can be obtained by reducing the level of alkyl sulphate and using an alkyl ether sulphate with an average of approximately two ethoxy groups per mole of alcohol.
- the average degree of ethoxylation is from 0.5 to 4, more preferably from 0.8 .to 2.0.
- the counter ion for the alkyl ethoxy sulphate can be any one of sodium, potassium, ammonium or alkanol-ammonium or a mixture thereof. However, for the purposes of obtaining the lowest possible chill point temperature, (the temperature at which inorganic salt crystals separate), it is desirable that at least 30% of the counter ions for the alkyl ethoxy sulphate should be ammonium. In compositions containing an alkyl benzene sulphonate component it is highly preferred that the alkyl ethoxy sulphate is completely neutralized by ammonium ions.
- the counter ions in association with the alkyl benzene sulphonate are independently selected in the same manner as those for the alkyl ethoxy sulphate, there being preferably at least 50% of ammonium ions.
- at least 70% of the neutralising cations for the anionic surfactants should be ammonium ions and most preferably ammonium constitutes the only cation present other than magnesium.
- the ethoxylated nonionic surfactant component of the invention is a C 6 -C, 3 aliphatic alcohol ethoxylate containing an average of from 1.5 to 25, more preferably from 2 to 15 and most preferably from 6 to 10 moles of ethylene oxide per mole of alcohol.
- the aliphatic alcohol ethoxylate contains not more than 1% by weight of unethoxylated alcohol where the ethoxylated alcohol contains an average of less than 9 moles of ethylene oxide and not more than 2% by weight of unethoxylated alcohol where the ethoxylated alcohol contains an average of from 9 to 25 moles of ethylene oxide per mole of alcohol.
- the starting alcohol may be a primary or secondary alcohol but is preferably a primary alcohol which may be derived from natural or synthetic sources.
- natural fats or oils, or products of Ziegler olefin build up reactions or OXO synthesis may all be used as the source of the hydrocarbon chain, the structure of which may be linear or branched in type.
- the preferred alcohol chain length range is from C 9 -C 11 as it has been found that performance, viz. sudsing volume and mileage, are optimum for ethoxylates made from such alcohols.
- the average degree of ethoxylation (E av ) lies in the range from 1.5 to 25 moles per mole of alcohol, but is preferably in the range from 2-15 and most preferably in the range from 6 to 10 moles per mole of alcohol. It is also desirable for performance reasons that the hydrophilic-lipophilic balance (HLB) of the ethoxylated alcohol is in the range from 8.0 to 17.0, more preferably from 11.0 to 17.0 and most preferably from 11.0 to 15.0.
- HLB hydrophilic-lipophilic balance
- a normal (base catalysed) ethoxylation process results in a wide distribution of ethoxylate species.
- this range extends from 1 to at least 15 moles of ethylene oxide per mole of alcohol and for an average in the range of from 20 to 25 moles per mole of alcohol the range may extend up to 50 moles/mole of alcohol.
- Increases in E av cause the ethoxylate distribution to become less peaked about the average value and also lead to a reduction in the level of unethoxylated material.
- Condensation products having an E av in the range from 3 to 9 moles per mole of alcohol contain 3-20% unethoxylated material while products having an E av in the range from 10 to 20 moles per mole of alcohol will still contain up to 2% of unethoxylated material.
- levels of unethoxylated material in the ethoxylated nonionic surfactant of greater than 2% by weight will give rise to phase stability/chill point problems and/or will result in a product having a fatty alcohol odour which is unacceptable to consumers and which is difficult to mask with conventional detergent perfumes.
- the maximum level of unethoxylated alcohol that can be tolerated in the ethoxylated alcohol component is 1 % by weight of the alcohol ethoxylate where the level of ethoxylation is less than 9 moles per mole of alcohol and 2% by weight where the level of ethoxylation is from 9 to 25 moles per mole of alcohol. More preferably the unethoxylated alcohol level is not more than 0.7% and most preferably is less than 0.5% by weight of the ethoxylated alcohol component.
- Distillation under vacuum is employed to remove the undesired material and this also removes a portion of the monoethoxylate fraction, thereby increasing the E av of the remaining material.
- the ethoxylated alcohol is a C 9 -C 11 primary alcohol ethoxylate the level of monoethoxylate is not more than 5% by weight of the ethoxylated alcohol.
- the level of usage of the ethoxylated alcohol component in compositions of the invention is from 1 to 10% by weight, more preferably from 1 to 5% and most preferably from 2% to 4% by weight.
- a highly preferred ingredient of the composition according to the invention is a suds-promoting agent present at a level of from 2% to 8% by weight of the composition, preferably from 3% to 6% and most preferably 3%-4%.
- the suds-promoting agent can be any of C 10 -C 16 mono- and di-C 2 -C 3 alkanolamide, and tertiary amine oxides containing a C 8 -C 18 alkyl group.
- alkanolamides examples include coconut alkyl monoethanolamide, coconut alkyl diethanolamide and palm kernel and coconut alkyl mono and di isopropanol amides.
- the palm kernel or coconut alkyl residue may either be 'whole cut', including the Cm and C 16 fractions or may be the so-called 'narrow-cut' C 12 -C 14 fraction. Synthetic sources of the C 10 -C 16 alkyl group can also be used.
- Amine oxides useful in the present invention have one alkyl or hydroxyalkyl moiety of 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms and two moieties selected from alkyl groups and hydroxyalkyl groups containing 1 to 3 carbon atoms.
- Examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl) dodecylamine oxide, methylethylhexadecylamine oxide, and dimethyl - 2 - hydroxyoctadecylamine oxide.
- tertiary amine oxide is a C 12 -C 14 alkyl dimethyl amine oxide in which the C 12 -C 14 alkyl group is derived from coconut oil.
- the balance of the formula comprises a hydrotrope-water system in which the hydrotrope may be urea, a C 1 -C 3 aliphatic alcohol, or a lower alkyl benzene sulphonate or mixtures of any of these.
- the hydrotrope may be urea, a C 1 -C 3 aliphatic alcohol, or a lower alkyl benzene sulphonate or mixtures of any of these.
- compositions in accordance with the present invention preferably employ a mixture such as urea-alcohol-water or alcohol-lower alkyl benzene sulphonate-water in order to achieve the desired viscosity, and to remain stable and easily pourable.
- the preferred alcoholic hydrotrope is ethanol which is employed at from 3% to 10% by weight of the composition, preferably at from 4% to 8%, usually in admixture with urea.
- Mixtures of hydrotropes can, of course, be employed for cost effectiveness reasons irrespective of any stability/viscosity considerations.
- Optional ingredients of the liquid detergent compositions of the invention include opacifiers such as ethylene glycol distearate, antibacterial agents such as glutaraldehyde and Bronopol (RTM), antitarnish agents such as benzoxytriazole, heavy metal chelating agents such as ETDA or ETDMP, perfumes and dyes.
- opacifiers such as ethylene glycol distearate
- antibacterial agents such as glutaraldehyde and Bronopol (RTM)
- antitarnish agents such as benzoxytriazole
- heavy metal chelating agents such as ETDA or ETDMP
- perfumes and dyes include opacifiers such as ethylene glycol distearate, antibacterial agents such as glutaraldehyde and Bronopol (RTM), antitarnish agents such as benzoxytriazole, heavy metal chelating agents such as ETDA or ETDMP, perfumes and dyes.
- the pH of the compositions may be anywhere within the range 6-7.5 but as
- compositions of the invention can be made in a number of ways but it is preferred that the ethoxylated nonionic surfactant is incorporated towards the end of the making process if not actually forming the last ingredient to be added. This is particularly important where the ethoxylated nonionic surfactant has an HLB 0.5 which is normally taken to be the value below which such materials are basically water insoluble.
- individual anionic surfactants can be made as aqueous solutions of alkali metal or ammonium salts which are then mixed together with the suds booster and with the hydrotrope, following which any magnesium ion can be introduced as a water soluble salt such as the chloride or sulphate.
- the ethoxylated nonionic surfactant and any optional minor ingredients are then added at the same time as the pH and viscosity are adjusted.
- This method has the advantage of utilising conventional techniques and equipment but does result in the introduction of additional chloride or sulphate ions which can increase the chill point temperature (the temperature at which inorganic salts precipitate as crystals in the liquid).
- An alternative and preferred method is to mix an alcohol and alcohol ethoxylate together and carry out a single sulphation and neutralisation.
- the alcohol and alcohol ethoxylate should be mixed in a weight ratio lying in the range 4:3 to 1:6.
- Sulphation can take place by means of any of the conventional sulphating agents such as e.g. sulphur trioxide or chlorosulphonic acid.
- Neutralisation of the alkyl ether sulphuric acid and the alkyl sulphuric acid is carried out with the appropriate alkali or with a magnesium oxide or hydroxide slurry which avoids the addition of chloride or sulphate ions.
- magnesium hydroxide slurry it is convenient to use a mixture of these acids, as the magnesium salt of the alkyl ether sulphuric acid has relatively greater aqueous solubility than the alkyl sulphuric acid component.
- the suds booster is then dissolved in this heel of alkyl sulphate and alkyl ether sulphate actives.
- the separately neutralised alkyl benzene sulphonate salt, and the neutralised alkyl and alkyl ether sulphate salts containing the suds booster and hydrotrope are then added to the final mixing tank and the ethoxylated nonionic surfactant and any optional ingredients added before the pH is adjusted as above.
- compositions in accordance with the invention are clear single phase liquids, but the invention also embraces opaque products containing dispersed phases provided that such products are physically stable (i.e., do not separate) on storage.
- Composition A In the preparation of Composition A, a mixture of alcohol and alcohol ethoxylate was sulphated using S0 3 -air sulphation, and was then neutralised in an alcoholic ammonium hydroxide solution to which magnesium hydroxide had been added in an amount corresponding to half the molar quantity of alkyl sulphate present. A separate sulphonation of the alkyl benzene was employed to produce alkyl benzene sulphonic acid which was added to the alkaline solution of the other actives and neutralised with the excess ammonia to pH 7. The monoethanolamide was then added before final pH trimming to pH 6.8. The chill point of Composition A was -5°C. Compositions B ⁇ E were prepared in a similar manner except that the ethoxylated nonionic surfactant was added during the final pH trimming operation.
- the free fatty acids comprise:
- the method uses 4 cylinders of length 30 cm and diameter 10 cm fixed side by side, and rotatable at a speed of 24 rpm about a central axis. Each cylinder is charged with 500 mls of product solution at a concentration of 0.12% by weight and a temperature of 45°C. The outer two cylinders are used for one of the products being compared and the inner two for the other product.
- the cylinders are rotated for 2 minutes, stopped, the initial suds are measured and a soil load is then added.
- the grease soil comprises a mixture of fatty acids in a cooking oil base and 1 ml of this mixture (MFFA) is added to each cylinder. All of the particulate soil is also added at this stage. After 1 minute the cylinders are restarted and allowed to rotate for 1 minute. The suds height is noted and 1 ml of the 2% by weight MFFA is added to each cylinder. After 1 minute the cylinders are restarted. This process continues until the suds height in the cylinder is lower than 0.5 cm.
- Product A is designated as the control and suds mileage figures are calculated for the other product versus the 'control' product on the following basis.
- Composition B showed the combination of a consistent mileage advantage in both hard and soft water, an acceptable chill point and an acceptable odour.
- compositions are in accordance with the present invention.
- compositions were made up in accordance with Example 1 except that the type, level * (% by weight) and HLB of ethoxylated primary alcohol surfactant was as follows
- compositions H-0 inclusive show advantages over the Comparison Composition A which does not contain an ethoxylated nonionic component. It can also be seen that Compositions H & I which represent preferred embodiments of the invention provide superior performance to other, less preferred, embodiments such as Compositions L & M.
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT84303044T ATE48634T1 (de) | 1983-05-14 | 1984-05-04 | Fluessige reinigungsmittelzusammensetzungen. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB838313348A GB8313348D0 (en) | 1983-05-14 | 1983-05-14 | Liquid detergent compositions |
| GB8313348 | 1983-05-14 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0125854A2 EP0125854A2 (en) | 1984-11-21 |
| EP0125854A3 EP0125854A3 (en) | 1987-08-05 |
| EP0125854B1 true EP0125854B1 (en) | 1989-12-13 |
Family
ID=10542766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84303044A Expired EP0125854B1 (en) | 1983-05-14 | 1984-05-04 | Liquid detergent compositions |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0125854B1 (enrdf_load_stackoverflow) |
| AT (1) | ATE48634T1 (enrdf_load_stackoverflow) |
| CA (1) | CA1228521A (enrdf_load_stackoverflow) |
| DE (1) | DE3480717D1 (enrdf_load_stackoverflow) |
| DK (1) | DK162608C (enrdf_load_stackoverflow) |
| ES (1) | ES532449A0 (enrdf_load_stackoverflow) |
| FI (1) | FI75597C (enrdf_load_stackoverflow) |
| GB (1) | GB8313348D0 (enrdf_load_stackoverflow) |
| GR (1) | GR81944B (enrdf_load_stackoverflow) |
| IE (1) | IE57396B1 (enrdf_load_stackoverflow) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8304144A (nl) * | 1983-12-02 | 1985-07-01 | Shell Int Research | Wasmiddelconcentraten. |
| GB8420945D0 (en) * | 1984-08-17 | 1984-09-19 | Unilever Plc | Detergents compositions |
| ES8708009A1 (es) * | 1984-11-07 | 1987-09-01 | Procter & Gamble | Un metodo para preparar una composicion detergente liquida |
| CA1276852C (en) * | 1985-06-21 | 1990-11-27 | Francis John Leng | Liquid detergent composition |
| GB8625104D0 (en) * | 1986-10-20 | 1986-11-26 | Unilever Plc | Detergent compositions |
| GB9002514D0 (en) * | 1990-02-05 | 1990-04-04 | Albright & Wilson | Surfactant mixtures |
| FR2667865B1 (fr) * | 1990-10-12 | 1992-12-11 | Saint Gobain Isover | Resine phenolique, procede de preparation de la resine et composition d'encollage de fibres minerales la contenant. |
| GB9105808D0 (en) * | 1991-03-19 | 1991-05-01 | Shell Int Research | A liquid aqueous concentrated alkylsulphate composition |
| FR2683939B1 (fr) * | 1991-11-20 | 1993-12-31 | Gec Alsthom Sa | Disjoncteur auto-sectionneur a moyenne tension et application a une cellule et a un poste a moyenne tension. |
| TW211595B (enrdf_load_stackoverflow) * | 1991-12-07 | 1993-08-21 | Hoechst Ag | |
| DE69231555T2 (de) * | 1992-03-17 | 2001-06-07 | The Procter & Gamble Company, Cincinnati | Verdünnbare Zusammensetzungen und Verfahren zur Reinigung harter Oberflächen |
| EP0616028A1 (en) * | 1993-03-19 | 1994-09-21 | The Procter & Gamble Company | Cleaning compositions with short chain nonionic surfactants |
| CA2158248C (en) * | 1993-03-19 | 1999-12-28 | Ricky Ah-Man Woo | Acidic liquid detergent compositions for bathrooms |
| US5384063A (en) * | 1993-03-19 | 1995-01-24 | The Procter & Gamble Company | Acidic liquid detergent compositions for bathrooms |
| EP0616026A1 (en) * | 1993-03-19 | 1994-09-21 | The Procter & Gamble Company | Concentrated cleaning compositions |
| US5981455A (en) * | 1993-03-19 | 1999-11-09 | The Procter & Gamble Company | Cleaning compositions with short chain nonionic surfactants |
| EP0616027A1 (en) * | 1993-03-19 | 1994-09-21 | The Procter & Gamble Company | Concentrated cleaning compositions |
| US5399280A (en) * | 1993-07-22 | 1995-03-21 | The Procter & Gamble Company | Acidic liquid detergent compositions for bathrooms |
| USH1632H (en) * | 1994-08-15 | 1997-02-04 | Shell Oil Company | Liquid laundry detergent formulations |
| DE19534369C2 (de) * | 1995-09-15 | 2000-06-15 | Cognis Deutschland Gmbh | Wäßrige Handgeschirrspülmittel |
| WO1997025397A1 (en) * | 1996-01-05 | 1997-07-17 | The Procter & Gamble Company | Light-duty liquid or gel dishwashing detergent compositions having beneficial skin conditioning, skin feel and rinsability aesthetics |
| US6566321B1 (en) * | 2002-04-24 | 2003-05-20 | Kay Chemical, Inc. | Low foaming washing liquid |
| ATE418596T1 (de) * | 2002-11-04 | 2009-01-15 | Unilever Nv | Waschmittel |
| US20050107275A1 (en) * | 2003-11-14 | 2005-05-19 | Hecht Stacie E. | Liquid detergent composition comprising a solubilizing nonionic surfactant |
| US7456139B2 (en) | 2004-05-07 | 2008-11-25 | Croda Uniqema, Inc. | Solvated nonionic surfactants |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2945301B1 (de) * | 1979-11-09 | 1980-06-19 | Adam Opel Ag, 6090 Ruesselsheim | Reinigungsflüssigkeit für Windschutzscheiben |
| NZ205345A (en) * | 1982-08-27 | 1985-08-30 | Unilever Plc | Aqueous,built liquid detergent compositions |
-
1983
- 1983-05-14 GB GB838313348A patent/GB8313348D0/en active Pending
-
1984
- 1984-05-04 DE DE8484303044T patent/DE3480717D1/de not_active Expired - Lifetime
- 1984-05-04 EP EP84303044A patent/EP0125854B1/en not_active Expired
- 1984-05-04 AT AT84303044T patent/ATE48634T1/de not_active IP Right Cessation
- 1984-05-10 GR GR74666A patent/GR81944B/el unknown
- 1984-05-11 IE IE1178/84A patent/IE57396B1/en not_active IP Right Cessation
- 1984-05-11 CA CA000454126A patent/CA1228521A/en not_active Expired
- 1984-05-11 ES ES532449A patent/ES532449A0/es active Granted
- 1984-05-11 DK DK236084A patent/DK162608C/da not_active IP Right Cessation
- 1984-05-11 FI FI841907A patent/FI75597C/fi not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DK236084D0 (da) | 1984-05-11 |
| ATE48634T1 (de) | 1989-12-15 |
| DK162608C (da) | 1992-04-06 |
| DK162608B (da) | 1991-11-18 |
| ES8603561A1 (es) | 1985-12-16 |
| ES532449A0 (es) | 1985-12-16 |
| DK236084A (da) | 1984-11-15 |
| FI75597B (fi) | 1988-03-31 |
| GB8313348D0 (en) | 1983-06-22 |
| CA1228521A (en) | 1987-10-27 |
| FI841907A0 (fi) | 1984-05-11 |
| EP0125854A3 (en) | 1987-08-05 |
| IE57396B1 (en) | 1992-08-26 |
| GR81944B (enrdf_load_stackoverflow) | 1984-12-12 |
| EP0125854A2 (en) | 1984-11-21 |
| FI75597C (fi) | 1988-07-11 |
| DE3480717D1 (de) | 1990-01-18 |
| FI841907A7 (fi) | 1984-11-15 |
| IE841178L (en) | 1984-11-14 |
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