EP0511261B1 - Systeme de gel stabilise et production de ce gel - Google Patents
Systeme de gel stabilise et production de ce gel Download PDFInfo
- Publication number
- EP0511261B1 EP0511261B1 EP91902313A EP91902313A EP0511261B1 EP 0511261 B1 EP0511261 B1 EP 0511261B1 EP 91902313 A EP91902313 A EP 91902313A EP 91902313 A EP91902313 A EP 91902313A EP 0511261 B1 EP0511261 B1 EP 0511261B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- tenside
- detergent composition
- built detergent
- stabilised
- 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 - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 claims abstract description 91
- 239000003599 detergent Substances 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 54
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 24
- 239000000693 micelle Substances 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000013618 particulate matter Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims description 37
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 29
- 239000004115 Sodium Silicate Substances 0.000 claims description 28
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- 239000003945 anionic surfactant Substances 0.000 claims description 23
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 18
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 239000000194 fatty acid Substances 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- 150000004665 fatty acids Chemical class 0.000 claims description 16
- 239000002736 nonionic surfactant Substances 0.000 claims description 16
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 150000007513 acids Chemical class 0.000 claims description 14
- 244000060011 Cocos nucifera Species 0.000 claims description 13
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 13
- 238000006386 neutralization reaction Methods 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 11
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 108090000790 Enzymes Proteins 0.000 claims description 7
- 102000004190 Enzymes Human genes 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 239000003205 fragrance Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003755 preservative agent Substances 0.000 claims description 4
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 4
- 238000004448 titration Methods 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- -1 alkali metal tripolyphosphate Chemical class 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 239000007844 bleaching agent Substances 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 239000003906 humectant Substances 0.000 claims description 3
- 230000005764 inhibitory process Effects 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- 239000004872 foam stabilizing agent Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 description 40
- 239000000499 gel Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000006188 syrup Substances 0.000 description 18
- 235000020357 syrup Nutrition 0.000 description 18
- 239000004615 ingredient Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- 239000000017 hydrogel Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001493 electron microscopy Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000003752 hydrotrope Substances 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 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 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- WFRXSOIFNFJAFL-UHFFFAOYSA-N P1(OCCCCO1)=O.C(CN)N Chemical class P1(OCCCCO1)=O.C(CN)N WFRXSOIFNFJAFL-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-H [oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O YDHWWBZFRZWVHO-UHFFFAOYSA-H 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 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 1
- 238000000498 ball milling Methods 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008131 herbal destillate Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
Definitions
- This invention relates to a stabilised gel system for supporting finely divided particulate matter in suspension, to detergent compositions and abrasive preparations based on such a stabilised gel system, and to the production thereof.
- each type of preparation contains the same basic ingredients and in both cases it has been necessary to incorporate materials which can only be regarded as inert diluents of the active compounds in the formulation.
- the diluent has been alkali metal sulphates whilst in the case of the liquid it has simply been water.
- Such surface active ingredients normally include an anionic surfactant or tenside and may further include one or more non-ionic surfactants.
- anionic surfactants include the sodium salts of alkyl benzene sulphonic acids and of alkyl sulphonic acids.
- non-ionic surfactants there can be mentioned polyalkylene oxide ethers of alkyl alcohols or alkylphenols, as well as the monoethanolamides of fatty acids, such as coconut fatty acid monoethanolamide.
- US-A-3708428 and US-A-3899447 teach detergent compositions containing silica colloids.
- the colloidal silica is formed in situ as a sol by the reaction of a preheated solution of a water-soluble or dispersible alkali silicate with a preheated anionic, detergent-forming organic acid.
- builders such as complex phosphates (e.g. sodium tripolyphosphate) should be restricted to levels of concentration of the order of 4.0% by weight or lower.
- EP-A-0191372 relates to two-component alkaline cleaners having a pH of 11 or greater.
- the cleaners are said to be suitable for cleaning rigid materials such as metal and glass.
- One of the components of the system is an aqueous silicic acid dispersion which contains detergent builder.
- the component containing the silicic acid dispersion also requires the presence of from 0.3 to 3% by weight of a stabiliser, which is usually based on xanthan.
- the present invention accordingly seeks to provide an improved liquid built detergent composition and a process for making same in which the problems encountered in the prior art are substantially obviated. It also seeks to provide an improved system for supporting finely divided particulate matter in suspension.
- a stabilised gel system for supporting finely divided particulate matter in suspension, the stabilised gel system comprising a hydrosol of silicic acid stabilised by entanglement with micelles of a tenside.
- the tenside is one containing one or more sulphonate groups.
- Such a stabilised gel system can conveniently be produced by at least partially neutralising a sodium silicate solution with a tenside-forming acid containing one or more sulphonic acid groups.
- Such a stabilised gel system is normally acidic or near neutral in character.
- the pH of a liquid support system in accordance with the invention lies in the range of from 1.0 to 9.0. Normally it will have a pH of not more than 8.0, e.g. in the range of from 4.0 to 7.5.
- a liquid built detergent composition comprising a stabilised gel system comprising a hydrosol of silicic acid stabilised by entanglement with micelles of a tenside and particles of a builder substantially uniformly distributed therein.
- an abrasive preparation comprising a hydrosol of silicic acid stabilised by entanglement with micelles of a tenside in which are dispersed finely divided particles of an abrasive material.
- the tenside in such an abrasive preparation is one containing one or more sulphonate groups.
- Such an abrasive composition can be formulated as an oven cleaner, for example, or as a cleaner for hard surfaces.
- a process for the production of a stabilised gel system for supporting finely divided particulate matter in suspension which comprises neutralising a solution of an alkali metal silicate to a pH in the range of from 1.0 to 7.0 in the presence of a tenside thereby to produce a hydrosol of silicic acid stabilised by entanglement with tenside micelles.
- Neutralisation may be effected by addition of an acid to a solution of an alkali metal silicate that contains also at least one surfactant.
- the acid may be selected from hydrochloric acid, sulphuric acid, sulphamic acid, phosphoric acid, formic acid, acetic acid, citric acid, and mixtures of two or more thereof.
- neutralisation may be effected by titration of the solution of alkali metal silicate with a tenside-forming acid containing one or more sulphonic acid groups.
- a solution having a pH of not more than 7.0 is produced by dissolving in an aqueous medium a tenside-forming acid containing one or more sulphonic acid groups and an alkali metal tripolyphosphate and a solution of an alkali metal silicate is added thereto.
- the invention further relates to a process for the production of a liquid built detergent which comprises neutralising a solution of an alkali metal silicate such as sodium silicate, to a pH in the range of from 1.0 to 7.0 in the presence of a tenside thereby to produce a hydrosol of silicic acid stabilised by entanglement with tenside micelles and, either before or after completion of the neutralisation step, incorporating a builder in the composition.
- neutralisation can be effected by addition of an acid to a solution of an alkali metal silicate that also contains at least one surfactant and in which the builder is thereafter added.
- neutralisation can be effected by titration of the solution of alkali metal silicate with a tenside-forming acid containing one or more sulphonic acid groups.
- a solution having a pH of not more than 7.0 is produced by dissolving in an aqueous medium a tenside-forming acid containing one or more sulphonic acid groups and an alkali metal tripolyphosphate and a solution of an alkali metal silicate is added thereto.
- a stabilised gel system according to the invention comprises a hydrosol of silicic acid stabilised by entanglement with micelles of a tenside. Further evidence for such a structure is provided by electron microscopy studies on a liquid built detergent composition prepared from a stabilised gel system according to the invention.
- anionic surfactants which can be utilised in the present invention include alkyl benzene sulphonic acids, in which the alkyl group contains from 6 to 20 carbon atoms, for example from 10 to 14 carbon atoms, alkyl sulphonic acids containing from 10 to 26 carbon atoms, for example from 10 to 14 carbon atoms, and alpha-olefin sulphonic acids obtained by sulphonation of an alpha-olefin containing, for example from 10 to 22 carbon atoms, such as a C 16 to C 18 olefin or a mixture containing same.
- a surfactant containing a sulphonate group there may also be present a sulphated fatty alcohol or a sodium salt thereof;
- typical sulphated fatty alcohols include those containing from 10 to 26 carbon atoms, for example a sulphated fatty alcohol mixture containing C 10 , C 12 , C 14 , C 16 and C 18 fatty alcohols.
- Typical of such a fatty alcohol mixture is one containing alcohols in the following proportions: C 10 3.0%, C 12 57.0%, C 14 20.0%, C 16 9.0% and C 18 11.0%.
- a liquid built detergent composition according to the invention contains from 2% w/w up to 30% w/w of anionic surfactant (calculated as sulphonic acid) based upon the total weight of the composition.
- composition of the invention may further include one or more non-ionic surfactants.
- Typical non-ionic surfactants include fatty acid monoethanolamides such as coconut fatty acid monoethanolamide, a typical formulation for which is a mixture of monoethanolamides of fatty acids as follows: C 6 0.5%, C 8 6.5%, C 10 6.0%, C 12 49.5%, C 14 19.5%, C 16 8.5%, C 18 (stearic) 2.0%, C 18 (oleic) 6.0%, and C 18 (linoleic) 1.5%.
- non-ionic surfactants include polyoxyalkylene ethers of alkanols, typically polyoxyethylene ethers of alkanols containing from about 6 to about 20 ethylene oxide groups and based upon alkanols containing from about 6 to about 26 carbon atoms.
- alkanols and alkanol mixtures can be produced by hydrogenation of methyl esters produced by transesterification of naturally occurring vegetable oils such as coconut oil, sunflower oil, palm oil, rape seed oil, and the like, or of animal fats, such as tallow or lard.
- a typical polyoxyethylene ether of an alkanol is based upon lauryl alcohol condensed with approximately 8 moles of ethylene oxide.
- the concentration of non-ionic surfactant, if present, in the liquid built detergent composition ranges from 0.5% w/w up to 30% w/w based upon the total weight of the composition.
- liquid built detergent composition of the invention examples include preservatives, optical brighteners, bleaches, fragrances, zeolites, foam depressants, foam boosters and/or stabilisers, soaps, dyes, buffers, corrosion inhibition agents, bleach activators, enzymes, humectants, enzyme stabilisers, and the like.
- Such minor ingredients do not usually comprise more than 5% w/w each of the total composition, mostly less than 1% w/w each of the total composition, and more usually do not together amount to more than 5% w/w in total based upon the weight of the composition.
- a builder there can be mentioned in particular sodium tripolyphosphate. Potassium tripolyphosphate can alternatively be used.
- the pyrophosphates, metaphosphates, orthophosphates, tetraphosphate, phosphonates such as acetonodiphosphonates, aminotrismethylenephosphonates, ethylenediamine tetramethylene phosphonates, and carbonates of sodium and potassium have also been suggested as builders, as have also zeolites and organic sequestering agents, such as nitrilotriacetic acid, ethylene diamine tetraacetic acid, and polymeric carboxylic acids and their salts, such as polyacrylic acid and polymethacrylic acid.
- a typical liquid built detergent composition according to the invention comprises from 5% w/w up to 40% w/w based upon the total weight of the composition of a builder or builders.
- the pH is typically in the range of from 1.0 to 8.0, preferably about pH 4.0.
- a pH increase is often observed. In some cases the pH may rise above 7.0, when starting from a stabilised gel system at a pH of about 4.0; hence the final pH may be as high as 9.0 or even a little higher.
- the liquid built detergents of GB-B-2123846 are characterised by the fact that, upon centrifuging at 800 times normal Earth gravity for 17 hours at 25°C, these compositions separate into a first, predominantly aqueous, liquid phase, containing dissolved electrolyte, and at least one other phase. It is an advantage of our invention that, if a stabilised gel system is prepared of sufficient strength, then this may be used to prepare a liquid built detergent composition which does not separate into two or more phases upon centrifuging at 800 times normal Earth gravity for 17 hours at 25°C.
- the liquid built detergent composition if starting from sodium silicate as the precursor for the silicic acid hydrosol, from a mixture of ingredients that includes at least 3.0% by weight of sodium silicate (or an equivalent amount of another soluble silicate) up to 8% by weight based upon the total weight of the liquid built detergent composition.
- sodium silicate or equivalent
- alkylbenzene sulphonic acid or mixture of alkylbenzene sulphonic acids, is dissolved in about twice its own weight of water and added to the sodium silicate which was previously diluted with three times its weight of water. To the resulting transparent syrup, with slow stirring, are added all the other ingredients to produce a shining white, or glossy, pourable syrup which is further diluted with water to give the full batch of product at 100% by weight basis.
- a suitable alkyl benzene sulphonic acid is dodecyl benzene sulphonic acid.
- the sodium alkylbenzene sulphonate (e.g. sodium dodecyl benzene sulphonate) is twice diluted with water and placed in a pan and to it is added the sodium silicate syrup which can, if desired, be diluted with three volumes of water before addition to the pan.
- the mixture is slowly stirred and the pH value of the solution reduced to 8.0 by the use of the correct aliquot of the 25% hydrochloric acid. Once the reaction is over, which is about two minutes after the last addition of hydrochloric acid, the remainder of the water is added followed by the addition of the other ingredients in any order. Final adjustment to the required weight is by the last addition of water.
- a product similar to that of Example 1 is obtained.
- a liquid built detergent composition is prepared from the following ingredients: Dodecylbenzenesulphonic acid 10.0% Sodium silicate (47%) syrup about 6.5% Coconut Fatty Acid Monoethanolamide 1.4% Sodium carboxymethylcellulose 0.1% Sodium tripolyphosphate 24.2% Preservative 0.2% Alcohol ethoxylate 1.3% Hydrotrope H66 0.5% Antifoam 0.2% Fragrance 0.2% Enzyme - Esperase 0.4% Termamyl 0.4% Optical brightener 0.1% Water To 100%
- the alcohol ethoxylate used in this Example was a polyoxyethylene ether obtained by condensing 7 moles of ethylene oxide with a C 13/15 alcohol.
- the sodium carboxymethyl cellulose is dissolved in water.
- the coconut fatty acid monoethanolamide is also dissolved in hot water.
- the dodecylbenzene sulphonic acid is diluted with about twice its own weight of water.
- the sodium silicate syrup which has previously been diluted with about three times its own weight of water.
- Sufficient of this diluted sodium silicate syrup is added to give a pH of about 4.0.
- the sodium carboxymethyl cellulose solution is added, followed by the coconut fatty acid monoethanolamide solution, while continuing to stir.
- the sodium tripolyphosphate is added with stirring, followed by the other minor ingredients.
- the composition is diluted to the desired strength with water.
- the resulting composition is stable and does not separate out into separate layers even after several months storage. Moreover, upon centrifugation at 800g for 17 hours, no separation of phases can be detected. There is no sign of any formation of vesicles or spherulites, nor is there any evidence of any of the surfactant being present as a lamellar liquid crystal or solid hydrate. Hence, upon electron microscopic evaluation of the detergent composition of this Example, the observations recorded were consistent with a largely featureless granular structure with crystals of sodium tripolyphosphate distributed at random.
- a liquid built detergent composition is produced from the same ingredients as are used in Example 3 except that the addition of the sodium silicate syrup is delayed until after addition of the sodium tripolyphosphate.
- the sodium carboxymethyl cellulose and the coconut fatty acid monoethanolamide are each dissolved separately in hot water.
- the dodecylbenzene sulphonic acid is diluted with about twice its own weight of water.
- the sodium carboxymethyl cellulose solution and the coconut fatty acid ethanolamide solution are added in turn to the dodecylbenzene sulphonic acid solution with vigorous stirring to yield a solution having a pH of about 7.0 or lower, followed by the other minor ingredients.
- the sodium silicate syrup which has previously been diluted with twice its own weight of water, is added whilst continuing to stir vigorously. Finally the composition is diluted with water to the desired strength.
- the resulting liquid built detergent composition is similar to that of Example 3 except that it exhibits initially a somewhat lower viscosity. It does not separate into layers upon centrifugation at 800 g for 17 hours. It does not show any indication that any spherulites or vesicles are present, nor is there any evidence of any of the surfactant being present in the form of a lamellar liquid crystal or solid hydrate. Moreover, the results of electron microscopy evaluation indicate that the liquid built detergent composition of this Example has a largely featureless granular structure with randomly distributed crystals of sodium tripolyphosphate.
- a soft anionic gel or syrup can be loaded with fine abrasive and used as an oven, or hard surface, cleaner.
- the invention is not restricted, in its application, to pourable gel systems in heavy duty laundry detergents.
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Claims (40)
- Utilisation d'un système de gel stabilisé destiné à supporter une matière particulaire finement divisée en suspension, le système de gel stabilisé comprenant un hydrosol d'acide silicique stabilisé par enchevêtrement avec les micelles d'un tensioactif.
- Utilisation selon la revendication 1, dans laquelle le pH du système de gel stabilisé est compris entre 1,0 et 9,0.
- Utilisation selon la revendication 1 ou la revendication 2, dans laquelle le pH du système de gel stabilisé est compris entre 4,0 et 7,5.
- Utilisation selon l'une quelconque des revendications 1 à 3, dans laquelle le tensioactif du système de gel stabilisé comprend un tensioactif anionique choisi parmi les tensioactifs anioniques dérivés des acides alkylbenzène-sulfoniques, les tensioactifs anioniques dérivés des acides alkyl-sulfoniques et les tensioactifs anioniques dérivés des acides alpha-oléfine-sulfoniques.
- Utilisation selon la revendication 4, dans laquelle le système de gel stabilisé comprend en outre au moins un tensioactif non ionique.
- Utilisation selon la revendication 5, dans laquelle ledit au moins un tensioactif non ionique comprend du monoéthanolamide d'acide gras de coco.
- Utilisation selon l'une quelconque des revendications 1 à 6, dans laquelle le système de gel stabilisé a été préparé par un procédé qui comprend le fait de neutraliser une solution d'un silicate de métal alcalin à un pH compris entre 1,0 et 7,0 en présence d'un tensioactif, de manière à produire un hydrosol d'acide silicique stabilisé par enchevêtrement avec les micelles de tensioactif.
- Composition de détergent liquide contenant un adjuvant comprenant un système de gel stabilisé comprenant un hydrosol d'acide silicique stabilisé par enchevêtrement avec les micelles d'un tensioactif et des particules d'un adjuvant distribué de façon sensiblement uniforme dans celui-ci.
- Composition de détergent liquide contenant un adjuvant selon la revendication 8, dans laquelle le tensioactif comprend un tensioactif contenant un ou plusieurs groupes sulfonates.
- Composition de détergent liquide contenant un adjuvant selon la revendication 9, qui contient* au moins un tensioactif anionique (calculé comme acide sulfonique) sur la base du poids total de la composition qui est choisi parmi les tensioactifs anioniques dérivés des acides alkylbenzène-sulfoniques, dans lesquels le groupe alkyle contient de 6 à 20 atomes de carbone, des tensioactifs anioniques dérivés des acides alkyl-sulfoniques contenant de 10 à 26 atomes de carbone, des acides alpha-oléfine-sulfoniques contenant de 10 à 22 atomes de carbone et des mélanges de ceux-ci.
- Composition de détergent liquide contenant un adjuvant selon la revendication 10, dans laquelle le tensioactif anionique est dérivé de l'acide dodécylbenzène-sulfonique.
- Composition de détergent liquide contenant un adjuvant selon l'une quelconque des revendications 9 à 11, qui comprend en outre un alcool gras sulfaté ou un sel de sodium de celui-ci.
- Composition de détergent liquide contenant un adjuvant selon l'une quelconque des revendications 9 à 12, qui contient de 2 % p/p à 30 % p/p d'au moins un tensioactif anionique (calculé comme acide sulfonique) sur la base du poids total de la composition.
- Composition de détergent liquide contenant un adjuvant selon l'une quelconque des revendications 8 à 13, qui comprend en outre de 0,5 % p/p à 30 % p/p d'au moins un tensioactif non ionique.
- Composition de détergent liquide contenant un adjuvant selon la revendication 14, dans laquelle ledit au moins un tensioactif non ionique comprend le monoéthanolamide d'acide gras de coco.
- Composition de détergent liquide contenant un adjuvant selon la revendication 14 ou la revendication 15, dans laquelle ledit au moins un tensioactif non ionique comprend un éther polyoxyalkylénique d'un alcanol contenant d'environ 6 à environ 20 groupes oxyde d'éthylène et basé sur un alcanol contenant d'environ 6 à environ 26 atomes de carbone.
- Composition de détergent liquide contenant un adjuvant selon l'une quelconque des revendications 8 à 16, dans laquelle la quantité d'adjuvant ou d'adjuvants comprend de 5 % p/p à 40 % p/p sur la base du poids de la composition.
- Composition de détergent liquide contenant un adjuvant selon l'une quelconque des revendications 8 à 17, dans laquelle l'adjuvant comprend du tripolyphosphate de sodium.
- Composition de détergent liquide contenant un adjuvant selon l'une quelconque des revendications 8 à 18, dans laquelle la quantité d'acide silicique correspond à 3 % p/p à 8 % p/p (calculé comme silicate de sodium) sur la base du poids de la composition.
- Composition de détergent liquide contenant un adjuvant selon l'une quelconque des revendications 8 à 19, qui comprend en outre au moins un matériau choisi dans l'ensemble formé par les conservateurs, les azurants optiques, les agents de blanchiment, les parfums, les zéolites, les suppresseurs de mousse, les exalteurs de mousse, les stabilisateurs de mousse, les savons, les colorants, les tampons, les agents anticorrosion, les activateurs de blanchiment, les enzymes, les agents mouillants et les stabilisateurs enzymatiques.
- Composition de détergent liquide contenant un adjuvant selon l'une quelconque des revendications 8 à 20, dans laquelle le pH est compris entre 4,0 et 9,0.
- Composition de détergent liquide contenant un adjuvant selon l'une quelconque des revendications 8 à 21, qui ne se sépare pas en deux ou plusieurs phases lors d'une centrifugation à 800 fois l'attraction terrestre normale pendant 17 heures à 25°C.
- Préparation abrasive comprenant un système de gel stabilisé comprenant un hydrosol d'acide silicique stabilisé par enchevêtrement avec les micelles d'un tensioactif et les particules abrasives finement divisées distribuées de façon sensiblement uniforme dans celui-ci.
- Procédé de fabrication d'une composition de détergent liquide contenant un adjuvant selon la revendication 8, qui comprend le fait de neutraliser une solution de silicate de métal alcalin à un pH compris entre 1,0 et 7,0 en présence d'un tensioactif de manière à produire un hydrosol d'acide silicique stabilisé par enchevêtrement avec les micelles de tensioactif et, soit avant soit après la fin de l'étape de neutralisation, le fait d'incorporer un adjuvant à la composition.
- Procédé selon la revendication 24, dans lequel la quantité d'adjuvant ou d'adjuvants comprend de 5 % p/p à 40 % p/p sur la base du poids de la composition.
- Procédé selon la revendication 24 ou la revendication 25, dans lequel l'adjuvant comprend le tripolyphosphate de sodium.
- Procédé selon l'une quelconque des revendications 24 à 26, dans lequel la neutralisation est réalisée par addition d'un acide à une solution de silicate de métal alcalin qui contient également au moins un tensioactif.
- Procédé selon la revendication 27, dans lequel l'acide est choisi dans l'ensemble formé par l'acide chlorhydrique, l'acide sulfurique, l'acide sulfamique, l'acide phosphorique, l'acide formique, l'acide acétique, l'acide citrique, et des mélanges de deux ou plusieurs de ceux-ci.
- Procédé selon l'une quelconque des revendications 24 à 26, dans lequel une solution ayant un pH ne dépassant pas 7,0 est produite en dissolvant dans un milieu aqueux un acide formant un tensioactif contenant un ou plusieurs groupes acide sulfonique et en ajoutant à celui-ci un tripolyphosphate de métal alcalin, puis une solution de silicate de métal alcalin est ajoutée.
- Procédé selon l'une quelconque des revendications 24 à 26, dans lequel la neutralisation est réalisée par titrage de la solution de silicate de métal alcalin avec un acide formant un tensioactif contenant un ou plusieurs groupes acide sulfonique.
- Procédé selon l'une quelconque des revendications 24 à 30, dans lequel le silicate de métal alcalin est le silicate de sodium.
- Procédé selon l'une quelconque des revendications 24 à 31, dans lequel le tensioactif est un tensioactif anionique choisi parmi les tensioactifs anioniques dérivés des acides alkylbenzène-sulfoniques, des acides alkyl-sulfoniques, et les tensioactifs anioniques dérivés des acides alpha-oléfine-sulfoniques.
- Procédé selon l'une quelconque des revendications 24 à 32, dans lequel on ajoute en outre au moins un tensioactif non ionique.
- Procédé selon la revendication 33, dans lequel le tensioactif non ionique comprend le monoéthanolamide d'acide gras de coco.
- Procédé selon l'une quelconque des revendications 24 à 34, dans lequel on incorpore à la composition, soit avant soit après l'étape de neutralisation, un alcool gras sulfaté ou un sel de sodium de celui-ci.
- Procédé selon l'une quelconque des revendications 24 à 35, dans lequel on utilise de 2 % p/p à 30 % p/p de tensioactif anionique (calculé comme acide sulfonique) sur la base du poids total de la composition.
- Procédé selon l'une quelconque des revendications 24 à 36, dans lequel on incorpore à la composition, soit avant soit après l'étape de neutralisation, de 0,5 % p/p à 30 % p/p d'au moins un tensioactif non ionique comprenant le monoéthanolamide d'acide gras de coco, un éther polyoxyalkylénique d'un alcanol contenant de 6 à 20 groupes oxyde d'éthylène et basé sur un alcanol contenant de 6 à 26 atomes de carbone, ou un mélange de ceux-ci.
- Procédé selon l'une quelconque des revendications 24 à 37, dans lequel on utilise de 3 % p/p à 8 % p/p de** silicate de sodium sur la base du poids de la composition.
- Procédé selon l'une quelconque des revendications 24 à 38, qui comprend en outre le fait d'incorporer dans la composition, soit avant soit après l'étape de neutralisation, au moins un matériau choisi dans l'ensemble formé par les conservateurs, les azurants optiques, les agents de blanchiment, les parfums, les zéolites, les suppresseurs de mousse, les exalteurs de mousse, les stabilisateurs de mousse, les savons, les colorants, les tampons, les agents anticorrosion, les activateurs de blanchiment, les enzymes, les agents mouillants et les stabilisateurs enzymatiques.
- Procédé selon l'une quelconque des revendications 24 à 39, dans lequel le pH de la composition résultante est compris entre 4,0 et 9,0.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9000833 | 1990-01-15 | ||
GB909000833A GB9000833D0 (en) | 1990-01-15 | 1990-01-15 | Detergent and production thereof |
GB9024563 | 1990-11-12 | ||
GB909024563A GB9024563D0 (en) | 1990-11-12 | 1990-11-12 | Stabilised gel system and production thereof |
PCT/GB1991/000052 WO1991010720A1 (fr) | 1990-01-15 | 1991-01-15 | Systeme de gel stabilise et production de ce gel |
Publications (2)
Publication Number | Publication Date |
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EP0511261A1 EP0511261A1 (fr) | 1992-11-04 |
EP0511261B1 true EP0511261B1 (fr) | 1997-06-25 |
Family
ID=26296501
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91902313A Expired - Lifetime EP0511261B1 (fr) | 1990-01-15 | 1991-01-15 | Systeme de gel stabilise et production de ce gel |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0511261B1 (fr) |
AT (1) | ATE154827T1 (fr) |
AU (1) | AU7178991A (fr) |
CA (1) | CA2073759C (fr) |
DE (1) | DE69126660T2 (fr) |
ES (1) | ES2102392T3 (fr) |
IE (1) | IE910108A1 (fr) |
NZ (1) | NZ236770A (fr) |
PT (1) | PT96485B (fr) |
WO (1) | WO1991010720A1 (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US20020039566A1 (en) * | 2000-05-16 | 2002-04-04 | Carl Triplett | Gel air freshener and method of manufacturing same |
US20020065209A1 (en) * | 2000-10-10 | 2002-05-30 | Valesky Robert J. | Surfactant system used to improve processing of gel air fresheners |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2920045A (en) * | 1955-09-06 | 1960-01-05 | Colgate Palmolive Co | Heavy duty liquid detergent compositions |
US3708428A (en) * | 1968-01-24 | 1973-01-02 | L Mcdonald | Detergent compositions containing silica colloids |
US3709823A (en) * | 1970-06-16 | 1973-01-09 | Mizusawa Industrial Chem | Method of manufacturing highly viscous,acidic base materials for detergents |
US4561993A (en) * | 1982-08-16 | 1985-12-31 | The Clorox Company | Thixotropic acid-abrasive cleaner |
DE3504172A1 (de) * | 1985-02-07 | 1986-08-07 | Henkel KGaA, 4000 Düsseldorf | Wirkstoffkonzentrate fuer alkalische zweikomponentenreiniger, verfahren zu ihrer herstellung und ihre verwendung |
-
1991
- 1991-01-14 IE IE010891A patent/IE910108A1/en not_active IP Right Cessation
- 1991-01-15 AU AU71789/91A patent/AU7178991A/en not_active Abandoned
- 1991-01-15 NZ NZ236770A patent/NZ236770A/en unknown
- 1991-01-15 PT PT96485A patent/PT96485B/pt not_active IP Right Cessation
- 1991-01-15 ES ES91902313T patent/ES2102392T3/es not_active Expired - Lifetime
- 1991-01-15 AT AT91902313T patent/ATE154827T1/de not_active IP Right Cessation
- 1991-01-15 WO PCT/GB1991/000052 patent/WO1991010720A1/fr active IP Right Grant
- 1991-01-15 CA CA002073759A patent/CA2073759C/fr not_active Expired - Fee Related
- 1991-01-15 DE DE69126660T patent/DE69126660T2/de not_active Expired - Fee Related
- 1991-01-15 EP EP91902313A patent/EP0511261B1/fr not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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CA2073759C (fr) | 2001-07-03 |
EP0511261A1 (fr) | 1992-11-04 |
DE69126660T2 (de) | 1997-10-23 |
WO1991010720A1 (fr) | 1991-07-25 |
IE910108A1 (en) | 1991-07-17 |
ES2102392T3 (es) | 1997-08-01 |
NZ236770A (en) | 1993-12-23 |
ATE154827T1 (de) | 1997-07-15 |
DE69126660D1 (de) | 1997-07-31 |
AU7178991A (en) | 1991-08-05 |
PT96485A (pt) | 1991-10-31 |
PT96485B (pt) | 1998-08-31 |
CA2073759A1 (fr) | 1991-07-16 |
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