CA2073759C - Liquid built detergent composition and process for its production - Google Patents
Liquid built detergent composition and process for its production Download PDFInfo
- Publication number
- CA2073759C CA2073759C CA002073759A CA2073759A CA2073759C CA 2073759 C CA2073759 C CA 2073759C CA 002073759 A CA002073759 A CA 002073759A CA 2073759 A CA2073759 A CA 2073759A CA 2073759 C CA2073759 C CA 2073759C
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- Prior art keywords
- acid
- process according
- composition
- tenside
- builder
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 105
- 239000003599 detergent Substances 0.000 title claims abstract description 59
- 239000007788 liquid Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims description 49
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 26
- 239000002736 nonionic surfactant Substances 0.000 claims description 25
- 239000004115 Sodium Silicate Substances 0.000 claims description 24
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 24
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 22
- 239000004615 ingredient Substances 0.000 claims description 20
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 20
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 20
- 238000006386 neutralization reaction Methods 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 17
- 239000000194 fatty acid Substances 0.000 claims description 17
- 229930195729 fatty acid Natural products 0.000 claims description 17
- 150000004665 fatty acids Chemical class 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 150000007513 acids Chemical class 0.000 claims description 16
- 239000003945 anionic surfactant Substances 0.000 claims description 16
- 244000060011 Cocos nucifera Species 0.000 claims description 15
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 15
- 108090000790 Enzymes Proteins 0.000 claims description 13
- 102000004190 Enzymes Human genes 0.000 claims description 13
- 239000006260 foam Substances 0.000 claims description 12
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000007844 bleaching agent Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 150000002191 fatty alcohols Chemical class 0.000 claims description 9
- 239000003205 fragrance Substances 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- 239000003755 preservative agent Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 6
- 239000000975 dye Substances 0.000 claims description 6
- 239000003906 humectant Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- -1 optical brighteners Substances 0.000 claims description 6
- 239000000344 soap Substances 0.000 claims description 6
- 238000004448 titration Methods 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 4
- 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 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 8
- 239000002979 fabric softener Substances 0.000 claims 6
- 239000003112 inhibitor Substances 0.000 claims 5
- 230000009919 sequestration Effects 0.000 claims 5
- 239000004872 foam stabilizing agent Substances 0.000 claims 3
- 239000000049 pigment Substances 0.000 claims 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims 2
- 239000001117 sulphuric acid Substances 0.000 claims 2
- 235000011149 sulphuric acid Nutrition 0.000 claims 2
- 239000000693 micelle Substances 0.000 abstract description 9
- 239000013618 particulate matter Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000000725 suspension Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000000499 gel Substances 0.000 description 19
- 239000006188 syrup Substances 0.000 description 17
- 235000020357 syrup Nutrition 0.000 description 17
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 238000009472 formulation Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 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 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001493 electron microscopy Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000017 hydrogel 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
- 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
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000004480 active ingredient Substances 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
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 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
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WLNBMPZUVDTASE-HXIISURNSA-N (2r,3r,4s,5r)-2-amino-3,4,5,6-tetrahydroxyhexanal;sulfuric acid Chemical compound [O-]S([O-])(=O)=O.O=C[C@H]([NH3+])[C@@H](O)[C@H](O)[C@H](O)CO.O=C[C@H]([NH3+])[C@@H](O)[C@H](O)[C@H](O)CO WLNBMPZUVDTASE-HXIISURNSA-N 0.000 description 1
- 241000517645 Abra Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 241000446313 Lamella Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241001024099 Olla Species 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
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 241001562042 Physa Species 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 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
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates 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
- 125000000129 anionic 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
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 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
- 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
- 239000006185 dispersion Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-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
- 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
- 239000003701 inert diluent Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 150000004702 methyl esters Chemical class 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
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 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
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Detergent Compositions (AREA)
- Colloid Chemistry (AREA)
- Silicon Compounds (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
A stabilised gel system for supporting finely divided particulate matter in suspension comprises a hydrosol of silicic acid stabilised by entanglement with micelles of a tensile. Such a stabilised gel system can be used as the basis for a liquid built detergent composition or for an abrasive preparation.
Description
LIQUID BUILT DETERGENT COMPOSITION AND PROCESS FOR ITS PRODUCTION
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.
In recent years, mainly for reasons of manufacturing economics, heavy duty built liquid detergents have made in-roads into the spray-dried washing powder market with the result that much work has taken place both on the physics and on the chemistry of product formulation.
Each type of preparation contains the same basa.c 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. In the case of solid preparations the diluent has been alkali metal sulphates whilst in the case of the liquid it has simply been water.
Herein lies the problem in the case of the heavy duty built liquid detergents because the desired performance in a washing machine requires the presence of high percentages of alkaline materials (builders) along with percentages of surface active agents in the region of 9% to 20% (active ingredients). At these concentrations the chemical groupings are incompatible as far as homogeneity of the product is concerned. Such surr3ce active ingredients normally include an anionic surfactant or tenside and may further include one or more non-ionic surfactants. Ex~ples of anionic surfactants include the sodium salts of alkyl benzene sulphonic acids and of alkyl sulphonic acids. As examples of 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 iy0 91110720 PGT/GB91/0(M52 '~~~~~ ~~~
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.
In recent years, mainly for reasons of manufacturing economics, heavy duty built liquid detergents have made in-roads into the spray-dried washing powder market with the result that much work has taken place both on the physics and on the chemistry of product formulation.
Each type of preparation contains the same basa.c 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. In the case of solid preparations the diluent has been alkali metal sulphates whilst in the case of the liquid it has simply been water.
Herein lies the problem in the case of the heavy duty built liquid detergents because the desired performance in a washing machine requires the presence of high percentages of alkaline materials (builders) along with percentages of surface active agents in the region of 9% to 20% (active ingredients). At these concentrations the chemical groupings are incompatible as far as homogeneity of the product is concerned. Such surr3ce active ingredients normally include an anionic surfactant or tenside and may further include one or more non-ionic surfactants. Ex~ples of anionic surfactants include the sodium salts of alkyl benzene sulphonic acids and of alkyl sulphonic acids. As examples of 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 iy0 91110720 PGT/GB91/0(M52 '~~~~~ ~~~
coconut fatty, acid monoethanolamide.
It follows therefore that conventional heavy duty laundry detergents are composed of trao physical phases a~~:
consist essentially of saturated solutions of the buildsrs, saith excess buildLr particles present in the liquid mass' as a dispersion, and an aqueous solution of surfactant micelles some of which haves been salted-ou-t by the electrolytic action of the saturated solution or the builders.
Such a complex mixture of materials with their o~an interactions and incompatibilities poses a problem to ~th~
detergent formulator.
In order to produce a smooth, pourable, homogeneous product for entry into the market place a very large amount of experimental work has bean undertaken by laboratories throughout the world and some of the relevant ' teachings are to~be found, for example, in US-A-3351557, US-A-3574122, CA-A-917631, GB-A-948617 and GB-A-2153839.
Refe~enee can also be made to GB-H-2123846, EP-B-086614,.,EP-B-0170091, EP-B-0151884, GB-B-2153380 and EP-A-0295021. In all cases the sun has been to produce some sort of structured liquid system which can hold the excess inorganic builder particles in a thixotropic suspension. This has been. accomplished in various ways such as by an emulsion technique,, by micronising, or. by ball-milling. Typically such a conventional liquid built detergent composition has a strorage life of at least several months. However, upon centrifuging at~800g for 17 hours at 25°C such compositions normally separate into two or more phases. Although such compositions have good storage properties, it would be desirable to provide liquid built detergent compositions with even better storage characterisitias.
It is apparent that in such heavy duty built systems the guilders and the surfactants physically interact so that each is above the limits of its water solubility:
~'~3'~
It follows therefore that conventional heavy duty laundry detergents are composed of trao physical phases a~~:
consist essentially of saturated solutions of the buildsrs, saith excess buildLr particles present in the liquid mass' as a dispersion, and an aqueous solution of surfactant micelles some of which haves been salted-ou-t by the electrolytic action of the saturated solution or the builders.
Such a complex mixture of materials with their o~an interactions and incompatibilities poses a problem to ~th~
detergent formulator.
In order to produce a smooth, pourable, homogeneous product for entry into the market place a very large amount of experimental work has bean undertaken by laboratories throughout the world and some of the relevant ' teachings are to~be found, for example, in US-A-3351557, US-A-3574122, CA-A-917631, GB-A-948617 and GB-A-2153839.
Refe~enee can also be made to GB-H-2123846, EP-B-086614,.,EP-B-0170091, EP-B-0151884, GB-B-2153380 and EP-A-0295021. In all cases the sun has been to produce some sort of structured liquid system which can hold the excess inorganic builder particles in a thixotropic suspension. This has been. accomplished in various ways such as by an emulsion technique,, by micronising, or. by ball-milling. Typically such a conventional liquid built detergent composition has a strorage life of at least several months. However, upon centrifuging at~800g for 17 hours at 25°C such compositions normally separate into two or more phases. Although such compositions have good storage properties, it would be desirable to provide liquid built detergent compositions with even better storage characterisitias.
It is apparent that in such heavy duty built systems the guilders and the surfactants physically interact so that each is above the limits of its water solubility:
~'~3'~
In the case of the builders the system is saturated with respect to the soluble salts and the excess must be homogeneously held in stable suspension, while in the~case of the surfactants the tenside micelles are either forced to contract from a linear conformation to gathered-up bundles, or at the limit, to be salted out of solution as high strength surfactant hydrates. Overall, therefore, the separated phases are in equilibrium with their own moieties in the continuous aqueous system: i~lormally, upon salting out, anionic surfactants give rise to formation of solid hydrates. The presence of such solid anionic surfactant hydratss can give rise to formation of a composition in which the presence of spheruulites of surfactant hydrate caii be detected or in Which the composition contains the surfactant as a lamellar liquid crystal or solid hydrate interspersed with~an aqueous phase containing dissolved electrolyte. On the other hand non-ionic surfactants do not, generally speaking, form hydrates, although they may be salted out of solution due to the presence of high concentrations of dissolved electrolyte.
There is accordingly a need in the art to provide an.:Lmproved system for supporting finely divided particulate matter, such as builders or abrasives, in suspension. There is also a need for an improved liquid built detergent formulation which is stable under normal storage conditions foz extended periods. There is a further need in the art to provide a -liquid built detergent composition, and a process for making same, in which the problems of the prior art are substantially obviated.
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 era substantially obviated. It also seeks to provide an improved system for supporting finely divided W~ 91/10720 PCT/GB91/00052 >.~ :, ,.~ c.~
particulate matter in sus'oension, According to the present invention them is provided a stabil iced gel s~~stem ~:~or supporting finehl .
divided particulate matter in suspension comprising a hydrosol of si l icic :~c~_d s'abi i ised by er..tangl errant ~.aith micelles of a tenside. Preferabl~r the tenside is one containing On° 01" ?T.10'~ '~ 71:.11 ~:.:Oi''..'' .~. a.c' d O~ 5~,:1 ''JJ' hOn.a.,'~ ~ gr'OLpS .
Such a stabilised g°1 :~3't%S'~CT:I C_.:~.'~J::qT~:!? 8T1~~1 ~1 .O~-~.
~=OdllC~d by at least partiall~T ne,.a-tral? ;3lng 3 50d1um Si li cake solution with a tenside containing ona or .:zoLe su1jW10n1C aCld grOU:p3.
Such a stabilised gel system is normally acidic or near neutral c a~-acte°~. ~..~;cai'',; v::a ~'' ow _ ?: ~~i~? sL'ccort ir_ h__ _ _ .. _ _ ..
system in accordance ,wi'tn tine invention 115 1n tile range of fromwabout 1.0 to about 9Ø Dlormally it will have a pH of nat more than about 8.0, e.g. in the range of from about 4.0 .
to about 7.5. .
In another aspect of the invention there is provided a liquid built detergent composition comprising a hydrosol of silicic acid stabilised by entanglement with micelles of a tenside containing one or more sulphonic acid or sulphonate groups.
Also provided in accordance with the present invention is 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 abras~.ve material. Preferably the tenside in such an abrasive preparation is one containing one or more sulphonic acid or sulphonate groups. Such an abrasive composition can be formulated as an oven cleaner, for example, or as a cleaner for hard surfaces.
There is further proposed, according to a still further aspect of the invention, a process for the production of a stabilised gsl system fo-r jupporting =finely divided particulate matter in suspensi on lailicil comprises dV0 91110720 PCT1GB91/00052 n~
neutralising a solution of an al'.tal 7 '_??°'tal Si 1 icate to a pH
in the range of from about 1.0 to about 7.0 in the presence of a tenside thereby to produce a :nvdrosol of silicic acid stabilised by entanglement with tenside micelles.
~leutralisa~tion ~:a~,T ':e yrf=c ted '.or additi on of an .
acid to a solution of an alkali metal silicate that contains also at lzast one .surfacta.nt. ~h:a aci: may 'oe selected rrom hydrochloric acid, sul phur i c ~zc i d, .sul; na::,ic acid, phosphoric acid, formic acid, acetic acid, citric acid, and mixtures of two or more t:nereoz. Alternatively neutralisation may be effectAd b;r titration of the solution .
Oi alkal.l. T.llet''cl a'_!? Oa°..r J~~ .,'~~:a-~a:~ L..:J:'~:,L11111.j v:12 Cr more sulphonic acid groups.
In another mode of production of a stabilised gel system according to the invention a solution having a pH of .
not more than 7.0 is produced by disolving in an aqueous medium a tenside containing one or more sulphonic acid groups and an alkali metal tripolyphosphate and a solution of an alka7.i metal silicate is added thereto.
The invention further provides a process for the production of a liquid built detergent composition which comprises neutralising a solution of an alkali metal silicate, such as sodium silicate, to a pH in the range of from about 1.0 to about 7.0 by titration with a tenside containing one or more sulphonic acid groups.
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 to a pH
in the range of from about l.0 to about 7.O 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 the neutralisation step, incorporating a builder in the composition. In such a procsss neutralisation can be effected by addition of an acid to a , c~ ~ ; ~ :) 9 ~ t~ _ 6 _ r~
solution of an alkali metal silicate that also contains at least one surfactant and in which the builder is thereafter added. Alt~rna~tively neutralisation can be effected by titration of the solution of alkali metal silicate with a tenside containing one or more sulphonic acid groups.
In another form of such a process a solution having a pH of rot more 'than 7.0 is produced by dissolving in an aqueous mediu~-n a tenside containing one or more sulphonic acid groups and an alkali metal tripolyphosphate and a solution of an alkali metal silicate is added thereto.
In the detergency technology of the prior art there arw no a;amples disclosed; so far as is known, in which a pourable gel system, based on silicates, has been produced by a chemical reaction. The reason for this can be found in the fact that chemical theory does not indicate that such gel or-colloidal systems are possible by this route. However, according to the present invention it is possible to produce a very stable, pourable gel or viscous colloidal system by the chemical interaction of an anionic surfactant with an alkali metal silicate constituent of the builder system.
Amongst the known effects of acids on solutions of alkali metal silicates it is known that:-(1) When a strong acid is added to a sodium silicate solution a precipitate of silicic acid separates as a gelatinous mass (hydrogel) but some still remains in colloidal solution (hydrosol). It is possible to dialyse the hydrosol but a 5$ solution of colloidal silica is about the maximum strength that can be obtained.
(2) The passage of silicic acid from the sol to the gel condition-is retarded by the presence of a little acid, or hydroxide, but it is very much accelerated by the addition of sodiu.-n carbonate or of a phosphate; in fact the addition of one of the latter compounds invariably leads to rapid coagulation.
(3) When the pH value of a solution of sodium silicate is reduced from its normal value, which is typically in the range of from about 11.0 to about 13.0, to a value in the range of from about 8.0 to about 9.0 by the use of sodium hydrogen carbonate, the hydrosol produced is stable for a matter of hours, before coagulation occurs, and as such is used in water and sewage treatment as "activated silica".
In the new silicate chemistry work, which forms the basis of this invention, the following unexpected results can be disclosed:-(4) When a strong solution of sodium silicate, for example one produced by a few dilutions of the 47% grade known as CRYSTAh*120 H; is titra.ted with an anionic detergent, in the free sulphoniQ acid form, to a pH value in the range of from about 1.0 to about 8.0, a soft gel is produced which can be diluted with water to give a stable syrup without precipitates.
When a 5~ solution of sodium metasilicate or sodium silicate soluble glass is titrated to pH 7.0 with a 10~ w/w solution of dodecylbenzene sulphonic acid, a transparent syrup is produced which is stable for an extended period and is not precipitated, or coagulated, by the addition of a solution either of an alkali metal carbonate, or of a phosphate, or of a polyphosphate.
(6) When a quaternary ammonium chloride (QAC) such as a benzalkonium chloride is added to a sodium silicate solution and the pH value is reduced to 7.0 to 8.0, a transparent syrup is produced which is stable and does not precipitate silicic acid even though a m_::eral acid, such as hydrochloric acid, is used to neutralise the silicate solution. Such a syrup can be used as a stabilised gel system for supporting, for example, abrasive particles, to form an abrasive preparation such as an oven cleaner.
* Trade-mark dfO 91/10720 PCT/GB91/00052 _$_ ( 7 ) S1m11ar re9L11tS t0 'thoSa S~_T~lfi3T_'lSe~ 2t ( ~J ) abot7e were obtained when a sodium silicate solution containing a non-ionic surfactant, e.g. Sunwarc.nic A7 Tip, ,aas ti"trat~ed to pH 7.0 to 8.0 using hydrochloric acid. Again; the resulting syrup Can be used ~S ? 3LC'~.~J? 1 i S?rl rN~al ~~S ~S',~,:1 :.'.~.?' S~"lap?ndin~
finely divided particulate matter such as abrasive parties or builder particles.
Z'''rOm thl;a :JOr~C )_t Ca:~: .~.S S.-~..°r: :~alr.'W'.. ~~ a.3 ~OSS1b12 to interfere with normal hvdro ol-nvdrogei react;ons of.
acidified sodium silicat s solutions, as described above at (1), and thus force the separating sa_licic acid into a physa.cal entangl .-"~y:tt;°:'1' '.~lt~~L ~~ i~ '''~ ,a=.s~."'." :u-C2' ~ _ ~ .v i ~ :S 3J la:a:.
mutual stability is attained with respect to the colloidal silica and the surfactant moieties.
Tn particular it can be shown that it is not possible to precipitate hydrogels of silicic acid when sodium silicate is decomposed, even at pH 1.0, by detergent sulphonic acids. This result would not be chemically predictable. The resulting pourable colloidal visc~us syrups are excellent media for uniting the separate phases of 'heavy duty laundry detergent liquids. During manufacture of these liquids little attention n4ed be paid to the order in which the ingredients of a liquid detergent formulation are added, according to the teachings of this invention, so long as the sodium silicate in aqueous solution is first neutralised, or partly neutralised, by the tensile sulphonic acid, or acids, of the formulation or by neutralisation or partial neutralisation with non-tensile acids in the presence of tensides or surfactants.
Even though an anionic surfactant in the free sulphonic acid form, such as dodecyl-benzene sulphonic acid, is a strong acid, a gelatinous precipitate of silicic acid, i.e. a hydrogel, is not produced when it is used vo neutralise a sodium silicata solutio. Instead a viscous _g_ solution, i.e. a hydrosol, is produced. This result is consistent with the theory that 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.
Such studies indicated that the liquid built detergent contained a largely featureless granular structure with crystals of builder distributed apparently at random.
In particular such electron microscopy studies showed no sign of any spherulitesand no sign of any lamellar structure. Hence there was no evidence that ny of the surfactant was present as a lamellar liquid crystal or solid hydrate. Thus there did not appear to be any salting out of the anionic surfactant (i.e. sodium salt of dodecyl benzene sulphonic acid) despite the presence of large amounts of builder (i.e. sodium tripolyphosphate) in excess of its solubility limit. This is in contrast to the results reported in EP-B-0086614 and in GB-B-2123846, in which a vesicular, spherulitic or lamellar structure was apparent in a liquid built detergent composition containing comparable amounts of builder and of anionic surfactant added as a sodium salt.
Examples of anionic surfactants (named here, for convenience, in the free acid form, as elsewhere in the description and claims) which can be utilised in the present invention include alkyl benzene sulphonic acids, in which the alkyl group contains from about 6 to about 20 carbon atoms, for example from 10 to 14 carbon atoms, alkyl sulphonic acids containing from about 10 to about 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 about 10 to about 22 carbon atoms, such as a C,6 to C,8 olefin or a mixture containing same.
Beside a surfactant ...............................................................................
..............................
~~r~~ a containing a sulphonic acid group there may also be present a sulphated fatty alcohol or a sodium salt thereof; typical sulphated fatty alcohols include those containing from about to about 2o carbon atoms, for example a sulphated fatty alcohol mixture containing C10, C12, C14~ C16 and C~,g fatty alcohols. Typical of such a fatty alcohol mixture is one containing alcohols in the following proportions: C10 3.0~, C12 57.0, C14 20.0, C16 9.0~ and C18 11Ø
Typically a Liquid built detergent composi-~ion according'to the invention contains from about 2% w/w up to about 30% w/w of anionic surfactant (calculated as sulphonic acid) based »pon the total weight of the composition.
The 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: C6 0.5%, C8 6.5%, C10 6.0%, C12 49.5%, C14 19.5%, C16 8.5$, C18 (stearic) 2.0%, X18 (oleic) 6.0%, and C18 (linoleic) 1.5%. Other suitable non-ionic surfactants include polyaxyalkylene 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.
Such 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.
Typically the concentration of non-ionic surfactant, if present, in the liquid built detergent r - m -composition ranges from about 0.5~ w/w up to about 30~ w/w based upon the total weight of the composition.
Other ingredients which may be included in the liquid built detergent composition of the invention 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 mare than about 5~ w/w each of the total composition, mostly less than'about 1~ w/w each of the total composition, and mere usually do not together ~~mount to more than about 5~ w/w in total based upon the weight of the composition.
As an example of a builder there can be mentioned in particular sodium tripolyphosphate. Potassium tripolyphosgihate can alternatively be used. The pyrophosphates, metaphosphates, arthophosphates, 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, anal polymeric carboxylic acids and their salts, such as polyacrylie acid and polymethacrylic acid.
A typical liquid built detergent composition according to the invention comprises from about 5~ w/w up to about 40~ w/w based upon the total weight of the composition of a builder or builders.
For further details of ingredients which can be included in a liquid built detergent composition reference may be made to GB-3-2123846.
Upon preparing a stabilised gel system according to l~fO 91/10720 PCT/GB91/0(1052 c!
the invention the bH is tynicalljr in the range of from about 1.0 to about 8.0, preferably about/ pH ct,p. Upon addition of the builder in the production of a liauid built detergent according to the iimawtion a pri :increase is oLten observed.
In same cases thS ~~ TI:.'-.1Z7 .T_:!..52 r_'~,1JOV° ._?~0~1t 70~, T,n7~'le.T.1 starting from a stabilised gel system at a pii or about 4.0; hence the final pH may be a :nigh as .~.boi::t 9 . 0 ~.or a;Taaz a 1 ittle higher.
The liquid built detergents oY GH-5-2:L2384o are characterised by the Tact that, upon canrriluging at 800 times normal Earth gravity for 17 hours at 25°C, these COmpoSltlOhS Sr?Na?:,-.'~.i:~ ~ Ti ~~D 1 '~i r.-t ,.~.,~~ran-y~__, ~'' lr qu..ous liquid phase, containing dissolved eiectrolyta, and at laast 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. For this purpose it is desirable to formulate 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 about 3.0~ by weight of sodium silicate (or an equivalent amount of another soluble silicate) up to about.3~ by weight based upon the total weight of the liquid built detergent composition. By selecting an appropriate quantity of sodium silicate (or equivalent) as an ingredient for manufacture of the liquid built detergent composition 'of the invention it is possible to support amounts as high as about 25~ or more of builder in a manner such that no separation or phases occurs upon centrifugation at 800 times normal Earth gravity at 25°C.
In the course of our experiments °He :.ay2 nroducsd liquid built detergent compositions -that exhibit lit.le or no W~ 91/10720 PCT/G)391/00052 .: :i<e'er'~;
v 1~' ~ ~ i ::.3 a separation of ph3SeS, even when centrifuged at 2000 times normal Earth gravity at 25°~ for 17 hours. These experimental results,indicate that our liquid built .
detergent compos:i~cions should ~:cnibi-t superior storage stability to thc:~e o= GE-B-;?1238=~5.
The invention is further illustra'c~d inwthe following E xamnl rs ~_. ~;rhich al'. ;~~~r~:?ntagas ar= by weight.
Example 1 This descri.'oas arepa:ration of a cy~a oz liquid which has been sho;~n to be very a tabla in car:as of time (shelf-life) and thermal cycling (environmental stability) .
Linear Alkylbenzene Sulphonic Acid 11% ' Coconut Fatty Acid Monoethanolamide 2%
Sodium Tripolyphosphate 20$
Sodium Silicate (-47%) Syrup 6%
Sodium Carbonate Anhydrous ~%
Hydrotrope H-66 (trade mark) 2%
Optical Brightener 0.15%
"? Formaldehyde (40%) Solution 0.75%
Silicone Antifoam Emulsion 0.01%
Fragrance 0.50%
Water to produce on a W/5~ basis 100%.
The alkylbenzene sulphonic acid, or mixture of alkylbenzene sulphonic acids, is dissolved in about twice its own weight of iaater 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, ar.e 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 a~.:. 100%
by weight basis, A suitable alkyl benzene sulphonic acid is dodecyl benzene sulphonic acid.
ctr)r9t~ -' 14 -Example 2 In this.Example a stable colloidal syrup, or pourable gel, is obtained by acidification of alkali metal silicate solutions which contain surfactants before the titration is attempted. This method of ,production of heatrfr duty laundry detergents utilises the following ingredients:-Sodium Alkyl Benzene Sulphonate 11'~
Coconut Fatty Acid Monoethanolamide 2~
Sodium Tripol.yphosphate 20~
Sodium Silicate (470) Syrup 5.5~
Sodium Carbonate Anhydrous, 3~
Optical Brightener O.iS'~
Formaldehyde (40~) Solution 0.75 Silicone Antifoam Emulsion 0Ø1 Hydrotrope H-65 (trade mark) 2.00$ .
Fragrance v 0.50$
Hydrochloric Acid (25$) as required Water to produce W/W 100 The sodium alkylbenzene sulphonate (e. g. sodiwm 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. Tlie 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.
Example ~
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 013/15 alcohol.
First of all the sodium carboxymethyl cellulose is dissolved in water. The coconut fatty acid monoethanolamide is also dissolved in hot water. Then the dodecylbenzene sulphonic acid is diluted with about twice its own weight of water. To this is added with vigorous stirring 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 4Ø Then the sodium carboxymethyl cellulose solution is added, followed by the coconut fatty acid monoethanolamide solution, while continuing to stir. Next the sodium tripolyphosphate is added with stirring, followed by the other minor ingredients. Finally 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 * Trade-marks ~'O 91/10720 PCT/GB91/00052 ~~~r~~'~' - 16 - , hours, no separation of phases can be detected. There is no sign of any formation of vesicles or spherulites, nor is there any evidence o:~ any of the surfactant being present as a lamellas liquid crystal or solid hydrate. Fence, upon electron mi crosco?~ic e~mJ_~sation of the detergent composition of this Example, the o:oservations recorded were consistent with a lart3?1;% .~a~tSw :153 Cranlll ar ,StiV.Ctur? wlth Cry5ta18 Of SOdllL"Il ~:ri7t~~'YL71103'Olla'i~? d1S'C'.~i~lli:c..-''(_~ 3t r3ndo:ITl.
Exam'ole 4 3 li:~uid builw c~carg~anc composition is produced from the same ingredients as are used in Example 3 except that the aid i ti cn oz the :;odi "-~ .;; 1 ; c;~te syr,,~ i S del aged until after additi or_ of -the sodiuu-W tripol yphosphate. The sodium earboxymethyl cellulose and the coconut fatty acid monoethanolamide are each dissolved separately in hot water..
Then 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. Lastly 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 th4 =orm of a lainellar liquid crystal or solid hydrates. 2dorsover, the results of WO 91/10720 PCf/GB91/00052 _ 17 _ electron microscopy evaluation j_ndicate that the liquid built detergent composition of 'this Example has a largely featureless r~ranular structure caith randomly distributed crystals of sodium tripolyphosphate.
Zlt.~cw~~!: it i a not r~quirad that this innovation.
be explained in terms of physical chemistry it is lnterestlng t0 isv~.~ 41d'~. "i0~~1 C'Jnc°n'trated hydrosols Of silicic acid ::~uw,'. ee p.Loduced, ~,aithcut any tendency to coagulate or precipitat.°_ to rigid gals, because as the alkylbenzer_e sulpnonic acid is t:itrated to the neutral point with silicate sol?ztion the electrical conductivity of the solution dacrras.=s -due °-o t:~a ,aisapp eara:,ce of hydroxon?um 'ions as dona~ced from the sulphonic acid. This type of tenside/silicic acid hydrosol reaction is not restricted in its application to the production of heavy duty laundry detergents.
In another example a soft anionic gel or syrup can be loaded with fine abrasive and used as an oven, or hard surface, cleaner.
Henee the invention is not restricted, in its application, to pourable gel systems in heavy duty laundry detezgents.~
There is accordingly a need in the art to provide an.:Lmproved system for supporting finely divided particulate matter, such as builders or abrasives, in suspension. There is also a need for an improved liquid built detergent formulation which is stable under normal storage conditions foz extended periods. There is a further need in the art to provide a -liquid built detergent composition, and a process for making same, in which the problems of the prior art are substantially obviated.
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 era substantially obviated. It also seeks to provide an improved system for supporting finely divided W~ 91/10720 PCT/GB91/00052 >.~ :, ,.~ c.~
particulate matter in sus'oension, According to the present invention them is provided a stabil iced gel s~~stem ~:~or supporting finehl .
divided particulate matter in suspension comprising a hydrosol of si l icic :~c~_d s'abi i ised by er..tangl errant ~.aith micelles of a tenside. Preferabl~r the tenside is one containing On° 01" ?T.10'~ '~ 71:.11 ~:.:Oi''..'' .~. a.c' d O~ 5~,:1 ''JJ' hOn.a.,'~ ~ gr'OLpS .
Such a stabilised g°1 :~3't%S'~CT:I C_.:~.'~J::qT~:!? 8T1~~1 ~1 .O~-~.
~=OdllC~d by at least partiall~T ne,.a-tral? ;3lng 3 50d1um Si li cake solution with a tenside containing ona or .:zoLe su1jW10n1C aCld grOU:p3.
Such a stabilised gel system is normally acidic or near neutral c a~-acte°~. ~..~;cai'',; v::a ~'' ow _ ?: ~~i~? sL'ccort ir_ h__ _ _ .. _ _ ..
system in accordance ,wi'tn tine invention 115 1n tile range of fromwabout 1.0 to about 9Ø Dlormally it will have a pH of nat more than about 8.0, e.g. in the range of from about 4.0 .
to about 7.5. .
In another aspect of the invention there is provided a liquid built detergent composition comprising a hydrosol of silicic acid stabilised by entanglement with micelles of a tenside containing one or more sulphonic acid or sulphonate groups.
Also provided in accordance with the present invention is 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 abras~.ve material. Preferably the tenside in such an abrasive preparation is one containing one or more sulphonic acid or sulphonate groups. Such an abrasive composition can be formulated as an oven cleaner, for example, or as a cleaner for hard surfaces.
There is further proposed, according to a still further aspect of the invention, a process for the production of a stabilised gsl system fo-r jupporting =finely divided particulate matter in suspensi on lailicil comprises dV0 91110720 PCT1GB91/00052 n~
neutralising a solution of an al'.tal 7 '_??°'tal Si 1 icate to a pH
in the range of from about 1.0 to about 7.0 in the presence of a tenside thereby to produce a :nvdrosol of silicic acid stabilised by entanglement with tenside micelles.
~leutralisa~tion ~:a~,T ':e yrf=c ted '.or additi on of an .
acid to a solution of an alkali metal silicate that contains also at lzast one .surfacta.nt. ~h:a aci: may 'oe selected rrom hydrochloric acid, sul phur i c ~zc i d, .sul; na::,ic acid, phosphoric acid, formic acid, acetic acid, citric acid, and mixtures of two or more t:nereoz. Alternatively neutralisation may be effectAd b;r titration of the solution .
Oi alkal.l. T.llet''cl a'_!? Oa°..r J~~ .,'~~:a-~a:~ L..:J:'~:,L11111.j v:12 Cr more sulphonic acid groups.
In another mode of production of a stabilised gel system according to the invention a solution having a pH of .
not more than 7.0 is produced by disolving in an aqueous medium a tenside containing one or more sulphonic acid groups and an alkali metal tripolyphosphate and a solution of an alka7.i metal silicate is added thereto.
The invention further provides a process for the production of a liquid built detergent composition which comprises neutralising a solution of an alkali metal silicate, such as sodium silicate, to a pH in the range of from about 1.0 to about 7.0 by titration with a tenside containing one or more sulphonic acid groups.
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 to a pH
in the range of from about l.0 to about 7.O 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 the neutralisation step, incorporating a builder in the composition. In such a procsss neutralisation can be effected by addition of an acid to a , c~ ~ ; ~ :) 9 ~ t~ _ 6 _ r~
solution of an alkali metal silicate that also contains at least one surfactant and in which the builder is thereafter added. Alt~rna~tively neutralisation can be effected by titration of the solution of alkali metal silicate with a tenside containing one or more sulphonic acid groups.
In another form of such a process a solution having a pH of rot more 'than 7.0 is produced by dissolving in an aqueous mediu~-n a tenside containing one or more sulphonic acid groups and an alkali metal tripolyphosphate and a solution of an alkali metal silicate is added thereto.
In the detergency technology of the prior art there arw no a;amples disclosed; so far as is known, in which a pourable gel system, based on silicates, has been produced by a chemical reaction. The reason for this can be found in the fact that chemical theory does not indicate that such gel or-colloidal systems are possible by this route. However, according to the present invention it is possible to produce a very stable, pourable gel or viscous colloidal system by the chemical interaction of an anionic surfactant with an alkali metal silicate constituent of the builder system.
Amongst the known effects of acids on solutions of alkali metal silicates it is known that:-(1) When a strong acid is added to a sodium silicate solution a precipitate of silicic acid separates as a gelatinous mass (hydrogel) but some still remains in colloidal solution (hydrosol). It is possible to dialyse the hydrosol but a 5$ solution of colloidal silica is about the maximum strength that can be obtained.
(2) The passage of silicic acid from the sol to the gel condition-is retarded by the presence of a little acid, or hydroxide, but it is very much accelerated by the addition of sodiu.-n carbonate or of a phosphate; in fact the addition of one of the latter compounds invariably leads to rapid coagulation.
(3) When the pH value of a solution of sodium silicate is reduced from its normal value, which is typically in the range of from about 11.0 to about 13.0, to a value in the range of from about 8.0 to about 9.0 by the use of sodium hydrogen carbonate, the hydrosol produced is stable for a matter of hours, before coagulation occurs, and as such is used in water and sewage treatment as "activated silica".
In the new silicate chemistry work, which forms the basis of this invention, the following unexpected results can be disclosed:-(4) When a strong solution of sodium silicate, for example one produced by a few dilutions of the 47% grade known as CRYSTAh*120 H; is titra.ted with an anionic detergent, in the free sulphoniQ acid form, to a pH value in the range of from about 1.0 to about 8.0, a soft gel is produced which can be diluted with water to give a stable syrup without precipitates.
When a 5~ solution of sodium metasilicate or sodium silicate soluble glass is titrated to pH 7.0 with a 10~ w/w solution of dodecylbenzene sulphonic acid, a transparent syrup is produced which is stable for an extended period and is not precipitated, or coagulated, by the addition of a solution either of an alkali metal carbonate, or of a phosphate, or of a polyphosphate.
(6) When a quaternary ammonium chloride (QAC) such as a benzalkonium chloride is added to a sodium silicate solution and the pH value is reduced to 7.0 to 8.0, a transparent syrup is produced which is stable and does not precipitate silicic acid even though a m_::eral acid, such as hydrochloric acid, is used to neutralise the silicate solution. Such a syrup can be used as a stabilised gel system for supporting, for example, abrasive particles, to form an abrasive preparation such as an oven cleaner.
* Trade-mark dfO 91/10720 PCT/GB91/00052 _$_ ( 7 ) S1m11ar re9L11tS t0 'thoSa S~_T~lfi3T_'lSe~ 2t ( ~J ) abot7e were obtained when a sodium silicate solution containing a non-ionic surfactant, e.g. Sunwarc.nic A7 Tip, ,aas ti"trat~ed to pH 7.0 to 8.0 using hydrochloric acid. Again; the resulting syrup Can be used ~S ? 3LC'~.~J? 1 i S?rl rN~al ~~S ~S',~,:1 :.'.~.?' S~"lap?ndin~
finely divided particulate matter such as abrasive parties or builder particles.
Z'''rOm thl;a :JOr~C )_t Ca:~: .~.S S.-~..°r: :~alr.'W'.. ~~ a.3 ~OSS1b12 to interfere with normal hvdro ol-nvdrogei react;ons of.
acidified sodium silicat s solutions, as described above at (1), and thus force the separating sa_licic acid into a physa.cal entangl .-"~y:tt;°:'1' '.~lt~~L ~~ i~ '''~ ,a=.s~."'." :u-C2' ~ _ ~ .v i ~ :S 3J la:a:.
mutual stability is attained with respect to the colloidal silica and the surfactant moieties.
Tn particular it can be shown that it is not possible to precipitate hydrogels of silicic acid when sodium silicate is decomposed, even at pH 1.0, by detergent sulphonic acids. This result would not be chemically predictable. The resulting pourable colloidal visc~us syrups are excellent media for uniting the separate phases of 'heavy duty laundry detergent liquids. During manufacture of these liquids little attention n4ed be paid to the order in which the ingredients of a liquid detergent formulation are added, according to the teachings of this invention, so long as the sodium silicate in aqueous solution is first neutralised, or partly neutralised, by the tensile sulphonic acid, or acids, of the formulation or by neutralisation or partial neutralisation with non-tensile acids in the presence of tensides or surfactants.
Even though an anionic surfactant in the free sulphonic acid form, such as dodecyl-benzene sulphonic acid, is a strong acid, a gelatinous precipitate of silicic acid, i.e. a hydrogel, is not produced when it is used vo neutralise a sodium silicata solutio. Instead a viscous _g_ solution, i.e. a hydrosol, is produced. This result is consistent with the theory that 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.
Such studies indicated that the liquid built detergent contained a largely featureless granular structure with crystals of builder distributed apparently at random.
In particular such electron microscopy studies showed no sign of any spherulitesand no sign of any lamellar structure. Hence there was no evidence that ny of the surfactant was present as a lamellar liquid crystal or solid hydrate. Thus there did not appear to be any salting out of the anionic surfactant (i.e. sodium salt of dodecyl benzene sulphonic acid) despite the presence of large amounts of builder (i.e. sodium tripolyphosphate) in excess of its solubility limit. This is in contrast to the results reported in EP-B-0086614 and in GB-B-2123846, in which a vesicular, spherulitic or lamellar structure was apparent in a liquid built detergent composition containing comparable amounts of builder and of anionic surfactant added as a sodium salt.
Examples of anionic surfactants (named here, for convenience, in the free acid form, as elsewhere in the description and claims) which can be utilised in the present invention include alkyl benzene sulphonic acids, in which the alkyl group contains from about 6 to about 20 carbon atoms, for example from 10 to 14 carbon atoms, alkyl sulphonic acids containing from about 10 to about 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 about 10 to about 22 carbon atoms, such as a C,6 to C,8 olefin or a mixture containing same.
Beside a surfactant ...............................................................................
..............................
~~r~~ a containing a sulphonic acid group there may also be present a sulphated fatty alcohol or a sodium salt thereof; typical sulphated fatty alcohols include those containing from about to about 2o carbon atoms, for example a sulphated fatty alcohol mixture containing C10, C12, C14~ C16 and C~,g fatty alcohols. Typical of such a fatty alcohol mixture is one containing alcohols in the following proportions: C10 3.0~, C12 57.0, C14 20.0, C16 9.0~ and C18 11Ø
Typically a Liquid built detergent composi-~ion according'to the invention contains from about 2% w/w up to about 30% w/w of anionic surfactant (calculated as sulphonic acid) based »pon the total weight of the composition.
The 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: C6 0.5%, C8 6.5%, C10 6.0%, C12 49.5%, C14 19.5%, C16 8.5$, C18 (stearic) 2.0%, X18 (oleic) 6.0%, and C18 (linoleic) 1.5%. Other suitable non-ionic surfactants include polyaxyalkylene 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.
Such 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.
Typically the concentration of non-ionic surfactant, if present, in the liquid built detergent r - m -composition ranges from about 0.5~ w/w up to about 30~ w/w based upon the total weight of the composition.
Other ingredients which may be included in the liquid built detergent composition of the invention 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 mare than about 5~ w/w each of the total composition, mostly less than'about 1~ w/w each of the total composition, and mere usually do not together ~~mount to more than about 5~ w/w in total based upon the weight of the composition.
As an example of a builder there can be mentioned in particular sodium tripolyphosphate. Potassium tripolyphosgihate can alternatively be used. The pyrophosphates, metaphosphates, arthophosphates, 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, anal polymeric carboxylic acids and their salts, such as polyacrylie acid and polymethacrylic acid.
A typical liquid built detergent composition according to the invention comprises from about 5~ w/w up to about 40~ w/w based upon the total weight of the composition of a builder or builders.
For further details of ingredients which can be included in a liquid built detergent composition reference may be made to GB-3-2123846.
Upon preparing a stabilised gel system according to l~fO 91/10720 PCT/GB91/0(1052 c!
the invention the bH is tynicalljr in the range of from about 1.0 to about 8.0, preferably about/ pH ct,p. Upon addition of the builder in the production of a liauid built detergent according to the iimawtion a pri :increase is oLten observed.
In same cases thS ~~ TI:.'-.1Z7 .T_:!..52 r_'~,1JOV° ._?~0~1t 70~, T,n7~'le.T.1 starting from a stabilised gel system at a pii or about 4.0; hence the final pH may be a :nigh as .~.boi::t 9 . 0 ~.or a;Taaz a 1 ittle higher.
The liquid built detergents oY GH-5-2:L2384o are characterised by the Tact that, upon canrriluging at 800 times normal Earth gravity for 17 hours at 25°C, these COmpoSltlOhS Sr?Na?:,-.'~.i:~ ~ Ti ~~D 1 '~i r.-t ,.~.,~~ran-y~__, ~'' lr qu..ous liquid phase, containing dissolved eiectrolyta, and at laast 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. For this purpose it is desirable to formulate 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 about 3.0~ by weight of sodium silicate (or an equivalent amount of another soluble silicate) up to about.3~ by weight based upon the total weight of the liquid built detergent composition. By selecting an appropriate quantity of sodium silicate (or equivalent) as an ingredient for manufacture of the liquid built detergent composition 'of the invention it is possible to support amounts as high as about 25~ or more of builder in a manner such that no separation or phases occurs upon centrifugation at 800 times normal Earth gravity at 25°C.
In the course of our experiments °He :.ay2 nroducsd liquid built detergent compositions -that exhibit lit.le or no W~ 91/10720 PCT/G)391/00052 .: :i<e'er'~;
v 1~' ~ ~ i ::.3 a separation of ph3SeS, even when centrifuged at 2000 times normal Earth gravity at 25°~ for 17 hours. These experimental results,indicate that our liquid built .
detergent compos:i~cions should ~:cnibi-t superior storage stability to thc:~e o= GE-B-;?1238=~5.
The invention is further illustra'c~d inwthe following E xamnl rs ~_. ~;rhich al'. ;~~~r~:?ntagas ar= by weight.
Example 1 This descri.'oas arepa:ration of a cy~a oz liquid which has been sho;~n to be very a tabla in car:as of time (shelf-life) and thermal cycling (environmental stability) .
Linear Alkylbenzene Sulphonic Acid 11% ' Coconut Fatty Acid Monoethanolamide 2%
Sodium Tripolyphosphate 20$
Sodium Silicate (-47%) Syrup 6%
Sodium Carbonate Anhydrous ~%
Hydrotrope H-66 (trade mark) 2%
Optical Brightener 0.15%
"? Formaldehyde (40%) Solution 0.75%
Silicone Antifoam Emulsion 0.01%
Fragrance 0.50%
Water to produce on a W/5~ basis 100%.
The alkylbenzene sulphonic acid, or mixture of alkylbenzene sulphonic acids, is dissolved in about twice its own weight of iaater 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, ar.e 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 a~.:. 100%
by weight basis, A suitable alkyl benzene sulphonic acid is dodecyl benzene sulphonic acid.
ctr)r9t~ -' 14 -Example 2 In this.Example a stable colloidal syrup, or pourable gel, is obtained by acidification of alkali metal silicate solutions which contain surfactants before the titration is attempted. This method of ,production of heatrfr duty laundry detergents utilises the following ingredients:-Sodium Alkyl Benzene Sulphonate 11'~
Coconut Fatty Acid Monoethanolamide 2~
Sodium Tripol.yphosphate 20~
Sodium Silicate (470) Syrup 5.5~
Sodium Carbonate Anhydrous, 3~
Optical Brightener O.iS'~
Formaldehyde (40~) Solution 0.75 Silicone Antifoam Emulsion 0Ø1 Hydrotrope H-65 (trade mark) 2.00$ .
Fragrance v 0.50$
Hydrochloric Acid (25$) as required Water to produce W/W 100 The sodium alkylbenzene sulphonate (e. g. sodiwm 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. Tlie 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.
Example ~
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 013/15 alcohol.
First of all the sodium carboxymethyl cellulose is dissolved in water. The coconut fatty acid monoethanolamide is also dissolved in hot water. Then the dodecylbenzene sulphonic acid is diluted with about twice its own weight of water. To this is added with vigorous stirring 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 4Ø Then the sodium carboxymethyl cellulose solution is added, followed by the coconut fatty acid monoethanolamide solution, while continuing to stir. Next the sodium tripolyphosphate is added with stirring, followed by the other minor ingredients. Finally 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 * Trade-marks ~'O 91/10720 PCT/GB91/00052 ~~~r~~'~' - 16 - , hours, no separation of phases can be detected. There is no sign of any formation of vesicles or spherulites, nor is there any evidence o:~ any of the surfactant being present as a lamellas liquid crystal or solid hydrate. Fence, upon electron mi crosco?~ic e~mJ_~sation of the detergent composition of this Example, the o:oservations recorded were consistent with a lart3?1;% .~a~tSw :153 Cranlll ar ,StiV.Ctur? wlth Cry5ta18 Of SOdllL"Il ~:ri7t~~'YL71103'Olla'i~? d1S'C'.~i~lli:c..-''(_~ 3t r3ndo:ITl.
Exam'ole 4 3 li:~uid builw c~carg~anc composition is produced from the same ingredients as are used in Example 3 except that the aid i ti cn oz the :;odi "-~ .;; 1 ; c;~te syr,,~ i S del aged until after additi or_ of -the sodiuu-W tripol yphosphate. The sodium earboxymethyl cellulose and the coconut fatty acid monoethanolamide are each dissolved separately in hot water..
Then 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. Lastly 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 th4 =orm of a lainellar liquid crystal or solid hydrates. 2dorsover, the results of WO 91/10720 PCf/GB91/00052 _ 17 _ electron microscopy evaluation j_ndicate that the liquid built detergent composition of 'this Example has a largely featureless r~ranular structure caith randomly distributed crystals of sodium tripolyphosphate.
Zlt.~cw~~!: it i a not r~quirad that this innovation.
be explained in terms of physical chemistry it is lnterestlng t0 isv~.~ 41d'~. "i0~~1 C'Jnc°n'trated hydrosols Of silicic acid ::~uw,'. ee p.Loduced, ~,aithcut any tendency to coagulate or precipitat.°_ to rigid gals, because as the alkylbenzer_e sulpnonic acid is t:itrated to the neutral point with silicate sol?ztion the electrical conductivity of the solution dacrras.=s -due °-o t:~a ,aisapp eara:,ce of hydroxon?um 'ions as dona~ced from the sulphonic acid. This type of tenside/silicic acid hydrosol reaction is not restricted in its application to the production of heavy duty laundry detergents.
In another example a soft anionic gel or syrup can be loaded with fine abrasive and used as an oven, or hard surface, cleaner.
Henee the invention is not restricted, in its application, to pourable gel systems in heavy duty laundry detezgents.~
Claims (52)
1. A liquid built detergent composition which contains suspended builder particles substantially uniformly distributed therein, said composition consisting essentially of a stable hydrosol of silicic acid formed by neutralising a solution of from about 3% w/w up to about 8% w/w (based upon the weight of the composition) of an alkali metal silicate to a pH in the range of from about 1.0 to about 8.0 in the presence of from about 2% w/w up to about 30% w/w (based upon the weight of the composition) of a tenside, said hydrosol containing (i) an amount in excess of its solubility limit and in the range of from about 5% w/w up to about 40% w/w of a particulate builder substantially uniformly distributed therein, (ii) from 0.5% w/w up to about 30% w/w of at least one non-ionic surfactant, (iii) from 0 to about 5% w/w of a bleach, (iv) from 0 to about 5% of a bleach activator, and (v) from 0 to about 5% w/w in total of one or more minor ingredients, any minor ingredient being present in an amount of up to about 2% w/w and being selected from preservatives, optical brighteners, fragrances, foam depressants, foam boosters, foam stabilisers, soaps, dyes, pigments, buffers, corrosion inhibitors, sequestration agents, anti-ingestion agents, humectants, enzymes, enzyme stabilisers, fabric softeners and fabric conditioners.
2. A liquid built detergent composition according to claim 1, wherein the pH
of the stable hydrosol of silicic acid lies in the range of from 4.0 to 9Ø
of the stable hydrosol of silicic acid lies in the range of from 4.0 to 9Ø
3. A liquid built detergent composition according to claim 1 or claim 2, in which the tenside is an anionic surfactant derived from a tenside acid selected from alkyl benzene sulphonic acids, in which the alkyl group contains from 6 to 20 carbon atoms, alkyl sulphonic acids containing from 10 to 26 carbon atoms, alpha-olefin sulphonic acids obtained by sulphonation of an alpha-olefin containing from 10 to 20 carbon atoms, and mixtures thereof.
4. A liquid built detergent composition according to any one of claims 1 to 3, which further comprises a sulphated fatty alcohol or a sodium salt thereof.
5. A liquid built detergent composition according to any one of claims 1 to 4, in which the builder comprises sodium tripolyphosphate.
6. A liquid built detergent composition according to any one of claims 1 to 5, in which the at least one non-ionic surfactant comprises coconut fatty acid monoethanolamide.
7. A liquid built detergent composition according to any one of claims 1 to 6, in which the at least one non-ionic surfactant comprises a polyoxyalkylene ether of an alkanol containing from 6 to 20 ethylene oxide groups and based upon an alkanol containing from 6 to 26 carbon atoms.
8. A liquid built detergent composition according to claim 2, in which the pH
is in the range of from 4.0 to 9Ø
is in the range of from 4.0 to 9Ø
9. A process for the production of a liquid built detergent composition containing substantially uniformly distributed therein suspended particles of a particulate builder, which process comprises neutralising a solution of an alkali metal silicate to a pH in the range of from 1.0 to about 8.0 in the presence of a tenside thereby to produce a stable hydrosol of silicic acid and, either before or after the neutralisation step, incorporating an amount in excess of its solubility limit of a particulate builder in the composition in an amount of from 5% w/w to 40%
w/w of the composition.
w/w of the composition.
10. A process according to claim 9, in which neutralisation is 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.
11. A process according to claim 10, in which the acid is selected from hydrochloric acid, sulphuric acid, sulphamic acid, phosphoric acid, formic acid, acetic acid, citric acid, and mixtures of two or more thereof.
12. A process according to claim 9, in which neutralisation is effected by titration of the solution of alkali metal silicate with a tenside acid containing one sulphonic acid group.
13. A process according to claim 9, in which a solution having a pH of not more than 7.0 is produced by dissolving in an aqueous medium (1) a tenside acid containing one sulphonic acid group and (2) an alkali metal tripolyphosphate and a solution of an alkali metal silicate is added thereto.
14. A process according to claim 9 or claim 13, in which the alkali metal silicate is sodium silicate.
15. A process according to claim 9 or claim 13, in which the tenside is an anionic surfactant derived from a tenside acid selected from alkyl benzene sulphonic acids, alkyl sulphonic acids and alpha-olefin sulphonic acids.
16. A process according to any one of claims 9 to 15, in which there is further added at least one non-ionic surfactant.
17. A process according to claim 16, in which the non-ionic surfactant comprises coconut fatty acid ethanolamide.
18. A process according to any one of claims 9 to 15, in which there is incorporated in the composition, either before or after the neutralisation step, a sulphated fatty alcohol or a sodium salt thereof.
19. A process according to claim 15, in which there is used from 2% w/w up to 30% w/w of anionic surfactant (calculated as sulphonic acid) based upon the total weight of the composition.
20. A process according to any one of claims 9 to 15, in which the amount of builder or builders comprises from 5% w/w up to 40% w/w based upon the weight of the composition.
21. A process according to any one of claims 9 to 15, in which the builder comprises sodium tripolyphosphate.
22. A process according to any one of claims 9 to 15, in which there is incorporated in the composition, either before or after the neutralisation step 0.5%
w/w up to 30% w/w of at least one non-ionic surfactant.
w/w up to 30% w/w of at least one non-ionic surfactant.
23. A process according to claim 22, in which the at least one non-ionic surfactant comprises coconut fatty acid monoethanolamide.
24. A process according to claim 22, in which the at least one non-ionic surfactant comprises a polyoxyalkylene ether or an alkanol containing from 6 to 20 ethylene oxide groups and based upon an alkanol containing from 6 to 26 carbon atoms.
25. A process according to claim 9, in which there is used from 3% w/w up to 8% w/w of sodium silicate based upon the weight of the composition.
26. A process according to claim 9 or claim 13, which further comprises incorporating in the composition, either before or after the neutralisation step, at least one material selected from preservatives, optical brighteners, bleaches, fragrances, foam depressants, foam boosters, soaps, dyes, buffers, corrosion inhibitors, sequestration agents, bleach activators, enzymes, humectants, and enzyme stabilisers.
27. A process according to claim 9 or claim 13, in which the pH of the resulting composition is in the range of from 4.0 to 9Ø
28. A liquid built detergent composition which has a pH in the range of from 4.0 to 9.0 and contains suspended particles of sodium tripolyphosphate builder substantially uniformly suspended therein, said composition comprising a stable hydrosol of silicic acid formed by neutralising a solution of from 3% w/w up to 8%
w/w (based upon the weight of the composition) of an alkali metal silicate to a pH in the range of from 1.0 to 8.0 in the presence of from 2% w/w up to 30% w/w (based upon the weight of the composition) of a tenside, said hydrosol containing (a) an amount in excess of its solubility limit and up to 40% w/w of a particulate sodium tripolyphosphate builder substantially uniformly distributed therein, (b) from 0.5%
w/w up to 30% w/w of at least one non-ionic surfactant, (c) from 0 to 5% w/w of a bleach, (d) from 0 to 5% of a bleach activator, and (e) from 0 to 5% w/w in total of one or more minor ingredients, any minor ingredient being present in an amount of up to 2% w/w and being selected from preservatives, optical brighteners, fragrances, foam depressants, foam boosters, foam stabilisers, soaps, dyes, pigments, buffers, corrosion inhibitors, sequestration agents, anti-ingestion agents, humectants, enzymes, enzyme stabilisers, fabric softeners and fabric conditioners.
w/w (based upon the weight of the composition) of an alkali metal silicate to a pH in the range of from 1.0 to 8.0 in the presence of from 2% w/w up to 30% w/w (based upon the weight of the composition) of a tenside, said hydrosol containing (a) an amount in excess of its solubility limit and up to 40% w/w of a particulate sodium tripolyphosphate builder substantially uniformly distributed therein, (b) from 0.5%
w/w up to 30% w/w of at least one non-ionic surfactant, (c) from 0 to 5% w/w of a bleach, (d) from 0 to 5% of a bleach activator, and (e) from 0 to 5% w/w in total of one or more minor ingredients, any minor ingredient being present in an amount of up to 2% w/w and being selected from preservatives, optical brighteners, fragrances, foam depressants, foam boosters, foam stabilisers, soaps, dyes, pigments, buffers, corrosion inhibitors, sequestration agents, anti-ingestion agents, humectants, enzymes, enzyme stabilisers, fabric softeners and fabric conditioners.
29. A liquid built detergent composition having a pH in the range of from 4.0 to 9.0 and containing suspended particles of sodium tripolyphosphate builder substantially uniformly suspended therein, said composition consisting essentially of a stable hydrosol of silicic acid formed by neutralising a solution of from 3% w/w up to 8% w/w (based upon the weight of the composition) of an alkali metal silicate to a pH in the range of from 1.0 to 8.0 in the presence of from 2% w/w up to 30%
w/w (based upon the weight of the composition) of a tenside, said hydrosol containing (a) an amount in excess of its solubility limit and up to 40% w/w of particulate sodium tripolyphosphate builder substantially uniformly distributed therein, (b) from 0.5% w/w up to 30% w/w of at least one non-ionic surfactant, (c) from 0 to 5% w/w of a bleach, (d) from 0 to 5% of a bleach activator, and (e) from 0 to about. 5% w/w in total of one or more minor ingredients, any minor ingredient being present in an amount of up to 2% w/w and being selected from preservatives, optical brighteners, fragrances, foam depressants, foam boosters, foam stabilisers, soaps, dyes, pigments, buffers, corrosion inhibitors, sequestration agents, anti-ingestion agents, humectants, enzymes, enzyme stabilisers, fabric softeners and fabric conditioners.
w/w (based upon the weight of the composition) of a tenside, said hydrosol containing (a) an amount in excess of its solubility limit and up to 40% w/w of particulate sodium tripolyphosphate builder substantially uniformly distributed therein, (b) from 0.5% w/w up to 30% w/w of at least one non-ionic surfactant, (c) from 0 to 5% w/w of a bleach, (d) from 0 to 5% of a bleach activator, and (e) from 0 to about. 5% w/w in total of one or more minor ingredients, any minor ingredient being present in an amount of up to 2% w/w and being selected from preservatives, optical brighteners, fragrances, foam depressants, foam boosters, foam stabilisers, soaps, dyes, pigments, buffers, corrosion inhibitors, sequestration agents, anti-ingestion agents, humectants, enzymes, enzyme stabilisers, fabric softeners and fabric conditioners.
30. A liquid built detergent composition according to claim 29, in which the tenside is an anionic surfactant derived from a tenside acid selected from alkyl benzene sulphonic acids, in which the alkyl group contains from 6 to 20 carbon atoms, alkyl sulphonic acids containing from 10 to 26 carbon atoms, alpha-olefin sulphonic acids obtained by sulphonation of an alpha-olefin containing from 10 to 22 carbon atoms, and mixtures thereof.
31. A liquid built detergent composition according to claim 29 or claim 30, which further comprises a sulphated fatty alcohol or a sodium salt thereof.
32. A liquid built detergent composition according to any one of claims 29 to 31, in which the at least one non-ionic surfactant comprises coconut fatty acid monoethanolamide.
33. A liquid built detergent composition according to any one of claims 29 to 32, in which the at least one non-ionic surfactant comprises a polyoxyalkylene ether of an alkanol containing from 6 to 20 ethylene oxide groups and based upon an alkanol containing from 6 to 26 carbon atoms.
34. A liquid built detergent composition according to any one of claims 1 to 4, in which the builder comprises a zeolite.
35. A process for the production of a liquid built detergent composition containing substantially uniformly distributed therein suspended particles of sodium tripolyphosphate builder, which process comprises neutralising a solution of an alkali metal silicate to a pH in the range of from 1.0 to 8.0 in the presence of a tenside thereby to produce a stable hydrosol of silicic acid and, either before or after the neutralisation step, incorporating an amount in excess of its solubility limit of particulate sodium tripolyphosphate builder in the composition in an amount of from 5% w/w to 40% w/w of the composition.
36. A process according to claim 35, in which neutralisation is 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 sodium tripolyphosphate builder is thereafter added.
37. A process according to claim 36, in which the acid is selected from hydrochloric acid, sulphuric acid, sulphamic acid, phosphoric acid, formic acid, acetic acid, citric acid, and mixtures of two or more thereof.
38. A process according to claim 35, in which neutralisation is effected by titration of the solution of alkali metal silicate with a tenside acid containing one sulphonic acid group.
39. A process according to claim 38, in which a solution having a pH of not more than 7.0 is produced by dissolving in an aqueous medium (1) a tenside acid containing one sulphonic acid and (2) sodium tripolyphosphate and a solution an alkali metal silicate is added thereto.
40. A process according to any one of claims 35 to 38, in which the alkali metal silicate is sodium silicate.
41. A process according to any one of claims 35 to 37, in which the tenside is an anionic surfactant derived from a tenside acid selected from alkyl benzene sulphonic acids, alkyl sulphonic acids and alpha-olefin sulphonic acids.
42. A process according to any one of claims 35 to 41, in which there is further added at least one non-ionic surfactant.
43. A process according to claim 42, in which the non-ionic surfactant comprises coconut fatty acid monoethanolamide.
44. A process according to any one of claims 35 to 38, in which there is incorporated in the composition, either before or after the neutralisation step, a sulphated fatty alcohol or a sodium salt thereof.
45. A process according to claim 41, in which there is used from 2% w/w up to 30% w/w of anionic surfactant (calculated as sulphonic acid) based upon the total weight of the composition.
46. A process according to any one of claims 35 to 38, in which there is incorporated in the composition, either before or after the neutralisation step 0.5%
w/w up to 30% w/w of at least one non-ionic surfactant.
w/w up to 30% w/w of at least one non-ionic surfactant.
47. A process according to claim 46, in which the at least one non-ionic surfactant comprises coconut fatty acid monoethanolamide.
48. A process according to claim 46, in which the at least one non-ionic surfactant comprises a polyoxyalkylene ether of an alkanol containing from 6 to 20 ethylene oxide groups and based upon an alkanol containing from 6 to 26 carbon atoms.
49. A process according to claim 40, in which there is used from 3% w/w up to 8% w/w of sodium silicate based upon the weight of the composition.
50. A process according to any one of claims 35 to 38, which further includes incorporating in the composition, either before or after the neutralisation step, at least one material selected from preservatives, optical brighteners, bleaches, fragrances, foam depressants, foam boosters, soaps, dyes, buffers, corrosion inhibitors, sequestration agents, bleach activators, enzymes, humectants, and enzyme stabilisers.
51. A process according to any one of claims 35 to 38, in which the pH of the resulting composition is in the range of from 4.0 to 9Ø
52. A process according to any one of claims 9 to 19, in which the builder comprises a zeolite.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909000833A GB9000833D0 (en) | 1990-01-15 | 1990-01-15 | Detergent and production thereof |
| GB9000833.5 | 1990-01-15 | ||
| GB909024563A GB9024563D0 (en) | 1990-11-12 | 1990-11-12 | Stabilised gel system and production thereof |
| GB9024563.0 | 1990-11-12 | ||
| PCT/GB1991/000052 WO1991010720A1 (en) | 1990-01-15 | 1991-01-15 | Stabilised gel system and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2073759A1 CA2073759A1 (en) | 1991-07-16 |
| CA2073759C true CA2073759C (en) | 2001-07-03 |
Family
ID=26296501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002073759A Expired - Fee Related CA2073759C (en) | 1990-01-15 | 1991-01-15 | Liquid built detergent composition and process for its production |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0511261B1 (en) |
| AT (1) | ATE154827T1 (en) |
| AU (1) | AU7178991A (en) |
| CA (1) | CA2073759C (en) |
| DE (1) | DE69126660T2 (en) |
| ES (1) | ES2102392T3 (en) |
| IE (1) | IE910108A1 (en) |
| NZ (1) | NZ236770A (en) |
| PT (1) | PT96485B (en) |
| WO (1) | WO1991010720A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (en) * | 1985-02-07 | 1986-08-07 | Henkel KGaA, 4000 Düsseldorf | ACTIVE CONCENTRATES FOR ALKALINE TWO-COMPONENT CLEANERS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
-
1991
- 1991-01-14 IE IE010891A patent/IE910108A1/en not_active IP Right Cessation
- 1991-01-15 PT PT96485A patent/PT96485B/en not_active IP Right Cessation
- 1991-01-15 WO PCT/GB1991/000052 patent/WO1991010720A1/en active IP Right Grant
- 1991-01-15 NZ NZ236770A patent/NZ236770A/en unknown
- 1991-01-15 CA CA002073759A patent/CA2073759C/en not_active Expired - Fee Related
- 1991-01-15 DE DE69126660T patent/DE69126660T2/en not_active Expired - Fee Related
- 1991-01-15 AT AT91902313T patent/ATE154827T1/en not_active IP Right Cessation
- 1991-01-15 ES ES91902313T patent/ES2102392T3/en not_active Expired - Lifetime
- 1991-01-15 EP EP91902313A patent/EP0511261B1/en not_active Expired - Lifetime
- 1991-01-15 AU AU71789/91A patent/AU7178991A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| PT96485A (en) | 1991-10-31 |
| PT96485B (en) | 1998-08-31 |
| WO1991010720A1 (en) | 1991-07-25 |
| IE910108A1 (en) | 1991-07-17 |
| AU7178991A (en) | 1991-08-05 |
| ATE154827T1 (en) | 1997-07-15 |
| ES2102392T3 (en) | 1997-08-01 |
| CA2073759A1 (en) | 1991-07-16 |
| DE69126660T2 (en) | 1997-10-23 |
| DE69126660D1 (en) | 1997-07-31 |
| NZ236770A (en) | 1993-12-23 |
| EP0511261A1 (en) | 1992-11-04 |
| EP0511261B1 (en) | 1997-06-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |