AU693445B2 - Structuring liquid nonionic surfactants prior to granulation process - Google Patents
Structuring liquid nonionic surfactants prior to granulation process Download PDFInfo
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- AU693445B2 AU693445B2 AU67804/94A AU6780494A AU693445B2 AU 693445 B2 AU693445 B2 AU 693445B2 AU 67804/94 A AU67804/94 A AU 67804/94A AU 6780494 A AU6780494 A AU 6780494A AU 693445 B2 AU693445 B2 AU 693445B2
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- Australia
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- international
- structuring agent
- document
- nonionic surfactant
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- 238000000034 method Methods 0.000 title claims description 60
- 239000002736 nonionic surfactant Substances 0.000 title claims description 57
- 239000007788 liquid Substances 0.000 title claims description 7
- 238000005469 granulation Methods 0.000 title description 11
- 230000003179 granulation Effects 0.000 title description 11
- 239000000203 mixture Substances 0.000 claims description 56
- 239000003599 detergent Substances 0.000 claims description 50
- -1 PVNO Polymers 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 29
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000004615 ingredient Substances 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 235000000346 sugar Nutrition 0.000 claims description 7
- 150000008163 sugars Chemical class 0.000 claims description 7
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 7
- 238000005054 agglomeration Methods 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 239000008101 lactose Substances 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000008122 artificial sweetener Substances 0.000 claims description 4
- 235000021311 artificial sweeteners Nutrition 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000008121 dextrose Substances 0.000 claims description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 3
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 3
- 229940081974 saccharin Drugs 0.000 claims description 3
- 235000019204 saccharin Nutrition 0.000 claims description 3
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims 2
- 241000185791 Asonus Species 0.000 claims 1
- 241000283986 Lepus Species 0.000 claims 1
- 241000282320 Panthera leo Species 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 230000001419 dependent effect Effects 0.000 claims 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims 1
- 229940124530 sulfonamide Drugs 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 description 36
- 125000000217 alkyl group Chemical group 0.000 description 35
- 239000000463 material Substances 0.000 description 24
- 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 18
- 229910000323 aluminium silicate Inorganic materials 0.000 description 18
- 238000005342 ion exchange Methods 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- 229910052708 sodium Inorganic materials 0.000 description 17
- 239000008187 granular material Substances 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 150000001768 cations Chemical class 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 125000005907 alkyl ester group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007859 condensation product Substances 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 4
- GHPCICSQWQDZLM-UHFFFAOYSA-N 1-(4-chlorophenyl)sulfonyl-1-methyl-3-propylurea Chemical compound CCCNC(=O)N(C)S(=O)(=O)C1=CC=C(Cl)C=C1 GHPCICSQWQDZLM-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229920013820 alkyl cellulose Polymers 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000002563 ionic surfactant Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 159000000001 potassium salts Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
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- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
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- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
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- SXKQTYJLWWQUKA-UHFFFAOYSA-N O.O.O.O.O.O.O.O.O.O.OB(O)O.OB(O)O.OB(O)O.OB(O)O Chemical compound O.O.O.O.O.O.O.O.O.O.OB(O)O.OB(O)O.OB(O)O.OB(O)O SXKQTYJLWWQUKA-UHFFFAOYSA-N 0.000 description 1
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 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 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000006177 alkyl benzyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- IRWXQQKCMXBFST-UHFFFAOYSA-L benzyl-dodecyl-dimethylazanium methyl hydrogen sulfate trimethyl(tetradecyl)azanium bromide chloride Chemical compound [Cl-].C(CCCCCCCCCCC)[N+](CC1=CC=CC=C1)(C)C.S(=O)(=O)(OC)O.C(CCCCCCCCCCCCC)[N+](C)(C)C.[Br-] IRWXQQKCMXBFST-UHFFFAOYSA-L 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QYGPTZZWDVCBSD-UHFFFAOYSA-L decyl(triethyl)azanium bromide chloride Chemical compound [Cl-].C(CCCCCCCCC)[N+](CC)(CC)CC.[Br-].C(CCCCCCCCC)[N+](CC)(CC)CC QYGPTZZWDVCBSD-UHFFFAOYSA-L 0.000 description 1
- GFNWBSUGVDMEQI-UHFFFAOYSA-L decyl-(2-hydroxyethyl)-dimethylazanium;bromide;chloride Chemical compound [Cl-].[Br-].CCCCCCCCCC[N+](C)(C)CCO.CCCCCCCCCC[N+](C)(C)CCO GFNWBSUGVDMEQI-UHFFFAOYSA-L 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229960002598 fumaric acid Drugs 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical class OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Chemical class 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical compound OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000004026 tertiary sulfonium compounds Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- 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
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/221—Mono, di- or trisaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3792—Amine oxide containing polymers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
- Glanulating (AREA)
- General Preparation And Processing Of Foods (AREA)
Description
1.
V
if,' WO 94/25553 PCT/US94/04843 1 jI Structuring Liquid Nonionic Surfactants Prior to Granulation Process Background of the Invention The present invention relates to improving storage stability and physical properties of granular detergents which are rich in nonionic surfactant.
It is most useful with nonionic surfactants which are liquid at ambient temperature, and are therefore mobile.
Without a suitable structurant, the nonionic surfactant tends to leak from the powder and soak into the cardboard container which forms an unsightly stain. Although it is possible to avoid this problem by using lower levels of i, ~i~L1 4 i:I WO 94/25553 PCT/US94/04843 2 nonionic surfactant in the composition, or by selecting nonionic surfactants which have a higher solidification temperature, this limits the flexibility of formulation.
The use of nonionic surfactants in granular detergent applications has been widely discussed in the prior art.
The following references describe various processes and compositions for making granules which comprise nonionic surfactants.
US 3 868 336, published 25th February, 1975 discloses the use of a powder premix comprising perborate, tripolyphosphate, nonionic surfactant and polyvinyl alcohol. The premix is dry added to other detergent components.
GB 2 137 221, published 3rd October, 1984 discloses a nonionic premix which comprises dissolved polyvinyl pyrrolidone (PVP) and soil release polymer. The premix is sprayed on to an absorbant detergent carrier particle. The PVP is used as a stabiliser for the soil release polymer.
EPA 0 215 637, published on 25th March, 1987 discloses the use of sugars and derivatives as structurants of spray dried detergent powders. Although nonionic surfactant may be present in such powders it is incorporated at relatively low levels 4% in examples 1 to Furthermore the spray dried powder has a low bulk density (324 574 g/l).
EPA 0 513 824, published 19th November, 1992, describes a process for granulating nonionic detergent and the use of a surface coating agent having a particle size of less than micrometers to give a powder having a high content of nonionic surfactant (10-60%) and a bulk density of 0.6 to 1.2 g/ml. The use of polymers including polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone and carboxymethyl cellulose is disclosed (page 13, lines 17- J WO 94/25553 PCT/US94/04843 3 18). However, the benefits of using any of these polymers to structure or thicken the nonionic surfactant is not disclosed.
WO 92 6160, published on 16th April, 1992. This application describes (example 14) a granular detergent composition prepared by fine dispersion mixing in an Eirich RV02 mixer of a paste which comprises N-methyl glucose amide and nonionic surfactant in the presence of sodium carbonate and zeolite. There is no suggestion to use polymers as structuring agents.
One aspect of the present invention is a process for making granular nonionic detergent agglomerates having a bulk density of at least 650 g/1 and which comprise higher levels of nonionic surfactant than those of the prior art, but do not have problems of mobile nonionic surfactants nonionic surfactants with low solidification temperatures) leaking from the granules and soaking into the carton.
This problem is addressed by structuring the liquid nonionic surfactant before the dispersion and/or granulation process. This is done by dissolving a structuring agent which comprises a polymer in the nonionic surfactant. Preferred structuring agents are polymers, especially polymers having more than one functional hydroxyl group, especially polyvinyl alcohols, polyhydroxyacrylic acid polymers, and polymers such as polyvinyl pyrrolidone and PVNO. Also useful as components of the structuring agent are sugars and artificial sweeteners and their derivatives.
It is a further aspect of the present invention to provide a process for incorporating sticky materials into detergent granules while still maintaining desirable physical Sproperties including free-flowing particles which have a Si i 1 WO 94/25553 PCTUS94/04843 4 good resistance to caking. Sticky materials if present at or close to the surface of the granules have a negative effect on flow properties. These materials also tend to gel upon contact with water which prevents effective dispensing of the granules from the dispensing drawer of a washing machine or from a dispensing device which is added to the wash with soiled load. In this aspect of the present invention these problems are overcome by using sticky materials as structuring agents of the nonionic surfactants thereby improving the surface properties of the granules.
In a further aspect of the invention, high bulk density granular detergent compositions and components are provided which comprise nonionic surfactants and structuring agents.
Summary of the Invention A process for making a granular laundry detergent component or composition having a bulk density of at least 650 g/l, by dissolving a structuring agent in a nonionic surfactant, said structuring agent comprising a polymer, to form a pumpable premix and finely dispersing said premix with an effective amount of powder at a given operating temperature wherein the premix has a viscosity of at least 350 mPas when measured at said operating temperature and at a shear rate of 25s l. Preferred structurants comprise polymers having more than one functional hydroxyl group, especially polyvinyl alcohols, polyhydroxyacrylic acid polymers, and polymers such as polyvinyl pyrrolidone and PVNO, as well as sugars, artificial sweeteners and their derivatives.
The premix is then processed into a granular detergent by any suitable process. Fine dispersion mixing, agglomeration, or spraying the premix onto a granular base product are preferred.
I
l.
-4a- Another aspect of the present invention is components or compositions comprising nonionic surfactant and structuring agents.
Throughout the description and claims of this specification, the word "comprise" and variations of the word, such as "comprising" and "comprises", is not intended to exclude other additives or components or integers.
fife if, ii if ii f I ii if ier, f t ft C i :14 i WO 94/25553 PCT/US94/04843 Detailed Description of the Invention 4 CC
I
e4 I 44 *t 4 4 Il The process aspect of the present invention comprises two essential steps. The first process step is the formation of a nonionic surfactant premix which comprises a structuring agent. The second process step is the processing of the surfactant premix into the form of a granular detergent having the desired physical properties of bulk density, flow properties and storage characteristics.
The first process step of the invention is the preparation of a structured nonionic surfactant premix. This premix comprises two essential components which will be described in more detail below. These components are the nonionic surfactant and the structuring agent. In the first process step the structuring agent is dissolved in the nonionic surfactant.
The second process step may be based upon any of the techniques of forming granules which are known to the man skilled in the art. However, the most preferred granulation techniques for use in the present invention are fine dispersion of the structured nonionic surfactant paste in the presence of powders. One example of such a process is to pump or spray the surfactant paste into a high shear mixer. The high shear conditions in the mixer break up the surfactant paste into small droplets and distribute those droplets onto and around the powder. The process is often described as "agglomeration".
Another example of such a process is to spray the surfactant paste cn'o a powder under low shear conditions %(such as a rotating drum). In this case the energy to break LI ~LX.-
L
*f WO 94/25553 PCT/US94/04843 6 the paste into fine droplets comes at the spray nozzle, and in the low shear mixer the droplets are absorbed on to the surface, or into the pores of the powder. Preferred granulation processes are described in more detail below.
For the purposes of the invention described herein, the term structuring has been used to mean thickening or raising the solidification point of the nonionic surfactant, or both of these. It is an essential feature of the present invention that the viscosity of the premix is greater than 350 mPas when measured at the operating temperature and at a shear rate of 25s 1 The operating temperature, as defined herein, is the temperature of the surfactant paste at the point which is sprayed or dispersed onto the powders during the granulation step of the process.
A pumpable paste is defined herein to mean a paste which has a viscosity of less than 100 000 mPas when measured at 1 at the required operating temperature. Preferably the viscosity of the paste will be less than 60 000 mPas, and even more preferably less than 40 000 mPas.
Nonionic Surfactant Suitable nonionic surfactants include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
I
I
i WO 94/25553 PCT/US94/04843 7 Particularly preferred for use in the present invention are nonionic surfactants such as the polyethylene oxide condensates of alkyl phenols, the condensation products of alkyl phenols having an alkyl group containing from about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 4 to moles of ethylene oxide per mole of alkyl phenol.
Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to carbon atoms, in either straight chain or branched configuration, with an average of from 1 to 25 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl .group containing from about 9 to 15 carbon atoms with from about 2 to 10 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide. Most preferred are condensation products of alcohols having an alkyl group containing from about 12 to 15 carbon atoms with an average of about 3 moles of ethylene oxide per mole of alcohol.
Many of the nonionic surfactants which fall within the definitions given above have are liquid at temperatures below 40 0 C (that is to say the solidification temperature is below 40 0 The present invention has been found to be particularly useful for such nonionic surfactants.
Structuring Agent Although any structuring agent may be chosen which has the effect of raising the viscosity or "stickiness" of the Ssurfactant premix to the required operating window and or increasing the solidification temperature of the premix, it has been found that structuring agents which comprise at i least one polymer are particularly useful.
WO 94/25553 PCT/US94/04843 8 Preferably at least one of the components of the structuring agent is a polymer having an average molecular weight of at least 2000, and preferably at least 10000.
The group of polymers useful as structuring agents in the present invention includes the group of polymers which are derived from monomers having at least one hydroxyl functional group such as polyvinyl alcohols, polyethylene glycol and polyhydroxyacrylic acid polymers and mixtures and derivatives of these. Other polymers which are useful components of the strucuring agent include polyvinyl pyrollidone, PVNO.
The structuring agent may also comprise other ingredients.
One group of such ingredients which have been found to be particularly useful comprises the group of sugars and artificial sweeteners and their derivatives.
The group of sugars useful in the present invention includes fructose, lactose, dextrose, sucrose, saccharin and sorbitol.
One particularly preferred group of structuring agents is the derivatives of sugars such as polyhydroxy fatty acid amides. Such derivatives may be prepared by reacting a fatty acid ester and an N-alkyl polyhydroxy amine. The preferred amine for use in the present invention is N-(Ri)- CH2(CH20H)4-CH2-OH and the preferred ester is a C12-C20 fatty acid methyl ester. Most preferred is the reaction product of N-methyl glucamine (which may be derived from glucose) with C12-C20 fatty acid metnyl ester.
Methods of manufacturing polyhydroxy fatty acid amides have been described in WO 92 6073, published on 16th April, 1992. This application describes the preparation of polyhydroxy fatty acid amides in the presence of solvents.
i WO 94/255S3 PCT/US94/04843 9 In a highly preferred embodiment of the invention N-methyl glucamine is reacted with a C12-C20 methyl ester. It also says that the formulator of granular detergent compositions may find it convenient to run the amidation reaction in the presence of solvents which comprise alkoxylated, especially ethoxylated (EO 3-8) C12-C14 alcoh"ils (page 15, lines 22- 27). This directly yields nonionic surfactant systems which are preferred in the present invention, such as those comprising N-methyl glucamide and C12-C14 alcohols with an average of 3 ethoxylate groups per molecule.
Polyhydroxy fatty acid amides are also active in the washing process as surfactants in their own right.
Other ingredients which have been found to be useful as components of the structuring agent include phthalimide, para-toluene sulphonamide, and maleimide.
The ratio of nonionic surfactant to structuring agent will vary according to exactly which nonionic surfactant and which structurant is chosen. Any ratio may be used in the present invention provided that a premix having a viscosity of at least 350 mPas when measured at the operating temperature and a shear rate of 25s-1 is produced.
Typically ratios of nonionic surfactant to structuring agent in the range of 20:1 to 1:1 have been found to be particularly suitable, and preferably from 5:1 to 2:1.
Normally the detergent compositions made according to the present invention may include a wide range of other ingredients and components which are known to the man skilled in the art to have a function in the washing process. Typical examples of such ingredients which may be used in detergent compositions are given below.
WO 94/25553 PCTIUS94/04843 Granulation Processes An essential step of the present invention is the process of forming granules which comprise the surfactant premix described above. Many processes for granulating surfactant pastes are known to the man skilled in the art. One of these processes is spray drying of a slurry containing the surfactant. However, this is not a preferred process in the present invention because it does not generally yield a powder with a high bulk density, and further processing is needed in order to increase the bulk density.
A process which is more suited to the present invention is that of fine dispersion mixing or agglomeration. In this process a powder having a relatively small particle size is mixed with a finely dispersed paste which causes the powder to stick together (or agglomerate). The result is a granular composition which generally has a particle size distribution in the range of 250 to 1200 micrometers and has a bulk density of at least 650 g/l. In the present invention the surfactant premix is used as the paste which is finely dispersed with an effective amount of powder in a suitable mixer. Suitable mixers for carrying out the fine dispersion mixing are described in more detail below. Any sui"-able powder may be chosen by mixing one or more of the ingredients listed below which may be conveniently handled in powder form. Powders comprising zeolite, carbonate, silica, silicate,sulphate, phosphate, citrate, citric acid and mixtures of these are particularly preferred.
It has further been found that a particularly preferred embodiment of the present invention is to spray water on to the detergent granules after the granulation step. In this embodiment of the invention at least one of the powders used should be an anhydrous powder which may be fully or partially hydrated when it comes into contact with water. A i similar process has been described in GB 2 113 707, n WO 94/25553 PCT/US94/04843 11 published on 10th August 1983. This application describes a process in which anhydrous powders such as phosphate, carbonate, borate or sulphate are metered into a high shear Smixer (a K-G Schugi [Trade name] Blender- Agglomerator) i together with a liquid surfactant and water.The amount of water added is sufficient to completely hydrate the hydratable salts. The resulting agglomerates are fed into a low shear mixer having a longer residence time in order for the hydration reaction to proceed.
In the process of the present invention, in contrast, it is highly preferred to add the water into the low shear mixer, after the agglomerates have been formed. Without wishing to be bound by theory, it is believed that adding the water after the initial formation of the agglomerates promotes hydration at the surface of the agglomerates which gives rise to the desired physical characteristics.
Most preferred in th process of the present invention is the use of anhydrous sodium carbonate, or anhydrous sodium citrate, or mixtures of these. The anhydrous salts are agglomerated in the presence of a structured nonionic surfactant premix and then water is sprayed ,n to the result.ng agglomerates in a low shear mixer. The agglomerates are finally dried in a fluid bed dryer.
Still another process which is suited to the present invention is that of preparing a granular detergent powder and spraying the surfactant premix onto that powder. The base powder may be made by any one of the processes known to the man skilled in the art, including spray drying, granulation,. (including agglomeration). Preferably different processes which are suited to the preparation of different components will be used, and then the components will be mixed together, ifor example by dry mixing in a rotating drum or a low shear mixer. In a preferred embodiment of the invention the surfactant premix is sprayed onto the base powder in the rotating drum or low shear mixer.
1 WO 94/25553 PCTIUS94/04843 12 Suitable pieces of equipment in which to carry out the fine dispersion mixing or granulation of the present invention are mixers of the FukaeR FS-G series manufactured by Fukae Powtech Kogyo Co., Japan; this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall. The stirrer and cutter may be operated independently of one another and at separately variable speeds. The vessel can be fitted with a cooling jacket or, if necessary, a cryogenic unit.
Other similar mixers found to be suitable for use in the process of the invention include DiosnaR V series ex Dierks S6hne, Germany; and the Pharma MatrixR ex T K Fielder Ltd., England. Other mixers believed to be suitable for use in the process of the invention are the FujiR VG-C series ex Fuji Sangyo Co., Japan; and the RotoR ex Zanchetta Co srl, Italy.
Other preferred suitable equipment can include EirichR, series RV, manufactured by Gustau Eirich Hardheim, Germany; L6digeR, series FM for batch mixing, series Baud KM for continuous mixing/agglomeration, manufactured by Lbdige Machinenbau GmbH, Paderborn Germany; DraisR T160 series, manufactured by Drais Werke GmbH, Mannheim Germany; and WinkworthR RT 25 series, manufactured by Winkworth Machinery Ltd., Berkshire, England.
The Littleford Mixer, Model #FM-130-D-12, with internal chopping blades and the Cuisinart Food Processor, Model #DCX-Plus, with 7.75 inch (19.7 cm) blades are two examples of suitable mixers. Any other mixer with fine dispersion mixing and granulation capability ind having a residence time in the order of 0.1 to 10 minutes can be -'used. The "turbine-type" impeller mixer, having several I i
V
(I
WO 94/25553 PCT/US94/04843 blades on an axis of rotation, is preferred. The invention can be practiced as a batch or a continuous process.
Further Processing Steps The granular components or compositions described above may be suitable for use directly, or they may be treated by additional process steps. Commonly used process steps include drying, cooling and/or dusting the granules with a finely divided flow aid. In addition the granules may be blended with other components in order to provide a composition suitable for the desired end use.
Any type of mixer or dryer (such as fluid bed dryers) may be found to be suitable for this purpose, The finely divided flow aid, if used, may be chosen from a wide variety of suitable ingredients such as zeolite, silica, talc, clay or mixtures of these.
Compositions Another aspect of the present invention is the composition of detergent components comprising nonionic surfactant.
Components having a bulk density of greater than 650 g/l and comprising from 10% to 50% by weight of nonionic surfactant and from 5% to 30% by weight of one of the structuring agents listed above fall within the scope of the present invention. The ratio of nonionic surfactant to structuring-agent will vary according to exactly which nonionic surfactant and which structurant is chosen. Any ratio may be used in the present invention provided that a premix having a viscosity of at least 350 mPas when measured at the operating temperature and a shear rate of 1 is produced. Typically ratios of nonionic surfactant to structuring agent in the range of 20:1 to 1:1 have been i tl t: V
-I
WO 94/25553 PCT/US94/04843 14 found to be particularly suitable, and preferably from 5:1 to 2:1.
Other ingredients which may be used in making the compositions of the present invention will be described below.
Normally the granular detergent will also contain other optional ingredients. Examples of such ingredients which are commonly used in detergents are given in more detail hereinbelow Anionic Surfactants Alkyl Ester Sulfonate Surfactant Alkyl Ester sulfonate surfactants hereof include linear esters of C 8 -C20 carboxylic acids fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society'" 52 (1975), pp. 323- 329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprises alkyl ester sulfonate surfactants of the structural formula: 0 3 4 R CH C OR
SSO
3
M
1 f 11 s o w' micrometers to give a powder having a high content of nonionic surfactant (10-60%) and a bulk density of 0.6 to 1.2 g/ml. The use of polymers including polyethylene glycol, polyvinyl alcohol, poyvinyl pyrrolidone and carboxymethyl cellulose is disclosed (page 13, lines 17combination thereof, R 4 is a C-C 6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R 3 is
C
10
-C
16 alkyl, and R 4 is methyl, ethyl or isopropyl.
Especially preferred are the methyl ester sulfonates wherein R 3 is C 14
-C
16 alkyl.
Alkyl Sulfate Surfactant Alkyl sulfate surfactants hereof are water soluble salts or acids or the formula ROSO 3 M wherein R preferably is a C 10
C
24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10
-C
20 alkyl component, more preferably a C 12
-C
18 alkyl or hydroxyalkyl, and M is H or a cation, an alkali metal cation sodium, potassium, lithium), or ammonium or substituted ammonium methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quarternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
Typically, alkyl chains of C 12 -1 6 are preferred for lower wash temperatures below about 50 0 C) and C 16 18 alkyl chains are preferred for higher wash temperatures above about-501C).
Alkyl Alkoxylated Sulfate Surfactant Alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) SO M wherein R is an unsubstituted CI0-C24 alkyl or hydroxyalkyl group having a C 0
C
24 alkyl component, preferably a C 12 J10- 24 12- 0 1
~X(
WO 94/25553 PCT/US94/04843 16
C
20 alkyl or hydroxyalkyl, more preferably C 12
-C
18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethylammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are C 12
-C
18 alkyl polyethoxylate sulfate, C 12
-C
18
C
12
-C
18 alkyl polyethoxylate (2.25) sulfate, C 12
-C
18 E(2.25)M), C 12
C
18 alkyl polyethoxylate sulfate C 12
-C
18 and C12-C18 alkyl polyethoxylate sulfate C 12
-C
18 wherein M is conveniently selected from sodium and potassium.
Other Anionic Surfactants Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C -C 20 linear alkylbenzenesulphonates, C -C 22 primary or secondary alkanesulphonates, C -C 24 olefinsulphonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179,
C
8
-C
24 alkylpolyglycolethersulfates (containing up to moles of ethylene oxide); acyl glycerol sulfonates, fatty ir
'B
I
v
L
I
i WO 94/25553 PCTIUS94/04843 17 oleyl glycerol sulfates, alkyl phenol ethylene oxide.ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12
-C
18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6
-C
14 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside, branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH 2
CH
2 0)kCH 2 COO-M wherein R is a alkyl, k is an integer from 0 to 10, and M is a soutA salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
When included therein, the laundry detergent compositions of the present invention typically comprise from about 1 to about 40 preferably from about 3 to about 20 by weight of such anionic surfactants.
Other Surfactants The laundry detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as nonionic surfactants other than those already described herein, including the semi-polar nonionic amine oxides described below.
SCationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are r 1 .i-iil WO 94/25553 PCT/US94/04843 18 those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula
R
1
R
2
R
3
R
4
N+X-
wherein R 1 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each of R 2
R
3
R
4 is independently Cl-C 4 alkyl, C 1
-C
4 hydroxy alkyl, benzyl, and -(C 2
H
4 )xH where x has a value from 2 to and X- is an anion. Not more than one of R2, R 3
R
4 should be benzyl.
The preferred alkyl chain length for R 1 is C12-C15, particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat, or is derived synthetically by olefin build up or OXO alcohols synthesis. Preferred groups for R 2
R
3
R
4 are methyl and hydroxyethyl groups, and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds for use herein are: coconut trimethyl ammonium chloride or bromide coconut methyl dihydroxyethyl ammonium chloride or bromide decyl triethyl ammonium chloride or bromide decyl dimethyl hydroxyethyl ammonium chloride or bromide C12-14 dimethyl hydroxyethyl ammonium chloride or bromide myristyl trimethyl ammonium methyl sulphate lauryl dimethyl benzyl ammonium chloride or bromide lauryl methyl (ethenoxy) 4 ammonium chloride or bromide The above water-soluble cationic components of the compositions of the present invention, are capable of rij WO 94/25553 PCT/US94/04843 19 existing in cationic form in a 0.1% aqueous solution at pHl0.
Other cationic surfactants useful herein are also described in US Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference.
When included therein, the laundry detergent compositions of the present invention typically comprise from 0 to about 25 preferably form about 3 to about 15 by weight of such cationic surfactants.
Ampholytic surfactants are also suitable for use in the laundry detergent compositions of the present invention.
These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched chain. One of the aliphatic substituents contains at least 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic watersolubilizing group e.g. carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 (herein incorporated by reference) for examples of ampholytic surfactants.
When included therein, the laundry detergent compositions of the present invention typically comprise form 0 to about 15 preferably from about 1 to about 10 by weight of such ampholytic surfactants.
SZwitterionic surfactants are also suitable for use in laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivates of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quarternary Il~i L. F* WO 94/25553 PCT/US94/04843 phosphonium or tertiary sulfonium compounds. See U.S.
Patent No. 3,929,678 to Laughlin et al., issued December 1975 at columns 19, line 38 through column 22, line 48 (herein incorporated by reference) for examples of zwitterionic surfactants.
When included therein, the laundry detergent compositions of the present invention typically comprise form 0 to about 15 preferably from about 1 to about 10 by weight of such zwitterionic surfactants.
Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting af alkyl groups and hydrocyalkyl groups containing form about 1 to about 3 carbon atoms; watersoluble phosphine oxides containing one alkyl moiety of form about 10 to about 18 carbon atoms and 2 moieties selected form the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula 0
R
3
(OR
4 )xN(R 5 2 wherein R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is form 0 to about 3; and each R 5 is an alkyl or hydroxyalkyl group containing form about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R 5 groups !r j E 1 l-
I
WO 94/25553 PCT/US94/04843 21 can be attached to each other, through an oxygen or nitrogen atom, to form a ring structure.
There amine oxide surfactants in particular include C 10
-C
18 alkyl dimenthyl amine oxides and C 8
-C
12 alkoxy ethyl dihydroxy ethyl amine oxides.
When included therein, the laundry detergent compositions of the present invention typically comprise form 0 to about 15 preferably from about 1 to about 10 by weight of such semi-polar nonionic surfactants.
Builders and Other Optional Ingredients Sodium aluminosilicate may take many forms. One example is crystalline aluminosilicate ion exchange material of the formula 2 )z-(SiO2)y]-xH 2 0 wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.4 and z is from about to about 264. Amorphous hydrated aluminosilicate materials useful herein have the empirical formula Mz(zA102"ySiO 2 wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaC03 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about 1 to 10 microns is preferred.
SThe aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous.
Highly preferred crystalline aluminosilicate ion exchange 1 t WO 94/25553 PCT/US94/04843 22 materials contain from about 18% to about 22% water in their crystal matrix. The crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns.
Amorphous materials are often smaller, down to less than about 0.01 micron. Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns. The term "particle size diameter" herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
The crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg equivalent of CaCO 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg eq./g to about 352 mg eq./g.
The aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca++/gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness. Optimum aluminosilicate for builder purposes exhibit a ca',d' m ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.
The amorphous aluminosilicate ion exchange materials i usually have a Mg++ exchange of at least about 50 mg eq.
CaCO 3 /g (12 mg and a Mg exchange rate of at least Sabout 1 grain/gallon/minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern c when examined by Cu radiation (1.54 Angstrom Units).
ifi f WO 94/25553 PCT/US94/04843 23 Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available. The aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976, incorporated herein by reference.
Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite M and Zeolite X.
In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula Nal2[(Alo 2 )12(SiO2)12]'xH20 wherein x is from about 20 to about 30, especially about 27 and has a particle size generally less than about microns.
Other ingredients which are known for use in the components and compositions may also be used as optional ingredients in the present invention.
The granular detergents of the present invention can contain neutral or alkaline salts which have a pH in solution of seven or greater, and can be either organic or inorganic in nature. The builder salt assists in providing the desired density and bulk to the detergent granules herein. While some of the salts are inert, many of them also function as detergency builder materials in the laundering solution.
Examples of neutral water-soluble salts include the alkali metal, ammonium or substituted ammonium chlorides, fluorides and sulfates. The alkali metal, and especially I sodium, salts of the above are preferred. Sodium sulfate is typically used in detergent granules and is particularly preferred salt. Citric acid and, in general, i^ WO 94/25553 PCT/US94/04843 24 any other organic or inorganic acid may be incorporated into the granular detergents of the present invention as long as it is chemically compatible with the rest of the agglomerate composition.
Other useful water-soluble salts inc'.ude the compounds commonly known as detergent builder materials. Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, and polyhyroxysulfonates. Preferred are the alkali metal, especially sodium, salts of the above.
Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane l-hydroxy-l,l-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid. Other phosphorus builder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, incorporated herein by reference.
Examples of nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a mclar ratio of SiO 2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1 0 to about 2.4.
As mentioned above powders normally used in detergents such as zeolite, carbonate, silica, silicate, citrate, phosphate, perborate, etc. and process acids such as INTERNATIONAL SEARCH REPORT InternLonal application No.
Dr-DPTIO IOAIA A'I
B:
1. i WO 94/25553 PCT/US94/04843 starch, can be used in preferred embodiments of the present invention.
Polymers Also useful are various organic polymers, some of which also may function as builders to improve detergency.
Included among such polymers may be mentioned sodium carboxy-lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, polyvinyl alcohols (which often also include some polyvinyl acetate), polyacrylamides, polyacrylates and various copolymers, such as those of maleic and acrylic acids. Molecular weights for such polymers vary widely but most are within the range of 2,000 to 100,000,.
Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
Other Optionals Ingredients Other ingredients commonly used in detergent compositions can be included in the components and compositions of the present invention. These include color speckles, bleaching agents and bleach activators, suds boosters or suds suppressors, antitarnish and anticorrosion agents, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, nonbuilder alkalinity sources, hydrotropes, enzymes, enzyme-stabilizing agents, and perfumes.
It i i j i WO 94/25553 PCT/US94/04843 Examples In these examples the following abbreviations have been used: C25E3:
GA:
C25AE3S:
PVP:
PVNO:
C12-15 alkyl ethoxylate, with an average of 3 ethoxy groups per molecule N-methyl glucamide C12-15 alkyl sulphate C14-15 alkyl sulphate C12-15 alkyl ethoxy sulphate, with an average of 3 ethoxy groups per molecule Polyvinyl Pyrrolidone Polyvinyl Pyrridine N oxide /1 r i WO 94/25553 PCT/US94/04843 Examples In these examples the following abbreviations have been used: C25E3:
GA:
C25AE3S:
PVP:
PVNO:
C12-15 alkyl ethoxylate, with an average cf 3 ethoxy groups per molecule N-methyl glucamide C12-15 alkyl sulphate C14-15 alkyl sulphate C12-15 alkyl ethoxy sulphate, with an average of 3 ethoxy groups per molecule Polyvinyl Pyrrolidone Polyvinyl Pyrridine N oxide WO 94/25553 WO 9425553PCT[US94/04843 27 TABLE 1 C25E3
PVP
PVNO
lactose dextrose sucrose water Operating Temp. 0
C)
Viscosity (mPas) 46 46 46 13 13 30 30 30 30 15 15 20 20 900 1300 2000 2000 23000 23000 23000 C25E3
GA
PVP
PVNO
75 12.5 12 9 10 A 67 86 97.5 11 22 14 Operating Temp. (OC) viscosity (mPas) 40 40 20 24000 15000 380 I. k A WO 94/25553 PCT/US94/04843 28 Example 1 The C25E3/PVP paste defined in Table 1 was sprayed into a Loedige CB mixer [Trade Name] at a rate of 1120 kg/hr and at a temperature of 30 0 C. At the same time zeolite A was added to the mixer at a rate of 1340 kg/hr, as well as anhydrous carbonate 1340 kg/hr.
Dispersion of the paste premix and high intensity mixing of the premix and the powders occurred in the Loedige mixer.
The residence time was approximately eight seconds.
The resulting mixture was fed into a Loedige KM mixer [Trade Name] and distinct agglomerates were lmed. Two high speed choppers in the first half of the Loedige KM mixer prevented a high proportion of oversize agglomerates being formed.
In the second half of the Loedige KM mixer water was sprayed on to the agglomerates at a rate of 225 kg/hr promoting the hydration of the carbonate in the agglomerate.
After the water spray on, a mixture of zeolite and silica was added at a rate of 160 kg/hr.
The agglomerates leaving the Loedige KM mixer were then passed through a fluid bed cooler elutriator The resulting agglomerates had excellent physical properties including flowability, and were found to be physically stable under stressed storage conditions.
Example 2 The process of example 1 was repeated using the components listed in Table 1.
Example 3 The process of example 1 was repeated using the components listed in Table 1 and at an operating temperature of the paste premix of 150C.
S77J I :i ~I 1 0 WO 94/25553 PCT/US94/04843 29 Example 4 The process of example 3 was repeated using the components listed in Table with the Zeolite A being replaced by anhydrous citrate, and the rate of water addition being increased to 190 kg /hr.
Example The C25E3/PVNO/lactose paste defined in Table 1 was sprayed into a Loedige CB mixer [Trade Name] at a rate of 1400 kg/hr and at a temperature of 20 0 C. At the same time zeolite A was added to the mixer at a rate of 1200 kg/hr, as well as anhydrous carbonate 1200 kg/hr.
The remainder of the process was carried out as in example 1 with water being sprayed on to the agglomerates at a rate of 200 kg/hr.
Examples 6-10 The process of example 5 was repeated using the components listed in Table 1.
In each of the examples 2 to 10, a free flowing granular products were produced which were found to be physically stable under stressed storage conditions.
Comparative Example A The process of example 5 was repeated using the components listed in Table 1. Due to the lower viscosity of the surfactant premix it was not possible to make granules having the desired particle size or physical properties.
Claims (15)
1. A process for making a granular laundry detergent component or composition having a bulk density of at least 650 g/1 comprising the steps of a) dissolving a structuring agent, said structuring agent comprising a polymer, in a nonionic surfactant to form a pumpable premix; and b) finely dispersing said premix with an effective amount of powder characterised in that the fine dispersing of the premix is carried out at an operating temperature at which the premix has a viscosity of at least 350 mPas when measured at said operating temperature and at a shear rate of 25s-1.
2. A process according to claim 1 wherein the structuring agent comprises at least one ingredient having more than one hydroxyl functional group.
3. A process according to claim either of the claims I or 2 wherein the structuring agent comprises at least one ingredient chosen from the group comprising polyvinyl pyrrolidone, PVNO, polyvinyl alcohols, polyhydroxyacrylic acid polymers, and mixtures of these.
4. A process according to either of claims 2 or 3 wherein the structuring agent comprises at least one ingredient chosen from the group comprising dextrose, lactose, sucrose, saccharin and derivatives, including polyhydroxy fatty acid amides. F. .i WO 94/25553 PCTUS94/04843 31 A process according to any of the previous claims wherein the structuring agent comprises at least one ingredient chosen from the group comprising phthalimide, para-toluene sulphonamide, maleimide and mixtures of these
6. A process according to any of the previous claims characterised in that the structuring agent is a polymer having a molecular weight of at least 2000.
7. A process according to any of the previous claims wherein the granular laundry detergent component or composition comprises at least 10% by weight of nonionic surfactant.
8. A process according to any of the previous claims in which the powder in step b) is chosen from the group comprising zeolite, silica, carbonate, silicate, sulphate, phosphate, citrate, citric acid or mixtures of these
9. A process for making a granular laundry detergent component or composition comprising the steps of a) dissolving a structuring agent, said structuring agent comprising a polymer, in a nonionic surfactant to form a premix b) mixing said premix with an effective amount of powder by spraying said premix onto said powder in a low shear mixer or a rotating drum characterised in that the premix is sprayed at an operating temperature at which said premix has a viscosity of at least 350 mPas when measured at said operating temperature and at a shear rate of 25s 1 i: 1-1- WO 94/25553 PCT/US94/04843 I IIII I Itt II I I I A process according to claim 9 in which the powder in step b) is a granular detergent which comprises particles prepared by spray drying, agglomeration, or mixtures of these.
11. A process for making a granular laundry detergent component or composition having a bulk density of at least 650 g/1 comprising the steps of a) disolving a structuring agent comprising a potymer in a nonionic surfactant to form a pumpable premix; and b) finely dispersing said premix with an effective amount of powder characterised in that the fine dispersing of the premix is carried out at an operating temperature at which the premix has a viscosity of at least 350 mPas when measured at said operating temperature and at a shear rate of 25s- 1 and that at least some of said powder is in a hydratable form; and c) spraying water on to the product of step b)
12. A detergent component or composition having a bulk density of at least 650 9/1 comprising: i) from 10% to 50% by weight of a nonionic surfactant ii) from 5% to 30% by weight of a structuring agent which is chosen from the group comprising sugars and artificial sweeteners, polyvinyl alcohols, polyhydroxyacryllc acid polymers, and their derivatives; and polyvinyl pyrrolidone, PVNO, phthalimide, para-toluene sulphonamide, maleimide, and mixtures of these.
13. A detergent component or composition according to claim 12 wherein the ratio of the nonionic surfactant to the structuring agent is from 20:1 to 1:1. ;T- i I i t it ft.., ''ft. f t ft. ft f f f f ft i a ci t t -33-
14. A detergent component or composition according to either of claims 12 or 13 wherein the nonionic surfactant comprises an ethoxylated alcohol, the alcohol having a chain length of from 8 to 20 carbon atoms, and an average of from 1 to 25, preferably from 2 to 10 ethoxy groups per molecule of alcohol. A detergent component or composition according to claim 14 wherein the nonionic surfactant is a liquid at temperatures below 400C.
16. A process according to claim 1 substantially as herein described with 10 reference to any one of the Examples.
17. A detergent composition according to claim 12 substantially as herein described with reference to any one of the Examples. 15 DATED: 19 May 1998 PHILLIPS ORMONDE FITZPATRICK Attorneys for: THE PROCTER GAMBLE COMPANY I' I 1 1 INTERNATIONAL SEARCH REPORT International application No. PCT/US94/04843 A. CLASSI FICATION OF SUBJ EC'i'MATTER :C1ID 1/66, 1/72, 17/06 US CL 252/89.1, 135, 174.17, 174.21, 174.23, 174.24. 544, 545 According to International Patent Classification (lPC) or to both national classification and IPC B. FIELDS SEARCIIED Minimum documentation serched (classification system followed by classification symbols) U.S. 252/89.1, 135, 174.17, 174.21, 174.23, 174.24, 544, 545 Documentation searched othcr than inimiium documentatioin to thc cxtent that such documents are included in the fields searched Electronic data base consultcd during- the international search (name of data base and, where practicable, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. A USA4,652,391 (Balk) 24 March 1987, see the whole 1-3,9-11 document. X 12-15 A USA3,849,327 (DiSaivo et al) 19 November 1974, see the 1-3, 9-15 whole document A JPA62-263,299 (LION CORP.) 16 November 1987, see 1, 9, 11,12 abstract A USA 4,908,159 (Davies et al) 13 March 1990, col. 2 lines 1,2,9,10,12
43-59. Further documents are listed in the continuation of Box C. El See patent family annex. Special categories of cited documentsv: 'T later document published after the international Filing date or priority date arid not in conflict with the application but cited to understand the document defining the general state of the an which it not consitdered principle or theory underlying the invention to be of prinicular relevanceI *E earlier document published an or after the intemratinnl Filing date X. document of particular relevance: the claimed invention cannot be considered novel or cannot be considered to involve an inventive step L documnt which inay thi,,w doubts an piority claiivl or which i. when the document u; Laken alone cited to enthiob the publlication daite or anotcr citntion or tither Y apeci asonu (ais Specified) document of particular relevance; the claimed invention cannot be considered to involve an inventive step when the document ia .0 document referrng to an andm dlsvscum. use. exhbit~iion or mother combined with one or more other such documents, such combination means being obvious to a person skilled in the ant .p docunent published prior to the internationalfriling date but later than documentmmber ofthe me ptet famnily the priority date Date of the actual completion of the international search 06 JULY 1994 Date of mailing of the international search report JUL Z20 1994 Name and mailing address of the ISA/US Commissioner of Patents and Trildcnarks Box PC7 Washington. D.C, 20231 Facsimile No. (703) 305-3230 Form PCT/15A/210 (second slict)(July 1992)* Autthorized, relephone No. (703) 308-25i23 I. 1 4~ INTERNATIONAL SEARCH REPORT International application No. PCT/US94/04843 C (Continuation), DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation o f document. with indication, where appropriate, of' the relevant passages Relevant to claim No. US,A,4,399,049 (Gray et al), 16 August 1983, col. 5 line 15 to col. 6 line 45, claim 9. Form PCT/ISA/210 (continuation of scond shect)(July 1992)* N I 1 INTERNATIONAL SEARCH REPORT Inten..ional application No. PCT/US94/04843 Box I Observations where certain claims were found unseaclhable (Continiution of item I of first sheet) This international report has not been established in respect of certain caims under Article 17(2)(a) for the following reasons: I. F Claims Nos.: S because they relate to subject matter not required to be searched by this Authority, namely: 2. [c Claims Nos.: S because they relate to parts of the international application that do not comply with the prescribed requirements to such an extent that no meaningful international search can be carried out, specifically: 3. X Claims Nos.: 4-8 because they are dependent claims and are not drfted in accordance with the second and third sentences of Rule 6.4(a). Box II Ohservations where unity of invention is lacking (Continuation of item 2 of first sheet) This International Searching Authority found multiple inventions in this international application, as follows: 1. j As all required additional search fees were timely paid hb, ,e applicant, this international search report covers all searchable claims. 2. O As all searchable claims could be searched without effort justifying an additional fee, this Authority did not invite payment of any additional fee. 3. As only some of the required additional search fees were timely paid by the applicant, this international search reportcovers only those claims for which fees were paid, specirically claims Nos.: 4. O No required additional search fees were timely paid by the applicant. Consequently, this international search report is restricted to the invention first mentioned in the claims; it is covered by claims Nos.: Remark on Protest D The additional search fees were accompanied by the applicant's protest. No protest accompanied the payment of additional search fees. Form PCT/IISA/210 (continuation of first shee(l))(July 1992)* 4 q I.INTERNATIONAL SEARCH RI .j A ,PORT lnterr,.ional application No. PCT/U S94/04843 B. FIELDS SEARCHED Electronic dauw hases consulted (Name Of datal base aod where practicable terms used); APS search terms: bulk density, nonionie, polyiners, -ranular, polyvinyl alcohol, pyrrolidone, acrylic, dext".ase, lactose, sucrose, saccharin, phithalimide, maleimnide, sulphonamide, premix Formn PCTIISA/2I0 (extra sheet)(Muy 1992)*
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP93870075 | 1993-04-30 | ||
| EP93870075A EP0622454A1 (en) | 1993-04-30 | 1993-04-30 | Structuring liquid nonionic surfactants prior to granulation process |
| PCT/US1994/004843 WO1994025553A1 (en) | 1993-04-30 | 1994-04-29 | Structuring liquid nonionic surfactants prior to granulation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU6780494A AU6780494A (en) | 1994-11-21 |
| AU693445B2 true AU693445B2 (en) | 1998-07-02 |
Family
ID=8215339
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| AU67804/94A Ceased AU693445B2 (en) | 1993-04-30 | 1994-04-29 | Structuring liquid nonionic surfactants prior to granulation process |
Country Status (15)
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| EP (1) | EP0622454A1 (en) |
| JP (1) | JP2888983B2 (en) |
| KR (1) | KR960701980A (en) |
| CN (1) | CN1125462A (en) |
| AU (1) | AU693445B2 (en) |
| CA (1) | CA2160662C (en) |
| CZ (1) | CZ283895A3 (en) |
| EG (1) | EG20591A (en) |
| FI (1) | FI955143A (en) |
| HU (1) | HU216904B (en) |
| MA (1) | MA23182A1 (en) |
| NO (1) | NO954308L (en) |
| PE (1) | PE54094A1 (en) |
| PH (1) | PH31661A (en) |
| WO (1) | WO1994025553A1 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0643130B2 (en) * | 1993-09-13 | 2007-09-19 | The Procter & Gamble Company | Granular detergent compositions comprising nonionic surfactant and process for making such compositions |
| GB9404821D0 (en) * | 1994-03-11 | 1994-04-27 | Unilever Plc | Detergent composition |
| CA2192549A1 (en) * | 1994-06-13 | 1995-12-21 | Charles Louis Stearns | Detergent composition containing anionic surfactants and water-soluble saccharides |
| US5858957A (en) * | 1995-01-26 | 1999-01-12 | The Procter & Gamble Company | Process for the manufacture of granular detergent compositions comprising nonionic surfactant |
| WO1996023048A1 (en) * | 1995-01-26 | 1996-08-01 | The Procter & Gamble Company | Process for the manufacture of granular detergent compositions comprising nonionic surfactant |
| EA000899B1 (en) * | 1995-09-04 | 2000-06-26 | Унилевер Н.В. | Detergent compositions and process for preparing them |
| US5726139A (en) * | 1996-03-14 | 1998-03-10 | The Procter & Gamble Company | Glass cleaner compositions having good filming/streaking characteristics containing amine oxide polymers functionality |
| DE69707480T2 (en) * | 1996-08-26 | 2002-08-14 | THE PROCTER & GAMBLE COMPANY, CINCINNATI | SPRAY DRYING METHOD FOR PRODUCING DETERGENT COMPOSITIONS WITH PRE-MIXING OF A MODIFIED POLYAMINE |
| EP0922087A1 (en) * | 1996-08-26 | 1999-06-16 | The Procter & Gamble Company | Agglomeration process for producing detergent compositions involving premixing modified polyamine polymers |
| GB9618875D0 (en) * | 1996-09-10 | 1996-10-23 | Unilever Plc | Process for preparing high bulk density detergent compositions |
| GB9618877D0 (en) * | 1996-09-10 | 1996-10-23 | Unilever Plc | Process for preparing high bulk density detergent compositions |
| US5733863A (en) * | 1997-01-17 | 1998-03-31 | The Procter & Gamble Company | Process for making a free-flowing particule detergent admix containing nonionic surfactant |
| WO1999011749A1 (en) * | 1997-08-28 | 1999-03-11 | The Procter & Gamble Company | Agglomeration process for producing a particulate modifier polyamine detergent admix |
| JP2001515955A (en) * | 1997-09-11 | 2001-09-25 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン | Manufacturing method of granular detergent |
| GB9805193D0 (en) * | 1998-03-10 | 1998-05-06 | Unilever Plc | Process for preparing granular detergent compositions |
| DE10021113A1 (en) * | 2000-05-02 | 2001-11-15 | Henkel Kgaa | Particulate compounds containing non-ionic surfactants |
| GB0111863D0 (en) | 2001-05-15 | 2001-07-04 | Unilever Plc | Granular composition |
| GB0111862D0 (en) | 2001-05-15 | 2001-07-04 | Unilever Plc | Granular composition |
| EP2085461A1 (en) * | 2008-01-11 | 2009-08-05 | Unilever PLC | Laundry composition |
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|---|---|---|---|---|
| GB2137221A (en) * | 1983-03-29 | 1984-10-03 | Colgate Palmolive Co | Soil releasing detergent |
| EP0208534A2 (en) * | 1985-07-09 | 1987-01-14 | The Procter & Gamble Company | Making of spray-dried granular detergent compositions |
| US4652391A (en) * | 1984-09-22 | 1987-03-24 | Henkel Kommanditgesellschaft Auf Aktien | High powder density free-flowing detergent |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4839208B1 (en) * | 1968-11-18 | 1973-11-22 | ||
| US3849327A (en) * | 1971-11-30 | 1974-11-19 | Colgate Palmolive Co | Manufacture of free-flowing particulate heavy duty synthetic detergent composition containing nonionic detergent and anti-redeposition agent |
| US4399049A (en) * | 1981-04-08 | 1983-08-16 | The Procter & Gamble Company | Detergent additive compositions |
| GB2174712B (en) * | 1985-05-10 | 1988-10-19 | Unilever Plc | Detergent granules |
| GB8522621D0 (en) * | 1985-09-12 | 1985-10-16 | Unilever Plc | Detergent powder |
| JPH0774355B2 (en) * | 1986-05-09 | 1995-08-09 | ライオン株式会社 | Method for producing granular nonionic detergent composition |
| DE3835918A1 (en) * | 1988-10-21 | 1990-04-26 | Henkel Kgaa | METHOD FOR PRODUCING TENSIDE CONTAINING GRANULES |
| EP0508034B1 (en) * | 1991-04-12 | 1996-02-28 | The Procter & Gamble Company | Compact detergent composition containing polyvinylpyrrolidone |
| JP3192469B2 (en) * | 1991-05-17 | 2001-07-30 | 花王株式会社 | Method for producing nonionic detergent particles |
-
1993
- 1993-04-30 EP EP93870075A patent/EP0622454A1/en not_active Withdrawn
-
1994
- 1994-04-20 PH PH48115A patent/PH31661A/en unknown
- 1994-04-27 EG EG23894A patent/EG20591A/en active
- 1994-04-28 MA MA23488A patent/MA23182A1/en unknown
- 1994-04-29 HU HU9503082A patent/HU216904B/en not_active IP Right Cessation
- 1994-04-29 CZ CZ952838A patent/CZ283895A3/en unknown
- 1994-04-29 WO PCT/US1994/004843 patent/WO1994025553A1/en not_active Application Discontinuation
- 1994-04-29 CA CA002160662A patent/CA2160662C/en not_active Expired - Fee Related
- 1994-04-29 AU AU67804/94A patent/AU693445B2/en not_active Ceased
- 1994-04-29 JP JP6524624A patent/JP2888983B2/en not_active Expired - Lifetime
- 1994-04-29 KR KR1019950704756A patent/KR960701980A/en not_active Application Discontinuation
- 1994-04-29 PE PE1994241261A patent/PE54094A1/en not_active Application Discontinuation
- 1994-04-29 CN CN94192424A patent/CN1125462A/en active Pending
-
1995
- 1995-10-27 FI FI955143A patent/FI955143A/en unknown
- 1995-10-27 NO NO954308A patent/NO954308L/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2137221A (en) * | 1983-03-29 | 1984-10-03 | Colgate Palmolive Co | Soil releasing detergent |
| US4652391A (en) * | 1984-09-22 | 1987-03-24 | Henkel Kommanditgesellschaft Auf Aktien | High powder density free-flowing detergent |
| EP0208534A2 (en) * | 1985-07-09 | 1987-01-14 | The Procter & Gamble Company | Making of spray-dried granular detergent compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| KR960701980A (en) | 1996-03-28 |
| AU6780494A (en) | 1994-11-21 |
| HU9503082D0 (en) | 1995-12-28 |
| FI955143A0 (en) | 1995-10-27 |
| CN1125462A (en) | 1996-06-26 |
| MA23182A1 (en) | 1994-12-31 |
| PE54094A1 (en) | 1995-01-05 |
| FI955143A (en) | 1995-10-27 |
| NO954308L (en) | 1995-11-16 |
| EG20591A (en) | 1999-09-30 |
| PH31661A (en) | 1999-01-12 |
| HUT72275A (en) | 1996-04-29 |
| CA2160662A1 (en) | 1994-11-10 |
| CZ283895A3 (en) | 1996-02-14 |
| WO1994025553A1 (en) | 1994-11-10 |
| NO954308D0 (en) | 1995-10-27 |
| JP2888983B2 (en) | 1999-05-10 |
| CA2160662C (en) | 1999-08-31 |
| JPH08509775A (en) | 1996-10-15 |
| EP0622454A1 (en) | 1994-11-02 |
| HU216904B (en) | 1999-10-28 |
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