EP2162522A1 - Compositions détergentes enzymatiques granulaires - Google Patents
Compositions détergentes enzymatiques granulairesInfo
- Publication number
- EP2162522A1 EP2162522A1 EP08760075A EP08760075A EP2162522A1 EP 2162522 A1 EP2162522 A1 EP 2162522A1 EP 08760075 A EP08760075 A EP 08760075A EP 08760075 A EP08760075 A EP 08760075A EP 2162522 A1 EP2162522 A1 EP 2162522A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- detergent composition
- composition according
- weight
- sodium
- thiosulphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 79
- 239000003599 detergent Substances 0.000 title claims abstract description 49
- 230000002255 enzymatic effect Effects 0.000 title description 2
- 102000004190 Enzymes Human genes 0.000 claims abstract description 31
- 108090000790 Enzymes Proteins 0.000 claims abstract description 31
- 239000008187 granular material Substances 0.000 claims abstract description 29
- 239000004094 surface-active agent Substances 0.000 claims abstract description 24
- 239000000194 fatty acid Substances 0.000 claims abstract description 18
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims abstract description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 16
- 229930195729 fatty acid Natural products 0.000 claims abstract description 16
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 16
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 8
- 229940088598 enzyme Drugs 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 14
- 108091005804 Peptidases Proteins 0.000 claims description 11
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 150000004702 methyl esters Chemical class 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 102000004882 Lipase Human genes 0.000 claims description 5
- 108090001060 Lipase Proteins 0.000 claims description 5
- 239000007844 bleaching agent Substances 0.000 claims description 5
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 5
- 108010065511 Amylases Proteins 0.000 claims description 4
- 102000013142 Amylases Human genes 0.000 claims description 4
- 239000004367 Lipase Substances 0.000 claims description 4
- 239000004365 Protease Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 235000019421 lipase Nutrition 0.000 claims description 4
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 102000004316 Oxidoreductases Human genes 0.000 claims description 3
- 108090000854 Oxidoreductases Proteins 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000007046 ethoxylation reaction Methods 0.000 claims description 3
- 229920005646 polycarboxylate Polymers 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000004382 Amylase Substances 0.000 claims description 2
- 102100032487 Beta-mannosidase Human genes 0.000 claims description 2
- 108010059892 Cellulase Proteins 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 235000019418 amylase Nutrition 0.000 claims description 2
- 108010055059 beta-Mannosidase Proteins 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 229940106157 cellulase Drugs 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 229920003086 cellulose ether Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 238000004900 laundering Methods 0.000 claims description 2
- 239000002304 perfume Substances 0.000 claims description 2
- 150000004965 peroxy acids Chemical class 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 235000019419 proteases Nutrition 0.000 claims description 2
- 239000003352 sequestering agent Substances 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- ZRGKYCBSAYCCTD-UAIGNFCESA-M sodium;(z)-but-2-enedioic acid;prop-2-enoate Chemical compound [Na+].[O-]C(=O)C=C.OC(=O)\C=C/C(O)=O ZRGKYCBSAYCCTD-UAIGNFCESA-M 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004492 methyl ester group Chemical group 0.000 claims 1
- -1 alkylbenzene sulphonate Chemical class 0.000 description 13
- 239000004133 Sodium thiosulphate Substances 0.000 description 10
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 10
- 235000019345 sodium thiosulphate Nutrition 0.000 description 10
- 235000002639 sodium chloride Nutrition 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 108010020132 microbial serine proteinases Proteins 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- DZXBHDRHRFLQCJ-UHFFFAOYSA-M sodium;methyl sulfate Chemical compound [Na+].COS([O-])(=O)=O DZXBHDRHRFLQCJ-UHFFFAOYSA-M 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- YWHLKYXPLRWGSE-UHFFFAOYSA-N Dimethyl trisulfide Chemical compound CSSSC YWHLKYXPLRWGSE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 101710117655 Maltogenic alpha-amylase Proteins 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 108010075550 termamyl Proteins 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000002888 zwitterionic surfactant Substances 0.000 description 2
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 101710130006 Beta-glucanase Proteins 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RKWGIWYCVPQPMF-UHFFFAOYSA-N Chloropropamide Chemical compound CCCNC(=O)NS(=O)(=O)C1=CC=C(Cl)C=C1 RKWGIWYCVPQPMF-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 108010059820 Polygalacturonase Proteins 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- GBFLZEXEOZUWRN-VKHMYHEASA-N S-carboxymethyl-L-cysteine Chemical compound OC(=O)[C@@H](N)CSCC(O)=O GBFLZEXEOZUWRN-VKHMYHEASA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 241000223258 Thermomyces lanuginosus Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 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
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 239000000828 canola oil Substances 0.000 description 1
- 235000019519 canola oil Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NPNIZCVKXVRCHF-UHFFFAOYSA-N dihydrocarbyl tetrasulfide Natural products CSSSSC NPNIZCVKXVRCHF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 108010093305 exopolygalacturonase Proteins 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 108010087558 pectate lyase Proteins 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- UJRYDUDEJGXDNA-UHFFFAOYSA-N quinoline-4-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=NC2=C1 UJRYDUDEJGXDNA-UHFFFAOYSA-N 0.000 description 1
- RYMZZMVNJRMUDD-HGQWONQESA-N simvastatin Chemical compound C([C@H]1[C@@H](C)C=CC2=C[C@H](C)C[C@@H]([C@H]12)OC(=O)C(C)(C)CC)C[C@@H]1C[C@@H](O)CC(=O)O1 RYMZZMVNJRMUDD-HGQWONQESA-N 0.000 description 1
- 239000002002 slurry 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
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 1
- 235000018341 sodium sesquicarbonate Nutrition 0.000 description 1
- HXWNOTVHFBYTKF-UHFFFAOYSA-M sodium;1-methoxy-1-oxohexadecane-2-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCC(S([O-])(=O)=O)C(=O)OC HXWNOTVHFBYTKF-UHFFFAOYSA-M 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RJSZFSOFYVMDIC-UHFFFAOYSA-N tert-butyl n,n-dimethylcarbamate Chemical compound CN(C)C(=O)OC(C)(C)C RJSZFSOFYVMDIC-UHFFFAOYSA-N 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
-
- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38672—Granulated or coated enzymes
Definitions
- the present invention relates to granular detergent compositions, more in particular to granular detergent compositions comprising alkyl ester, in particular methyl ester fatty acid sulphonate surfactant and enzyme granules,
- Laundry detergent compositions have for many years contained anionic sulphonate or sulphate surfactant, for example, linear alkylbenzene sulphonate (LAS) or primary alkyl sulphate (PAS) , together with ethoxylated alcohol nonionic surfactants.
- anionic sulphonate or sulphate surfactant for example, linear alkylbenzene sulphonate (LAS) or primary alkyl sulphate (PAS)
- ethoxylated alcohol nonionic surfactants used in laundry detergent compositions include typically ethoxylated Cio ⁇ Ci6 alcohols having an average degree of ethoxylation of 3 to 9.
- MES methyl ester fatty acid sulphonate
- the IUPAC name for e.g. a so-called C16 MES is Hexadecanoic acid, 2-sulfo-, 1-methylester, sodium salt (C17H33NaO5S) - -
- Methyl ester sulphonate can be obtained by sulphonation of various renewable oleo-based methyl ester feedstocks derived from eg. coconut (C12-14), palm kernel (C8-18), palm stearin C16-18) or tallow (C16-18).
- MES is of special interest due to good biodegradability, detergency and calcium hardness tolerance.
- EP-A-I 634 941 (Lion) or WO-A-01/90284 (Huish) disclose high bulk density granular detergents containing surfactants (including ⁇ -sulpho-fatty acid esters), (bi) carbonate, zeolite and a polymer containing of monoethylenic unsaturated mono- and di-carboxylic acid units.
- surfactants including ⁇ -sulpho-fatty acid esters
- carbonate zeolite
- zeolite a polymer containing of monoethylenic unsaturated mono- and di-carboxylic acid units.
- the granular detergent composition according to the invention comprising 1 to 30% by weight of an alkyl ester fatty acid sulphonate surfactant and enzyme granules, wherein said composition is substantially free of thiosulphate .
- a granular detergent composition comprising 1 to 30% by weight of an alkyl ester fatty acid sulphonate surfactant and 0.1 to 10% by weight enzyme granules, wherein said composition is substantially free of thiosulphate.
- a detergent tablet obtained by compressing the granular detergent composition according to the invention.
- a process for laundering textile fabrics by machine or hand characterised in that it comprises the step of immersing the fabrics in a wash liquor comprising water in which a granular detergent composition or detergent tablet according to the invention is dissolved or dispersed.
- a process for manufacturing a granular detergent composition or tablet according to the invention is provided.
- the granular detergent composition of the invention comprises 1 to 30% by weight of an alkyl ester fatty acid sulphonate surfactant, preferably methyl ester fatty acid sulphonate surfactant, and enzyme granules.
- an alkyl ester fatty acid sulphonate surfactant preferably methyl ester fatty acid sulphonate surfactant
- enzyme granules Preferably, the amount of ⁇ -sulpho-fatty acid esters is 1 to 15% by weight, more preferably 3 to 8% by weight.
- ⁇ -sulfofatty acid esters can be prepared from a variety of sources, including beef tallow, palm kernel oil, palm kernel (olein) oil, palm kernel (stearin) oil, coconut oil, soybean oil, canola oil, cohune - -
- Suitable fatty acids to make ⁇ -sulfofatty acid esters include, but are not limited to, caprylic (Cs) , capric ( (Cio) , lauric (C12) , myristic (Ci 4 ) , myristoleic (Ci 4 ) , palmitic (Ci ⁇ ) , palmitoleic (Ci ⁇ ) , stearic (Cis) , oleic (Cis) , linoleic (Cis) , linolenic (Cis) , ricinoleic (Cis) , arachidic (C20) , gadolic (C20) , behenic (C22) t and erucic (C22) fatty acids.
- ⁇ -Sulfofatty acid esters prepared from one or more of these sources are examples of these sources.
- Samples of alkyl ester fatty acid sulphonate surfactant prepared in dry powder form via above mentioned production processes typically contain about 75-85 % by weight of the desired surfactant.
- the other components in a typical production sample there is one of specific relevance for the present invention, which is sodium methylsulphate, typically present at (but not restricted to) a level of about 1-10 % based on the weight of the MES as such.
- the composition may also comprise one or more other surfactants.
- the other surfactant is present in an amount of from 5 to 40 wt.%, preferably from 7 to 30 wt.%, based on the weight of the total composition.
- alkylbenzene sulphonates examples include alkylbenzene sulphonates, branched or linear alkyl benzene sulphonates, primary and secondary alcohol sulphates, particularly C8 ⁇ Ci6 primary alcohol sulphates; alkyl ether sulphates, olefin sulphonates, including alpha olefin sulphonates, alkane sulphonates, alkyl xylene sulphonates, dialkyl sulphosuccinates, and alkyl carboxylates . These may be present as sodium, potassium, calcium or magnesium salts or mixtures of these. Sodium salts are generally preferred.
- the other surfactant is preferably a sulphonate or sulphate anionic surfactant or a combination thereof. More preferably, the anionic surfactant is linear alkylbenzene sulphonate or primary alkyl sulphate. Most preferably the other surfactant is linear alkylbenzene sulphonate.
- the linear alkyl benzene sulphonate may be present as sodium, potassium, or alkaline earth metal salts, or mixtures of these salts. Sodium salts are generally preferred.
- the other surfactant may also comprise a nonionic surfactant, preferably an ethoxylated alcohol nonionic surfactant with an average degree of ethoxylation ranging from about 3 to 9, preferably from about 3 to 7.
- the alcohol may be derived from natural or synthetic feedstock. Preferred alcohol feedstocks are coconut and palm kernel, predominantly C 12 -C 14 , and oxo C 12 -C 15 alcohols.
- the nonionic surfactant is suitably present in an amount of from 1 to 20 wt %, preferably from 1 to 10, more preferably from 2 to 6 wt %, most preferably from 3 to 5 wt %, based on the weight of the total composition.
- Additional surfactants or detergent active compounds may comprise other nonionics such as alkylpolyglucosides, polyhydroxyamides (glucamide) , methyl ester ethoxylates and glycerol monoethers .
- cationic, amphoteric surfactants and/or zwitterionic surfactants may be present.
- Preferred cationic surfactants are quaternary ammonium salts of the general formula R 1 R 2 R3R 4 N + X-, for example where Ri is a C 12 - Ci 4 alkyl group, R 2 and R3 are methyl groups, R 4 is a
- 2-hydroxyethyl group, and X- is a chloride ion.
- This material is available commercially as Praepagen (Trade Mark) HY from Clariant GmbH, in the form of a 40 wt% aqueous solution .
- Preferred amphoteric surfactants are amine oxides, for example coco dimethyl amine oxide.
- Preferred zwitterionic surfactants are betaines, and especially amidobetaines .
- Preferred betaines are C8 to C18 alkyl amidoalkyl betaines, for example coco amido betaine. These may be included as co- surfactants, preferably present in an amount of from 0 to 10 wt %, more preferably 1 to 5 wt %, based on the weight of the total composition.
- the detergent compositions of the present invention comprise one or more other enzymes, which provide cleaning performance, fabric care and/or sanitation benefits.
- Suitable enzymes for incorporation in detergent compositions preferably include protease, lipase, amylase, cellulase, mannanase and oxidase, peroxidise, oxidoreductase, beta- glucanase, pectinase and/or pectate lyase. Most preferably, the compositions contain a proteolytic enzyme or protease. - -
- composition may contain additional enzymes as found in WO-A-01/007681 page 15, line 25 to pagel9, line 29 as well as those found in WO-A-02/02726 page 16 line 21 to page 19 line 16 and those found in WO-A-02/02726 page 33 line 28 to page 39 line 34, the contents of which are herein incorporated by reference. It also may contain maltogenic ⁇ -amylases as described in WO-A-02/02726 page 5, line 14 to page 11 line 29. Commercially available maltogenic ⁇ -amylases are NovamylTM and MaltogenaseTM from Novozymes.
- composition may also contain a lipase variant of the Humicola lanuginosa lipase with substitutions T231R + N233R, commercially available as LipexTM from Novozymes or another variant as described in WO-A-00/60063.
- composition may also contain other commercial enzymes not described in any of the previous specifications such as the new enzymes from Novozymes: MannawayTM, NatalaseTM, RenozymeTM, OvozymeTM, CelluCleanTM, PolarzymeTM, StainzymeTM, CoronaseTM, PectaawayTM, PectawashTM, Termamyl UltraTM. And the new enzymes from Genencor: FN-3, FN-4, Purafect PrimeTM, ProperaseTM. - -
- detergency enzymes are employed in granular form in amounts of from about 0.1 to about 10.0 wt %, preferably from about 0.2 to about 3% by weight, more preferably from about 0.2 to about 1% by weight.
- the detergent compositions are substantially free of thiosulphate . Since enzyme granules sometimes contain thiosulphate, it was found to be important to use thiosulphate free enzyme granules. Preferably enzyme granules contain less than 3% by weight, more preferably less than 1% by weight, most preferably less than 0.1% by weight of thiosulphate. The amount of thiosulphate in the compositions can be determined using standard analytical techniques. Thiosulphate in the context of this invention means any salt thereof, such as alkalimetal, especially sodium, but also ammonium, Monoethanolamine or Triethanolamine salts.
- compositions of the invention may contain a detergency builder.
- the builder is present in an amount of from 1 to less than 80 wt % based on the weight of the total composition. More preferably the amount of builder is from 1 to 60 wt %.
- Builders are well-known to those skilled in the art. Many suitable builder compounds are available. Examples are zeolites, sodium tripolyphosphate, layered silicate, sodium carbonate, sodium bicarbonate, burkeite, sodium silicate and mixtures thereof. - -
- compositions may optionally contain other active ingredients to enhance performance and properties.
- compositions of the invention may contain from 0 to 85 wt % of an inorganic non-builder salt, such as sodium sulphate, sodium sesquicarbonate, sodium chloride, calcium chloride, magnesium chloride and calcite, preferably from 0 to 60 wt %, preferably from 0 to 40 wt %, based on the weight of the total composition.
- an inorganic non-builder salt such as sodium sulphate, sodium sesquicarbonate, sodium chloride, calcium chloride, magnesium chloride and calcite
- compositions of the invention may contain a polycarboxylate polymer.
- polycarboxylate polymer include homopolymers and copolymers of acrylic acid, maleic acid and acrylic/maleic acids.
- the publication ⁇ Polymeric Dispersing Agents, Sokalan' a printed publication of BASF Aktiengesellschaft, D-6700 Ludwigshaven, Germany describes organic polymers which are useful.
- the polycarboxylate polymer is selected from the group consisting of sodium polyacrylate, sodium acrylate maleate and mixtures thereof.
- suitable polymers include Sokalan CP5, ex BASF polyacrylate, namely maleic acid-acrylic acid copolymer, with a sodium salt.
- the detergent compositions of the invention may comprise one or more optional ingredients selected from soap, peroxyacid and persalt bleaches, bleach activators, air bleach catalysts, sequestrants, cellulose ethers and esters, cellulosic polymers, other antiredeposition agents, sodium bicarbonate, other inorganic salts, fluorescers, photobleaches, polyvinyl pyrrolidone, other dye transfer inhibiting polymers, foam controllers, foam boosters, - -
- citric acid soil release polymers, silicone, fabric conditioning compounds, coloured speckles such as blue speckles, and perfume. This list is not intended to be exhaustive .
- compositions of the invention are granular detergent compositions, preferably in powder form, having a mean particle size between 200 and 800 micrometer. Alternatively, the compositions may be in tablet form.
- the compositions can be formulated for use as hand wash or machine wash detergents .
- compositions of the invention may be prepared by any suitable process. Powders of low to moderate bulk density may be prepared by spray-drying a slurry, and optionally postdosing (dry-mixing) further ingredients. “Concentrated” or “compact” powders may be prepared by mixing and granulating processes, for example, using a highspeed mixer/granulator, or other non-tower processes.
- Tablets may be prepared by compacting powders, especially "concentrated" powders.
- the choice of processing route may be in part dictated by the stability or heat-sensitivity of the surfactants involved, and the form in which they are available. In all cases, all ingredients may be added separately.
- Sodium LAS sodium C10-C13 alkylbenzene sulphonate (anionic surfactant)
- Nonionic 7EO C13-C15 fatty alcohol ethoxylated with an average of 7 ethyleneoxide units per mole (nonionic surfactant)
- Zeolite 4A sodium alumino silicate with Si:Al ratio 1 (ion- exchange builder)
- Polymer acrylic acid/maleic acid type of polymer (anti- redeposition, anti-ashing or co-builder)
- SCMC sodium carboxy methyl cellulose (anti-redeposition polymer)
- Polarzyme 12.0 T protease enzyme granule from Novozymes; granule contains sodium thiosulphate as stabilizer.
- Savinase 24.0 GTT (12.0 or 24.0 T): protease enzyme granule from Novozymes; granule contains sodium thiosulphate as stabilizer.
- Stainzyme 12.0 T amylase enzyme granule from Novozymes; granule contains sodium thiosulphate as stabilizer.
- Termamyl 60 T amylase enzyme granule from Novozymes; granule contains sodium thiosulphate as stabilizer.
- Properase 100OM protease enzyme granule from Genencor; granule is free of sodium thiosulphate.
- Purafect 3450M protease enzyme granule from Genencor; granule is free of sodium thiosulphate.
- Lipex 100 T lipase enzyme granule from Novozymes; granule is free of sodium thiosulphate. - -
- Savinase pure pure protease enzyme powder from Novozymes; without coating and sodium thiosulphate .
- Dummy granule granule from Novozymes without enzymes and sodium thiosulphate.
- BSA Bovine Serum Albumin
- model protein model protein
- the malodour molecule generated during storage has been identified via GC/MS headspace analyses to be a dimethyl- sulfide (abbr. DMS), predominantly dimethyl-disulfide, dimethyl-trisulfide and dimethyl-tetrasulfide .
- DMS dimethyl- sulfide
- the severity of malodour due to dimethylsulfides can be best assessed olfactively using following intensity scale:
- Malodour is due to an interaction of MES/MS and thiosulphate (which is present within enzyme-granules of Novozymes) , since - i
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Abstract
Priority Applications (1)
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EP08760075.5A EP2162522B1 (fr) | 2007-06-22 | 2008-05-27 | Compositions détergentes enzymatiques granulaires |
Applications Claiming Priority (3)
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EP07110850 | 2007-06-22 | ||
PCT/EP2008/056477 WO2009000605A1 (fr) | 2007-06-22 | 2008-05-27 | Compositions détergentes enzymatiques granulaires |
EP08760075.5A EP2162522B1 (fr) | 2007-06-22 | 2008-05-27 | Compositions détergentes enzymatiques granulaires |
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EP2162522A1 true EP2162522A1 (fr) | 2010-03-17 |
EP2162522B1 EP2162522B1 (fr) | 2018-07-04 |
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EP (1) | EP2162522B1 (fr) |
CN (1) | CN101688152B (fr) |
AR (1) | AR067053A1 (fr) |
BR (1) | BRPI0813386A2 (fr) |
CL (1) | CL2008001858A1 (fr) |
TR (1) | TR201810838T4 (fr) |
WO (1) | WO2009000605A1 (fr) |
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CH619264A5 (fr) * | 1977-02-02 | 1980-09-15 | Savonnerie Union Generale | |
JPH07506618A (ja) * | 1992-05-08 | 1995-07-20 | ザ、プロクター、エンド、ギャンブル、カンパニー | リパーゼを含有する粒状洗剤組成物 |
CA2176697C (fr) * | 1993-12-21 | 2000-01-11 | Michael Alan John Moss | Composition detergente contenant du percarbonate et de l'amylase |
-
2008
- 2008-05-27 WO PCT/EP2008/056477 patent/WO2009000605A1/fr active Application Filing
- 2008-05-27 TR TR2018/10838T patent/TR201810838T4/tr unknown
- 2008-05-27 EP EP08760075.5A patent/EP2162522B1/fr active Active
- 2008-05-27 CN CN2008800213871A patent/CN101688152B/zh not_active Ceased
- 2008-05-27 BR BRPI0813386-7A2A patent/BRPI0813386A2/pt active IP Right Grant
- 2008-06-19 AR ARP080102602A patent/AR067053A1/es active IP Right Grant
- 2008-06-20 CL CL2008001858A patent/CL2008001858A1/es unknown
Non-Patent Citations (1)
Title |
---|
See references of WO2009000605A1 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2762725C2 (ru) * | 2009-09-25 | 2021-12-22 | Д-Р Редди'С Лабораторис Лтд. | Композиции, содержащие триптановые соединения |
US11499124B2 (en) | 2020-03-13 | 2022-11-15 | YFY Consumer Products, Co. | Solid granules used for cleaning agents |
US11767495B2 (en) | 2020-03-13 | 2023-09-26 | YFY Consumer Products, Co. | Systems and methods for manufacturing solid granules |
Also Published As
Publication number | Publication date |
---|---|
AR067053A1 (es) | 2009-09-30 |
EP2162522B1 (fr) | 2018-07-04 |
CL2008001858A1 (es) | 2009-03-06 |
CN101688152A (zh) | 2010-03-31 |
TR201810838T4 (tr) | 2018-08-27 |
WO2009000605A1 (fr) | 2008-12-31 |
BRPI0813386A2 (pt) | 2014-12-30 |
CN101688152B (zh) | 2012-06-27 |
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