CA2325709A1 - Process for the production of an enzyme preparation of low water content - Google Patents
Process for the production of an enzyme preparation of low water content Download PDFInfo
- Publication number
- CA2325709A1 CA2325709A1 CA 2325709 CA2325709A CA2325709A1 CA 2325709 A1 CA2325709 A1 CA 2325709A1 CA 2325709 CA2325709 CA 2325709 CA 2325709 A CA2325709 A CA 2325709A CA 2325709 A1 CA2325709 A1 CA 2325709A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- enzyme preparation
- acid
- detergent composition
- water
- 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.)
- Abandoned
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 48
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000008569 process Effects 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000003599 detergent Substances 0.000 claims abstract description 39
- 239000007844 bleaching agent Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 5
- 229940088598 enzyme Drugs 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- 239000002736 nonionic surfactant Substances 0.000 claims description 11
- 239000012190 activator Substances 0.000 claims description 9
- 239000012141 concentrate Substances 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 108091005804 Peptidases Proteins 0.000 claims description 5
- 239000004365 Protease Substances 0.000 claims description 5
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 235000019419 proteases Nutrition 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 4
- 238000000855 fermentation Methods 0.000 claims description 4
- 230000004151 fermentation Effects 0.000 claims description 4
- 239000002304 perfume Substances 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 3
- 102000013142 Amylases Human genes 0.000 claims description 2
- 108010065511 Amylases Proteins 0.000 claims description 2
- 102000004882 Lipase Human genes 0.000 claims description 2
- 239000004367 Lipase Substances 0.000 claims description 2
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- 235000019421 lipase Nutrition 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims 2
- 239000004382 Amylase Substances 0.000 claims 1
- 108010059892 Cellulase Proteins 0.000 claims 1
- 229940106157 cellulase Drugs 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 claims 1
- 239000003352 sequestering agent Substances 0.000 claims 1
- 238000010348 incorporation Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 36
- 150000003839 salts Chemical class 0.000 description 28
- 239000011734 sodium Substances 0.000 description 25
- -1 frucxose Chemical compound 0.000 description 20
- 229910052708 sodium Inorganic materials 0.000 description 20
- 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 19
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 150000007513 acids Chemical class 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 13
- 235000019832 sodium triphosphate Nutrition 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 235000021317 phosphate Nutrition 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
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- 229910052700 potassium Inorganic materials 0.000 description 8
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- 239000002245 particle Substances 0.000 description 7
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- 239000002562 thickening agent Substances 0.000 description 7
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 7
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000875 corresponding effect Effects 0.000 description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
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- 150000001298 alcohols Chemical class 0.000 description 5
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000001226 triphosphate Substances 0.000 description 5
- 229920001353 Dextrin Polymers 0.000 description 4
- 239000004375 Dextrin Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 235000019425 dextrin Nutrition 0.000 description 4
- 239000001177 diphosphate Substances 0.000 description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 4
- 235000011180 diphosphates Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 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 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003240 coconut oil Substances 0.000 description 3
- 235000019864 coconut oil Nutrition 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000004691 decahydrates Chemical class 0.000 description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 description 3
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- 235000011009 potassium phosphates Nutrition 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 235000019351 sodium silicates Nutrition 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- RUZAHKTXOIYZNE-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid;iron(2+) Chemical compound [Fe+2].OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O RUZAHKTXOIYZNE-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 description 2
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- 238000002425 crystallisation Methods 0.000 description 2
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- 238000009472 formulation Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000008101 lactose Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
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- 150000004682 monohydrates Chemical class 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
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- 230000001590 oxidative effect Effects 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
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- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 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
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- 239000001993 wax Substances 0.000 description 2
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- NPMRPDRLIHYOBW-UHFFFAOYSA-N 1-(2-butoxyethoxy)propan-2-ol Chemical compound CCCCOCCOCC(C)O NPMRPDRLIHYOBW-UHFFFAOYSA-N 0.000 description 1
- GQCZPFJGIXHZMB-UHFFFAOYSA-N 1-tert-Butoxy-2-propanol Chemical compound CC(O)COC(C)(C)C GQCZPFJGIXHZMB-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- RIZUCYSQUWMQLX-UHFFFAOYSA-N 2,3-dimethylbenzoic acid Chemical compound CC1=CC=CC(C(O)=O)=C1C RIZUCYSQUWMQLX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical group COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
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- 150000003388 sodium compounds Chemical class 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 150000003527 tetrahydropyrans Chemical class 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229940062627 tribasic potassium phosphate Drugs 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid 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
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
-
- 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
- C11D3/2068—Ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D3/38618—Protease or amylase in liquid compositions only
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
The invention relates to a process far the production of an enzyme preparation of low water content, in which an aqueous enzyme preparation is mixed with an organic solvent having a boiling point above 100°C and the water is distilled off. The enzyme preparation obtained is particularly suitable for incorporation in liquid bleach-containing detergents.
Description
Process for the Production of an Enzyme Preparation of Low Water Content This invention relates to a process for the producxion of an enzyme preparation of low water content, to the use of this enzyme preparation in l detergents and to a detergent.
Enzymes for industrial further processing are generally ava~aab~ as liquid enzyme concentrates which are isolated from a fannentatieon broth and marketed in ooncer>ttatsd form. The stabilit~r of the enzymes in a water-cor~tainlng environment is limited. In order to convert the enzyns:
concentrates obtained into a water free form, the concentrate may be spray-dried, for example in the ptesenoe of a polymeric binder in which the dried enzyme particles are taKen up by the binder and form aggregates. To produce liquid preparations, the spray-dried particles are redispersed.
A pn'cess for the prnducx~n of enzyme dispersions is disclosed in WO 94121. The process descxibed therein comprises emulsifying a solid enzyme preparation in a water-immisable liquid in the presence of a polymeric dispersion stabilizer so that a stable dispersion of the watef containing enzyme parades, which have a particle size below 30 Nm, is formed and dehydrating the dispersed particles by azeotropic distillation. A
saf~~ent feature of the descrided process is that an organic liquid which is less volatile than the water-immiscible liquid and which is selected from surfactants and water-misdble liquids is adds! during or after the dehydration of the particles, so that redispersion occxrcs, and the water immisat>fe liquid is distilled off from the disperxion unfit the quantity of this liquid introduced at the outset in the dispersion is below 20 Nm which, pecause of the possible dust formation, involves risKs to health through inhalation of the dust during production and processing and also the danger of a dust exp~ion. In addition, some of the enzyme activity is lost by denaturing during these drying processes. This problem also arises in the redispersion described above.
A significant field of application for enzymes are detergents. The enzymes are incorporated in detergents either as solid aanstituents or in the form of liquid fonnutations.
In the production of liquid detergerns. it is particularly advantageous and cost-efficient if the starting materials are also present in liquid or dispersed form. So far as the use of the enzymes is concerned, enzyme 7 0 concentrates obtained from the producxion process may he directly employed. Unfortunately, these concentrates have a relatively high water vonten~
For liquid bleach-containing formulations, the water content must be low in order to stabilize the bleaching agent. This means that the water content of the raw materials used must be correspondingly lover.
On the other hand, the production of the enzyme dispersions irnolves several steps which partly involve denaturing and hence the loss of the enzyme acxivit~r.
Acooroingiy. the problem address by the present invention wa$ to 2Q provide an enzyme preparation which would have a minimal water content and which could be obtained in simple form from water-containing enzyme concentrates withmt any significant reduction in enzyme activittr.
It has surprisingly been found that an enzyme preparation of tow water content can be obtained by r~-solubilization, t.e. by adding an organic solvent with a higher thing point than water to the water containing enzyme concentrate and sut~ecting the whole to distillation.
~ Accortfingly, the present inventron relates to a process for the production of an enzyme preparation of low water content, characterized in that a water-containing enzyrr~e preparation is mixed with an organic solvent having a boiling point above 100'C and the mixture is subsequently distilled.
The advantage of the present invention is that dehydration and redispersion are avoided.
Any organic solverns with a boiling point above 100°C may be used 5~ as organic solvents in the process according to the invention. These solvents should preferat~y be se>B~i so that the water can be removed from them by distillatan without the for of an azeotrope. The organic solvent is preferably selected from (aj liquid nonionic surtactants, such as fatty alcohol alkoxyfates. (b) monohydric or (c) potyhydric aloohols, such as 7 0 ethylene glycol, propylene glycol, glycerol or tow molecxrlar weight polyethylene glycols containing 2 to 14 monomer units. The solvents mentioned hereinafter for the production of liquid or get-fomt detergents are also suitable providing they have a boiling point above 100°C.
In order to minimize the thermal str~esslng of the enzymes, the 15 distillation is carried out under reduced pressuro at a temperature preferably below 50°C. Distillation in a water jet vawum at ambient temperature is particularly suitable.
The water content of the enxyn~e preparation produt~d in acoondartce with the inventan is preferably below 15% by weight, more r 20 preferably below 10% by weight and most preferably below T% by weight, based on the preparation as a while.
The enzymes may be selecxed from the enzymes typically used for mss. Suitable enzymes ate, above aU, the professes, lipases, amylases andlor cellulases obtain! fn~m microorganisrt~s, such as 25 bacteria or fungi. They are obtained in known manner by fermentation from suitable microorganisms which are due, for example, in DE-J1-19 4a 488, D~~A-2A 44 181, D~-A-22 01 803 arid DE~J1~1 21 397, in US
3,632,857 and US 4,284,T38, in European patent ap~'~cation EP OOf B38 and in International patent application WO 811a1z792. if the preparation 30 produced in acodrrlance with the invention is a protease-containing preparation, its protease ac~iviH is preferably from 150,000 protease units (PU, as determined by the method described in Tenslde 7 (1970j. 125) to 1,500,000 PU and more preferably from 200.000 PU to 1,000,000 PU per gram of preparation.
The enzyme preparations of low water content obtained in - accordance with the invention may be put to their inters~d uses in lam manner and further processed them tn a pr~efemed embodiment, the enzyme preparat~ns of low water content are used in detergents.
Accordingly. the present invention also relates to the use of the - enzyme preparation of low water oontertt otxained by the above-desaibed process in detergents. prefierably in liquid to gel-form bleach-containing detergents.
The present invention also relates to detergents containing surfactants and builders and optionally other typical ingredients, characterized in that they contain enzymes in the form of a preparat~n of low water content obtainable by the pnxz;ss described above.
The detergents according to fife invention contain surfactants, for exampha nonionic, anionic and amphoteric surfactants, and bleaching ag~ts and optionaNy other typical ir~gredien~.
Preferred rronionic surfaccarns an: alkoxylated, adva~sly ethoxytated. mono particularly primary ahtiols preferably containing 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene ox~ie (EO) per mole of alcohd. in which the alcohol residue may be linear or, preferably, 2-n>ethy<-branrfv~J or may contain linear and methyl-branc~d residues in the form of the mixtures typically present in oxoelcohol residues. However, alcohol ethwcylates containing linear residues of ala~hds of native origin with 12 to 18 carbon atoms, fior example coconut oil alcohol, palm oil alcohol, tallowr alcohol or oleyl e~ot~ol, and an average of 2 to 8 EO per mole of alcohol are partculariy profen~ed. Proferr~
ethoxylated akrohols include, for example, C~2_~4 alcohols containing 3 EO
or 4 EO, C&,~ alcohols containing 7 EO, C»~s alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C~~.~a alcotwls containing 3 EO, 5 EO or 7 EO and . mixturss thereof, such as mixtures of C,~» alcohol containing 3 EO and 5 C,~~e alcohol containing 5 EO. The degrees of ethoxylation mentioned are statistical mean values which, for a epees! product, may be eider a whole number or a broken number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO may also be used. Examples of such fatty alcohols are tallow akx~hols containing 14 EO, 25 EO, 30 EO or 40 EO.
Another lass of preferred nonionic surfactants which arse used either as sole nonionic surfactant or in combination with otte=r nonionic surfactants are atkoxylated. proferably ethoxylated or ethoxylated and propoxylated, fatty acki alkyl esters pnaferably cornaininp 1 to 4 carbon atoms in the alkyl chain, more particularly fatty acid methyl esters.
Another class of nonionic surtactants which may be used with advarnage are the alkyl polyglycosides (APGs). Suitable alkyl polyglycosidss con~espond to the general fomwla RO(Gk where R is a linear or branched, more particularly 2-methyl-branded, saturated or unsaturated aliphatic radical containing 8 to 22 and p~eferebly 12 to 18 carbon atoms, G is a glycose unit containing 5 or 8 carbon atoms, preferably gluoo$e. The degree of glyoosidation z is between 1.0 and 4.0, preferably between 1.o and 2.0 and more preferably been 1.1 and 1.4.
linear alkyl polyglucosides, i.e. alkyl polyglyoosides in which the polyglmoiety is a glucose unit and the alkyl moiety is an n-alkyl group, aro preferably us~i.
Nonionic surfactants of the amine o~ade type, fior example N
oocoslkyt-N,N-dimethylamine wdde and N-tal~owalkyl-N.N~ihydroxyethyl amine oxide, and the fatty sad alkanolamkie type are also suitablB. The l quantity in which these nonionic surfactants are used is preferably no more, in paraarlar no more than half, the quantity of ethoxyiated fatty alcohds uses!.
Other suitable surfactants are polyhydroxyfany acid amides cor-responding to totmula III):
R' R-CO-N-[ZJ (I l j in which RCO is an alr~atic acyl radical containing 6 to 22 carbon atoms, R' is hydrogen, an alley! or hydtoxyalkyl radical containing 1 to 4 carbon atoms and [ZJ is a lineal or branched pdyhydroxyalkyl radical containing 3 to 10 carbon atoms and 3 to 10 hydroxyl groin. The potyhydroxyfiatty acid amides are known sut~tatt~s which may nomtally be odtained by reductive amination of a redudng sugar with ammonia, sn alkylamine or an alkarldamine and subsequent acylation with a fatty aad, a fatty acid alkyl ester or a fatty aad chloride.
The group of pdyhydraxyfatty aad anodes also includes compounds corresponding to formula (III):
R'-O-R~
R-CO-N-jZ] tll) ' ~ in which R ~ a linear or brar~hed alkyl or alkenyl group containing 7 to carbon atoms, R' is a bnear, brand or cyclic alkyl group or an aryl group containing 2 to 8 carbon atoms and R2 is a linear, branched or cycaic alkyl group or an aryl group or an oxyalkyl 9n~up containing 1 to 8 carbon atoms, C,~ alkyl or phenyl groups being prefiarred, and [Z] is a lineal pdyhydroxy-alkyl group, of which the alkyl chain is substi~tea by at least two hydroxyl groups, or ahcoxylated, preferably ethoxylsted or propoxylated, derivatives of that group.
Enzymes for industrial further processing are generally ava~aab~ as liquid enzyme concentrates which are isolated from a fannentatieon broth and marketed in ooncer>ttatsd form. The stabilit~r of the enzymes in a water-cor~tainlng environment is limited. In order to convert the enzyns:
concentrates obtained into a water free form, the concentrate may be spray-dried, for example in the ptesenoe of a polymeric binder in which the dried enzyme particles are taKen up by the binder and form aggregates. To produce liquid preparations, the spray-dried particles are redispersed.
A pn'cess for the prnducx~n of enzyme dispersions is disclosed in WO 94121. The process descxibed therein comprises emulsifying a solid enzyme preparation in a water-immisable liquid in the presence of a polymeric dispersion stabilizer so that a stable dispersion of the watef containing enzyme parades, which have a particle size below 30 Nm, is formed and dehydrating the dispersed particles by azeotropic distillation. A
saf~~ent feature of the descrided process is that an organic liquid which is less volatile than the water-immiscible liquid and which is selected from surfactants and water-misdble liquids is adds! during or after the dehydration of the particles, so that redispersion occxrcs, and the water immisat>fe liquid is distilled off from the disperxion unfit the quantity of this liquid introduced at the outset in the dispersion is below 20 Nm which, pecause of the possible dust formation, involves risKs to health through inhalation of the dust during production and processing and also the danger of a dust exp~ion. In addition, some of the enzyme activity is lost by denaturing during these drying processes. This problem also arises in the redispersion described above.
A significant field of application for enzymes are detergents. The enzymes are incorporated in detergents either as solid aanstituents or in the form of liquid fonnutations.
In the production of liquid detergerns. it is particularly advantageous and cost-efficient if the starting materials are also present in liquid or dispersed form. So far as the use of the enzymes is concerned, enzyme 7 0 concentrates obtained from the producxion process may he directly employed. Unfortunately, these concentrates have a relatively high water vonten~
For liquid bleach-containing formulations, the water content must be low in order to stabilize the bleaching agent. This means that the water content of the raw materials used must be correspondingly lover.
On the other hand, the production of the enzyme dispersions irnolves several steps which partly involve denaturing and hence the loss of the enzyme acxivit~r.
Acooroingiy. the problem address by the present invention wa$ to 2Q provide an enzyme preparation which would have a minimal water content and which could be obtained in simple form from water-containing enzyme concentrates withmt any significant reduction in enzyme activittr.
It has surprisingly been found that an enzyme preparation of tow water content can be obtained by r~-solubilization, t.e. by adding an organic solvent with a higher thing point than water to the water containing enzyme concentrate and sut~ecting the whole to distillation.
~ Accortfingly, the present inventron relates to a process for the production of an enzyme preparation of low water content, characterized in that a water-containing enzyrr~e preparation is mixed with an organic solvent having a boiling point above 100'C and the mixture is subsequently distilled.
The advantage of the present invention is that dehydration and redispersion are avoided.
Any organic solverns with a boiling point above 100°C may be used 5~ as organic solvents in the process according to the invention. These solvents should preferat~y be se>B~i so that the water can be removed from them by distillatan without the for of an azeotrope. The organic solvent is preferably selected from (aj liquid nonionic surtactants, such as fatty alcohol alkoxyfates. (b) monohydric or (c) potyhydric aloohols, such as 7 0 ethylene glycol, propylene glycol, glycerol or tow molecxrlar weight polyethylene glycols containing 2 to 14 monomer units. The solvents mentioned hereinafter for the production of liquid or get-fomt detergents are also suitable providing they have a boiling point above 100°C.
In order to minimize the thermal str~esslng of the enzymes, the 15 distillation is carried out under reduced pressuro at a temperature preferably below 50°C. Distillation in a water jet vawum at ambient temperature is particularly suitable.
The water content of the enxyn~e preparation produt~d in acoondartce with the inventan is preferably below 15% by weight, more r 20 preferably below 10% by weight and most preferably below T% by weight, based on the preparation as a while.
The enzymes may be selecxed from the enzymes typically used for mss. Suitable enzymes ate, above aU, the professes, lipases, amylases andlor cellulases obtain! fn~m microorganisrt~s, such as 25 bacteria or fungi. They are obtained in known manner by fermentation from suitable microorganisms which are due, for example, in DE-J1-19 4a 488, D~~A-2A 44 181, D~-A-22 01 803 arid DE~J1~1 21 397, in US
3,632,857 and US 4,284,T38, in European patent ap~'~cation EP OOf B38 and in International patent application WO 811a1z792. if the preparation 30 produced in acodrrlance with the invention is a protease-containing preparation, its protease ac~iviH is preferably from 150,000 protease units (PU, as determined by the method described in Tenslde 7 (1970j. 125) to 1,500,000 PU and more preferably from 200.000 PU to 1,000,000 PU per gram of preparation.
The enzyme preparations of low water content obtained in - accordance with the invention may be put to their inters~d uses in lam manner and further processed them tn a pr~efemed embodiment, the enzyme preparat~ns of low water content are used in detergents.
Accordingly. the present invention also relates to the use of the - enzyme preparation of low water oontertt otxained by the above-desaibed process in detergents. prefierably in liquid to gel-form bleach-containing detergents.
The present invention also relates to detergents containing surfactants and builders and optionally other typical ingredients, characterized in that they contain enzymes in the form of a preparat~n of low water content obtainable by the pnxz;ss described above.
The detergents according to fife invention contain surfactants, for exampha nonionic, anionic and amphoteric surfactants, and bleaching ag~ts and optionaNy other typical ir~gredien~.
Preferred rronionic surfaccarns an: alkoxylated, adva~sly ethoxytated. mono particularly primary ahtiols preferably containing 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene ox~ie (EO) per mole of alcohd. in which the alcohol residue may be linear or, preferably, 2-n>ethy<-branrfv~J or may contain linear and methyl-branc~d residues in the form of the mixtures typically present in oxoelcohol residues. However, alcohol ethwcylates containing linear residues of ala~hds of native origin with 12 to 18 carbon atoms, fior example coconut oil alcohol, palm oil alcohol, tallowr alcohol or oleyl e~ot~ol, and an average of 2 to 8 EO per mole of alcohol are partculariy profen~ed. Proferr~
ethoxylated akrohols include, for example, C~2_~4 alcohols containing 3 EO
or 4 EO, C&,~ alcohols containing 7 EO, C»~s alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C~~.~a alcotwls containing 3 EO, 5 EO or 7 EO and . mixturss thereof, such as mixtures of C,~» alcohol containing 3 EO and 5 C,~~e alcohol containing 5 EO. The degrees of ethoxylation mentioned are statistical mean values which, for a epees! product, may be eider a whole number or a broken number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO may also be used. Examples of such fatty alcohols are tallow akx~hols containing 14 EO, 25 EO, 30 EO or 40 EO.
Another lass of preferred nonionic surfactants which arse used either as sole nonionic surfactant or in combination with otte=r nonionic surfactants are atkoxylated. proferably ethoxylated or ethoxylated and propoxylated, fatty acki alkyl esters pnaferably cornaininp 1 to 4 carbon atoms in the alkyl chain, more particularly fatty acid methyl esters.
Another class of nonionic surtactants which may be used with advarnage are the alkyl polyglycosides (APGs). Suitable alkyl polyglycosidss con~espond to the general fomwla RO(Gk where R is a linear or branched, more particularly 2-methyl-branded, saturated or unsaturated aliphatic radical containing 8 to 22 and p~eferebly 12 to 18 carbon atoms, G is a glycose unit containing 5 or 8 carbon atoms, preferably gluoo$e. The degree of glyoosidation z is between 1.0 and 4.0, preferably between 1.o and 2.0 and more preferably been 1.1 and 1.4.
linear alkyl polyglucosides, i.e. alkyl polyglyoosides in which the polyglmoiety is a glucose unit and the alkyl moiety is an n-alkyl group, aro preferably us~i.
Nonionic surfactants of the amine o~ade type, fior example N
oocoslkyt-N,N-dimethylamine wdde and N-tal~owalkyl-N.N~ihydroxyethyl amine oxide, and the fatty sad alkanolamkie type are also suitablB. The l quantity in which these nonionic surfactants are used is preferably no more, in paraarlar no more than half, the quantity of ethoxyiated fatty alcohds uses!.
Other suitable surfactants are polyhydroxyfany acid amides cor-responding to totmula III):
R' R-CO-N-[ZJ (I l j in which RCO is an alr~atic acyl radical containing 6 to 22 carbon atoms, R' is hydrogen, an alley! or hydtoxyalkyl radical containing 1 to 4 carbon atoms and [ZJ is a lineal or branched pdyhydroxyalkyl radical containing 3 to 10 carbon atoms and 3 to 10 hydroxyl groin. The potyhydroxyfiatty acid amides are known sut~tatt~s which may nomtally be odtained by reductive amination of a redudng sugar with ammonia, sn alkylamine or an alkarldamine and subsequent acylation with a fatty aad, a fatty acid alkyl ester or a fatty aad chloride.
The group of pdyhydraxyfatty aad anodes also includes compounds corresponding to formula (III):
R'-O-R~
R-CO-N-jZ] tll) ' ~ in which R ~ a linear or brar~hed alkyl or alkenyl group containing 7 to carbon atoms, R' is a bnear, brand or cyclic alkyl group or an aryl group containing 2 to 8 carbon atoms and R2 is a linear, branched or cycaic alkyl group or an aryl group or an oxyalkyl 9n~up containing 1 to 8 carbon atoms, C,~ alkyl or phenyl groups being prefiarred, and [Z] is a lineal pdyhydroxy-alkyl group, of which the alkyl chain is substi~tea by at least two hydroxyl groups, or ahcoxylated, preferably ethoxylsted or propoxylated, derivatives of that group.
~ is preferably obtained by reductive amination of a reduced sugar, for example glucose, frucxose, maltose. lactose. 9e, mannose or xylase. The N-,alicoxy- or N-aryloxy-sued compounds may then be converted into the required polyhydroxyfatly acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
The surfactants are present in the detergents according to the invention in a total quantity of preferably 2% by weight to 80% by weight and more preferably 3% by weight to ~0% by weight, based on the final detergent.
Su~able anionic sutfaaartts are, fior example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are pr~sferably Cs.~$ alkyl benzenesutfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates, and tfie disuffonates obtained. for example, from C,a,a monootefins with an intema! or temrinal doubts bond by sulinnation with gaseous sulfur trioxide and subsequent alKaline or acidic hydrolysis of the sulfonation products. Other Suitable surfacxants of the suifortate type are the alkane sullonates obtained from C,~.~a alkanes, for example by sulfachiorination yr sulfaxidarion and subsequent h~rolysis or neutralization. The esters of a-su<fo~ty acids (ester sutfonates), for example the a suifonated methyl esters of hydrogenated coconut oil, palm Kernel oi! or tallow fatty acids, are also suitable.
Other suitable an~nic surfaaants are sutfonated fatty acid glycerol esters. Fatty sect glycerol esters irt the context of the present invention arr3 tits monoesters, diesters and triesters and mixtures ther~sof which are obtained where production is carried ad by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesten of tr'iglycerides with 0.3 to 2 moles of glycerol. Pn~ferred sulfonated fatty acid glycerol estere are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms. for example capro~ acid, caprytic acid, captic ackf, i myrtstic sad, lauric sect, palmitic acid, stearic acid or behenic gad.
The surfactants are present in the detergents according to the invention in a total quantity of preferably 2% by weight to 80% by weight and more preferably 3% by weight to ~0% by weight, based on the final detergent.
Su~able anionic sutfaaartts are, fior example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are pr~sferably Cs.~$ alkyl benzenesutfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates, and tfie disuffonates obtained. for example, from C,a,a monootefins with an intema! or temrinal doubts bond by sulinnation with gaseous sulfur trioxide and subsequent alKaline or acidic hydrolysis of the sulfonation products. Other Suitable surfacxants of the suifortate type are the alkane sullonates obtained from C,~.~a alkanes, for example by sulfachiorination yr sulfaxidarion and subsequent h~rolysis or neutralization. The esters of a-su<fo~ty acids (ester sutfonates), for example the a suifonated methyl esters of hydrogenated coconut oil, palm Kernel oi! or tallow fatty acids, are also suitable.
Other suitable an~nic surfaaants are sutfonated fatty acid glycerol esters. Fatty sect glycerol esters irt the context of the present invention arr3 tits monoesters, diesters and triesters and mixtures ther~sof which are obtained where production is carried ad by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesten of tr'iglycerides with 0.3 to 2 moles of glycerol. Pn~ferred sulfonated fatty acid glycerol estere are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms. for example capro~ acid, caprytic acid, captic ackf, i myrtstic sad, lauric sect, palmitic acid, stearic acid or behenic gad.
Preferred alk(en~ sulfates are the alkali metal salts and, in particxilar. the sodium salts of the sulfuric aad semiesters of C,~.,e fatty aloohols, for example c;ocofariy alcohol, tallow fariy alcohol. lauryl, myrist)rt, catyl or stearyl alcohol, or C,~ oxoalcot>oIs and the corresponding semiesters of secondary aloohols with the same chin length. Other - preferred alk(enhrl sulfates are those with the chain length mentioned which contain a synthetic, linear alkyl chain based on a petrochemical and which are sin~lar in their degradation behavior to the corresponding compounds based on oleochemical raw materials. C».,s alkyl sulfates, '! O 0,2_15 alkyl sulfates and C".,s alkyl sulfates are preferred from the point of view of washing technology. Other suitable anionic surtactants are 2,3-alkyl sulfates which may be pnxiuc~d, for example, in accordance with US
3,234,258 or US S,O?5,041 and whicfi are commercially obtainable as products of the Shell Oil Company under the name of DAN~.
The sulfuric acid monoesters of linear or branched C~,~, alcohds ethoxylatsd with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cs." alcohols corr;aining on average 3.5 moles of ethylene oxide (!=O) or Cme fatty aloohols containing 7 to 4 EO, are also suitable. tn view of their high fioaming capacity, they are only used in relatively small quantities. for example in quantities of : to 5% by v~reight, in detergents.
Other suitable anionic surfactards are the salts of alkyl sulfosuccinic acid which are also known as sulfoeuccinates or as sulfosutxinic acid esters and which represent monoasters andlor diesters of sulfosuccinic acid wkh aicohols, preferably fatty alb and, more particularly, ethoxylaLed fatty aloohols. Psulfosuccit>ates contain C~,a fatty alcohol residues or rr~ctunes thereof. Particularly preferred sulfosuccinates contain a fatty alcohol moiety derived from ethoxylated fairy aicohols which, considered in isolation, nepresertt nonionic surtaclants (for a description, see below). Of these sulfosucxinates, those of which the fatty alcohol moieties are derived from narrow-range etfwxylated fatty alcohds are l ' particularly prefsmed. A!k(enhrl suc;cinic acid preferably containing 8 to carbon atoms in the a!k(enhrl chain or salts thereof may also be used.
Usher suitable anionic surfactants are, in particular, soaps. Suitable soaps are saturated fatty acid soaps. such as the salts of Iauric acid.
_ myristic aad, palmitic acid, stearic acid, hydragerucic acid and behenic acid. and soap mnctures derived in particular from natural fatty acids, for exan~le coconut oil, palm keme~ oil or taltasr fatty adds.
The anionic surfactants, including the soaps. may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts and. more preferably, in the form of their sodium salts.
Among the compounds yiekiin8 ~ in water which serve as bleaching agerns, sodium perborate tetrahydrate, sodium perborate monohydrate and sodarm petcarbonate are partic:ularty important. Other useful bl~ching agents are. for example, persulfates and mixed salts with persulfates, such as the salts commercially available as CAROAT~, peroxypyrophosphates, citrate perhydrates and HaOryielding peracidic salts or peracidS, such a8 pelbenzDateS, peroxophthalates, diperazelaic acid, phthaloiminoperaad or diperdodecane dioic acid. even where the bleaching agents are used, there is r~ need for surfactants andlor builders so that pure bleach tablets can be prnduc~d. If pure bleach tablets are to be used in the washing of laundry, a combination of sodium percarbonate and sodium sesquicart~onate is preferred irrespective of the other ingredients present in the tablets. If detergent or bleach tablets for dishvvasttirtg machines are being produced, bleaching agents from the l group of organic bmay also be used. Typical organic bleaching agents are diecyl peroxides, such as dibenzoyl peraxkfe for example.
Other typical organic bleaching agents are the pernxy acids, of which alkyl peroxy aads and aryl peroxy acids are particularly menttor~ed as examples.
Preferred representatives are (a) per,pxybenzoic aad and ring-SU
dernratives thereof, such as alkyl peroxybentoic aads, but also pay a-naphthoic aad and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxy adds, such as peroxylauric aad, peroxysteadc 5 acid, e-phthaticr>i<cioperoxycaproic aad (pMhaloiminoperoxyhaxanoic a~
(PAP)J. o-carboocybenzamid operoxycaproic acid, N-rronenylamidoperadipic aad and N-nonenylamidopersuccinates, and (c) aliphatic and araJiphatlc peroxydicarboxylic aads, such as 1.12-diperoxyccarboxylic aad, 1,9-diperoxyazelaic acid, dipenoxysebaac acrid, diperoxybrassylac acid, 10 diperoxyphthalic acids, 2-decylbipero~cybutane-1,4-dioic acid, N,N-terephthaloyl-di(B-aminopemaproic acid).
In order to obtain an improved bleaching effect where washing is carried out at temperatures of 60°C or lower, bleach activators may be incorporated in the detergent tablets. Suitable bleach activators atg compounds which form aliphatic peroxocarboxylic acids containing preferably 1 to 10 carbon atoms and more preferably 2 to a carbon atoms andlor optionally substituted perbenzoic acid under perhydrolysls conditions. Substances bearing O- andlor N-aryl gn~ups with the number of carbon atoms mentioned andlor optionally substituted ben~yl groups are suitab~. Prgfemed bleach activators arse polyaaylated alkyleno ' diamines, more part;cxrlariy tebaeeetyl ethylenediamine (TAEA). acylated triazine derivatives, more partlcularty 1,5-diacetyt-2.4.dioxohexahydro 1,5,5 triaxine (pApH~, acyla~ glyoolurils, more particularly 1,3,4,&
tetraacx:lyl glycduril (TAGU), N-~acylimides, more partkxrlatly N-nonanoyl succininude (NOSI), acylated phenol sulfonates, more partiarlarly n-nonanoyl or isononanoyloxyben~sutfonate (n- or iso-N4SS); acylated hydrxarboxylic ands. such as triethyl-O-acetyl cibate (TEOC). carboxylic anhydrides, more part«xrlerly phthalic anhydride, isatoic anhydride andlor succinic anhydride, carboxylic a~ ate, such as N-methyl diacetamide, glycaolide, acylat~d polyhydrie alcohols, more parti<cxrlarly triaeetin.
ethylene l glycol diacetate, 2,5-diacetwcy-2.5-dihydroiuran and the enol esters known from German patent appli~ns DE 196 16 893 and DE 196 16 767, acetylated sorbitol and mannitcl and she mixtures thereof (SORMAN) described in European patent application EP 0 525 239, asugar b derivatives, nacre pardutlariy pentaacetyl glucose (PAG), per>raacetyl fructose, teuaaoehll xylose and ocxaaoetyl lactose. and aoetylated, optionally N-alkylated gl~amine and gluconolactone, triazole or triazole derivatives andtor particulate caprotacxams andlor caprolactam derivatives, preferably N-acylated lactams, for example N-benzoyl caprolac~am and N-acetyl caprnlac~am~ which are known from lntemational patent applicat~ns WO,A-94127970, WO,Ar94128102, W0~14-94!28103, WO~A-9S/00626, WLl l A-95!14759 and WO-A~5117498. The substituted hydrophilic aryl acetals ' known from German patent appUcation DE~A-196 16 769 and the aryl lactams desk in German patent application DE~A-198 16 n0 and in International patent appli~on WO,A-9x114075 are also preferably used.
The combinations afi conventional bleach acavatons known from German patent application DE~11-44 43 177 may also be used. Nitrite aerivatrvas, such as cyanopyridines, nitrite gusts, for example N-alkyl ammonium acetonitriles, andla cyanamide derivatives may also be used. Preferred bleach activatam are sodium-4-(octartoyloxy~benzene sulfonate, n-nonanoyl or isononanoyloxybenzenesutfonate (n- or iso-NOBS), undecenoyloxybenzenesutfonate (IJpOBS), sodium c>Qdecanoyl-oxybenzenesssltonate (pOBS). decanoyloxybenzoic add (DOf3A, OSC 10) and~or dodecanoyloxybenzenesutEonate (OBS 12) and N-methyl morpholiium ac~onitrile (MMA). Bleach activators such as these are present in the usual quantities of 0.01 to 20% by weight, preferably in quantities of 0.1% by weight to 15% by weight and more preferably in quantities of 1 % by weight to 14% by weight, based on the composition as a whole.
In addition to or instead of the conventional bleach activators mentioned above, so-called bleadt catalysts may also be incorporated in the tablets. Bleach catalysts are bleach-boos~tir~ transition metal watts or transition metal complexes such as, for example, manganese-, iron-, cobalt . ruthenium- or mo~ybdene~m-eaten complexes or carbonyl complexes. Manganese. iron, cobah, nrthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt , iron-, copper and ruthenium-ammine complexes may also be used as bleach catalysts.
The content of ... in the detergents is from 1 to a0% by weight and preferably from 10 to 20% by we~ht, petborate monohydrate or percarbonate advar~eously being used.
The detergents acxording to the invention generaNy contain one or more builders, more pacdcularfy zeolites, silicates, carbonates, organic co-builders and - providing there are no ecological objections to their use - the phosphates. Phosphates are partiaulariy preferred builders for dishwasher tablets.
Suitable crystalAne layer-form sodium silicates correspond to the general formula NaMSi~~T,- y ~O, whero M is sodium or hydnagen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or ~. Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. Both Vii- and a-sodium disif~tes Na~Si~45~ y Hz0 are particularly preferred.
Other usetvl builders are amorphous sodium silicates with a modutus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1 ~ to 1:2.8 and more preferably 1:2 to i:2.6 which dissowe with delay and exhibit multiple wash cycle properties. The delay in dissolution in relation to conventional amorphous sodium silicates can have been obtained in various ways, for example by surface treatment, oon~wrnding, oorr~ading or by overdrying.
In the context of the invention, the term ~amorpltous" is also unde~d to l encompass ~X-ray amorphous'. tn other words, the ~licdo not produce any of the sharp X-ray reflexes typical of crystalline substances in X-ray diffr~ion experiments, but at best one or more maxima of the scattered X-radiation which have a width of several degrees of the diffraction angle. However, partiarlarly goad builder proper>xes may even -be achieved wherb the silicate particles produce crooked or even sharp diffraction maxima in elecaon diffraction experiments. This may be interpnted to mean that the products have microaystalline regions between 10 and a few hundred nm in size, values of up to at most 50 nm and. more part~arly, up to at most 20 nm being preferred. Compacted amorphous silicates, compounded amorphous siuand overdrred X-ray amorphous silicates are partladatly preferred.
T~ fi~Y dine, syr~theticc zeolite containing bound water used in acxordance with the invention is pn:ferably zed'~e A andlor zeoAfs P.
1S Zeoftte MA!'~ (Crlasfield) is a partiwlarly preferred P-type zeolite.
However, zeotite X and rnbduces of A, X andlot P are also suitable.
According to the invention, 'tt is also possible to use, for example. a commenciatly obtainable oo-aystallixate of zeolite X and zeolite A (ca. 80%
by weight zeolite X) which is marketed by CONDEA Augusta S.p.A. under 20 the name of VEGOSOND AX~ and which may be described by the following iomxrta:
nNaxO ~ ( 1-rl~O -AIzO3 ~ (2 - 2.5~S10Z ~ ( 3.5 - 5.5) HaO.
i 25 , Suitable zenlites have a mean particle sae of less than 90 ~m (volume dlatributton, as measured by the Coulter Courtier Method) and contain preferably 18 to 22% by weight and more preferably 20 to 2296 by weight of bound water.
Tire generaAy known ph~phates may of course also be used as 30 binders providMg their use should not be avo~ed on ecobgicsl grounds.
1~
Among the large number of commeraauyr available phosphates. alk~i l metal phosphates have the grea;est importance in the detergent industry, pentasodium triphosphate and p~tapotassium triphosphate (sodium and potassium tripolyphosphate) teeing particularly pr~efen~d.
Alkali metal phosphates' is the aolle~va terra for the alkali metal - (more particularly sodium and potassium) salts of the various phosphoric acids, inducting metaphosphoric ands (HPO~~, and orthophosphoric sect (H3PQ4) and representatives of higher molecular weight. The phosphates combine several advantages: they acx as alKalinity sources, prevent lime deposits on machine parts and lime incnrstations in fabrics and, in ad4ition, contribute towards the leaning effect.
Sodium dihydrogen phosphate (NaH2P4,,) exists as the dehydrate (density 1.91 gcrrr°, matting point 60°) ark as the monohydrate (density 2.04 gcrrr°). Both salts acs white readily water soluble powders which, on heating, lose the water of crystallization and, at 200". are converted into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na~lizP~) and, at higher temperatures, into sodium trirr>etaphosphate (Na'P30a) and Maddrolt's salt (see bebw). NaHzPO~, shows an acidic reaction. It is formed by actjustina phosphoric acid with sodium hydroxide to a pH value of 4.5 and spraying the resulting "mash". Potassium dihydrogen phosphate (Primary or monobasic potassium phosphate, potassium biphosphgte, KDP), KfizP04, is a white salt with a density of 2.33 gcrn~'. has a melting point of 253" [decomposition wish fom>ation of potassium polyphosphate (KPO~~] and is ready soluble in water Disodium hydrogen phosphate (secondary sodium pt~sphatte), Na,2HP0,. is a ca~orless, readilyy water-soluble crystalline salt. It exists in water-free form and with 2 moles (density 2.066 gcrrr', water loss at 85°), 7 moles (densit)r 1.68 gcm~. rneltirtg point 48° with toss of 5 Hue) and moles of water (c~nslty 1.52 gct~", metiing point 35" with loss of 5 H24), ~4 becomes water-free at 100° and, on fairly intensive heating, is converted into the diphosphate Na4P~r. ~isOdium hydrogen phosphate is prepara<t by neutralization of phosphoric act with soda solution using phend phthalein as indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate). K~zHPO,~, is an amorphous white salt which 5 is readily soluble in water.
- Ttisodium phosphate, tertiary sodium phosphate, Na3P04, consists of colorless aystals which have a density of 1.62 gcm~ and a matting point of T3-76° (deoomposr<iort) as the dod~ahydrate, a matting point of 100° as the decahydrate~ (c~r~esp~ding to 19-20% P2Os) and a density of 2.536 10 gcm~' in water free form (cornesir~ to 390!% PzOs). Trisadium phosphate is readily soluble in water through an alkaline r~eactinn and is prepared by concentrating a solution of exactly 7 mole of disodium phosphate and 1 mole of NaOH by evaporation. Tripotassurm phosphate (tertiary or tribasic potassium phosphate), K~P04, is a white deliquescent 15 granular powder with a density of 2.5fi gcm °, has a rnehing of 1340° and is readily soluble in water through an alkaline reacxion. It is form~d, for exempla, when Thomas slag is heated with coal and potassium sulfate.
pespite their higher price, the more readily soluble and therefore highly effective potassium phosphates are often preferred to corresponding sodium compounds in the detergent industry.
TetrBSOdium diphosphate (sodium pyrophosphate), Na~P~, exists in water free form (dens'tty 2.534 gcrr~, mehing point 988°, a figure of 880°
has also been n~ntiortod) and as the decahydrate (density 1.815 - 1.838 gcrrr°, mehing point 94° with loss of water). Both substances are colorless crystals which dissohre in water through an alkaline reaction. NasPZOr is formed when disodium phosphate is heated to >200° or by reacting phosphoric acid with soda in a stoichiometric ratio and spray-drying the solution. The decahydrate complexes heavy metal salts and hardness salts and, hence, reduces the ha~lness of water. Potassium diphosphate (potassium pyrophosphate), tG,P2O~, exists in the form of the t<ihydcate and l is a colorless hygrosoopic powder with a density of 2.33 gcrtr~ which is soluble in water, the pH value of a 1 % solution at 25° being 10.4.
Relatively high molecular weight sodium and potassium phosphates are formed by condensation of NaHzP04 or KHZPO~. They may be divided into cyclic types, namely the sodium and potasaium metaphosphates, and chain types. the sodium and potassium polyphosphates. The chain types in particular are known by various differ~ant names: fused or calcin~l phosphates, Graham's salt, Kumo1's salt and Maddrelf's salt. AU higher s~ium and potassium phosphates are known collectively as condensed phosphates.
The industrially important pentasodium triphosphate, NasPsO,o (sodium tripolyphosphate), is a nor-hygroscopic white water soluble salt which crystallizes without water or with 6 Hz0 and which has the general formula Na0-[P(OHONa)-O]~-Na where n = 3. Around 17 g of the salt frea from water of crystallization dissdve in 100 g of water at room temperature, around 20 g at fi0° and around 32 g at 700°. After heating of the solution for 2 hours to 100°, anxrnd 8% orthophosphate and 15% diphosphate are fiormed by hydrolysis. !n the prepar~n of pentasodium triphasphata, phosphoric aad is r~ea~d wigs soda solution or sodium hydroxide in a stoichiomstric ratio and the solution is spray-dried. Similarly to Kiraham's sah and sodium diphosphate. pentasodium triphosphate dissolves many insoluble metal compounds (indudir>g lime soaps, etc.). Pentapotassium triphosphate, KsPsO,o (potassium tripolyphosphate), is marketed for example in the form of a 50% by weight solution (~ 23% Pz05, 2596 K2O).
26 The potassium polyphosph~ are widely used in the detergent indusby.
Sodium potassium tripolypt~sphat8s, which may also be used in accordance with the invention. also exist. They are formed far example l when sodium trimetaphosph~tte is hydrolyzed with KOH:
(N8P03~ + 2 KOH -~ Na3iC2PsO~o + HZO
Acoordirs~ to the invention, they rnay be used in sxacHy the same way as sodium tripotyphosphate, potassium tripolyphosphate or mixtures thereof. Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripotyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripoiyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate may also be used in accordance with the irnention.
Organic cobuilders suitable for use in the detergent tablets according to the invention are, in particular, polYcarboxYlateslpolycarboxytic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuild~s (see below) a~ phosphonates. These classes of substances are described in the following.
useful organic builders are, for example, the pdycarboxylic acids usable in the form of their sodium sans, polycarboxylic acids in this context being understand to be carboxylic aads which bear more than one acid funcxion. Examples of such carboxylic acids ate citric acid, adipic acid, suocinic acid, glutaric aad, malic acid, tartaric aad, malefic acid, fumaric acid. sugar acids, aminocarbcxylic acids. nitrilotriacetic acid (NTA), ' 24 proving its use is not ecaologically unsafe, and mixtures thereof.
Preferred ' salts are the salts of the p~ycarboxylic aads. such as citric acid, adipic acid. succinic add, glutaric acid, tartaric aad. sugar acids and mixtures The sails per se may also be used. Besides their bu~dsr effect, the adds a~so typically have the property of an aadifying component arxi, hence, also serve to establish a relatively low and mild phi value in dete~ertts. Citric aad, suocinic aad, glutaric acid, adipic acid, gluconic acid and rr~ctures thereof are particularly mer>tioned in this regard.
Other suitable builders are polymeric polyrcarboxylates such as, for example, the alKali metal salts of polyacrylic or polymethacxylic aad, for l ~a example these with a relatwe molecular weight of 5~ to 70,000 glmole.
The mofecxrlar weights mentioned in this specfication for polyrrreric polycarbo~cylates are weight-average molecular weights Mr, of the partrcxular acid form which, dasica4y, were determined by gel permeation chromatography (GP'C) using a UV deter. The measurement was carried out against an extemat polyacxylic acrd standard which provides realistic molecular weight values by virtue of its structural similarity to the polymers investigated. These values differ distinctly from the rrblearlar weights measun~f against ~lystyrer~e sulfonic cads as standard. The rnvlecular we~hts measured against polystyrene sulfonic acids are generally hi8her than the molecular weights mentioned in this spe~tion.
Particularly suitable pohmuss are polyacrylates which preferably hare a molecular weight of 2.000 to 20,000 glmole. 8y virtue of their superux solubility, preferred represer>tatives of this group are the short '! 5 chain polyacrylates which have mdecular weights of 2,(100 to 10,000 glmole and, more particularly, 3,000 to 5,000 glmole.
Also suitable ane copolyrrreric polycarboxylates. particularly those of a<xylic acid with methacrylic aad and those of aaylic aad or msthacry<ic add with malefic aad. Acrylic addlmaleic acid copolymers dining 50 to 90% by weight of acrylic at~d and 50 to 10% by weight of maleiC acid have proved tn be pattiarlarly suitable. Their relative moleaalar weights, based on the free acids, are generally in the range from 2.000 to 70,000 glmole, preferably in the range from 20,000 to 50,000 gJmole and more preferably in the range from 30.000 to X0,000 glmde.
The (co)polymeric polycarboxylates may be used either in powder fomn or in the form of an aqueous solution. The oor~tent of (co)potyrneric polycarboxyiates in the detergent is preferably from 0.5 to 20% by weight ' and more prsfer~tdty from 3 to 1D% by weight.
In order to improrre solubility in wator, the polymers may also contain allyl sutfonic acids, such as ally~xybsnxene sulfonic acid and methatlyl sulfonic acid, as monomer.
Other particularly preferred polymers are biodegradable polymers of more than two different monomt3r units, for example those which contain salts of acrylic aad and malefic acid and vinyl alcohol or viny) alcohol ~ derivatives as monomers or those which contain sails of acrylic acid and 2~
.
alkylallyl sulfonic acid and sugar derivatives as morxamers.
Other preferred copolymers are those which preferably contain acxolein and acryl~ aadiacrytic acid salts or acrolein and vinyl acetate as monomers.
Other preferred builders are poly<rtetic arrdnod-K:arbaorylic acids. salas or pn3arrsors thereof. Polyaspartic acids or salts and derivatives thereof islare pa>t~rlaAy prefen~ed.
Other suitable builders are ~lyacetals which may be obtained by reaction of dialdehydes with poiyal carboxylic aads containing 5 to 7 carbon atoms and at least three hydroxyl groups. Preferred polyacetals are obtained from diaidehydes, such as glyoxai, glutaraldehyde, terrephthal akiehyde and mixtures thereof and from polyol carboxylic acids, such as t gfuconic aad andlor giuooheptortic acid.
' Othsr suitable organic binders are dexains, fior example ol'rs or polyrr>ers of carboh~ra~a which may be obtained by partial hydrolysis of stances. The hydrolysis may be carried out by standard methods, for example acid- or enzyme-cataly~d methods. The end pnxiurxs are preferably hydrolysis products with average mole~lar weights of 400 to 500,000 glmole. A polysaccharide with a dextrose equivaisrrt (DE) of 0.5 m 40 and, more particularly, 2 to 30 is preferred, the DE being an accepted messur~e of the reducing effect of a polysaccharide by comparison with dextrose whic~r has a pE of 100. Both mahodextrins with a DE of 3 to 20 and dry glucose sirups with a DE of 20 to 37 and also so-called yellow dextrins arid white dextrins with relattve~r high molecular weights of 2,000 to 30,000 glrnole may be used.
t The oxidized derivatives of such dextrins are their reaction products with oxidizing which are capat>!e of oxidizing at least one alcohol function of the saarharide ring to the carboxylic acid fun~n. An oxidized oiigosac~aride, such as a pn~du~ oxidized at C6 of the saccharide ring. is 5 also suitable.
- Other suitable co-builders are oxydisu~tate$ and other derivatives of dis~ra~nates, preferably ethytenediamine disuocinate. Ethyteneaiamine~
N.N'~iisuacinate (EDDS) is preferably used in the form of its sodium or magnesium saics. Glycerol disucar>ates and glycerol trisucxinates era also prefemsd irt this corn. The quantities used in zeolke-containing andlor silicate-ootttaining formulations are from 3 to 15% by weight.
Other useful organic oo-builders aria, for example, acetylated hYd~xYl~ acids and salts which may optionally be present in lactose form and which contain at feast 4 carton atoms. at teast one 15 hydroxy grcx~P and ai most two acid groups.
Anothsr class of substances with oo-bu~der properties are the Phosphonates, more particularly hydroxyalkane and aminoalkane phos-phonates. Amrong the hydroxyalkane phosphonates, ~-hyrdroxyethane,~,1-diphosphonate (HEDP) is particularly important as a co-buildder. It is 20 prefen~bly used in the form of the sodium salt, the disodium salt showing a neutral reacxion and the tstrasodium salt an alkaline reaction (pH 9).
Preferred amirwalkane phosphonates ane ethylenediamine tetramethylene phosphonate (EDTMP), diethylenefiri~ruae pentamethylenephosphortate (DTPMP) and higher homol~s . They are preferably used in the i forim of the r~utraNy roa~g sodium, salts, for example as the heacasodium salt of EDTMP or as the hepta- and octasodium salts of DTPMP. Of the phosphOnates, HEDP is preferably used as a builder. In addition, the aminoalkane phosphonates here a pronounced heavy metal binding capacity. Accordingly. it can be of advantage, particularly where the deterper~ts also contain bleach. to use anunoalkane phosphonates, moro particularly DTPMP, or mixtures of the phosphonates mentioned.
In addition, any compounds capable of forming complexes with alkaline earth metal ions may be used as oo-builders.
In one preferred embodiment, the detergents according to the invention are liquids or gels.
Solvents which may de used in the liquid or gel-form compositions belong, for example, to the group of monohydric or polyhydric atcohols, alkanolamines and glycol ethers providing they are miscible with water in the concentration range indicated. The adove-mentioned organic solvents used for the production of the enzyme preparation may also pe used. The solvents are preferably seJeded from ethanol, n- ar i-propanol, butanols, ethylene glycd methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether. ethylene glycol mono-n-butyl ether. diethylene glycol methyl ether. diethylene glycol ethyl ether. propylene glyrcol methyl, ethyl or propyl 1 S ether, dipropylene glycol monomethyl or monoethyl ether. diisopropylene ' glycol monomethyl or monoethyl ether, methoxy, ettroxy or butoxy triglycol, 1-butoxyethoxy-2-propanol. 3-rnethyl-3-methoxybutanol. propylene glycol-t butyl ether and mixtures of these soiverns. Solvents may be used in the liquid or gel form detergents according to ttte invent~n in quantities of 0.1 to 20% by weight, preferably below 15% by weight and more preferably below 10% by weight.
One or more thickeners or tti~ckening systems may be added to the composition detergent according to the invention to adjust its viscostty.
The viscosity of the composites according to the invention can be measurod by standard methods for example Brookfleki RVD-VII
v~cosirrreter at 20 r.p.m. and 20~C, spindle 3) and is preferably in the range from 100 to 5,000 mPas. Prefeme<i compositions have viscosities of 200 to 4.000 mPas, vescosides in the range from 400 to 2,000 mPas being l particularly preferred.
Suitable thickeners arse inorganic or polymeric organic compounds.
These generaNy cuganic, high mdeaular wr3ight aorr>pounds, which are also known as swelling agents, generally take up the Iiquids and awed in the process and. finally. atar>ge into viscous true or c~ilo~ia! solutions.
The inorganic thickeners indude, for exempla, polysiliac acids, day minerals, such as montmor~Onites. zeofites. s~ic:as and ber~nites.
The organic thickeners belong W the groups of nat<ual polymers.
modified natural polymers and fully synth~ic polymers.
Nawrally occurring polymers uses as thickeners aro, lfor example, agar agar. carrageen, tragacar>:h. gum arati;c, alginates, p~na, polyose~, guar gum, kx:ust bean gum, starch. de~arins. gelatin and casein.
Modified natural materials belong above all bo the group of modified starches and celluloses, of which carboxyrnetttyl t~lluiose and other cellulose etrlors, hydroxyethyi cellulose and hydroxypropyl cellulose and also gum ethers are mentioned as examples.
A large group of thickeners which are widely used in various fields of applicat'ron are the fully synthetic polymers. such as polyacrylic and polY-methacxyuc compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyankdes and pdyurethanes.
Ths thickeners may be present in a quantity of up to 5% by wesght, proferably in a quantity of 0.05 to 2% by weight and more preferably in a quantity of 0.1 to ~ .5% by weight, based on the final ition.
The detergent aconrding to the invention may contain in partkxrlar sequestering ants, eledxolytes, pli regulators and other auxiliaries, such as optical brighteners, redeposintlon inhib<tors, dye transfer inhibitors, foam regulators, additional bleach activators, dyes and perfumes, as further _ typicsl auxiliaries.
Besides the surfadartts, bhaching agents ark builders, a number of compounds - for example foam inhibitors, phosphorrates, enzymes aril optics! brighteners - may be present in laundry detergents.
Where the detergents are used in washing machines, it can be of advantage to 8dd typical foam inh~itors to them. Suitable foam inhibiteors see. for exampl~, soaps of natural or synthetic origin which have a high percentage aontant of C,a~, fatty acids. Suitable non-surtaae~-at~ive foam inhibitors .are, for example, organopoiys~oxanes and mixtures ttteceof with miaofine, optionally silsanized, silica and also paraffins, waxes, microcrystaliine waxes and mixtures thereof with silanized silica or bis-stearyl ethylenediamide. Mixtures of different foam inhibitors, for example mixt<rres of silicones, paraiflns and wakes, may also be used with advantage. The foam inhibitors. more particularly silicone- andlor paraffin-containing foam inhibitors, are preferably faced to a granular water-Soluble or wateriiispersible support. Mbdur~ of parafi'tns and biaryl ethylenediamides are particularly pnefemed.
If the detergent ac~orading to the invention is used as a so-called liquid or gel-form perboratc-containing dete~ent, it preferably contains 0 to 7 5 20% by weight of surfactants. ~0 to 80% by weight of nonionic surfactants, 2 to 25% by weight of bu~dert, 0 to 20% by weight of bleaching agents, 0 to 20% by weight of bleach activators, 0 to 5% by weight of enzymes, perfumes and other ingredients.
After removal of the fermentation residues, a harvest $luny obtained after fermentation (cf. International patent application WO 91l2T9Z) vontaining 75,00 protease units per g (PUIg) was concentrated by decantation and microfiltration in an utttaflltration module. After further oonceby evaporation in vaaro, the aqueous enzyme suspension contained 700,000 PUlg for a water content of about 70%. The con-centrate thus obtained was mbced with 1.2-propylene 9lycot (~~Cam~ ~ ) and with glycerol (Ex~l~) in such a quantity that the mixture obtained contained 40% by weight ~Ivent and ~0% by weight water.
The mixt<rre was distilled in a water jet vawum at n~rtt temperature in a rotary evaporator uM7 It had the neauirsd water content.
The fortnutation oin ~gg~;l~a 1 ootrtained 6696 of 1.2 propylene gtyool and 9.5% of water (as determined by the Karl Fischer method) and had 1n ec~rtt)r of bout 7t70,00Q WPUIg.
The preparation obtained in ~pcontained 68% of glycerol and 6.496 of water (as determined dy the Ka~i Fisc~er method) and had the same acxivity as the preparation of Exempts 1.
3,234,258 or US S,O?5,041 and whicfi are commercially obtainable as products of the Shell Oil Company under the name of DAN~.
The sulfuric acid monoesters of linear or branched C~,~, alcohds ethoxylatsd with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cs." alcohols corr;aining on average 3.5 moles of ethylene oxide (!=O) or Cme fatty aloohols containing 7 to 4 EO, are also suitable. tn view of their high fioaming capacity, they are only used in relatively small quantities. for example in quantities of : to 5% by v~reight, in detergents.
Other suitable anionic surfactards are the salts of alkyl sulfosuccinic acid which are also known as sulfoeuccinates or as sulfosutxinic acid esters and which represent monoasters andlor diesters of sulfosuccinic acid wkh aicohols, preferably fatty alb and, more particularly, ethoxylaLed fatty aloohols. Psulfosuccit>ates contain C~,a fatty alcohol residues or rr~ctunes thereof. Particularly preferred sulfosuccinates contain a fatty alcohol moiety derived from ethoxylated fairy aicohols which, considered in isolation, nepresertt nonionic surtaclants (for a description, see below). Of these sulfosucxinates, those of which the fatty alcohol moieties are derived from narrow-range etfwxylated fatty alcohds are l ' particularly prefsmed. A!k(enhrl suc;cinic acid preferably containing 8 to carbon atoms in the a!k(enhrl chain or salts thereof may also be used.
Usher suitable anionic surfactants are, in particular, soaps. Suitable soaps are saturated fatty acid soaps. such as the salts of Iauric acid.
_ myristic aad, palmitic acid, stearic acid, hydragerucic acid and behenic acid. and soap mnctures derived in particular from natural fatty acids, for exan~le coconut oil, palm keme~ oil or taltasr fatty adds.
The anionic surfactants, including the soaps. may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts and. more preferably, in the form of their sodium salts.
Among the compounds yiekiin8 ~ in water which serve as bleaching agerns, sodium perborate tetrahydrate, sodium perborate monohydrate and sodarm petcarbonate are partic:ularty important. Other useful bl~ching agents are. for example, persulfates and mixed salts with persulfates, such as the salts commercially available as CAROAT~, peroxypyrophosphates, citrate perhydrates and HaOryielding peracidic salts or peracidS, such a8 pelbenzDateS, peroxophthalates, diperazelaic acid, phthaloiminoperaad or diperdodecane dioic acid. even where the bleaching agents are used, there is r~ need for surfactants andlor builders so that pure bleach tablets can be prnduc~d. If pure bleach tablets are to be used in the washing of laundry, a combination of sodium percarbonate and sodium sesquicart~onate is preferred irrespective of the other ingredients present in the tablets. If detergent or bleach tablets for dishvvasttirtg machines are being produced, bleaching agents from the l group of organic bmay also be used. Typical organic bleaching agents are diecyl peroxides, such as dibenzoyl peraxkfe for example.
Other typical organic bleaching agents are the pernxy acids, of which alkyl peroxy aads and aryl peroxy acids are particularly menttor~ed as examples.
Preferred representatives are (a) per,pxybenzoic aad and ring-SU
dernratives thereof, such as alkyl peroxybentoic aads, but also pay a-naphthoic aad and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxy adds, such as peroxylauric aad, peroxysteadc 5 acid, e-phthaticr>i<cioperoxycaproic aad (pMhaloiminoperoxyhaxanoic a~
(PAP)J. o-carboocybenzamid operoxycaproic acid, N-rronenylamidoperadipic aad and N-nonenylamidopersuccinates, and (c) aliphatic and araJiphatlc peroxydicarboxylic aads, such as 1.12-diperoxyccarboxylic aad, 1,9-diperoxyazelaic acid, dipenoxysebaac acrid, diperoxybrassylac acid, 10 diperoxyphthalic acids, 2-decylbipero~cybutane-1,4-dioic acid, N,N-terephthaloyl-di(B-aminopemaproic acid).
In order to obtain an improved bleaching effect where washing is carried out at temperatures of 60°C or lower, bleach activators may be incorporated in the detergent tablets. Suitable bleach activators atg compounds which form aliphatic peroxocarboxylic acids containing preferably 1 to 10 carbon atoms and more preferably 2 to a carbon atoms andlor optionally substituted perbenzoic acid under perhydrolysls conditions. Substances bearing O- andlor N-aryl gn~ups with the number of carbon atoms mentioned andlor optionally substituted ben~yl groups are suitab~. Prgfemed bleach activators arse polyaaylated alkyleno ' diamines, more part;cxrlariy tebaeeetyl ethylenediamine (TAEA). acylated triazine derivatives, more partlcularty 1,5-diacetyt-2.4.dioxohexahydro 1,5,5 triaxine (pApH~, acyla~ glyoolurils, more particularly 1,3,4,&
tetraacx:lyl glycduril (TAGU), N-~acylimides, more partkxrlatly N-nonanoyl succininude (NOSI), acylated phenol sulfonates, more partiarlarly n-nonanoyl or isononanoyloxyben~sutfonate (n- or iso-N4SS); acylated hydrxarboxylic ands. such as triethyl-O-acetyl cibate (TEOC). carboxylic anhydrides, more part«xrlerly phthalic anhydride, isatoic anhydride andlor succinic anhydride, carboxylic a~ ate, such as N-methyl diacetamide, glycaolide, acylat~d polyhydrie alcohols, more parti<cxrlarly triaeetin.
ethylene l glycol diacetate, 2,5-diacetwcy-2.5-dihydroiuran and the enol esters known from German patent appli~ns DE 196 16 893 and DE 196 16 767, acetylated sorbitol and mannitcl and she mixtures thereof (SORMAN) described in European patent application EP 0 525 239, asugar b derivatives, nacre pardutlariy pentaacetyl glucose (PAG), per>raacetyl fructose, teuaaoehll xylose and ocxaaoetyl lactose. and aoetylated, optionally N-alkylated gl~amine and gluconolactone, triazole or triazole derivatives andtor particulate caprotacxams andlor caprolactam derivatives, preferably N-acylated lactams, for example N-benzoyl caprolac~am and N-acetyl caprnlac~am~ which are known from lntemational patent applicat~ns WO,A-94127970, WO,Ar94128102, W0~14-94!28103, WO~A-9S/00626, WLl l A-95!14759 and WO-A~5117498. The substituted hydrophilic aryl acetals ' known from German patent appUcation DE~A-196 16 769 and the aryl lactams desk in German patent application DE~A-198 16 n0 and in International patent appli~on WO,A-9x114075 are also preferably used.
The combinations afi conventional bleach acavatons known from German patent application DE~11-44 43 177 may also be used. Nitrite aerivatrvas, such as cyanopyridines, nitrite gusts, for example N-alkyl ammonium acetonitriles, andla cyanamide derivatives may also be used. Preferred bleach activatam are sodium-4-(octartoyloxy~benzene sulfonate, n-nonanoyl or isononanoyloxybenzenesutfonate (n- or iso-NOBS), undecenoyloxybenzenesutfonate (IJpOBS), sodium c>Qdecanoyl-oxybenzenesssltonate (pOBS). decanoyloxybenzoic add (DOf3A, OSC 10) and~or dodecanoyloxybenzenesutEonate (OBS 12) and N-methyl morpholiium ac~onitrile (MMA). Bleach activators such as these are present in the usual quantities of 0.01 to 20% by weight, preferably in quantities of 0.1% by weight to 15% by weight and more preferably in quantities of 1 % by weight to 14% by weight, based on the composition as a whole.
In addition to or instead of the conventional bleach activators mentioned above, so-called bleadt catalysts may also be incorporated in the tablets. Bleach catalysts are bleach-boos~tir~ transition metal watts or transition metal complexes such as, for example, manganese-, iron-, cobalt . ruthenium- or mo~ybdene~m-eaten complexes or carbonyl complexes. Manganese. iron, cobah, nrthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt , iron-, copper and ruthenium-ammine complexes may also be used as bleach catalysts.
The content of ... in the detergents is from 1 to a0% by weight and preferably from 10 to 20% by we~ht, petborate monohydrate or percarbonate advar~eously being used.
The detergents acxording to the invention generaNy contain one or more builders, more pacdcularfy zeolites, silicates, carbonates, organic co-builders and - providing there are no ecological objections to their use - the phosphates. Phosphates are partiaulariy preferred builders for dishwasher tablets.
Suitable crystalAne layer-form sodium silicates correspond to the general formula NaMSi~~T,- y ~O, whero M is sodium or hydnagen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or ~. Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. Both Vii- and a-sodium disif~tes Na~Si~45~ y Hz0 are particularly preferred.
Other usetvl builders are amorphous sodium silicates with a modutus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1 ~ to 1:2.8 and more preferably 1:2 to i:2.6 which dissowe with delay and exhibit multiple wash cycle properties. The delay in dissolution in relation to conventional amorphous sodium silicates can have been obtained in various ways, for example by surface treatment, oon~wrnding, oorr~ading or by overdrying.
In the context of the invention, the term ~amorpltous" is also unde~d to l encompass ~X-ray amorphous'. tn other words, the ~licdo not produce any of the sharp X-ray reflexes typical of crystalline substances in X-ray diffr~ion experiments, but at best one or more maxima of the scattered X-radiation which have a width of several degrees of the diffraction angle. However, partiarlarly goad builder proper>xes may even -be achieved wherb the silicate particles produce crooked or even sharp diffraction maxima in elecaon diffraction experiments. This may be interpnted to mean that the products have microaystalline regions between 10 and a few hundred nm in size, values of up to at most 50 nm and. more part~arly, up to at most 20 nm being preferred. Compacted amorphous silicates, compounded amorphous siuand overdrred X-ray amorphous silicates are partladatly preferred.
T~ fi~Y dine, syr~theticc zeolite containing bound water used in acxordance with the invention is pn:ferably zed'~e A andlor zeoAfs P.
1S Zeoftte MA!'~ (Crlasfield) is a partiwlarly preferred P-type zeolite.
However, zeotite X and rnbduces of A, X andlot P are also suitable.
According to the invention, 'tt is also possible to use, for example. a commenciatly obtainable oo-aystallixate of zeolite X and zeolite A (ca. 80%
by weight zeolite X) which is marketed by CONDEA Augusta S.p.A. under 20 the name of VEGOSOND AX~ and which may be described by the following iomxrta:
nNaxO ~ ( 1-rl~O -AIzO3 ~ (2 - 2.5~S10Z ~ ( 3.5 - 5.5) HaO.
i 25 , Suitable zenlites have a mean particle sae of less than 90 ~m (volume dlatributton, as measured by the Coulter Courtier Method) and contain preferably 18 to 22% by weight and more preferably 20 to 2296 by weight of bound water.
Tire generaAy known ph~phates may of course also be used as 30 binders providMg their use should not be avo~ed on ecobgicsl grounds.
1~
Among the large number of commeraauyr available phosphates. alk~i l metal phosphates have the grea;est importance in the detergent industry, pentasodium triphosphate and p~tapotassium triphosphate (sodium and potassium tripolyphosphate) teeing particularly pr~efen~d.
Alkali metal phosphates' is the aolle~va terra for the alkali metal - (more particularly sodium and potassium) salts of the various phosphoric acids, inducting metaphosphoric ands (HPO~~, and orthophosphoric sect (H3PQ4) and representatives of higher molecular weight. The phosphates combine several advantages: they acx as alKalinity sources, prevent lime deposits on machine parts and lime incnrstations in fabrics and, in ad4ition, contribute towards the leaning effect.
Sodium dihydrogen phosphate (NaH2P4,,) exists as the dehydrate (density 1.91 gcrrr°, matting point 60°) ark as the monohydrate (density 2.04 gcrrr°). Both salts acs white readily water soluble powders which, on heating, lose the water of crystallization and, at 200". are converted into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na~lizP~) and, at higher temperatures, into sodium trirr>etaphosphate (Na'P30a) and Maddrolt's salt (see bebw). NaHzPO~, shows an acidic reaction. It is formed by actjustina phosphoric acid with sodium hydroxide to a pH value of 4.5 and spraying the resulting "mash". Potassium dihydrogen phosphate (Primary or monobasic potassium phosphate, potassium biphosphgte, KDP), KfizP04, is a white salt with a density of 2.33 gcrn~'. has a melting point of 253" [decomposition wish fom>ation of potassium polyphosphate (KPO~~] and is ready soluble in water Disodium hydrogen phosphate (secondary sodium pt~sphatte), Na,2HP0,. is a ca~orless, readilyy water-soluble crystalline salt. It exists in water-free form and with 2 moles (density 2.066 gcrrr', water loss at 85°), 7 moles (densit)r 1.68 gcm~. rneltirtg point 48° with toss of 5 Hue) and moles of water (c~nslty 1.52 gct~", metiing point 35" with loss of 5 H24), ~4 becomes water-free at 100° and, on fairly intensive heating, is converted into the diphosphate Na4P~r. ~isOdium hydrogen phosphate is prepara<t by neutralization of phosphoric act with soda solution using phend phthalein as indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate). K~zHPO,~, is an amorphous white salt which 5 is readily soluble in water.
- Ttisodium phosphate, tertiary sodium phosphate, Na3P04, consists of colorless aystals which have a density of 1.62 gcm~ and a matting point of T3-76° (deoomposr<iort) as the dod~ahydrate, a matting point of 100° as the decahydrate~ (c~r~esp~ding to 19-20% P2Os) and a density of 2.536 10 gcm~' in water free form (cornesir~ to 390!% PzOs). Trisadium phosphate is readily soluble in water through an alkaline r~eactinn and is prepared by concentrating a solution of exactly 7 mole of disodium phosphate and 1 mole of NaOH by evaporation. Tripotassurm phosphate (tertiary or tribasic potassium phosphate), K~P04, is a white deliquescent 15 granular powder with a density of 2.5fi gcm °, has a rnehing of 1340° and is readily soluble in water through an alkaline reacxion. It is form~d, for exempla, when Thomas slag is heated with coal and potassium sulfate.
pespite their higher price, the more readily soluble and therefore highly effective potassium phosphates are often preferred to corresponding sodium compounds in the detergent industry.
TetrBSOdium diphosphate (sodium pyrophosphate), Na~P~, exists in water free form (dens'tty 2.534 gcrr~, mehing point 988°, a figure of 880°
has also been n~ntiortod) and as the decahydrate (density 1.815 - 1.838 gcrrr°, mehing point 94° with loss of water). Both substances are colorless crystals which dissohre in water through an alkaline reaction. NasPZOr is formed when disodium phosphate is heated to >200° or by reacting phosphoric acid with soda in a stoichiometric ratio and spray-drying the solution. The decahydrate complexes heavy metal salts and hardness salts and, hence, reduces the ha~lness of water. Potassium diphosphate (potassium pyrophosphate), tG,P2O~, exists in the form of the t<ihydcate and l is a colorless hygrosoopic powder with a density of 2.33 gcrtr~ which is soluble in water, the pH value of a 1 % solution at 25° being 10.4.
Relatively high molecular weight sodium and potassium phosphates are formed by condensation of NaHzP04 or KHZPO~. They may be divided into cyclic types, namely the sodium and potasaium metaphosphates, and chain types. the sodium and potassium polyphosphates. The chain types in particular are known by various differ~ant names: fused or calcin~l phosphates, Graham's salt, Kumo1's salt and Maddrelf's salt. AU higher s~ium and potassium phosphates are known collectively as condensed phosphates.
The industrially important pentasodium triphosphate, NasPsO,o (sodium tripolyphosphate), is a nor-hygroscopic white water soluble salt which crystallizes without water or with 6 Hz0 and which has the general formula Na0-[P(OHONa)-O]~-Na where n = 3. Around 17 g of the salt frea from water of crystallization dissdve in 100 g of water at room temperature, around 20 g at fi0° and around 32 g at 700°. After heating of the solution for 2 hours to 100°, anxrnd 8% orthophosphate and 15% diphosphate are fiormed by hydrolysis. !n the prepar~n of pentasodium triphasphata, phosphoric aad is r~ea~d wigs soda solution or sodium hydroxide in a stoichiomstric ratio and the solution is spray-dried. Similarly to Kiraham's sah and sodium diphosphate. pentasodium triphosphate dissolves many insoluble metal compounds (indudir>g lime soaps, etc.). Pentapotassium triphosphate, KsPsO,o (potassium tripolyphosphate), is marketed for example in the form of a 50% by weight solution (~ 23% Pz05, 2596 K2O).
26 The potassium polyphosph~ are widely used in the detergent indusby.
Sodium potassium tripolypt~sphat8s, which may also be used in accordance with the invention. also exist. They are formed far example l when sodium trimetaphosph~tte is hydrolyzed with KOH:
(N8P03~ + 2 KOH -~ Na3iC2PsO~o + HZO
Acoordirs~ to the invention, they rnay be used in sxacHy the same way as sodium tripotyphosphate, potassium tripolyphosphate or mixtures thereof. Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripotyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripoiyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate may also be used in accordance with the irnention.
Organic cobuilders suitable for use in the detergent tablets according to the invention are, in particular, polYcarboxYlateslpolycarboxytic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuild~s (see below) a~ phosphonates. These classes of substances are described in the following.
useful organic builders are, for example, the pdycarboxylic acids usable in the form of their sodium sans, polycarboxylic acids in this context being understand to be carboxylic aads which bear more than one acid funcxion. Examples of such carboxylic acids ate citric acid, adipic acid, suocinic acid, glutaric aad, malic acid, tartaric aad, malefic acid, fumaric acid. sugar acids, aminocarbcxylic acids. nitrilotriacetic acid (NTA), ' 24 proving its use is not ecaologically unsafe, and mixtures thereof.
Preferred ' salts are the salts of the p~ycarboxylic aads. such as citric acid, adipic acid. succinic add, glutaric acid, tartaric aad. sugar acids and mixtures The sails per se may also be used. Besides their bu~dsr effect, the adds a~so typically have the property of an aadifying component arxi, hence, also serve to establish a relatively low and mild phi value in dete~ertts. Citric aad, suocinic aad, glutaric acid, adipic acid, gluconic acid and rr~ctures thereof are particularly mer>tioned in this regard.
Other suitable builders are polymeric polyrcarboxylates such as, for example, the alKali metal salts of polyacrylic or polymethacxylic aad, for l ~a example these with a relatwe molecular weight of 5~ to 70,000 glmole.
The mofecxrlar weights mentioned in this specfication for polyrrreric polycarbo~cylates are weight-average molecular weights Mr, of the partrcxular acid form which, dasica4y, were determined by gel permeation chromatography (GP'C) using a UV deter. The measurement was carried out against an extemat polyacxylic acrd standard which provides realistic molecular weight values by virtue of its structural similarity to the polymers investigated. These values differ distinctly from the rrblearlar weights measun~f against ~lystyrer~e sulfonic cads as standard. The rnvlecular we~hts measured against polystyrene sulfonic acids are generally hi8her than the molecular weights mentioned in this spe~tion.
Particularly suitable pohmuss are polyacrylates which preferably hare a molecular weight of 2.000 to 20,000 glmole. 8y virtue of their superux solubility, preferred represer>tatives of this group are the short '! 5 chain polyacrylates which have mdecular weights of 2,(100 to 10,000 glmole and, more particularly, 3,000 to 5,000 glmole.
Also suitable ane copolyrrreric polycarboxylates. particularly those of a<xylic acid with methacrylic aad and those of aaylic aad or msthacry<ic add with malefic aad. Acrylic addlmaleic acid copolymers dining 50 to 90% by weight of acrylic at~d and 50 to 10% by weight of maleiC acid have proved tn be pattiarlarly suitable. Their relative moleaalar weights, based on the free acids, are generally in the range from 2.000 to 70,000 glmole, preferably in the range from 20,000 to 50,000 gJmole and more preferably in the range from 30.000 to X0,000 glmde.
The (co)polymeric polycarboxylates may be used either in powder fomn or in the form of an aqueous solution. The oor~tent of (co)potyrneric polycarboxyiates in the detergent is preferably from 0.5 to 20% by weight ' and more prsfer~tdty from 3 to 1D% by weight.
In order to improrre solubility in wator, the polymers may also contain allyl sutfonic acids, such as ally~xybsnxene sulfonic acid and methatlyl sulfonic acid, as monomer.
Other particularly preferred polymers are biodegradable polymers of more than two different monomt3r units, for example those which contain salts of acrylic aad and malefic acid and vinyl alcohol or viny) alcohol ~ derivatives as monomers or those which contain sails of acrylic acid and 2~
.
alkylallyl sulfonic acid and sugar derivatives as morxamers.
Other preferred copolymers are those which preferably contain acxolein and acryl~ aadiacrytic acid salts or acrolein and vinyl acetate as monomers.
Other preferred builders are poly<rtetic arrdnod-K:arbaorylic acids. salas or pn3arrsors thereof. Polyaspartic acids or salts and derivatives thereof islare pa>t~rlaAy prefen~ed.
Other suitable builders are ~lyacetals which may be obtained by reaction of dialdehydes with poiyal carboxylic aads containing 5 to 7 carbon atoms and at least three hydroxyl groups. Preferred polyacetals are obtained from diaidehydes, such as glyoxai, glutaraldehyde, terrephthal akiehyde and mixtures thereof and from polyol carboxylic acids, such as t gfuconic aad andlor giuooheptortic acid.
' Othsr suitable organic binders are dexains, fior example ol'rs or polyrr>ers of carboh~ra~a which may be obtained by partial hydrolysis of stances. The hydrolysis may be carried out by standard methods, for example acid- or enzyme-cataly~d methods. The end pnxiurxs are preferably hydrolysis products with average mole~lar weights of 400 to 500,000 glmole. A polysaccharide with a dextrose equivaisrrt (DE) of 0.5 m 40 and, more particularly, 2 to 30 is preferred, the DE being an accepted messur~e of the reducing effect of a polysaccharide by comparison with dextrose whic~r has a pE of 100. Both mahodextrins with a DE of 3 to 20 and dry glucose sirups with a DE of 20 to 37 and also so-called yellow dextrins arid white dextrins with relattve~r high molecular weights of 2,000 to 30,000 glrnole may be used.
t The oxidized derivatives of such dextrins are their reaction products with oxidizing which are capat>!e of oxidizing at least one alcohol function of the saarharide ring to the carboxylic acid fun~n. An oxidized oiigosac~aride, such as a pn~du~ oxidized at C6 of the saccharide ring. is 5 also suitable.
- Other suitable co-builders are oxydisu~tate$ and other derivatives of dis~ra~nates, preferably ethytenediamine disuocinate. Ethyteneaiamine~
N.N'~iisuacinate (EDDS) is preferably used in the form of its sodium or magnesium saics. Glycerol disucar>ates and glycerol trisucxinates era also prefemsd irt this corn. The quantities used in zeolke-containing andlor silicate-ootttaining formulations are from 3 to 15% by weight.
Other useful organic oo-builders aria, for example, acetylated hYd~xYl~ acids and salts which may optionally be present in lactose form and which contain at feast 4 carton atoms. at teast one 15 hydroxy grcx~P and ai most two acid groups.
Anothsr class of substances with oo-bu~der properties are the Phosphonates, more particularly hydroxyalkane and aminoalkane phos-phonates. Amrong the hydroxyalkane phosphonates, ~-hyrdroxyethane,~,1-diphosphonate (HEDP) is particularly important as a co-buildder. It is 20 prefen~bly used in the form of the sodium salt, the disodium salt showing a neutral reacxion and the tstrasodium salt an alkaline reaction (pH 9).
Preferred amirwalkane phosphonates ane ethylenediamine tetramethylene phosphonate (EDTMP), diethylenefiri~ruae pentamethylenephosphortate (DTPMP) and higher homol~s . They are preferably used in the i forim of the r~utraNy roa~g sodium, salts, for example as the heacasodium salt of EDTMP or as the hepta- and octasodium salts of DTPMP. Of the phosphOnates, HEDP is preferably used as a builder. In addition, the aminoalkane phosphonates here a pronounced heavy metal binding capacity. Accordingly. it can be of advantage, particularly where the deterper~ts also contain bleach. to use anunoalkane phosphonates, moro particularly DTPMP, or mixtures of the phosphonates mentioned.
In addition, any compounds capable of forming complexes with alkaline earth metal ions may be used as oo-builders.
In one preferred embodiment, the detergents according to the invention are liquids or gels.
Solvents which may de used in the liquid or gel-form compositions belong, for example, to the group of monohydric or polyhydric atcohols, alkanolamines and glycol ethers providing they are miscible with water in the concentration range indicated. The adove-mentioned organic solvents used for the production of the enzyme preparation may also pe used. The solvents are preferably seJeded from ethanol, n- ar i-propanol, butanols, ethylene glycd methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether. ethylene glycol mono-n-butyl ether. diethylene glycol methyl ether. diethylene glycol ethyl ether. propylene glyrcol methyl, ethyl or propyl 1 S ether, dipropylene glycol monomethyl or monoethyl ether. diisopropylene ' glycol monomethyl or monoethyl ether, methoxy, ettroxy or butoxy triglycol, 1-butoxyethoxy-2-propanol. 3-rnethyl-3-methoxybutanol. propylene glycol-t butyl ether and mixtures of these soiverns. Solvents may be used in the liquid or gel form detergents according to ttte invent~n in quantities of 0.1 to 20% by weight, preferably below 15% by weight and more preferably below 10% by weight.
One or more thickeners or tti~ckening systems may be added to the composition detergent according to the invention to adjust its viscostty.
The viscosity of the composites according to the invention can be measurod by standard methods for example Brookfleki RVD-VII
v~cosirrreter at 20 r.p.m. and 20~C, spindle 3) and is preferably in the range from 100 to 5,000 mPas. Prefeme<i compositions have viscosities of 200 to 4.000 mPas, vescosides in the range from 400 to 2,000 mPas being l particularly preferred.
Suitable thickeners arse inorganic or polymeric organic compounds.
These generaNy cuganic, high mdeaular wr3ight aorr>pounds, which are also known as swelling agents, generally take up the Iiquids and awed in the process and. finally. atar>ge into viscous true or c~ilo~ia! solutions.
The inorganic thickeners indude, for exempla, polysiliac acids, day minerals, such as montmor~Onites. zeofites. s~ic:as and ber~nites.
The organic thickeners belong W the groups of nat<ual polymers.
modified natural polymers and fully synth~ic polymers.
Nawrally occurring polymers uses as thickeners aro, lfor example, agar agar. carrageen, tragacar>:h. gum arati;c, alginates, p~na, polyose~, guar gum, kx:ust bean gum, starch. de~arins. gelatin and casein.
Modified natural materials belong above all bo the group of modified starches and celluloses, of which carboxyrnetttyl t~lluiose and other cellulose etrlors, hydroxyethyi cellulose and hydroxypropyl cellulose and also gum ethers are mentioned as examples.
A large group of thickeners which are widely used in various fields of applicat'ron are the fully synthetic polymers. such as polyacrylic and polY-methacxyuc compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyankdes and pdyurethanes.
Ths thickeners may be present in a quantity of up to 5% by wesght, proferably in a quantity of 0.05 to 2% by weight and more preferably in a quantity of 0.1 to ~ .5% by weight, based on the final ition.
The detergent aconrding to the invention may contain in partkxrlar sequestering ants, eledxolytes, pli regulators and other auxiliaries, such as optical brighteners, redeposintlon inhib<tors, dye transfer inhibitors, foam regulators, additional bleach activators, dyes and perfumes, as further _ typicsl auxiliaries.
Besides the surfadartts, bhaching agents ark builders, a number of compounds - for example foam inhibitors, phosphorrates, enzymes aril optics! brighteners - may be present in laundry detergents.
Where the detergents are used in washing machines, it can be of advantage to 8dd typical foam inh~itors to them. Suitable foam inhibiteors see. for exampl~, soaps of natural or synthetic origin which have a high percentage aontant of C,a~, fatty acids. Suitable non-surtaae~-at~ive foam inhibitors .are, for example, organopoiys~oxanes and mixtures ttteceof with miaofine, optionally silsanized, silica and also paraffins, waxes, microcrystaliine waxes and mixtures thereof with silanized silica or bis-stearyl ethylenediamide. Mixtures of different foam inhibitors, for example mixt<rres of silicones, paraiflns and wakes, may also be used with advantage. The foam inhibitors. more particularly silicone- andlor paraffin-containing foam inhibitors, are preferably faced to a granular water-Soluble or wateriiispersible support. Mbdur~ of parafi'tns and biaryl ethylenediamides are particularly pnefemed.
If the detergent ac~orading to the invention is used as a so-called liquid or gel-form perboratc-containing dete~ent, it preferably contains 0 to 7 5 20% by weight of surfactants. ~0 to 80% by weight of nonionic surfactants, 2 to 25% by weight of bu~dert, 0 to 20% by weight of bleaching agents, 0 to 20% by weight of bleach activators, 0 to 5% by weight of enzymes, perfumes and other ingredients.
After removal of the fermentation residues, a harvest $luny obtained after fermentation (cf. International patent application WO 91l2T9Z) vontaining 75,00 protease units per g (PUIg) was concentrated by decantation and microfiltration in an utttaflltration module. After further oonceby evaporation in vaaro, the aqueous enzyme suspension contained 700,000 PUlg for a water content of about 70%. The con-centrate thus obtained was mbced with 1.2-propylene 9lycot (~~Cam~ ~ ) and with glycerol (Ex~l~) in such a quantity that the mixture obtained contained 40% by weight ~Ivent and ~0% by weight water.
The mixt<rre was distilled in a water jet vawum at n~rtt temperature in a rotary evaporator uM7 It had the neauirsd water content.
The fortnutation oin ~gg~;l~a 1 ootrtained 6696 of 1.2 propylene gtyool and 9.5% of water (as determined by the Karl Fischer method) and had 1n ec~rtt)r of bout 7t70,00Q WPUIg.
The preparation obtained in ~pcontained 68% of glycerol and 6.496 of water (as determined dy the Ka~i Fisc~er method) and had the same acxivity as the preparation of Exempts 1.
Claims (16)
1. A process for the production of an enzyme preparation of low water content, wherein an aqueous enzyme preparation is mixed with an organic solvent having a boiling point above 100°C and the water is distilled off.
2. A process as claimed in claim 1, wherein the organic solvent is selected from (a) liquid nonionic surfactants, (b) monohydric or (c) polyhydric alcohols.
3. A process as claimed in claim 2, wherein the liquid nonionic surfactants are C8-22 fatty alcohol alkoxylates.
4. A process as claimed in claim 2 or 3, wherein the polyhydric alcohols are selected from ethylene glycol, propylene glycol, glycerol or low molecular weight polyethylene glycols containing 2 to 14 monomer units.
5. A process as claimed in any of claims 1 to 4, wherein the distillation is carried out under reduced pressure at a temperature below 50°C.
6. A process as claimed in claim 5, wherein the temperature is ambient temperature.
7. A process as claimed in any of claims 1 to 6, wherein the water content of the enzyme preparation obtained is below 15% by weight, based on the weight of the low-water enzyme preparation as a whole.
8. A process as claimed in any of claims 1 to 7, wherein the enzymes are selected from protease, amylase, lipase and/or cellulase.
9. A process as claimed in any of claims 1 to 8, wherein the aqueous enzyme preparation is an enzyme concentrate emanating from the fermentation process.
10. The use of the enzyme preparation of low water content produced by the process claimed in any of claims 1 to 9 in a detergent composition.
11. The use claimed in claim 10, wherein the detergent composition is a liquid or gel-form bleach-containing detergent.
12. A detergent composition comprising surfactants and builders and optionally other typical ingredients, wherein enzymes are used in the form of a preparation obtained by the process claimed in any of claims 1 to 9.
13. A detergent composition as claimed in claim 12, in the form of a liquid or gel-form detergent.
14. A detergent composition as claimed in claim 12 or 13, wherein bleaching agents are present.
15. A detergent composition as claimed in any of claims 12 to 14, wherein there are present sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, redeposition inhibitors, dye transfer inhibitors, foam regulators, additional bleach activators, dyes and perfumes.
16. A detergent composition as claimed in any of claims 12 to 15, wherein there are present 0 to 20% by weight of anionic surfactants, 40 to 80% by weight of nonionic surfactants, 2 to 25% by weight of builders, 0 to 20% by weight of bleaching agents, 0 to 20% by weight of bleach activators, 0 to 5% by weight of enzymes, perfumes and other ingredients.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1999153870 DE19953870A1 (en) | 1999-11-10 | 1999-11-10 | Process for the preparation of a low-water enzyme preparation |
DE19953870.0 | 1999-11-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2325709A1 true CA2325709A1 (en) | 2001-05-10 |
Family
ID=7928419
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2325709 Abandoned CA2325709A1 (en) | 1999-11-10 | 2000-11-10 | Process for the production of an enzyme preparation of low water content |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1099750A3 (en) |
CA (1) | CA2325709A1 (en) |
DE (1) | DE19953870A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8809392B2 (en) | 2008-03-28 | 2014-08-19 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
US8344026B2 (en) | 2008-03-28 | 2013-01-01 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
US8871807B2 (en) | 2008-03-28 | 2014-10-28 | Ecolab Usa Inc. | Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids |
US9321664B2 (en) | 2011-12-20 | 2016-04-26 | Ecolab Usa Inc. | Stable percarboxylic acid compositions and uses thereof |
AU2013240312C1 (en) | 2012-03-30 | 2018-02-01 | Ecolab Usa Inc. | Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water |
US8822719B1 (en) | 2013-03-05 | 2014-09-02 | Ecolab Usa Inc. | Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring |
US10165774B2 (en) | 2013-03-05 | 2019-01-01 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
US20140256811A1 (en) | 2013-03-05 | 2014-09-11 | Ecolab Usa Inc. | Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3472783A (en) * | 1966-02-02 | 1969-10-14 | Winston B Smillie | Nonionic detergent compositions |
US3860536A (en) * | 1970-01-02 | 1975-01-14 | Cpc International Inc | Enzyme-detergent combination |
NL8000452A (en) * | 1979-02-07 | 1980-08-11 | Unilever Nv | PREPARATION FOR LAUNDRY. |
US4465619A (en) * | 1981-11-13 | 1984-08-14 | Lever Brothers Company | Built liquid detergent compositions |
JPS60156395A (en) * | 1984-01-17 | 1985-08-16 | Mihama Hisaharu | Preparation of ester by modification lipase |
US5275753A (en) * | 1989-01-10 | 1994-01-04 | The Procter & Gamble Company | Stabilized alkaline liquid detergent compositions containing enzyme and peroxygen bleach |
GB9309243D0 (en) * | 1993-05-05 | 1993-06-16 | Allied Colloids Ltd | Enzyme dispersions,their production and compositions containing them |
US5834415A (en) * | 1994-04-26 | 1998-11-10 | Novo Nordisk A/S | Naphthalene boronic acids |
IL117948A0 (en) * | 1995-04-18 | 1996-08-04 | Horiuchi Co Ltd | Reusable cleaning solutions containing stabilized enzymes |
DE19717329A1 (en) * | 1997-04-24 | 1998-10-29 | Henkel Ecolab Gmbh & Co Ohg | Liquid enzyme preparation and its use |
-
1999
- 1999-11-10 DE DE1999153870 patent/DE19953870A1/en not_active Withdrawn
-
2000
- 2000-11-03 EP EP00123432A patent/EP1099750A3/en not_active Withdrawn
- 2000-11-10 CA CA 2325709 patent/CA2325709A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
DE19953870A1 (en) | 2001-05-17 |
EP1099750A2 (en) | 2001-05-16 |
EP1099750A3 (en) | 2002-09-18 |
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