CN106978403B - 酶颗粒剂 - Google Patents
酶颗粒剂 Download PDFInfo
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- CN106978403B CN106978403B CN201610849442.2A CN201610849442A CN106978403B CN 106978403 B CN106978403 B CN 106978403B CN 201610849442 A CN201610849442 A CN 201610849442A CN 106978403 B CN106978403 B CN 106978403B
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- 239000008187 granular material Substances 0.000 title claims description 81
- 102000004190 Enzymes Human genes 0.000 title abstract description 35
- 108090000790 Enzymes Proteins 0.000 title abstract description 35
- 150000003839 salts Chemical class 0.000 claims abstract description 80
- 238000000576 coating method Methods 0.000 claims abstract description 64
- 239000011248 coating agent Substances 0.000 claims abstract description 61
- 239000003599 detergent Substances 0.000 claims abstract description 51
- 230000002378 acidificating effect Effects 0.000 claims abstract description 17
- 239000000872 buffer Substances 0.000 claims abstract description 17
- 150000001768 cations Chemical class 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 50
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 30
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 22
- 108010059892 Cellulase Proteins 0.000 claims description 20
- 235000011152 sodium sulphate Nutrition 0.000 claims description 17
- 108010065511 Amylases Proteins 0.000 claims description 14
- 102000013142 Amylases Human genes 0.000 claims description 14
- 108091005804 Peptidases Proteins 0.000 claims description 14
- 235000019418 amylase Nutrition 0.000 claims description 14
- 238000004061 bleaching Methods 0.000 claims description 14
- 239000004382 Amylase Substances 0.000 claims description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 13
- 239000004365 Protease Substances 0.000 claims description 13
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
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- 239000011777 magnesium Substances 0.000 claims description 9
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- 229940106157 cellulase Drugs 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
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- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 3
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- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 claims description 3
- 159000000021 acetate salts Chemical class 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
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- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 9
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
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- 239000000945 filler Substances 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 7
- 229920002125 Sokalan® Polymers 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 7
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
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- 150000003871 sulfonates Chemical class 0.000 description 6
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- 239000012141 concentrate Substances 0.000 description 5
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 5
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- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 5
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- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 description 5
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 5
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- 229910000406 trisodium phosphate Inorganic materials 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
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- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
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- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 1
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- PYLIXCKOHOHGKQ-UHFFFAOYSA-L disodium;hydrogen phosphate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O PYLIXCKOHOHGKQ-UHFFFAOYSA-L 0.000 description 1
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- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
- UZABCLFSICXBCM-UHFFFAOYSA-N ethoxy hydrogen sulfate Chemical compound CCOOS(O)(=O)=O UZABCLFSICXBCM-UHFFFAOYSA-N 0.000 description 1
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- 239000002979 fabric softener Substances 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229960003943 hypromellose Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
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- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
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- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
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- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-L malate(2-) Chemical compound [O-]C(=O)C(O)CC([O-])=O BJEPYKJPYRNKOW-UHFFFAOYSA-L 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920000196 poly(lauryl methacrylate) Polymers 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- 235000010388 propyl gallate Nutrition 0.000 description 1
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- 108010038196 saccharide-binding proteins Proteins 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 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
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- IABJTGIZDNKNAJ-UHFFFAOYSA-M sodium naphthalen-1-ol formate Chemical compound C(=O)[O-].[Na+].OC1=CC=CC2=CC=CC=C12 IABJTGIZDNKNAJ-UHFFFAOYSA-M 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- DGSDBJMBHCQYGN-UHFFFAOYSA-M sodium;2-ethylhexyl sulfate Chemical compound [Na+].CCCCC(CC)COS([O-])(=O)=O DGSDBJMBHCQYGN-UHFFFAOYSA-M 0.000 description 1
- LIAJJWHZAFEJEZ-UHFFFAOYSA-M sodium;2-hydroxynaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=CC2=C(S([O-])(=O)=O)C(O)=CC=C21 LIAJJWHZAFEJEZ-UHFFFAOYSA-M 0.000 description 1
- AXMCIYLNKNGNOT-UHFFFAOYSA-N sodium;3-[[4-[(4-dimethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)-[4-[ethyl-[(3-sulfophenyl)methyl]amino]phenyl]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 AXMCIYLNKNGNOT-UHFFFAOYSA-N 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
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- 230000000087 stabilizing effect Effects 0.000 description 1
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- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
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- 229940095064 tartrate Drugs 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
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- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002264 triphosphate group Chemical class [H]OP(=O)(O[H])OP(=O)(O[H])OP(=O)(O[H])O* 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
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 239000012588 trypsin Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/105—Aliphatic or alicyclic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/142—Amino acids; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/163—Sugars; Polysaccharides
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/189—Enzymes
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K40/00—Shaping or working-up of animal feeding-stuffs
- A23K40/10—Shaping or working-up of animal feeding-stuffs by agglomeration; by granulation, e.g. making powders
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K40/00—Shaping or working-up of animal feeding-stuffs
- A23K40/30—Shaping or working-up of animal feeding-stuffs by encapsulating; by coating
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
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Abstract
酶在粉状去污剂中的稳定性可以通过四个措施的组合得到非常显著地改善:将还原剂/过氧化物分解催化剂/抗氧化剂加入核心或涂层;将多价阳离子加入核心;将酸性缓冲剂加入核心或涂层;将盐涂层应用于核心上。
Description
本申请是基于申请日为2011年4月15日,优先权日为2010年4月26日,申请号为201180025872.8,发明名称为“酶颗粒剂”的专利申请的分案申请。
发明领域
本发明涉及包含由保护涂层包围的含酶核心的颗粒剂及其在颗粒(或粉末)去污剂中的用途。更具体而言,它涉及在粉末去污剂中具有改善稳定性的酶颗粒剂。
发明背景
以颗粒剂形式的酶通常加入粉状去污剂中,以改善去污力。本领域已知将酶掺入颗粒剂内,将稳定剂掺入此类颗粒剂内且用保护涂层包围颗粒剂,以便保护酶不受由环境中的攻击性材料引起的失活,例如以改善当颗粒剂加入颗粒状去污剂时酶的贮存稳定性。
因此,有涂层的酶颗粒剂公开于WO 00/01793、WO 2004/003188(US 2004/033927)、WO 2004/067739、WO 99/32595、WO 2006/034710(US 2006/073193)和WO 2007/044968中。WO 99/37746公开了多层去污剂片剂。
发明概述
本发明人已发现酶在粉状去污剂中的稳定性可以通过四个措施的组合得到非常显著地改善:
·将还原剂、过氧化物分解催化剂或抗氧化剂加入核心或涂层中
·将多价阳离子加入核心中
·将酸性缓冲剂加入核心或涂层中
·将盐涂层应用于核心上。
本发明人已发现这四个措施的组合导致颗粒剂中酶活性的贮存稳定性的协同改善。相应地,本发明提供了包含核心和保护涂层的颗粒剂,其中:
a)该核心包含酶,和
b)该核心和/或该涂层包含还原剂或过氧化物分解催化剂或抗氧化剂,和
c)该核心包含多价阳离子的盐,和
d)该核心和/或该涂层包含酸性缓冲剂组分,和
e)该涂层包含盐。
此外,本发明提供了表面活性剂和颗粒剂。
发明详述
核心
该核心包含酶和多价阳离子的盐,并且它还可以包含一般作为同质掺和物的还原剂/抗氧化剂/过氧化物分解催化剂和/或酸性缓冲剂组分。该掺和物还可以包括粘合剂(例如合成聚合物、蜡、脂肪或碳水化合物)。该掺和物可以进一步包括另外的材料,例如填充剂、纤维材料(纤维素或合成纤维)、稳定剂、增溶剂、悬浮剂、粘性调节剂、轻球体(lightspheres)、增塑剂、盐、润滑剂和香料。
该核心可以通过例如通过使用造粒技术将该掺和物粒化进行制备,所述造粒技术包括:结晶、沉淀、盘涂覆(pan-coating)、流化床涂覆、流化床成块、旋转雾化、挤出、成球(prilling)、滚圆(spheronization)、粉碎法、转鼓造粒和/或高剪切制粒。
核心可以由具有掺和物吸附到其内,或具有例如经由流化床涂覆应用于表面上的掺和物的惰性颗粒组成。
核心颗粒可以具有20-2000μm,特别是50-1500μm、100-1500μm或250-1200μm的直径。
酶
颗粒剂的核心包含酶,例如淀粉酶、糖酶、蛋白酶、脂肪酶、纤维素酶、氧化还原酶、甘露聚糖酶或果胶酸裂合酶。
本发明的颗粒剂一般包括在干重基础上相对于该核心约0.005-约500mg/g的酶组分(作为活性酶蛋白)。例如,在本发明的实施方案中的酶量包含在颗粒剂中的约0.05-300mg/g、约0.1-250mg/g、约0.5-200mg/g、约0.5-200mg/g、约1.0-150mg/g,或相对于该核心约5.0-150mg/g。
淀粉酶
淀粉酶可以是得自芽孢杆菌属(Bacillus)例如枯草芽孢杆菌(B.subtilis)和地衣芽孢杆菌(B.licheniformis)的α-淀粉酶,特别是在GB 1,296,839中更详细地描述的来自地衣芽孢杆菌的特定菌株的淀粉酶。
有用的淀粉酶的例子,尤其是在一个或多个下述位置中具有取代的变体:15、23、105、106、124、128、133、154、156、181、188、190、197、202、208、209、243、264、304、305、391、408和444,在WO 94/02597、WO 94/18314、WO 1995/010603、WO 1995/026397、WO 96/23873、WO 97/43424和WO 00/60060、WO 2001/066712、WO 2006/002643中描述。
在特定实施方案中,α-淀粉酶衍生自芽孢杆菌属菌种菌株NCIB 12289、NCIB12512、NCIB 12513和DSM 9375。尤其优选的是显示于WO 95/26397的SEQ ID NOS 1和2中的α-淀粉酶。
商购可得的淀粉酶是NATALASETM、STAINZYMETM、STAINZYME PLUSTM、TERMAMYLTMULTRA、DURAMYLTM、TERMAMYLTM、FUNGAMYLTM和BANTM(Novozymes A/S)、RAPIDASETM、PURASTARTM和PURASTAR OXAMTM(来自Genencor International Inc.)。
蛋白酶
合适的蛋白酶包括具有动物、植物或微生物来源的那些。微生物来源是优选的。包括化学修饰或蛋白质工程改造的突变体。蛋白酶可以是丝氨酸蛋白酶或金属蛋白酶,优选碱性微生物蛋白酶或胰蛋白酶样蛋白酶。碱性蛋白酶的例子是枯草杆菌蛋白酶(subtilisins),尤其是衍生自芽孢杆菌属的那些,例如枯草杆菌蛋白酶Novo、枯草杆菌蛋白酶Carlsberg、枯草杆菌蛋白酶309、枯草杆菌蛋白酶147和枯草杆菌蛋白酶168(WO 89/06279中描述的)。胰蛋白酶样蛋白酶的例子是WO 89/06270和WO 94/25583中所述的胰蛋白酶(例如具有猪或牛来源)和镰孢属(Fusarium)蛋白酶。
有用的蛋白酶的例子是在WO 92/19729、WO 98/20115、WO 98/20116和WO 98/34946中描述的变体,尤其是在一个或多个下述位置中具有取代的变体:27、36、57、76、87、97、101、104、120、123、167、170、194、206、218、222、224、235和274。
优选的商购可得的蛋白酶包括AlcalaseTM、SavinaseTM、PrimaseTM、DuralaseTM、EsperaseTM和KannaseTM(Novozymes A/S)、MaxataseTM、MaxacalTM、MaxapemTM、ProperaseTM、PurafectTM、Purafect OxPTM、FN2TM和FN3TM(Genencor International Inc.)。
脂肪酶
脂肪酶可以是疏棉状嗜热丝孢菌(Thermomyces lanuginosus)脂肪酶(TLL,在WO2009/109500中显示为SEQ ID NO:2)、产碱菌属菌种(Alcaligenes sp.)脂肪酶、无色杆菌属菌种(Achromobacter sp.)脂肪酶、洋葱伯克霍尔德菌(Burkholderia cepacia)脂肪酶、施氏假单胞菌(Pseudomonas stutzeri)脂肪酶,或它可以是具有与这些之一具有至少80%同一性,特别是至少85%、至少90%、至少95%或至少98%同一性的氨基酸序列的变体。
TLL同系物的例子在WO 1992/005249、Lipolase Ultra)、WO0060063、WO9707202、WO0032758、WO02055679、WO04099400、WO07087508和WO 2009/109500中描述。商业脂肪酶包括下述Novozymes A/S产品:NovozymTM 435、Novozym 735、LipozymeTM RM、Novozym 388、LipolaseUltraTM、LipexTM、LipoprimeTM、LipolaseTM、LipocleanTM和LipolexTM。
纤维素酶
合适的纤维素酶包括具有细菌或真菌来源的完全纤维素酶或单组分内切葡聚糖酶。包括化学或遗传修饰的突变体。纤维素酶可以例如是单组分或单组分内切-1,4-β-葡聚糖酶(通常仅称为“内切葡聚糖酶”)(EC 3.2.1.4)的混合物。某些木葡聚糖酶还可以具有内切葡聚糖酶活性,并且也视为在本发明中合适的纤维素酶。合适的纤维素酶公开于US 4,435,307中,其公开了由特异腐质霉(Humicola insolens)产生的真菌纤维素酶。尤其合适的纤维素酶是具有纺织品护理利益的纤维素酶。此类纤维素酶的例子是在欧洲专利申请号0 495257中描述的纤维素酶。
合适的单组分内切葡聚糖酶可以得自下述菌种中的一个或多个:黑耳(Exidiaglandulosa)、柄毛皮伞(Crinipellis scabella)、木蹄(Fomes fomentarius)、绵皮孔菌属菌种(Spongipellis sp.)、红根囊壶菌(Rhizophlyctis rosea)、微小根毛霉(Rhizomucorpusillus)、闪光须霉(Phycomyces nitens)和弗雷生剌枝霉(Chaetostylum fresenii)、棉色二胞(Diplodia gossypina)、小球壳孢属菌种(Microsphaeropsis sp.)、Ulosporabilgramii、短梗霉属菌种(Aureobasidium sp.)、菜豆壳球孢菌(Macrophominaphaseolina)、Ascobolus stictoides、Saccobolus dilutellus、盘菌属(Peziza)、疣孢青霉(Penicillium verruculosum)、产黄青霉(Penicillium chrysogenum)和疣状顶孢霉(Thermomyces verrucosus)、里氏木霉(Trichoderma reesei)即红褐肉座菌(Hypocreajecorina)、Diaporthe syngenesia、葫芦科毛盘孢(Colletotrichum lagenarium)、鹿角炭角菌(Xylaria hypoxylon)、黑孢霉属菌种(Nigrospora sp.)、多节孢属菌种(Nodulisporum sp.)和点孔座壳(Poronia punctata)、柱孢属菌种(Cylindrocarponsp.)、Nectria pinea、Volutella colletotrichoides、粪生粪壳(Sordaria fimicola)、大孢粪壳(Sordaria macrospora)、嗜热梭孢壳(Thielavia thermophila)、Syspastosporaboninensis、Cladorrhinum foecundissimum、突孢毛壳(Chaetomium murorum)、变绿毛壳(Chaetomium virescens)、巴西毛壳(Chaetomium brasiliensis)、Chaetomium cuni-colorum、嗜热毁丝菌(Myceliophthora thermophila)、链孢粘帚霉(Gliocladiumcatenulatum)、Scytalidium thermophila、枝顶孢属菌种(Acremonium sp)、茄病镰孢(Fusarium solani)、Fusarium anguioides、梨孢镰孢(Fusarium poae)、尖镰孢番茄专化型(Fusarium oxysporum ssp.lycopersici)、尖镰孢西番莲专化型(Fusarium oxysporumssp.passiflora)、黑腐质霉(Humicola nigrescens)、灰腐质霉(Humicola grisea)、尖镰孢、土生梭孢壳或特异腐质霉。一种优选的内切葡聚糖酶作为SEQ ID NO:9公开于WO 96/29397(在此引入作为参考)中,或与之具有至少70%同一性的酶及其如公开于WO 98/12307的实施例1中的变体。另一种优选的内切葡聚糖酶公开于WO 91/017243(SEQ ID NO:2)中或如公开于WO 94/007998中的内切葡聚糖酶变体。
具有抗再沉积效应的内切葡聚糖酶可以得自来自许多细菌来源的缺乏碳水化合物结合模块(CBM)的真菌内切葡聚糖酶。某些来源是特异腐质霉、作为DSM 12648保藏的芽孢杆菌属菌种、作为FERM P-16067保藏的芽孢杆菌属菌种KSMS237、多粘类芽孢杆菌(Panibacillus polymyxa)、和饲料类芽孢杆菌(Panibacillus pabuli)。特异性抗再沉积内切葡聚糖酶公开于WO 91/17244(图14)(在此引入作为参考)、WO 2002/099091SEQ IDNO:2的位置1-773(在此引入作为参考)、WO 04/053039SEQ ID NO:2(在此引入作为参考)、JP 2000210081 SEQ ID NO:1的位置1–824(在此引入作为参考)中。
具有抗再沉积效应的木葡聚糖酶可以得自许多细菌来源。某些来源是地衣芽孢杆菌、Bacillus agaradhaerens(WO 99/02663)、多粘类芽孢杆菌和饲料类芽孢杆菌(WO01/62903)。木葡聚糖酶的合适变体还在PCT/EP2009/056875中描述。商购可得的木葡聚糖酶是(Novozymes A/S)。
商购可得的纤维素酶包括由里氏木霉产生的由特异腐质霉产生的商购可得的内切葡聚糖酶是 和(Novozymes A/S),和KAC-500(B)TM(Kao Corporation)和ClazinaseTM、PuradaxTM EG L和Puradax HA(Danisco A/S)。
果胶酸裂合酶
果胶酸裂合酶可以是衍生自芽孢杆菌属特别是地衣芽孢杆菌或B.agaradhaerens的野生型酶,或例如如US 6,124,127(NZ 5543)、WO 1999/027083(NZ 5377)、WO 1999/027084(NZ 5378)、WO 2002/006442(NZ 10044)、WO 2002/092741(NZ 10171)或WO 2003/095638(NZ 10190)中所述的这些衍生的变体。
甘露聚糖酶
甘露聚糖酶可以是家族5或26的碱性甘露聚糖酶。它可以是来自芽孢杆菌属或腐质霉属,特别是B.agaradhaerens、地衣芽孢杆菌、耐盐芽孢杆菌(B.halodurans)、克劳氏芽孢杆菌(B.clausii)或特异腐质霉的野生型。合适的甘露聚糖酶在WO 1999/064619(NZ5440)中描述。
还原剂、过氧化物分解催化剂和/或抗氧化剂
颗粒剂在核心和/或涂层中含有还原剂、过氧化物分解催化剂和/或抗氧化剂(能够减慢或预防其他分子氧化的分子)。例子是亚硫酸盐、硫代硫酸盐、异抗坏血酸盐(erythorbates)、抗坏血酸盐和亚硝酸盐,例如作为碱金属和碱土金属的盐。其他合适的材料是甲硫氨酸、半胱氨酸、没食子酸丙酯、叔丁基氢醌、生育酚、硫代二丙酸、丁羟甲苯(BHT)、丁羟基茴香醚(BHA)或鞣酸。
进一步合适的例子是作为还原剂和/或过氧化物分解催化剂的过渡金属,如例如V、Co、Mn和Fe,一般作为盐,例如硫酸盐、乙酸盐、硝酸盐或氯化物-盐或氧化物,例如FeSO4、FeCl3、CoSO4、MnSO4或MnO2。过渡金属的水溶性盐是优选的。作为过氧化物分解催化剂,还可以使用酶例如过氧化氢酶。
抗氧化剂、过氧化物分解催化剂或还原剂的量可以是相对于核心按重量计至少0.1%,特别是至少0.2%、至少0.5%、至少1%或至少1%。该量可以是相对于核心按重量计至多10%,特别是至多5%、至多4%、至多3%或至多2%。此处,盐的量以无水形式计算。过氧化物分解催化剂在甚至更低的浓度可以是有效的,例如至少0.001%或至少0.01%;该量可以是至多5%或至多1%。
多价阳离子的盐
颗粒剂在核心中含有多价阳离子的盐,特别是二价或三价阳离子,例如Mg、Zn、Cu、Mn、Ca或Al的盐。盐可以包括有机或无机阴离子例如硫酸盐、氯化物或乙酸盐。特别的盐包括硫酸镁和硫酸锌,例如七水硫酸镁。
盐可以以按核心的重量计至少0.1%,特别是按重量计至少0.5%,例如按重量计至少1%的量使用。该量可以是至多15%、10%或5%。百分比指示无水形式的盐的量。
多价阳离子可以以按核心的重量计至少0.02%,特别是按重量计至少0.1%,例如按重量计至少0.2%的量使用。该量可以是至多6%、至多4%或至多2%。百分比指示多价阳离子的量。
酸性缓冲剂组分
颗粒剂在核心或涂层中含有酸性缓冲剂组分(酸性缓冲试剂)。该量可以是按核心的重量计至少0.1,特别是按重量计至少1%。该量一般是按核心的重量计至多10%,特别是按重量计至多5%。百分比指示无水形式的量。
当测量为按水溶液的重量计1%(或可替代地10%溶液)时,酸性缓冲剂组分具有低于7的pH。酸性缓冲剂组分可以具有1至低于7的pH,例如3至低于7的pH,特别是4–5的pH。酸性缓冲剂组分一般是包含弱酸和相应碱的混合物;它至少部分是其酸形式。
此外,酸性缓冲剂组分具有2–9的pKa,特别是4–9的pKa,特别是5–8的pKa,特别是2–6的pKa,特别是2–5的pKa,特别是2–4的pKa,特别是5–7的pKa。为了利用大多数潜在的缓冲能力,水溶液的pH一般低于pKa。
特别合适的酸性缓冲剂组分是H3PO4的盐例如NaH2PO4、KH2PO4和Ca(H2PO4)2,多磷酸盐例如六偏磷酸钠,聚丙烯酸和部分中和的聚丙烯酸及其共聚物,简单有机酸(小于10个碳原子,例如6个或更少的碳原子)例如柠檬酸及其盐例如柠檬酸氢盐(hydrogen citrate)例如柠檬酸氢二钠,丙二酸、琥珀酸、戊二酸、己二酸。
在特定实施方案中,酸性缓冲剂组分选自聚丙烯酸和部分中和的聚丙烯酸及其共聚物、柠檬酸和Na3-柠檬酸盐。
盐涂层
颗粒剂包含由至少一个涂层包围的核心。该涂层可以包含按重量w/w计至少60%的盐,例如按重量w/w计至少65%、至少70%、至少75%、至少80%、至少85%、至少90%、至少95%或至少99%。
该涂层可以以按核心的重量计至少5%,例如至少10%、10%或15%的量应用。该量可以是至多70%、50%、40%或30%。
为了提供可接受的保护,盐涂层优选厚至少1μm,特别是至少2μm、至少4μm或至少8μm。涂层越厚,开始产生颗粒剂越费时和越昂贵。在特定实施方案中,盐涂层的厚度低于100μm。在更特定的实施方案中,盐涂层的厚度低于60μm。在甚至更特定的实施方案中,盐涂层的总厚度低于40μm。
涂层应通过形成基本上连续的层封装核心单元。基本上连续的层应理解为具有更少的孔或无孔的涂层,从而使得它封装的核心单元具有更少的无涂层的区域或没有涂层的区域。层或涂层应特别在厚度中是同质的。盐可以自盐完全溶解于其中的盐溶液或自其中细颗粒小于50μm、例如小于10μm或小于5μm的盐悬液加入。
如果在相对高湿度条件下在流化床中应用,则盐涂层是尤其有效的。
还原剂/抗氧化剂/过氧化物分解催化剂可以是盐涂层的部分,例如作为整个盐涂层的同质部分,或作为这个涂层的部分,或仅作为盐和/抗氧化剂/过氧化物分解催化剂的内层。使用例如FeSO4作为还原剂/过氧化物分解催化剂可能在金属氧化时诱导变色,其可以通过使组分作为内层得到隐藏。
盐涂层可以进一步含有如本领域已知的其他材料,例如填充剂、防粘剂、色素、染料、增塑剂和/或粘合剂,例如二氧化钛、高岭土、碳酸钙或滑石。
盐
盐涂层可以包含单一盐或两种或多种盐的混合物。盐可以是水溶性的,特别具有在20℃在100g水中至少0.1克的溶解度,优选至少0.5g/100g水,例如至少1g/100g水,例如至少5g/100g水。
盐可以是无机盐,例如硫酸盐、亚硫酸盐、磷酸盐、膦酸盐、硝酸盐、氯化物或碳酸盐,或简单有机酸(小于10个碳原子,例如6个或更少的碳原子)的盐,例如柠檬酸盐、丙二酸盐或乙酸盐。在这些盐中的阳离子的例子是碱金属或碱土金属离子,第一个过渡系列的铵离子或金属离子,例如钠、钾、镁、钙、锌或铝。阴离子的例子包括氯化物、溴化物、碘化物、硫酸盐、亚硫酸盐、亚硫酸氢盐、硫代硫酸盐、磷酸盐、一碱式磷酸盐(monobasic phosphate)、二碱式磷酸盐(dibasic phosphate)、次磷酸盐、焦磷酸二氢盐、四硼酸盐、硼酸盐、碳酸盐、碳酸氢盐、偏硅酸盐、柠檬酸盐、苹果酸盐、马来酸盐、丙二酸盐、琥珀酸盐、乳酸盐、甲酸盐、乙酸盐、丁酸盐、丙酸盐、苯甲酸盐、酒石酸盐、抗坏血酸盐或葡糖酸盐。具体而言,可以使用硫酸盐、亚硫酸盐、磷酸盐、膦酸盐、硝酸盐、氯化物或碳酸盐的碱金属或碱土金属盐,或简单有机酸的盐例如柠檬酸盐、丙二酸盐或乙酸盐。特定例子包括NaH2PO4、Na2HPO4、Na3PO4、(NH4)H2PO4、K2HPO4、KH2PO4、Na2SO4、K2SO4、KHSO4、ZnSO4、MgSO4、CuSO4、Mg(NO3)2、(NH4)2SO4、硼酸钠、乙酸镁和柠檬酸钠。
盐可以以无水形式,或它可以是水合盐,即例如WO 99/32595中所述的具有结合的结晶水的结晶盐水合物。特定例子包括无水硫酸钠(Na2SO4)、无水硫酸镁(MgSO4)、七水硫酸镁(MgSO4(7H2O))、七水硫酸锌(ZnSO4(7H2O))、七水磷酸氢二钠(Na2HPO4(7H2O))、七水硝酸镁(Mg(NO3)2(6H2O))、十水硼酸钠、二水柠檬酸钠和四水乙酸镁。
涂层中的盐可以具有在20℃按重量计超过60%,特别是超过70%、超过80%或超过85%的恒定湿度,或它可以是此类盐的另一种水合物形式(例如无水合物(anhydrate))。盐涂层可以根据在此引入作为参考的WO 00/01793。
合适盐的特定例子是NaCl(CH20℃=按重量计76%)、Na2CO3(CH20℃=按重量计92%)、NaNO3(CH20℃=按重量计73%)、Na2HPO4(CH20℃=按重量计95%)、Na3PO4(CH25℃=按重量计92%)、NH4Cl(CH20℃=按重量计79.5%)、(NH4)2HPO4(CH20℃=按重量计93,0%)、NH4H2PO4(CH20℃=按重量计93.1%)、(NH4)2SO4(CH20℃=按重量计81.1%)、KCl(CH20℃=按重量计85%)、K2HPO4(CH20℃=按重量计92%)、KH2PO4(CH20℃=按重量计96.5%)、KNO3(CH20℃=按重量计93.5%)、Na2SO4(CH20℃=按重量计93%)、K2SO4(CH20℃=按重量计98%)、KHSO4(CH20℃=按重量计86%)、MgSO4(CH20℃=按重量计90%)、ZnSO4(CH20℃=按重量计90%)和柠檬酸钠(CH25℃=按重量计86%)。
在特定实施方案中,盐选自下组:NaCl、Na2CO3、NaNO3、Na2HPO4、Na3PO4、NH4Cl、(NH4)2HPO4、NH4H2PO4、(NH4)2SO4、KCl、K2HPO4、KH2PO4、KNO3、Na2SO4、K2SO4、KHSO4、MgSO4、ZnSO4、NaCl和柠檬酸钠或其混合物。在更特定的实施方案中,盐选自下组:NaCl、Na2CO3、NaNO3、Na2HPO4、Na3PO4、NH4Cl、(NH4)2HPO4、NH4H2PO4、(NH4)2SO4、KCl、K2HPO4、KH2PO4、KNO3、Na2SO4、K2SO4、KHSO4、NaCl和柠檬酸钠或其混合物。
在特定实施方案中,在颗粒剂的涂层中包含的盐选自下组:NaCl、Na2CO3、NaNO3、Na2HPO4、Na3PO4、NH4Cl、(NH4)2HPO4、NH4H2PO4、(NH4)2SO4、KCl、K2HPO4、KH2PO4、KNO3、Na2SO4、K2SO4、KHSO4、MgSO4、ZnSO4、NaCl和柠檬酸钠或其混合物。
优选地,盐例如使用流化床作为盐溶液应用。
任选的额外涂层
任选地,颗粒剂可以包括例如以按核心的重量计至少0.5%,特别是至少1%,例如至多20%或10%的量,在盐涂层的外部上的额外涂层。额外涂层可以包含聚乙二醇(PEG)、羟丙基甲基纤维素(HPMC或MHPC)、聚乙烯醇(PVA)或其他成膜剂,并且可以进一步含有填充剂、防粘剂、色素、染料、增塑剂等。
在盐涂层内部或外部上的其他的额外涂层可以如本领域技术人员已知的应用。
去污剂组合物
颗粒剂特别适合于掺入包含表面活性剂的颗粒状去污剂组合物中。当颗粒剂掺入去污剂,即使包含攻击性组分例如漂白***的去污剂中时,根据本发明的酶颗粒剂导致改善的酶贮存稳定性。
去污剂组合物可以例如配制为用于手洗或机洗的洗衣去污剂组合物,包括适合于预处理被沾污织物的清洁添加剂组合物或织物柔顺剂组合物,或用于在一般的家居硬表面清洁操作中使用的去污剂组合物,或用于手洗或机洗洗碟操作的组合物。
本发明的去污剂组合物可以是任何方便的干燥形式,例如条、片剂、粉末、颗粒剂或糊剂。它还可以是液体去污剂,水性或非水性液体去污剂。
表面活性剂
去污剂组合物包含一种或多种表面活性剂,其可以是非离子型包括半极性和/或阴离子和/或阳离子和/或两性离子型的。表面活性剂一般以按重量计0.1%-60%的水平存在。
当包括在其中时,去污剂通常含有约1%至约40%的阴离子型表面活性剂例如直链烷基苯磺酸盐、α-烯烃磺酸盐、烷基硫酸盐(脂肪醇硫酸盐)、醇乙氧基硫酸盐、仲链烷磺酸盐、α-磺基脂肪酸甲酯、烷基或烯基琥珀酸或肥皂。
当包括在其中时,去污剂通常会含有约0.2%至约40%的非离子型表面活性剂例如醇乙氧基化物、壬基酚乙氧基化物、烷基多糖苷、烷基二甲基氧化胺、乙氧基化脂肪酸单乙醇酰胺、脂肪酸单乙醇酰胺、多羟基烷基脂肪酰胺或葡糖胺的N-酰基N-烷基衍生物(“葡糖酰胺”)。
去污剂组合物可以包含一种或多种表面活性剂,其可以是阴离子和/或阳离子和/或非离子和/或半极性和/或两性离子型的,或其混合物。在特定实施方案中,去污剂组合物包括一种或多种非离子型表面活性剂和一种或多种阴离子型表面活性剂的混合物。表面活性剂一般以按重量计约0.1%-60%,例如约1%-约40%、或约3%-约20%、或约3%-约10%的水平存在。
当包括在其中时,去污剂通常会含有按重量计约1%-约40%,例如约5%-约30%,包括约5%-约15%、或约20%-约25%的阴离子型表面活性剂。阴离子型表面活性剂的非限制性例子包括硫酸盐和磺酸盐,特别是直链烷基苯磺酸盐(LAS)、支链烷基苯磺酸盐(BABS)、苯基链烷磺酸盐、α-烯烃磺酸盐(AOS)、烯烃磺酸盐、链烯烃磺酸盐、链烷-2,3-二基双(硫酸盐)、羟基链烷磺酸盐和二磺酸盐、烷基硫酸盐(AS)例如十二烷基硫酸钠(SDS)、脂肪醇硫酸盐(FAS)、伯醇硫酸盐(PAS)、醇醚硫酸盐(AES或AEOS或FES,也称为醇乙氧基硫酸盐或脂肪醇醚硫酸盐)、仲链烷磺酸盐(SAS)、石蜡磺酸盐(PS)、磺酸酯、磺化脂肪酸甘油酯、α-磺基脂肪酸甲酯(α-SFMe或SES)包括甲酯磺酸盐(MES)、烷基或烯基琥珀酸、十二烯/十四烯琥珀酸(DTSA)、氨基酸的脂肪酸衍生物、磺基-琥珀酸的二酯和单酯或肥皂、及其组合。
阳离子型表面活性剂的非限制性例子包括烷基二甲基乙醇胺季铵化合物(ADMEAQ)、十六烷基三甲基溴化铵(CTAB)、二甲基双十八烷基氯化铵(DSDMAC)和烷基苯甲基二甲铵、及其组合。
当包括在其中时,去污剂通常会含有按重量计约0.2%-约40%,例如约0.5%-约30%,特别是约1%-约20%、约3%-约10%,例如约3%-约5%、或约8%-约12%的非离子型表面活性剂。非离子型表面活性剂的非限制性例子包括醇乙氧基化物(AE或AEO)、醇丙氧基化物、丙氧基化脂肪醇(PFA)、烷氧基化脂肪酸烷基酯,例如乙氧基化和/或丙氧基化脂肪酸烷基酯、烷基酚乙氧基化物(APE)、壬基酚乙氧基化物(NPE)、烷基多糖苷(APG)、烷氧基化胺、脂肪酸单乙醇酰胺(FAM)、脂肪酸二乙醇酰胺(FADA)、乙氧基化脂肪酸单乙醇酰胺(EFAM)、丙氧基化脂肪酸单乙醇酰胺(PFAM)、多羟基烷基脂肪酰胺、或葡糖胺的N-酰基N-烷基衍生物(葡糖酰胺,GA,或脂肪酸葡糖酰胺,FAGA),以及以商品名SPAN和TWEEN获得的产品,及其组合。
半极性表面活性剂的非限制性例子包括氧化胺(AO)例如烷基二甲基氧化胺、N-(椰油烷基)-N,N-二甲基氧化胺和N-(牛脂-烷基)-N,N-双(2-羟乙基)氧化胺、脂肪酸链烷醇酰胺和乙氧基化脂肪酸链烷醇酰胺、及其组合。
两性离子型表面活性剂的非限制性例子包括甜菜碱、烷基二甲基甜菜碱、和磺基甜菜碱、及其组合。
增洁剂或络合剂
去污剂可以含有0-65%去污剂增洁剂或络合剂,例如沸石、二磷酸盐、三磷酸盐、膦酸盐、碳酸盐、柠檬酸盐、次氮基三乙酸、乙二胺四乙酸、二乙烯三胺五乙酸、烷基或烯基琥珀酸、可溶性硅酸盐或层状硅酸盐(例如来自Hoechst的SKS-6)。
在洗碟洗涤去污剂中,增洁剂的水平一般为40-65%,特别是50-65%。增洁剂和/或共增洁剂(co-builder)可以特别是螯合剂,其与Ca和Mg形成水溶性络合物。增洁剂的非限制性例子包括沸石、二磷酸盐(焦磷酸盐)、三磷酸盐例如三磷酸钠(STP或STPP)、碳酸盐例如碳酸钠、可溶性硅酸盐例如偏硅酸钠、层状硅酸盐(例如来自Hoechst的SKS-6)、乙醇胺例如2-氨基乙-1-醇(MEA)、亚氨基二乙醇(DEA)和2,2’,2”-次氮基三乙醇(TEA)、和羧甲基菊粉(CMI)、及其组合。
去污剂组合物可以包括单独或与增洁剂例如沸石增洁剂组合的共增洁剂。共增洁剂的非限制性例子包括聚丙烯酸盐的同聚物或其共聚物,例如聚(丙烯酸)(PAA)或共聚(丙烯酸/马来酸)(PAA/PMA)。进一步的非限制性例子包括柠檬酸盐、螯合剂例如氨基羧酸盐、氨基多羧酸盐和膦酸盐、和烷基或烯基琥珀酸。另外的特定例子包括2,2’,2”-次氮基三乙酸(NTA)、乙二胺四乙酸(EDTA)、二乙烯三胺五乙酸(DTPA)、亚氨基二琥珀酸(IDS)、乙二胺-N,N’-二琥珀酸(EDDS)、甲基甘氨酸二乙酸(MGDA)、谷氨酸-N,N-二乙酸(GLDA)、1-羟基乙烷-1,1-二基双(膦酸)(HEDP)、乙二胺四(甲叉)四(膦酸)(EDTMPA)、二乙烯三胺五(甲叉)五(膦酸)(DTPMPA)、N-(2-羟乙基)亚氨基二乙酸(EDG)、天冬氨酸-N-单乙酸(ASMA)、天冬氨酸-N,N-二乙酸(ASDA)、天冬氨酸-N-单丙酸(ASMP)、亚氨基二琥珀酸(IDA)、N-(2-磺甲基)天冬氨酸(SMAS)、N-(2-磺乙基)天冬氨酸(SEAS)、N-(2-磺甲基)谷氨酸(SMGL)、N-(2-磺乙基)谷氨酸(SEGL)、N-甲基亚氨基二乙酸(MIDA)、α-丙氨酸-N,N-二乙酸(α-ALDA)、丝氨酸-N,N-二乙酸(SEDA)、异丝氨酸-N,N-二乙酸(ISDA)、苯丙氨酸-N,N-二乙酸(PHDA)、邻氨基苯甲酸-N,N-二乙酸(ANDA)、磺胺酸-N,N-二乙酸(SLDA)、牛磺酸-N,N-二乙酸(TUDA)和磺甲基-N,N-二乙酸(SMDA)、N-(羟乙基)-乙二胺三乙酸盐(N-(hydroxyetheyl)-ethylidenediaminetriacetate)(HEDTA)、二乙醇甘氨酸(DEG)、二亚乙基三胺五(甲叉膦酸)(DTPMP)、氨基三(甲叉膦酸)(ATMP)、及其组合和盐。进一步的示例性增洁剂和/或共增洁剂在例如WO 09/102854、US 5977053中描述。
聚合物
去污剂可以包含一种或多种聚合物。例子是羧甲基纤维素、聚(乙烯吡咯烷酮)、聚(乙二醇)、聚(乙烯醇)、聚(乙烯吡啶-N-氧化物)、聚(乙烯咪唑)、聚羧酸盐例如聚丙烯酸盐、马来酸/丙烯酸共聚物和月桂基甲基丙烯酸盐/丙烯酸共聚物。
漂白体系
去污剂可以含有漂白体系,其可以包含H2O2来源例如过硼酸盐或过碳酸盐,其可以与过酸形成漂白活化剂例如四乙酰乙二胺或壬酰氧苯磺酸盐组合。可替代地,漂白体系可以包含例如酰胺、亚胺或砜类型的过酸。
合适的漂白体系组分包括漂白催化剂、光漂白剂、漂白活化剂、过氧化氢来源例如过碳酸钠和过硼酸钠、预制成的过酸及其混合物。合适的预制成的过酸包括但不限于过氧羧酸和盐、过碳酸和盐、过亚胺酸和盐、过一硫酸和盐例如臭氧(R)、及其混合物。漂白体系的非限制性例子包括与过酸形成漂白活化剂组合的基于过氧化物的漂白体系,其可以包含例如无机盐,包括碱金属盐例如过硼酸盐的钠盐(通常为单或四水合物)、过碳酸盐、过硫酸盐、过磷酸盐、过硅酸盐。合适的光漂白剂可以例如是磺化锌酞菁。合适的漂白活化剂包括4-(十二烷酰氧基)苯磺酸盐(LOBS)、4-(癸酰氧基)苯磺酸盐、4-(癸酰氧基)苯甲酸盐(DOBS)、4-(3,5,5-三甲基己酰氧基)苯磺酸盐(ISONOBS)、四乙酰基乙二胺(TAED)和4-(壬酰氧基)苯磺酸盐(NOBS)和/或公开于WO98/17767中的那些。可替代地,漂白体系可以包含例如酰胺、亚胺或砜类型的过酸。漂白体系还可以包含过酸例如6-(邻苯二甲酰氨基)过己酸(PAP)。漂白体系还可以包括漂白催化剂。在一些实施方案中,漂白组分可以是选自具有下式的有机催化剂的有机催化剂:
(iii)及其混合物;其中每个R1独立地是含有9–24个碳的支链烷基或含有11–24个碳的直链烷基,优选地,每个R1独立地是含有9–18个碳的支链烷基或含有11–18个碳的直链烷基,更优选地,每个R1独立地选自2-丙基庚基、2-丁基辛基、2-戊基壬基、2-己基癸基、正十二烷基、正十四烷基、正十六烷基、正十八烷基、异壬基、异癸基、异十三烷基和异十五烷基。其他示例性漂白体系例如在WO2007/087258、WO2007/087244、WO2007/087259、WO2007/087242中描述。
助水溶物
助水溶物是溶解水溶液中的疏水化合物(或相反地,非极性环境中的极性物质)的化合物。一般地,助水溶物具有亲水和疏水两种特征(如由表面活性剂已知的所谓的两亲性质);然而,助水溶物的分子结构一般不支持自发性自聚集,参见例如通过Hodgdon和Kaler(2007),Current Opinion in Colloid&Interface Science 12:121-128的综述。如对于表面活性剂和脂质形成微团、薄层或其他定义明确的中间相发现的,助水溶物不显示超过该浓度即发生自聚集的临界浓度。相反,许多助水溶物显示连续类型的聚集过程,其中聚集物的大小随着浓度增加而增长。然而,许多助水溶物改变含有极性和非极性特征的物质的体系的相行为、稳定性和胶体性质,包括水、油、表面活性剂和聚合物的混合物。助水溶物常规地跨越从药学(pharma)、个人护理、食品到技术应用的工业使用。助水溶物在去污剂组合物中的使用允许例如更浓缩的表面活性剂制剂(如在通过去除水来压缩液体去污剂的工艺中),而不诱导不希望有的现象例如相分离或高粘度。
去污剂可以含有按重量计0-5%、例如约0.5-约5%或约3%-约5%的助水溶物。助水溶物的非限制性例子包括苯磺酸钠、对甲苯磺酸钠(STS)、二甲苯磺酸钠(SXS)、异丙苯磺酸钠(SCS)、伞花烃磺酸钠、氧化胺、醇和聚乙二醇醚、羟基萘甲酸钠、羟基萘磺酸钠、乙基己基硫酸钠及其组合。
织物固色剂(Fabric hueing agents)
本发明的去污剂组合物还可以包括织物固色剂例如染料或色素,当配制在去污剂组合物中时,当所述织物与包含所述去污剂组合物的洗液接触时,所述织物固色剂可以沉积到织物上,从而通过可见光的吸收/反射改变所述织物的色调。荧光增白剂发出至少某些可见光。相比之下,当织物固色剂吸收至少部分可见光谱时,它们改变表面的色调。合适的织物固色剂包括染料和染料-粘土缀合物,并且还可以包括色素。合适的染料包括小分子染料和聚合染料。合适的小分子染料包括选自下述的小分子染料:属于Direct Blue、DirectRed、Direct Violet、Acid Blue、Acid Red、Acid Violet、Basic Blue、Basic Violet和Basic Red的颜色指数(C.I.)分类的染料,或其混合物,例如如WO2005/03274、WO2005/03275、WO2005/03276和EP1876226(在此引入作为参考)中所述的。去污剂组合物优选包含约0.00003重量%-约0.2重量%、约0.00008重量%-约0.05重量%、或甚至约0.0001重量%-约0.04重量%织物固色剂。该组合物可以包含0.0001重量%-0.2重量%织物固色剂,当该组合物是单位剂量小袋的形式时,这可以是尤其优选的。合适的固色剂还公开于例如WO 2007/087257、WO2007/087243中。
去污剂制剂
酶颗粒剂可以包括在如WO09/092699、EP1705241、EP1382668、WO07/001262、US6472364、WO04/074419或WO09/102854中所述配制的颗粒状去污剂中。其他有用的去污剂制剂在下述中描述:WO09/124162、WO09/124163、WO09/117340、WO09/117341、WO09/117342、WO09/072069、WO09/063355、WO09/132870、WO09/121757、WO09/112296、WO09/112298、WO09/103822、WO09/087033、WO09/050026、WO09/047125、WO09/047126、WO09/047127、WO09/047128、WO09/021784、WO09/010375、WO09/000605、WO09/122125、WO09/095645、WO09/040544、WO09/040545、WO09/024780、WO09/004295、WO09/004294、WO09/121725、WO09/115391、WO09/115392、WO09/074398、WO09/074403、WO09/068501、WO09/065770、WO09/021813、WO09/030632、WO09/015951、WO2011025615、WO2011016958、WO2011005803、WO2011005623、WO2011005730、WO2011005844、WO2011005904、WO2011005630、WO2011005830、WO2011005912、WO2011005905、WO2011005910、WO2011005813、WO2010135238、WO2010120863、WO2010108002、WO2010111365、WO2010108000、WO2010107635、WO2010090915、WO2010033976、WO2010033746、WO2010033747、WO2010033897、WO2010033979、WO2010030540、WO2010030541、WO2010030539、WO2010024467、WO2010024469、WO2010024470、WO2010025161、WO2010014395、WO2010044905、WO2010145887、WO2010142503、WO2010122051、WO2010102861、WO2010099997、WO2010084039、WO2010076292、WO2010069742、WO2010069718、WO2010069957、WO2010057784、WO2010054986、WO2010018043、WO2010003783、WO2010003792、WO2011023716、WO2010142539、WO2010118959、WO2010115813、WO2010105942、WO2010105961、WO2010105962、WO2010094356、WO2010084203、WO2010078979、WO2010072456、WO2010069905、WO2010076165、WO2010072603、WO2010066486、WO2010066631、WO2010066632、WO2010063689、WO2010060821、WO2010049187、WO2010031607或WO2010000636。
实施例
实施例1:
典型的制剂是如例如WO 2004/003188(国际申请号PCT/DK03/000456)的实施例1中产生的高剪切T-颗粒剂(含有酶、硫酸钠、纤维素纤维、碳酸钙和粘合剂例如蔗糖或糊精),在核心中具有下述制剂(按无涂层的干燥颗粒剂的重量计的%):
·按重量计2%的硫代硫酸钠或按重量计2%的甲硫氨酸
·按重量计5%的七水硫酸镁
·按重量计2%的二水柠檬酸钠
·按重量计0.5%的一水柠檬酸(至酶浓缩饲料中4.5-5的pH)
这些稳定剂优选在造粒前加入含水酶浓缩物中。
在造粒且干燥后,在流化床中在相对潮湿的条件(在排出的空气中按重量计约50%的RH)下应用按重量计25%(按干燥无涂层的颗粒剂的重量计的%)的硫酸钠涂层(例如如WO03/000456的实施例4中产生的)。在流化床中进一步应用化妆品和粉尘减少外部薄膜(例如PEG4000、高岭土和TiO2)。
残留活性基于洗涤性能分析,即50%残留活性指示在贮存后的洗涤性能对应于具有50%酶剂量的未经贮存去污剂的那种。在含漂白剂的去污剂中在37℃和按重量计70%RH贮存1周后,如果排除稳定技术之一,则残留活性一般小于按重量计10%,并且如果存在所有四种技术,则一般为按重量计>75%。使用具有含漂白剂的去污剂的小型洗涤机器人(60ml洗涤溶液)测量洗涤性能,使用15°dH的水硬度、在40℃在30分钟内洗涤,去污剂剂量5g/L且在基于米淀粉的样片(来自荷兰的CFT的CS-28)上测量反射率(在Zeiss分光光度计上460nm)。
实施例2:
用下述组成制备淀粉酶颗粒剂。给出与原始(无涂层的)颗粒剂有关的量。颗粒剂通过高剪切制粒制备且通过流化床涂覆涂布
实施例3:
通过混合如下表中所示的酶和稳定剂且在混合器中造粒来制备许多酶颗粒剂。如所示的应用盐涂层和膜涂层。随后将每种颗粒剂加入颗粒状漂白去污剂中且贮存于37℃、70%相对湿度。测试的酶是两种芽孢杆菌属淀粉酶变体(分别指定为淀粉酶X和Y)。量作为与核心的重量有关的按重量计的%给出。膜涂层以按核心的重量计3%的量应用。膜涂层由Sepifilm LP030(作为成膜聚合物的羟丙甲纤维素(HPMC)、微晶纤维素(MCC)和硬脂酸的混合物)组成。
淀粉酶颗粒剂作为与WO 2004/003188的实施例2中一样的高剪切T-颗粒剂(基于含水淀粉酶浓缩物、纤维素纤维和作为填充剂的硫酸钠)产生。在造粒且干燥后,在流化床中应用硫酸钠涂层(来自硫酸钠溶液)。
通过在3天和7天贮存后测定洗涤性能估计颗粒剂的贮存稳定性。结果显示于下文(基于洗涤性能的贮存稳定性数据如上所述以%残留活性给出)。
结果证实加入还原剂/抗氧化剂、多价阳离子、微量酸性缓冲剂且应用盐涂层的协同效应。因此,关于颗粒剂B和C的结果比较显示加入多价阳离子的效应;关于颗粒剂A和D的结果比较显示加入微量酸性缓冲剂的效应;关于颗粒剂B和D的结果比较或比较G和H与E和F显示加入还原剂/抗氧化剂的效应;并且关于颗粒剂I和J与E和F的结果比较显示应用盐涂层的效应。颗粒剂G显示没有膜涂层也可以获得极佳的稳定效应。K和J显示将过氧化物分解催化剂加入盐涂层中的效应。
实施例4:
纤维素酶颗粒剂作为与WO 2004/003188的实施例2中一样的高剪切T-颗粒剂(基于纤维素纤维和作为填充剂的硫酸钠)产生,并且在核心中包括下述稳定剂(按无涂层的干燥颗粒剂的重量计的%):
·2%硫代硫酸钠
·5%七水硫酸镁
·2%二水柠檬酸钠
·0.5%一水柠檬酸(至酶浓缩饲料中4.5-5的pH)
这些稳定剂在造粒前加入含水酶浓缩物中。
在造粒且干燥后,在流化床中应用按重量计27%(按干燥无涂层的颗粒剂的重量计的%)的硫酸钠:TiO2 25:2w/w涂层(来自25:2:73硫酸钠:TiO2:水溶液)。在流化床中进一步应用化妆品和粉尘减少外部薄膜(2.5%PEG4000:TiO2 1:1w/w)。
将一部分无涂层的颗粒剂在混合器中用8%熔化的PEG4000和14%TiO2:碳酸钙1:3w/w进行涂蜡。
实施例5(参考):
纤维素酶颗粒剂作为与WO 2004/003188的实施例2中一样的高剪切T-颗粒剂(基于纤维素纤维和作为填充剂的硫酸钠)产生,无需添加稳定剂。
在造粒且干燥后,在流化床中应用按重量计27%(按干燥无涂层的颗粒剂的重量计的%)的硫酸钠:TiO2 25:2w/w涂层(来自25:2:73硫酸钠:TiO2:水溶液)。在流化床中进一步应用化妆品和粉尘减少外部薄膜(2.5%PEG4000:TiO21:1w/w)。
将一部分无涂层的颗粒剂在混合器中用8%熔化的PEG4000和14%TiO2:碳酸钙1:3进行涂布。
在37℃和55%相对湿度经过8周后测试来自实施例4和5的4种颗粒剂在含漂白剂的去污剂中的稳定性(通过标准纤维素酶测定测量的残留活性):
可以观察到对于涂蜡的颗粒剂加入稳定剂实际上略微减少稳定性,而对于盐涂布的颗粒剂加入稳定剂显著改善稳定性。具有稳定剂和盐涂层二者的颗粒剂显著优于其他样品。
实施例6:
碱性蛋白酶颗粒剂作为与WO 2004/003188的实施例2中一样的高剪切T-颗粒剂(基于喷雾干燥的蛋白酶、纤维素纤维和作为填充剂的硫酸钠)产生,在核心中具有下述稳定剂(按无涂层的干燥颗粒剂的重量计的%):
·0.7%硫代硫酸钠
·5%七水硫酸镁
·2.1%二水柠檬酸钠
·0.5%一水柠檬酸
这些稳定剂在造粒前加入造粒液体(水)中。
在造粒且干燥后,在流化床中应用按重量计27%(按干燥无涂层的颗粒剂的重量计的%)的硫酸钠:TiO2:糊精25:1:1w/w涂层(来自25:1:1:73硫酸钠:TiO2:糊精:水溶液)。在流化床中进一步应用化妆品和粉尘减少外部薄膜(2.0%PEG4000:TiO2:高岭土4:3:3w/w)。
实施例7(参考):
碱性蛋白酶颗粒剂作为与WO 2004/003188的实施例2中一样的高剪切T-颗粒剂(基于喷雾干燥的蛋白酶、纤维素纤维和作为填充剂的硫酸钠)产生,在核心中具有下述稳定剂(按无涂层的干燥颗粒剂的重量计的%):
·0.7%硫代硫酸钠
稳定剂在造粒前加入造粒液体(水)中。
将无涂层的颗粒剂在混合器中用6%熔化的PEG4000和14%TiO2:碳酸钙1:1进行涂布。
在37℃和70%相对湿度经过2周后测试来自实施例6和7的2种颗粒剂在含漂白剂的去污剂中的稳定性(通过标准蛋白酶测定测量的残留活性):
ID | 核心中的稳定剂 | 涂层 | %残留活性 |
实施例6盐涂层 | 是 | 硫酸钠 | 91% |
实施例7蜡涂层 | 否 | 蜡 | 16% |
具有盐涂层的稳定剂混合物显著增加蛋白酶的贮存稳定性。
Claims (19)
1.一种包含核心和保护涂层的颗粒剂,其中:
a)所述核心包含淀粉酶、脂肪酶、蛋白酶、纤维素酶、甘露聚糖酶或果胶酸裂合酶,
并且
b)所述核心包含相对于所述核心按重量计以0.1-5%的量存在的硫代硫酸盐或甲硫氨酸,并且
c)所述核心包含按所述核心的重量计以0.1-10%的量存在的作为无水盐的镁盐或锌盐,并且
d)所述核心包含相对于所述核心按重量计以0.1-10%的量存在的柠檬酸和柠檬酸盐的混合物的酸性缓冲剂组分,并且
e)所述涂层包含盐,其中相对于所述核心按重量计涂层构成5-70%,并且包含在20℃下具有至少60%恒定湿度的按重量计至少60%的盐。
2.权利要求1所述的颗粒剂,其中所述核心包含淀粉酶。
3.权利要求1或2所述的颗粒剂,其中所述核心包含以相对于所述核心重量计0.05%-20%的量的淀粉酶、脂肪酶、蛋白酶、纤维素酶、甘露聚糖酶或果胶酸裂合酶。
4.权利要求1或2所述的颗粒剂,其中所述镁或锌的盐是镁或锌的硫酸盐、盐酸盐或乙酸盐。
5.权利要求1或2所述的颗粒剂,其中所述镁或锌的盐是硫酸镁或硫酸锌。
6.权利要求1或2所述的颗粒剂,其中所述镁或锌的盐按所述核心重量计以0.02-4%存在,以多价阳离子计算。
7.权利要求1或2所述的颗粒剂,其中所述酸性缓冲剂组分以相对于所述核心重量计1-5%的量存在。
8.权利要求1或2所述的颗粒剂,其中所述涂层中的盐具有至少80%的恒定湿度。
9.权利要求1或2所述的颗粒剂,其中所述涂层包含按重量计至少75%的盐。
10.权利要求9所述的颗粒剂,其中所述涂层包含按重量计至少95%的盐。
11.权利要求1或2所述的颗粒剂,其中所述盐涂层包含硫酸钠。
12.权利要求1或2所述的颗粒剂,其中所述涂层占相对于所述核心重量计的10-50%。
13.权利要求12所述的颗粒剂,其中所述涂层占相对于所述核心重量计的10-30%。
14.权利要求1或2所述的颗粒剂,其进一步包含在所述盐涂层的外部上的额外涂层,其中所述额外涂层包含成膜剂。
15.权利要求14的颗粒剂,其中所述额外涂层包含聚乙二醇、羟丙基甲基纤维素或聚乙烯醇(PVA)。
16.一种颗粒状去污剂组合物,其包含表面活性剂和任一前述权利要求的颗粒剂。
17.权利要求16的去污剂组合物,其进一步包括漂白体系。
18.权利要求17的去污剂组合物,其中所述漂白体系包含H2O2源。
19.权利要求18的去污剂组合物,其中所述漂白体系包含过硼酸盐或过碳酸盐。
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US9107433B2 (en) | 2015-08-18 |
AU2011246662A1 (en) | 2012-10-25 |
JP2013529072A (ja) | 2013-07-18 |
CA2797032A1 (en) | 2011-11-03 |
EP2840134A1 (en) | 2015-02-25 |
US20130040872A1 (en) | 2013-02-14 |
PL2840134T3 (pl) | 2018-02-28 |
EP3279319B1 (en) | 2020-06-10 |
MX2012012096A (es) | 2012-12-17 |
KR20130066612A (ko) | 2013-06-20 |
EP2563910B1 (en) | 2015-09-30 |
JP5944887B2 (ja) | 2016-07-05 |
RU2573907C2 (ru) | 2016-01-27 |
ZA201207687B (en) | 2013-06-26 |
CN102906251B (zh) | 2016-11-16 |
KR101904484B1 (ko) | 2018-11-30 |
EP3279319A1 (en) | 2018-02-07 |
ES2646166T3 (es) | 2017-12-12 |
WO2011134809A1 (en) | 2011-11-03 |
CN102906251A (zh) | 2013-01-30 |
AU2011246662B2 (en) | 2014-09-25 |
BR112012024674A2 (pt) | 2016-06-07 |
EP2563910A1 (en) | 2013-03-06 |
MX349735B (es) | 2017-08-10 |
BR112012024674B1 (pt) | 2019-07-02 |
CN106978403A (zh) | 2017-07-25 |
RU2012150279A (ru) | 2014-06-10 |
EP2840134B1 (en) | 2017-08-30 |
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