CA2052077A1 - Detergent composition - Google Patents
Detergent compositionInfo
- Publication number
- CA2052077A1 CA2052077A1 CA002052077A CA2052077A CA2052077A1 CA 2052077 A1 CA2052077 A1 CA 2052077A1 CA 002052077 A CA002052077 A CA 002052077A CA 2052077 A CA2052077 A CA 2052077A CA 2052077 A1 CA2052077 A1 CA 2052077A1
- Authority
- CA
- Canada
- Prior art keywords
- detergent composition
- composition according
- liquid
- detergent
- stabiliser
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 116
- 239000003599 detergent Substances 0.000 title claims abstract description 79
- 102000004190 Enzymes Human genes 0.000 claims abstract description 60
- 108090000790 Enzymes Proteins 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 49
- 230000002366 lipolytic effect Effects 0.000 claims abstract description 46
- 230000003019 stabilising effect Effects 0.000 claims abstract description 20
- 108090001060 Lipase Proteins 0.000 claims description 40
- 102000004882 Lipase Human genes 0.000 claims description 40
- 239000003381 stabilizer Substances 0.000 claims description 40
- 239000004367 Lipase Substances 0.000 claims description 34
- 235000019421 lipase Nutrition 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 31
- 108091005804 Peptidases Proteins 0.000 claims description 25
- 102000035195 Peptidases Human genes 0.000 claims description 25
- 239000003792 electrolyte Substances 0.000 claims description 23
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 239000011149 active material Substances 0.000 claims description 10
- 238000005185 salting out Methods 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000000344 soap Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910003204 NH2 Inorganic materials 0.000 claims description 2
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical group [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 3
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 11
- 229940088598 enzyme Drugs 0.000 description 54
- 108010020132 microbial serine proteinases Proteins 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 15
- 239000004094 surface-active agent Substances 0.000 description 14
- 239000011734 sodium Substances 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- 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 12
- -1 N-acetyl casein Chemical compound 0.000 description 11
- 239000004615 ingredient Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 229940024999 proteolytic enzymes for treatment of wounds and ulcers Drugs 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000006641 stabilisation Effects 0.000 description 8
- 239000004365 Protease Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-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
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 235000019419 proteases Nutrition 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- HXITXNWTGFUOAU-UHFFFAOYSA-N dihydroxy-phenylborane Natural products OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 5
- TYIKXPOMOYDGCS-UHFFFAOYSA-N (2,3-dichlorophenyl)boronic acid Chemical compound OB(O)C1=CC=CC(Cl)=C1Cl TYIKXPOMOYDGCS-UHFFFAOYSA-N 0.000 description 4
- QPKFVRWIISEVCW-UHFFFAOYSA-N 1-butane boronic acid Chemical compound CCCCB(O)O QPKFVRWIISEVCW-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- QBLFZIBJXUQVRF-UHFFFAOYSA-N (4-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Br)C=C1 QBLFZIBJXUQVRF-UHFFFAOYSA-N 0.000 description 3
- 108010056079 Subtilisins Proteins 0.000 description 3
- 102000005158 Subtilisins Human genes 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000009260 cross reactivity Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 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
- 238000009472 formulation Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 230000001900 immune effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 125000003703 phosphorus containing inorganic group Chemical group 0.000 description 2
- 229940081066 picolinic acid Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 230000002797 proteolythic effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- QNEGDGPAXKYZHZ-UHFFFAOYSA-N (2,4-dichlorophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Cl)C=C1Cl QNEGDGPAXKYZHZ-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 241000588986 Alcaligenes Species 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- OPEGATMYTNYFQQ-UHFFFAOYSA-N B(O)O.CCCCCCCCCCCCCCCCCC Chemical compound B(O)O.CCCCCCCCCCCCCCCCCC OPEGATMYTNYFQQ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- MFMJAIAPTREHPB-UHFFFAOYSA-N ClOBOCl Chemical compound ClOBOCl MFMJAIAPTREHPB-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 108010067770 Endopeptidase K Proteins 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 108090000787 Subtilisin Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 1
- 241000223258 Thermomyces lanuginosus Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 125000005620 boronic acid group Chemical group 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 229940042399 direct acting antivirals protease inhibitors Drugs 0.000 description 1
- PMPJQLCPEQFEJW-HPKCLRQXSA-L disodium;2-[(e)-2-[4-[4-[(e)-2-(2-sulfonatophenyl)ethenyl]phenyl]phenyl]ethenyl]benzenesulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC=C1\C=C\C1=CC=C(C=2C=CC(\C=C\C=3C(=CC=CC=3)S([O-])(=O)=O)=CC=2)C=C1 PMPJQLCPEQFEJW-HPKCLRQXSA-L 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000010353 genetic engineering Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 229940045996 isethionic acid Drugs 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- JMZFEHDNIAQMNB-UHFFFAOYSA-N m-aminophenylboronic acid Chemical compound NC1=CC=CC(B(O)O)=C1 JMZFEHDNIAQMNB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000001683 neutron diffraction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000000137 peptide hydrolase inhibitor Substances 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical class [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 235000013966 potassium salts of fatty acid Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 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 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D3/38663—Stabilised liquid enzyme compositions
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)
- Detergent Compositions (AREA)
- Enzymes And Modification Thereof (AREA)
Abstract
C7248 (R) ABSTRACT
DETERGENT COMPOSITION
The stability of lipolytic enzymes in detergent compositions can be improved by addition of a stabilising material which is capable of reversibly forming a complex with the active site of the lipolytic enzyme. Preferred stabilising materials are bornic acid derviatives.
DETERGENT COMPOSITION
The stability of lipolytic enzymes in detergent compositions can be improved by addition of a stabilising material which is capable of reversibly forming a complex with the active site of the lipolytic enzyme. Preferred stabilising materials are bornic acid derviatives.
Description
5~
l C 72~8 (R) Detergent composition The present invention relates to detergent compositions comprising a lipolytic enzyme. In particular the present invention relates to liguid detergent compositions comprising a lipolytic enzyme.
It has previously been suggested to incorporate lipolytic enzymes into detergent compositions. For example US 4,566,985 (Applied Biochemists, Inc) describes the combined use of cellulase, protease, amylase and lipase type enzymes in liquid detergent compositions.
A problem in using lipolytic enzymes in detergent compositions is often the occurrence of enzyme instability, leading to a reduction in enzyme activity upon use of the compositions, for example in the washing of fabrics. These instability problems are especially apparent in detergent compositions comprising lipolytic enzymes in combination with proteolytic enzymes.
Surprisingly it has now been found that the stability of lipolytic enzymes in detergent compositions can markedly be improved by the use of a stabilising material which is capable of reversibly forming a complex with the active site of the lipolytic enzyme, said stabiliser-enzyme complex being less prone to destabilisation reactions.
Preferably the formation of a stabiliser-lipolytic enzyme complex prevents the destabilisation reaction i.e between lipolytic enzymes and proteolytic enzymes and/or 7~
l C 72~8 (R) Detergent composition The present invention relates to detergent compositions comprising a lipolytic enzyme. In particular the present invention relates to liguid detergent compositions comprising a lipolytic enzyme.
It has previously been suggested to incorporate lipolytic enzymes into detergent compositions. For example US 4,566,985 (Applied Biochemists, Inc) describes the combined use of cellulase, protease, amylase and lipase type enzymes in liquid detergent compositions.
A problem in using lipolytic enzymes in detergent compositions is often the occurrence of enzyme instability, leading to a reduction in enzyme activity upon use of the compositions, for example in the washing of fabrics. These instability problems are especially apparent in detergent compositions comprising lipolytic enzymes in combination with proteolytic enzymes.
Surprisingly it has now been found that the stability of lipolytic enzymes in detergent compositions can markedly be improved by the use of a stabilising material which is capable of reversibly forming a complex with the active site of the lipolytic enzyme, said stabiliser-enzyme complex being less prone to destabilisation reactions.
Preferably the formation of a stabiliser-lipolytic enzyme complex prevents the destabilisation reaction i.e between lipolytic enzymes and proteolytic enzymes and/or 7~
2 C 7248 (R) improves the resistance against denaturation and against proteolytic breakdown of the lipolytic enzyme, such that the half-life time of the lipase in the composition at 37C is increased by a least 25 %, more preferably at least 50 %, most preferably at least 100 %~ For the purpose of this invention, the half-life time of the lipolytic enzyme is the time-period starting at the moment of preparation of the detergent fGrmulation until the moment that only 50% of the enzyme-activity is left.
Most preferably the stabilisation reaction is an inhibitory reaction, whereby the stabiliser-lipolytic enzyme complex is inactivated.
The reversibility of complex formation can generally be effected by adding the stabilisation material in a concentration of from 2 to 100 times the Ki, wherein the Ki is the concentration at which 50 % of the lipase enzymes have formed the complex~ More preferably the concentration is from 5-25 times the Ki, most preferably from 8 to 15 times. In use the detergent composition will generally be diluted 50 to 500 times, especially about 100 times, providing a concentration of stabiliser such that the stabiliser-lipolytic enzyme complex will be dissociated, thus providing active lipolytic enzymes in the wash liquor.
Accordingly the present invention relates to a detergent composition comprising a lipolytic enzyme and a stabilising material capable of reversibly forming a complex with the active site of the lipolytic enzyme, therewith increasing the half-lifetime of the lipase material.
~5~7 ~' 3 c 7248 (R) In a preferred embodiment of the invention the stabiliser material is added to the detergent composition in a concentration of from 2 to 100 times the Ki.
For the purpose of the present invention any material capable of reversible forming a complex with the active site of the lipolytic enzyme may be used. In a preferred embodiment of the invention, boronic acid materials are used.
Surprisingly it has now been found that the stability of lipolytic enzymes in detergent compositions can markedly be improved by specific boronic acid derivatives as stabilising m~terials. Boronic acid derivatives which are especially advantageous for stabilising lipase enzymes are of the following formula:
R1---(Ph)n---B \ (I) wherein:
Ph is a phenyl group, optionally substituted by haloyen groups or NH2 groups;
n is O or l;
R1 is Hydrogen, halogen, NH2 or a Cl_24 alkyl or alkenyl group, Provided that when n is O then R1 contains at least 3, most preferably 8-20 carbon atoms;
R2 and R3 are independently selected from -OH, -Cl, -F, -Br and Cl_8 alkyl or alkenyl groups.
2~5~
Most preferably the stabilisation reaction is an inhibitory reaction, whereby the stabiliser-lipolytic enzyme complex is inactivated.
The reversibility of complex formation can generally be effected by adding the stabilisation material in a concentration of from 2 to 100 times the Ki, wherein the Ki is the concentration at which 50 % of the lipase enzymes have formed the complex~ More preferably the concentration is from 5-25 times the Ki, most preferably from 8 to 15 times. In use the detergent composition will generally be diluted 50 to 500 times, especially about 100 times, providing a concentration of stabiliser such that the stabiliser-lipolytic enzyme complex will be dissociated, thus providing active lipolytic enzymes in the wash liquor.
Accordingly the present invention relates to a detergent composition comprising a lipolytic enzyme and a stabilising material capable of reversibly forming a complex with the active site of the lipolytic enzyme, therewith increasing the half-lifetime of the lipase material.
~5~7 ~' 3 c 7248 (R) In a preferred embodiment of the invention the stabiliser material is added to the detergent composition in a concentration of from 2 to 100 times the Ki.
For the purpose of the present invention any material capable of reversible forming a complex with the active site of the lipolytic enzyme may be used. In a preferred embodiment of the invention, boronic acid materials are used.
Surprisingly it has now been found that the stability of lipolytic enzymes in detergent compositions can markedly be improved by specific boronic acid derivatives as stabilising m~terials. Boronic acid derivatives which are especially advantageous for stabilising lipase enzymes are of the following formula:
R1---(Ph)n---B \ (I) wherein:
Ph is a phenyl group, optionally substituted by haloyen groups or NH2 groups;
n is O or l;
R1 is Hydrogen, halogen, NH2 or a Cl_24 alkyl or alkenyl group, Provided that when n is O then R1 contains at least 3, most preferably 8-20 carbon atoms;
R2 and R3 are independently selected from -OH, -Cl, -F, -Br and Cl_8 alkyl or alkenyl groups.
2~5~
4 ~ 7248 (R) Accordingly a second embodiment of the invention relates to a detergent composition comprising a lipolytic enzyme in combination with one or more boronic acid derivatives of formula I as indicated above.
Although applicants do not wish to be hound by any theory, it is believed that the stabilisation of the lipase enzyme by the boronic acid derivatives works via lQ an inhibitory mechanism, whereby the boronic acid derivative reacts with the active site o~ the lipolytic enzyme, therewith protecting the enzyme against destabilisation. In using the detergent composition, generally a dilution step will take place, for example by the addition of the detergent composition to the wash liquor. It is believed that due to this dilution, generally the protective boronic acid group will be detached form the active site of the lipolytic enzyme, therewith providing an active enzyme material under use conditions. This mechanism of stabilisation is believed to be especially advantageous if lipase enzymes are used in combination with proteolytic enzymes, because the boronic acid derivative tends to be bound to the active site of the lipase, therewith preventing the destabilisation reaction (= proteolytic breakdown) with the proteolytic enzyme.
Preferred borcnic acid derivatives are of the formula I, whereby at least of the groups R2 and R3 is -OH, most preferably groups R2 and ~3 both are -OH or one of these groups is -OH and the other is a Cl-8 alkyl or alkenyl group.
;2 ~5~077 C 7248 (R) For environmental reasons it is further preferred that the in formula I n is 0 and Rl is a C3-C24 group.
Especially preferred boronic acid derivatives are of the following formula;
OH
R4~ B ~ (II) wherein:
R4 is a phenyl group or a C8_24 alkyl or alkenyl group;
R5 is a -OH or a Cl_8 alkyl or alkenyl group.
The level of boronic acid derivatives in the detergent compositions according to the present invention may be varied within a broad range, dependant on the level of lipolytic enzyme and the reactivity of the boronic acid derivative. Generally the level of boronic acid derivatives will be from 0.00001 to 3 % by weight of the composition, more preferred from 0.0001 to 1 %, most preferred from 0.001 to 0.5 ~.
The added amount of lipolytic enzyme in the composition is preferably from 50-30,000 LU/g of detergent composition, whereby LU (lipase units) are defined as they are in EP 258 068. The level of lipolytic enzymes is often at least 100 LU/g, very usefully at least 250 LU/g, preferably less than 5000 LU/g, more preferably less than 2000 LU/g or less than 1000 LUtg.
The lipolytic enzyme can be chosen from among a wide range of lipases: in particular the lipases described in for example the following patent specifications, EP 214 761 (NOVO), EP 258 068 (NOVO) and EP 305 216 (NOVO), and especially lipolytic enzymes showing immunological ;~5~
6 C 7248 (R) cross-reactivity with antisera raised against lipases from Thermomyces lanuginosus ATCC 22070, EP 205 208 (UNILEVER) and EP 206 390 (UNILEVER), and especially lipases showing immunological cross-reactivity with antisera raised against lipase from Chromobacter viscosum var lipolyticum NRRL B-3673 , or against lipase from Alcaligenes PL-679, ATCC 31371 and FERM-P
3783, also the lipases described in specifications Wo 87/00859 (Gist-Brocades), WO 89/09263 (Gist Brocades), EP 331 376 (AMANO), DE 39 08 131 (Toyo Jozo) and EP 204 284 (SAPPORO BREWERIES). Suitable in particular are for example the following commercially available lipase preparations: Novo Lipolase, Amano Lipase CE, P, B, AP, M-AP, AML and CES, and Meito lipases MY-30, OF, and PL, also esterase MM. lipozym, SP 225, SP 285, Siaken lipase, Enzeco lipase, Toyo Jozo lipase and Diosynth lipase.
These commercially available enzymes are preferably used at levels of from 0.01 to 10 ~ by weight of the detergent composition, more preferred 0.05 to 5 %, most preferred 0.1 to 2 %, whereby the levels relate to the enzyme preparation in the form as supplied.
Also lipase enzymes produced by genetic engineering may be used, such as for example described in WO 89~09263 (Gist-Brocades) and EP 218 272 (Gist-Brocades) as well as EP 258 068 (Novo) and EP 305 216 (Novo).
As stated above the use of boronic acid derivatives for the stabilisation of lipolytic enzymes is especially advantageous for detergent compositions comprising lipases in combination with proteolytic enzymes.
~:~5~
7 C 7248 (R) Protease can preferably be included in the composition in amounts of the order of about 1 to 100 GU/mg detergent composition. Preferably the amount ranges from 2-50 and more preferably from 5 to 20 GU/mg. A GU is a Glycine unit, defined as the proteolytic enzyme activity which, under standard conditions, during a 15 minute incubation at 40C, with N-acetyl casein as substrate, produces an amount of NH2 groups equivalent to 1 micromole of glycine.
A preferred example of a protease enzyme which may be used in compositions according to the invention is the subtilisin variety sold as Savinase (TM of Novo-Nordisk A/S) or Maxacal (TM of Gist-Brocades/IBIS) or as Opticlean (ex MKC) or API22 (ex Showa Denko). Other useful examples of proteases include Maxatase, Esperase, Alcalase, proteinase K and subtilisin BPN', or variants obtained by enzyme engineering.
Commercially available proteolytic enzymes are preferably used at a level of from 0.01 to lO % by weight of the composition, more preferably 0.05 to 2 %, most preferred 0.1 to 2 %, whereby the levels relate to the enzyme preparation in the form as supplied.
Protease with a high isoelectric point (e.g Savinase or Maxacal) have been found more stable under the conditions generally encountered in detergent compositions of the invention. Particularly good results have been obtained while using a hiqh pI protease (ie pI
above 9, say about 10) in a liquid detergent composition of pH less than about 9.
~5.~(~7~
8 C 7248 (R) Detergent compositions of the invention may take any suitable physical form such as powders, pastes, tablets and liquids. A preferred embodiment of the present invention relates to liquid detergent compositions, in particular liquid detergent compositions comprising an aqueous phase.
Compositions of the present invention also comprise detergent active materials. In the widest definition the detergent active materials in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof. For example, they may be chosen from any of the classes, sub-classes and specific materials described in "Surface Active Agents" Vol. I, by Schwartz & Perry, Interscience 1949 and "Surface Active Agents" Vol. II by Schwartz, Perry & Berch (Interscience 1958), in the current edition of "McCutcheon's Emulsifiers & Detergents"
published by the McCutcheon division of Manufacturing Confectioners Company or in Tensid-Taschenbuch", H.
Stache, 2nd Edn., Carl Hanser Verlag, Munchen & Wien, 19~1 .
Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl tC6-C18) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the .eaction products of propylene oxide and ~ ~D 5 r~
9 C 7248 (R) ethylenediamine. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
Also possible is the use of salting out resistant active materials, such as for example described in EP 328 177, especially the use of alkyl poly glycoside surfactants, such as for example disclosed in EP 70 074.
Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alXyl radicals containing from about S to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (Cg-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts o~ sulphuric acid esters of higher (C8-C18) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products;
the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-C 7248 ~R) olefins (c8-C20) with sodium bisulphite and those derived from reacting paraffins with SO2 and C12 and then hydrolysing with a base to produce a random sulphonate; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly Cl~-C20 alpha-olefins, with SO3 and then neutralising and hydrolysing the reaction product. The preferred anionic detergent compounds are sodium (C11-C15) alkyl benzene sulphonates and sodium or potassium primary (C10-Cl8) alkyl sulphates.
It is also possible, and sometimes preferred, to include an alkali metal soap of a fatty acid, especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, and fatty acids derived from castor oil, alkylsuccinic acid, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof. The sodium or potassium soaps of these acids can be used.
In many (but not all) cases, the total detergent active material may be present at from 2% to 60% by weight of the total composition, for example from 5% to 50~ and typically from 10% to 40% by weight. However, one preferred class of compositions comprises at least 20%, most preferably at least 25% and especially at least 30%
of detergent active material based on the weight of the total composition.
Liquid detergent compositions of the invention may be un-structured (isotropic) or structured. --Structured liquids of the invention may be internally structured whereby the structure is formed by the detergent active materials in the composition or 11 C 7248 (R) externally structured, whereby the structure is provided by an external structurant. Preferably compositions of the invention are internally structured. Most preferably compositions of the invention comprise a structure of lamellar droplets comprising surfactant materials.
Some of the different kinds of active-structuring which are possible are described in the reference H.A. Barnes, "Detergents", Ch.2. in K. Walters (Ed), "~heometry:
Industrial Applications", J. Wiley & Sons, Letchworth 1980. In general, the degree of ordering of such systems increases with increasing surfactant and/or electrolyte concentrations. At very low concentrations, the surfactant can exist as a molecular solution, or as a solution of spherical micelles, both of these being isotropic. With the addition of further surfactant and/or electrolyte, structured (antisotropic) systems can form. They are referred to respectively, by various terms such as rod-micelles, planar lamellar structures, lamellar droplets and liquid crystalline PhaseS. Often, different workers have used different terminology to refer to the structures which are really the same. For instance, in European patent specification EP-A-151 884, lamellar droplets are called "spherulites". The presence and identity of a surfactant structuring system in a liquid may be determined by means known to those skilled in the art for example, optical techniques, various rheometrical measurements, x-ray or neutron diffraction, and sometimes, electron microscopy.
When the compositions are of lamellar droplet structure then in many cases it is preferred for the aqueous continuous phase to contain dissolved electrolyte. As used herein, the term electrolyte means any ionic water Q~77 12 c 7248 (R) soluble material. However, in lamellar dispersions, not all the electrolyte is necessarily dissolved but may be suspended as particles of solid because the total electrolyte concentration of the liquid is higher than the solubility limit of the electrolyte. Mixtures of electrolytes also may be used, with one or more of the electrolytes being in the dissolved aqueous phase and one or more being substantially only in the suspended solid phase. Two or more electrolytes may also be distributed approximately proportionally, between these two phases. In part, this may depend on processing, e.g.
the order of addition of components. On the other hand, the term "salts" includes all organic and inorganic materials which may be included, other than surfactants and water, whether or not they are ionic, and this term encompasses the sub-set of the electrolytes (water soluble materials).
The selection of surfactant types and their proportions, in order to obtain a stable liquid with the required structure will be fully within the capability of those skilled in the art. However, it can be mentioned that an important sub-class of useful compositions is those where the detergent active material comprises blends of different surfactant types. Typical blends useful for fabric washing compositions include those where the primary surfactant(s) comprise nonionic and/or a non-alkoxylated anionic and/or an alkoxylated anionic surfactant.
In the case of blends of surfactants, the precise proportions of each component which will result in such stability and viscosity will depend on the type(s) and ~s~
13 C 7248 (R) amount(s) of the electrolytes, as is the case with conventional structured liquids.
Preferably though, the compositions contain from 0% to 60%, especially from 1- 60 %, more preferably 10 to 45%
of a salting-out electrolyte. Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646, that is salting-out electrolytes have a lyotropic number of less than 9.5. Optionally, some salting-in electrolyte (as defined in the latter specification) may also be included, provided it is of a kind and in an amount compatible with the other components and the composition is still in accordance with the definition -of the invention claimed herein. Some or all of the electrolyte (whether salting-in or salting-out), or any substantially water insoluble salt which may be present, may have detergency builder properties. In any event, it is preferred that compositions according to the present invention include detergency builder material, some or all of which may be electrolyte. The builder material is any capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the dispersion of the fabric softening clay material. Preferably the salting-out electrolyte comprises citrate.
Examples of phosphorus-containing inorganic detergency builders, when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and 14 c 7248 (R) hexametaphosphates. Phosphonate sequestrant builders may also be used.
Examples of non-phosphorus-containing inorganic detergency builders, when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and - 10 potassium bicarbonates, silicates and zeolites.
Examples of organic detergency builders, when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates.
Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilitriacetic acid, oxydisuccinic acid, CMOS, TMS, TDS, melitic acid, benzene polycarboxylic acids and citric acid.
Preferably the level of non-soap builder material is from 0-50% by weight of the composition, more preferred from 5-40%, most preferred 10-35%.
In the context of organic builders, it is also desirable to incorporate polymers which are only partly dissolved, in the aqueous continuous phase as described in EP
301.882. This allows a viscosity reduction (due to the polymer which is dissolved) whilst incorporating a sufficiently high amount to achieve a secondary benefit, especially building, because the part which is not dissolved does not bring about the instability that ~ ~ ~r~
C 7248 (R) would occur if substantially all were dissolved. Typical amounts are from 0.5 to 4.5% by weight.
It is further possible to include in the compositions of the present invention, alternatively, or in addition`to the partly dissolved polymer, yet another polymer which is suostantially totally soluble in the aqueous phase and has an electrolyte resistance of more than 5 grams sodium nitrilotriacetate in 100ml of a 5% by weight aqueous solution of the polymer, said second polymer also having a vapour pressure in 20% aqueous solution, equal to or less than the vapour pressure of a ref~rence 2~ by weight or greater aqueous solution of polyethylene glycol having an average molecular weight of 6000; said second polymer having a molecular weight of at least 1000. Use of such polymers is generally described in our EP 301,883. Typical levels are from 0.5 to 4.5% by weight.
The viscosity of compositions according to the present is preferably less than 1500 mPas, more preferred less than 1000 mPas, especially preferred between 30 and 900 mPas at 21 s~1.
One way of regulating the viscosity and stability of compositions according to the present invention is to include viscosity regulating polymeric materials.
Viscosity and/or stability regulating polymers which are preferred for incorporation in compositions according to the invention include deflocculating polymers having a hydrophilic backbone and at least one hydrophobic side chain. Such polymers are for instance described in our ~5~(~7~
16 C 7248 (R) co-pending European application EP 89201530.6 (EP 346 995).
Preferably the amount of viscosity regulating polymer is from 0.1 to 5% by weight of the total composition, more preferred from 0.2 to 2%.
Compositions of the invention may also comprise materials for adjusting the pH. For lowering the pH it is preferred to use weak acids, especially the use of organic acids is preferred, more preferred is the use of C1_8 carboxylic acids, most preferred is the use of citric acid.
Apart from the ingredients already mentioned, a number of optional ingredients may also be present, for example bleach materials such as percarbonates or perborates, bleach precursors such as TAED, lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, fabric softeners such as clays, amines and amine oxides, lather depressants, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, germicides colorants and other enzymes such as cellulases and amylases.
Liquid compositions of the invention preferably comprise from 10 -80 % by weight of water, more preferably from 15- 60%, most preferably from 20-50 %.
Liquid detergent compositions according to the invention are preferably physically stable in that they show less 17 C 7248 (R) than 2% by volume phase separation upon storage for 21 days after preparation at 25C.
In use the detergent compositions of the invention will be diluted with wash water to form a wash liquor for instance for use in a washing machine. The concentration of liquid detergent composition in the wash liquor is preferably from O.OS to 10 %, more preferred from 0.1 to 3% by weight.
To ensure effective detergency, the liquid detergent compositions preferably are alkaline, and it is preferred that they should provide a pH within the range of about 7.0 to 12, preferably about 8 to about 11, when used in aqueous solutions of the composition at the recommended concentration. To meet this requirement, the undiluted liquid composition should preferably be of a pH above 7, for example about pH 8.0 to about 12.5. It should be noted that an excessively high pH, e.g. over about pH 13, is less desirable for domestic safety. If hydrogen peroxide is present in the liquid composition, then the pH is generally from 7.5 to 10.5, preferably 8 to 10, and especial]y 8.5 to 10, to ensure the combined effect of good detergency and good physical and chemical stability. The ingredients in any such highly alkaline detergent composition should, of course, be chosen for alkaline sta~ility, especially for pH-sensitive materials such as enzymes, and a particularly suitable proteolytic enzyme. The pH may be adjusted by addition of a suitable alkaline or acid material.
Compositions according to the invention may be prepared by any method for the preparation of detergent compositions. A preferred method for the preparation of ~5~Q~7~
18 C 7248 (R) liquid detergent compositions of the invention comprises the addition of electrolyte materials -if any~ to the water, followed by the addition of deflocculating polymers -if any-, the detergent active materials, the stabiliser material and the lipolytic enzyme as a premix and finally the remaining ingredients The lipolytic enzyme is preferably added as a premix with the stabiliser after addition of all ingredients (including the proteolytic enzyme if any).
The invention will now be illustrated by way of the following Examples. In all Examples, unless stated to the contrary, all percentages are by weight.
~:~5~7~
19 C 7248 (R) EXAMPLE I
Determination of the Ki for the stabilising reaction between several stabilising materials and lipolytic enzymes.
The Ki of the stabilisation reaction between Lipolase TM
~ex NOVO) and the stabiliser materials as indicated below was calculated from the Km values in the absence and presence of stabiliser. The Km was determined by variation of the concentration of substrate (=olive oil emulsion, stabilised by gum arabic in a weight ratio of 1 : 1) both in the absence and presence of a stabiliser/Lipolase premix. If present the stabiliser was added as a premix with the lipolytic enzyme. The Ki was calculated from the Km values.
The following results were obtained:
20 STABILISER _ Ki ~microM~ _ Butane boronic acid 67 - Phenyl boronic acid 20 p-Bromophenyl boronic acid 0.4 p,o Dichlorophenyl boronic acid 0.36 These results indicate that a stabiliser/lipolytic enzyme complex can be formed at very low concentrations of stabiliser material (micromolar ran~e) ~a~c5~
C 7248 (R) EXAMPLE II
The capability of several stabilisers to form complexes with Proteolytic enzymes was tested by mixing a premix of Savinase TM and the stabiliser material to a 0.1 mg/ml solution of purified Lipolase TM (=substrate) in 2 g/l LAS, buffered with 10 m~ Tris/HCl. While keeping the pH at 9.0 in a pH-stat apparatus, the alkali consumption was measured. From this the Savinase activity was calculated. A Savinase activity of 50 % was found at about the concentrations of stabilisers as indicated in the following table:
STABILISER 50 % Sav. Act at fmM) 15 Butane Boronic acid 9 Phenyl Boronic acid 5 p-Bromo phenyl Boronic acid 2 p,o Dichloro Boronic acid These results indicate that although the stabiliser materials are capable of forming a complex with Savinase, this complex is only formed at relatively high concentrations (millimolar range).
~5~ 7 21 C 7248 (R) EXAMPLE III
The stability of lipolytic enzymes in the presence of proteolytic enzymes at various levels of stabilising materials was determined as follows:
180 LU/ml Lipolase TN was incubated with 10,000 GU/ml Savinase TM in 2 g/l LAS and 20 mM Tris/HCl at a pH of 9.0 in the presence of various concentrations of stabilising materials. The residual Lipolase activity after 30 minutes at 30C was determined.
When butane boronic acid was used (Ki = 67 micromolair) as the stabilising material a steep increase in stability of the Lipolytic enzyme was observed when raising the concentration of stabiliser from 0 to 2 times the Ki. By further increasing the concentration of stabiliser material a slight increase of the lipolytic enzyme stability could be observed.
When p,o Dichlorophenylboronic acid ( Ki is 0.36 micromolair) was used as the stabilising material, again a steep increase in stability of the lipolytic enzyme was observed by raising the level of stabilising material from 0 to about 2 times the Ki value. By further increasing the stabiliser concentration a slight increase of the stability of the lipolytic enzymes could be observed.
These results indicate that if mixtures of Lipolytic and proteolytic enzymes are used, stabilisation take place at very low levels of stabiliser material, corresponding to the Ki of the formation of a stabiliser/lipolytic 5~07~
22 C 7248 (R) enzyme complex. The formation of this complex renders it possible to stabilise lipolytic enzymes by using only minor amounts of stabilising materials. Therefore if mixtures of Lipolytic enzymes and Proteolytic enzymes are used in combination wi~h micromolar concentrations of stabilising materials, the stabilisation takes place via an inhibitory reaction on the active site of the Lipolytic enzyme and not via the formation of a Proteolytic enzyme/stabiliser complex.
2~s~
23 C 7248 (~) EXAMPLE IV
The following compositions where prepared by adding the ingredients to the water in the following order:
electrolytes, actives (as a premix~, other ingredients except for lipase and stabiliser which were added as a premix as the final ingredient.
Ingredient (wt parts) A
10 Water 50 LAS 6.8 LES 4.8 Nonionic 4.8 zeolite 19 15 Sokolan CP-5 3 NaOH to pH 8.5 CaC12 0.15 Glycerol 8 Borax 5.7 20 Lipase 0.5 LU/mg Savinase var - stabiliser var Material specification:
LAS: C12_14 Linear alkyl benzene sulphonate(Dobanic 113) LES: mixtu.re Lauryl 3EO ether sulphate and Lauryl 7EO
ether sulphate in a weight ratio of 1 : 1.
Nonionic: 1.2% synperonic A3, 3.6% synperonic A7.
Zeolite: Wessalith P
Lipase: Lipolase SP~00 (ex NOVO) Savinase: Savinase 16.0 L DX (ex NOVO) Sample I contained lipase in the absence of savinase and stabilisers, sample II contained Lipase and Savinase, 24 C 7248 (R) but no stabiliser, the remaining samples contained Lipase and Savinase and a stabiliser as indicated below.
The level of Savinase in samples II-VIII was 10 GU/mg, the level of stabiliser in samples III-VIII was 0.25 ~.
The half life time of the Lipase enzyme at 37C was determined for each sample the results were as follows:
SAMPLE_ _STABILISER _ to 5 ~37C. days) wherein:
A : iminodiacetic acid B : picolinic acid C : formula II, wherein R4 is phenyl and R5 is -OH;
D : formula I, wherein R1 is -H, x=1, Ph = meta NH2 benzene, R2 and R3 are -OH;
E : formula I, wherein R1 is -H, x=l, Ph = para Br-benzene, R2 and R3 are -OH;
F : formula I, wherein R1 is -H, x=1, Ph = ortho, para diCl benzene, R2 and R3 are -OH;
These results indicate that the half-life time of lipase is markedly decreased by the addition of proteolytic enzymes (samples I and II). The addition of two carboxylic protease inhibitors, iminodiacetic acid and picolinic acid did not result in an enhancement of lipase stability (samples III and IV). If however 37~
C 7248 (R) boronic acid derivatives like phenylboronic acid, m-amino phenyl boronic acid, 2,4 dichloro phenyl boronic acid and p-bromo phenyl boronic acid are added a clear increase of the half life time of lipase can be observed.
Other useful boronic acid derivatives are: octadecane boronic acid and phenyl, butyl boronic acid.
7~
26 C 7248 (R) EXAMPLE V
The following formulations were prepared by mixing the ingredients in the order listed to water.
5 INGREDIENTS 1~ wt~ A B _ _ C
Sodium-citrate 2aq -- 15 7 Borax 1.0 Glycerol 3-5 ~~ ~~
Propyleneglycol 12 -- --10 Dobanic 113 7.5 18 16 Synperonic A7 19 18 8 Soap 15 9 16 Tinopal CBS-X -- 0.1 --Polymer 1) -- 1.0 __ 15 Silicone Q2-3300 -- 0.1 --Perfume -- 0.4 --Triethanolamine -- -- 2 Monoethanolamine -- -- 2 20 Savinase TM ~GU/mg) 10 10 10 Lipolase TM (LU/mg) 3) 0.4 0.5 0.5 Stabiliser 2) 0/0.250/0.250/0.25 Water <---------balance-------->
1) Polymer All of EP 346,995.
2) O,p dichlorophenyl boronic acid.
3) Added as a premix with the stabiliser.
The half life time of the lipase was determined at 37C.
For composition A the half life time in the absence of stabiliser was 1 day, in the presence of stabiliser 3 days. For composition B, the half life time in the absence of stabiliser was 14 days, in the presence of stabiliser 32 days. For composition C, the half-life time in the absence of stabiliser was 1 day, in the presence of stabiliser 2 days.
27 2~ f;;~1~7~7 Example VI
To determine the enhancement of lipase stability in an isotropic liquid formulation using dichlorophenyl boronic acid DCPBA, the following isotropic composition was prepared anionic surfactant 22.5%
nonionic surfactant 7.5%
Sodium hydroxide 2.0%
Propylene glycol 11.4%
Lipase 0.5 LU/mg Savinase (1) DCPBA (2) Water to 100%
(1) 0 or 10 GU/mg (2) DCPBA inoremental amounts 0.001% - 0.25%
-Upon storage at 37 C over 50 hours, it was found that concentrations as low as 0.001% yive a measurable improvement in lipase stability. For the formulation contaning the protease, the stability is increased by at least a factor of three (50 hours, 0.25% DCPBA). In the absence of the protease, the improvement is less but still significant.
These results show that the lipolase stability enhancement is obtained not only in structured liquid compositions but also in isotropic liquids.
Although applicants do not wish to be hound by any theory, it is believed that the stabilisation of the lipase enzyme by the boronic acid derivatives works via lQ an inhibitory mechanism, whereby the boronic acid derivative reacts with the active site o~ the lipolytic enzyme, therewith protecting the enzyme against destabilisation. In using the detergent composition, generally a dilution step will take place, for example by the addition of the detergent composition to the wash liquor. It is believed that due to this dilution, generally the protective boronic acid group will be detached form the active site of the lipolytic enzyme, therewith providing an active enzyme material under use conditions. This mechanism of stabilisation is believed to be especially advantageous if lipase enzymes are used in combination with proteolytic enzymes, because the boronic acid derivative tends to be bound to the active site of the lipase, therewith preventing the destabilisation reaction (= proteolytic breakdown) with the proteolytic enzyme.
Preferred borcnic acid derivatives are of the formula I, whereby at least of the groups R2 and R3 is -OH, most preferably groups R2 and ~3 both are -OH or one of these groups is -OH and the other is a Cl-8 alkyl or alkenyl group.
;2 ~5~077 C 7248 (R) For environmental reasons it is further preferred that the in formula I n is 0 and Rl is a C3-C24 group.
Especially preferred boronic acid derivatives are of the following formula;
OH
R4~ B ~ (II) wherein:
R4 is a phenyl group or a C8_24 alkyl or alkenyl group;
R5 is a -OH or a Cl_8 alkyl or alkenyl group.
The level of boronic acid derivatives in the detergent compositions according to the present invention may be varied within a broad range, dependant on the level of lipolytic enzyme and the reactivity of the boronic acid derivative. Generally the level of boronic acid derivatives will be from 0.00001 to 3 % by weight of the composition, more preferred from 0.0001 to 1 %, most preferred from 0.001 to 0.5 ~.
The added amount of lipolytic enzyme in the composition is preferably from 50-30,000 LU/g of detergent composition, whereby LU (lipase units) are defined as they are in EP 258 068. The level of lipolytic enzymes is often at least 100 LU/g, very usefully at least 250 LU/g, preferably less than 5000 LU/g, more preferably less than 2000 LU/g or less than 1000 LUtg.
The lipolytic enzyme can be chosen from among a wide range of lipases: in particular the lipases described in for example the following patent specifications, EP 214 761 (NOVO), EP 258 068 (NOVO) and EP 305 216 (NOVO), and especially lipolytic enzymes showing immunological ;~5~
6 C 7248 (R) cross-reactivity with antisera raised against lipases from Thermomyces lanuginosus ATCC 22070, EP 205 208 (UNILEVER) and EP 206 390 (UNILEVER), and especially lipases showing immunological cross-reactivity with antisera raised against lipase from Chromobacter viscosum var lipolyticum NRRL B-3673 , or against lipase from Alcaligenes PL-679, ATCC 31371 and FERM-P
3783, also the lipases described in specifications Wo 87/00859 (Gist-Brocades), WO 89/09263 (Gist Brocades), EP 331 376 (AMANO), DE 39 08 131 (Toyo Jozo) and EP 204 284 (SAPPORO BREWERIES). Suitable in particular are for example the following commercially available lipase preparations: Novo Lipolase, Amano Lipase CE, P, B, AP, M-AP, AML and CES, and Meito lipases MY-30, OF, and PL, also esterase MM. lipozym, SP 225, SP 285, Siaken lipase, Enzeco lipase, Toyo Jozo lipase and Diosynth lipase.
These commercially available enzymes are preferably used at levels of from 0.01 to 10 ~ by weight of the detergent composition, more preferred 0.05 to 5 %, most preferred 0.1 to 2 %, whereby the levels relate to the enzyme preparation in the form as supplied.
Also lipase enzymes produced by genetic engineering may be used, such as for example described in WO 89~09263 (Gist-Brocades) and EP 218 272 (Gist-Brocades) as well as EP 258 068 (Novo) and EP 305 216 (Novo).
As stated above the use of boronic acid derivatives for the stabilisation of lipolytic enzymes is especially advantageous for detergent compositions comprising lipases in combination with proteolytic enzymes.
~:~5~
7 C 7248 (R) Protease can preferably be included in the composition in amounts of the order of about 1 to 100 GU/mg detergent composition. Preferably the amount ranges from 2-50 and more preferably from 5 to 20 GU/mg. A GU is a Glycine unit, defined as the proteolytic enzyme activity which, under standard conditions, during a 15 minute incubation at 40C, with N-acetyl casein as substrate, produces an amount of NH2 groups equivalent to 1 micromole of glycine.
A preferred example of a protease enzyme which may be used in compositions according to the invention is the subtilisin variety sold as Savinase (TM of Novo-Nordisk A/S) or Maxacal (TM of Gist-Brocades/IBIS) or as Opticlean (ex MKC) or API22 (ex Showa Denko). Other useful examples of proteases include Maxatase, Esperase, Alcalase, proteinase K and subtilisin BPN', or variants obtained by enzyme engineering.
Commercially available proteolytic enzymes are preferably used at a level of from 0.01 to lO % by weight of the composition, more preferably 0.05 to 2 %, most preferred 0.1 to 2 %, whereby the levels relate to the enzyme preparation in the form as supplied.
Protease with a high isoelectric point (e.g Savinase or Maxacal) have been found more stable under the conditions generally encountered in detergent compositions of the invention. Particularly good results have been obtained while using a hiqh pI protease (ie pI
above 9, say about 10) in a liquid detergent composition of pH less than about 9.
~5.~(~7~
8 C 7248 (R) Detergent compositions of the invention may take any suitable physical form such as powders, pastes, tablets and liquids. A preferred embodiment of the present invention relates to liquid detergent compositions, in particular liquid detergent compositions comprising an aqueous phase.
Compositions of the present invention also comprise detergent active materials. In the widest definition the detergent active materials in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof. For example, they may be chosen from any of the classes, sub-classes and specific materials described in "Surface Active Agents" Vol. I, by Schwartz & Perry, Interscience 1949 and "Surface Active Agents" Vol. II by Schwartz, Perry & Berch (Interscience 1958), in the current edition of "McCutcheon's Emulsifiers & Detergents"
published by the McCutcheon division of Manufacturing Confectioners Company or in Tensid-Taschenbuch", H.
Stache, 2nd Edn., Carl Hanser Verlag, Munchen & Wien, 19~1 .
Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl tC6-C18) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the .eaction products of propylene oxide and ~ ~D 5 r~
9 C 7248 (R) ethylenediamine. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
Also possible is the use of salting out resistant active materials, such as for example described in EP 328 177, especially the use of alkyl poly glycoside surfactants, such as for example disclosed in EP 70 074.
Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alXyl radicals containing from about S to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (Cg-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts o~ sulphuric acid esters of higher (C8-C18) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products;
the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-C 7248 ~R) olefins (c8-C20) with sodium bisulphite and those derived from reacting paraffins with SO2 and C12 and then hydrolysing with a base to produce a random sulphonate; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly Cl~-C20 alpha-olefins, with SO3 and then neutralising and hydrolysing the reaction product. The preferred anionic detergent compounds are sodium (C11-C15) alkyl benzene sulphonates and sodium or potassium primary (C10-Cl8) alkyl sulphates.
It is also possible, and sometimes preferred, to include an alkali metal soap of a fatty acid, especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, and fatty acids derived from castor oil, alkylsuccinic acid, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof. The sodium or potassium soaps of these acids can be used.
In many (but not all) cases, the total detergent active material may be present at from 2% to 60% by weight of the total composition, for example from 5% to 50~ and typically from 10% to 40% by weight. However, one preferred class of compositions comprises at least 20%, most preferably at least 25% and especially at least 30%
of detergent active material based on the weight of the total composition.
Liquid detergent compositions of the invention may be un-structured (isotropic) or structured. --Structured liquids of the invention may be internally structured whereby the structure is formed by the detergent active materials in the composition or 11 C 7248 (R) externally structured, whereby the structure is provided by an external structurant. Preferably compositions of the invention are internally structured. Most preferably compositions of the invention comprise a structure of lamellar droplets comprising surfactant materials.
Some of the different kinds of active-structuring which are possible are described in the reference H.A. Barnes, "Detergents", Ch.2. in K. Walters (Ed), "~heometry:
Industrial Applications", J. Wiley & Sons, Letchworth 1980. In general, the degree of ordering of such systems increases with increasing surfactant and/or electrolyte concentrations. At very low concentrations, the surfactant can exist as a molecular solution, or as a solution of spherical micelles, both of these being isotropic. With the addition of further surfactant and/or electrolyte, structured (antisotropic) systems can form. They are referred to respectively, by various terms such as rod-micelles, planar lamellar structures, lamellar droplets and liquid crystalline PhaseS. Often, different workers have used different terminology to refer to the structures which are really the same. For instance, in European patent specification EP-A-151 884, lamellar droplets are called "spherulites". The presence and identity of a surfactant structuring system in a liquid may be determined by means known to those skilled in the art for example, optical techniques, various rheometrical measurements, x-ray or neutron diffraction, and sometimes, electron microscopy.
When the compositions are of lamellar droplet structure then in many cases it is preferred for the aqueous continuous phase to contain dissolved electrolyte. As used herein, the term electrolyte means any ionic water Q~77 12 c 7248 (R) soluble material. However, in lamellar dispersions, not all the electrolyte is necessarily dissolved but may be suspended as particles of solid because the total electrolyte concentration of the liquid is higher than the solubility limit of the electrolyte. Mixtures of electrolytes also may be used, with one or more of the electrolytes being in the dissolved aqueous phase and one or more being substantially only in the suspended solid phase. Two or more electrolytes may also be distributed approximately proportionally, between these two phases. In part, this may depend on processing, e.g.
the order of addition of components. On the other hand, the term "salts" includes all organic and inorganic materials which may be included, other than surfactants and water, whether or not they are ionic, and this term encompasses the sub-set of the electrolytes (water soluble materials).
The selection of surfactant types and their proportions, in order to obtain a stable liquid with the required structure will be fully within the capability of those skilled in the art. However, it can be mentioned that an important sub-class of useful compositions is those where the detergent active material comprises blends of different surfactant types. Typical blends useful for fabric washing compositions include those where the primary surfactant(s) comprise nonionic and/or a non-alkoxylated anionic and/or an alkoxylated anionic surfactant.
In the case of blends of surfactants, the precise proportions of each component which will result in such stability and viscosity will depend on the type(s) and ~s~
13 C 7248 (R) amount(s) of the electrolytes, as is the case with conventional structured liquids.
Preferably though, the compositions contain from 0% to 60%, especially from 1- 60 %, more preferably 10 to 45%
of a salting-out electrolyte. Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646, that is salting-out electrolytes have a lyotropic number of less than 9.5. Optionally, some salting-in electrolyte (as defined in the latter specification) may also be included, provided it is of a kind and in an amount compatible with the other components and the composition is still in accordance with the definition -of the invention claimed herein. Some or all of the electrolyte (whether salting-in or salting-out), or any substantially water insoluble salt which may be present, may have detergency builder properties. In any event, it is preferred that compositions according to the present invention include detergency builder material, some or all of which may be electrolyte. The builder material is any capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the dispersion of the fabric softening clay material. Preferably the salting-out electrolyte comprises citrate.
Examples of phosphorus-containing inorganic detergency builders, when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and 14 c 7248 (R) hexametaphosphates. Phosphonate sequestrant builders may also be used.
Examples of non-phosphorus-containing inorganic detergency builders, when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and - 10 potassium bicarbonates, silicates and zeolites.
Examples of organic detergency builders, when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates.
Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilitriacetic acid, oxydisuccinic acid, CMOS, TMS, TDS, melitic acid, benzene polycarboxylic acids and citric acid.
Preferably the level of non-soap builder material is from 0-50% by weight of the composition, more preferred from 5-40%, most preferred 10-35%.
In the context of organic builders, it is also desirable to incorporate polymers which are only partly dissolved, in the aqueous continuous phase as described in EP
301.882. This allows a viscosity reduction (due to the polymer which is dissolved) whilst incorporating a sufficiently high amount to achieve a secondary benefit, especially building, because the part which is not dissolved does not bring about the instability that ~ ~ ~r~
C 7248 (R) would occur if substantially all were dissolved. Typical amounts are from 0.5 to 4.5% by weight.
It is further possible to include in the compositions of the present invention, alternatively, or in addition`to the partly dissolved polymer, yet another polymer which is suostantially totally soluble in the aqueous phase and has an electrolyte resistance of more than 5 grams sodium nitrilotriacetate in 100ml of a 5% by weight aqueous solution of the polymer, said second polymer also having a vapour pressure in 20% aqueous solution, equal to or less than the vapour pressure of a ref~rence 2~ by weight or greater aqueous solution of polyethylene glycol having an average molecular weight of 6000; said second polymer having a molecular weight of at least 1000. Use of such polymers is generally described in our EP 301,883. Typical levels are from 0.5 to 4.5% by weight.
The viscosity of compositions according to the present is preferably less than 1500 mPas, more preferred less than 1000 mPas, especially preferred between 30 and 900 mPas at 21 s~1.
One way of regulating the viscosity and stability of compositions according to the present invention is to include viscosity regulating polymeric materials.
Viscosity and/or stability regulating polymers which are preferred for incorporation in compositions according to the invention include deflocculating polymers having a hydrophilic backbone and at least one hydrophobic side chain. Such polymers are for instance described in our ~5~(~7~
16 C 7248 (R) co-pending European application EP 89201530.6 (EP 346 995).
Preferably the amount of viscosity regulating polymer is from 0.1 to 5% by weight of the total composition, more preferred from 0.2 to 2%.
Compositions of the invention may also comprise materials for adjusting the pH. For lowering the pH it is preferred to use weak acids, especially the use of organic acids is preferred, more preferred is the use of C1_8 carboxylic acids, most preferred is the use of citric acid.
Apart from the ingredients already mentioned, a number of optional ingredients may also be present, for example bleach materials such as percarbonates or perborates, bleach precursors such as TAED, lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, fabric softeners such as clays, amines and amine oxides, lather depressants, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, germicides colorants and other enzymes such as cellulases and amylases.
Liquid compositions of the invention preferably comprise from 10 -80 % by weight of water, more preferably from 15- 60%, most preferably from 20-50 %.
Liquid detergent compositions according to the invention are preferably physically stable in that they show less 17 C 7248 (R) than 2% by volume phase separation upon storage for 21 days after preparation at 25C.
In use the detergent compositions of the invention will be diluted with wash water to form a wash liquor for instance for use in a washing machine. The concentration of liquid detergent composition in the wash liquor is preferably from O.OS to 10 %, more preferred from 0.1 to 3% by weight.
To ensure effective detergency, the liquid detergent compositions preferably are alkaline, and it is preferred that they should provide a pH within the range of about 7.0 to 12, preferably about 8 to about 11, when used in aqueous solutions of the composition at the recommended concentration. To meet this requirement, the undiluted liquid composition should preferably be of a pH above 7, for example about pH 8.0 to about 12.5. It should be noted that an excessively high pH, e.g. over about pH 13, is less desirable for domestic safety. If hydrogen peroxide is present in the liquid composition, then the pH is generally from 7.5 to 10.5, preferably 8 to 10, and especial]y 8.5 to 10, to ensure the combined effect of good detergency and good physical and chemical stability. The ingredients in any such highly alkaline detergent composition should, of course, be chosen for alkaline sta~ility, especially for pH-sensitive materials such as enzymes, and a particularly suitable proteolytic enzyme. The pH may be adjusted by addition of a suitable alkaline or acid material.
Compositions according to the invention may be prepared by any method for the preparation of detergent compositions. A preferred method for the preparation of ~5~Q~7~
18 C 7248 (R) liquid detergent compositions of the invention comprises the addition of electrolyte materials -if any~ to the water, followed by the addition of deflocculating polymers -if any-, the detergent active materials, the stabiliser material and the lipolytic enzyme as a premix and finally the remaining ingredients The lipolytic enzyme is preferably added as a premix with the stabiliser after addition of all ingredients (including the proteolytic enzyme if any).
The invention will now be illustrated by way of the following Examples. In all Examples, unless stated to the contrary, all percentages are by weight.
~:~5~7~
19 C 7248 (R) EXAMPLE I
Determination of the Ki for the stabilising reaction between several stabilising materials and lipolytic enzymes.
The Ki of the stabilisation reaction between Lipolase TM
~ex NOVO) and the stabiliser materials as indicated below was calculated from the Km values in the absence and presence of stabiliser. The Km was determined by variation of the concentration of substrate (=olive oil emulsion, stabilised by gum arabic in a weight ratio of 1 : 1) both in the absence and presence of a stabiliser/Lipolase premix. If present the stabiliser was added as a premix with the lipolytic enzyme. The Ki was calculated from the Km values.
The following results were obtained:
20 STABILISER _ Ki ~microM~ _ Butane boronic acid 67 - Phenyl boronic acid 20 p-Bromophenyl boronic acid 0.4 p,o Dichlorophenyl boronic acid 0.36 These results indicate that a stabiliser/lipolytic enzyme complex can be formed at very low concentrations of stabiliser material (micromolar ran~e) ~a~c5~
C 7248 (R) EXAMPLE II
The capability of several stabilisers to form complexes with Proteolytic enzymes was tested by mixing a premix of Savinase TM and the stabiliser material to a 0.1 mg/ml solution of purified Lipolase TM (=substrate) in 2 g/l LAS, buffered with 10 m~ Tris/HCl. While keeping the pH at 9.0 in a pH-stat apparatus, the alkali consumption was measured. From this the Savinase activity was calculated. A Savinase activity of 50 % was found at about the concentrations of stabilisers as indicated in the following table:
STABILISER 50 % Sav. Act at fmM) 15 Butane Boronic acid 9 Phenyl Boronic acid 5 p-Bromo phenyl Boronic acid 2 p,o Dichloro Boronic acid These results indicate that although the stabiliser materials are capable of forming a complex with Savinase, this complex is only formed at relatively high concentrations (millimolar range).
~5~ 7 21 C 7248 (R) EXAMPLE III
The stability of lipolytic enzymes in the presence of proteolytic enzymes at various levels of stabilising materials was determined as follows:
180 LU/ml Lipolase TN was incubated with 10,000 GU/ml Savinase TM in 2 g/l LAS and 20 mM Tris/HCl at a pH of 9.0 in the presence of various concentrations of stabilising materials. The residual Lipolase activity after 30 minutes at 30C was determined.
When butane boronic acid was used (Ki = 67 micromolair) as the stabilising material a steep increase in stability of the Lipolytic enzyme was observed when raising the concentration of stabiliser from 0 to 2 times the Ki. By further increasing the concentration of stabiliser material a slight increase of the lipolytic enzyme stability could be observed.
When p,o Dichlorophenylboronic acid ( Ki is 0.36 micromolair) was used as the stabilising material, again a steep increase in stability of the lipolytic enzyme was observed by raising the level of stabilising material from 0 to about 2 times the Ki value. By further increasing the stabiliser concentration a slight increase of the stability of the lipolytic enzymes could be observed.
These results indicate that if mixtures of Lipolytic and proteolytic enzymes are used, stabilisation take place at very low levels of stabiliser material, corresponding to the Ki of the formation of a stabiliser/lipolytic 5~07~
22 C 7248 (R) enzyme complex. The formation of this complex renders it possible to stabilise lipolytic enzymes by using only minor amounts of stabilising materials. Therefore if mixtures of Lipolytic enzymes and Proteolytic enzymes are used in combination wi~h micromolar concentrations of stabilising materials, the stabilisation takes place via an inhibitory reaction on the active site of the Lipolytic enzyme and not via the formation of a Proteolytic enzyme/stabiliser complex.
2~s~
23 C 7248 (~) EXAMPLE IV
The following compositions where prepared by adding the ingredients to the water in the following order:
electrolytes, actives (as a premix~, other ingredients except for lipase and stabiliser which were added as a premix as the final ingredient.
Ingredient (wt parts) A
10 Water 50 LAS 6.8 LES 4.8 Nonionic 4.8 zeolite 19 15 Sokolan CP-5 3 NaOH to pH 8.5 CaC12 0.15 Glycerol 8 Borax 5.7 20 Lipase 0.5 LU/mg Savinase var - stabiliser var Material specification:
LAS: C12_14 Linear alkyl benzene sulphonate(Dobanic 113) LES: mixtu.re Lauryl 3EO ether sulphate and Lauryl 7EO
ether sulphate in a weight ratio of 1 : 1.
Nonionic: 1.2% synperonic A3, 3.6% synperonic A7.
Zeolite: Wessalith P
Lipase: Lipolase SP~00 (ex NOVO) Savinase: Savinase 16.0 L DX (ex NOVO) Sample I contained lipase in the absence of savinase and stabilisers, sample II contained Lipase and Savinase, 24 C 7248 (R) but no stabiliser, the remaining samples contained Lipase and Savinase and a stabiliser as indicated below.
The level of Savinase in samples II-VIII was 10 GU/mg, the level of stabiliser in samples III-VIII was 0.25 ~.
The half life time of the Lipase enzyme at 37C was determined for each sample the results were as follows:
SAMPLE_ _STABILISER _ to 5 ~37C. days) wherein:
A : iminodiacetic acid B : picolinic acid C : formula II, wherein R4 is phenyl and R5 is -OH;
D : formula I, wherein R1 is -H, x=1, Ph = meta NH2 benzene, R2 and R3 are -OH;
E : formula I, wherein R1 is -H, x=l, Ph = para Br-benzene, R2 and R3 are -OH;
F : formula I, wherein R1 is -H, x=1, Ph = ortho, para diCl benzene, R2 and R3 are -OH;
These results indicate that the half-life time of lipase is markedly decreased by the addition of proteolytic enzymes (samples I and II). The addition of two carboxylic protease inhibitors, iminodiacetic acid and picolinic acid did not result in an enhancement of lipase stability (samples III and IV). If however 37~
C 7248 (R) boronic acid derivatives like phenylboronic acid, m-amino phenyl boronic acid, 2,4 dichloro phenyl boronic acid and p-bromo phenyl boronic acid are added a clear increase of the half life time of lipase can be observed.
Other useful boronic acid derivatives are: octadecane boronic acid and phenyl, butyl boronic acid.
7~
26 C 7248 (R) EXAMPLE V
The following formulations were prepared by mixing the ingredients in the order listed to water.
5 INGREDIENTS 1~ wt~ A B _ _ C
Sodium-citrate 2aq -- 15 7 Borax 1.0 Glycerol 3-5 ~~ ~~
Propyleneglycol 12 -- --10 Dobanic 113 7.5 18 16 Synperonic A7 19 18 8 Soap 15 9 16 Tinopal CBS-X -- 0.1 --Polymer 1) -- 1.0 __ 15 Silicone Q2-3300 -- 0.1 --Perfume -- 0.4 --Triethanolamine -- -- 2 Monoethanolamine -- -- 2 20 Savinase TM ~GU/mg) 10 10 10 Lipolase TM (LU/mg) 3) 0.4 0.5 0.5 Stabiliser 2) 0/0.250/0.250/0.25 Water <---------balance-------->
1) Polymer All of EP 346,995.
2) O,p dichlorophenyl boronic acid.
3) Added as a premix with the stabiliser.
The half life time of the lipase was determined at 37C.
For composition A the half life time in the absence of stabiliser was 1 day, in the presence of stabiliser 3 days. For composition B, the half life time in the absence of stabiliser was 14 days, in the presence of stabiliser 32 days. For composition C, the half-life time in the absence of stabiliser was 1 day, in the presence of stabiliser 2 days.
27 2~ f;;~1~7~7 Example VI
To determine the enhancement of lipase stability in an isotropic liquid formulation using dichlorophenyl boronic acid DCPBA, the following isotropic composition was prepared anionic surfactant 22.5%
nonionic surfactant 7.5%
Sodium hydroxide 2.0%
Propylene glycol 11.4%
Lipase 0.5 LU/mg Savinase (1) DCPBA (2) Water to 100%
(1) 0 or 10 GU/mg (2) DCPBA inoremental amounts 0.001% - 0.25%
-Upon storage at 37 C over 50 hours, it was found that concentrations as low as 0.001% yive a measurable improvement in lipase stability. For the formulation contaning the protease, the stability is increased by at least a factor of three (50 hours, 0.25% DCPBA). In the absence of the protease, the improvement is less but still significant.
These results show that the lipolase stability enhancement is obtained not only in structured liquid compositions but also in isotropic liquids.
Claims (21)
1. A detergent composition comprising a lipolytic enzyme and a stabilising material capable of reversibly forming a complex with the active site of the lipolytic enzyme, thereby increasing the half-life of the lipase material.
2. A detergent composition according to claim 1, wherein the stabiliser material is added to the detergent composition in a concentration of from 2 to 100 times the Ki.
3. A detergent composition according to claim 1, wherein the stabilising material is a boronic acid derivative of formula (II) (II) wherein:
R4 is a phenyl group or a C8 24 alkyl or alkenyl group;
R5 is an -OH or a C1 8 alkyl or alkenyl group.
R4 is a phenyl group or a C8 24 alkyl or alkenyl group;
R5 is an -OH or a C1 8 alkyl or alkenyl group.
4. A detergent composition according to claim 1, comprising from 0.00001 to 3 % by weight of stabilising material.
5. A detergent composition according to claim 1, comprising an amount of lipolytic enzyme of 50-30,000 LU/g of detergent composition.
6. A detergent composition according to claim 1, also comprising a proteolytic enzyme, preferably in an amount of 1 to 100 GU/mg of detergent composition.
C7248 (R) US
C7248 (R) US
7. A detergent composition according to claim 1, in liquid form, said liquid preferably comprising:
(a) 2-60 % by weight of detergent active materials;
(b) 0-60 % of salting out electrolytes;
(c) 0-50 % of non-soap builder materials;
(d) 10-80% of water.
(a) 2-60 % by weight of detergent active materials;
(b) 0-60 % of salting out electrolytes;
(c) 0-50 % of non-soap builder materials;
(d) 10-80% of water.
8. A liquid detergent composition according to claim 7, having a viscosity of less than 1,500 mPas at 21 s 1.
9. A liquid detergent composition according to claim 7, which composition comprises a suspension of lamellar droplets. `
10. A liquid detergent composition according to claim 7, which composition is isotropic.
11. A detergent composition comprising a lipolytic enzyme in combination with a stabiliser material which is a boronic acid derivative of formula (I) (I) wherein:
Ph is a phenyl group, optionally substituted by at least one halogen group and/or NH2 group;
n is 0 or 1;
R1 is hydrogen, halogen, NH2 or a C1 24 alkyl or alkenyl group, provided that when n is 0 then R1 contains at least 3, most preferably 8-20 carbon atoms;
R2 and R3 are independently selected from -PH, -C1, -F, -Br and C1 8 alkyl or alkenyl groups.
Ph is a phenyl group, optionally substituted by at least one halogen group and/or NH2 group;
n is 0 or 1;
R1 is hydrogen, halogen, NH2 or a C1 24 alkyl or alkenyl group, provided that when n is 0 then R1 contains at least 3, most preferably 8-20 carbon atoms;
R2 and R3 are independently selected from -PH, -C1, -F, -Br and C1 8 alkyl or alkenyl groups.
12. A detergent composition according to claim 11, wherein the stabiliser material is added to the detergent composition in a concentration of from 2 to C7248(R) US
100 times the Ki
100 times the Ki
13. A detergent composition according to Claim 11, wherein the stabilising material is a boronic acid derivative of formula (II) (II) wherein:
R4 is a phenyl group or a C8 24 alkyl or alkenyl group;
R5 is a -OH or a C1-8 alkyl or alkenyl group.
R4 is a phenyl group or a C8 24 alkyl or alkenyl group;
R5 is a -OH or a C1-8 alkyl or alkenyl group.
14. A detergent composition according to claim 11, comprising from 0.00001 to 3 % by weight of stabilising material.
15. A detergent composition according to claim 11, comprising an amount of lipolytic enzyme of 50-30,000 LU/g of detergent composition.
16. A detergent composition according to claim 11, the preceding claims also comprising a proteolytic enzyme, preferably in an amount of 1 to 100 GU/mg of detergent composition.
17. A detergent composition according to claim 11, in liquid form, said liquid preferably comprising:
(a) 2-60 % by weight of detergent active materials;
(b) 0-60 % of salting out electrolytes;
(c) 0 50 % of non-soap builder materials;
(d) 10-80% of water.
(a) 2-60 % by weight of detergent active materials;
(b) 0-60 % of salting out electrolytes;
(c) 0 50 % of non-soap builder materials;
(d) 10-80% of water.
18. A liquid detergent composition according to claim 17, having a viscosity of less than 1,500 mPas at 21 s-l.
31 C7248(R) US
31 C7248(R) US
19. A liquid detergent composition according to claim 17, which composition comprises a suspension of lamellar droplets.
20. A liquid detergent composition according to claim 17, which composition is isotropic.
21. A detergent composition as claimed in claim 1 and substantially as described herein.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP90202513.9 | 1990-09-24 | ||
EP90202513 | 1990-09-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2052077A1 true CA2052077A1 (en) | 1992-03-25 |
Family
ID=8205125
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002052077A Abandoned CA2052077A1 (en) | 1990-09-24 | 1991-09-23 | Detergent composition |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0478050A1 (en) |
JP (1) | JPH04283298A (en) |
AU (1) | AU8465791A (en) |
BR (1) | BR9104059A (en) |
CA (1) | CA2052077A1 (en) |
NO (1) | NO913733L (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015184209A1 (en) * | 2014-05-30 | 2015-12-03 | The Procter & Gamble Company | Water cluster-dominant boronic acid alkali surfactant compositions and their use |
Families Citing this family (29)
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US5422030A (en) * | 1991-04-30 | 1995-06-06 | The Procter & Gamble Company | Liquid detergents with aromatic borate ester to inhibit proteolytic enzyme |
AU2014892A (en) * | 1991-04-30 | 1992-12-21 | Procter & Gamble Company, The | Liquid detergents with an aryl boronic acid |
US5354491A (en) * | 1992-08-14 | 1994-10-11 | The Procter & Gamble Company | Liquid detergent compositions containing protease and certain β-aminoalkylboronic acids and esters |
US5442100A (en) * | 1992-08-14 | 1995-08-15 | The Procter & Gamble Company | β-aminoalkyl and β-N-peptidylaminoalkyl boronic acids |
EP0583536B1 (en) * | 1992-08-14 | 1997-03-05 | The Procter & Gamble Company | Liquid detergents containing an alpha-amino boronic acid |
AU7121394A (en) * | 1993-07-09 | 1995-02-06 | Borax Consolidated Ltd | Boronic acid or borinic acid derivatives as enzyme stabilizers |
TR28578A (en) * | 1993-08-13 | 1996-11-04 | Procter & Gamble | Liquid detergent compositions containing protease and some of -aminoalkylboronic acid and esters. |
US5431842A (en) * | 1993-11-05 | 1995-07-11 | The Procter & Gamble Company | Liquid detergents with ortho-substituted phenylboronic acids for inhibition of proteolytic enzyme |
US5693617A (en) * | 1994-03-15 | 1997-12-02 | Proscript, Inc. | Inhibitors of the 26s proteolytic complex and the 20s proteasome contained therein |
US5834415A (en) * | 1994-04-26 | 1998-11-10 | Novo Nordisk A/S | Naphthalene boronic acids |
US6083903A (en) * | 1994-10-28 | 2000-07-04 | Leukosite, Inc. | Boronic ester and acid compounds, synthesis and uses |
JP3895377B2 (en) * | 1995-06-13 | 2007-03-22 | ノボザイムス アクティーゼルスカブ | 4-Substituted phenylboronic acids as enzyme stabilizers |
DE19950019A1 (en) * | 1999-10-16 | 2001-04-19 | Henkel Kgaa | Surfactant-containing detergents or cleaning agents for cleaning the skin or hard surfaces contain inhibitors against proteinase-caused skin flaking |
US7041280B2 (en) | 2001-06-29 | 2006-05-09 | Genzyme Corporation | Aryl boronate functionalized polymers for treating obesity |
US6858592B2 (en) | 2001-06-29 | 2005-02-22 | Genzyme Corporation | Aryl boronic acids for treating obesity |
DE102007011236A1 (en) | 2007-03-06 | 2008-09-11 | Henkel Ag & Co. Kgaa | Carboxyl-bearing benzophenone or benzoic acid anilide derivatives as enzyme stabilizers |
DE102007041754A1 (en) | 2007-09-04 | 2009-03-05 | Henkel Ag & Co. Kgaa | Polycyclic compounds as enzyme stabilizers |
DE102008010429A1 (en) | 2008-02-21 | 2009-08-27 | Henkel Ag & Co. Kgaa | Detergent or cleaning agent, useful for washing and/or cleaning textiles, and/or hard surfaces, comprises a protease, preferably serine-protease, and one urea- or thiourea- derivative, as an enzyme stabilizer |
DE102008014760A1 (en) | 2008-03-18 | 2009-09-24 | Henkel Ag & Co. Kgaa | Imidazolium salts as enzyme stabilizers |
DE102010038499A1 (en) | 2010-07-27 | 2012-02-02 | Henkel Ag & Co. Kgaa | Stabilized liquid enzyme-containing surfactant preparation |
DE102010038497A1 (en) | 2010-07-27 | 2012-02-02 | Henkel Ag & Co. Kgaa | Stabilized liquid enzyme-containing surfactant preparation |
DE102010038502A1 (en) | 2010-07-27 | 2012-02-02 | Henkel Ag & Co. Kgaa | Stabilized liquid enzyme-containing surfactant preparation |
DE102010038496A1 (en) | 2010-07-27 | 2012-02-02 | Henkel Ag & Co. Kgaa | Stabilized liquid enzyme-containing surfactant preparation |
DE102010038498A1 (en) | 2010-07-27 | 2012-02-02 | Henkel Ag & Co. Kgaa | Stabilized liquid enzyme-containing surfactant preparation |
DE102010038501A1 (en) | 2010-07-27 | 2012-02-02 | Henkel Ag & Co. Kgaa | Stabilized liquid enzyme-containing surfactant preparation |
EP2551335A1 (en) * | 2011-07-25 | 2013-01-30 | The Procter & Gamble Company | Enzyme stabilized liquid detergent composition |
DE102011118027A1 (en) | 2011-09-12 | 2013-03-14 | Henkel Ag & Co. Kgaa | A method of adapting a hydrolytic enzyme to a hydrolytic enzyme stabilizing component |
BR112020010630A2 (en) | 2017-11-29 | 2020-11-10 | Basf Se | liquid enzyme preparation, process for making an enzyme preparation, methods for stabilizing at least one enzyme and for removing stains, and detergent formulation. |
WO2020069913A1 (en) | 2018-10-05 | 2020-04-09 | Basf Se | Compounds stabilizing hydrolases in liquids |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1353317A (en) * | 1970-03-03 | 1974-05-15 | Koninklijke Gist Spiritus | Enzyme-polymer complexes |
US3912595A (en) * | 1974-02-25 | 1975-10-14 | Us Health | Method of purifying enzymes using boronic acids covalently bonded to an insoluble support |
AU528853B2 (en) * | 1979-10-17 | 1983-05-19 | Peter Michael John Bedding | Cleaning soft contact lenses |
US4668630A (en) * | 1984-10-01 | 1987-05-26 | Beckman Instruments, Inc. | Stabilized enzymatic composition |
US4908150A (en) * | 1989-02-02 | 1990-03-13 | Lever Brothers Company | Stabilized lipolytic enzyme-containing liquid detergent composition |
EP0385526A3 (en) * | 1989-02-27 | 1991-09-11 | Unilever N.V. | Enzymatic liquid detergent composition |
-
1991
- 1991-09-16 EP EP91202359A patent/EP0478050A1/en not_active Withdrawn
- 1991-09-20 AU AU84657/91A patent/AU8465791A/en not_active Abandoned
- 1991-09-23 NO NO91913733A patent/NO913733L/en unknown
- 1991-09-23 CA CA002052077A patent/CA2052077A1/en not_active Abandoned
- 1991-09-23 BR BR919104059A patent/BR9104059A/en unknown
- 1991-09-24 JP JP3315608A patent/JPH04283298A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015184209A1 (en) * | 2014-05-30 | 2015-12-03 | The Procter & Gamble Company | Water cluster-dominant boronic acid alkali surfactant compositions and their use |
CN106459841A (en) * | 2014-05-30 | 2017-02-22 | 宝洁公司 | Water cluster-dominant boronic acid alkali surfactant compositions and their use |
Also Published As
Publication number | Publication date |
---|---|
NO913733L (en) | 1992-03-25 |
JPH04283298A (en) | 1992-10-08 |
AU8465791A (en) | 1992-04-09 |
BR9104059A (en) | 1992-06-02 |
EP0478050A1 (en) | 1992-04-01 |
NO913733D0 (en) | 1991-09-23 |
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