MXPA99001186A - Detergent compositions comprising improved amylase for dingy fabric clean-up - Google Patents
Detergent compositions comprising improved amylase for dingy fabric clean-upInfo
- Publication number
- MXPA99001186A MXPA99001186A MXPA/A/1999/001186A MX9901186A MXPA99001186A MX PA99001186 A MXPA99001186 A MX PA99001186A MX 9901186 A MX9901186 A MX 9901186A MX PA99001186 A MXPA99001186 A MX PA99001186A
- Authority
- MX
- Mexico
- Prior art keywords
- amylase
- amino acid
- detergent composition
- asn
- laundry detergent
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 183
- 239000003599 detergent Substances 0.000 title claims abstract description 108
- 102000013142 Amylases Human genes 0.000 title claims abstract description 58
- 108010065511 Amylases Proteins 0.000 title claims abstract description 58
- 239000004744 fabric Substances 0.000 title claims abstract description 34
- 235000019418 amylase Nutrition 0.000 title claims description 45
- 239000004382 Amylase Substances 0.000 title claims description 39
- 239000002689 soil Substances 0.000 claims abstract description 17
- -1 nonionic Chemical group 0.000 claims description 63
- 108090000637 alpha-Amylases Proteins 0.000 claims description 47
- 102000004139 alpha-Amylases Human genes 0.000 claims description 46
- 229940024171 alpha-amylase Drugs 0.000 claims description 40
- 102000004190 Enzymes Human genes 0.000 claims description 32
- 108090000790 Enzymes Proteins 0.000 claims description 32
- 238000004140 cleaning Methods 0.000 claims description 29
- 239000011780 sodium chloride Substances 0.000 claims description 22
- 125000003275 alpha amino acid group Chemical group 0.000 claims description 21
- 108091005771 Peptidases Proteins 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 20
- 230000000694 effects Effects 0.000 claims description 19
- 239000004365 Protease Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 102000033147 ERVK-25 Human genes 0.000 claims description 17
- 229940088598 Enzyme Drugs 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 230000001629 suppression Effects 0.000 claims description 11
- 238000004061 bleaching Methods 0.000 claims description 9
- 125000000539 amino acid group Chemical group 0.000 claims description 8
- 229920001850 Nucleic acid sequence Polymers 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 102000004965 antibodies Human genes 0.000 claims description 5
- 108090001123 antibodies Proteins 0.000 claims description 5
- 230000001900 immune effect Effects 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 108010075550 termamyl Proteins 0.000 claims description 5
- 241000193830 Bacillus <bacterium> Species 0.000 claims description 4
- 230000000996 additive Effects 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 239000011256 inorganic filler Substances 0.000 claims description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
- 241000894007 species Species 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000001264 neutralization Effects 0.000 claims description 3
- 230000002829 reduced Effects 0.000 claims description 3
- 125000001429 N-terminal alpha-amino-acid group Chemical group 0.000 claims description 2
- 230000000875 corresponding Effects 0.000 claims description 2
- 230000001747 exhibiting Effects 0.000 claims description 2
- 239000000523 sample Substances 0.000 claims description 2
- 239000002280 amphoteric surfactant Substances 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 description 49
- 239000007844 bleaching agent Substances 0.000 description 36
- 229920000642 polymer Polymers 0.000 description 35
- 239000004094 surface-active agent Substances 0.000 description 30
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 24
- 125000004432 carbon atoms Chemical group C* 0.000 description 23
- 239000000463 material Substances 0.000 description 23
- 229920000768 polyamine Polymers 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 229920001577 copolymer Polymers 0.000 description 20
- 239000002736 nonionic surfactant Substances 0.000 description 19
- 239000010457 zeolite Substances 0.000 description 19
- 239000000975 dye Substances 0.000 description 18
- 108090001060 lipase Proteins 0.000 description 17
- 102000004882 lipase Human genes 0.000 description 17
- 239000004367 Lipase Substances 0.000 description 16
- 150000001204 N-oxides Chemical class 0.000 description 16
- 239000002253 acid Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 16
- 239000007859 condensation product Substances 0.000 description 16
- 235000019421 lipase Nutrition 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 108010084185 Cellulases Proteins 0.000 description 15
- 102000005575 Cellulases Human genes 0.000 description 15
- 150000001412 amines Chemical class 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 15
- 239000011734 sodium Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 13
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 13
- 230000002401 inhibitory effect Effects 0.000 description 12
- 239000002304 perfume Substances 0.000 description 12
- 229920005646 polycarboxylate Polymers 0.000 description 12
- 229920001296 polysiloxane Polymers 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 11
- 239000006260 foam Substances 0.000 description 11
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 11
- 229940106157 CELLULASE Drugs 0.000 description 10
- 108010059892 Cellulase Proteins 0.000 description 10
- 241000880493 Leptailurus serval Species 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 10
- 108010089804 glycyl-threonine Proteins 0.000 description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 10
- 229940040461 Lipase Drugs 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 229920002472 Starch Polymers 0.000 description 9
- FRPJTGXMTIIFIT-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 235000011152 sodium sulphate Nutrition 0.000 description 9
- 235000019698 starch Nutrition 0.000 description 9
- 229940025131 Amylases Drugs 0.000 description 8
- KLKHFFMNGWULBN-VKHMYHEASA-N Asn-Gly Chemical compound NC(=O)C[C@H](N)C(=O)NCC(O)=O KLKHFFMNGWULBN-VKHMYHEASA-N 0.000 description 8
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N DTPMP Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 8
- 108010047857 aspartylglycine Proteins 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 125000000623 heterocyclic group Chemical group 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 235000019832 sodium triphosphate Nutrition 0.000 description 8
- 239000008107 starch Substances 0.000 description 8
- 150000003512 tertiary amines Chemical class 0.000 description 8
- WQZGKKKJIJFFOK-VFUOTHLCSA-N β-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N D-Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 7
- FUESBOMYALLFNI-VKHMYHEASA-N Gly-Asn Chemical compound NCC(=O)N[C@H](C(O)=O)CC(N)=O FUESBOMYALLFNI-VKHMYHEASA-N 0.000 description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinylpyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 7
- HYLXOQURIOCKIH-VQVTYTSYSA-N Thr-Arg Chemical compound C[C@@H](O)[C@H](N)C(=O)N[C@H](C(O)=O)CCCNC(N)=N HYLXOQURIOCKIH-VQVTYTSYSA-N 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 7
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 7
- 108010068265 aspartyltyrosine Proteins 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000004927 clay Substances 0.000 description 7
- 229910052570 clay Inorganic materials 0.000 description 7
- 239000008103 glucose Substances 0.000 description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 description 7
- 108010064235 lysylglycine Proteins 0.000 description 7
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 6
- VKZRWSNIWNFCIQ-UHFFFAOYSA-N 2-[2-(1,2-dicarboxyethylamino)ethylamino]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NCCNC(C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-UHFFFAOYSA-N 0.000 description 6
- JSLGXODUIAFWCF-UHFFFAOYSA-N Arginyl-Asparagine Chemical compound NC(N)=NCCCC(N)C(=O)NC(CC(N)=O)C(O)=O JSLGXODUIAFWCF-UHFFFAOYSA-N 0.000 description 6
- NALWOULWGHTVDA-UWVGGRQHSA-N Asp-Tyr Chemical compound OC(=O)C[C@H](N)C(=O)N[C@H](C(O)=O)CC1=CC=C(O)C=C1 NALWOULWGHTVDA-UWVGGRQHSA-N 0.000 description 6
- 240000007170 Cocos nucifera Species 0.000 description 6
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- 101700015827 FYPP3 Proteins 0.000 description 6
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- BIYXEUAFGLTAEM-WUJLRWPWSA-N Thr-Gly Chemical compound C[C@@H](O)[C@H](N)C(=O)NCC(O)=O BIYXEUAFGLTAEM-WUJLRWPWSA-N 0.000 description 6
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N Trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 150000008051 alkyl sulfates Chemical class 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 150000001720 carbohydrates Chemical group 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 108010005400 cutinase Proteins 0.000 description 6
- 230000002209 hydrophobic Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- RZVAJINKPMORJF-UHFFFAOYSA-N p-acetaminophenol Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 6
- 101700004450 phpP Proteins 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K 2qpq Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 5
- FFMIYIMKQIMDPK-BQBZGAKWSA-N Asn-His Chemical compound NC(=O)C[C@H](N)C(=O)N[C@H](C(O)=O)CC1=CN=CN1 FFMIYIMKQIMDPK-BQBZGAKWSA-N 0.000 description 5
- NPDLYUOYAGBHFB-UHFFFAOYSA-N Asparaginyl-Arginine Chemical compound NC(=O)CC(N)C(=O)NC(C(O)=O)CCCNC(N)=N NPDLYUOYAGBHFB-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- HGNRJCINZYHNOU-LURJTMIESA-N Lys-Gly Chemical compound NCCCC[C@H](N)C(=O)NCC(O)=O HGNRJCINZYHNOU-LURJTMIESA-N 0.000 description 5
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- 241000048284 Potato virus P Species 0.000 description 5
- ILVGMCVCQBJPSH-WDSKDSINSA-N Ser-Val Chemical compound CC(C)[C@@H](C(O)=O)NC(=O)[C@@H](N)CO ILVGMCVCQBJPSH-WDSKDSINSA-N 0.000 description 5
- QSKQNALVHFTOQX-UHFFFAOYSA-M Sodium nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O QSKQNALVHFTOQX-UHFFFAOYSA-M 0.000 description 5
- CKHWEVXPLJBEOZ-UHFFFAOYSA-N Threoninyl-Valine Chemical compound CC(C)C(C(O)=O)NC(=O)C(N)C(C)O CKHWEVXPLJBEOZ-UHFFFAOYSA-N 0.000 description 5
- HPYDSVWYXXKHRD-VIFPVBQESA-N Tyr-Gly Chemical compound [O-]C(=O)CNC(=O)[C@@H]([NH3+])CC1=CC=C(O)C=C1 HPYDSVWYXXKHRD-VIFPVBQESA-N 0.000 description 5
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- ULUAUXLGCMPNKK-UHFFFAOYSA-L 2-sulfobutanedioate Chemical class OS(=O)(=O)C(C([O-])=O)CC([O-])=O ULUAUXLGCMPNKK-UHFFFAOYSA-L 0.000 description 4
- XMBSYZWANAQXEV-UHFFFAOYSA-N 4-amino-5-[(1-carboxy-2-phenylethyl)amino]-5-oxopentanoic acid Chemical compound OC(=O)CCC(N)C(=O)NC(C(O)=O)CC1=CC=CC=C1 XMBSYZWANAQXEV-UHFFFAOYSA-N 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 4
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
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- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 4
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- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 4
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- 159000000003 magnesium salts Chemical class 0.000 description 4
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 4
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- IOUPEELXVYPCPG-UHFFFAOYSA-N val-gly Chemical compound CC(C)C(N)C(=O)NCC(O)=O IOUPEELXVYPCPG-UHFFFAOYSA-N 0.000 description 4
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- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
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- ZQFAGNFSIZZYBA-UHFFFAOYSA-N γ-glutamyl-Tryptophan Chemical compound C1=CC=C2C(CC(NC(=O)C(CCC(N)=O)N)C(O)=O)=CNC2=C1 ZQFAGNFSIZZYBA-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to the use of a specific amylase enzyme in a laundry detergent composition for boosting fabric laundry performance, especially on dingy stains and soils.
Description
DETERGENT COMPOSITIONS COMPRISING AN IMPROVED AMYLASE, FOR THE CLEANING OF DIRTY FABRICS
TECHNICAL FIELD
The present invention relates to the use of a specific amylase enzyme in laundry detergent compositions to promote cleaning performance of fabrics, especially in dull stains and dirt.
BACKGROUND OF THE INVENTION
For many years, amylase enzymes have been used for several different purposes, the most important of which are starch liquefaction, textile sizing elimination, starch modification in the pulp and paper industry, and for brewing and in baking. An additional use of the amylases that is becoming increasingly important is the removal of dirt and stains containing starch during the washing of fabrics, hard surfaces and dishes. In addition, amylase enzymes have long been recognized in laundry, dishwashing, and hard surface cleaning compositions to provide for the removal of amylaceous residues from food or amylaceous films of crockery, cutlery, glass, and hard surfaces, or to provide cleaning performance on amylaceous soils, as well as other dirt found typically in laundry applications. WO94 / 02597, Novo Nordisk A / S, published on February 3, 1994, describes cleaning compositions that incorporate mutant amylases. See also WO94 / 18314, Genencor, published August 18, 1994, and WO95 / 10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known to be used in cleaning compositions include α- and β-amylases . A-amylases are known in the art and include those described in the U.S. Patent. No. 5,003,257;
EP 252,666; WO91 / 00353; FR 2,676,456; EP 285,123; EP 525,610; and EP
368,341; and British Patent Specification No. 1, 296,839 (Novo). Examples of commercial a-amylases products are Termamyl®, Ban® and Fungamyl®, all available from Novo Nordisk A / S, Denmark, and Maxamyl®, available from Gist Brocades, and Purafact Ox Am® from Genencor. Recently, new amylases have been identified, and are described in WO95 / 26397, Novo Nordisk A / S, published on October 5, 1995, where an α-amylase having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25 ° C to 55 ° C and a pH value on the scale of 8 to 10. The variants of these new amylases demonstrate at least one of the following properties with respect to the progenitor enzymes: 1) improved thermal stability, 2) oxidation stability and 3) reduced dependency properties of calcium ions. Examples of other convenient improvements or modifications of properties (with respect to the parent a-amylase) that can be achieved with a variant in accordance with the present invention are: improved stability and / or a-amylolytic activity to
values from neutral to relatively high pH, improved a-amylolytic activity at relatively high temperature, and increase or decrease of the isoelectric point (pl) in order to better match the pl value for the α-amylase variant or the pH of the medium , and have been described in copending application PCT / DK96 / 00056 by Novo Nordisk, and are hereinafter referred to as "specific amylase".
Therefore, although it is known that amylase acts on amylaceous stains, a substantial technical challenge remains to formulate laundry components comprising a specific amylase in a manner that satisfies the consumer's need for superior cleaning performance on starchy soils, as well as other dirt found typically in laundry applications. Moreover, said detergent compositions must provide an excellent value and a safe and environmentally acceptable product that leaves the fabrics washed, especially those particularly prone to starchy soiling., in a condition free of starchy and undamaged dirt. Therefore, there is a need for the development of detergent compositions comprising specific amylase enzymes designed to be especially effective in cleaning amylaceous soils. It has been surprisingly discovered that the specific amylase enzymes provide an unexpectedly superior starch cleanliness, maintenance of whiteness and total cleaning performance. Said performance is illustrated but not limited to an excellent removal of amylaceous soils present, for example, in pillow cases, shirts and bottoms of socks.
Therefore, an object of the present invention is to provide effective removal of starchy stains and overall cleaning benefits by means of laundry compositions containing a specific amylase.
BRIEF DESCRIPTION OF THE INVENTION
This invention relates to the use of a specific amylase in a laundry detergent composition to provide an especially effective cleaning of the fabric surface. The present invention relates to the washing of fabrics to maintain or increase the whiteness and provide the cleaning of starchy stains, by contacting the fabrics in need of whiteness and / or cleaning of starchy stains with an aqueous solution formed from a detergent composition. which comprises a specific amylase at a concentration and for a sufficient period such that said cleaning performance of starchy soils of said composition is increased.
DETAILED DESCRIPTION OF THE INVENTION
Without being limited to theory, it is believed that dirt and starchy stains are the result of combinations of various types of dirt. For example, greasy soils comprise lipids, proteins and pigments that are deposited on fabrics from contact with human or animal skin. Most lipids are secreted from the sebaceous gland such as sebum. Proteins and pigments from skin fragments are released by the degradation of dermal cells. It is believed that sebum is the main dirt present in the clothes and its removal is important since the non-removed fat acts as a matrix to keep dirt in particles. It is further believed that the compounds present in the tallow are oxidized to contribute to the yellowing of the fabrics. Particulate soils mainly comprise airborne dirt and floor / soil dust and include soil and products produced during incomplete combustion of petroleum products. The term "cleaning of starchy soils" means the ability of a detergent composition to remove said accumulation of starchy soils, during one or more washes, resulting in a measurable improvement in the appearance of the fabric.
The maintenance of whiteness is the monitoring of the whiteness of fabrics that are washed and used throughout a number of wash cycles. A suitable performance detergent has a good whiteness maintenance profile, that is, it ensures that the whiteness of the washed fabrics is maintained at a high level during the entire wash and use life cycle.
Specific Amylase Enzymes An essential component of the detergent compositions of the present invention is a specific amylase enzyme. Said specific amylase enzymes include those described in WO85 / 26397 and in copending application PCT / DK96 / 00056 by Novo Nordisk. These enzymes are incorporated in the detergent compositions at a level of 0.0001% to 0.1% pure enzyme enzyme by weight of the total composition, preferably at a level of 0.00018% to 0.060%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition. Specific amylase enzymes for use in the detergent compositions of the present invention then include: (a) α-amylases characterized as having a specific activity at least 25% greater than the specific activity of Termamyl® at a temperature range of 25 ° C at 55 ° C, and at a pH value on the scale of 8 a
, measured by the Phadebas® α-amylase activity test. Said Phadebas® α-amylase activity test is described on pages 9 to 10 of WO95 / 26397. (b) α-amylases according to (a) comprising the amino acid sequence shown in SEQ ID No. 1 or an α-amylase that is at least 80% homologous with the amino acid sequence shown in SEQ ID No. 1 (c) α-amylases according to (a) comprising the amino acid sequence shown in SEQ ID No. 2 or an α-amylase which is at least 80% homologous with the amino acid sequence shown in SEQ ID No. 2. (d) α-amylases according to (a) which comprise the following N-terminal amino acid sequence: His-His-Asn -Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp- (SEQ ID No. 3) or an α-amylase that is at least 80% homologous to the amino acid sequence shown in (SEQ ID No. 3) at the N-terminus. A polypeptide is considered X% homologous to the progenitor amylase if a comparison of the respective amino acid sequence, carried out by means of algorithms, such as that described by Limpan and Pearson in Science 227, 1985, p 1435, reveals an identity of X%. (e) α-amylases according to (a-d) in which the α-amylase is obtainable from a Bacillus alkalophilic species; and in particular, of any of the strains NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935.
In the context of the present invention, the term "obtainable from" is intended not only to indicate an amylase produced by a Bacillus strain. but also an amylase encoded by a DNA sequence isolated from said Bacillus strain and produced in a host organism transformed with said DNA sequence. (f) α-amylase showing positive immunological cross-reactivity with antibodies raised against an α-amylase having an amino acid sequence corresponding respectively to SEQ ID No. 1, ID No. 2 or ID No. 3. (g) variants of the following progenitor a-amylases which (i) have one of the amino acid sequences shown in SEQ ID No. 1, ID No. 2 or ID No. 4 respectively, or (ii) display at least 80% homology with one or more of said amino acid sequences, and / or displaying immunological cross-reactivity with an antibody produced against an α-amylase having one of said amino acid sequences and / or which is encoded by a DNA sequence that hybridizes thereto probe the DNA sequence encoding an α-amylase having one of said amino acid sequences; variants in which: 1. at least one amino acid residue of said progenitor α-amylase has been removed; and / or 2. at least one amino acid residue of said progenitor α-amylase has been replaced by a different amino acid residue and / or 3. at least one amino acid residue has been inserted in relation to said progenitor α-amylase.; said variant having an α-amylase activity and exhibiting at least one of the following properties in relation to said progenitor α-amylase: increased thermostability, increased stability towards oxidation, reduced dependence on calcium ions, increased stability and / or activity a-amylolytic at relatively high neutral values, a-amylolytic activity increased at relatively high temperatures and an increase or decrease in the isoelectric point (pl) so that the pl value for a variant of α-amylase can be better the pH of the medium. Said variants are described in copending application PCT / DK96 / 00056.
Detergent components The detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components and the levels of incorporation thereof will depend on the physical form of the composition and the nature of the cleaning operation for which it will be used. The compositions of the invention can be formulated as machine or hand laundry detergent compositions that include additive laundry compositions and compositions suitable for use in soaking and / or pretreatment of soiled fabrics, and fabric softening compositions added during rinsing. When formulated as suitable compositions for use in a machine washing method, the compositions of the invention preferably contain both a surfactant and a builder and additionally one or more detergent components preferably selected from organic polymeric compounds, bleaching agents. , additional enzymes, suds suppressors, dispersants, lime soap dispersants, suspending and antiredeposition agents for dirt and corrosion inhibitors. The laundry compositions may also contain softening agents as additional detergent components. The compositions of the invention can also be used as detergent additive products. Said additive products are designed to complement or enhance the performance of conventional detergent compositions. If required, the density of the laundry granular detergent compositions herein ranges from 400 to 1200 g / liter, preferably 600 to 950 g / liter of the composition, measured at 20 ° C. The "compact" form of the laundry granular detergent compositions herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt; the inorganic filler salts are conventional ingredients of the powder detergent compositions; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, and most preferably not exceeding 5% by weight of the composition. The inorganic filler salts such as those required in the present compositions are selected from alkali and alkali metal salts of sulfates and chlorides. A preferred filler salt is sodium sulfate. The liquid detergent compositions according to the present invention may also be in "concentrated form". In such a case, the liquid detergent compositions according to the present invention will contain a smaller amount of water, as compared to conventional liquid detergents. Typically, the water content of the concentrated liquid detergent is preferably less than 40%, most preferably less than 30% and more preferably less than 20% by weight of the detergent composition.
Surfactant System The detergent compositions according to the present invention may further comprise a surfactant system in which the surfactant may be selected from the group consisting of anionic and / or nonionic and / or cationic surfactants and / or ampholytic and / or zwiterionic and / or semi-polar. The surfactant is typically present at a level of 0.1% to 60% by weight. The most preferred levels of incorporation are from 1 to 35% by weight, most preferably from 1 to 30% by weight of the laundry compositions according to the invention. The systems that are preferred to be used in accordance with the present invention comprise as one surfactant one or more of the nonionic and / or anionic surfactants described herein. The polyethylene oxide, polypropylene and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being more preferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, either in a straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, most preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include igepal ™ CO-630, marketed by GAF Corporation; and Triton ™ X-45, X-114, X-100 and X-102, all sold by Rohm & Haas Company. These surfactants are commonly known as alkylphenol alkoxylates (alkylphenol ethoxylates). The condensation products of the primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. The condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, most preferably from about 10 to about 18 carbon atoms, with from about 2 to about 10 moles of ethylene oxide are preferred. mol of alcohol. Approximately 2 to about 7 moles of ethylene oxide, and most preferably 2 to 5 moles of ethylene oxide per mole of alcohol are present in said condensation products. Examples of commercially available nonionic surfactants of this type include Tergitol ™ 15-S-9 (the linear alcohol condensation product of C- | 1-C-15 with 9 moles of ethylene oxide), Tergitol ™ 24-L -6 NMW (the primary alcohol condensation product of C12-14 with 6 moles of ethylene oxide with a limited molecular weight distribution), both marketed by Union Carbide Corporation; Neodol ™ 45-9 (the linear condensation product of C14-C15 with 9 moles of ethylene oxide), Neodol ™ 23-3 (the linear alcohol condensation product of C ^ -13 with 3.0 moles of ethylene oxide), Neodol ™ 45-7 (the linear alcohol condensation product of C-14-C-15 with 7 moles of ethylene oxide), Neodol ™ 45-5 (the C14 linear alcohol condensation product -C15 with 5 moles of ethylene oxide) marketed by Shell Chemical Company, Kyro ™ EOB (the alcohol condensation product of C-J3-C-J5 with 9 moles of ethylene oxide), marketed by The Procter & amp;; Gamble Company, and Genapol LA O3O or O5O (the condensation product of C12-C14 alcohol with 3 to 5 moles of ethylene oxide) marketed by Hoechst. The preferred scale of HLB in these products is 8-11 and most preferred is 8-10. Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkyl polysaccharides described in the U.S.A. No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e.g. , a polyglycoside, a hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 units of saccharide. Any reducing saccharide containing 5 to 6 carbon atoms can be used, eg, glucose, the galactose and galactosium portions can be replaced by the glucosyl portions (optionally the hydrophobic group is fixed in the 2- positions), 3-, 4-, etc., thus giving a glucose or galactose unlike a glycoside or galactoside). The linkages between saccharides can be, eg, between position one of the additional saccharide units and positions 2-, 3-, 4- and / or 6- of the above saccharide units. Preferred alkyl polyglycosides have the formula R 2? (CnH 2nO) t (glycosyl) x in which R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, in which the alkyl groups contain about 10 to about 18, preferably about 12 to about 14 carbon atoms; n is 2 to 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glucosyl is preferably derived from glucose. To prepare these compounds, the alkylpolyethoxylated alcohol or alcohol is first formed, and then reacted with glucose or a source of glucose to form the glucoside (attachment at position 1). The additional glucosyl units can then be fixed between their position 1 and the preceding glucosyl units in the 2-, 3-, 4- and / or 6- position, preferably e predominantly in the 2-position. The condensation products of ethylene with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant system of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800, and will exhibit insolubility in water. The addition of polyoxethylene portions to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained to the point where the polyoxethylene content is about 50% of the total weight of the condensation product, which corresponds to the condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain Pluronic ™ surfactants commercially available as Pluronic ™, marketed by BASF. Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic portion is condensed with ethylene oxide to the extent that the product of The condensate contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic ™ compounds., marketed by BASF. Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are the polyethylene oxide condensates of alkylphenols, the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of sodium oxide. ethylene, alkyl polysaccharides and mixtures thereof. The most preferred are ethoxylates of C8-C14 alkylphenol having 3 to 15 ethoxy groups and the alcohol ethoxylates of Cs-C-is (preferably of average C10) having from 2 to 10 ethoxy groups, and mixtures thereof. thereof. The highly preferred nonionic surfactants are the polyhydroxy fatty acid amide surfactants of the formula R2-C-N-Z, III or R1 wherein R1 is H, or R1 is C1-C4 hydrocarbyl, 2-hydroxyethyl , 2-hydroxy propyl or a mixture thereof, R2 is C5-31 hydrocarbyl yzs polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R ^ is methyl, R2 is a C11-C15 alkyl chain or straight C16-18 alkyl or alkenyl such as coconut alkyl or mixtures thereof, and z is derived from a reducing sugar such as glucose, fructose, maltose and lactose, in a reductive amination reaction. When laundry detergents are included in said laundry detergent compositions, the nonionic surfactant systems of the present invention act to improve the oily / greasy stain removal properties of said laundry detergent compositions through a wide range of cleaning conditions. . Suitable anionic surfactants to be used are the linear alkylbenzenesulfonate surfactants and alkyl ester sulfonate which include linear esters of C8-C20 carboxylic acids (ie, fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society ", 52 (1975), pp. 323-329. Suitable starting materials could include natural fatty substances such as those derived from tallow, palm oil, etc. The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprises alkyl ester sulfonate surfactants the structural formula:
I I R3 - CH - C - OR4
SO3M wherein R3 is a C8-C20 hydrocarbyl. preferably an alkyl or combination thereof, R 4 is a Ci-Cβ hydrocarbyl, preferably an alkyl or a combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. Preferably, R3 is C ^ Q-C ^ Q alkyl and R4 is methyl, ethyl or isopropyl. Methyl ester sulfonates in which R3 is C- | o-Ci6 alkyl are especially preferred. Other suitable anionic surfactants include the alkyl sulfate surfactants which are salts or water-soluble acids of the formula ROSO3M, in which R it is preferably a hydrocarbon of C 10-24. preferably an alkyl or hydroxyalkyl having an alkyl component of C 10-20, most preferably an alkyl or hydroxyalkyl of C 12 -C 8. and M is H or a cation, e.g., an alkali metal cation (eg, sodium, potassium, lithium), or substituted ammonium or ammonium (e.g., methyl-, dimethyl- cations, and trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like). Typically, the alkyl chains of C- | 2_C < 6 are preferred for lower wash temperatures (e.g., below about 50 ° C) and alkyl chains of Ci6_i8 are preferred for higher wash temperatures (e.g., about 50 ° C). Other anionic surfactants useful for the detersive purposes may also be included in the detergent compositions of the present invention. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, primary or secondary alkane sulphonates of C8-C22 olefinsulfonates of C8-C24, sulfonated polycarboxylic acids prepared by the sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in the description of British Patent No. 1, 082,179, C 8 -C 24 alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, oleylglycerol fatty sulphonates, ethylene oxide sulphates of alkylphenol, parafin sulfonates, alkyl phosphates, isethionates, such as acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated monounsters of unsaturated saturated C-12-18) and diesters of sulfosuccinates (especially saturated and unsaturated C6-C12 diesters), acyl sarcosinates, alkylpolyacharide sulfates such as alkylpolyglucoside sulfates (the non-sulphonated nonionic compounds being subsequently described ), branched primary alkyl sulphates and alkyl polyethoxycarboxylates such as those of the formula RO (CH 2 CH 2?) k-CH 2 COO-M + wherein R is a C 8 -C 22 alkyl is an integer from 1 to 10 and M is a cation forming of soluble salt. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and rosin acids, as well as hydrogenated rosin acids present in or derived from tallow oil. Additional examples are described in "Surface Active Agents and
Detergents "(Vol. I and II by Schwartz, Perry and Berch.) A variety of such surfactants are also generally described in U.S. Patent No. 3,929,678, issued December 30, 1975 to Laughlin, and others, in Column 23, line 58 to Column 29, line 23 (incorporated herein by reference.) Highly preferred anionic surfactants include alkoxylated alkylsulphate surfactants which are water soluble salts or acids of the formula RO (A) mSO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having an alkyl component of C-10-24, preferably an alkyl or hydroxyalkyl of C-12-C2O 'most preferably alkyl or hydroxyalkyl of C-j2- C- | 8 >; A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, most preferably between about 0.5 and about 3, and M is H or a cation which may be, for example, a metal cation ( e.g., sodium, potassium, lithium, calcium, magnesium, etc.) or an ammonium or substituted ammonium cation. The ethoxylated alkyl sulfates as well as the propoxylated alkyl sulphates are also contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those derivatives of hereiamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like . Exemplary surfactants are C12-C18 (1 0) polyethoxylated alkyl sulfate (C < 2-CidE (-0) M), C12-C18 polyethoxylated alkyl sulfate (2-25) (C-12-Ci8E (2.25) ) M), polyethoxylated alkyl sulphate of C < 2-Cl8 (3- °) (C- | 2-Cl8E (3 0) M). and polyethoxylated alkyl sulfate of C-12-C 8 (4.0) C-i2-Ci8E (4 °) M). in the < l M is conveniently selected from sodium and potassium. Suitable cationic detersive surfactants for use in the detergent compositions of the present invention are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants such as alkyltrimethyl ammonium halides and those surfactants having the formula: [R2 (OR3) and] [R4 (OR3) and] 2R5N + X- wherein R2 is an alkyl or alkylbenzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH (CH3) -, -CH2CH (CH2? H) -, -CH2CH2CH2-, and mixtures thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two groups R4 -CH2CHOH-, -CHOHCOR6CHOHCH2OH, wherein R6 is any hexose or polymer of hexose having a molecular weight less than about 1000, and hydrogen when and not being 0; R ^ is the same as R4 or is an alkyl chain in which the total number of carbon atoms of R2 plus R5 is not greater than about 18; each y is from 0 to approximately 10 and the sum of the values and ranges from 0 to approximately 15; and X is any compatible anion. Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition, having the formula: R < j R2R3R4N + X "(i) wherein R- | is C8-C16 alkyl, each of R2, R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl and - (C2H4o) x ^, where x has a value of 2 to 5 and x is an anion.Not more than one of R2, R3 or R4 must be benzyl.The preferred length of the alkyl chain for Rj is C-12-C15, particularly when the Alkyl group is a mixture of chain lengths derived from palm or coconut seed fat, or is derived synthetically by the olefin accumulation or the synthesis of OXO alcohols.
The preferred groups for R2, R3 and R4 are methyl and hydroxyethyl groups, and the anion X can be selected from halide, methosulfate, acetate and phosphate ions. Examples of quaternary ammonium compounds of the formula (i) to be used herein are: coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; chloride C-C15 dimethyl hydroxyethyl ammonium bromide; coconut dimethyl hydroxyethyl ammonium chloride or bromide; Methyl Trimethyl Ammonium Methyl Sulfate; chloride or bromide of lauryl dimethyl benzyl ammonium chloride or bromide of lauryl dimethyl (ethenoxy) 4 ammonium; Hill esters (compounds of the formula i wherein R- | is alkyl of CH2-CH2-O-C-12-I4 and R2R3R4 are methyl). I I or di-alkyl imidazolines [compounds of the formula (i)]. Other cationic surfactants useful herein are also described in the U.S.A. No. 4,228, 044, Cambre, issued October 14, 1980, and in the European patent application EP 000,224.
The quaternary ammonium surfactants suitable for the present invention have the formula (I):
Formula I wherein R1 is a short chain alkyl (C6-C10) or alkylamidoalkyl of the formula (II):
Formula II and is 2-4, preferably 3, wherein R2 is H or a C1-C3 alkyl, wherein x is 0-4, preferably 0-2, most preferably 0, wherein R3, R4 and R5 are each one the same or different, and can be either a short chain alkyl (C1-C3) or alkoxylated alkyl of the formula (III), wherein X "is a counterion, preferably a halogenide, e.g., chloride or methylsulfate.
R6 is C- | -C4 and z is 1 to 2. The quaternary ammonium surfactants are those as defined in formula I wherein R- | is Cs, C-jo or mixtures thereof, x = o, R3, R4 = CH3 and R5 = CH2CH2OH. When included therein, the detergent compositions of the present invention typically comprise from about 0.2% to about 25%, preferably about 1% to about 8%, by weight of said cationic surfactants. The ampholytic surfactants are also suitable for use in the detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or as aliphatic derivatives of heterocyclic secondary or tertiary amines in which the aliphatic radical can be a straight or branched chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic group soluble in water, e.g., carboxy, sulfate, sulfonate. See the patent of E.U.A. No. 3,929,678 to Laughiin et al., Issued December 30, 1975, column 19, lines 18-35, for examples of ampholytic surfactants. When included therein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of said ampholytic surfactants. Zwitterionic surfactants are also suitable for use in detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or quaternary ammonium derivatives, quaternary phosphonium or tertiary sulfonium compounds. See the patent of E.U.A. No. 3,929,678 to Laughiin et al., Issued December 30, 1975, in column 19, line 38 to column 22, line 48, for examples of zwitterionic surfactants. When included therein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of said zwitterionic surfactants. Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing an alkyl portion of from about 10 to about 18 carbon atoms and 2 portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing an alkyl portion of about 10 to about 18 carbon atoms and two portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water soluble sulfoxides containing an alkyl portion of from about 10 to about 18 carbon atoms and a portion selected from the group consisting of alkyl and hydroxyalkyl portions of from about 1 to about 3 carbon atoms. Semi-polar nonionic surfactants include the amine oxide surfactants having the formula: wherein R3 is an alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof, containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms, or mixtures thereof; x is from 0 to about 3; and each R 5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms, or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R ^ groups may be attached to each other, eg, through an oxygen or nitrogen atom to form a ring structure. These amine oxide surfactants include in particular alkyl oxime dimethylamine oxides of CJ OCJ S and alkoxyethyldihydroxyethylamine oxides of C8-C-J2- When included therein, the detergent compositions of the present invention typically comprise from about 0.2 to about 15%, preferably from about 1% to about 10% by weight of said semipolar nonionic surfactants. The detergent composition of the present invention may further preferably comprise a co-surfactant selected from the group of primary or tertiary amines. Primary amines suitable for use herein include amines according to the formula R-1 NH2, wherein R < | is an alkyl chain of CQ-C < \ Q, preferably Cß-Cifj. or R4X (CH2) n > X is -O-, - C (O) NH_ or -NH-, R4 is a C6-C12 alkyl chain, n is between 1 to 5, preferably 3. The alkyl chains of R- | they can be straight or branched and can be interrupted with up to 12, preferably less than 5 portions of ethylene oxide. Preferred amines according to the above formula are the n-alkylamines. Amines suitable for use herein may be selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines include oxy-propylamine of Cs-C-io, octyloxypropylamine, 2-ethylexyl-oxypropylamine, lauryl amido propylamine and amido propylamine. Tertiary amines suitable for use herein include tertiary amines having the formula R-j R2R3N, wherein R-j and R2 are alkyl chains of C- | -C8 or R5
- (CH2__CH- O) xH R3 is an alkyl chain of C6-C-12. preferably C6-C10. ° 3 is 4X (CH2) n? wherein X is -O-, - C (O) NH_ or -NH-, R4 is a C4-C12. n is between 1 to 5, preferably 2-3. R5 is H or C1-C2 alkyl and x is between 1 to 6. R3 and R4 can be linear or branched; the alkyl chains of R3 can be interrupted with up to 12, preferably less than 5, portions of ethylene oxide. Preferred tertiary amines are R < | R2R3N, wherein R-j is an alkyl chain of C-C-12, R2 and R3. they are C1-C3 alkyl or R5
- (CH2_-CH- O) xH where R-5 is H or CH-3 and x = 1 -2. Amidoamines of the formula are also preferred:
OR
R1-C- NH- (CH2) n-N- (R2) 2 wherein R- | is C5-C-12 alkyl; n is 2-4, preferably n is 3; R2 and R3 is C- | -C4. Highly preferred amines of the present invention include 1-octylamine, 1-exylamine, 1-decylamine, 1-dodecylamine, oxy-propylamine of Cs-C 1 O. N coco 1-3-diaminopropane, cocoalkyldimethylamine, lauryldimethylamine, lauryl bis (hydroxyethylamine) amine , coco bis (hydroxyethyl) amine, lauryl amine propoxylated with 2 moles, propoxylated octyl amine of 2 moles, lauryl amidopropyldimethylamine, amidopropyldimethylamine of CS-CJ O and amidopropyldimethylamine of C10. The most preferred amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especially desirable are n-dodecyldimethylamine and bishydroxyethylcocoalkylamine and 7-fold ethoxylated oleylamine, lauryl amido propylamine and cocoamidopropylamine.
Other detergent enzymes The detergent compositions may contain, in addition to the specific amylase enzymes, one or more enzymes that provide performance benefits of cleaning and / or fabric care. The preferred enzymes are proteases. Said enzymes include the selected enzymes of cellulases, hemicellulases, peroxidases, proteases, glucoamylases, other amylases, xylanases, lipases, esterases, cutinases, pectinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases, β- glucanases, arabinosidases, chondroitinase, laccase or mixtures thereof. A preferred combination is a cleaning composition having a cocktail of conventional applicable enzymes such as protease, amylase, lipase, cutinase and / or cellulase in conjunction with one or more plant cell wall degrading enzymes. The cellulases usable in the present invention include cellulases of both fungi and bacteria. Preferably, they will have an optimum pH between 5 and 9.5. Suitable cellulases are described in the US patent. 4,435,307, Barbesgoard et al., Which describes fungal cellulases produced from Humicola insolens. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. Examples of said cellulases are the cellulases produced by a strain of Humicola insolens (Humicola grísea var.thermoidea), particularly the DMS 1800 strain of Humicola. Other suitable cellulases are the cellulases originated from Humicola insolens which have a molecular weight of approximately 50KDa, an isoelectric point of 5.5 and which contain 415 amino acids. Especially suitable cellulases are cellulases that have color care benefits. Examples of said cellulases are the cellulases described in the European patent application No. 91202879.2, filed on November 6, 1991 (Novo).
Peroxidase enzymes are used in combination with oxygen sources, eg, percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "bleaching in solution", that is, to avoid the transfer of dyes or pigments removed from substrates during washing operations, to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Detergent compositions containing peroxidase are described, for example, in the international PCT application WO89 / 099813 and European patent application No. 91202882.6, filed on November 6, 1991. Said cellulases and / or peroxidases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Preferred commercially available protease enzymes include those sold under the trade names Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A / S (Denmark), those sold under the trade name Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genecor International and those sold under the trade name Opticlean and Optimase by Solvay Enzimes. The protease enzyme can be incorporated in the compositions according to the invention at a level of 0.0001% to 2% active enzyme by weight of the composition.
Other preferred enzymes that may be included in the detergent compositions of the present invention include lipases. Suitable lipase enzymes for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, such as those described in British Patent 1, 372, 034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P " Amano ", hereinafter referred to as" Amano-P ". Especially suitable lipases are lipases such as M1 Lipase® and Lipomax® (Gist-Brocades) and Lipolase® and Lipolase Ultra® (Novo), which are found to be very effective when used in combination with the compositions of the present invention. Also suitable are cutinases [EC 3.1.1.50] that can be considered as a special type of lipase, namely lipases that do not require interfacial activation. Suitable cutinases are described in WO 94/14963 and WO 94/14964. The addition of cutinases to detergent compositions has been described in e.g., WO-A88 / 09367 (Genencor). Lipases and / or cutinases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition.
Other amylases (a and / or ß) can be included for the removal of carbohydrate-based stains. Suitable amylases are Termamyl®, (Novo Nordisk), BanR and Fungamyl® (Novo Nordisk). The aforementioned enzymes can be of any suitable origin such as vegetable, animal, bacterial, fungal and yeast. Said enzymes are normally incorporated in the detergent composition at levels of 0.0001% to 2% of active enzyme per weight of the detergent composition. Other suitable detergent ingredients that may be added are the enzyme oxidation scavengers which are described in co-pending European patent application 92870018.6, filed on January 31, 1992. Examples of said enzyme oxidation scavengers are the ethoxylated tetraethylene polyamines.
Benefits of color care Technologies that provide a type of color care benefit can also be included. Examples of these technologies are metallocatalysts for color maintenance. Said metallocatalysts are described in European patent EP 0 596 184 and in co-pending European patent application No. 94870206.3.
Bleaching agent Bleaching systems that can be included in the bleaching compositions of the present invention include bleaching agents such as PB1, PB4 and percarbonate with a particle size of 400-800 microns. These bleaching agent components can include one or more oxygen bleaching agents and, depending on the bleaching agent chosen, one or more bleach activators. When present, oxygen bleach compounds will typically be present at levels of from about 1% to about 25%. In general, bleaching compounds are optional components in non-liquid formulations, e.g., granular detergents. The bleaching agent component for use herein may be any of the bleaching agents useful for detergent compositions including oxygen bleach, as well as others known in the art. The bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent. One category of oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxidedecanedioic acid. Said bleaching agents are described in the patent of E.U.A. No. 4, 483,781, patent application of E.U.A. No. 740,446, European patent application No. 0,133,354 and US patent. No. 4,412,934. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in the US patent. No. 4,634,551. Another category of bleaching agents that can be used encompasses halide bleaching agents. Examples of hypohalogenite bleaching agents, for example, include trichloro isocyanuric acid and the dichloroisocyanurates of sodium and potassium and N-chloro and N-bromoalkane sulfonamides. Said materials are normally added to 0.5-10% by weight of the finished product, preferably 1 -5% by weight. The hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylene amine (TAED), nonanoyloxybenzene sulfonate (NOBS, described in US 4,412,934), 3,5-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591). or pentaacetylglucose (PAG) or N-nonanoyl-6-aminocaproic acid phenolsulfonate ester (NACA-OBS, described in WO94 / 28106), which are perhydrolyzed to form a peracid as the active bleaching species, leading to an improved bleaching effect . Also suitable activators are acylated citrate esters such as those described in copending European patent application No. 91870207.7. Useful bleaching agents, including peroxyacids and bleaching systems comprising bleach activators and peroxygen bleach compounds useful in the detergent compositions according to the invention, are described in co-pending applications of applicant USSN 08 / 136,626, PCT / US95 / 07823, WO95 / 27772, WO95 / 27773, WO95 / 27774 and WO95 / 27775. Hydrogen peroxide may also be present by adding an enzyme system (i.e., an enzyme and a substrate therefor) that is capable of generating hydrogen peroxide at the beginning or during the washing and / or rinsing process. Such enzymatic systems are described in European patent application 91202655.6, filed October 9, 1991. Bleaching agents that are not oxygen bleaching agents are also known in the art and can be used herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated zinc and / or aluminum phthalocyanines. These materials can be deposited on the substrate during the washing process. After irradiating light, in the presence of oxygen such as by hanging clothes to be dried in daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached. The preferred zinc phthalocyanine and the photoactivated bleaching process are described in the U.S.A. No. 4,033,718. Typically, the detergent compositions will contain from about 0.025% to about 1.25% by weight of sulfonated zinc phthalocyanine.
Builder System The compositions according to the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein, including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylene diamine tetraacetate, diethylenetriamine pentamethylene acetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediaminetetra-methylene phosphonic acid. and diethylenetriaminpentamethylenephosphonic acid. Phosphate builders such as sodium tripolyphosphate can also be used herein. Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, most particularly a synthetic hydrated zeolite such as hydrated zeolite A, X, B, HS or MAP. Another suitable inorganic builder material is the layered silicate, e.g., SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na 2 Si 2? 5). Suitable polycarboxylates contain a carboxy group and include lactic acid, glycolic acid and ether derivatives thereof, such as those described in Belgian patents Nos. 831, 368, 821, 369 and 821, 370. Polycarboxylates containing two carboxy groups include the water soluble salts of succinic acid, malonic acid (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Patent 2,446,686. and 2,446,687 and in the US patent No. 3,935,257, and the sulfinyl carboxylates described in Belgian Patent No. 840,623. Polycarboxylates containing three carboxy groups include, in particular, the water-soluble citrates, aconitrates and citraconates, as well as the succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1, 379,241, the lactoxysuccinates described in the Dutch application. 7205873, and oxypolycarboxylate materials such as 2-oxa-1, 1-3-propane tricarboxylates described in British Patent No. 1, 387,447. Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent No. 1, 261, 829, 1, 1, 2,2-ethane tetracarboxylates, 1, 1, 3,3-propane tetracarboxylates and 1, 1, 2 , 3-propane tetracarboxylates. Polycarboxyiates containing sulfo substituents include the sulfosuccinate derivatives described in British Patents Nos. 1, 398,421 and 1, 398,422, and in the US patent. No. 3,936,448, as well as the sulfonated pyrolysed citrates described in British Patent No. 1, 082,179, while polycarboxylates containing phosphone substituents are described in British Patent No. 1, 439,000. Alicyclic and heterocyclic polycarboxylates include cyclopentan-cis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis -dicarboxylates, 2,2 , 5, 5-tetrahydrofuran-tetracarboxylates, 1, 2,3,4,5,6-hexan-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives described in British Patent No. 1, 425, 433. Of the above, preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, most particularly citrates. Preferred builder systems for use in the present compositions include a mixture of a water insoluble aluminosilicate builder such as zeolite A, or a layered silicate (SKS-6) and a water soluble carboxylate chelating agent. such as citric acid. A suitable chelator to be included in the detergent compositions according to the invention is ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. the same. The compounds of
Preferred EDDS are the free acid form and the sodium or magnesium salt thereof. Examples of said preferred sodium salts of EDDS include
Na2EDDS and Na4EDDS. Examples of said preferred magnesium salts of EDDS include MgEDDS and Mg2 EDDS. Magnesium salts are most preferred for inclusion in the compositions according to the invention. Preferred builder systems include a mixture of a water insoluble aluminosilicate builder such as zeolite A and a water soluble carboxylate chelating agent such as citric acid. Other detergency builders that may form part of the builder system for use in the granular compositions include inorganic materials such as carbonates, bicarbonates, alkali metal silicates and organic materials such as organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates. Other suitable water-soluble organic salts are homo- or copolymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this type are described in GB-A-1, 596,756. Examples of such salts are the polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, said copolymers have a molecular weight of from 20,000 to 70,000, especially about 40,000. Builder salts are usually included in amounts of from 10% to 80% by weight of the composition, preferably from 20% to 70% and most commonly from 30% to 60% by weight.
Foam suppressor Another optional ingredient is a suds suppressor exemplified by silicones and silica-siiicon blends. The silicones can generally be represented by the alkylated polysiloxane materials while the silicas are normally used in finely divided forms exemplified by silica aerogels and gerogels and hydrophobic silicas of various types. These materials can be incorporated as particles in which the foam suppressor is advantageously and releasably incorporated in a detergent impermeable vehicle substantially non-active on surfaces, dispersible or soluble in water. Alternatively, the foam suppressant can be dissolved or dispersed in a liquid vehicle and applied by spraying on one or more of the other components. A preferred silicone foam control agent is described in Bartollota et al., U.S. Pat. No. 3,933,672. Other particularly useful foam suppressors are the self-emulsifying silicone foam suppressors described in the German patent application DTOS 2 646 126, published on April 28, 1977. An example of said compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Especially preferred foaming control agents are the suds suppressor system comprising a mixture of silicone oils and 2-alkyl alkanols. Suitable 2-alkyl-alkanols are 2-bityloctanol which are commercially available under the trade name Isofol 12 R. Such foam suppressor systems are described in copending European patent application No. 92870174.7, filed on November 10, 1992. Particularly preferred silicone foam control agents are described in copending European patent application No.
92201649. 8. Said compositions may comprise a silica / silicone mixture in combination with non-porous fumed silica such as Aerosil.RTM. The foam suppressors described above are normally employed at levels from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
Other components Other components used in detergent compositions may be employed, such as soil suspending agents, dirt release agents, optical brighteners, abrasives, bactericides, stain inhibitors, color supply agents and / or encapsulated and non-encapsulated perfumes. Particularly suitable encapsulating materials are water-soluble capsules consisting of a matrix of polysaccharide and polyhydroxy compounds such as those described in GB 1, 464,616. Other suitable water-soluble encapsulating materials comprise dextrins derived from non-gelatinized starch acid esters of substituted dicarboxylic acids such as those described in US 3,455,838. These acid-ester dextrins are preferably prepared from starches such as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of such encapsulating materials include N-Lok, manufactured by National Starch. The N-Lok encapsulating material consists of a modified corn starch and glucose. The starch is modified by adding monofunctional substituted groups such as octenyl succinic acid anhydride. Suitable antiredeposition and slurry suspending agents herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymeric polycarboxylic acids or their salts. Polymers of this type include the polyacrylates and the maleic anhydride-acrylic acid copolymers mentioned above as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, constituting maleic anhydride at least 20 mol% of the copolymer. These materials are normally used at levels of from 0.5% to 10% by weight, most preferably from 0.75% to 8%, more preferably from 1% to 6% by weight of the composition. Preferred optical brighteners are of an anionic character, examples of which are 4, '- bis- (2-diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2: 2'-disulfonate disodium, 4, -4 , -bis- (2-morpholino-4-anilino-s-triazin-6-ylamino-stilben-2: 2-disulfonate, 4,4'-bis- (2,4-dianilino-s-triazin- Disodium 6-ylamino) stilben-2: 2'-disulfonate, 4 ', 4"-bis- (2,4-dianilino-s-triazin-6-ylamino) stilben-2-sulfonate monosodium, 4,4'-bis - (2-anilin-4- (N-methyl-N-2-hydroxyethylamino) -s-triazin-6-ylamino) stilbene-2,2'-disulfonate, 4,4'-bis- (4-phenyl) Disodium 2,1, 3-triazol-2-yl) -estilben-2,2'-disulfonate, 4,4'bis (2-anilino-4- (1-methyl-2-hydroxyethylamino) -s-triazin-6) -alkylamine) stilbene-2,2'-disulfonate disodium, 2 (stilbene-4"- (naphtho-1,, 2,: 4,5) -1, sodium 2,3-triazole-2'-sulfonate and , 4'-bis (2-sulfostyril) biphenyl The highly preferred brighteners are the specific brighteners of the co-pending European patent application No. 95201943.8. useful polymers are polyethylene glycols, particularly those of a molecular weight of 1000-10000, very particularly 2000 to 8000 and most preferably approximately 4000. These are used at levels of from 0.20% to 5%, most preferably from 0.25% to 2.5% in weight. These polymers and the aforementioned homo- or copolymeric polycarboxylate salts are valuable because they improve the maintenance of whiteness, prevent the deposition of ashes in the fabric and improve the cleaning performance on clay, proteinaceous and oxidizable soils in the presence of impurities of transition metal. The soil release agents useful in the compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and propylene glycol units in various arrangements. Examples of such polymers are described in the patents of E.U.A. Nos. 4116885 and 4711730 commonly assigned, and in published European patent application No. 0 272 033. A particularly preferred polymer according to EP-A-0 272 033 has the formula: (CH3 (PEG) 43) o.75 (POH) 0.25 [T-PO) 2.8 (T-PEG) o.4] T (POH) o.25 ((PEG) 43CH3) o.75 where PEG is - (OCH2H4) 0-, PO is ( OC3H6O) and T is (PCOC6H4CO).
Also very useful are modified polyesters such as random polymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1-2 propanediol, the end groups consisting primarily of sulfobenzoate and secondarily of monoesters of ethylene glycol and / or propane diol. The objective is to obtain a polymer blocked at both ends by sulfobenzoate groups; "primarily", in the present context, means that the majority of said copolymers herein will be blocked at their ends by sulfobenzoate groups. However, some copolymers will be less than completely blocked and therefore their end groups may consist of monoester of ethyleneglucol and / or propane 1-2 diol, thereof, which consist "secondarily" of said species. The polyesters selected herein contain about 46% by weight of dimethylterephthalic acid, about 16% by weight of propane-1,2-diol, about 10% by weight of ethylene glycol, about 13% by weight of methylsulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and have a molecular weight of about 3,000. The polyesters and their method of preparation are described in detail in EPA 311 342. It is well known in the art that free chlorine in the tap water rapidly deactivates the enzymes comprised in the detergent compositions. Therefore, using a chlorine scavenger such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine at a level above 0.1% by weight of the total composition, in the formulas will provide improved stability through the washing of the amylases enzymes. Compositions comprising a chlorine scavenger are described in European Patent Application No. 92870018.6, filed January 21, 1992.
Softening agents Fabric softening agents can also be incorporated into laundry detergent compositions according to the present invention. These agents may be of inorganic or organic type. Inorganic softening agents are exemplified by the smectite clays described in BG-A-1 400 898 and in the US patent. No. 5,019,292. Organic fabric softening agents include water-insoluble tertiary amines such as those described in GB-A1 514 276 and EP-BO 011 340 and their combination with C12-C14 monoquaternary ammonium salts are described in EP-BO 026 527 and EP -BO- 026 528 and the long chain diamides as described in EP-BO 242 919. Other useful organic ingredients of fabric softening systems include the high molecular weight polyethylene oxide materials as described in EP-AO 299 575 and 0 313 146. The smectite clay levels are usually in the range from 2% to 20%, most preferably from 5% to 15% by weight, the material being added as a dry mixed component to the rest of the formulation . Organic fabric softening agents such as water-soluble tertiary amines or long-chain amide materials are incorporated at levels of 0.5% to 5% by weight, usually from 1% to 3% by weight, while the materials of High molecular weight polyethylene oxide and water soluble cationic materials are added at levels from 0.1% to 2%, usually from 0.15% to 1.5% by weight. These materials are usually added to the spray-dried portion of the composition, although in some cases it may be more convenient to add them as a dry-mixed particulate material, or to spray them as a molten liquid over the other solid components of the composition.
Inhibition of dye transfer The detergent composition of the present invention may also include compounds for inhibiting the transfer of dyes from one fabric to another, of solubilized and suspended dyes encountered during fabric washing operations including dyed fabrics.
Polymeric dye transfer inhibiting agents The detergent compositions according to the present invention also comprise from 0.001% to 10%, preferably 0.01% a
2%, most preferably 0.05% to 1% by weight of polymeric dye transfer inhibiting agents. Said polymeric dye transfer inhibiting agents are normally incorporated into the detergent compositions to inhibit the transfer of dyes from the dyed fabrics onto the fabrics washed therewith. These polymers have the ability to complex or adsorb washed fugitive dyes from dyed fabrics before the dyes have the opportunity to bind to other articles in the wash. Especially suitable dye transfer inhibiting polymeric agents are polymers of polyamine N-oxide, copolymers of N-vinylpyrrolidone and N-vinyiimidazole, polymers of polyvinylpyrrolidone, polyvinyloxazolidones and polyvinylimidazolones or mixtures thereof. The addition of said polymers also improves the yield of the enzymes according to the invention.
(a) Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use contain units having the following structural formula: P
(I) A,
R wherein P is a polymerizable unit, to which the group R-N-O may be attached or in which the group R-N-O forms part of the polymerizable unit, or a combination of both.
O O O
A is NC, CO, C, -O-, -S-, -N-; X is O or 1; R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group may be attached or in which the nitrogen of the N-O group is part of these groups. The N-O group can be represented by the following general structures: O O
(R1) x -N- (R2) y = N- (R1) x I (R3) z wherein R1, R2, and R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, X and / or / yz is 0 or 1 and wherein the nitrogen of the NO group can be attached to, or where the nitrogen of the NO group forms part of these groups. The N-O group can be part of the polymerizable unit (P) or it can be attached to the polymeric base structure or a combination of both. Suitable polyamine N-oxides in which the N-O group forms part of the polymerizable unit comprise the polyamine N-oxides in which R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. A class of said polyamine N-oxides comprises the group of polyamine N-oxides in which the nitrogen of the group NO is part of the group R. The preferred N-oxides of poiiamine are those in which R is a heterocyclic group such such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Another class of said polyamine N-oxides comprises the group of polyamine N-oxides in which the nitrogen of the NO group is attached to the R group. Other suitable N-oxides of polyamine are the polyamine oxides to which the NO group it is fixed to the polymerizable unit. The preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) in which R is an aromatic, heterocyclic or alicyclic group wherein the nitrogen of the functional group is NOT part of said group R. Examples of these classes are polyamine oxides in which R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof. Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R is a heterocyclic or alicyclic aromatic group in which the nitrogen of the functional group is NOT attached to said R groups. Examples of these The classes are the polyamine oxides in which the R groups can be aromatic, such as phenyl. Any polymer base structure can be used, so long as the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polymeric base structures are polyvinyls, polyalkylene, polyesters, polyethers, polyamines, polyamides, polyacrylates and mixtures thereof. The amine N-oxide polymers of the present invention typically have a ratio of amine to amine N-oxide from 10: 1 to 1: 1000000. However, the amount of amine oxide groups present in the polyamine oxide polymer can be varied by suitable copolymerization or by an appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2: 3 to 1: 1000000, most preferably from 1: 4 to 1: 1000000, and more preferably from 1: 7 to 1: 1000000. The polymers of the present invention actually comprise random or block copolymers in which one type of monomer is an amine N-oxide and the other type of monomer is or is not an amine N-oxide. The amine oxide unit of the polyamine N-oxides has a Pka <; 10, preferably Pka < 7, most preferably Pka < 6. Polyamine oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical, as long as the material has the solubility in water and the suspension power of the desired dyes. Typically, the average molecular weight is within the range of 500 to 1,000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000 and still more preferably from 3,000 to 20,000.
(b) Copolymers of N-vinyipyrrolidone and N-vinyimidazole The polymers of N-vinylimidazole and N-vinylpyrrolidone used in the present invention have an average molecular weight in the range of 5,000-1,000,000, preferably 5,000-200,000. Highly preferred polymers for use in the detergent compositions according to the present invention comprise a polymer selected from copolymers of N-vinylimidazole and N-vinylpyrrolidone wherein said polymer has an average molecular weight scale of from 5,000 to 50,000, most preferably from 8,000 to 30,000, more preferably 10,000 to 20,000. The average molecular weight scale was determined by light screening as described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113, "Modern Methods of polymer characterization". The highly preferred N-vinylimidazole and N-vinylpyrrolidone copolymers have an average molecular weight scale of 5,000 to 50,000; most preferably from 8,000 to 30,000; more preferably from 10,000 to 20,000. The copolymers of N-vinylimidazole and N-vinylpyrrolidone characterized in that they have said average molecular weight scale provide excellent dye transfer inhibiting properties and do not adversely affect the cleaning performance of the detergent compositions formulated therewith. The copolymer of N-vinylimidazole and N-vinylpyrrolidone of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, most preferably from 0.8 to 0.3 and more preferably from 0.6 to 0.4.
c) Polyvinylpyrrolidone The detergent compositions of the present invention can also use polyvinylpyrrolidone ("PVP") having an average molecular weight from about 2500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000 and still more preferably from about 5,000 to about 15,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada, under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000) and PVP K-90 (average molecular weight of 360,000). Other suitable polyvinyl pyrrolidones which are commercially available from BASF Corporation include Sokalan HP 165 and Sokalan HP 12; the polyvinylpyrrolidones known to those skilled in the field of detergents (see, for example, EP-A-262,897 and EP-A-256,696).
d) Polyvinyloxazolidone: The detergent compositions of the present invention can also use polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, most preferably from about 5,000 to about 50,000 and still more preferably from about 5,000 to about 15,000.
e) Polyvinylimidazole: The detergent compositions of the present invention can also use polyvinylimidazole as a polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average molecular weight of from 2,500 to about 400,000, preferably from about 5,000 to about 200,000, most preferably from about 5,000 to about 50,000 and more preferably from about 5,000 to about 15,000.
f) Interlaced polymers: Interlaced polymers are polymers whose base structures are interconnected to a certain degree; these links can be of a chemical or physical nature, possibly with active groups in the base structure or on the ramifications; the entangled polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039.
In one embodiment, the entangled polymers are made in such a way that they form a rigid three-dimensional structure that can trap dyes in the pores formed by the three-dimensional structure. In another embodiment, the entangled polymers trap the dyes by swelling. Said entangled polymers are described in co-pending patent application 94870213.9
Washing method The detergent compositions according to the invention can be liquid, paste, gel, stick, tablet, powder or granulated forms. The granulated compositions may also be in "compact" form, the liquid compositions may also be in a "concentrated" form. The compositions of the invention can be used essentially in any washing or cleaning method, including soaking methods, pretreatment methods and methods in which rinsing steps are used for which an auxiliary rinsing composition is needed or can be added. separated. The process described herein comprises making contact between the fabrics and a washing solution in the usual manner and exemplified hereinafter.
The process of the invention is conveniently carried out in the course of the cleaning process. The cleaning method is preferably carried out at 5 ° C to 95 ° C, especially between 10 ° C and 60 ° C. However, the specific amylase enzymes within the specified enzymatic concentration have shown superior cleaning of starchy soils even in wash cycles that occur at very low temperatures (between 10 ° C and 25 ° C). The pH of the treatment solution is preferably from 7 to 11. The following examples are designed to exemplify compositions of the present invention, but are not necessarily designed to limit or otherwise define the scope of the invention. In detergent compositions, the enzyme levels are expressed as pure enzyme by weight of the total composition and unless otherwise specified, the ingredients of the detergent are expressed by weight of the total compositions. The identifications of the abbreviated components have the following meanings: LAS: C12 linear sodium alkylbenzene sulfonate TAS: Sodium alkyl sulphate sodium CXYAS: Sodium alkyl sulphate C- |? - C- | ? 25EY: A primary alcohol of C-12-C-j 5 predominantly linear condensed with an average of Y moles of ethylene oxide CXYEZ: A primary alcohol of C ?? - C- |? Predominantly linear condensed with an average of Z moles of ethylene oxide XYEZS: Sodium alkylsulfate of C - ?? - Ci? condensed with an average of Z moles of ethylene oxide per mole. QAS: R2.N + (CH3) 2 (C2H OH) with R2 = C? 2-C < | 4 Soap: Linear sodium alkylcarboxylate derived from an 80/20 mixture of tallow and coconut oils. Non-ionic: Ethoxylated / propoxylated mixed C13-C-15 fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold under the trade name Plurafac LF404 by BASF Gmbh CFAA: alkyl N-methyl glucamide of C12-C14 TFAA: C-QC alkyl N-methyl glucamide TPKFA: C-12-C14 whole-cut fatty acids. DEQA: Di- (tallowoxyethyl) dimethylammonium chloride. DTDMAMS: Disodbodimethylammonium methylsulfate. SDASA: 1: 2 ratio of stearyldimethylamine: pressed triple stearic acid NEODOL 45-13: C14-C15 linear primary alcohol ethoxylated, sold by Shell Chemical Co. Silicate: Amorphous sodium silicate (Si? 2 ratio: Na2? = 2.0) NaSKS-6: Crystalline layered silicate of the formula Ü-Na2Si2? 5 Carbonate: Anhydrous sodium carbonate with a particle size between 200 μm and 900 μm. Bicarbonate: Anhydrous sodium carbonate with a particle size between 200 μm and 1200 μm. STPP: MA / AA sodium tripolyphosphate: Maleic acid / acrylic acid 1: 4 copolymer with an average molecular weight of approximately 80,000
Polyacrylate: Polyacrylate homopolymer with an average molecular weight of 8, 000 sold under the trade name PA30 by BASF GmbH. Zeolite A: Hydrated sodium aluminosilicate of the formula Nai2 (A1? 2Si? 2) i2 27? 2 ?, which has a primary particle size on the scale of 1 to 10 microns. Citrate: trisodium citrate dihydrate of 86.4% activity with a particle size distribution between 425 μm and 850 μm. Citrus: Anhydrous citric acid. PB1: Anhydrous sodium perborate bleach monohydrate, empirical formula NaB? 2-H2? 2. PB4: Sodium perborate anhydrous tetrahydrated tetracarbonate: Anhydrous sodium percarbonate bleach of the empirical formula 2Na2C? 3.3H2? TAED: Tetraacetylethylenediamine NOBS: Nonanoyloxybenzenesulfonate in the form of the sodium salt. Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in soluble dextrin polymer. Protease: Proteolytic enzyme sold under the trade name Savinase, Alcalase, Durazym by Novo Nordisk A / S, Maxacal, Maxapem sold by Gist-Brocades and proteases described in patents WO91 / 06637 and / or WO95 / 10591 and / or EP 251 446 Amylase: Specific amylase according to the present invention. Lipase: Lipolytic enzyme sold under the trade name Lipolase and Lipolase Ultra, by Novo Nordisk A / S Cellulase: Cellulose enzyme sold under the trade name Carezyme, Celluzyme and / or Endolase by Novo Nordisk A / S.
CMC: Sodium carboxymethyl cellulose HEDP: 1, 1-hydroxydanediphosphonic acid DETPMP: Diethylenetriaminpentamethylenephosphonic acid, marketed by Monsanto under the trade name Dequest 2060. PVNO: N-oxide of poly (4-vinylpyridine). PVPVI: Poly (4-vinylpyridine) N-oxide / vinylimidazole copolymer and vinylpyrrolidone. Brightener 1: 4,4'-bis (2-sulphotyryl) biphenyl disodium Brightener 2: 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) stilbene-2: Disodium 2'-disulfonate Silicon Anti-foams: Polydimethylsiloxane foam controller with a siloxane-oxyalkylene copolymer as the dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1. Granulated foam suppressant: 12% silicone / silica, 18% stearyl alcohol, 70% starch in granulated form SRP 1: Esters blocked at the ends with sulfobenzoyl with base structure of oxyethyleneoxy and terephthaloyl. SRP 2: Poly (1, 2 propylene terephthalate) diethoxylated short block polymer. Sulfate: Anhydrous sodium sulfate HMWPEO: High molecular weight polyethylene oxide PEG: Polyethylene glycol. Encapsulated perfume particles: nsoluble fragrance delivery technology using 13x zeolite, perfume and a dextrose / glycerin agglomeration binder.
EXAMPLE 1
The following laundry detergent compositions according to the invention were prepared:
1 II III IV V VI
LAS 8.0 8.0 8.0 8.0 8.0 8.0
C25E3 3.4 3.4 3.4 3.4 3.4 3.4
QAS - 0.8 0.8 - 0.8 0.8
Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1
Carbonate 13.0 13.0 13.0 27.0 27.0 27.0
Silicate 1.4 1.4 1.4 3.0 3.0 3.0
Sulfate 26.1 26.1 26.1 26.1 26.1 26.1
PB4 9.0 9.0 9.0 9.0 9.0 9.0
TAED 1.5 1.5 1.5 1.5 1.5 1.5
DETPMP 0.25 0.25 0.25 0.25 0.25 0.25
HEDP 0.3 0.3 0.3 0.3 0.3 0.3
Protease 0.0026 0.0026 0.0026 0.0026 0.0026 0.0026 Amylase 0.0009 0.0003 0.0009 0.05 0.002 0.01
MA / AA 0.3 0.3 0.3 0.3 0.3 0.3 EXAMPLE 1 (CONTINUED)
CMC 0.2 0.2 0.2 0.2 0.2 0.2
Bleach 15 15 15 15 15 15 photoactivated (ppm) Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Antifoams 0.5 0.5 0.5 0.5 0.5, 0.5 silicone Mise / minors 850 850 850 850 850 850 to 100% Density in 850 850 850 850 850 850 g / liter
EXAMPLE 2
The following granulated laundry detergent compositions were prepared with an overall density of 750 g / liter, according to the invention.
LAS 5.25 5.61 4.76 TAS 1.25 1.86 1.57 C45AS 2-24 3.89 C25AE3S - 0.76 1.18 C45E7 3.25 - 5.0 C25E3 - 5.5 - QAS 0.8 2.0 2.0 STPP 19.7 - - Zeolite A - 19.5 19.5 NaSKS-6 / - 19.5 19.5 Citric acid (79: 21) Carbonate -6.1 21.4 21.4 EXAMPLE 2 (CONTINUED) Bicarbonate - 2.0 2.0
Silicate 6.8 4.3 TAED 0.5 3.1 - DETPMP 0.25 0.2 0.2
HEDP - 0.3 0.3
Protease 0.0026 0.0085 0.045
Lipasa 0.003 0.003 0.003
Cellulase 0.0006 0.0006 0.0006
Amylase 0.0008 0.005 0.0002
MA / AA 0.8 1.6 1.6
CMC 0.2 0.4 0.4
Bleach 15 ppm 27 ppm 27 ppm photoactivated (ppm) Brightener 1 0.08 0.19 0.19
EXAMPLE 2 (CONTINUED)
Rinse aid 2 - 0.04 0.04
0.3 0.3 0.3 perfume particles encapsulated Antiespumas 0.5 2.4 2.4 silicone Mise / less than 100%
EXAMPLE 3
The following detergent formulations according to the invention were prepared, wherein I is a phosphorus-containing detergent composition, II is a detergent composition containing zeolite and III is a compact detergent composition:
Ivo blown
STPP 24.0 - 24.0 Zeolite A - 24.0 - C45AS 9.0 6.0 13.0 MA / AA 2.0 4.0 2.0 LAS 6.0 8.0 11.0 TAS 2.0 - - Silicate 7.0 3.0 3.0 CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 EXAMPLE 3 (CONTINUED)
DETPMP 0.5 0.4 0.2
Asperjable C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone antifoams 0 0..33 0.3 0.3
Perfume 0.3 0.3 0.3
Carbonate dry additives 6.0 13.0 15.0
PB4 18.0 18.0 10.0
PB1 4.0 4.0 0
TAED 3.0 3.0 1.0
Bleach 0.02 0.02 0.02 photoactivated Protease 0.01 0.01 0.01
Lipasa 0.009 0.009 0.009
TABLE 3 (CONTINUED)
Amylase 0.002 0.0004 0.01
Sodium Sulphate Blended 3.0 3.0 5.0 in Dry Balance (Humidity and 100.0 100.0 100.0
Miscellaneous Density (g / liter) 630 670 670
EXAMPLE 4
The following formulations of detergent containing indigo bleach were prepared according to the present invention, of particular use in washing clothes with color:
Blown powder 1 II lll Zeolite A 15.0 15.0 - Sodium sulphate 0.0 5.0 - LAS 3.0 3.0 - DETPMP 0.4 0.5 - CMC 0.4 0.4 - MA / AA 4.0 4.0 - Agglomerates C45AS - - 11.0 LAS 6.0 5.0 - TAS 3.0 2.0 - Silicate 4.0 4.0 - Zeolite A 10.0 15.0 13.0 CMC - - 0.5 MA / AA - - 2.0 Carbonate 9.0 7.0 7.0 EXAMPLE 4 (CONTINUED)
Sprinkle Perfume 0.3 0.3 0.5
C45E7 4.0 4.0 4.0
C25E3 2.0 2.0 2.0 Dry additives MA / AA - - 3.0 NaSKS-6 - - 12.0
Citrate 10.0 - 8.0
Bicarbonate 7.0 3.0 5.0
Carbonate 8.0 5.0 7.0 '
PVPVI / PVNO 0.5 0.5 0.5 Protease 0.5 0.5 0.5
Lipasa 0.009 0.009 0.009
Amylase 0.005 0.003 0.01
Celulasa 0.004 0.004 0.004
Silicone antifoams 0.004 0.004 0.004
EXAMPLE 4 (CONTINUED)
Dry additives Sodium sulphate 0.0 9.0 0.0 Balance (humidity and 100.0 100.0 100.0 Miscellaneous) Density (g / liter) 700 700 700
EXAMPLE 5
The following detergent formulations were prepared according to the present invention
lll IV LAS 20.0 14.0 24.0 22.0 QAS 0.7 1.0 0.7 TFAA - 1.0 C25E5 / C45E7 -_ > 2.0 0.5 EXAMPLE 5 (CONTINUED)
C45E3S - 2.5 - - STPP 30.0 18.0 30.0 22.0
Silicate 9.0 5.0 10.0 8.0
Carbonate 13.0 7.5 - 5.0
Bicarbonate - 7.5 - - DETPMP 0.7 1.0 - - SRP 1 0.3 0.2 - 0.1
MA / AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Protease 0.008 0.01 0.025 0.026
Amylase 0.007 0.004 0.0003 0.002
Lipasa 0.004 0.002 0.004 0.002
Cellulase 0.00035 0.0001 _ _ Bleach 70 ppm 45 ppm 10 ppm
Photoactivated (ppm) Brightener 1 0.02 0.2 0.08 0.2
EXAMPLE 5 (CONTINUED)
PB1 6.0 2.0 NOBS 2.0 1.0 Balance (Humidity and 100 100 100 100 Miscellaneous)
EXAMPLE 6
The following detergent formulations were prepared according to the present invention
I II lll IV Blown powder Zeolite A 30.0 22.0 6.0 6.7 Na SkS-6 - - - 3.3 Polycarboxylate - - - 7.1 Sodium sulphate 19.0 5.0 7.0 EXAMPLE 6 (CONTINUED)
IVIGV G? 3.0 6.0 - LAS 14 12.0 22.0 21.5
C45AS 8.0 7.0 7.0 5.5
Cationic - - - 1.0
Silicate - 1.0 5.0 11.4
Soap - - 2.0 - Brightener 1 0.2 0.2 0.2 - Carbonate 8.0 16.0 20.0 10.0
DETPMP - 0.4 0.4 _
Asperjable C45E7 1.0 1.0 3.2
Dry Additives PVPVI / PVNO 0.5 0.5 0.5 0.5 Protease 0.052 0.01 0.01 0.01
EXAMPLE 6 (CONTINUED)
Lipasa 0.009 0.009 0.009 0.009
Amylase 0.0008 0.0015 0.02 0.004
Cellulase 0.0002 0.0002 0.0002 0.0002
NOBS - 6.1 4.5 3.2
PBI 1.0 5.0 6.0 3.9
Sodium sulfate - 6.0 - the rest
Balance (humidity and 100 100 100 miscellaneous)
EXAMPLE 7
The following high density detergent and bleach-containing detergent formulations were prepared according to the present invention:
lll Blown powder Zeolite A 15.0 15.0 15.0 Sodium sulphate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 QAS - 1.5 1.5 DETPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA / AA 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 EXAMPLE 7 (CONTINUED)
Sprinkle Perfume 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 Dry Additives Citrate 5.0 - 2.0
Bicarbonate - 3.0 - Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PB1 14.0 7.0 10.0
Polyethylene oxide of PM - - 0.2
,000,000 Bentonite Clay - - 10.0
Protease 0.01 0.01 0.01 Lipase 0.009 0.009 0.009
Amylase 0.005 0.003 0.02
Cellulase 0.002 0.002 0.002
Silicone antifoams 5.0 5.0 5.0
Dry additives Sodium sulphate 0.0 3.0 0.0
Balance (humidity and miscellaneous) 100.0 100.0 100.0 Density (g / liter) 850 850 850 EXAMPLE 8
The following high density detergent formulations were prepared in accordance with the present invention: I II Agglomerates C45AS 11.0 14.0 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA / AA 4.0 2.0 CMC 0.5 0.5 DETPMP 0.4 0.4 Aspergillable C25E5 5.0 5.0 Perfume 0.5 0.5 Additives dry HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonates 20.0 20.0 SRP 1 0.3 0.3 Protease 0.015 0.015 Lipase 0.009 0.009 EXAMPLE 8 (CONTINUED)
Cellulase 0.002 0.002 Amylase 0.005 0.005 Silicone antifoams 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 - Balance (moisture and miscellaneous) 100 100 Density (g / liter) 850 850
EXAMPLE 9
The following granular detergent formulations were prepared according to the present invention:
I II III IV V LAS 21.0 25.0 18.0 18.0 - Coco C12-14 AS - - - - 21.9
AE3S - - 1.5 1.5 2.3 Decil dimethyl - 0.4 0.7 0.7 0.8 Hydroxyethyl NH4 + CI Nonionic 1.2 - 0.9 0.5 EXAMPLE 9 (CONTINUED)
Fatty cocoalcohol of C12-14 - - - 1.0 STPP 44.0 25.0 22.5 22.5 22.5
Zeolite A 7.0 10.0 - - 8.0
MA / AA - - 0.9 0.9 ARP1 0.3 0.15 0.2 0.1 0.2
CMC 0.3 2.0 0.75 0.4 1.0 Carbonate 17.5 29.3 5.0 13.0 15.0
Silicate 2.0 - 7.6 7.9 Protease 0.007 0.007 0.007 0.007 0.007
Amylase 0.008 0.004 0.003 0.004 0.04
Lipasa 0.003 0.003 0.003 Celulasa - 0.001 0.001 0.001 0.001
NOBS - - - 1.2 1.0
PB1. . . 2.4 1.2 Diethylenetriamine-pentaacetic acid - - - 0.7 1.0 Diethylenetriamine-pentamethylphosphonic acid 0.6 Mg sulphate 0.8 Bleach 45 50 15 45 42 EXAMPLE 9 (CONTINUED)
photoactivated ppm ppm ppm ppm ppm
Polisher 1 0.05 - 0.04 0.04 0.04
Polisher 2 0.1 0.3 0.05 0.13 0.13
Water and minor components up to 100%
EXAMPLE 10
The following liquid detergent formulations were prepared according to the present invention.
IV V VI Vil VIII
LAS 10.0 13.0 9.0 25.0 C25AS 4.0 1.0 2.0 10.0 13.0 18.0 15.0
C25E3S 1.0 - - 3.0 2.0 2.0 4.0
C25E7 6.0 8.0 13.0 2.5 4.0 4.0
TFAA 4.5 6.0 8.0 8.0
QAS 3.0 1.0 TPKFA 2.0 13.0 2.0 - 15.0 7.0 7.0
Rapeseed fatty acids 5.0 4.0 4.0
Citrus 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 EXAMPLE 10 (CONTINUED)
Dodecenyl-tetradecenyl succinic acid 12.0 10.0 15.0 Oleic acid 4.0 2.0 1.0 1.0 Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0 1, 2 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.- Propanediol Monoethanolamine - - - 5.0 - - 9.0 9.0
Triethanolamine 8 NaOH (pH) 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 Tetraethylene ethoxylated pentaamine 0.5 0.5 0.2 0.4 0.3
DETPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0
SRP2 0.3 - 0.3 0.1 0.2 0.1
PVNO - 0.10 Protease .016 .016 .013 .008 .048 .016 0.01 .019
Lipasa .002 .001 .003 .003
Amylase .002 .002 .0005. 04 .0008 .0008 .005 .005
Cellulase .001 - - .002 .001
Boric acid 0.1 0.2 2.0 1.0 1.5 2.5 2.5 Na Formamide 1.0 EXAMPLE 10 (CONTINUED) Chloride of Ca - 0.01 - 0.01 - - - - Bentonite clay - - - 4.0 4.0 - - Suspension clay SD3 - - - - 0.6 0.3 - - Humidity and miscellaneous balance 100 100 100 100 100 100 100 100
EXAMPLE 11
Granular compositions were prepared for cleaning fabrics that provide "softening during washing", according to the present invention:
1 II 45AS - 10.0 LAS 7.6 - 68AS 1.3 - 45E7 4.0 _ 25E3 - 5.0 Cocoalkyl-dimethyl-hydroxyethylammonium chloride 1.4 1.0 Citrate 5.0 3.0 Na-SKS-6 _ 11.0 EXAMPLE 11 (CONTINUED)
Zeolite A 15.0 15.0
MA / AA 4.0 4.0
DETPMP 0.4 0.4
PB1 15.0 Percarbonate - 15.0
TAED 5.0 5.0
Smectite clay 10.0 10.0
HMWPEO - 0.1
Protease 0.02 0.01
Lipase 0.02 0.01
Amylase 0.03 0.005
Cellulase 0.001 - Silicate 3.0 5.0
Carbonate 10.0 10.0
Granulated foam suppressor 1.0 4.0
CMC 0.2 0.1
Water / c. Children Up to 100%
EXAMPLE 12
The following fabric softener composition added during the rinsing according to the present invention was prepared:
Active softener 20.0 Amylase 0.001 Cellulase 0.001 HCL 0.03 Antifoam agent 0.01 Blue dye 25 ppm CaCl2 0.20 Perfume 0.90 Water / c. Minors up to 100
EXAMPLE 13
The following fabric softening composition according to the present invention was prepared:
DEQA 2.60 19.00 DTDMAMS SDASA 70.0 Stearic acid IV = 0 0.30 Neodol 45-13 13.0 Hydrochloric acid 0.02 0.02 Ethanol 1.00 PEG - 0.60 - Amylase 0.001 0.0005 0.01 Perfume 1.00 1.00 0.75 Digeranyl succinate - - 0.38 Silicone antifoams 0.01 0.01 - Electrolyte - 600ppm - Coloring 100ppm 50ppm 0.01 Water and c. minors 100% 100% EXAMPLE 14
Cleaning compositions of synthetic bar fabrics according to the present invention were prepared:
I II III IV C26 AS 20.00 20.00 20.00 20.00 CFAA 5.0 5.0 5.0 5.0 LAS (C11-13) 10.0 10.0 10.0 10.0 Sodium carbonate 25.0 25.0 25.0 25.0 Sodium pyrophosphate 7.0 7.0 7.0 7.0 STPP 7.0 7.0 7.0 7.0 Zeolite A 5.0 5.0 5.0 5.0 CMC 0.2 0.2 0.2 0.2 Polyacrylate (PM 1400) 0.2 0.2 0.2 0.2 Coconut monoethanolamine 5.0 5.0 5.0 5.0 Amylase 0.01 0.02 0.01 0.01 Protease 0.3 - 0.5 0.05 Brightener, perfume 0.2 0.2 0.2 0.2 CaSO4 1.0 1.0 1.0 1.0 MgS04 1.0 1.0 1.0 1.0 Water 4.0 4.0 4.0 4.0 Filler: 100% balance * Can be selected from suitable materials such as CaCO3, talc, clay (kaolinite, smectite), silicates and the like.
SEQUENCE DESCRIPTION: SEQ ID No. 1
His His Asn Gly Thr Asn Gly Thr Met Met Gln Tyr Phe Glu Trp Tyr 1 5 10 15 Leu Pro Asn Asp Gly Asn His Trp Asn Arg Leu Arg Asp Asp Wing Wing 20 25 30 Asn Leu Lys Ser Lys Gly lie Thr Wing Val Trp He Pro Pro Wing Trp 35 40 45 Lys Gly Thr Ser Gln Asn Asp Val Gly Tyr Gly Wing Tyr Asp Leu Tyr 50 55 60 Asp Leu Gly Glu Phe Asn Gln Lys Gly Thr Val Arg Thr Lys Tyr Gly 65 70 75 80 Thr Arg Asn Gln Leu Gln Wing Wing Val Thr Ser Leu Lys Asn Asn Gly 85 80 95 lie Gln Val Tyr Gly Asp Val Val Met Asn His Lys Gly Gly Wing Asp 100 105 110 Gly Thr Glu lie Val Asn Wing Val Glu Val Asn Arg Ser Asn Arg Asn 115 120 125 Gln Glu Thr Ser Gly Glu Tyr Wing He Glu Wing Trp Thr Lys Phe Asp 130 135 140 Phe Pro Gly Arg Gly Asn Asn His Ser Ser Phe Lys Trp Arg Trp Tyr 145 150 155 160 His Phe Asp Gly Thr Asp Trp Asp Gln Ser Arg GIn Leu Gln Asn Lys 165 170 175
He Tyr Lys Phe Arg Gly Thr Gly Lys Wing Trp Asp Trp Glu Val Asp 180 185 190 Thr Glu Asn Gly Asn Tyr Asp Tyr Leu Met Tyr Wing Asp Val Asp Met 195 200 205 Asp His Pro Glu Val He His Glu Leu Arg Asn Trp Gly Val Trp Tyr 210 215 220 Thr Asn Thr Leu Asn Leu Asp Gly Phe Arg lie Asp Ala Val Lys His 225 230 235 240
He Lys Tyr Ser Phe Thr Arg Asp Trp Leu Thr His Val Arg Asn Thr 245 250 255 Thr Gly Lys Pro Met Phe Wing Val Wing Glu Phe Trp Lys Asn Asp Leu 260 265 270 Gly Wing He Glu Asn Tyr Leu Asn Lys Thr Ser Trp Asn His Ser Val 275 280 285 Phe Asp Val Pro Leu His Tyr Asn Leu Tyr Asn Wing Ser Asn Ser Gly
290 295 300 Gly Tyr Tyr Asp Met Arg Asn He Leu Asn Gly Ser Val Val Gln Lys 205 310 315 320
His Pro Thr His Wing Val Thra Phe Val Asp Asn His Asp Ser Gln Pro 325 330 335 Gly Glu Ala Leu Glu Ser Phe Val Gln Gln Trp Phe Lys Pro Leu Ala
340 345 350 Tyr Ala Leu Val leu Thr Arg Glu Gln Gly Tyr Pro Ser Val Phe Tyr 355 360 365 Gly Asp Tyr Tyr Gly lie Pro Thr His Gly Val Pro Wing Met Lys Ser 370 375 380 Lys He Asp Pro leu Leu Gln Ala Arg Gln Thr Phe Wing Tyr Gly Thr 385 380 395 400
Gln His Asp Tyr Phe Asp His His Asp He He Gly Trp Thr Arg Glu 405 410 415 Gly Asn Ser Ser His Pro Asn Ser Gly Leu Wing Thr He Met Ser Asp
420 425 430 Gly Pro Gly Gly Asn Lys Trp Met Tyr Val Gly Lys Asn Lys Wing Gly 435 440 445 Gln Val Trp Arg Asp Lie Thr Gly Asn Arg Thr Gly Thr Val Thr He 450 455 460 Asn Wing Asp Gly Trp Gly Asn Phe Ser Val Asn Gly Gly Ser Val Ser 465 470 475 480
Val Trp Val Lys Gln 485 SEQUENCE DESCRIPTION: SEQ ID No. 2
His His Asn Gly Thr Asn Gly Thr Met Met Gln Tyr Phe Glu Trp His 1 5 10 15 Leu Pro Asn Asp Gly Asn His Trp Asn Arg Leu Arg Asp Asp Wing Wing Ser 20 25 30 Asn Leu Arg Asn Arg Gly lie Thr Ala He Trp He Pro Pro Wing Trp 35 40 45 Lys Gly Thr Ser Gln Asn Asp Val Gly Tyr Gly Wing Tyr Asp Leu Tyr 50 55 60 Asp Leu Gly Glu Phe Asn Gln Lys Gly Thr Val Arg Thr Lys Tyr Gly 65 70 75 Thr Arg Asn Gln Leu Glu Ser Ala lie His Ala Leu Lys Asn Asn Gly 80 85 90 95 Val Gln Val Tyr Gly Asp Val Val Met Asn His Lys Gly Gly Wing Asp 100 105 1 10 Wing Thr Glu Asn Val Leu Wing Val Glu Val Asn Pro Asn Asn Arg Asn 1 15 120 125 Gln Glu He Ser Gly Asp Tyr Thr He Gly Wing Trp Thr Lys Phe Asp 130 130 140 Phe Pro Gly Arg Gly Asn Thr Tyr Ser Asp Phe Lys Trp Arg Trp Tyr 145 150 155 His Phe Asp Gly Val Asp Trp Asp Gln Ser Arg Gln Phe Gln Asn Arg 160 165 170 175 He Tyr Lys Phe Arg Gly Asp Gly Lys Wing Trl Asp Trp Glu Val Asp 180 185 190 Ser Glu Asn Gly Asn Tyr Asp Tyr Leu Met Tyr Wing Asp Val Asp Met 195 200 205 Asp His Pro Glu Val Val Asn Glu Leu Arg Arg Trp Gly Glu Trp Tyr 210 215 220 Thr Asn Thr Leu Asp Leu Asp Gly Phe Arg lie Asp Wing Val Lys His 225 230 235 He Lys Tys Ser Phe Thr Arg Asp Trp Leu Thr His Val Arg Asn Wing 240 245 250 255 THr Gly Lys Glu Met Phe Wing Wing Val Wing Glu Phe Trp Lys Asn Asp Leu Gly Wing Leu Glu Asn Tyr Leu Asn Lys Thr Asn Trp Asn His Ser Val 275 280 285 Phe Asp Val Pro Leu His Tyr Asn Leu Tyr Asn Wing Ser Asn Ser Gly 290 295 300 Gly Asn Tyr Asp Met Wing Lys Leu Leu Asn Gly Thr Val Val Gln Lys 305 310 315 His Pro Met His Wing Val Thr Phe Val Asp Asn His Asp Ser Gln Pro 320 325 330 335 Gly Glu Ser Leu Glu Ser Phe Val Gln Glu Trp Phe Lys Pro Leu Wing 340 345 350 Tyr Ala Leu He Leu Thr Arg Glu Gln Gly Tyr Pro Ser Val Phe Tyr
355 360 365 Gíy Asp Tyr Tyr Gly He Pro Thr His Ser Val Pro Wing Ala Lys Wing 370 375 380 Lys He Asp Pro He Leu Glu Wing Arg GIn Asn Phe Wing Tyr Gly Thr
385 380 395 Gln His Asp Tyr Phe Asp His His Asn lie He Gly Trp Thr Arg Glu 400 405 410 415
Gly Asn Thr Thr His Pro Asn Ser Gly Leu Wing Thr He Met Ser Asp
420 425 430 Gly Pro Gly Gly Glu Lys Trp Met Tyr Val Gly Gln Asn Lys Al Gly 435 440 445 Gln Val Trp His Asp He Thr Gly Asn Lys Pro Gly Thr Val Thr He 450 455 460 Asn Wing Asp Gly Trp Wing Asn Phe Ser Val Asn Gly Gly Ser Val Ser
465 470 475 He Trp Val Lys Arg 480
SEQUENCE DESCRIPTION: SEQ ID NO. 3
His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-GIn-Tyr-Phe-GIu-Trp-Trp-Tyr-Leu-Pro-Asn-Asp
SEQUENCE DESCRIPTION: SEQ ID NO. 4
AAPFNGTMMQ YFEWYLPDDG TLWTKVANEA NNLSSLG1TA LWLPPAYKGT
SRSDVGYGVY DLYDLGEFNQ KGAVRTKYGT KAQYLQAIQA AHAAGMQVYA
DWFDHKGGA DGTEWVDAVE VNPSDRNQEI SGTYQIQAWT KFDFPGRGNT
YSSFKWRWYH FDGVDWDESR KLSRIYKFRG IGKAWDWEVD
TENGNYDYLM
YADLDMDHPE WTELKSWGK WYVNTTNIDG FRLDAVKHK FSFFPDWLSD VRSQGKPLF TVGEYWSYDI NKLHNYIMKT NGTMSLFDAP LHNKFYTASK
SGGTFDMRTL TNTLMKDQP TLAVTFVDNH DTEPGQALOS WVDPWFKPLA
YAFILTRQEG YPCVFYGDYY GIPQYNIPSL KSKIDPLL1A RRDYAYGTOH
DYLDHSDIIG WTREGVTEKP GSGLAALITD GPGGSKWMYV GKQHAGKVFY
DLTGNRSDTV TINSDGWGEF KVNGGSVSVW VPRKTTVSTI AWSITTRPWT
DEFVRWTPR LVAWP
Claims (8)
1. - The use of a specific amylase in a laundry detergent composition, selected from: (a) α-amylases characterized by having a specific activity at least 25% greater than the specific activity of Termamyl® at a temperature scale of 25 ° C at 55 ° C and at a pH value on the scale of 8 to 10, as measured by the Phadebas® α-amylase activity test and / or; (b) α-amylase according to (a) comprising the amino acid sequence shown in SEQ ID No. 1 or an α-amylase that is at least 80% homologous with the amino acid sequence shown in SEQ ID No. 1 I; (c) α-amylase according to (a) comprising the amino acid sequence shown in SEQ ID No. 2 or an α-amylase that is at least 80% homologous with the amino acid sequence shown in SEQ ID No. 2 I; (d) α-amylase according to (a) comprising the following N-terminal amino acid sequence: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe- Glu-Trp-Tyr-Leu-Pro-Asn-Asp- (SEQ ID No. 3) or an α-amylase that is at least 80% homologous with the amino acid sequence shown in (SEQ ID No. 3) in the terminal N and / or; (e) α-amylase according to (ad) wherein the α-amylase is obtainable from an alkalophilic species of Bacillus and / or (f) α-amylase according to (e) wherein the α-amylase is obtainable from any of strains NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935 and / or; (g) α-amylase showing positive immunological cross-reactivity with antibodies raised against an α-amylase having an amino acid sequence corresponding respectively to SEQ ID No. 1, ID No. 2 or ID No. 3 and / or; (h) variant of a progenitor α-amylase having (i) one of the amino acid sequences shown in SEQ ID No. 1, ID No. 2 or ID No. 4 respectively, or (ii) displaying at least 80% of homology with one or more of said amino acid sequences, and / or display immunological cross-reactivity with an antibody produced against an α-amylase having one of said amino acid sequences, and / or which is encoded by a DNA sequence that hybridizes with the same probe as the DNA sequence encoding an α-amylase having one of said amino acid sequences; variants in which: (i) at least one amino acid residue of said progenitor α-amylase has been removed; and / or (ii) at least one amino acid residue of said progenitor α-amylase has been replaced by a different amino acid residue and / or (iii) at least one amino acid residue has been inserted relative to said a-amylase. progenitor amylase; said variant having an α-amylase activity and exhibiting at least one of the following properties in relation to said progenitor α-amylase: increased thermostability, increased stability towards oxidation, reduced dependence on calcium ions, increased stability and / or activity a-amylolytic at relatively high neutral values, a-amylolytic activity increased at relatively high temperatures and an increase or decrease in the isoelectric point (pl) so that the pl value for a variant of α-amylase can be better the pH of the medium; to provide effective cleaning and bleaching of soiled fabrics.
2. The use of a specific amylase according to claim 1, further characterized in that said α-amylase in a laundry detergent composition is comprised at a level of 0.0001% to 0.1%, preferably at a level of 0.00018% at 0.060. %, most preferably at a level of 0.00024% to 0.048% pure enzyme by weight of the total composition.
3. The use of a specific amylase in a laundry detergent composition according to any of the preceding claims, further characterized in that said laundry detergent composition further comprises a protease.
4. The use of a specific amylase in a laundry detergent composition according to any of the preceding claims, further characterized in that said laundry detergent composition further comprises one or more components selected from anionic, nonionic, cationic, amphoteric surfactants and zwitterionics, suds suppressors, suspending and antiredeposition agents for soils, smectite clays and the like.
5. The use of a specific amylase in a laundry detergent composition according to any of the preceding claims, further characterized in that said laundry detergent composition is a granular detergent composition containing not more than 15% by weight of inorganic filler salt.
6. The use of a specific amylase in a laundry detergent composition according to claims 1-4, further characterized in that said laundry detergent composition is a heavy duty liquid composition.
7. The use of a specific amylase in a laundry detergent composition according to any of the preceding claims, further characterized in that said laundry detergent composition further comprises other enzymes that provide performance benefits of cleaning and / or care of fabrics.
8. The use of a specific amylase in a laundry detergent composition according to claim 1, further characterized in that said laundry detergent composition is in the form of a detergent additive.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
USUS96/12612 | 1996-08-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
MXPA99001186A true MXPA99001186A (en) | 1999-06-01 |
Family
ID=
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