WO1997045513A9 - Detergent composition - Google Patents
Detergent compositionInfo
- Publication number
- WO1997045513A9 WO1997045513A9 PCT/US1997/008560 US9708560W WO9745513A9 WO 1997045513 A9 WO1997045513 A9 WO 1997045513A9 US 9708560 W US9708560 W US 9708560W WO 9745513 A9 WO9745513 A9 WO 9745513A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- detergent composition
- carbon atoms
- composition according
- acid
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 177
- 239000003599 detergent Substances 0.000 title claims abstract description 102
- -1 organic peroxyacid compound Chemical class 0.000 claims abstract description 83
- 230000002209 hydrophobic Effects 0.000 claims abstract description 48
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 38
- 150000004967 organic peroxy acids Chemical class 0.000 claims abstract description 37
- 238000004061 bleaching Methods 0.000 claims abstract description 19
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 72
- 150000001875 compounds Chemical class 0.000 claims description 64
- 125000000217 alkyl group Chemical group 0.000 claims description 59
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 31
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 19
- 125000003342 alkenyl group Chemical group 0.000 claims description 16
- 125000005466 alkylenyl group Chemical group 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 125000005418 aryl aryl group Chemical group 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 125000000732 arylene group Chemical group 0.000 claims description 9
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 3
- 230000000750 progressive Effects 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 10
- 238000010412 laundry washing Methods 0.000 abstract description 5
- 238000004851 dishwashing Methods 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 description 57
- 239000007844 bleaching agent Substances 0.000 description 44
- 239000011780 sodium chloride Substances 0.000 description 39
- 239000002253 acid Substances 0.000 description 36
- 150000003839 salts Chemical class 0.000 description 36
- 239000002518 antifoaming agent Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- 239000011734 sodium Substances 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 19
- 229920001296 polysiloxane Polymers 0.000 description 18
- 239000002689 soil Substances 0.000 description 18
- 239000004744 fabric Substances 0.000 description 17
- 229940091252 Sodium supplements Drugs 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052708 sodium Inorganic materials 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 102000004190 Enzymes Human genes 0.000 description 15
- 108090000790 Enzymes Proteins 0.000 description 15
- 239000004367 Lipase Substances 0.000 description 15
- 108090001060 lipase Proteins 0.000 description 15
- 235000019421 lipase Nutrition 0.000 description 15
- 102000004882 lipase Human genes 0.000 description 15
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 15
- 239000010457 zeolite Substances 0.000 description 15
- 229940040461 Lipase Drugs 0.000 description 14
- 150000007513 acids Chemical class 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- 229920000768 polyamine Polymers 0.000 description 14
- 108010065511 Amylases Proteins 0.000 description 13
- 102000013142 Amylases Human genes 0.000 description 13
- 150000001204 N-oxides Chemical class 0.000 description 13
- 229910052783 alkali metal Inorganic materials 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 13
- 239000003352 sequestering agent Substances 0.000 description 13
- 239000000344 soap Substances 0.000 description 13
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Natural products O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 12
- 102000014961 Protein Precursors Human genes 0.000 description 12
- 108010078762 Protein Precursors Proteins 0.000 description 12
- 235000019418 amylase Nutrition 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 150000004965 peroxy acids Chemical class 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 11
- 102000033147 ERVK-25 Human genes 0.000 description 11
- 229940088598 Enzyme Drugs 0.000 description 11
- 108091005771 Peptidases Proteins 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- 150000001768 cations Chemical class 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 229920005646 polycarboxylate Polymers 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 11
- KWIUHFFTVRNATP-UHFFFAOYSA-N Trimethylglycine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 10
- 150000008051 alkyl sulfates Chemical group 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 229910001385 heavy metal Inorganic materials 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000004382 Amylase Substances 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000004365 Protease Substances 0.000 description 9
- 150000001340 alkali metals Chemical class 0.000 description 9
- 239000003945 anionic surfactant Substances 0.000 description 9
- 239000004927 clay Substances 0.000 description 9
- 229910052570 clay Inorganic materials 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 241000894007 species Species 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- 230000001629 suppression Effects 0.000 description 9
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 8
- 125000000129 anionic group Chemical group 0.000 description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 7
- 229940106157 CELLULASE Drugs 0.000 description 7
- 108010059892 Cellulase Proteins 0.000 description 7
- 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 7
- 239000012190 activator Substances 0.000 description 7
- 125000002091 cationic group Chemical group 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 description 7
- 125000001867 hydroperoxy group Chemical group [*]OO[H] 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 229960003010 sodium sulfate Drugs 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 description 6
- 241000048284 Potato virus P Species 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
- 150000001408 amides Chemical class 0.000 description 6
- 230000027455 binding Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 235000019832 sodium triphosphate Nutrition 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Didronel Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 5
- 229960004106 citric acid Drugs 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 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 5
- 239000002304 perfume Substances 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 5
- 239000003760 tallow Substances 0.000 description 5
- 239000002888 zwitterionic surfactant Substances 0.000 description 5
- UJCHIZDEQZMODR-BYPYZUCNSA-N (2R)-2-acetamido-3-sulfanylpropanamide Chemical compound CC(=O)N[C@@H](CS)C(N)=O UJCHIZDEQZMODR-BYPYZUCNSA-N 0.000 description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-L 2-sulfobutanedioate Chemical class OS(=O)(=O)C(C([O-])=O)CC([O-])=O ULUAUXLGCMPNKK-UHFFFAOYSA-L 0.000 description 4
- 241001669680 Dormitator maculatus Species 0.000 description 4
- 101700015827 FYPP3 Proteins 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N Imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical compound O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N Sodium silicate Chemical class [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 239000004902 Softening Agent Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000002280 amphoteric surfactant Substances 0.000 description 4
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000003197 catalytic Effects 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N fumaric acid Chemical compound OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000003951 lactams Chemical class 0.000 description 4
- 230000003287 optical Effects 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 101700004450 phpP Proteins 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K 2qpq Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- 229940025131 Amylases Drugs 0.000 description 3
- 229960005261 Aspartic Acid Drugs 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 3
- 210000003141 Lower Extremity Anatomy 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinylpyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- MWNQXXOSWHCCOZ-UHFFFAOYSA-M Sodium percarbonate Chemical compound [Na+].OOC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-M 0.000 description 3
- 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 3
- 235000015450 Tilia cordata Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 235000003704 aspartic acid Nutrition 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001860 citric acid derivatives Chemical class 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 125000002993 cycloalkylene group Chemical group 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000008394 flocculating agent Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 230000002366 lipolytic Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 125000005342 perphosphate group Chemical group 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910052904 quartz Inorganic materials 0.000 description 3
- 101700002095 rsp-6 Proteins 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N (E)-but-2-enedioate;hydron Chemical class OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(E)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 2
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(E)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 2
- 229910016887 MnIV Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N Oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920000805 Polyaspartic acid Polymers 0.000 description 2
- 229960004063 Propylene glycol Drugs 0.000 description 2
- 241000589630 Pseudomonas pseudoalcaligenes Species 0.000 description 2
- JBUKJLNBQDQXLI-UHFFFAOYSA-N Sodium perborate Chemical compound [Na+].[Na+].O[B-]1(O)OO[B-](O)(O)OO1 JBUKJLNBQDQXLI-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- HWKQNAWCHQMZHK-UHFFFAOYSA-N Trolnitrate Chemical compound [O-][N+](=O)OCCN(CCO[N+]([O-])=O)CCO[N+]([O-])=O HWKQNAWCHQMZHK-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 125000004171 alkoxy aryl group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
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- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- UUUDMEBRZTWNAO-UHFFFAOYSA-N carbonic acid;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound OC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O UUUDMEBRZTWNAO-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cells Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010367 cloning Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- NERQXUOKJAXUHN-UHFFFAOYSA-L cobalt(3+);2-[3-[3-[(2-oxidophenyl)methylideneamino]propylazanidyl]propyliminomethyl]phenolate Chemical compound [Co+3].[O-]C1=CC=CC=C1C=NCCC[N-]CCCN=CC1=CC=CC=C1[O-] NERQXUOKJAXUHN-UHFFFAOYSA-L 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 229960005188 collagen Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 108010005400 cutinase Proteins 0.000 description 1
- 230000001461 cytolytic Effects 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([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])[H] 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003292 diminished Effects 0.000 description 1
- NTGONJLAOZZDJO-UHFFFAOYSA-M disodium;hydroxide Chemical compound [OH-].[Na+].[Na+] NTGONJLAOZZDJO-UHFFFAOYSA-M 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- JHUXOSATQXGREM-UHFFFAOYSA-N dodecanediperoxoic acid Chemical compound OOC(=O)CCCCCCCCCCC(=O)OO JHUXOSATQXGREM-UHFFFAOYSA-N 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N edta Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 230000002255 enzymatic Effects 0.000 description 1
- IGBSXRIJNMDLFB-UHFFFAOYSA-N ethane-1,2-diamine;pentanedioic acid Chemical compound NCCN.OC(=O)CCCC(O)=O.OC(=O)CCCC(O)=O IGBSXRIJNMDLFB-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000001530 fumaric acid Chemical class 0.000 description 1
- 230000002538 fungal Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DUCCPNVOQJMMAN-UHFFFAOYSA-O hexanoyloxy(dimethyl)azanium Chemical compound CCCCCC(=O)O[NH+](C)C DUCCPNVOQJMMAN-UHFFFAOYSA-O 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical class OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-M isethionate Chemical class OCCS([O-])(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FODOUIXGKGNSMR-UHFFFAOYSA-L magnesium;2-oxidooxycarbonylbenzoate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-]OC(=O)C1=CC=CC=C1C([O-])=O FODOUIXGKGNSMR-UHFFFAOYSA-L 0.000 description 1
- 239000011683 manganese gluconate Substances 0.000 description 1
- 235000014012 manganese gluconate Nutrition 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- YZTQKMVBEGUONQ-UHFFFAOYSA-N manganese(4+) Chemical class [Mn+4] YZTQKMVBEGUONQ-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking Effects 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M methanoate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([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])C([H])([H])[H] 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 201000002674 obstructive nephropathy Diseases 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000004430 oxygen atoms Chemical group O* 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- DMCJFWXGXUEHFD-UHFFFAOYSA-N pentatriacontan-18-one Chemical compound CCCCCCCCCCCCCCCCCC(=O)CCCCCCCCCCCCCCCCC DMCJFWXGXUEHFD-UHFFFAOYSA-N 0.000 description 1
- PNIJRIIGBGFYHF-UHFFFAOYSA-N perborate(2-) Chemical compound O[B-]1(O)OO[B-](O)(O)OO1 PNIJRIIGBGFYHF-UHFFFAOYSA-N 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- RRCSSMRVSNZOFR-UHFFFAOYSA-N phenyl 3,5,5-trimethylhexanoate;sodium Chemical compound [Na].CC(C)(C)CC(C)CC(=O)OC1=CC=CC=C1 RRCSSMRVSNZOFR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- NJKRDXUWFBJCDI-UHFFFAOYSA-J propane-1,1,2,3-tetracarboxylate Chemical class [O-]C(=O)CC(C([O-])=O)C(C([O-])=O)C([O-])=O NJKRDXUWFBJCDI-UHFFFAOYSA-J 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective Effects 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-M sarcosinate Chemical compound CNCC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-M 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000003385 sodium Chemical group 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000001187 sodium carbonate Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- VQOIVBPFDDLTSX-UHFFFAOYSA-M sodium;3-dodecylbenzenesulfonate Chemical class [Na+].CCCCCCCCCCCCC1=CC=CC(S([O-])(=O)=O)=C1 VQOIVBPFDDLTSX-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000004434 sulfur atoms Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 239000011975 tartaric acid Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000004026 tertiary sulfonium compounds Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 230000001052 transient Effects 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical class N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Definitions
- the present invention relates to detergent compositions containing a cationic surfactant and a hydrophobic organic peroxyacid bleaching system, which are suitable for use in laundry and dishwashing methods.
- hydrophobic organic peroxyacids can be employed in detergent products.
- Such organic peroxyacids generally comprise long chain ( > 7 carbon atoms) alkyl moieties.
- Hydrophobic bleaches are known to have a tendency to migrate rapidly to the surface of fabrics under wash conditions.
- Bleaches which may be hydrophobic are disclosed for example in EP-A-0170386. It is stated that these bleaches may be used in compositions which incorporate different types of surfactant materials. Anionic, nonionic, zwitterionic and amphoteric surfactants are disclosed. Hydrophobic bleaching agents are also described in WO95/3226 as useful suds suppressants in detergent compositions containing high levels of surfactant.
- Quaternary ammonium compounds are known cationic surfactants.
- alkoxylated nonionic and cationic surfactants and anionic surfactants are used in combination to produce detergents for fabric washing.
- hydrophobic bleaches despite their tendency to migrate to the fabric surface, they do not necessarily interact fully with the stain or soil components. It has been found that the hydrophobic bleaches can be prevented from migration onto the greasy stains/soils by deposited 'lime soaps' (formed by alkaline earth ions with fatty acids, present in the wash solution) on the fabric. Thereby, their bleaching performance can be diminished. This result in a lessening of the dingy soil cleaning performance of the hydrophobic bleach.
- a detergent composition according to a first aspect of the present invention comprises
- R 1 is a hydroxyalkyl group having no greater than 6 carbon atoms; each of R-- and R. is independently selected from Ci . 4 alkyl or alkenyl; R ⁇ is C5.1 1 alkyl or alkenyl and X " is an anion; and
- a hydrophobic organic peroxyacid bleaching system capable of providing a hydrophobic organic peroxyacid compound.
- Preferred cationic surfactants of formula I are those in which R* is -CH2CH2OH or -CH2CH2CH2OH; each of R 2 and R 3 are, independently, C1.4 alkyl; R 4 is C5.11 alkyl or alkenyl and X" is an anion.
- An essential feature of detergent compositions of the invention is a hydrophobic organic peroxyacid bleaching system capable of providing a hydrophobic organic peroxyacid compound.
- hydrophobic organic peroxyacid compound it is meant herein an organic peroxyacid whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre and wherein said critical micelle concentration is measured in aqueous solution at 20°-50°C.
- the hydrophobic organic peroxyacid contains at least 7 carbon atoms, more preferably at least 9 carbon atoms, most preferably at least 11 carbon atoms.
- the peroxyacid has an alkyl chain comprising at least 7 carbon atoms, more preferably at least 8 carbon atoms, most preferably at least 9 carbon atoms.
- a preferred hydrophobic organic peroxyacid bleaching system is capable of providing a peroxyacid compound of the formula:
- R ⁇ is an alkyl, aryl or aralkyl group containing from 1 to 14 carbon atoms
- R 7 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms
- R is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms.
- a detergent composition comprising
- R is a hydroxyalkyl group having no greater than 6 carbon atoms; each of R 2 and R ⁇ is independently selected from C .4 alkyl or alkenyl; R 4 is a C 2-14 alkyl or alkenyl and X " is an anion; and
- R ⁇ is an alkyl, aryl or aralkyl group containing from 1 to 14 carbon atoms
- R 7 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms
- R ⁇ is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms.
- Preferred detergent compositions of the invention additionally comprise a hard base polymeric component.
- alkyl or alkenyl as used herein may be branched, linear or substituted.
- Substituents may be for example, aromatic groups, heterocyclic groups containing one or more N, S or O atoms, or halo substituents.
- An essential element of the detergent compositions of the invention is a cationic quaternary ammonium surfactant.
- the cationic surfactant unless otherwise stated may be present in amounts up to 10.0% by weight of the detergent composition. However, preferably the maximum amount of the cationic surfactant in the detergent composition is below 5% . Most preferably, the cationic surfactant will be present in an amount below 4% or even 4.5% by weight of the detergent composition. Generally there will be at least 0.05% by weight or even at least 0.1 % or at least 0.5% by weight of the cationic surfactant in the composition.
- the — OH group in Rl in formula I is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms.
- Preferred R groups are — CH 2 -CH 2 OH, — CH 2 CH 2 CH 2 OH, CH 2 CH 2 (CH 3 )OH and — CH(CH3)CH2OH.
- CH2CH2OH and — CH2CH2CH2OH are most preferred and — CH2CH2OH is particularly preferred.
- R 2 and R 3 are each selected from ethyl and methyl groups and most preferably both R 2 and R3 are methyl groups.
- Preferred R4 groups have at least 6 or even at least 7 carbon atoms.
- R 4 may have no greater than 9 carbon atoms, or even no greater than 8 or 7 carbon atoms.
- Preferred R 4 groups are linear alkyl groups. Linear R 4 groups having from 8 to 11 carbon atoms, or from 8 to 10 carbon atoms are preferred.
- the cationic surfactant of formula I has a Rl group which is -CH2CH2OH.
- R 2 and R 3 are methyl groups.
- mixtures of the cationic surfactants of formula I may be particularly effective, for example surfactant mixtures in which R 4 may be a combination of Cg and C10 linear alkyl groups, or Co, and C ⁇ ⁇ linear alkyl groups.
- a mixture of cationic surfactants of formula I is present in the composition, the mixture comprising a shorter alkyl chain surfactant of formula I and a longer alkyl chain surfactant of formula I.
- the longer alkyl chain cationic surfactant is preferably selected from the surfactants of formula I where R 4 is an alkyl group having n carbon atoms where n is from 8 to 11; the shorter alkyl chain surfactant is preferably selected form those of formula I where R 4 is an alkyl group having (n-2) carbon atoms.
- the detergent compositions of the invention comprise a combination of cationic surfactants for formula I comprising 1 % to 65% of a shorter alkyl chain length R 4 group and 35% to 99% by weight of a longer alkyl chain length. Mixtures comprising R 4 groups of Cg and Cio alkyl groups are particularly preferred.
- the hydrophobic organic peroxyacid bleaching system comprises a hydrogen peroxide source and a hydrophobic organic peroxyacid bleach precursor compound.
- the production of the hydrophobic organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
- Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.
- the hydrophobic organic peroxyacid bleaching system comprises a preformed hydrophobic organic peroxyacid, which is incorporated directly into the composition.
- Compositions containing mixtures of a hydrogen peroxide source and hydrophobic organic peroxyacid precursor in combination with a preformed hydrophobic organic peroxyacid are also envisaged.
- Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the alkali metal, preferably sodium salt at a level of from 1 % to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight of the compositions. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection.
- Suitable executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
- Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.
- Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate NaBO 2 H2O 2 .3H 2 O.
- Alkali metal percarbonates particularly sodium percarbonate are preferred perhydrates herein.
- Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C ⁇ 3-3H2 ⁇ 2, and is available commercially as a crystalline solid.
- Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.
- Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
- peroxyacid bleach precursors may be represented as
- L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is O X C OOH
- X will thus contain at least 6 carbon atoms.
- the hydrophobic peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.05% to 20% by weight, more preferably from 0.1 % to 15% by weight, most preferably from 0.2% to 10% by weight of the detergent compositions.
- Suitable hydrophobic peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes.
- Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789.
- Suitable esters are disclosed in GB-A- 836988, 864798, 1147871 , 2143231 and EP-A-0170386.
- L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
- Preferred L groups are selected from the group consisting of:
- R is an alkyl, aryl, or alkaryl group containing
- R is an alkyl chain containing from 1 to 8 carbon atoms
- R 4 is H or R 3
- Y is H or a solubilizing group.
- Any of R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups
- M is an alkyl chain containing from 1 to 4 carbon atoms
- M is a cation which provides solubility to the bleach activator
- X is an anion which provides solubility to the bleach activator.
- M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred
- X is a halide, hydroxide, methylsulfate or acetate anion.
- R ⁇ is an aryl or alkaryl group with from about 1 to about 14 carbon atoms
- R 7 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms
- R is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
- R ⁇ preferably contains from about 6 to 12 carbon atoms.
- R- 7 preferably contains from about 4 to 8 carbon atoms.
- R5 may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat.
- precursor compounds of the benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
- R is an alkyl, alkaryl, aryl, or arylalkyl containing at least 5 carbon atoms.
- Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
- Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N*Nl tetra acetylated alkylene diamines wherein the alkylene group contains at least 7 carbon atoms.
- Still another class of hydrophobic bleach activators are the N-acylated precursor compounds of the lactam class disclosed generally in GB-A-955735.
- Preferred materials of this class comprise the caprolactams.
- Suitable caprolactam bleach precursors are of the formula:
- R 1 is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms.
- Preferred hydrophobic N-acyl caprolactam bleach precursor materials are selected from benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, 3,5,5- trimethylhexanoyl caprolactam and mixtures thereof. A most preferred is nonanoyl caprolactam.
- Suitable valero lactams have the formula: C H - C H .
- the organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed hydrophobic organic peroxyacid , typically at a level of from 0.05% to 20% by weight, more preferably from 1 % to 10% by weight of the composition.
- R ⁇ is an aryl or alkaryl group with from about 1 to about 14 carbon atoms
- R 7 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms
- R > is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
- R ⁇ preferably contains from about 6 to 12 carbon atoms.
- R 7 preferably contains from about 4 to 8 carbon atoms.
- R ⁇ may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 7 .
- R 7 can include alkyl, aryl, wherein said R 7 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
- R ⁇ is preferably H or methyl.
- R ⁇ and R ⁇ should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
- Suitable examples of this class of agents include (6-octylamino)-6- oxo-caproic acid, (6-nonylamino)-6-oxo-caproic acid, (6-decylamino)-6-oxo- caproic acid, magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
- Such bleaching agents are disclosed in U.S. 4,483,781 , U.S. 4,634,551 , EP 0, 133,354, U.S. 4.412,934 and EP 0.170,386.
- a preferred hydrophobic preformed peroxyacid bleach compound for the purpose of the invention is nonanonylamido peroxycarboxylic acid.
- Suitable organic peroxyacids for the first aspect of the invention include diperoxyalkanedioc acids having more than 7 carbon atoms, such as diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
- organic peroxyacids include diamino peroxyacids, which are disclosed in WO 95/ 03275, with the following general formula:
- R is selected from the group consisting of C ⁇ -C ⁇ 2 alkylene, C5-C12 cycloalkylene, Cg-Ci2 arylene and radical combinations thereof;
- R! and R ⁇ are independently selected from the group consisting of H, Cj-Cig alkyl and C6-C12 ar yl radicals and a radical that can form a C3-C12 ring together with R3 and both nitrogens;
- R ⁇ is selected from the group consisting of C -C12 alkylene, C5-C12 cycloalkylene and C6-C12 arylene radicals;
- n and n' each are an integer chosen such that the sum thereof is 1;
- m and m' each are an integer chosen such that the sum thereof is 1 ;
- M is selected from the group consisting of H, alkali metal, alkaline earth metal, ammonium, alkanolammonium cations and radicals and combinations thereof.
- Suitable organic peroxyacids are include the amido peroxyacids which are disclosed in WO 95/ 16673, with the following general structure:
- X represents hydrogen or a compatible substituent
- Ar is an aryl group
- the substituent X on the benzene nucleus is preferably a hydrogen or a meta or para substituent, selected from the group comprising halogen, typically chlorine atom, or some other non-released non-interfering species such as an alkyl group, conveniently up to C6 for example a methyl, ethyl or propyl group.
- X can represent a second amido-percarboxylic acid substituent of formula: -
- R, Y, Z and n are as defined above.
- R* is selected from the group consisting of C ⁇ -C ⁇ alkylene, C5-C12 cycloalkylene, C.5-C12 arylene and radical combinations thereof;
- Preferred detergent compositions according to the present invention additionally comprise a hard base organic polymeric component.
- a hard base organic polymeric component Preferably the total cationic surfactant and hard base polymeric component will be present in the detergent composition at a weight ratio 10: 1 to 1 :3, most preferably 5: 1 to 1 :2.
- the hard base polymeric component preferably comprises a polymer having a pendant group (that is to say a group which is not a polymeric linkage group, so that it does not form part of the polymer backbone) which is a harder base than a benzene sulphonate group
- the polymeric component comprises a polymer having a pendant group which is a harder base than a sulphonate group such as CH3CH2CH2-SO3-.
- the polymeric component is generally formed from at least 5%, preferably at least 25% by weight of monomers which result in such pendant groups.
- the polymeric component preferably has a molecular weight of from 1500 to 150000 most preferably from 2000 to 100000, especially 5000 to 80000. Molecular weight measurements are obtained by GPC using styrene as a standard.
- Particularly preferred pendant groups are carboxylic groups (references herein to acid groups also include their salts). Acrylic and maleic homopolymers or copolymers are particularly preferred.
- the hard base polymer may be any organic polymeric material having a hard base group commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions.
- organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic 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 the latter type are disclosed in GB-A-1, 596,756.
- Examples of such salts are polyacrylates of MWt 1500-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2,000 to 100,000, especially 5,000 to 80,000, or even 10,000 to 50,000.
- polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
- the hard base polymeric component is preferably present as components of any paniculate components where they may be beneficial as a binder.
- compositions of the invention preferably contain one or more additional detergent components selected from additional surfactants, additional bleaches, bleach catalysts, alkalinity systems, builders, organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
- additional detergent components selected from additional surfactants, additional bleaches, bleach catalysts, alkalinity systems, builders, organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
- the detergent compositions of the invention may contain an additional surfactant selected from anionic, nonionic, additional cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
- ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
- Anionic surfactant is generally used in combination with one or more anionic and/or nonionic surfactants.
- the detergent compositions of the present invention preferably comprise an additional anionic surfactant.
- anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
- Anionic sulfate surfactants are preferred.
- Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates. fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cj-C4 alkyl) and -N-(C ⁇ -C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
- Alkyl sulfate surfactants are preferably selected from the linear and branched primary branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
- Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C10-C18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a Cj i -Cjg, most preferably Ci 1 -C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
- a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
- Anionic sulfonate surfactant Anionic sulfonate surfactant
- Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C5-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
- Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
- Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x CH2C00 " M + wherein R is a C * to Cjg alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
- Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRj-CHR2- O)-R3 wherein R is a C5 to Ci8 alkyl group, x is from 1 to 25, Rj and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxy succinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
- Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
- Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l- decanoic acid, 2-propyl-l-nonanoic acid, 2-butyI-l-octanoic acid and 2-pentyl-l- heptanoic acid. Certain soaps may also be included as suds suppressors.
- alkali metal sarcosinates of formula R- CON (R 1 ) CH2 COOM, wherein R is a C 5 -C!7 linear or branched alkyl or alkenyl group, R* is a C1-C4 alkyl group and M is an alkali metal ion.
- R is a C 5 -C!7 linear or branched alkyl or alkenyl group
- R* is a C1-C4 alkyl group
- M is an alkali metal ion.
- myristyl and oleoyl methyl sarcosinates in the form of their sodium salts are preferred examples.
- any alkoxylated nonionic surfactants are suitable herein.
- the ethoxylated and propoxylated nonionic surfactants are preferred.
- Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxy lated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
- the condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
- the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
- Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
- Nonionic polvhvdroxy fatty acid amide surfactant Nonionic polvhvdroxy fatty acid amide surfactant
- Poly hydroxy fatty acid amides suitable for use herein are those having the structural formula R ⁇ CONRlZ wherein : Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably Ci or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C1 alkyl or alkenyl, most preferably straight- chain C12-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
- Z preferably
- Nonionic fatty acid amide surfactant Nonionic fatty acid amide surfactant
- Suitable fatty acid amide surfactants include those having the formula: R6cON(R 7 )2 wherein R ⁇ is an alkyl group containing from 7 to 21 , preferably from 9 to 17 carbon atoms and each R 7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4 ⁇ ) x H, where x is in the range of from 1 to 3.
- Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565.647, Llenado, issued January 21 , 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g. , a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
- Preferred alkylpolyglycosides have the formula
- R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
- the glycosyl is preferably derived from glucose.
- Amphoteric surfactant Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
- Suitable betaines are those compounds having the formula R(R')2N+R2C00 ⁇ wherein R is a C ⁇ -Cjg hydrocarbyl group, each R! is typically C1-C3 alkyl, and R2 is a C1 -C5 hydrocarbyl group.
- Preferred betaines are C12-I8 dimethyl- ammonio hexanoate and the C JO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
- Complex betaine surfactants are also suitable for use herein.
- Suitable cationic surfactants include the ethoxylated quaternary ammonium surfactants as described in GB-A-2040990, or ester surfactants.
- Suitable cationic ester surfactants, including choline ester surfactants have for example been disclosed in US Patents Nos. 4228042, 4239660 and 4260529.
- alkalinity system is present to achieve optimal cationic ester surfactant performance.
- the alkalinity system comprises components capable of providing alkalinity species in solution.
- alkalinity species it is meant herein: carbonate, bicarbonate, hydroxide, the various silicate anions, percarbonate, perborates, perphosphates, persulfate and persilicate.
- carbonates are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2,321 ,001 published on November 15, 1973.
- Suitable silicates include the water soluble sodium silicates with an Si ⁇ 2: Na2 ⁇ ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being most preferred.
- the silicates may be in the form of either the anhydrous salt or a hydrated salt.
- Sodium silicate with an Si ⁇ 2: Na2 ⁇ ratio of 2.0 is the most preferred silicate.
- Preferred crystalline layered silicates for use herein have the general formula
- M is sodium or hydrogen
- x is a number from 1.9 to 4 and y is a number from 0 to 20.
- Crystalline layered sodium silicates of this type are disclosed in EP- A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
- x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2.
- the most preferred material is ⁇ -Na2Si2 ⁇ 5, available from Hoechst AG as NaSKS-6.
- the detergent compositions of the present invention preferably contain a water- soluble builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
- Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixtures of any of the foregoing.
- the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
- Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
- 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 and the sulf yl carboxylates.
- Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
- Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed 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.
- Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
- Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
- the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
- Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
- Partially soluble or insoluble builder compound Partially soluble or insoluble builder compound
- the detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
- Examples of largely water insoluble builders include the sodium aluminosilicates.
- Suitable aluminosihcate zeolites have the unit cell formula Na z [(AlO2) z (SiO2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
- the aluminosihcate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
- the aluminosihcate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosihcate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula
- Zeolite X has the formula Nag6 [ ⁇ Al ⁇ 2)86 ⁇ Si ⁇ 2)l06]- 276 H 2 O.
- compositions optionally contain a transition metal containing bleach catalyst.
- a transition metal containing bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
- ethylenediaminetetraacetic acid ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
- bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include Mn ⁇ 2( u "0)3(l ' 4,7-trimethyl-l,4,7-triazacyclononane)2-(PF6)2, Mn III 2(u-O) (u-OAc)2(l,4,7-trimethyl-l ,4,7-triazacyclononane)2-(ClO4)2,
- Others are described in European patent application publication no. 549,272.
- ligands suitable for use herein include l ,5,9-trimethyl-l ,5,9-triazacyclododecane, 2-methyl-l ,4,7-triazacyclononane, 2-methyl-l ,4,7-triazacyclononane, 1 ,2,4,7- tetramethyl-l,4,7-triazacyclononane, and mixtures thereof.
- bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl-l,4,7-triazacyclononane)(OCH3)3_ (PFg).
- Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
- binuclear Mn complexed with tetra-N -dentate and bi-N-dentate ligands including N4Mn ⁇ (u-O)2Mn ⁇ N4) + and [Bipy2Mn*H(u- O)2Mn Iv bipy2]-(Cl ⁇ 4)3.
- bleach catalysts are described, for example, in European patent application No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosihcate catalyst), U.S. 4,601,845 (aluminosihcate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S.
- the detergent compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant.
- heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
- Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1 % to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions.
- Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1- hydroxy disphosphonates and nitrilo trimethylene phosphonates.
- organic phosphonates such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1- hydroxy disphosphonates and nitrilo trimethylene phosphonates.
- Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1 ,1 diphosphonate.
- Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
- Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
- iminodiacetic acid-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2- hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516, 102 are also suitable herein.
- EP-A-476,257 describes suitable amino based sequestrants.
- EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
- EP-A- 528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-l,2,4-tricarboxylic acid are also suitable.
- Glycinamide- N,N' -disuccinic acid (GADS), ethylenediamine-N-N' -diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N' -disuccinic acid (HPDDS) are also suitable.
- Another preferred ingredient useful in the detergent compositions is one or more additional enzymes.
- Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
- Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo
- Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the composition.
- Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described in more detail in GB-1 ,269,839 (Novo).
- Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S.
- Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001 % to 2% active enzyme by weight of the composition.
- Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001 % to 2% by weight, preferably 0.001 % to 1 % by weight, most preferably from 0.001 % to 0.5% by weight of the compositions.
- the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomvces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
- a preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.
- Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
- Organic polymeric compounds such as the hard base polymeric components described above are preferred additional components of the detergent compositions in accord with the invention, and are preferably present as components of any paniculate components where they may act such as to bind the paniculate component together.
- organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti- redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.
- Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1 % to 30% , preferably from 0.5% to 15% , most preferably from 1 % to 10% by weight of the compositions.
- organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic 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 the latter type are disclosed in GB-A-1, 596,756.
- polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
- Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
- organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxy methylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
- Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
- the detergent compositions of the invention when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01 % to 15 % , preferably from 0.05 % to 10% , most preferably from 0.1 % to 5% by weight of the composition.
- Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
- antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
- Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
- silicone antifoam compounds also typically contain a silica component.
- silica component The term "sihcone” as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
- Preferred sihcone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
- Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
- the monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
- Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
- Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g.
- fatty acid triglycerides fatty acid esters of monovalent alcohols
- aliphatic C ⁇ g-C40 ketones e.g. stearone
- N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
- aliphatic C ⁇ g-C40 ketones e.g. stearone
- N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with
- a preferred suds suppressing system comprises
- antifoam compound preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
- silica at a level of from 1 % to 50%, preferably 5% to 25% by weight of the silicone/si ica antifoam compound;
- silica/silicone antifoam compound is incorporated at a level of from 5% to 50% , preferably 10% to 40% by weight;
- a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10% , preferably 1 % to 10% by weight;
- a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544;
- an inert carrier fluid compound most preferably comprising a C ⁇ -Cj ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80% , preferably 10% to 70% , by weight;
- a highly preferred paniculate suds suppressing system is described in EP-A- 0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85 °C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
- the clay mineral compound is preferably a smectite clay compound.
- Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647.
- European Patents No.s EP-A-299,575 and EP-A-313, 146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
- the detergent compositions herein may also comprise from 0.01 % to 10 %, preferably from 0.05 % to 0.5% by weight of polymeric dye transfer inhibiting agents.
- the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
- the N-O group can be represented by the following general structures :
- Rl , R2, and R3 are aliphatic groups, aromatic, heterocychc or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
- the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
- Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocychc groups.
- R is selected from aliphatic, aromatic, alicyclic or heterocychc groups.
- One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
- Preferred polyamine N-oxides are those wherein R is a heterocychc group such as pyrridine, pyrrole, imidazole. pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
- the polyamine N-oxides can be obtained in almost any degree of polymerisation.
- the degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
- the average molecular weight is within the range of 500 to 1000,000.
- the detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents.
- Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
- the detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
- Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
- the detergent compositions herein also optionally contain from about 0.005% to 5 % by weight of certain types of hydrophilic optical brighteners.
- Hydrophilic optical brighteners useful herein include those having the structural formula:
- R is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl
- R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N- methylamino.
- M is a salt-forming cation such as sodium or potassium.
- the brightener is 4,4' ,-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
- This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
- R is anilino
- R2 is N-2-hydroxyethyl-N-2- methylamino
- M is a cation such as sodium
- the brightener is 4,4'-bis[(4- anilino-6-(N-2-hydroxyethy 1-N-methy lamino)-s-triazine-2-y l)amino]2 ,2 ' - stilbenedisulfonic acid disodium salt.
- This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
- the brightener is 4,4'-bis[(4-anilino-6-morphihno-s-triazine-2- yl)amino)2,2'-stilbenedisulfonic acid, sodium salt.
- This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
- Cationic fabric softening agents can also be incorporated into compositions in accordance with the present invention.
- Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 Oi l 340.
- Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15 % by weight, normally from 1 % to 5% by weight.
- compositions of the invention include colours and filler salts, with sodium sulfate being a preferred filler salt.
- the present compositions preferably have a pH measured as a 1 % solution in distilled water of at least 8.5, preferably from 9.0 to 12.5, most preferably from 9.5 to 11.0.
- compositions in accordance with the invention can take a variety of physical forms including granular, tablet, bar and liquid forms.
- the compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.
- granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.
- the mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5 % of particles are greater than 1.7mm in diameter and not more than 5 % of particles are less than 0.15mm in diameter.
- mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
- the bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre.
- Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel.
- the funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
- the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
- the cationic ester surfactant herein preferably with additional surfactants, is preferably present in granular compositions in the form of surfactant agglomerate particles, which may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules.
- the most preferred way to process the particles is by agglomerating powders (e.g. aluminosihcate, carbonate) with high active surfactant pastes and to control the particle size of the resultant agglomerates within specified limits.
- a high active surfactant paste comprising from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of surfactant is typically used.
- the paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the anionic surfactants used.
- An operating temperature of the paste of 50° C to 80° C is typical.
- Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention.
- an effective amount of the detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
- a dispensing device is employed in the washing method.
- the dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.
- the dispensing device containing the detergent product is placed inside the drum.
- water is introduced into the drum and the drum periodically rotates.
- the design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.
- Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle.
- Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157, 717, GB-B- 2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346.
- An article by J. Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette”.
- Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. WO94/11562.
- a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process .
- a portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium.
- the support ring is provided with a masking arrangement to prevent egress of wetted, undissolved. product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.
- the dispensing device may be a flexible container, such as a bag or pouch.
- the bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678.
- it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501 , 0011502, and 0011968.
- a convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
- Ci4_i5 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide
- Na 2(A102Si ⁇ 2)i2- 27H2O having a primary particle size in the range from 0.1 to 10 micrometers
- Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m
- Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
- Silicate Amorphous Sodium Silicate (SiO2:Na2O; 2.0 ratio)
- NACA 6 nonylamino - 6 oxo - capronic acid TAED Tetraacetylethylenediamme DTPMP Diethylene t ⁇ amine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest
- laundry detergent compositions A to F are compositions according to the invention:
- compositions G to I of bulk density 750 g/litre are compositions according to the invention:
- J is a phosphorus-containing detergent composition
- K is a zeolite-containing detergent composition
- L is a compact detergent composition
- Zeolite A 15.0 15.0 15.0
- liquid detergent formulations according to the present invention are liquid detergent formulations according to the present invention:
- NAC OBS 1.0 1.0 0.5 1.0 2.0 1.2 1.0 1.6
Abstract
There is provided a detergent composition suitable for use in laundry or dish washing methods comprising: (a) a quaternary ammonium cationic surfactant; and (b) a hydrophobic organic peroxyacid bleaching system, capable of providing a hydrophobic organic peroxyacid compound.
Description
Detergent compositions
Technical field
The present invention relates to detergent compositions containing a cationic surfactant and a hydrophobic organic peroxyacid bleaching system, which are suitable for use in laundry and dishwashing methods.
Background to the invention
The satisfactory removal of greasy soils/stains, that is soils/stains having a high proportion of triglycerides or fatty acids, is a challenge faced by the formulator of detergent compositions for use in laundry and dish washing methods. Surfactant components have traditionally been employed in detergent products to facilitate the removal of such greasy soils/stains. In particular, surfactant systems comprising cationic esters have been described for use in greasy soil/stain removal.
A particular challenge to the formulator of detergent compositions for use in a laundry washing method is the satisfactory removal of bleachable soils/stains such as tea, fruit juice and coloured vegetable soils from stained fabrics. It is known that stained fabrics have a tendency to present a 'dingy' appearance after frequent washing. Bleaches are traditionally employed in detergents to remove the bleachable stains or soils, and also those responsible for the 'dingy' appearance of the fabric. It is well established that peroxygen bleaches and bleaching systems, based on organic peroxyacids can provide stain and/or soil removal from fabrics. The organic peroxyacids are often obtained by the in situ perhydrolysis of organic peroxyacid bleach precursor compounds (bleach activators). To remove greasy stains/ soils, which are of hydrophobic nature, hydrophobic organic peroxyacids
can be employed in detergent products. Such organic peroxyacids generally comprise long chain ( > 7 carbon atoms) alkyl moieties. Hydrophobic bleaches are known to have a tendency to migrate rapidly to the surface of fabrics under wash conditions.
Bleaches which may be hydrophobic are disclosed for example in EP-A-0170386. It is stated that these bleaches may be used in compositions which incorporate different types of surfactant materials. Anionic, nonionic, zwitterionic and amphoteric surfactants are disclosed. Hydrophobic bleaching agents are also described in WO95/3226 as useful suds suppressants in detergent compositions containing high levels of surfactant.
Quaternary ammonium compounds are known cationic surfactants. For example in GB-A-2040990 alkoxylated nonionic and cationic surfactants and anionic surfactants are used in combination to produce detergents for fabric washing.
It has now been found that a problem with hydrophobic bleaches is that despite their tendency to migrate to the fabric surface, they do not necessarily interact fully with the stain or soil components. It has been found that the hydrophobic bleaches can be prevented from migration onto the greasy stains/soils by deposited 'lime soaps' (formed by alkaline earth ions with fatty acids, present in the wash solution) on the fabric. Thereby, their bleaching performance can be diminished. This result in a lessening of the dingy soil cleaning performance of the hydrophobic bleach.
The Applicants have found that this problem can be ameliorated by use of a particular combination of cationic surfactant and bleach resulting in a surprising enhancement of the bleach efficacy of the hydrophobic organic peroxyacid bleaching system. Thereby, the overall cleaning performance of the detergent are improved.
Three mechanisms are believed to be responsible for this unexpected benefit. First, the cationic surfactant is capable of reducing 'lime soap' deposition on the fabric surface, thereby facilitating the partition of the hydrophobic organic bleaches into the greasy stains/soils. Secondly, the cationic surfactant reduces the surface tension between the fabric and the wash solution. Thereby, the interaction with the greasy stains/ soils on the fabric by the hydrophobic organic bleach agent will be
facilitated. Thirdly, the cationic surfactant and the negatively charged hydrophobic organic peroxyacids, formed in the wash, can form a non-polar associated couple, which will partition rapidly into hydrophobic, greasy stains/ soils on the fabric.
All documents cited in the present description are, in relevant part, incorporated herein by reference.
Summary of the Invention
A detergent composition according to a first aspect of the present invention comprises
(a) a cationic surfactant of the formula I:
+
R
Rl N RΔ X"
R:
(I)
in which R1 is a hydroxyalkyl group having no greater than 6 carbon atoms; each of R-- and R. is independently selected from Ci . 4 alkyl or alkenyl; R^ is C5.1 1 alkyl or alkenyl and X" is an anion; and
(b) a hydrophobic organic peroxyacid bleaching system capable of providing a hydrophobic organic peroxyacid compound.
Preferred cationic surfactants of formula I are those in which R* is -CH2CH2OH or -CH2CH2CH2OH; each of R2 and R3 are, independently, C1.4 alkyl; R4 is C5.11 alkyl or alkenyl and X" is an anion.
An essential feature of detergent compositions of the invention is a hydrophobic organic peroxyacid bleaching system capable of providing a hydrophobic organic peroxyacid compound. By hydrophobic organic peroxyacid compound it is meant herein an organic peroxyacid whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre and wherein said critical micelle concentration is measured in aqueous solution at 20°-50°C.
Preferably, the hydrophobic organic peroxyacid contains at least 7 carbon atoms, more preferably at least 9 carbon atoms, most preferably at least 11 carbon atoms. In a preferred aspect the peroxyacid has an alkyl chain comprising at least 7 carbon atoms, more preferably at least 8 carbon atoms, most preferably at least 9 carbon atoms.
A preferred hydrophobic organic peroxyacid bleaching system is capable of providing a peroxyacid compound of the formula:
R 5 C N R7 - C OOH or R5 N - C R7 C OOH
O R6 O R6 O
wherein R^ is an alkyl, aryl or aralkyl group containing from 1 to 14 carbon atoms, R7 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, and R is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms.
According to a second aspect of the invention there is provided a detergent composition comprising
A detergent composition comprising
in which R is a hydroxyalkyl group having no greater than 6 carbon atoms; each of R2 and R^ is independently selected from C .4 alkyl or alkenyl; R4 is a C 2-14 alkyl or alkenyl and X" is an anion; and
(b) a hydrophobic organic peroxyacid bleaching system, capable of providing a peroxyacid compound of the formula:
R5 C N R7 C OOH or R5 N C R7 C OOH
O Rc O R6 O
wherein R^ is an alkyl, aryl or aralkyl group containing from 1 to 14 carbon atoms, R7 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms.
Particularly preferred cationic surfactants of formula I in which R^ is HOCH2CH2- or HOCH2CH2CH2-; each of R2 and R3 are, independently, .4 alkyl; R4 is C12-14 alkyl or alkenyl and X" is an anion.
Preferred detergent compositions of the invention additionally comprise a hard base polymeric component.
Unless otherwise stated alkyl or alkenyl as used herein may be branched, linear or substituted. Substituents may be for example, aromatic groups, heterocyclic groups containing one or more N, S or O atoms, or halo substituents.
Detailed description of the invention
Cationic surfactant
An essential element of the detergent compositions of the invention is a cationic quaternary ammonium surfactant. The cationic surfactant unless otherwise stated may be present in amounts up to 10.0% by weight of the detergent composition. However, preferably the maximum amount of the cationic surfactant in the detergent composition is below 5% . Most preferably, the cationic surfactant will be present in an amount below 4% or even 4.5% by weight of the detergent composition. Generally there will be at least 0.05% by weight or even at least 0.1 % or at least 0.5% by weight of the cationic surfactant in the composition.
Preferably the — OH group in Rl in formula I is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Preferred R groups are — CH2-CH2OH, — CH2CH2CH2OH, CH2CH2(CH3)OH and — CH(CH3)CH2OH. CH2CH2OH and — CH2CH2CH2OH are most preferred and — CH2CH2OH is particularly preferred. Preferably R2 and R3 are each selected from ethyl and methyl groups and most preferably both R2 and R3 are methyl groups. Preferred R4 groups have at least 6 or even at least 7 carbon atoms. R4 may have no greater than 9 carbon atoms, or even no greater than 8 or 7 carbon atoms. Preferred R4 groups are linear alkyl groups. Linear R4 groups having from 8 to 11 carbon atoms, or from 8 to 10 carbon atoms are preferred.
In accordance with a preferred aspect of the present invention the cationic surfactant of formula I has a Rl group which is -CH2CH2OH. Preferably each of R2 and R3 are methyl groups.
In a preferred aspect of the invention, R4 is a linear alkyl group, preferably a C6_ linear alkyl group.
It has been found that mixtures of the cationic surfactants of formula I may be particularly effective, for example surfactant mixtures in which R4 may be a combination of Cg and C10 linear alkyl groups, or Co, and C\ ι linear alkyl groups. According to one aspect of the invention a mixture of cationic surfactants of formula I is present in the composition, the mixture comprising a shorter alkyl
chain surfactant of formula I and a longer alkyl chain surfactant of formula I. The longer alkyl chain cationic surfactant is preferably selected from the surfactants of formula I where R4 is an alkyl group having n carbon atoms where n is from 8 to 11; the shorter alkyl chain surfactant is preferably selected form those of formula I where R4 is an alkyl group having (n-2) carbon atoms. Preferably the detergent compositions of the invention comprise a combination of cationic surfactants for formula I comprising 1 % to 65% of a shorter alkyl chain length R4 group and 35% to 99% by weight of a longer alkyl chain length. Mixtures comprising R4 groups of Cg and Cio alkyl groups are particularly preferred.
X in formula I may be any counteranion providing electrical neutrality, but is preferably selected from the group consisting of halide, methyl sulfate, sulfate and nitrate, more preferably being selected from methyl sulfate, chloride, bromide or iodide.
Hydrophobic organic peroxyacid bleaching system
Preferably the hydrophobic organic peroxyacid bleaching system comprises a hydrogen peroxide source and a hydrophobic organic peroxyacid bleach precursor compound. The production of the hydrophobic organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred execution the hydrophobic organic peroxyacid bleaching system comprises a preformed hydrophobic organic peroxyacid, which is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and hydrophobic organic peroxyacid precursor in combination with a preformed hydrophobic organic peroxyacid are also envisaged.
Inorganic perhydrate bleaches
Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the alkali metal, preferably sodium salt at a level of from 1 % to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight of the compositions.
Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.
Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaBθ2H2θ2 or the tetrahydrate NaBO2H2O2.3H2O.
Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2Cθ3-3H2θ2, and is available commercially as a crystalline solid.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.
Peroxyacid bleach precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as
O X C - L
where L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is
O X C OOH
For the purposes of the present invention X will thus contain at least 6 carbon atoms.
The hydrophobic peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.05% to 20% by weight, more preferably from 0.1 % to 15% by weight, most preferably from 0.2% to 10% by weight of the detergent compositions.
Suitable hydrophobic peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A- 836988, 864798, 1147871 , 2143231 and EP-A-0170386.
Leaving groups
The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
Preferred L groups are selected from the group consisting of:
O-CH=C— CH= =CH2 -O— CH=C- -CH=CH2 >
R I 3 O Y
II I
-O-C=CHR4 , and — N— S-CH- -R4
I , II R3 O
and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing
3 from 1 to 14 carbon atoms, R is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or R 3 , and Y is H or a solubilizing group. Any of R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups
The preferred solubilizing groups are -SO,, M + , -CO- - M + , -SO. - M + ,
-N + (R3)4X" and O< --N(R3)3 and most preferably -SO3 ~M + and -CO^"M + wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
Amide substituted alkyl peroxyacid precursors
The amide substituted alkyl peroxyacid precursors of the second aspect of the invention are also preferred in the first aspect of the invention. These include compounds of the following general formulae:
R5 — C — N — R7 — C — L or R5 - N — C — R7 -- C — L
O R6 O R6 O O
wherein R^ is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R7 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R^ preferably contains from about 6 to 12 carbon atoms. R-7 preferably contains from about 4 to 8 carbon atoms. R5 may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R -7. R' can include alkyl, aryl, wherein said R7 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R is preferably H or methyl. R^ and R^ should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
Preferred examples of bleach precursors of this type include amide substituted peroxyacid precursor compounds selected from (6-octanamido- caproyl)oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzene- sulfonate, and the highly preferred (6-nonanamidocaproyl)oxy benzene sulfonate, and mixtures thereof as described in EP-A-0170386.
Benzoxazin organic peroxyacid precursors
For the first aspect of the invention, also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
Alkyl percarboxylic acid bleach precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N*Nl tetra acetylated alkylene diamines wherein the alkylene group contains at least 7 carbon atoms.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri- methyl hexanoyloxybenzene sulfonate (iso-NOBS) and sodium nonanoyloxy benzene sulfonate (NOBS).
N-acylated lactam precursors
Still another class of hydrophobic bleach activators are the N-acylated precursor compounds of the lactam class disclosed generally in GB-A-955735. Preferred materials of this class comprise the caprolactams.
Suitable caprolactam bleach precursors are of the formula:
C H - CH .
CH .
C H - C H -
wherein R1 is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms. Preferred hydrophobic N-acyl caprolactam bleach precursor materials are selected from benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, 3,5,5- trimethylhexanoyl caprolactam and mixtures thereof. A most preferred is nonanoyl caprolactam.
Suitable valero lactams have the formula:
C H - C H .
N
C H - C H .
wherein R! is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms. More preferably, Rl is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.
Mixtures of any of the peroxyacid bleach precursor, herein before described, may also be used.
The cationic surfactant and hydrophobic organic peroxyacid precursor are preferably present in the detergent composition at a ratio of 25 : 1 to 1 : 1 , most preferably at a ratio of 10: 1 to 1 : 1.
Preformed organic peroxyacid
The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed hydrophobic organic peroxyacid , typically at a level of from 0.05% to 20% by weight, more preferably from 1 % to 10% by weight of the composition.
A preferred class of hydrophobic organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
R5 - C N - R7 C L or R5 N — C R7 C L
O R6 O R6 O O
wherein R^ is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R7 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R > is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. R^ preferably contains from about 6 to 12 carbon atoms. R7 preferably contains from about 4 to 8 carbon atoms. R^ may be straight chain or
branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R7. R7 can include alkyl, aryl, wherein said R7 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is preferably H or methyl. R^ and R^ should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. Suitable examples of this class of agents include (6-octylamino)-6- oxo-caproic acid, (6-nonylamino)-6-oxo-caproic acid, (6-decylamino)-6-oxo- caproic acid, magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. 4,483,781 , U.S. 4,634,551 , EP 0, 133,354, U.S. 4.412,934 and EP 0.170,386. A preferred hydrophobic preformed peroxyacid bleach compound for the purpose of the invention is nonanonylamido peroxycarboxylic acid.
Other suitable organic peroxyacids for the first aspect of the invention include diperoxyalkanedioc acids having more than 7 carbon atoms, such as diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
Other suitable organic peroxyacids include diamino peroxyacids, which are disclosed in WO 95/ 03275, with the following general formula:
O O O O
MOCR-(R1N)n C (NR2)n' R3 (R2N)m' C (NR1)m RCOOM wherein:
R is selected from the group consisting of C\-C\2 alkylene, C5-C12 cycloalkylene, Cg-Ci2 arylene and radical combinations thereof;
R! and R^ are independently selected from the group consisting of H, Cj-Cig alkyl and C6-C12 aryl radicals and a radical that can form a C3-C12 ring together with R3 and both nitrogens; R^ is selected from the group consisting of C -C12 alkylene, C5-C12 cycloalkylene and C6-C12 arylene radicals; n and n' each are an integer chosen such that the sum thereof is 1; m and m' each are an integer chosen such that the sum thereof is 1 ; and
M is selected from the group consisting of H, alkali metal, alkaline earth metal, ammonium, alkanolammonium cations and radicals and combinations thereof.
Other suitable organic peroxyacids are include the amido peroxyacids which are disclosed in WO 95/ 16673, with the following general structure:
X Ar CO NY R(Z) CO OOH
in which X represents hydrogen or a compatible substituent, Ar is an aryl group, R represents (CH2)n in which n = 2 or 3, and Y and Z each represent independently a substituent selected from hydrogen or an alkyl or aryl or alkaryl group or an aryl group substituted by a compatible substituent provided that at least one of Y and Z is not hydrogen if n = 3. The substituent X on the benzene nucleus is preferably a hydrogen or a meta or para substituent, selected from the group comprising halogen, typically chlorine atom, or some other non-released non-interfering species such as an alkyl group, conveniently up to C6 for example a methyl, ethyl or propyl group. Alternatively, X can represent a second amido-percarboxylic acid substituent of formula: -
CO NY R(Z) CO OOH
in which R, Y, Z and n are as defined above.
MOOC-R1CO-NR2-R3-NR4-CO-R5COOOM
wherein R*is selected from the group consisting of C^-C^ alkylene, C5-C12 cycloalkylene, C.5-C12 arylene and radical combinations thereof; R
Preferred detergent compositions according to the present invention additionally comprise a hard base organic polymeric component. Preferably the total cationic surfactant and hard base polymeric component will be present in the detergent composition at a weight ratio 10: 1 to 1 :3, most preferably 5: 1 to 1 :2.
The hard base polymeric component preferably comprises a polymer having a pendant group (that is to say a group which is not a polymeric linkage group, so
that it does not form part of the polymer backbone) which is a harder base than a benzene sulphonate group
/
SO^
in accordance with Pearson's classification of hard and soft behavior. Preferably the polymeric component comprises a polymer having a pendant group which is a harder base than a sulphonate group such as CH3CH2CH2-SO3-. The polymeric component is generally formed from at least 5%, preferably at least 25% by weight of monomers which result in such pendant groups. The polymeric component preferably has a molecular weight of from 1500 to 150000 most preferably from 2000 to 100000, especially 5000 to 80000. Molecular weight measurements are obtained by GPC using styrene as a standard.
Particularly preferred pendant groups are carboxylic groups (references herein to acid groups also include their salts). Acrylic and maleic homopolymers or copolymers are particularly preferred.
The hard base polymer may be any organic polymeric material having a hard base group commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions.
Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic 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 the latter type are disclosed in GB-A-1, 596,756. Examples of such salts are polyacrylates of MWt 1500-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2,000 to 100,000, especially 5,000 to 80,000, or even 10,000 to 50,000.
The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
The hard base polymeric component is preferably present as components of any paniculate components where they may be beneficial as a binder.
Additional detergent components
The detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the precise nature of the washing operation for which it is to be used.
The compositions of the invention preferably contain one or more additional detergent components selected from additional surfactants, additional bleaches, bleach catalysts, alkalinity systems, builders, organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
Additional surfactant
The detergent compositions of the invention may contain an additional surfactant selected from anionic, nonionic, additional cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S. P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S. P. 4,259,217 issued to Murphy on March 31, 1981.
Where present, ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
Anionic surfactant
The detergent compositions of the present invention preferably comprise an additional anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.
Other anionic surfactants include the isethionates such as the acyl isethionates, N- acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C. →-C O monoesters) diesters of sulfosuccinate (especially saturated and unsaturated Cs--C. . diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
Anionic sulfate surfactant
Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates. fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cj-C4 alkyl) and -N-(Cι-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched primary
branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C10-C18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant
is a Cj i -Cjg, most preferably Ci 1 -C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C5-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Anionic carboxylate surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2θ)x CH2C00"M+ wherein R is a C * to Cjg alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRj-CHR2- O)-R3 wherein R is a C5 to Ci8 alkyl group, x is from 1 to 25, Rj and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxy succinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-
decanoic acid, 2-propyl-l-nonanoic acid, 2-butyI-l-octanoic acid and 2-pentyl-l- heptanoic acid. Certain soaps may also be included as suds suppressors.
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of formula R- CON (R1) CH2 COOM, wherein R is a C5-C!7 linear or branched alkyl or alkenyl group, R* is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
Alkoxylated nonionic surfactant
Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxy lated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
Nonionic alkoxylated alcohol surfactant
The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Nonionic polvhvdroxy fatty acid amide surfactant
Poly hydroxy fatty acid amides suitable for use herein are those having the structural formula R^CONRlZ wherein : Rl is H, C1-C4 hydrocarbyl, 2-hydroxy
ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably Ci or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C1 alkyl or alkenyl, most preferably straight- chain C12-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
Nonionic fatty acid amide surfactant
Suitable fatty acid amide surfactants include those having the formula: R6cON(R7)2 wherein R^ is an alkyl group containing from 7 to 21 , preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4θ)xH, where x is in the range of from 1 to 3.
Nonionic alkylpolvsaccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565.647, Llenado, issued January 21 , 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g. , a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula
R2θ(CnH2nO)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.
Amphoteric surfactant
Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula R3(OR4)xN°(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R^ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are CJQ-C IS alkyl dimethylamine oxide, and C I Q-18 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone. manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
Suitable betaines are those compounds having the formula R(R')2N+R2C00~ wherein R is a C^-Cjg hydrocarbyl group, each R! is typically C1-C3 alkyl, and R2 is a C1 -C5 hydrocarbyl group. Preferred betaines are C12-I8 dimethyl- ammonio hexanoate and the C JO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.
Cationic surfactants
Additional cationic surfactants may also be used in the detergent compositions herein. Suitable cationic surfactants include the ethoxylated quaternary ammonium surfactants as described in GB-A-2040990, or ester surfactants. Suitable cationic
ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents Nos. 4228042, 4239660 and 4260529.
Alkalinity
In the detergent compositions of the present invention preferably a alkalinity system is present to achieve optimal cationic ester surfactant performance. The alkalinity system comprises components capable of providing alkalinity species in solution. By alkalinity species it is meant herein: carbonate, bicarbonate, hydroxide, the various silicate anions, percarbonate, perborates, perphosphates, persulfate and persilicate.
Such alkalinity species can be formed for example, when alkaline salts selected from alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate, including crystalline layered silicate, salts and percarbonate, perborates, perphosphates, persulfate and persilicate salts and any mixtures thereof are dissolved in water.
Examples of carbonates are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2,321 ,001 published on November 15, 1973.
Suitable silicates include the water soluble sodium silicates with an Siθ2: Na2θ ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an Siθ2: Na2θ ratio of 2.0 is the most preferred silicate.
Preferred crystalline layered silicates for use herein have the general formula
NaMSix02x + i .yH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP- A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. Herein, x in the general formula above preferably has a value of
2, 3 or 4 and is preferably 2. The most preferred material is δ-Na2Si2θ5, available from Hoechst AG as NaSKS-6.
Water-soluble builder compound
The detergent compositions of the present invention preferably contain a water- soluble builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. 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 and the sulf yl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1 ,379,241, lactoxysuccinates described in British Patent No. 1 ,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l ,l,3-propane tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed 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. Polycarboxylates
containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
Partially soluble or insoluble builder compound
The detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
Examples of largely water insoluble builders include the sodium aluminosilicates.
Suitable aluminosihcate zeolites have the unit cell formula Naz[(AlO2)z(SiO2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosihcate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
The aluminosihcate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosihcate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula
Na 12 [AIO2) 12 (SiO2)ι2]. xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6 [<Alθ2)86<Siθ2)l06]- 276 H2O.
Bleach catalyst
The compositions optionally contain a transition metal containing bleach catalyst. One suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include Mn^2(u"0)3(l '4,7-trimethyl-l,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-O) (u-OAc)2(l,4,7-trimethyl-l ,4,7-triazacyclononane)2-(ClO4)2,
MnIV4(u-O)6(l ,4,7-triazacyclononane)4-(ClO4)2, MnπιMnIV4(u-O)ι(u-OAc)2- (l ,4,7-trimethyl-l,4,7-triazacyclononane)2-(Clθ4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include l ,5,9-trimethyl-l ,5,9-triazacyclododecane, 2-methyl-l ,4,7-triazacyclononane, 2-methyl-l ,4,7-triazacyclononane, 1 ,2,4,7- tetramethyl-l,4,7-triazacyclononane, and mixtures thereof.
For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl-l,4,7-triazacyclononane)(OCH3)3_ (PFg). Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is
a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Other examples include binuclear Mn complexed with tetra-N -dentate and bi-N-dentate ligands, including N4Mn^(u-O)2Mn^N4) + and [Bipy2Mn*H(u- O)2MnIvbipy2]-(Clθ4)3.
Further suitable bleach catalysts are described, for example, in European patent application No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosihcate catalyst), U.S. 4,601,845 (aluminosihcate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S.
4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).
Heavy metal ion sequestrant
The detergent compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1 % to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions.
Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1- hydroxy disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1 ,1 diphosphonate.
Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof. Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2- hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516, 102 are also suitable herein. The β-alanine-N,N' -diacetic acid, aspartic acid-N,N '-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.
EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A- 528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-l,2,4-tricarboxylic acid are also suitable. Glycinamide- N,N' -disuccinic acid (GADS), ethylenediamine-N-N' -diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N' -disuccinic acid (HPDDS) are also suitable.
Enzyme
Another preferred ingredient useful in the detergent compositions is one or more additional enzymes.
Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into
detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo
Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the composition.
Preferred amylases include, for example, α-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1 ,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001 % to 2% active enzyme by weight of the composition.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001 % to 2% by weight, preferably 0.001 % to 1 % by weight, most preferably from 0.001 % to 0.5% by weight of the compositions.
The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomvces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase.
This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
Organic polymeric compound
Organic polymeric compounds such as the hard base polymeric components described above are preferred additional components of the detergent compositions in accord with the invention, and are preferably present as components of any paniculate components where they may act such as to bind the paniculate component together. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti- redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.
Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1 % to 30% , preferably from 0.5% to 15% , most preferably from 1 % to 10% by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic 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 the latter type are disclosed in GB-A-1, 596,756.
The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxy methylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
Suds suppressing system
The detergent compositions of the invention, when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01 % to 15 % , preferably from 0.05 % to 10% , most preferably from 0.1 % to 5% by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "sihcone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred sihcone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Cι g-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
A preferred suds suppressing system comprises
(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and
(ii) silica, at a level of from 1 % to 50%, preferably 5% to 25% by weight of the silicone/si ica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of from 5% to 50% , preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10% , preferably 1 % to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544;
(c) an inert carrier fluid compound, most preferably comprising a C^-Cj ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80% , preferably 10% to 70% , by weight;
A highly preferred paniculate suds suppressing system is described in EP-A- 0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85 °C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.
Clay softening system
The detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
The clay mineral compound is preferably a smectite clay compound. Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European Patents No.s EP-A-299,575 and EP-A-313, 146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
Polymeric dye transfer inhibiting agents
The detergent compositions herein may also comprise from 0.01 % to 10 %, preferably from 0.05 % to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
a) Polyamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :
(I) Ax
R
wherein P is a polymerisable unit, and
O O O
A is NC, CO, C, -0-, -S-, -N-; x is O or 1 ;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocychc or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein 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
A
O (R^ x -N-JRjJy A
(R3>z or N-(R-,)x
wherein Rl , R2, and R3 are aliphatic groups, aromatic, heterocychc or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocychc groups. One class of said polyamine
N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocychc group such as pyrridine, pyrrole, imidazole. pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocychc or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocychc compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
The polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrohdone from 1 to 0.2.
c) Polvvinylpyrrolidone
The detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrohdones 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). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrohdones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
d) Polvvinyloxazolidone
The detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
e) Polvvinylimidazole
The detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000. Optical brightener
The detergent compositions herein also optionally contain from about 0.005% to 5 % by weight of certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the structural formula:
wherein R is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N- methylamino. morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, Ri is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4' ,-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename
Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, R is anilino, R2 is N-2-hydroxyethyl-N-2- methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4- anilino-6-(N-2-hydroxyethy 1-N-methy lamino)-s-triazine-2-y l)amino]2 ,2 ' - stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
When in the above formula, Ri is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphihno-s-triazine-2- yl)amino)2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
Cationic fabric softening agents
Cationic fabric softening agents can also be incorporated into compositions in accordance with the present invention. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 Oi l 340.
Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15 % by weight, normally from 1 % to 5% by weight.
Other optional ingredients
Other optional ingredients suitable for inclusion in the compositions of the invention include colours and filler salts, with sodium sulfate being a preferred filler salt.
pH of the compositions
The present compositions preferably have a pH measured as a 1 % solution in distilled water of at least 8.5, preferably from 9.0 to 12.5, most preferably from 9.5 to 11.0.
Form of the compositions
The compositions in accordance with the invention can take a variety of physical forms including granular, tablet, bar and liquid forms. The compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.
In general, granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.
The mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5 % of particles are greater than 1.7mm in diameter and not more than 5 % of particles are less than 0.15mm in diameter.
The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
The bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre. Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90
mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
To carry out a measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup. The filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.
Surfactant agglomerate particles
The cationic ester surfactant herein, preferably with additional surfactants, is preferably present in granular compositions in the form of surfactant agglomerate particles, which may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules. The most preferred way to process the particles is by agglomerating powders (e.g. aluminosihcate, carbonate) with high active surfactant pastes and to control the particle size of the resultant agglomerates within specified limits. Such a process involves mixing an effective amount of powder with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS. Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH. D-4790 Paderborn 1 , Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a Lodige CB (Trade Name).
A high active surfactant paste comprising from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of surfactant is typically used. The paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the anionic surfactants used. An operating temperature of the paste of 50° C to 80° C is typical.
Laundry washing method
Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein
an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
In a preferred use aspect a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.
Once the washing machine has been loaded with laundry the dispensing device containing the detergent product is placed inside the drum. At the commencement of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.
To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass. Alternatively, the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.
Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle. Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157, 717, GB-B- 2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J. Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry
products which are of a type commonly know as the "granulette". Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. WO94/11562.
Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process . A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a masking arrangement to prevent egress of wetted, undissolved. product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.
Alternatively, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678. Alternatively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501 , 0011502, and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
Packaging for the compositions
Commercially marketed executions of the bleaching compositions can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials and any suitable laminates. A preferred packaging execution is described in European Application No . 94921505.7.
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have the following meanings:
LAS Sodium linear Cj2 alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate C45AS Sodium C 4-C 5 linear alkyl sulfate CxyEzS Sodium Cιx-Cjy branched alkyl sulfate condensed with z moles of ethylene oxide
C45E7 A Ci4_i5 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide
C25E3 A C 12-15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide
C25E5 A C12-15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide
CEQ I RlCOOCH CH2.N+(CH3)3 with R2 = Cπ-Cι3 CEQ II RlCOOCH2CH2CH2N + (CH3)3 with Rj = C1 }-
Cl3
CEQ HI R1COOCH2CH2N + (CH3)2(CH2CH2OH) with
Rl =Cπ-Ci 3
CEQ IV RlCOOCH2CH2N +(CH3CH2)2(CH ) with
Rl =cl l" 13
QAS I R2.N-t-(CH3)2(C2H4OH) with R2 = Ci 2 - C14 QAS II R2.N + (CH3)2(C2H OH) with R2 = Cg
QAS III R2.N + (CH3)2(C2H4OH) with R2 = 50% C9; 50%
Cl l
QAS IV R2.N + (CH3)2(C2H4OH) with R2 = 70% C IQ; 30% Cg
Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.
TFAA Cl6"Cl8 lkyl N-methyl glucamide
TPKFA C12-C14 topped whole cut fatty acids
STPP Anhydrous sodium tripolyphosphate
Zeolite A Hydrated Sodium Aluminosihcate of formula
Na 2(A102Siθ2)i2- 27H2O having a primary particle size in the range from 0.1 to 10 micrometers
NaSKS-6 Crystalline layered silicate of formula δ -Na2Si2θ5
Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200μm and 900μm
Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm
Silicate Amorphous Sodium Silicate (SiO2:Na2O; 2.0 ratio)
Sodium sulfate Anhydrous sodium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425μm and q 850μm
MA/AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70.000.
CMC Sodium carboxymethyl cellulose Protease Proteolytic enzyme of activity 4KNPU/g sold by
NOVO Industries A/S under the tradename Savinase
Alcalase Proteolytic enzyme of activity 3AU/g sold by NOVO
Industries A/S
Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by
NOVO Industries A/S under the tradename Carezyme
Amylase Amylolytic enzyme of activity 60KNU/g sold by
NOVO Industries A/S under the tradename Termamyl
60T
Lipase Lipolytic enzyme of activity lOOkLU/g sold by
NOVO Industries A/S under the tradename Lipolase
Endolase Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S
PB4 Sodium perborate tetrahydrate of nominal formula
NaBθ2.3H2O.H2θ2
PB1 Anhydrous sodium perborate bleach of nominal formula NaBθ2-H2θ2
Percarbonate Sodium Percarbonate of nominal formula 2Na2CO3.3H2θ2
NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt
NAC-OBS (Nonanamido caproyl) oxybenzene sulfonate in the form of the sodium salt.
NACA 6 nonylamino - 6 oxo - capronic acid TAED Tetraacetylethylenediamme DTPMP Diethylene tπamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest
2060
Photoactivated Sulfonated Zinc Phthlocyanine encapsulated in bleach dextrin soluble polymer
Brightener 1 Disodium 4,4'-bιs(2-sulphostyryl)bιphenyl Brightener 2 Disodium 4,4'-bιs(4-anιhno-6-morphohno-l 3 5- tπazιn-2-yl)amιno) stιlbene-2 2'-dιsulfonate
HEDP 1,1-hydroxyethane diphosphonic acid PVNO Polyvinylpyπdine N-oxide PVPVI Copolymer of polyvmylpyrohdone and vmyhmidazole SRP 1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone
SRP 2 Diethoxylated poly (1 , 2 propylene terephtalate) short block polymer
Silicone antifoam Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10 1 to 100 1
e following Examples all levels are quoted as % by weight of the composition
Example 1
The following laundry detergent compositions A to F are compositions according to the invention:
A B C D E F
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
CEQ I 0.8 0.8 2.0 2.0 1.0 0.7
CEQ II - - 0.5 - - 0.8
QAS I 0.2 0.5 0.8 - - 0.8
QAS II - - - 0.7 2.0 -
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
Sodium 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
NAC OBS 2.5 1.5 3.0 4.0 3.2 2.2
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 0.26 0.26 0.26 0.26 0.26 0.26
Amylase 0.1 0.1 0.1 0.1 0.1 0.1
MA/AA 0.3 0.3 0.3 0.3 0.3 0.3
CMC 0.2 0.2 0.2 0.2 0.2 0.2
Photoactivated 15 pp 15 pp 15 pp 15 pp 15 ppm 15 ppm bleach (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
Silicone antifoam 0.5 0.5 0.5 0.5 0.5 0.5
Misc/minors to 100%
Density in g/litre 850 850 850 850 850 850
Example 2
The following granular laundry detergent compositions G to I of bulk density 750 g/litre are compositions according to the invention:
G H I
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 II 0.8 2.0 2.0
QAS III 0.4 1.0 0.5
STPP 19.7 - -
Zeolite A - 19.5 19.5
NaSKS-6/citric acid (79:21) - 10.6 10.6
Carbonate 6.1 21.4 21.4
Bicarbonate - 2.0 2.0
Silicate 6.8 - -
Sodium sulfate 39.8 - 14.3
PB4 5.0 12.7 -
TAED 0.5 0.2 -
NAC OBS 1.0 2.2 1.3
DETPMP 0.25 0.2 0.2
HEDP - 0.3 0.3
Protease 0.26 0.85 0.85
Lipase 0.15 0.15 0.15
Cellulase 0.28 0.28 0.28
Amylase 0.1 0.1 0.1
MA/AA 0.8 1.6 1.6
CMC 0.2 0.4 0.4
Photoactivated bleach (ppm) 15 ppm 27 ppm 27 ppm
Brightener 1 0.08 0.19 0.19
Brightener 2 - 0.04 0.04
Perfume 0.3 0.3 0.3
Silicone antifoam 0.5 2.4 2.4
Minors/misc to 100%
Example 3
The following are detergent formulations, according to the present invention where J is a phosphorus-containing detergent composition, K is a zeolite-containing detergent composition and L is a compact detergent composition:
J K L
Blown Powder
STPP 24.0 - 24.0
Zeolite A - 24.0 -
C45AS 9.0 6.0 13.0
QAS II - 2.0 -
QAS III - - 2.0
QAS IV 2.0 - -
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
DTPMP 0.4 0.4 0.2
Spray On
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone antifoam 0.3 0.3 0.3
Perfume 0.3 0.3 0.3
Dry additives
Carbonate 6.0 13.0 15.0
PB4 18.0 18.0 10.0
PB1 4.0 4.0 0
NOBS 3.0 4.2 1.0
Photoactivated bleach 0.02 0.02 0.02
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.25 0.30 0.15
Dry mixed sodium sulfate 3.0 3.0 5.0
Balance (Moisture & to 100.0 to 100.0 to 100.0 Miscellaneous)
Density (g/litre) 630 670 670
Example 4
The following are detergent formulations according to the present invention:
P Q R S
LAS 20.0 14.0 24.0 22.0
QAS I 0.7 1.0 - 0.7
CEQ III 0.4 0.4 2.2 1.5
CEQ IV 1.5 0.4 1.0 1.5
TFAA - 1.0 - -
C25E5/C45E7 - 2.0 - 0.5
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 - -
DTPMP 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 0.8 1.0 0.5 0.5
Amylase 0.8 0.4 - 0.25
Lipase 0.2 0.1 0.2 0.1
Cellulase 0.15 0.05 - -
Photoactivated 70ppm 45ppm - lOppm bleach (ppm)
Brightener 1 0.2 0.2 0.08 0.2
PB1 6.0 2.0 - -
NAC OBS 2.0 1.0 0.9 3.1
Balance 100 100 100 100 (Moisture and Miscellaneous)
Example 5
The following are detergent formulations according to the present invention:
T u V
Blown Powder
QAS IV - 0.4 1.5
QAS II 1.5 1.5 1.5
Zeolite A 30.0 22.0 6.0
Sodium sulfate 19.0 5.0 7.0
MA/AA 3.0 3.0 6.0
LAS 14.0 12.0 22.0
C45AS 8.0 7.0 7.0
Silicate - 1.0 5.0
Soap - - 2.0
Brightener 1 0.2 0.2 0.2
Carbonate 8.0 16.0 20.0
Spray On
C45E7 1.0 1.0 1.0
Dry additives
PVPVI/PVNO 0.5 0.5 0.5
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.1 0.1 0.1
Cellulase 0.1 0.1 0.1
NACA 3.4 6.1 4.5
Sodium sulfate - 6.0 -
Balance (Moisture and 100 100 100 Miscellaneous)
Example 6
The following are high density and bleach-containing detergent formulations according to the present invention:
W X Y
Blown Powder
Zeolite A 15.0 15.0 15.0
Sodim sulfate 0.0 5.0 0.0
LAS 3.0 3.0 3.0
QAS I - 1.5 1.5
QAS II 0.9 - -
CEQ II 0.5 0.5 2.7
CEQ III - 1.2 -
DTPMP 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
Spray On
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
NAC OBS 6.0 2.0 5.0
NACA 2.0 1.8 1.2
PB1 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2 5,000,000
Bentonite clay - - 10.0
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and 100.0 100.0 100.0 Miscellaneous)
Density (g/litre) 850 850 850
Example 7
The following are high density detergent formulations according to the present invention:
Z AA
Agglomerate
C45AS 11.0 14.0
QAS II 1.8 2.2
Zeolite A 15.0 6.0
Carbonate 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 0.5
DTPMP 0.4 0.4
Spray On
C25E5 5.0 5.0
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate 3.0 1.0
NAC OBS 4.1 6.2
TAED 0.8 1.0
Percarbonate 20.0 20.0
SRP 1 0.3 0.3
Protease 1.4 1.4
Lipase 0.4 0.4
Cellulase 0.6 0.6
Amylase 0.6 0.6
Silicone antifoam 5.0 5.0
Brightener 1 0.2 0.2
Brightener 2 0.2 -
Balance (Moisture and 100 100 Miscellaneous)
Density (g/litre) 850 850
Example 8
The following are liquid detergent formulations according to the present invention:
AB AC AD AE AF AG AH Al
CEQ I O.4 1.0 - - 2.0 2.5 - -
CEQ II - - 0.7 - 1.2 - - -
LAS 10.0 13.0 9.0 - 25.0 - - -
C25AS 4.0 1.0 2.0 10. - 13.0 18.0 15.0 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 I - - - - 3.0 1.0 - -
QAS III 0.6 1.2 - - 3.5 -
QAS IV - - 0.8 0.8 - 3.5
TPKFA 2.0 - 13.0 2.0 - 15.0 7.0 7.0
Rapeseed fatty - - - 5.0 - - 4.0 4.0 acids
Citric acid 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0
Dodecenyl/ 12.0 10.0 15.0 tetradecenyl succinic acid
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 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-
Mono Ethanol - - - 5.0 - - 9.0 9.0 Amine
Tri Ethanol - - 8 - - - - - Amine
NaOH up to pH 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2
Ethoxylated 0.5 0.5 0.2 0.4 0.3 tetraethylene pentamine
NAC OBS 1.0 1.0 0.5 1.0 2.0 1.2 1.0 1.6
NACA 0.7 1.1 1.8 1.5 1.9 2.1 1.4 1.0
PB4 2.0 2.6 3.1 3.0 3.1 3.5 2.9 2.5
SRP 2 0.3 - 0.3 0.1 - - 0.2 0.1
PVNO - - - - - - - 0.10
Protease 0.5 0.5 0.4 0.2 - 0.5 0.3 0.6 5
Alcalase - - - - 1.5 - - -
Lipase - 0.10 - 0.0 - - 0.15 0.15 1
Amylase 0.25 0.25 0.6 0.5 0.25 0.9 0.6 0.6
Cellulase - - - 0.0 - - 0.15 0.15
5
Endolase - - - 0.1 - - 0.07 - 0
Boric acid 0.1 0.2 - 2.0 1.0 1.5 2.5 2.5
Na formate - - 1.0 - - - - -
Ca chloride - 0.01 - 0.0 - - - -
5 1
Bentonite clay - - - - 4.0 4.0 - -
Suspending clay - - - - 0.6 0.3 - - SD3
Balance 100 100 100 100 100 100 100 100 (Moismre and Miscellaneous)
Claims
Claims
A detergent composition comprising
(a) a cationic surfactant of the formula:
in which R is a hydroxyalkyl group having no greater than 6 carbon atoms; each of R-- and R^ is independently selected from C\. 4 alkyl or alkenyl; R^ is a ..γ { alkyl or alkenyl; and X" is a counterion; and
(b) a hydrophobic organic peroxyacid bleaching system capable of providing a hydrophobic organic peroxyacid compound.
A detergent composition according to claim 1 in which the cationic surfactant of formula I is selected from those in which R^ is -CH2CH2OH or -CH2CH2CH2OH; each of R2 and R3 are, independently, C1.4 alkyl; R is C5. alkyl or alkenyl and X" is an anion.
A detergent composition according to claim 1 or claim 2 in which the hydrophobic bleaching system is capable of providing a peroxyacid compound of the formula
R: N - R7 C - OOH or RD N — C - R 7 - C — OOH
wherein R^ is an alkyl, aryl or aralkyl group containing from 1 to 14 carbon atoms, R7 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms.
4. A detergent composition according to any preceding claim in which the cationic surfactant is present in an amount below 5 % by weight of the total detergent composition.
5. A detergent composition comprising
(a) less than 5 % by weight of a cationic surfactant of the formula
in which R is a hydroxyalkyl group having no greater than 6 carbon atoms; each of R2 and R-→ is independently selected from C _ 4 alkyl or alkenyl ; R4 is C12-14 alkyl or alkenyl and X- is an anion; and
(b) a hydrophobic organic peroxyacid bleaching system, capable of providing a peroxyacid compound of the formula:
R: N — R7 - C - OOH or R3 N C R' C - OOH
O Rc O R 6 O O
(II) (III)
wherein R^ is an alkyl, aryl or aralkyl group containing from 1 to 14 carbon atoms, R7 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, and R is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms.
6. A detergent composition according to claim 5 in which the cationic surfactant of formula I is selected from those in which R is -CH2CH2OH or - CH2CH2CH2OH; each of R2 and R3 are, independently, C1.4 alkyl.
7. A detergent composition according to any preceding claim wherein said hydrophobic organic peroxyacid bleaching system comprises a hydrogen peroxide source and a hydrophobic organic peroxyacid precursor.
8. A detergent composition according to claim 7 wherein said hydrophobic organic peroxyacid precursor is an amide substituted alkyl peroxyacid precursor compound selected from the group consisting of:
R5 __ C _ N _ R C -- L and R5 C - R7 - - C - L
O R6 O R6 O O
wherein L can be any leaving group, R^ is an aryl or alkaryl group with from 1 to 14 carbon atoms, R7 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms and R^ is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms such that R^ and R6 in total contain no more than 18 carbon atoms.
9. A detergent composition according to claim 7 or claim 8 wherein the cationic surfactant and hydrophobic organic peroxyacid precursor are present in the composition at a ratio of 25: 1 to 1:1.
10. A detergent composition according to any preceding claim wherein the cationic surfactant is present in an amount from 0.05% to 4.5% by weight of the detergent composition.
11. A detergent composition according to claim 10 wherein the cationic surfactant is present in an amount no greater than 4.0% by weight.
12. A detergent composition according to any preceding claim wherein Rl is - CH2CH2OH and each of R2 and R3 is methyl.
13. A detergent composition according to any preceding claim wherein R^ is a straight chain alkyl group.
14. A detergent composition according to any preceding claim additionally comprising a hard base polymeric component, the ratio of cationic surfactant to hard base polymeric component in the composition being from 10:1 to 1 :3.
15. A detergent composition according to claim 12 wherein the amount of hard base polymeric component is less than 1.7% by weight of the detergent composition.
16. A detergent composition according to claim 12 or claim 13 wherein the hard base polymeric component has pendant carboxylic functionality and a molecular weight of 20,000 to 150,000.
17. A method of washing laundry in a domestic washing machine in which a dispensing device containing an effective amount of a solid detergent composition according to any of claims 1 to 16 is introduced into the drum of the washing machine before the commencement of the wash, wherein said dispensing device permits progressive release of said detergent composition into the wash liquor during the wash.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/194,670 US6207632B1 (en) | 1996-05-31 | 1997-05-20 | Detergent composition comprising a cationic surfactant and a hydrophobic peroxyacid bleaching system |
EP97926631A EP0968266A1 (en) | 1996-05-31 | 1997-05-20 | Detergent composition |
CA002256703A CA2256703C (en) | 1996-05-31 | 1997-05-20 | Detergent composition |
BR9709506A BR9709506A (en) | 1996-05-31 | 1997-05-20 | Detergent composition |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9611320A GB2303143A (en) | 1995-07-08 | 1996-05-31 | Detergent compositions |
GB9611320.4 | 1996-05-31 | ||
GB9621791A GB2318362A (en) | 1996-10-18 | 1996-10-18 | Detergent compositions |
GB9621791.4 | 1996-10-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1997045513A1 WO1997045513A1 (en) | 1997-12-04 |
WO1997045513A9 true WO1997045513A9 (en) | 1998-03-12 |
Family
ID=26309411
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/008560 WO1997045513A1 (en) | 1996-05-31 | 1997-05-20 | Detergent composition |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0968266A1 (en) |
AR (1) | AR008383A1 (en) |
BR (1) | BR9709506A (en) |
CA (1) | CA2256703C (en) |
WO (1) | WO1997045513A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0934378B1 (en) * | 1996-10-18 | 2003-06-11 | The Procter & Gamble Company | Detergent compositions comprising a mixture of cationic, anionic and nonionic surfactants |
EP2423180B1 (en) | 2002-12-04 | 2016-07-06 | Clariant International Ltd | Quaternary ammonium composition |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4045358A (en) * | 1973-06-04 | 1977-08-30 | Colgate Palmolive Company | Softener and bleaching composition |
US4222905A (en) * | 1978-06-26 | 1980-09-16 | The Procter & Gamble Company | Laundry detergent compositions having enhanced particulate soil removal performance |
US4239659A (en) * | 1978-12-15 | 1980-12-16 | The Procter & Gamble Company | Detergent compositions containing nonionic and cationic surfactants, the cationic surfactant having a long alkyl chain of from about 20 to about 30 carbon atoms |
US4634551A (en) * | 1985-06-03 | 1987-01-06 | Procter & Gamble Company | Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain |
GB8415909D0 (en) * | 1984-06-21 | 1984-07-25 | Procter & Gamble Ltd | Peracid compounds |
US4686063A (en) * | 1986-09-12 | 1987-08-11 | The Procter & Gamble Company | Fatty peroxyacids or salts thereof having amide moieties in the fatty chain and low levels of exotherm control agents |
US5174927A (en) * | 1990-09-28 | 1992-12-29 | The Procter & Gamble Company | Process for preparing brightener-containing liquid detergent compositions with polyhydroxy fatty acid amines |
US5516449A (en) * | 1992-04-03 | 1996-05-14 | The Procter & Gamble Company | Detergent compositions |
US5445755A (en) * | 1994-05-31 | 1995-08-29 | The Procter & Gamble Company | Detergent compositions containing a peroxidase/accelerator system without linear alkylbenzenesulfonate |
GB2292155A (en) * | 1994-08-11 | 1996-02-14 | Procter & Gamble | Handwash laundry detergent composition comprising three surfactants |
GB2303143A (en) * | 1995-07-08 | 1997-02-12 | Procter & Gamble | Detergent compositions |
-
1997
- 1997-05-20 WO PCT/US1997/008560 patent/WO1997045513A1/en not_active Application Discontinuation
- 1997-05-20 BR BR9709506A patent/BR9709506A/en not_active Application Discontinuation
- 1997-05-20 CA CA002256703A patent/CA2256703C/en not_active Expired - Fee Related
- 1997-05-20 EP EP97926631A patent/EP0968266A1/en not_active Withdrawn
- 1997-05-30 AR ARP970102356 patent/AR008383A1/en unknown
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