CN1031647C - 洗涤漂白组合物 - Google Patents
洗涤漂白组合物 Download PDFInfo
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- CN1031647C CN1031647C CN92111815A CN92111815A CN1031647C CN 1031647 C CN1031647 C CN 1031647C CN 92111815 A CN92111815 A CN 92111815A CN 92111815 A CN92111815 A CN 92111815A CN 1031647 C CN1031647 C CN 1031647C
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- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 44
- 239000003599 detergent Substances 0.000 title claims abstract description 29
- 239000011572 manganese Substances 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002978 peroxides Chemical class 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- -1 hydroperoxide compound Chemical class 0.000 claims description 38
- 238000004061 bleaching Methods 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 239000000344 soap Substances 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 235000017550 sodium carbonate Nutrition 0.000 claims description 10
- 230000003287 optical effect Effects 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N peroxyacetic acid Substances CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims 2
- 230000005591 charge neutralization Effects 0.000 claims 1
- 239000002736 nonionic surfactant Substances 0.000 abstract 2
- 239000011149 active material Substances 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 150000004965 peroxy acids Chemical class 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000010457 zeolite Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 239000000654 additive Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 229940077388 benzenesulfonate Drugs 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 150000002148 esters Chemical group 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 235000019832 sodium triphosphate Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 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 2
- 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 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- 235000013616 tea Nutrition 0.000 description 2
- 125000005425 toluyl group Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- GWJCHQBHRSDASG-UHFFFAOYSA-N (diacetyloxyamino) acetate;sodium Chemical compound [Na].CC(=O)ON(OC(C)=O)OC(C)=O GWJCHQBHRSDASG-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- JWAWEQBUZOGIBZ-UHFFFAOYSA-N 1-methyltriazole Chemical compound CN1C=CN=N1 JWAWEQBUZOGIBZ-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- JBNHKYQZNSPSOR-UHFFFAOYSA-N 4-(carboxymethylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOCC(O)=O JBNHKYQZNSPSOR-UHFFFAOYSA-N 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
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- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- 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 1
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- 238000013459 approach Methods 0.000 description 1
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- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
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- 229940106157 cellulase Drugs 0.000 description 1
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- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了洗涤漂白组合物，它含有表面活性物质，过氧化物漂白剂和作为漂白催化剂的双核锰配合物，其特征在于该组合物含有按重累计0-25%的阴离子表面活性剂和按重量计7.5-55%的非离子表面活性剂，如果该组合物含按重量计不大于7.5%的碳酸盐，用碳酸钠表示，非离子表面活性剂与阴离子表面活性剂的重量比至少0.75，而如果该组合物含按重量计大于7.5%的碳酸盐时，其比值至少为2.2。
Description
本发明涉及洗涤漂白组合物。更具体地说，涉及改良洗涤漂白组合物，尤其是，但不仅仅适用于织物洗涤和清洗，它含有表面活性剂物质、过氧化物漂白剂和作为漂白催化剂的锰配合物。
本发明所用的锰配合物是双核锰配合物，其通式为：式中Mn是能独立以III或IV价氧化态存在的锰；X1、X2和X3各自任意代表一个配位或桥连基，它们选自H2O、O2 2-、O2-、OH-、HO2 -、SH-、S2-、＞SO、CI-、N3-、SCN-、RCOO-、RSO3 -、NH2 -、NR3其R是H，烷基、芳基，两者任选地被取代，或R’COO-，其中R’是烷基、芳基，两者任选地被取代；L是有机分子的配位体，该分子至少含3个氮原子，通过全部或其中的一些氮原子与锰中心配位；Z代表配合物的电荷并且是一个正整数或负整数；Y是一价或多价的相反离子，它能中和电荷，相反离子取决于配合物的电荷Z；q＝Z/[电荷Y]。
优选的锰配合物是那些其中X1、X2和X3或者为CH3COO-或O2-，或者为其混合的配合物，最好其中的锰是IV氧化态的且X1、X2和X3是O2-。
特别好的配合物是那些其中的配位体通式为的配位体，其中t是2—3的整数； s是3—4的整数；u是零或1；R1、R2和R3分别独立选自II、烷基、芳基，两者是任选地被取代的。
其它优选的配合物是那些包含两个配位体的配合物，其配位体通式为其中t是2—3的整数；s是3—4的整数；u是零或1；R1和R2分别独立选自II、烷基、芳基，两者是任选地被取代的；以及R3独立选自氢、烷基、芳基，两者是任选地被取代的，但桥连单位R4必须由各配位体中的1个R3单位生成的，R4是基团CnR5R6—(D)p—CmR5R6，其中p是零或1；D选自杂原子如氧和NR7，或部分为芳族或饱和同核或异核环，n为1—4的整数；m为1—4的整数；但须假若P为零或P为1和D部分是芳香族的或饱和的同核或异核环，则n＋m＝＜4；假若P是1而D是杂原子如氧或NR7，则n＋m＝＜3；R5和R6分别独立选自II、NR8和OR9、烷基、芳基，它们是任选地被取代的，和R7、R8、R9分别独立选自H、烷基、芳基，两者是任选地被取代的。
最简单形式的合适配位体实例是：
(I)1，4，7—三氮杂环壬烷；
1，4，7—三氮杂环癸烷；
1，4，8—三氮杂环十一烷；
1，5，9—三氮杂环十二烷；
1，4，7—三甲基—1，4，7—三氮杂环壬烷；
1，4，7—三甲基—1，4，7—三氮杂环癸烷；
1，4，8—三甲基—1，4，8—三氮杂环十一烷；
1，5，9—三甲基—1，5，9—三氮杂环十二烷；
1，2—双—(4，7—二甲基—1，4，7—三氮杂—1，—环壬基)乙烷。(II)三(吡啶—2—基)甲烷；
三(吡唑—1—基)甲烷；
三(咪唑—2—基)甲烷；
三(三唑—1—基)甲烷。(III)三(吡啶—2—基)硼酸酯；
三(三唑—1—基)硼酸酯；
三(吡唑—1—基)硼酸酯；
三(咪唑—2—基)膦；
三(咪唑—2—基)硼酸酯。(IV)1，3，5—三氨基—环已烷；
1，1，1—三(甲氨基)乙烷。(V)双(吡啶—2—基—甲基)胺；
双(吡唑—1—基—甲基)胺；
双(三唑—1—基—甲基)胺；
双(咪唑—2—基—甲基)胺，全部在胺的N-原子和/或CH2碳原子和/或芳环上任选地取代。
组(I)及其碳取代的衍生物的那些配位体是特别优选的，尤其是：(1)1，4，7—三甲基—1，4，7—三氮杂环壬3烷(Me3TACN
)，和(2)1，2，4，7—四甲基—1，4，7—三氮杂环壬烷(Me4TACN)(3)1，2，2，4，7—五甲基—1，4，7—三氮杂环壬烷
(Me5TACN)(4)2—苄基—1，4，7—三甲基—1，4，7—三氮杂环壬
烷(5)1，2—双(4，7—二甲基—1，4，7—三氮杂—1—
环壬基乙烷(Et-桥连的(Me2TACN)2)
用于中和电荷的相反离子y的类型对于配合物的活性并不重要，并且能选自例如下述任何相反离子：氯离子；硫酸根；硝酸根；甲基硫酸根；阴离子表面活性剂，例如长链的烷基硫酸根、烷基磺酸根、烷基苯磺酸根、甲苯磺酸根；三氟甲基磺酸根；高氯酸根(ClO4 -)、Bph4 -和PF6 -，尽管一些相反离子比其它的好得多，但由于产品性质和安全性的原因而受到限制。
然而用于本发明的最佳锰配合物是：(I)[(Me3TACN)MnIV(μ—O)3MnIV(Me3TACN)]2+(PF6-)2(II)[(Me4TACN)MnIV(μ—O)3MnIV(Me4TACN)]2+(PF6-)2(III)[(Me3TACN)MnIII(μ—O)(μ—OAC)2MnIIII(Me3TACN)]2+(PF6 -)2(IV)[(Me4TACN)MnIII(μ—O)(μ—OAC)2MnIII(Me4TACN)]2+(PF6 -)2(V)[(Et—桥连的(Me2TACN)2)MnIIIMnIV(μ—O)2(μ—OAO]2+
(ClO4 -)2
这些在下文也可缩写为：(I)[Mn2 IV(μ—O)3(Me3TACN)2](PF6)2(II)[Mn2 IV(μ—O)3(Me4TACN)2](PF6)2(III)[Mn2 III(μ—O)(μ—OAC)2(Me3TACN)2](PF6)2(IV)[Mn2 III(μ—O)(μ—OAC)2(Me4TACN)2](PF6)2
认为配合物I的结构式如下所述：
在申请人的待批欧洲专利说明书458397和458398中报导了这些锰配合物具有显著有效的漂白和氧化催化剂作用。在本发明的进一步描述中，上述配合7物还可称为“漂白催化剂”或简单地称之为“催化剂”。
本发明目前涉及的洗涤漂白组合物包括表面活性物质、过氧化物漂白剂和上述作为漂白催化剂的双核锰配合物。
过氧化物漂白剂
过氧化物漂白剂通常是一类能在水溶液中产生过氧化氢的化合物。过氧化氢源在现有技术中是已知的。它们包括碱金属过氧化物，有机物过氧化物如过氧化脲，以及无机过酸盐，如碱金属过硼酸盐、过碳酸盐、过磷酸盐、过硅酸盐和过硫酸盐。两种或两种以上的这类化合物的混合物也是适用的。特别好的是四水过硼酸钠，尤其是一水过硼酸钠。一水过硼酸钠是优选的，因为它的活性氧含量高。鉴于环境因素，过碳酸钠也是优选的。它们在本发明组合物中的用量一般按重量计在约5—35％的范围内，最好为10—25％。
烷基羟基过氧化物是另一类过氧化物漂白剂。这些物质的实例包括氢过氧化枯烯和叔一丁基氢过氧化物。
有机过氧酸也可用作过氧化物漂白剂。这类物质通常具有的通式为：式中R是含1—约20个碳原子的亚烷基或取代的亚烷基基团，最好具有内酰胺键；或亚苯基或取代的亚苯基基团；Y是氢、卤素、烷基、芳基、亚氨—芳族或非芳族基团、COOH或
基团或季铵基团。
可用于本发明的典型单过氧酸包括例如：(I)过苯甲酸和环上取代的过苯甲酸，例如过氧—α—萘甲酸；(II)脂族、取代的脂族和芳烷基单过氧酸，例如过月桂酸、过硬
脂酸和N，N—邻苯二甲酰氨基过已酸(PAP)；和(III)6—辛氨基—6—氧代—过已酸。
用于本发明的典型二过氧酸包括例如：(IV)1，1 2—二过氧十二双酸(DPDA)；(V)1，9—二过氧壬二酸；(VI)二过氧巴西基酸；二过氧癸二酸(sebasic acid)和二过氧
间苯二甲酸；(VII)2—癸基二过氧丁烷—1，4—双酸；和(VIII)4，4’—磺酰双过氧苯甲酸。
无机过氧酸化合物也是适用的，例如一过硫酸钾(MPS)。如果使用有机或无机过氧酸作为过氧化合物，其用量一般按重量计约为2—10％，最好为4—8％。
所有这些过氧化物都可单独使用或与过氧酸漂白产物母体和/或有机漂白催化剂结合使用。
过氧酸漂白产物母体是已知的，在文献中有详细的描述，例如英国专利836,988；864,798；907,356；1,003,310和1,519,351；德国专利3,337,921；EP—A—0185522；EP—A—0174132；EP—A—0120591 US1,246,339；3,332,882；4,128,494；4,412,934以及4,675,393。
另外一类过氧酸漂白产物母体是阳离子的过氧酸漂白产物母体，即季铵取代的过氧酸产物母体，正如US 4,751,015和4,397,757；EP—A—284，292和EP—A—331，229中所描述的。这种过氧酸漂白产物母体的实例是：
2—(N，N，N—三甲基铵)乙基钠—4—磺苯基(Sulphonphenyl)碳酸盐氯化物—(SPCC)；
N—辛基，N，N—二甲基—N10—苯氧甲酰基(carbophenoxy)癸基氯化铵—(ODC)；
3—(N，N，N—三甲基铵)丙基钠—4—磺苯基羧酸酯；和
N，N，N—三甲基铵甲苯甲酰氧基苯磺酸酯。
另外一种特殊的阳离子过氧酸漂白产物母体是由阳离子腈生成的，EP—A—0303520、欧洲专利说明书458396和464880对其作了描述。
这些过氧酸漂白产物母体的任何一种都能在本发明中使用，尽管有一些比其它的可能更好些。
在上述漂白产物母体中，最好的是酯，包括酰基苯酚磺酸酯和酰基烷基(苯)酚磺酸酯；酰基一酰胺；和包括阳离子腈在内的季铵取代过氧酸产物母体。
所述最佳过氧酸漂白产物母体或活化剂的实例是钠—4—苯氧基苯磺酸酯(SBOBS)；N，N，N’，N’—四乙酰基亚乙基二胺(TAED)；钠—1—甲基—2—苯甲酰氧基苯—4—磺酸酯；钠—4—甲基—3—苯氧基(benzoloxy)苯甲酸酯；SPCC；三甲基铵甲苯甲酰氧基—苯磺酸酯；钠壬酰氧代苯磺酸酯(SNOBS)；钠3，5，5—三甲基已酰氧代苯磺酸酯(STHOBS)；和取代的阳离子腈。
产物母体用量可为组合物重量的1—8％左右，最好为2—5％。对本发明最合适的有机漂白催化剂是通常所说的磺酰亚胺(Suphonimide)，如EP—A—0,453,003和EP—A—O,446,982所描述的。
表面活性物质
通常用于洗涤漂白组合物中的表面活性物质可以是天然物质衍生的，例如皂，或选自阴离子、非离子、两性的、两性离子的、阳离子活性剂及其混合物的合成原料。许多合适的活性剂可由市售得到并且在文献中例如Schwartz，Perry和Berch的“表面活性剂和洗涤剂”(“Surface Active Agents and Detergents”)，卷I和II中作了充分地描述。
典型的合成阴离子表面活性剂通常是水溶性碱金属有机硫酸盐和具有约8—22个碳原子烷基的磺酸盐，使用的术语烷基包括高级芳基的烷基部分。
例如，合适的合成阴离子洗涤剂化合物是烷基硫酸钠和铵，尤其是经硫酸处理的高级(C8—C18)醇(如由脂或椰子油产生)的化合物；烷基(C9—C10)苯磺酸钠和铵，尤其是直链仲烷基(C10—C15)苯磺酸钠；烷基甘油基醚硫酸钠，尤其是由脂或椰子油衍生的高级醇的酯和由石油产生的合成醇的酯；椰子油脂肪酸—甘油酯硫酸钠和磺酸钠；高级(C9—C18)脂肪醇烯化氧(尤其是环氧乙烷)的反应产物的硫酸酯钠盐和铵盐；用羟乙磺酸酯化和用氢氧化钠中和的脂肪酸如椰子脂肪酸的反应产物；甲基牛磺酸的脂肪酸酰胺的钠和铵盐；烷烃—磺酸盐，如由α—烯烃(C8—C20)与亚硫酸氢钠反应产生的和由烷烃(C12)与SO2反应产生的然后用碱水解以产生无规磺酸盐；C7—C12二烷基磺基丁二酸钠和铵盐；以及烯烃磺酸盐，该术语用于描述烯烃尤其是C10—C20α—烯烃与SO3反应然后中和再水解反应产物所生成的物质。最好的阴离子洗涤剂化合物是(C10—15)烷基苯磺酸钠、(C16—18)烷基醚硫酸钠。
所使用的合适的非离子表面活性化合物，最好与阴离子表面活性化合物一起使用，其实例特别包括烯化氧，通常为环氧乙烷与烷基(C6—C22)酚的反应产物，通常为5—25EO，即每分子有5—25个单元的环氧乙烷；脂族(C8—C18)伯或仲直链或支链醇与环氧乙烷的缩合产物，一般为2—30EO，以及产物可以是环氧乙烷和环氧丙烷和乙二胺反应产物的缩合物。其它所谓非离子表面活性剂包括烷基多糖苷、糖酯、长链氧化季胺、长链氧化季膦以及二烷基亚砜。
一定量的两性或两性离子表面活性化合物也可以用于本发明的组合物中，但是由于它们的价格较高，所以通常并不理想。假若使用任何两性或两性离子洗涤剂化合物，那么按照最普通使用的合成阴离子和非离子活性剂，它可少量用于组合物中。
然而，现已发现假若在洗涤漂白组合物中使用上述催化剂，其性能在很大程度上取决于活性洗涤剂体系和组合物的助洗剂体系。实验表明普通的阴离子表面活性剂和特定的长链C16—C22脂肪酸皂类对催化剂活性具有很大的负作用，因此显著地降低了性能，而非离子洗涤表面活性剂与催化剂相互不作用。最高约10％(按重量计)的较低浓度的短链C12—C14脂肪酸皂类对催化剂活性具有积极作用，但在高浓时，例如＞20％(按重量计)，它们也开始变得有害。
产生这些作用的机理并不完全清楚，但是可以假设借助某些机理，可以认为在阴离子表面活性剂存在的条件下，部分催化剂从溶液中消失。举例来说，这可能是由于正电荷的催化剂分子沉淀负电荷的活性剂，或仅因为形成能造成催化失活的离子对的结果。其它的一种可能性可能是催化剂被包裹在阴离子表面活性剂的胶粒中。
不管是什么原因，应该清楚的是，假若活性洗涤剂包含了阴离子表面活性物质时，含有双核锰配合物所催化的过氧化物漂白体系的洗涤漂白组合物的漂白性能是不佳的。
因此本发明的目的是提供一种洗涤漂白组合物，它含有表面活性物质、过氧化物漂白剂和一种如上所述的具有最佳漂白作用的双核锰配合物。
现在已经异外地发现包含足够量的非离子表面活性剂，能够作为漂白作用至最佳程度。
没有必要受任何理论的束缚，可以认为提供足够数量的非离子表面活性剂能补偿由于催化剂的再增溶作用造成的阴离子表面活性剂的最大负作用。
本发明提供一种洗涤漂白组合物，该组合物含有表面活性剂物质，过氧化物漂白剂和作为漂白催化剂的双核锰配合物，该组合物的特征在于其含有0—25％(wt)的阴离子表面活性剂和7.5—55％(wt)的非离子表面活性剂，如果组合物含有0—7.5％(wt)的碳酸盐助洗剂(用碳酸钠表示)，非离子表面活性剂与阴离子表面活性剂的重量比为0.75，如果组合物含7.5％(wt)以上的碳酸盐助洗剂时，其重量比至少为2.2。
组合物最好含有0—15％(wt)的阴离子表面活性剂和10—40％(wt)的非离子表面活性剂。
在另外一个优选实施方案中，洗涤剂活性体系中不含C16—C22的脂肪皂类。在另一优选实施方案中洗涤漂白组合物基于配方除去了任何阴离子表面活性剂，所以全部是非离子表面活性剂。
本发明组合物通常最好还含有5—80％(wt)去垢助洗剂，最好为10—60％。
去垢助洗剂
助洗剂原料可选自1)钙的螯合剂、2)沉淀物质、3)钙离子交换物质和4)它们的混合物。
钙螯合助洗剂的实例包括碱金属聚磷酸盐，例如三聚磷酸钠；次氮基三乙酸及其水溶性盐；羧甲氧基丁二酸的碱金属盐、乙二胺四乙酸、氧代二丁二酸、苯六甲酸、苯多甲酸.柠檬酸以及如US4,144,226和4,146,495所述的聚缩醛羧酸酯。
沉淀助洗剂的实例包括正磷酸钠和碳酸钠。
钙离子交换助洗剂的实例包括各种类型的非水溶性的晶体或无定形的铝硅酸盐，其中已知的最有代表性的是沸石，例如沸石A、沸石B(也称作沸石P)、沸石C、沸石X、沸石Y和EP—A—0,384,070所述的沸石P型。
特别是，本发明的组合物可以含有任何一种有机或无机助洗剂，然而考虑到环境因素，最好不用磷酸盐助洗剂或仅少量使用。
用于本发明的典型的助洗剂是例如碳酸钠、方解石/碳酸盐、次氮基三乙酸钠盐、柠檬酸钠、羧甲氧基丙二酸酯、羧甲氧基丁二酸酯和非水溶性晶体或无定形铝硅酸盐助洗剂，其中的每一种都能用作主要助洗剂，或单独使用或与其它助洗剂或作为共助洗剂的聚合物混合来使用。
就助洗剂体系而论，已观察到碱金属的碳酸盐和磷酸盐，尤其是碳酸钠、碳酸氢钠和三聚磷酸钠，也对氢过氧化物漂白剂的催化漂白性能具有负作用，出乎意料的是，对过氧酸漂白剂的催化漂白性能影响程度则小得多。然而碳酸盐的影响与PH相关，当PH增加到10以上时，特别是10.5和10.5以上时，这种负作用被大大削弱。
因此，当使用氢过氧化物如过硼酸钠或过碳酸钠作为漂白剂时，优选的组合物含有5％(wt)以下碳酸盐助洗剂(用碳酸钠表示)，如果组合物的PH在高达10的较低碱性区域内时，最优选的是其含量不大于2.5％到基本上是零。
除了上述早已指出的成分以外，本发明洗涤剂组合物可含任意的常用添加剂，其量按通常用于织物洗涤用的洗涤剂组合物。这些添加剂的实例包括缓冲剂，例如碳酸盐，泡沫促进剂，例如链烷醇酰胺，尤其是由棕榈仁脂肪酸和椰子脂肪酸衍生的单乙醇酰胺；泡沫抑制剂，例如烷基磷酸酯和硅氧烷；抗再沉积剂，例如羧甲基纤维素钠盐和烷基或取代的烷基纤维素醚；稳定剂，例如乙二胺四乙酸(EDTA)和膦酸衍生物(即Dequest型)；织物柔软剂；无机盐和碱性缓冲剂，例如硫酸钠、硅酸钠等；以及通常用量很小的荧光剂；香料；酶，例如蛋白酶、纤维素酶、脂梅、淀粉酶和氧化酶；杀菌剂和染料。
当使用氢过氧化物，如过硼酸钠或过碳酸钠作漂白剂时，优选组合物含有按重量计不大于5％的碳酸盐缓冲剂(用碳酸钠表示)，如果组合物的pH处于高达10的较低碱性区域内时，按其用量不大于2.5％到基本上是零是比较好的。
其添加剂中，过渡金属螯合剂，例如EDTA和膦酸衍生物，例如乙二胺四(亚甲基膦酸酯)—EDTMP—是特别重要的，因为它们不仅改进了催化剂/H2O2系统和敏感成分(如酶、荧光剂、香料等)的稳定性，而且还改进了漂白性能，尤其是在10以上的较高pH区域，特别是在PH10.5和10.5以上时。
因此，当洗涤漂白组合物包含表面活性物质、过氧化物漂白剂、锰配合物漂白催化剂、碳酸盐助洗剂和过渡金属螯合剂，使溶液的PH在10以上，特别是在10.5和10.5以上时，则落入本发明的范围之内。
还有落入本发明范围之内的是洗涤漂白组合物含有表面活性物质、过氧酸漂白剂，例如DPDA，PAP和MPS，漂白催化剂和磷酸盐助洗剂，最好是三磷酸钠。
另外任选但非常理想的洗涤组合物中具有多功能特性的添加剂成分，其用量为0.1％—约3％(wt)的聚合物材料，其分子量为1000—2,000,000，它可以是丙烯酸、马来酸或盐或其酐、乙烯基吡咯烷酮、甲基或乙基乙烯基醚以及其它的可聚合的乙烯基单体的均聚物或共聚物。
这种聚合材料最好的实例是聚丙烯酸或聚丙烯酸酯；聚马来酸/丙烯酸共聚物；70∶30丙烯酸/羟乙基马来酸酯共聚物； 1∶1苯乙烯/马来酸共聚物；异丁烯/马来酸和二异丁烯/马来酸共聚物；甲基和乙基乙烯基醚/马来酸共聚物；乙烯/马来酸共聚物；聚乙烯吡咯烷酮和乙烯基吡咯烷酮/马来酸共聚物。
本发明洗涤漂白组合物，当按非流动颗粒配制时，例如粉末状或颗粒状，可通过任何一种用于生产洗涤组合物的常规技术来生产，例如通过制浆，随后喷雾干燥以形成洗涤剂基粉末，该粉未热敏成分包括过氧化物漂白剂以及接需要任选的某些其它的成人和漂白催化剂，可作为干质状态加进去。
然而，据估计向其加入了漂白催化剂的洗涤剂基粉末组合物本身，能以各种其它方式制成，例如所称的分部法(part—part processing)、非塔路线法(non—tower route processing)、干混法、附聚法、造粒法、挤压法、压紧密实法等，这些方法对所属技术领域的一般技术人员来说是已知的而且不构成本发明的基本部分。
本发明将通过下列非限制性实例予以说明。
实施例1
下列实验是在玻璃容器内完成的，装有可控温度的加热螺旋石英管、磁性搅拌、热电偶和PH电极。
在40℃等温下，在PH10的软化水中测量皂类、伯醇硫酸酯(PAS)、烷基苯磺酸盐(ABS)和非离子表面活性剂(NI)对于作为漂白催化剂的一水合过硼酸钠(PBM)和(Mn2 IV(μ-0)3(Mc-TACN)2)(PF6)2，即配合物(I)的漂白性能的效果，在标准茶污染的试验布上。
如果按6g/l的剂量配制洗涤漂白剂，洗涤溶液中所加漂白剂的浓度则为2.5μmol/l催化剂和8.6mmol/1PBM，对应于重量为0.03％的催化剂和14.3％的PBM。
在实施例的每一种组合物中浸泡试验布30分钟，用自来水漂洗后，在转鼓式干燥器中干燥，在zeiss Elrephometer上测量洗涤前后的反差(R460*)。值差(ΔR460*)给出洗涤效果的量度。
结果示于下列表1中
表1
| 添加物 | - | C18—皂 | C12-皂 | C12 PAS1) | ABS | NI2) | |
| Wt.％ | - | 1.6 | 9 | 9 | 9 | 9 | 4 |
| ΔR460* | 25.0 | 22.8 | 8.7 | 28.6 | 15.7 | 16.6 | 26.8 |
1)＝Empicol LXV，购自Albright & Wilson
2)＝Synperonic A7，购自ICI
结果表明，当C18-皂的用量很低如1∶6％(重量)时，可检测出催化剂性能下降。当C18—皂为9％(wt)时，性能显著地从25ΔR单位降低到约9个单位。令人惊奇地是，9％的C12—皂能将催化漂白性能提高到29个单位。两种合成的阴离子表面活性剂PAS(9％)和ABS(9％)对于催化剂的活性也具有很强的负作用，将催化漂白性能由25个单位降至约16个单位。
另一方面，4％的NI几乎对催化剂的活性没有影响。
实施例2
该例表明添加非离子表面活性剂对含9％C18—皂配方的漂白性能的影响。该实验是在与实施例1所用条件完全相同情况下完成的。
结果列于表2中
表2
| 含有物 | — | 9％C18—皂 | ||
| 添加物 | — | — | NI2) | NI2) |
| Wt、％ | — | — | 4 | 16 |
| ΔR460* | 25.0 | 8.7 | 21.0 | 25.7 |
这些结果清楚地表明，添加4％的NI不足以充分地改进漂白性能，相反添加16％(NI与阴离子表面活性剂比为1∶8)，能将催化漂白性能提高至最佳25ΔR单位左右。
实施例3
该例表明添加非离子表面活性剂对含9％的ABS配方漂白性能的影响。该实验是在与例II所用条件完全相同的情况下完成的，结果列于表3中。
表3
| 含有物 | — | 9％ABS | ||
| 添加物 | — | — | NI2) | NI2) |
| wt、％ | — | — | 4 | 8 |
| ΔR460* | 25.0 | 16.6 | 23.9 | 26.7 |
这些结果清楚地表明，添加4％的NI不足以充分改进漂白性能，相反添加8％(NI：阴离子表面活性剂的比0.9)，改进了催化漂白性能，其结果比没有活性剂时对比实验更好一些。
实施例IV
该例表明增加C12-皂的用量对催化剂/PBM漂白体系在茶污染的试验布上的催化漂白性能的影响。实验是在与实施例1条件完全相同的情况下完成的。结果列于表4
表4
| C12-皂(％按重量计) | 0 | 9 | 21 | 33 | 74 |
| mmol/l | 0 | 2.4 | 5.8 | 9.0 | 20 |
| ΔR460* | 25.0 | 28.6 | 25.1 | 23.4 | 20.2 |
实施例V
该例表明Na2CO3对下列标定配方的洗涤漂白组合物的漂白性能的影响，所述配方：
洗涤实验是在40℃等温下，采用16°FH的自来水在PH10和PH10.5的条件下完成的。仅在含剂量为6g/l的漂白组合物的洗涤溶液中，将茶污染的试验布浸泡30分钟。
| 配方 | ％按重量计 |
| 烷基苯磺酸盐(ABS) | 3.0 |
| C18—皂 | 1.7 |
| 非离子的(Synperonic A3/A7) | 9.8 |
| 沸石 | 24.0 |
| 聚合物(Sokalan cp5购自BASF) | 4.0 |
| 羧甲基纤维素钠 | 0.6 |
| 一水合过硼酸钠 | 14.3 |
| Mn—配合物(I)催化剂 | 0.03 |
按反差差值ΔR460*表示的结果列于下列的表中。
表5(PH10)
| 添加Na2CO3(％按重量计) | — | 2.5 | 5.0 | 10.0 | 20.0 |
| ΔR460* | 25.6 | 21.6 | 21.7 | 16.8 | 15.7 |
上表清楚地显示含量达5.0％的碳酸钠对催化漂白性能有轻微负作用，添加较高含量，即10％和20％的碳酸钠而使催化漂白性能显著降低。
表6(PH10.5)
| 添加Na2CO3(％按重量计) | — | 10.0 | 20.0 |
| ΔR460*(-EDTA) | 24.9 | 22.0 | 18.1 |
| ΔR460*(+0.3％EDTA) | 28.0 | 26.1 | — |
根据表6的结果表明提高PH和增加EDTA的积极作用。
实施例VI
重复例1的步骤，只是使用的漂白催化剂是MnIIIMnIV(μ—O)2(μ—OAC)(Et—桥连的(Me2TACN)2)#和微孔过滤的水(即通过Milli—Q plus water purification System(购自MilliporeCorporation)处理(进一步纯化的软化水)。
假若洗涤漂白配方剂量为6g/l，催化剂的含量相应于按重量计0.037％和PBM的含量按重量计14.3％。
[*—按prof Wieghardt所述方法制备的(1991 ICBIC会议，牛津，UK)]。
所获结果列于表7。
表7
*Synperonic A7购自ICI。
| 添加物 | — | ABS | NI* | ABS＋NI* | |||
| wt.％ | — | 9 | 4 | 9＋8 | 9＋16 | 7＋16 | 4＋16 |
| Mn2 IV(μ—O)3(Me3TACN)2 | |||||||
| ΔR460* | 25.0 | 16.6 | 26.8 | 26.7 | — | — | — |
| MnIIIMnIV(μ—O)2(μ—OAO(Et—桥连(Me2TACN)2 | |||||||
| ΔR460* | 27.2 | 14.0 | 27.6 | 19.1 | 22.3 | 24.8 | 28.0 |
结果表明有关Mn2 (IV)(μ—O)3(Me3TACN)2桥连物质能催化过硼酸盐的漂白剂。由于使用ABS而不是使用非离子表面活性剂，因此漂白催化显著地降低。然而，当ABS和非离子表面活性剂都存在时，非离子表面活性剂的需求量比使用未桥连的配合物作漂白催化剂时的用量大，以补偿ABS的不良作用。
Claims (13)
1.一种洗涤漂白组合物，其中包括表面活性物质，过氧化物漂白剂和作为漂白催化剂的双核锰配合物，该配合物通式为：式中Mn是可单独以III或IV氧化态存在的锰；X1、X2和X3可分别任选表示选自H2O、O2 2-、O2-、OH-、HO2 -、SH-、S2-、＞SO、Cl-、N3-、SCN-、RCOO-、RSO3 -、NH2 -和NR3的配位或桥连基团，其中R是H、烷基、芳基，两者是任选地被取代的，或R′COO-，其中R′是烷基、芳基，两者是任选地被取代的；L是一种配位体，其通式为式中t是2-3的整数；s是3-4的整数；u是零或1；R1、R2和R3分别选自H、烷基、芳基，两者是任选地被取代的；Z表示配合物的电荷并可为正或负的整数；Y是一价或多价的相反离子，可使电荷中和，这取决于配合物的电荷Z；而q＝z/[电荷Y]，其特征在于组合物中按重量计包含0-25％的阴离子表面活性剂和7.5-55％的非离子表面活性剂，如果组合物按重量计含0-7.5％的碳酸盐(用碳酸钠表示)，非离子表面活性剂与阴离子表面活性剂的重量比至少为0.75，如果组合物按重量计含7.5％以上的碳酸盐时，该比值至少为2.2。
2.按权利要求1的组合物，其特征在于按重量计其中包含0-15％的阴离子表面活性剂和按重量计10-40％的非离子表面活性剂。
3.按权利要求1的组合物，其特征在于洗涤剂活性系统不含C16-C22脂肪酸皂。
4.按权利要求1、2或3的组合物，其特征在于表面活性剂是非离子表面活性剂。
5.按上述权利要求1-3中的任一项的组合物，其特征在于漂白剂是氢过氧化物化合物。
6.按权利要求4的组合物，其特征在于漂白剂是氢过氧化物化合物。
7.按权利要求5的组合物，其特征在于其pH最高为10且按重量计含有不大于5％的碳酸盐，用碳酸钠表示。
8.按权利要求7的组合物，其特征在于基本上不含碳酸盐。
9.按权利要求1-3中任一项的组合物，其特征在于漂白剂是过氧酸化合物。
10.按权利要求4的组合物，其特征在于漂白剂是过氧酸化合物。
11.按权利要求1的组合物，其中漂白催化剂包括两个配位体，其通式为
式中t是2-3的整数；s是3-4的整数；u是零或1；R1和R2分别选自H、烷基、芳基，两者是任选地被取代的；和R3分别选自氢、烷基、芳基，两者是任选地被取代的，但须桥连单位R4是由各配位体中的1个R3单位生成的，R4是CnR5R6-(D)p-CmR5R6基团，其中p是零或1；D选自如氧和NR7的杂原子或是芳族或饱和同核或异核环的一部分，n是1-4的整数；m是1-4的整数；如果p为零或p为1，而D为芳族或饱和的同核或异核环的一部分，则n＋m＜＝4；如果p是1，而D是如氧或NR7的杂原子，则n＋m＜＝3；R5和R6分别选自H、NR8和OR9、烷基、芳基，任选地被取代的，而R7、R8、R9分别选自H、烷基、芳基，两者是任选地被取代的。
12.按权利要求1-3和6-8中任一项的组合物，其特征在于漂白催化剂选自配合物：
(I)[Mn2 IV(μ—O)3(Me3TACN)](PF6)2
(II)[Mn2 IV(μ—O)3(Me4TACN)](PF6)2
(III)[Mn2 III(μ—O)(μ—OAC)2(Me3TACN)2](PF6)2
(IV)[Mn2 III(μ—O)(μ—OAC)2(Me4TACN)2](PF6)2
(V)[(Et—桥连(Me2TACN)2)MnIIIMNIV(μ—O)2(μ—OAC)]2+
(ClO4 -)2。
13.按权利要求12的组合物，其特征在于所述漂白催化剂是配合物(I)。
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| EP91203078 | 1991-11-26 |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9003741D0 (en) * | 1990-02-19 | 1990-04-18 | Unilever Plc | Bleach activation |
| ES2100924T3 (es) * | 1990-05-21 | 1997-07-01 | Unilever Nv | Activacion de blanqueador. |
-
1992
- 1992-11-24 CA CA002083661A patent/CA2083661A1/en not_active Abandoned
- 1992-11-24 EP EP92310719A patent/EP0544490A1/en not_active Withdrawn
- 1992-11-25 MX MX9206779A patent/MX9206779A/es not_active Application Discontinuation
- 1992-11-25 BR BR9204549A patent/BR9204549A/pt not_active Application Discontinuation
- 1992-11-25 CN CN92111815A patent/CN1031647C/zh not_active Expired - Fee Related
- 1992-11-25 AU AU29620/92A patent/AU661522B2/en not_active Ceased
- 1992-11-26 JP JP4317228A patent/JPH0768543B2/ja not_active Expired - Lifetime
- 1992-11-26 ZA ZA928188A patent/ZA928188B/xx unknown
- 1992-11-26 KR KR1019920022431A patent/KR960000205B1/ko not_active IP Right Cessation
- 1992-11-26 TR TR01152/92A patent/TR27075A/xx unknown
- 1992-12-04 TW TW081109741A patent/TW234144B/zh active
Also Published As
| Publication number | Publication date |
|---|---|
| AU661522B2 (en) | 1995-07-27 |
| ZA928188B (en) | 1994-05-26 |
| AU2962092A (en) | 1993-06-17 |
| BR9204549A (pt) | 1993-06-01 |
| KR960000205B1 (ko) | 1996-01-03 |
| EP0544490A1 (en) | 1993-06-02 |
| CA2083661A1 (en) | 1993-05-27 |
| JPH0641586A (ja) | 1994-02-15 |
| KR930010171A (ko) | 1993-06-22 |
| TW234144B (zh) | 1994-11-11 |
| MX9206779A (es) | 1993-05-01 |
| CN1073714A (zh) | 1993-06-30 |
| TR27075A (tr) | 1994-10-18 |
| JPH0768543B2 (ja) | 1995-07-26 |
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