CA2085720A1 - Bleach activation - Google Patents
Bleach activationInfo
- Publication number
- CA2085720A1 CA2085720A1 CA002085720A CA2085720A CA2085720A1 CA 2085720 A1 CA2085720 A1 CA 2085720A1 CA 002085720 A CA002085720 A CA 002085720A CA 2085720 A CA2085720 A CA 2085720A CA 2085720 A1 CA2085720 A1 CA 2085720A1
- Authority
- CA
- Canada
- Prior art keywords
- integer
- alkyl
- complex
- manganese
- aryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 63
- 230000004913 activation Effects 0.000 title description 4
- 239000011572 manganese Substances 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 18
- 239000003446 ligand Substances 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 230000001419 dependent effect Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 64
- -1 peroxy compound Chemical class 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 238000004061 bleaching Methods 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 5
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000003599 detergent Substances 0.000 description 30
- 239000000463 material Substances 0.000 description 22
- 150000004965 peroxy acids Chemical class 0.000 description 18
- 239000002243 precursor Substances 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 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 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000011976 maleic acid Substances 0.000 description 7
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 150000002696 manganese Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 229910016884 MnIII Inorganic materials 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229910003177 MnII Inorganic materials 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229960001484 edetic acid Drugs 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910001914 chlorine tetroxide Inorganic materials 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
- 235000019864 coconut oil Nutrition 0.000 description 3
- 239000003240 coconut oil Substances 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical class CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NZCIWANIJJJEML-UHFFFAOYSA-N 2-methyl-1,4,7-triazonane Chemical compound CC1CNCCNCCN1 NZCIWANIJJJEML-UHFFFAOYSA-N 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- 102000005575 Cellulases Human genes 0.000 description 2
- 108010084185 Cellulases Proteins 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004367 Lipase Substances 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 102000004316 Oxidoreductases Human genes 0.000 description 2
- 108090000854 Oxidoreductases Proteins 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 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 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 235000019421 lipase Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 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
- 150000004967 organic peroxy acids Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- QSKQNALVHFTOQX-UHFFFAOYSA-M sodium nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O QSKQNALVHFTOQX-UHFFFAOYSA-M 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- RDMHXWZYVFGYSF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RDMHXWZYVFGYSF-LNTINUHCSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- UYXFOIMFLBVYDL-UHFFFAOYSA-N 1,2,4,7-tetramethyl-1,4,7-triazonane Chemical compound CC1CN(C)CCN(C)CCN1C UYXFOIMFLBVYDL-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
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- YMZSLCSDMHLNPW-UHFFFAOYSA-N 2-benzyl-1,4,7-trimethyl-1,4,7-triazonane Chemical compound CN1CCN(C)CCN(C)CC1CC1=CC=CC=C1 YMZSLCSDMHLNPW-UHFFFAOYSA-N 0.000 description 1
- XQAGETLPAKZRHB-UHFFFAOYSA-N 2-decyl-1,4,7-trimethyl-1,4,7-triazonane Chemical compound CCCCCCCCCCC1CN(C)CCN(C)CCN1C XQAGETLPAKZRHB-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
- QDDADYIRBDHPRY-UHFFFAOYSA-N 3-(carboxymethoxy)-3-oxopropanoic acid Chemical compound OC(=O)COC(=O)CC(O)=O QDDADYIRBDHPRY-UHFFFAOYSA-N 0.000 description 1
- GNSKZCHHQSPRNM-UHFFFAOYSA-N 3-carbonoperoxoyltridecanoic acid Chemical compound CCCCCCCCCCC(CC(O)=O)C(=O)OO GNSKZCHHQSPRNM-UHFFFAOYSA-N 0.000 description 1
- LMYSNFBROWBKMB-UHFFFAOYSA-N 4-[2-(dipropylamino)ethyl]benzene-1,2-diol Chemical compound CCCN(CCC)CCC1=CC=C(O)C(O)=C1 LMYSNFBROWBKMB-UHFFFAOYSA-N 0.000 description 1
- IQPXIMWCGCTQAP-UHFFFAOYSA-N 4-carboxyoxy-3-ethylbenzenesulfonic acid Chemical compound CCC1=C(C=CC(=C1)S(=O)(=O)O)OC(=O)O IQPXIMWCGCTQAP-UHFFFAOYSA-N 0.000 description 1
- FCZZQVBGZFNATF-UHFFFAOYSA-N 6-(octylamino)-6-oxohexaneperoxoic acid Chemical compound CCCCCCCCNC(=O)CCCCC(=O)OO FCZZQVBGZFNATF-UHFFFAOYSA-N 0.000 description 1
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- VPJQUVWSQPHJLN-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OOC=1C=CC=CC1C.[Na] Chemical compound C(C1=CC=CC=C1)(=O)OOC=1C=CC=CC1C.[Na] VPJQUVWSQPHJLN-UHFFFAOYSA-N 0.000 description 1
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- 101100112336 Homo sapiens CASP5 gene Proteins 0.000 description 1
- SHBUUTHKGIVMJT-UHFFFAOYSA-N Hydroxystearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OO SHBUUTHKGIVMJT-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
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- 101100273286 Mus musculus Casp4 gene Proteins 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
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- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 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
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004973 alkali metal peroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- RMKNCYHVESPYFD-UHFFFAOYSA-N decan-1-amine;hydrochloride Chemical compound [Cl-].CCCCCCCCCC[NH3+] RMKNCYHVESPYFD-UHFFFAOYSA-N 0.000 description 1
- UNWDCFHEVIWFCW-UHFFFAOYSA-N decanediperoxoic acid Chemical compound OOC(=O)CCCCCCCCC(=O)OO UNWDCFHEVIWFCW-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 description 1
- BRDYCNFHFWUBCZ-UHFFFAOYSA-N dodecaneperoxoic acid Chemical compound CCCCCCCCCCCC(=O)OO BRDYCNFHFWUBCZ-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000009897 hydrogen peroxide bleaching Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229940045996 isethionic acid Drugs 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical group COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 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
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 125000005650 substituted phenylene group Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 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
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—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
- C11D3/39—Organic or inorganic per-compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Catalysts (AREA)
Abstract
C7295 (L) ABSTRACT
Bleach catalysts comprising a complex of formula (I) [L Mn Xp ]Z Yg (I) wherein Mn is manganese in the II, III or IV oxidation state, X represents a coordinating or bridging species; p is an integer from 1 to 3; Y is a counter-ion the type of which is dependent upon the charge z of the complex which can be positive, zero or negative; q = z [charge Y]; and L
is a ligand which is a macrocyclic organic molecule.
Bleach catalysts comprising a complex of formula (I) [L Mn Xp ]Z Yg (I) wherein Mn is manganese in the II, III or IV oxidation state, X represents a coordinating or bridging species; p is an integer from 1 to 3; Y is a counter-ion the type of which is dependent upon the charge z of the complex which can be positive, zero or negative; q = z [charge Y]; and L
is a ligand which is a macrocyclic organic molecule.
Description
- 1 - C7295 (L) BLEACH ACTIVATION
This invention relates to the activation of bleaches employing peroxy compounds, including hydrogen peroxide or hydrogen peroxide adducts which liberate hydrogen peroxide in aqueous solution, as well as peroxy acids; to compounds that activate or catalyse peroxy compounds; to bleach compositions including detergent bleach compositions which contain a catalyst for peroxy compounds; and to process for bleaching and/or washing of substrates employing the above mentioned types of compositions. In particular, the present invention is concerned with the novel use of a specific class of manganese complexes as effective catalyst for the bleach activation of peroxy compound bleaches.
Complexes having the general formula:
L LnMn,,, Xp]Z yq (A) wherein Mn is manganese which can be either in the II, III, IV or V oxidation state, or mixtures thereof; n and m are independently integers from 1-4; X represents a coordinating or bridging species; p is an integer from C-12; Y is a counter-ion, the type of which is dependent
This invention relates to the activation of bleaches employing peroxy compounds, including hydrogen peroxide or hydrogen peroxide adducts which liberate hydrogen peroxide in aqueous solution, as well as peroxy acids; to compounds that activate or catalyse peroxy compounds; to bleach compositions including detergent bleach compositions which contain a catalyst for peroxy compounds; and to process for bleaching and/or washing of substrates employing the above mentioned types of compositions. In particular, the present invention is concerned with the novel use of a specific class of manganese complexes as effective catalyst for the bleach activation of peroxy compound bleaches.
Complexes having the general formula:
L LnMn,,, Xp]Z yq (A) wherein Mn is manganese which can be either in the II, III, IV or V oxidation state, or mixtures thereof; n and m are independently integers from 1-4; X represents a coordinating or bridging species; p is an integer from C-12; Y is a counter-ion, the type of which is dependent
2~85720 - 2 - C7295 (L) upon the charge z of the complex; z is the charge of the complex and is an integer which can be positive, zero or negative; q = Z/[charge Y]; and L is a ligand being a macrocyclic molecule of general formula:
r ~CRlR2)t ~ D - (CR1R2)t ~ 1 wherein R1 and R2 can each be zero, H, alkyl, optionally substituted; and each D can independently be N, NR, PR, O
or S wherein R is H, alkyl, aryl optionally substituted;
have been described in EP-A-0,458,397 as effective catalysts for bleaching with peroxy compounds. Though this definition covers both mono- and polynuclear complexes the specification makes no reference to mono-nuclear manganese-complexes and preference is clearly given to multi-nuclear manganese complexes, particularly the dinuclear manganese complexes of the general formula (A) wherein both n and m are > 2.
Applicants copending US Patent Application 798396 describes mononuclear manganese of formula [L MnIV (OR) 3] Y
where Mn is manganese in the +4 oxidation state;
R iS a C1-C20 radical selected from alkyl, cycloalkyl, aryl, benzyl and radical combinations thereof;
at least two R radicals may also be connected to one another so as to form a bridging unit between two oxygens that coordinate with the manganese;
~)~5~
r ~CRlR2)t ~ D - (CR1R2)t ~ 1 wherein R1 and R2 can each be zero, H, alkyl, optionally substituted; and each D can independently be N, NR, PR, O
or S wherein R is H, alkyl, aryl optionally substituted;
have been described in EP-A-0,458,397 as effective catalysts for bleaching with peroxy compounds. Though this definition covers both mono- and polynuclear complexes the specification makes no reference to mono-nuclear manganese-complexes and preference is clearly given to multi-nuclear manganese complexes, particularly the dinuclear manganese complexes of the general formula (A) wherein both n and m are > 2.
Applicants copending US Patent Application 798396 describes mononuclear manganese of formula [L MnIV (OR) 3] Y
where Mn is manganese in the +4 oxidation state;
R iS a C1-C20 radical selected from alkyl, cycloalkyl, aryl, benzyl and radical combinations thereof;
at least two R radicals may also be connected to one another so as to form a bridging unit between two oxygens that coordinate with the manganese;
~)~5~
- 3 - C7295 (L) L is a ligand selected from a C3-C60 radical having at least 3 nitrogen atoms coordinating with the manganese;
and Y is an oxidatively-stable counterion; and their use as bleach catalysts.
It has now surprisingly been found, however, that other mono-nuclear manganese coordination complexes of the general formula:
[L MnXp]Z Yq (I) wherein Mn can be either in the II, III or IV oxidation state; X represents a coordinating species such as Cl-, Br~
O o~
I-, F-, NCS-, N3-, I3-, NH3, NR3, RCOO-, RO-, R3CCCHCCR3, RSO3-, RSO4- in which R is hydrogen, alkyl, aryl, both optionally substituted, or R'COO- where R' is alkyl or aryl, both optionally substituted, OH-, o22-, o2-, HOO-, H20, SH, CN-, OCN-, S~2- and mixtures thereof; p is an integer from 1-3; z denotes the charge of the complex and is an integer which can be positive, zero or negative; Y is a counter-ion the type of which is dependent upon the charge z of the complex; q = Z/[charge Y]; and L is a ligand and being a macrocyclic organic molecule of the following formula:
I{NR3- (CRl (R2) U) C}~
wherein t is an integer from 2-3; s is an integer from 3-
and Y is an oxidatively-stable counterion; and their use as bleach catalysts.
It has now surprisingly been found, however, that other mono-nuclear manganese coordination complexes of the general formula:
[L MnXp]Z Yq (I) wherein Mn can be either in the II, III or IV oxidation state; X represents a coordinating species such as Cl-, Br~
O o~
I-, F-, NCS-, N3-, I3-, NH3, NR3, RCOO-, RO-, R3CCCHCCR3, RSO3-, RSO4- in which R is hydrogen, alkyl, aryl, both optionally substituted, or R'COO- where R' is alkyl or aryl, both optionally substituted, OH-, o22-, o2-, HOO-, H20, SH, CN-, OCN-, S~2- and mixtures thereof; p is an integer from 1-3; z denotes the charge of the complex and is an integer which can be positive, zero or negative; Y is a counter-ion the type of which is dependent upon the charge z of the complex; q = Z/[charge Y]; and L is a ligand and being a macrocyclic organic molecule of the following formula:
I{NR3- (CRl (R2) U) C}~
wherein t is an integer from 2-3; s is an integer from 3-
4; u is zero or one and Rl, R2 and R3 are each independently selected from H, alkyl, aryl, both optionally substitutedi with the proviso that when p is 3 and Mn is manganese in the IV oxidation state X cannot each be RO-; can also be used as bleach catalysts for peroxy compounds in the same effective way as the 2~ ZO
- 4 - C7295 (L) dinuclear manganese complexes of EP-A-0,458,397 and EP-A-0,458,398.
The choice of X is less crucial for the catalytic activity, but may be of importance for the physical properties of the complex, such as solubility and stability.
Preferred ligands are those in which t = 2; s = 3; u=l; Rl, R2, R3 are each independently H or CH3, particularly wherein Rl and R2 are both H and R3 = CH3.
Examples of preferred ligands are:
1,4,7-triazacyclononane (TACN); 1,4,7-trimethyl-15 1,4,7-triazacyclononane (1,4,7-Me3TACN); 2-methyl-1,4,7-triazacyclononane (2-Me-TACN); and 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (1,2,4,7-Me4TACN); and 1,2,2,4,7-pentamethyl-1,4,7, triazacyclononane (1,2,2,4,7-MesTACN);
2-benzyl-1,4,7-trimethyl-1,4,7-triazacyclononane; and 20 2-decyl-1,4,7-trimethyl-1,4,7-triazacyclononane.
The aforementioned ligands may be synthesised by the methods described in K Wieghardt et al., Inorganic Chemistry 1982, 21, page 3086 et seq, incorporated herein by reference.
Examples of suitable complexes are:
~ N ~ \ M III ~ C~
~ N / ~ Cl /
. ~ = [ (TACN)MnIIICl3]
~2~8S720
- 4 - C7295 (L) dinuclear manganese complexes of EP-A-0,458,397 and EP-A-0,458,398.
The choice of X is less crucial for the catalytic activity, but may be of importance for the physical properties of the complex, such as solubility and stability.
Preferred ligands are those in which t = 2; s = 3; u=l; Rl, R2, R3 are each independently H or CH3, particularly wherein Rl and R2 are both H and R3 = CH3.
Examples of preferred ligands are:
1,4,7-triazacyclononane (TACN); 1,4,7-trimethyl-15 1,4,7-triazacyclononane (1,4,7-Me3TACN); 2-methyl-1,4,7-triazacyclononane (2-Me-TACN); and 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (1,2,4,7-Me4TACN); and 1,2,2,4,7-pentamethyl-1,4,7, triazacyclononane (1,2,2,4,7-MesTACN);
2-benzyl-1,4,7-trimethyl-1,4,7-triazacyclononane; and 20 2-decyl-1,4,7-trimethyl-1,4,7-triazacyclononane.
The aforementioned ligands may be synthesised by the methods described in K Wieghardt et al., Inorganic Chemistry 1982, 21, page 3086 et seq, incorporated herein by reference.
Examples of suitable complexes are:
~ N ~ \ M III ~ C~
~ N / ~ Cl /
. ~ = [ (TACN)MnIIICl3]
~2~8S720
- 5 - C7295 (L) (2) ~\ CIH3 CH3--N~ ~/Mn -- C
[ (1, 4, 7-Me3TACN)MnIIICl3]
( 3 ) ~\ ICH3 _ 2 CH3--~= M~NH
[ ( 1, 4, 7 -Me3TACN) MnII (NH3 ) 3 ] 2 (4)/\ CIH3 2 0 ' N N=N=N
CH3--N T = MnIII ~ N-N-N~
= [ (1,4,7-Me3TACN)MnIII(N3)3]
f N SCN
~/C~I ~ SCN
[ ( 1, 4, 7 -Me3TACN) MnIII ( SCN) 3 ]
-- 6 - C7295 (L~
_ _ .
~6) ,,~ fH3 CH3- N ~ \~ MnII _ _ S - S
~ ~ OH2 = [ (1,4,7-Me3TACN~MnIIS40H2]
(7) [(1,4,7-Me3TACN) Mn(AcAc)(EtO)]BPh4 where AcAc is acetylacetonate.
Some complexes usable as bleach catalysts of the invention were prepared and synthesized as illustrated below:
- Svnthesis of Complex (4) and Complex ~
To a sollltion of [Mn 2 (~ - ) (~-OAc) 2 (1~ 4,7-Me3TACN)2](ClO4)2, (0.5g in 30 ml ethanol), was added solid sodium azide (0.5g) or sodium thiocyanate at room temperature while stirring. Small red-brown crystalline material precipitated. (Yields: 0.3-0.4g)-(K. Wieghardt et al, Inorg. Chim. Acta, 126,39 (1987)) - ~y_thesis of Com~lex (6):
A solution of Mn(OAc)3.2H2O (lg) and 1,4,7-Me3TACN
(lg) in methanol was stirred at room temperature for 30 minutes under argon atmosphere, after which an aqueous solution of (NH4)2S (2 mli40%) was added.
After reducing the volume to 15 ml under reduced pressure and standing for 24 hr in the refrigerator, pale yellow crystals formed, which were collected by filtration. Yield: 0.48g.
(K. Wieghardt et al, Inorg. Chirn. Acta, 126,39 (1987).
z~
- 7 - C7295 (L) - Synthesis of Complex (2) To a solution of [Mn 2 (~ - 0) ( OAc)2(1,4,7_ Me3TACN)2](ClO4)2, (lg in 20 ml CH3CN) was added 10 drops of concentrated hydrochloric acid at room temperature. Yield: 0.25g.
(K. Wieghardt et al, J. Am. Chem. Soc. 110,7398 (1988~.
- Svnthesis of ComPlex (3): [MeTACN MnII(NH~)ll(ClO~
0.5g of 1,4,7-Me3TACN was dissolved in 15 ml of methanol with 0.5 ml of ammonia under argon. To this solution, 1.0g of Mn(ClO4)2 in 15 ml of methanol under argon was added. The white precipitate was isolated under argon.
- Svnthesis of ComPlex (7):
0.5g of 1,4,7-Me3TACN was dissolved in 25 ml of ethanol. Thereafter, 1.35g Mn(AcAc)3 was added and the resulting mixture stirred for 30 minutes.
To this was added 0.7g sodium tetraphenylborate dissolved in 20 ml of water. A yellow-green coloured precipitate formed. This was filtered off and dried in vacuo (Yield 1.4 g).
(K Wieghardt et al, Z Naturforsch, 43b, 1184-1194, 1988).
Instead of using these neat crystalline materials the mononuclear manganese complexes of the invention may also be obtained and presented as a solution by adding a Mn-salt, such as Mn(NO3)2, to an acid solution of the ligand, e.g. 1,4,7-Me3TACN, in water. The solution as obtained can be added to a bleaching solution containing a - 8 - C7295 (L) peroxycompound to give comparable results to those obtained with the isolated Mn-complexes.
The mononuclear manganese complexes of the present invention find particular application in bleach compositions and in bleach compositions.
Thus, according to another aspect of the invention there is provided a bleach composition comprising a peroxy compound, and a complex of formula (I) as hereinbefore defined. Preferably, the composition will also comprise a surface active material and detergent additives such as builders.
An advantage of the bleach catalysts of the invention is that they are hydrolytically and oxidatively stable and function in a variety of detergent formulations. The catalysts of the invention enhance the bleaching action of hydrogen peroxide bleaching agents and of organic and inorganic peroxyacid compounds.
A further surprising feature is that the bleach catalysts are compatible with detergent enzymes, such as proteases, cellulases, lipases, amylases, oxidases etc.
The bleach composition according to the invention are effective on a wide range of stains including both hydrophilic and hydrophobic stains.
Accordingly, in a further aspect, the invention provides a method of bleaching a stained substrate, the method comprising contacting the stained substrate in aqueous media with a bleaching agent selected from the group of peroxy compound bleaches including hydrogen peroxi~e, hydrogen peroxide-liberating or generating compounds, ~¢~
- 9 - C7295 (L) peroxyacids and their salts, and peroxyacid bleach precursors and mixtures thereof, and a manganese complex of formula (I), as hereinbefore defined, each in an effective amount to interact with one another and provide a cleaning effect upon the substrate.
The effective level of the complex, expressed in terms of parts per million (ppm) of the manganese in an aqueous bleaching solution, will normally range from 0.001 ppm to 100 ppm, preferably from 0.01 ppm to 20 ppm, most preferably from 0.1 ppm to 10 ppm. Higher levels may be desired and applied in industrial bleaching processes, such as textile and paper pulp-bleaching. The lower levels quoted are primarily intended and preferably used in domestic laundry operations.
Compositions comprising a peroxy compound bleach and the bleach catalyst are effective over a wide pH range of between 7 and 13, with optimal pH range lying between 8 and 11.
As stated above, the peroxy bleach compounds which can be utilized in the bleaching composition and detergent bleach composition of the present invention :include hydrogen peroxide, hydrogen peroxide-liberating compounds, hydrogen peroxide-generating systems, peroxyacids and their salts, and peroxyacid bleach precursor systems, and mixtures thereof.
Hydrogen peroxide sources are well known in the art. They include the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates persilicates and persulphates. Mixtures of two or more of such compounds 208S7ZI) - 10 - C7295 (L) may also be used. Particularly preferred are sodium percarbonate and sodium perborate and, especially, sodium perborate monohydrate. Sodium perborate monohydrate is preferred to sodium perborate tetrahydrate because of its excellent storage stability combined with its ability to dissolve very ~uickly in aqueous bleaching solutions.
Sodium percarbonate may be preferred for environmental reasons.
Alkylhydroxy peroxides are another class of peroxide bleaching agents. Examples of these materials include cumene hydroperoxide and t-butyl hydroperoxide.
Organic peroxyacids may also be suitable as the peroxide bleaching agent. Such materials normally have the general formula:
~0 HOO - C - R - Y
wherein R is an alkylene or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally having an internal amide linkage; or a phenylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic or non-aromatic group, a COOH or CIOOH group or a ~uaternary ammonium group.
o ~ypical monoperoxy acids useful herein include, for example.
i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g. peroxy-a-naphthoic acid;
ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids, e.g. peroxylauric acid, ~ C7295 (L) peroxystearic acid and N,N-phthaloylaminoperoxy caproic acid (PAP); and iii) 6-octylamino-6-oxo-peroxyhexanoic acid.
Typical diperoxyacids useful herein include, for example:
iv) 1,12-diperoxydodecanedioic acid (DPDA);
v) 1,9-diperoxyazelaic acid; 0 vi) diperoxybrassilic acid; diperoxysebasic acid and diperoxyisophthalic acid;
vii) 2-decylperoxybutane-1, 4-dioic acid;
viii) 4,4'-sulphonylbisperoxybenzoic acid.
Also inorganic peroxyacid compounds are suitable, such as for example potassium monopersulphate (MPS).
All these peroxide compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor. An advantage of using a peroxyacid bleach precursor is that it may improve the overall whiteness of white fabrics.
Such materials may also be used because of the hygiene benefits they confer on materials treated therewith.
Peroxyacid bleach precursors are known and amply described in literature, such as in British Patents 836,988;
864,798; 907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; European Patent Specification Nos 0185522;
0174132 and 0120591; and US Patents 1,246,339; 3,332,882;
4,128,494; 4,412,934 and 4,675,393.
Another useful class of peroxyacid bleach precursors are the quaternary ammonium substituted peroxyacid precursors disclosed in US Patents 4,751,015 and 4,397,75'7, and in European Patent Specification Nos 284,292, 331,229 and 2C&57Z:O
- 12 - C7295 (L) 303,520. Examples of peroxyacid bleach precursors of this class are:
2-(N,N,N-trimethyl ammonium) ethyl-4-sulphophenyl carbonate - (SPCC);
N-octyl,N,N-dimethyl-N10-carbophenoxy decyl ammonium chloride - (ODC)i 3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate; and N,N,N-trimethyl ammonium toluyloxy benzene sulphonate.
A further special class of cationic peroxyacid bleach precursors is formed by the cationic nitriles as disclosed in European Patent Specification No 303520, 458396 and 464880.
Any one of these peroxyacid bleach precursors may be used in the present invention. Of the above classes of bleach precursors, the preferred materials are esters, including acyl phenol sulphonates and acyl alkyl phenol sulphonates;
the acyl-amides; the ~uaternary ammonium substituted peroxyacid precursors including the cationic nitriles.
Examples of said preferred peroxyacid bleach precursors or activators are sodium-4-benzoloxy benzene sulphonate (SBOBS); N,N,N'N'-tetraacetyl ethylene diamine (TAED);
sodium-l-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-benzoloxy benzoate; SPCC; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3,5,5-trimethyl hexanoyloxybenzene sulphonate (STHOBS); and the substituted cationic nitriles.
ZC857~(~
- 13 - C7295 (L) Particularly suitable materials are the so-called sulphonimides as disclosed in European Patent Specification Nos 453,003 and 446,982.
A detergent bleach composition of the invention can be formulated by combining effective amounts of the components. The term ~effective amounts" as used herein means the components are present in quantitites such that each of them is operative for its intended purpose when the resulting mixture is combined with water to form an aqueous medium which may be used to wash and clean clothes, fabrics and other articles.
In particular, the detergent bleach composition can be formulated to contain, for example, from about 2% to 30%
by weight, preferably from 5 to 25% by weight, of a peroxide compound.
Peroxyacids may be used in somewhat lower amounts, for example from 1% to about 15% by weight, preferably from 2%
to 10% by weight.
Peroxyacid precursors may be used in combination with a peroxide compound at approximately the same level as peroxyacids, i.e. 1% to 15%, preferably from 2% to 10% by weight.
The complex will be present in the bleach and detergent bleach compositions in amounts so as to provide the required level of in the wash liquor. Normally, the manganese content in the formulation is from 0.0005% to about 0.5% by weight, preferably 0.001% to 0.25% by weight.
~857~l~
- 14 - C7295 (L) When used in a detergent bleach composition to be dosed at low levels, for example by Japanese and US consumers at dosages of about 1 and 2 g/l respectively the Mn content in the formulation is at 0.0025 to O.S% by weight, preferably 0.005 to 0.25%. At higher product dosages as used, for example, by European consumers, the Mn content in the formulation is from 0.0005 to 0.1% by weight, preferably from 0.001 to 0.05%.
The bleach catalyst of the invention is compatible with substantially any known and common surface-active agents and detergency builder materials.
The surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof. Many suitable actives are commercially available and are described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch. The total level oE the surface-active material may be from 0.5% up to 50% by weight, and is preferably from about 1% to 40~ by weight of the composition, most preferably 4 to 25% by weight.
Synthetic anionic surface-actives are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl groups containing from about 8 to 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher aryl groups.
Examples of suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (Cg-C20) benzene sulphonates, particularly ~85720 - ~L5 - C7295 (L) sodium linear secondary alkyl (Cl0-Cls) benzene sulphonates;
sodium alkyl glyceryl ether sulphates, especially those esters of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum;
sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (Cg-Cl8) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (C8-C20) with sodium bisulphite and those derived by reacting paraffins with SO2 and Cl2 and then hydrolyzing with a base to produce a random sulphonate; sodium and a~nonium C7-Cl2 dialkyl sulfosuccinates; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly Cl0-C20 alpha-olefins, with SO3 and then neutralizing and hydrolyzing the reaction product.
The preferred anionic detergent compounds are sodium (Cll-Cls) alkylbenzene sulphonates, sodium (Cl6-Cl8) alkyl sulphates and sodium (Cl6-Cl8) alkyl ether sulphates.
Examples of suitable nonionic surface-active compounds which may be used include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6-C22) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; the condensation products of aliphatic (C8-Cl8) primary, secondary linear or branched alcohols with ethylene oxide, generally 3-30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.
Other so-called nonionic surface-actives include alkyl -- 16 - C7295 (L) polyglycosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
Amounts of amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If amphoteric or zwitterionic detergent compounds are used it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives.
As stated above, soaps may also be incorporated in the compositions of the invention. However~ the bleach performance of the bleaching and detergent bleach composition is improved if the amount of long-chain C16 - C22 fatty acid soaps is kept to a minimum. Short chain C12 - C1~ fatty acid soaps may be included preferably at levels not more than about 10~ by weight.
High levels of anionic surfactant are also believed to reduce bleach performance to below optimum levels.
Preferably the detergent bleach composition comprises a surface-active material, a peroxide bleaching agent, a complex of general formula (I) as hereinbefore defined, 0 to 25% by weight of anionic surfactant and 7.5 to 55% by weight of nonionic surfactant, the weight ratio of nonionic surfactant to anionic surfactant being at least 0.75.
The detergent bleach composition of the invention will normally also contain a detergency builder. Builder materials may be selected from calcium se~uestrant materials; precipitating materials; calcium ion-exchange materials and mixtures thereof.
2~85~2~3 - 17 - C7295 (L) Examples of calcium se~uestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitri.lotriacetic acid and its water-soluble salts; the alkali metal salts of ether polycarboxylates, such as carboxymethyloxy succinic acid, oxydisuccinic acid, mellitic acid; ethylene diamine tetraacetic acid; benzene polycarboxylic acids; citric acid; and polyacetal carboxylates as described in US
Patents 4,144,226 and 4,146,495.
Examples of precipitating builder materials include sodium orthophosphate, sodium carbonate and sodium carbonate/
calcite.
Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are well-known examples.
In particular, the compositions of the invention may contain any one of the organic or inorganic builder materials, such as sodium or potasssium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate or sodium carbonate/calcite mixtures, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.
If a phosphate builder is used, preferably a peroxyacid is present as the bleach agent.
2~8S72~
- 18 - C7295 (L) The builder materials may be present at a level of, for example, from 5 to 80% by weight, preferably from 10 to 60% by weight.
The detergent compositions of the invention may also contain conventional additives in the amounts at which such materials are normally employed in fabric washing detergent compositions. Examples of these additives include buffers, such as carbonates, lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palmkernel fatty acids and coconut fatty acids, lather depressants, such as alkyl phosphates and silicones, anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers, other stabilizers, such as ethylene diamine tetraacetic acid (EDTA) and the phosphonic acid derivatives (i.e. Dequest R types), fabric softening agents, inorganic salts, such as sodium sulphate, and, usually present in very small amounts, fluorescent agents, perfumes, enzymes, such as proteases, cellulases, lipases, amylases and oxidases, germicides and colourants.
Of these additives, transition metal sequestrants, such as EDTA and the phosphoric acid derivatives, e.g. ethylene diamine tetra-(methylene phosphonate) EDTMP are particularly important.
Another optional but highly desirable additive with multi-functional characteristics is a polymeric material having a molecular weight of from 1,000 to 2,000,000 and which can be a homo- or co-polymer of acrylic acid, maleic acid, or salt or anhydride thereof, vinyl pyrrolidone, methyl-or ethyl-vinyl ethers, and other polymerisable vinyl monomers. Preferred examples of such polymeric materials are polyacrylic acid or polyacrylate; polymaleic 2C~572~3 - 19 - C7295 (L) acid/acrylic acid copolymer; 70:30 acrylic acid~hydroxyethyl maleate copolymer; 1:1 styrene/maleic acid copolymer; isobutylene/maleic acid and diisobutylene/
maleic acid copolymers; methyl- and ethyl-vinylether/
maleic acid copolymers; ethylene/maleic acid copolymer;
polyvinyl pyrrolidone; and vinyl pyrrolidone/maleic acid copolymer. Such a polymeric additive is usually present at a level from about 0.1% to about 3~ by weight.
When using a hydroperoxide, such as sodium perborate or sodium percarbonate, as the bleaching agent, it is preferred that the composition contains not more than 5%
by weight of carbonate, expressed as sodium carbonate, more preferably not more than 2.5% by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.
Detergent bleach compositions of the invention, when formulated as free-flowing particles, e.g. in powdered or granulated form, can be produced by any of the conventional techniques employed in the manufacture of detergent compositions, for instance by slurry-making, followed by spray-drying, to form a detergent base powder to which heat-sensitive ingredients including the peroxy compound bleach, conventional additives, and the complex can be added as dry substances.
It will be appreciated, however, that the detergent base powder compositions, to which the complex is added, can itself be made in a variety of other ways, such as the so-called part-part processing, non-tower route processing, dry-mixing, agglomeration, granulation, extrusion, compacting and densifying processes etc., such ways being well known to those skilled in the art and not forming an essential part of the present invention.
Z085~
- 20 - C7295 (L) Alternatively, the complex may be added separately to a wash/bleach water containing the peroxy bleaching agent.
In that case, the complex is included as a detergent additive product. Such additive products are intended to supplement or boost the performance of conventional detergent compositions and may contain any of the components of such compositions, although they will not comprise all of the components present in a fully formulated detergent composition. Additive products in accordance with this aspect of the invention will normally be added to an aqueous liquor containing a source of (alkaline) hydrogen peroxide, although in certain circumstances the additive product may be used as separate treatment in a pre-wash or in the rinse.
Additive products in accordance with this aspect of the invention may comprise the complex alone or, preferably, in combination with a carrier, such as a compatible agueous or non-aqueous liquid medium or a particulate substrate or a flexible non-particulate substrate.
Examples of compatible particulate substrates include inert materials, such as clays and other aluminosilicates, including zeolites, both of natural and synthetic origin.
Other compatible particulate carrier materials include hydratable inorganic salts, such as carbonates and sulphates.
The complex can also be formulated in detergent bleach compositions of other product forms, such as flakes, tablets, bars and liquids and particularly non-aqueous liquid detergent compositions.
2~8S7~0 - 21 - C7295 (L) Such non-aqueous li~uid detergent compositions in which the complex may be incorporated are known in the art and various formulations have been proposed, e.g. in US
Patents 2,864,770i 3,368,977; 4,772,412; GB Patents 1,205,711; 1,370,377; 2,914,536; DE-A-2,233,771 and European Patent Specification No. 0,028,849.
These are compositions which normally comprise a non-aqueous liquid medium, with or without a solid phase dispersed therein. The non-aqueous liquid medium may be a liquid surfactant, preferably a liquid nonionic surfactant; a non-polar liquid medium, e.g. liquid paraffin; a polar solvent, e.g. polyols, such as glycerol, sorbitol, ethylene glycol, optionally combined with low-molecular monohydrix alcohols, e.g. ethanol orisopropanol; or mixtures thereof.
The solid phase can be builders, alkalis, abrasives, polymers, clays, other solid ionic surfactants, bleaches, fluorescent agents and other usual solid detergent ingredients.
The invention will now be illustrated by way of the following example:
Exam~le I
The following examples were carried out in glass vessels, equipped with a temperature controlled heating spiral in quartz, magnetic stirrer, thermo-couple and pH electrode.
At 40C isothermal, experiments in demineralised water at pH 10, were carried out to determine the bleach performance of sodium perborate monohydrate (PBM) and a 21~8~720 - 22 - C7295 (L) mononuclear complex as bleach catalyst on standard tea-stained test cloths.
The bleach system in the wash solution was added at a concentration of 8.6 mmol/l PBM which corresponds to 14.3%
by weight of PB~ if a detergent bleach formulation is dosed at 6g/1.
Test cloths were immersed for 30 minutes in each of the compositions of the examples. After rinsing with tap water, the cloths were dried in a tumble drier. The reflectance (R460~) was measured on a Zeiss Elrephometer before and after treatment. The difference (oR460r) in the value gives a measure of the effectiveness of the treatment.
The results are shown in the following Table I.
21~85720 - 23 - C7295 (L) TABLE I
_ I
~R
(A) Blank (no catalyst) 5.5 ... _ I
(B) + Free Mn(NO3) 2 12.0 (5 x 10-6 mol/l _ (C) ~ [Mn2IVt~-o)3(l~4~7- 25.1 Me3TACN) 2 ] ( PF6 ) 2 (2.5 x 10-6 mol/l .
I -~ [1,4,7-Me3TACN.MnIIICl3] 26.3 (5 x 10-6 mol/l II + [1,4,7-Me3TACN.MnII(NH3)3] 2~ 25.3 (5 x 10-6 mol/l) III + [1,4,7-Me3TACN MnIII(N3)3] 22.0 (5 x 10-6 mol/l) IV + [1,4,7-Me3TACN MnIII(SCN)3] 25.0 (5 x 10-6 mol/l) V + [1,4,7-Me3TACN Mn (AcAc) 26.0 (EtO)] BPh4 (5 x 10-6 mol/l dissolved in 5 ml of ethanol and added to 995 ml of bleach solution contai.ning PBM) The level of mononuclear Mn complex corresponds to 0.03~
by weight of catalyst if a detergent composition is dosed at 6 g/l.
- 24 - C7295 (L) Experiments (A), (B), and (C) were used as controls. The above results clearly show that the mononuclear manganese coordination complexes (2), (3), (4), (5) and (7) were at least as effective as the preferred dinuclear complex catalyst [Mn2IV(~-0)3(1,4,7-Me3TACN) 2] (PF6) 2~ described in EP-A-458 397 and EP-A-458 398.
[ (1, 4, 7-Me3TACN)MnIIICl3]
( 3 ) ~\ ICH3 _ 2 CH3--~= M~NH
[ ( 1, 4, 7 -Me3TACN) MnII (NH3 ) 3 ] 2 (4)/\ CIH3 2 0 ' N N=N=N
CH3--N T = MnIII ~ N-N-N~
= [ (1,4,7-Me3TACN)MnIII(N3)3]
f N SCN
~/C~I ~ SCN
[ ( 1, 4, 7 -Me3TACN) MnIII ( SCN) 3 ]
-- 6 - C7295 (L~
_ _ .
~6) ,,~ fH3 CH3- N ~ \~ MnII _ _ S - S
~ ~ OH2 = [ (1,4,7-Me3TACN~MnIIS40H2]
(7) [(1,4,7-Me3TACN) Mn(AcAc)(EtO)]BPh4 where AcAc is acetylacetonate.
Some complexes usable as bleach catalysts of the invention were prepared and synthesized as illustrated below:
- Svnthesis of Complex (4) and Complex ~
To a sollltion of [Mn 2 (~ - ) (~-OAc) 2 (1~ 4,7-Me3TACN)2](ClO4)2, (0.5g in 30 ml ethanol), was added solid sodium azide (0.5g) or sodium thiocyanate at room temperature while stirring. Small red-brown crystalline material precipitated. (Yields: 0.3-0.4g)-(K. Wieghardt et al, Inorg. Chim. Acta, 126,39 (1987)) - ~y_thesis of Com~lex (6):
A solution of Mn(OAc)3.2H2O (lg) and 1,4,7-Me3TACN
(lg) in methanol was stirred at room temperature for 30 minutes under argon atmosphere, after which an aqueous solution of (NH4)2S (2 mli40%) was added.
After reducing the volume to 15 ml under reduced pressure and standing for 24 hr in the refrigerator, pale yellow crystals formed, which were collected by filtration. Yield: 0.48g.
(K. Wieghardt et al, Inorg. Chirn. Acta, 126,39 (1987).
z~
- 7 - C7295 (L) - Synthesis of Complex (2) To a solution of [Mn 2 (~ - 0) ( OAc)2(1,4,7_ Me3TACN)2](ClO4)2, (lg in 20 ml CH3CN) was added 10 drops of concentrated hydrochloric acid at room temperature. Yield: 0.25g.
(K. Wieghardt et al, J. Am. Chem. Soc. 110,7398 (1988~.
- Svnthesis of ComPlex (3): [MeTACN MnII(NH~)ll(ClO~
0.5g of 1,4,7-Me3TACN was dissolved in 15 ml of methanol with 0.5 ml of ammonia under argon. To this solution, 1.0g of Mn(ClO4)2 in 15 ml of methanol under argon was added. The white precipitate was isolated under argon.
- Svnthesis of ComPlex (7):
0.5g of 1,4,7-Me3TACN was dissolved in 25 ml of ethanol. Thereafter, 1.35g Mn(AcAc)3 was added and the resulting mixture stirred for 30 minutes.
To this was added 0.7g sodium tetraphenylborate dissolved in 20 ml of water. A yellow-green coloured precipitate formed. This was filtered off and dried in vacuo (Yield 1.4 g).
(K Wieghardt et al, Z Naturforsch, 43b, 1184-1194, 1988).
Instead of using these neat crystalline materials the mononuclear manganese complexes of the invention may also be obtained and presented as a solution by adding a Mn-salt, such as Mn(NO3)2, to an acid solution of the ligand, e.g. 1,4,7-Me3TACN, in water. The solution as obtained can be added to a bleaching solution containing a - 8 - C7295 (L) peroxycompound to give comparable results to those obtained with the isolated Mn-complexes.
The mononuclear manganese complexes of the present invention find particular application in bleach compositions and in bleach compositions.
Thus, according to another aspect of the invention there is provided a bleach composition comprising a peroxy compound, and a complex of formula (I) as hereinbefore defined. Preferably, the composition will also comprise a surface active material and detergent additives such as builders.
An advantage of the bleach catalysts of the invention is that they are hydrolytically and oxidatively stable and function in a variety of detergent formulations. The catalysts of the invention enhance the bleaching action of hydrogen peroxide bleaching agents and of organic and inorganic peroxyacid compounds.
A further surprising feature is that the bleach catalysts are compatible with detergent enzymes, such as proteases, cellulases, lipases, amylases, oxidases etc.
The bleach composition according to the invention are effective on a wide range of stains including both hydrophilic and hydrophobic stains.
Accordingly, in a further aspect, the invention provides a method of bleaching a stained substrate, the method comprising contacting the stained substrate in aqueous media with a bleaching agent selected from the group of peroxy compound bleaches including hydrogen peroxi~e, hydrogen peroxide-liberating or generating compounds, ~¢~
- 9 - C7295 (L) peroxyacids and their salts, and peroxyacid bleach precursors and mixtures thereof, and a manganese complex of formula (I), as hereinbefore defined, each in an effective amount to interact with one another and provide a cleaning effect upon the substrate.
The effective level of the complex, expressed in terms of parts per million (ppm) of the manganese in an aqueous bleaching solution, will normally range from 0.001 ppm to 100 ppm, preferably from 0.01 ppm to 20 ppm, most preferably from 0.1 ppm to 10 ppm. Higher levels may be desired and applied in industrial bleaching processes, such as textile and paper pulp-bleaching. The lower levels quoted are primarily intended and preferably used in domestic laundry operations.
Compositions comprising a peroxy compound bleach and the bleach catalyst are effective over a wide pH range of between 7 and 13, with optimal pH range lying between 8 and 11.
As stated above, the peroxy bleach compounds which can be utilized in the bleaching composition and detergent bleach composition of the present invention :include hydrogen peroxide, hydrogen peroxide-liberating compounds, hydrogen peroxide-generating systems, peroxyacids and their salts, and peroxyacid bleach precursor systems, and mixtures thereof.
Hydrogen peroxide sources are well known in the art. They include the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates persilicates and persulphates. Mixtures of two or more of such compounds 208S7ZI) - 10 - C7295 (L) may also be used. Particularly preferred are sodium percarbonate and sodium perborate and, especially, sodium perborate monohydrate. Sodium perborate monohydrate is preferred to sodium perborate tetrahydrate because of its excellent storage stability combined with its ability to dissolve very ~uickly in aqueous bleaching solutions.
Sodium percarbonate may be preferred for environmental reasons.
Alkylhydroxy peroxides are another class of peroxide bleaching agents. Examples of these materials include cumene hydroperoxide and t-butyl hydroperoxide.
Organic peroxyacids may also be suitable as the peroxide bleaching agent. Such materials normally have the general formula:
~0 HOO - C - R - Y
wherein R is an alkylene or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally having an internal amide linkage; or a phenylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic or non-aromatic group, a COOH or CIOOH group or a ~uaternary ammonium group.
o ~ypical monoperoxy acids useful herein include, for example.
i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g. peroxy-a-naphthoic acid;
ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids, e.g. peroxylauric acid, ~ C7295 (L) peroxystearic acid and N,N-phthaloylaminoperoxy caproic acid (PAP); and iii) 6-octylamino-6-oxo-peroxyhexanoic acid.
Typical diperoxyacids useful herein include, for example:
iv) 1,12-diperoxydodecanedioic acid (DPDA);
v) 1,9-diperoxyazelaic acid; 0 vi) diperoxybrassilic acid; diperoxysebasic acid and diperoxyisophthalic acid;
vii) 2-decylperoxybutane-1, 4-dioic acid;
viii) 4,4'-sulphonylbisperoxybenzoic acid.
Also inorganic peroxyacid compounds are suitable, such as for example potassium monopersulphate (MPS).
All these peroxide compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor. An advantage of using a peroxyacid bleach precursor is that it may improve the overall whiteness of white fabrics.
Such materials may also be used because of the hygiene benefits they confer on materials treated therewith.
Peroxyacid bleach precursors are known and amply described in literature, such as in British Patents 836,988;
864,798; 907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; European Patent Specification Nos 0185522;
0174132 and 0120591; and US Patents 1,246,339; 3,332,882;
4,128,494; 4,412,934 and 4,675,393.
Another useful class of peroxyacid bleach precursors are the quaternary ammonium substituted peroxyacid precursors disclosed in US Patents 4,751,015 and 4,397,75'7, and in European Patent Specification Nos 284,292, 331,229 and 2C&57Z:O
- 12 - C7295 (L) 303,520. Examples of peroxyacid bleach precursors of this class are:
2-(N,N,N-trimethyl ammonium) ethyl-4-sulphophenyl carbonate - (SPCC);
N-octyl,N,N-dimethyl-N10-carbophenoxy decyl ammonium chloride - (ODC)i 3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate; and N,N,N-trimethyl ammonium toluyloxy benzene sulphonate.
A further special class of cationic peroxyacid bleach precursors is formed by the cationic nitriles as disclosed in European Patent Specification No 303520, 458396 and 464880.
Any one of these peroxyacid bleach precursors may be used in the present invention. Of the above classes of bleach precursors, the preferred materials are esters, including acyl phenol sulphonates and acyl alkyl phenol sulphonates;
the acyl-amides; the ~uaternary ammonium substituted peroxyacid precursors including the cationic nitriles.
Examples of said preferred peroxyacid bleach precursors or activators are sodium-4-benzoloxy benzene sulphonate (SBOBS); N,N,N'N'-tetraacetyl ethylene diamine (TAED);
sodium-l-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-benzoloxy benzoate; SPCC; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3,5,5-trimethyl hexanoyloxybenzene sulphonate (STHOBS); and the substituted cationic nitriles.
ZC857~(~
- 13 - C7295 (L) Particularly suitable materials are the so-called sulphonimides as disclosed in European Patent Specification Nos 453,003 and 446,982.
A detergent bleach composition of the invention can be formulated by combining effective amounts of the components. The term ~effective amounts" as used herein means the components are present in quantitites such that each of them is operative for its intended purpose when the resulting mixture is combined with water to form an aqueous medium which may be used to wash and clean clothes, fabrics and other articles.
In particular, the detergent bleach composition can be formulated to contain, for example, from about 2% to 30%
by weight, preferably from 5 to 25% by weight, of a peroxide compound.
Peroxyacids may be used in somewhat lower amounts, for example from 1% to about 15% by weight, preferably from 2%
to 10% by weight.
Peroxyacid precursors may be used in combination with a peroxide compound at approximately the same level as peroxyacids, i.e. 1% to 15%, preferably from 2% to 10% by weight.
The complex will be present in the bleach and detergent bleach compositions in amounts so as to provide the required level of in the wash liquor. Normally, the manganese content in the formulation is from 0.0005% to about 0.5% by weight, preferably 0.001% to 0.25% by weight.
~857~l~
- 14 - C7295 (L) When used in a detergent bleach composition to be dosed at low levels, for example by Japanese and US consumers at dosages of about 1 and 2 g/l respectively the Mn content in the formulation is at 0.0025 to O.S% by weight, preferably 0.005 to 0.25%. At higher product dosages as used, for example, by European consumers, the Mn content in the formulation is from 0.0005 to 0.1% by weight, preferably from 0.001 to 0.05%.
The bleach catalyst of the invention is compatible with substantially any known and common surface-active agents and detergency builder materials.
The surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof. Many suitable actives are commercially available and are described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch. The total level oE the surface-active material may be from 0.5% up to 50% by weight, and is preferably from about 1% to 40~ by weight of the composition, most preferably 4 to 25% by weight.
Synthetic anionic surface-actives are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl groups containing from about 8 to 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher aryl groups.
Examples of suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (Cg-C20) benzene sulphonates, particularly ~85720 - ~L5 - C7295 (L) sodium linear secondary alkyl (Cl0-Cls) benzene sulphonates;
sodium alkyl glyceryl ether sulphates, especially those esters of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum;
sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (Cg-Cl8) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (C8-C20) with sodium bisulphite and those derived by reacting paraffins with SO2 and Cl2 and then hydrolyzing with a base to produce a random sulphonate; sodium and a~nonium C7-Cl2 dialkyl sulfosuccinates; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly Cl0-C20 alpha-olefins, with SO3 and then neutralizing and hydrolyzing the reaction product.
The preferred anionic detergent compounds are sodium (Cll-Cls) alkylbenzene sulphonates, sodium (Cl6-Cl8) alkyl sulphates and sodium (Cl6-Cl8) alkyl ether sulphates.
Examples of suitable nonionic surface-active compounds which may be used include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6-C22) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; the condensation products of aliphatic (C8-Cl8) primary, secondary linear or branched alcohols with ethylene oxide, generally 3-30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.
Other so-called nonionic surface-actives include alkyl -- 16 - C7295 (L) polyglycosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
Amounts of amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If amphoteric or zwitterionic detergent compounds are used it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives.
As stated above, soaps may also be incorporated in the compositions of the invention. However~ the bleach performance of the bleaching and detergent bleach composition is improved if the amount of long-chain C16 - C22 fatty acid soaps is kept to a minimum. Short chain C12 - C1~ fatty acid soaps may be included preferably at levels not more than about 10~ by weight.
High levels of anionic surfactant are also believed to reduce bleach performance to below optimum levels.
Preferably the detergent bleach composition comprises a surface-active material, a peroxide bleaching agent, a complex of general formula (I) as hereinbefore defined, 0 to 25% by weight of anionic surfactant and 7.5 to 55% by weight of nonionic surfactant, the weight ratio of nonionic surfactant to anionic surfactant being at least 0.75.
The detergent bleach composition of the invention will normally also contain a detergency builder. Builder materials may be selected from calcium se~uestrant materials; precipitating materials; calcium ion-exchange materials and mixtures thereof.
2~85~2~3 - 17 - C7295 (L) Examples of calcium se~uestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitri.lotriacetic acid and its water-soluble salts; the alkali metal salts of ether polycarboxylates, such as carboxymethyloxy succinic acid, oxydisuccinic acid, mellitic acid; ethylene diamine tetraacetic acid; benzene polycarboxylic acids; citric acid; and polyacetal carboxylates as described in US
Patents 4,144,226 and 4,146,495.
Examples of precipitating builder materials include sodium orthophosphate, sodium carbonate and sodium carbonate/
calcite.
Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are well-known examples.
In particular, the compositions of the invention may contain any one of the organic or inorganic builder materials, such as sodium or potasssium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate or sodium carbonate/calcite mixtures, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.
If a phosphate builder is used, preferably a peroxyacid is present as the bleach agent.
2~8S72~
- 18 - C7295 (L) The builder materials may be present at a level of, for example, from 5 to 80% by weight, preferably from 10 to 60% by weight.
The detergent compositions of the invention may also contain conventional additives in the amounts at which such materials are normally employed in fabric washing detergent compositions. Examples of these additives include buffers, such as carbonates, lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palmkernel fatty acids and coconut fatty acids, lather depressants, such as alkyl phosphates and silicones, anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers, other stabilizers, such as ethylene diamine tetraacetic acid (EDTA) and the phosphonic acid derivatives (i.e. Dequest R types), fabric softening agents, inorganic salts, such as sodium sulphate, and, usually present in very small amounts, fluorescent agents, perfumes, enzymes, such as proteases, cellulases, lipases, amylases and oxidases, germicides and colourants.
Of these additives, transition metal sequestrants, such as EDTA and the phosphoric acid derivatives, e.g. ethylene diamine tetra-(methylene phosphonate) EDTMP are particularly important.
Another optional but highly desirable additive with multi-functional characteristics is a polymeric material having a molecular weight of from 1,000 to 2,000,000 and which can be a homo- or co-polymer of acrylic acid, maleic acid, or salt or anhydride thereof, vinyl pyrrolidone, methyl-or ethyl-vinyl ethers, and other polymerisable vinyl monomers. Preferred examples of such polymeric materials are polyacrylic acid or polyacrylate; polymaleic 2C~572~3 - 19 - C7295 (L) acid/acrylic acid copolymer; 70:30 acrylic acid~hydroxyethyl maleate copolymer; 1:1 styrene/maleic acid copolymer; isobutylene/maleic acid and diisobutylene/
maleic acid copolymers; methyl- and ethyl-vinylether/
maleic acid copolymers; ethylene/maleic acid copolymer;
polyvinyl pyrrolidone; and vinyl pyrrolidone/maleic acid copolymer. Such a polymeric additive is usually present at a level from about 0.1% to about 3~ by weight.
When using a hydroperoxide, such as sodium perborate or sodium percarbonate, as the bleaching agent, it is preferred that the composition contains not more than 5%
by weight of carbonate, expressed as sodium carbonate, more preferably not more than 2.5% by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.
Detergent bleach compositions of the invention, when formulated as free-flowing particles, e.g. in powdered or granulated form, can be produced by any of the conventional techniques employed in the manufacture of detergent compositions, for instance by slurry-making, followed by spray-drying, to form a detergent base powder to which heat-sensitive ingredients including the peroxy compound bleach, conventional additives, and the complex can be added as dry substances.
It will be appreciated, however, that the detergent base powder compositions, to which the complex is added, can itself be made in a variety of other ways, such as the so-called part-part processing, non-tower route processing, dry-mixing, agglomeration, granulation, extrusion, compacting and densifying processes etc., such ways being well known to those skilled in the art and not forming an essential part of the present invention.
Z085~
- 20 - C7295 (L) Alternatively, the complex may be added separately to a wash/bleach water containing the peroxy bleaching agent.
In that case, the complex is included as a detergent additive product. Such additive products are intended to supplement or boost the performance of conventional detergent compositions and may contain any of the components of such compositions, although they will not comprise all of the components present in a fully formulated detergent composition. Additive products in accordance with this aspect of the invention will normally be added to an aqueous liquor containing a source of (alkaline) hydrogen peroxide, although in certain circumstances the additive product may be used as separate treatment in a pre-wash or in the rinse.
Additive products in accordance with this aspect of the invention may comprise the complex alone or, preferably, in combination with a carrier, such as a compatible agueous or non-aqueous liquid medium or a particulate substrate or a flexible non-particulate substrate.
Examples of compatible particulate substrates include inert materials, such as clays and other aluminosilicates, including zeolites, both of natural and synthetic origin.
Other compatible particulate carrier materials include hydratable inorganic salts, such as carbonates and sulphates.
The complex can also be formulated in detergent bleach compositions of other product forms, such as flakes, tablets, bars and liquids and particularly non-aqueous liquid detergent compositions.
2~8S7~0 - 21 - C7295 (L) Such non-aqueous li~uid detergent compositions in which the complex may be incorporated are known in the art and various formulations have been proposed, e.g. in US
Patents 2,864,770i 3,368,977; 4,772,412; GB Patents 1,205,711; 1,370,377; 2,914,536; DE-A-2,233,771 and European Patent Specification No. 0,028,849.
These are compositions which normally comprise a non-aqueous liquid medium, with or without a solid phase dispersed therein. The non-aqueous liquid medium may be a liquid surfactant, preferably a liquid nonionic surfactant; a non-polar liquid medium, e.g. liquid paraffin; a polar solvent, e.g. polyols, such as glycerol, sorbitol, ethylene glycol, optionally combined with low-molecular monohydrix alcohols, e.g. ethanol orisopropanol; or mixtures thereof.
The solid phase can be builders, alkalis, abrasives, polymers, clays, other solid ionic surfactants, bleaches, fluorescent agents and other usual solid detergent ingredients.
The invention will now be illustrated by way of the following example:
Exam~le I
The following examples were carried out in glass vessels, equipped with a temperature controlled heating spiral in quartz, magnetic stirrer, thermo-couple and pH electrode.
At 40C isothermal, experiments in demineralised water at pH 10, were carried out to determine the bleach performance of sodium perborate monohydrate (PBM) and a 21~8~720 - 22 - C7295 (L) mononuclear complex as bleach catalyst on standard tea-stained test cloths.
The bleach system in the wash solution was added at a concentration of 8.6 mmol/l PBM which corresponds to 14.3%
by weight of PB~ if a detergent bleach formulation is dosed at 6g/1.
Test cloths were immersed for 30 minutes in each of the compositions of the examples. After rinsing with tap water, the cloths were dried in a tumble drier. The reflectance (R460~) was measured on a Zeiss Elrephometer before and after treatment. The difference (oR460r) in the value gives a measure of the effectiveness of the treatment.
The results are shown in the following Table I.
21~85720 - 23 - C7295 (L) TABLE I
_ I
~R
(A) Blank (no catalyst) 5.5 ... _ I
(B) + Free Mn(NO3) 2 12.0 (5 x 10-6 mol/l _ (C) ~ [Mn2IVt~-o)3(l~4~7- 25.1 Me3TACN) 2 ] ( PF6 ) 2 (2.5 x 10-6 mol/l .
I -~ [1,4,7-Me3TACN.MnIIICl3] 26.3 (5 x 10-6 mol/l II + [1,4,7-Me3TACN.MnII(NH3)3] 2~ 25.3 (5 x 10-6 mol/l) III + [1,4,7-Me3TACN MnIII(N3)3] 22.0 (5 x 10-6 mol/l) IV + [1,4,7-Me3TACN MnIII(SCN)3] 25.0 (5 x 10-6 mol/l) V + [1,4,7-Me3TACN Mn (AcAc) 26.0 (EtO)] BPh4 (5 x 10-6 mol/l dissolved in 5 ml of ethanol and added to 995 ml of bleach solution contai.ning PBM) The level of mononuclear Mn complex corresponds to 0.03~
by weight of catalyst if a detergent composition is dosed at 6 g/l.
- 24 - C7295 (L) Experiments (A), (B), and (C) were used as controls. The above results clearly show that the mononuclear manganese coordination complexes (2), (3), (4), (5) and (7) were at least as effective as the preferred dinuclear complex catalyst [Mn2IV(~-0)3(1,4,7-Me3TACN) 2] (PF6) 2~ described in EP-A-458 397 and EP-A-458 398.
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A bleach catalyst comprising a complex of formula (I):
[L MnXp]ZYq (I) wherein:-Mn is manganese in the II, III or IV oxidation state;
X represents a coordinating species selected from Cl-, Br-, I-, F-, NCS-, I3, -OH, O22-, O2-, HOO-, H2O, SH, CN-, OCN-, S42-, NH3, NR3, RCOO-, RO-, , RSO3-and RSO4- in which R is selected from hydrogen, alkyl, aryl, both optionally substituted, and R'COO- where R' is selected from alkyl and aryl, both optionally substituted; and mixtures thereof;
p is an integer from 1 to 3;
z is the charge of the complex and is an integer which can be positive, negative or zero;
y is a counterion, the type of which is dependent upon z;
q = Z/[charge Y]; and L is a ligand which is a macrocyclic organic molecule of formula where t is an integer from 2 to 3;
s is an integer from 3 to 4;
u is zero or one; and R1, R2 and R3 are each independently selected from hydrogen, alkyl and aryl, both optionally substituted;
C7295 (L) US
with the proviso that when p is 3 and Mn is manganese in the IV oxidation state X cannot each be RO-.
[L MnXp]ZYq (I) wherein:-Mn is manganese in the II, III or IV oxidation state;
X represents a coordinating species selected from Cl-, Br-, I-, F-, NCS-, I3, -OH, O22-, O2-, HOO-, H2O, SH, CN-, OCN-, S42-, NH3, NR3, RCOO-, RO-, , RSO3-and RSO4- in which R is selected from hydrogen, alkyl, aryl, both optionally substituted, and R'COO- where R' is selected from alkyl and aryl, both optionally substituted; and mixtures thereof;
p is an integer from 1 to 3;
z is the charge of the complex and is an integer which can be positive, negative or zero;
y is a counterion, the type of which is dependent upon z;
q = Z/[charge Y]; and L is a ligand which is a macrocyclic organic molecule of formula where t is an integer from 2 to 3;
s is an integer from 3 to 4;
u is zero or one; and R1, R2 and R3 are each independently selected from hydrogen, alkyl and aryl, both optionally substituted;
C7295 (L) US
with the proviso that when p is 3 and Mn is manganese in the IV oxidation state X cannot each be RO-.
2. A bleach catalyst according to claim 1 wherein in the ligand L t is 2, s = 3, u = 1 and R1, R2 and R3 are each independently hydrogen or methyl.
3. A bleaching composition comprising:
i) from 2 to 30% by weight of a peroxy compound;
and ii) a bleach catalyst as claimed in claim 1, present in an effective amount for catalysing bleaching activity of the peroxy compound.
i) from 2 to 30% by weight of a peroxy compound;
and ii) a bleach catalyst as claimed in claim 1, present in an effective amount for catalysing bleaching activity of the peroxy compound.
4. A bleaching composition according to claim 3 comprising a bleach catalyst at a level corresponding to a manganese content of from 0.0005 to 0.5% by weight based on the composition.
5. A bleaching composition according to claim 3 further comprising a surface-active material in an amount from 0.5 to 50% by weight.
6. A bleaching composition according to claim 3 further comprising a detergency builder in an amount from 5 to 80% by weight.
7. A method of bleaching a stained substrate the method comprising contacting the stained substrate in aqueous media with a peroxy compound and a manganese complex each in an effective amount to interact with one another and provide a cleaning effect upon the substrate, the complex having the formula (I):
C7295 (L) US
[L MnXp]ZYq (I) wherein:-Mn is manganese in the II, III or IV oxidation state;
X represents a coordinating species selected from Cl-, Br-, I-, F-, NCS-, I3, -OH, O22-, O2-, HOO-, H2O, SH, CN-, OCN-, S42-, NH3, NR3, RCOO-, RO-, , RSO3-and RSO4- in which R is selected from hydrogen, alkyl, aryl, both optionally substituted, and R'COO- where R' is selected from alkyl and aryl, both optionally substituted, and mixtures thereof p is an integer from 1 to 3;
z is the charge of the complex and is an integer which can be positive, negative or zero;
y is a counterion, the type of which is dependent upon z;
q = Z/[charge Y]; and L is a ligand which is a macrocyclic organic molecule of formula where t is an integer from 2 to 3;
s is an integer from 3 to 4;
u is zero or one; and R1, R2 and R3 are each independently selected from hydrogen, alkyl and aryl, both optionally substituted; and with the proviso that when p is 3 and Mn is manganese in the IV oxidation state X cannot each be RO-.
C7295 (L) US
[L MnXp]ZYq (I) wherein:-Mn is manganese in the II, III or IV oxidation state;
X represents a coordinating species selected from Cl-, Br-, I-, F-, NCS-, I3, -OH, O22-, O2-, HOO-, H2O, SH, CN-, OCN-, S42-, NH3, NR3, RCOO-, RO-, , RSO3-and RSO4- in which R is selected from hydrogen, alkyl, aryl, both optionally substituted, and R'COO- where R' is selected from alkyl and aryl, both optionally substituted, and mixtures thereof p is an integer from 1 to 3;
z is the charge of the complex and is an integer which can be positive, negative or zero;
y is a counterion, the type of which is dependent upon z;
q = Z/[charge Y]; and L is a ligand which is a macrocyclic organic molecule of formula where t is an integer from 2 to 3;
s is an integer from 3 to 4;
u is zero or one; and R1, R2 and R3 are each independently selected from hydrogen, alkyl and aryl, both optionally substituted; and with the proviso that when p is 3 and Mn is manganese in the IV oxidation state X cannot each be RO-.
8. A bleach catalyst as claimed in claim 1 and substantially as described herein.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB919127060A GB9127060D0 (en) | 1991-12-20 | 1991-12-20 | Bleach activation |
GB9127060.3 | 1991-12-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2085720A1 true CA2085720A1 (en) | 1993-06-21 |
Family
ID=10706591
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002085720A Abandoned CA2085720A1 (en) | 1991-12-20 | 1992-12-17 | Bleach activation |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0549272A1 (en) |
JP (1) | JPH05263098A (en) |
KR (2) | KR930012103A (en) |
CN (1) | CN1074237A (en) |
AU (1) | AU3029792A (en) |
BR (1) | BR9205100A (en) |
CA (1) | CA2085720A1 (en) |
GB (2) | GB9127060D0 (en) |
MX (1) | MX9207471A (en) |
NO (1) | NO924895L (en) |
TW (1) | TW232706B (en) |
ZA (2) | ZA929850B (en) |
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1991
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1992
- 1992-03-04 GB GB929204706A patent/GB9204706D0/en active Pending
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- 1992-12-17 NO NO92924895A patent/NO924895L/en unknown
- 1992-12-18 EP EP92311580A patent/EP0549272A1/en not_active Withdrawn
- 1992-12-18 BR BR9205100A patent/BR9205100A/en not_active Application Discontinuation
- 1992-12-18 ZA ZA929850A patent/ZA929850B/en unknown
- 1992-12-18 AU AU30297/92A patent/AU3029792A/en not_active Abandoned
- 1992-12-18 ZA ZA929851A patent/ZA929851B/en unknown
- 1992-12-19 CN CN92115249A patent/CN1074237A/en active Pending
- 1992-12-19 KR KR1019920024785A patent/KR930012103A/en not_active Application Discontinuation
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GB9127060D0 (en) | 1992-02-19 |
BR9205100A (en) | 1993-06-22 |
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EP0549272A1 (en) | 1993-06-30 |
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AU3029792A (en) | 1993-06-24 |
KR960002630B1 (en) | 1996-02-24 |
NO924895L (en) | 1993-06-21 |
ZA929850B (en) | 1994-06-20 |
NO924895D0 (en) | 1992-12-17 |
JPH05263098A (en) | 1993-10-12 |
GB9204706D0 (en) | 1992-04-15 |
CN1074237A (en) | 1993-07-14 |
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