WO2010006861A1 - A process for treating stains on fabric - Google Patents
A process for treating stains on fabric Download PDFInfo
- Publication number
- WO2010006861A1 WO2010006861A1 PCT/EP2009/057342 EP2009057342W WO2010006861A1 WO 2010006861 A1 WO2010006861 A1 WO 2010006861A1 EP 2009057342 W EP2009057342 W EP 2009057342W WO 2010006861 A1 WO2010006861 A1 WO 2010006861A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- hydrogen
- transition metal
- optionally substituted
- catalyst
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000004744 fabric Substances 0.000 title claims abstract description 16
- 230000008569 process Effects 0.000 title description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000003624 transition metals Chemical class 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000004061 bleaching Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 43
- -1 alkylene ether Chemical compound 0.000 claims description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 17
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 11
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000006514 pyridin-2-ylmethyl group Chemical group [H]C1=C([H])C([H])=C([H])C(=N1)C([H])([H])* 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 6
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 125000002883 imidazolyl group Chemical group 0.000 claims description 6
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 6
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 6
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 6
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 6
- 125000000335 thiazolyl group Chemical group 0.000 claims description 6
- 125000001425 triazolyl group Chemical group 0.000 claims description 6
- 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 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 150000003973 alkyl amines Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000005021 aminoalkenyl group Chemical group 0.000 claims description 4
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 4
- 150000003857 carboxamides Chemical class 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical compound OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004450 alkenylene group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- KCNKJCHARANTIP-SNAWJCMRSA-N allyl-{4-[3-(4-bromo-phenyl)-benzofuran-6-yloxy]-but-2-enyl}-methyl-amine Chemical group C=1OC2=CC(OC/C=C/CN(CC=C)C)=CC=C2C=1C1=CC=C(Br)C=C1 KCNKJCHARANTIP-SNAWJCMRSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000006294 amino alkylene group Chemical group 0.000 claims description 2
- 125000004103 aminoalkyl group Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 150000004698 iron complex Chemical group 0.000 claims description 2
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims 1
- 239000003990 capacitor Substances 0.000 claims 1
- 238000010412 laundry washing Methods 0.000 claims 1
- 239000000872 buffer Substances 0.000 description 30
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 21
- 239000003599 detergent Substances 0.000 description 19
- 239000003352 sequestering agent Substances 0.000 description 18
- 150000002978 peroxides Chemical class 0.000 description 16
- 239000007983 Tris buffer Substances 0.000 description 14
- 238000002203 pretreatment Methods 0.000 description 14
- 239000011572 manganese Substances 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 12
- MLCJWRIUYXIWNU-OWOJBTEDSA-N (e)-ethene-1,2-diamine Chemical compound N\C=C\N MLCJWRIUYXIWNU-OWOJBTEDSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 244000025254 Cannabis sativa Species 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000007844 bleaching agent Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000004965 peroxy acids Chemical class 0.000 description 6
- 229920005646 polycarboxylate Polymers 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229960003330 pentetic acid Drugs 0.000 description 4
- PTMHPRAIXMAOOB-UHFFFAOYSA-L phosphoramidate Chemical compound NP([O-])([O-])=O PTMHPRAIXMAOOB-UHFFFAOYSA-L 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 235000021438 curry Nutrition 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-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
- VKZRWSNIWNFCIQ-UHFFFAOYSA-N 2-[2-(1,2-dicarboxyethylamino)ethylamino]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NCCNC(C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-UHFFFAOYSA-N 0.000 description 2
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 description 2
- NJMWXCOSLAUOGE-UHFFFAOYSA-N 4,11-dimethyl-1,4,8,11-tetrazabicyclo[6.6.2]hexadecane Chemical compound C1CN(C)CCCN2CCN(C)CCCN1CC2 NJMWXCOSLAUOGE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001860 citric acid derivatives Chemical class 0.000 description 2
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- 229910017052 cobalt Inorganic materials 0.000 description 2
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- XWENCHGJOCJZQO-UHFFFAOYSA-N ethane-1,1,2,2-tetracarboxylic acid Chemical class OC(=O)C(C(O)=O)C(C(O)=O)C(O)=O XWENCHGJOCJZQO-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 2
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- DXDLGEBECYSKMW-UHFFFAOYSA-N n'-[(1-methylimidazol-2-yl)methyl]ethane-1,2-diamine Chemical compound CN1C=CN=C1CNCCN DXDLGEBECYSKMW-UHFFFAOYSA-N 0.000 description 2
- NFUIKQGGOZQIFJ-UHFFFAOYSA-N n,n',n'-tris(1h-benzimidazol-2-ylmethyl)-n-methylethane-1,2-diamine Chemical compound C1=CC=C2NC(CN(CCN(CC=3NC4=CC=CC=C4N=3)CC=3NC4=CC=CC=C4N=3)C)=NC2=C1 NFUIKQGGOZQIFJ-UHFFFAOYSA-N 0.000 description 2
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 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
- 102000005575 Cellulases Human genes 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910014569 C—OOH Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- CVRXLMUYFMERMJ-UHFFFAOYSA-N N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine Chemical compound C=1C=CC=NC=1CN(CC=1N=CC=CC=1)CCN(CC=1N=CC=CC=1)CC1=CC=CC=N1 CVRXLMUYFMERMJ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical class O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 108700020962 Peroxidase Proteins 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004614 Process Aid Substances 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-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
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- ZBRIYBRFOLLBPI-UHFFFAOYSA-N acetic acid;n-(2-aminoethyl)hydroxylamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNO ZBRIYBRFOLLBPI-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
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- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- NRPLRRGSZGUINK-UHFFFAOYSA-N benzenesulfonyl 6-aminohexaneperoxoate Chemical compound C1(=CC=CC=C1)S(=O)(=O)OOC(CCCCCN)=O NRPLRRGSZGUINK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical class O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- RLVFFCFUTQINPR-UHFFFAOYSA-N manganese;1,4,7-trimethyl-1,4,7-triazonane Chemical compound [Mn].CN1CCN(C)CCN(C)CC1 RLVFFCFUTQINPR-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- RFDIFEYLTLSCIF-UHFFFAOYSA-N n'-(1h-imidazol-2-ylmethyl)ethane-1,2-diamine Chemical compound NCCNCC1=NC=CN1 RFDIFEYLTLSCIF-UHFFFAOYSA-N 0.000 description 1
- CSJKSEYRYGOSHO-UHFFFAOYSA-N n'-[2-[bis[(5-methyl-1h-imidazol-4-yl)methyl]amino]ethyl]-n,n-diethyl-n'-[(5-methyl-1h-imidazol-4-yl)methyl]ethane-1,2-diamine Chemical compound N1=CNC(C)=C1CN(CCN(CC)CC)CCN(CC1=C(NC=N1)C)CC=1N=CNC=1C CSJKSEYRYGOSHO-UHFFFAOYSA-N 0.000 description 1
- CLAWTVFJBDKCHZ-UHFFFAOYSA-N n,n',n'-tris(1h-imidazol-2-ylmethyl)-n-methylethane-1,2-diamine Chemical compound N=1C=CNC=1CN(C)CCN(CC=1NC=CN=1)CC1=NC=CN1 CLAWTVFJBDKCHZ-UHFFFAOYSA-N 0.000 description 1
- IWLGIQSOLLGCTK-UHFFFAOYSA-N n,n'-bis(1h-imidazol-2-ylmethyl)-n,n'-dimethylethane-1,2-diamine Chemical compound N=1C=CNC=1CN(C)CCN(C)CC1=NC=CN1 IWLGIQSOLLGCTK-UHFFFAOYSA-N 0.000 description 1
- HSYNBGMTLRKRNO-UHFFFAOYSA-N n-ethyl-n,n',n'-tris(1h-imidazol-2-ylmethyl)ethane-1,2-diamine Chemical compound N=1C=CNC=1CN(CC)CCN(CC=1NC=CN=1)CC1=NC=CN1 HSYNBGMTLRKRNO-UHFFFAOYSA-N 0.000 description 1
- BLPXLFREPYJZJC-UHFFFAOYSA-N n-hexyl-n,n',n'-tris(1h-imidazol-2-ylmethyl)ethane-1,2-diamine Chemical compound N=1C=CNC=1CN(CCCCCC)CCN(CC=1NC=CN=1)CC1=NC=CN1 BLPXLFREPYJZJC-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 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
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 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
- VVTMNCICAIKIRN-UHFFFAOYSA-N phenyl benzoate;sodium Chemical compound [Na].C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 VVTMNCICAIKIRN-UHFFFAOYSA-N 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
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- ODBPOHVSVJZQRX-UHFFFAOYSA-M sodium;[2-[2-[bis(phosphonomethyl)amino]ethyl-(phosphonomethyl)amino]ethyl-(phosphonomethyl)amino]methyl-hydroxyphosphinate Chemical compound [Na+].OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)([O-])=O ODBPOHVSVJZQRX-UHFFFAOYSA-M 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GYBINGQBXROMRS-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)butanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(C([O-])=O)NC(C([O-])=O)CC([O-])=O GYBINGQBXROMRS-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 230000037331 wrinkle reduction Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—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
- C11D3/3947—Liquid compositions
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/15—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using organic agents
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/70—Multi-step processes
- D06L4/75—Multi-step processes combined with cleaning or washing
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/40—Specific cleaning or washing processes
- C11D2111/44—Multi-step processes
Definitions
- the present invention relates to a process for treating stains on fabric.
- EP 0458397 discloses the use of manganese 1, 4, 7-Trimethyl- 1 , 4 , 7-triazacyclononane (Me 3 -TACN) complexes as bleaching and oxidation catalysts and use for paper/pulp bleaching and textile bleaching processes.
- 1, 4, 7-Trimethyl-l, 4, 7- triazacyclononane (Me 3 -TACN) has been used in dishwashing for automatic dishwashers, SUNTM, and has also been used in a laundry detergent composition, OMO PowerTM.
- Patt et al discloses the use of PF 6 ⁇ salts of 1, 2, -bis- (4, 7, -dimethyl- 1, 4, 7, -triazacyclonon-1-yl) -ethane and Me 3 -TACN (Me4-DTNE) .
- United States Application 2002/010120 discloses the bleaching of substrates in an aqueous medium, the aqueous medium comprising a transition metal catalyst and hydrogen peroxide .
- WO 2006/125517 discloses a method of catalytically treating a cellulose or starch substrate with a Mn(III) or Mn(IV) preformed transition metal catalyst salt and hydrogen peroxide in an aqueous solution.
- the preformed transition metal catalyst salt is described as having a non- coordinating counter ion and having a water solubility of at least 30 g/1 at 20 0 C.
- Exemplified ligands of the catalysts described in WO 2006/125517 are 1, 4, 7-Trimethyl-l, 4, 7- triazacyclononane (M ⁇ 3 -TACN) and 1, 2, -bis- (4, 7, -dimethyl- 1,4,7, -triazacyclonon-1-yl) -ethane (Me 4 -DTNE) .
- An objective of the invention is to provide an improved stain pretreatment process which uses less chemicals, water etc. without sacrificing cleaning efficiency, especially for white fabrics and light coloured fabrics, relied upon by the modern consumer.
- the present invention provides a method of bleaching a fabric comprising the following steps: (i) a pretreatment step in which the fabric is treated with an the aqueous solution having a initial pH from 10.5 to 11.5 and comprising 0.5-50 mM (millimol/litre) hydrogen peroxide; followed by
- transition metal catalyst present in a concentration from 0.1 to 100 micromolar of an aqueous solution wherein the initial pH of this second step is from 7-10.
- the initial pH of the pretreatment step is 10.7-11.3 and more preferably 8-9.7.
- the initial pH of the second step is 10.9-11.1 and more preferably 8.5-9.5.
- the arrangement of the invention affords judicious use of a bleaching catalyst for effective cleaning of stains without the need for buffers, builders, chorine-based bleaching agents.
- the method is particularly applicable to laundering machines that have capabilities to control the pH during the washing processes.
- the method is most particularly applicable to the bleaching of stains found on white garments or light coloured garments.
- the preformed transition metal catalyst may be Fe (II) or Fe (III) or Mn (II) or Mn (III) or Mn(IV) . Preferred are Mn (III) or Mn (IV) .
- the preformed transition metal catalyst salt may be a mononuclear Mn complex, or a dinuclear Mn(III) or Mn(IV) complex with at least one O 2 ⁇ bridge.
- the ligand of the catalyst may be a tridentate, tetradentate, pentadentate or hexadentate nitrogen and oxygen donor.
- the manganese transition metal catalyst used may be non- deliquescent by using counter ions such as hexafluorophosphate, acetate, chloride, sulphate, nitrate, being most preferred.
- the preformed transition metal catalyst may be a mononuclear or dinuclear complex of a Mn H-V transition metal catalyst, the ligand of the transition metal catalyst of formula (I) :
- R is selected from: hydrogen, Cl-C6-alkyl, C2OH, ClCOOH, benzyl, and pyridin-2-ylmethyl or one of R is linked to the N of another Q via an ethylene bridge;
- Rl, R2, R3, and R4 are selected from: H, Cl-C4-alkyl, and Cl-C4-alkylhydroxy.
- R may be selected from: hydrogen, CH3, C2H5, CH2CH2OH, benzyl and CH2COOH.
- R, Rl, R2, R3, and R4 may be selected from: H and Me.
- the catalyst may be derived from a ligand selected from the group consisting 1, 4, 7-Trimethyl-l, 4, 7- triazacyclononane (Me3-TACN) , 1, 2, -bis- (4, 7, -dimethyl- 1, 4, 7, -triazacyclonon-1-yl) -ethane (Me4-DTNE) , 5,12- dimethyl-1, 5, 8, 12-tetraazabicyclo [6.6.2] hexadecane, 5, 12-dibenzyl-l, 5, 8, 12-tetraaza- bicyclo [ 6.6.2 ] hexadecane, .
- a ligand selected from the group consisting 1, 4, 7-Trimethyl-l, 4, 7- triazacyclononane (Me3-TACN) , 1, 2, -bis- (4, 7, -dimethyl- 1, 4, 7, -triazacyclonon-1-yl) -ethane (Me4-DTNE) , 5,12- dimethyl-1, 5, 8,
- the preformed catalyst may be an iron complex of a tetradentate, pentadentate or hexadentate nitrogen donor ligand, wherein the ligand is selected from the group consisting of:
- each R is selected from: hydrogen, F, Cl, Br, hydroxyl, Cl-C4-alkylO-, -NH-CO-H, -NH-CO-Cl-C4-alkyl,
- Rl and R2 are selected from Cl-C24-alkyl, C6-C10- aryl, and, a group containing a heteroatom capable of coordinating to a transition metal;
- R3 and R4 are selected from hydrogen, C1-C8 alkyl, Cl-
- R5 is selected from: hydrogen, Cl-C4-alkyl, n is from 0 to 4, and mixtures thereof;
- each R 1 R 2 represents -R 4 -R 5 ,
- R represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or -R 4 -R 5 , each R 4 represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and each R 5 represents an optionally N-substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl;
- each R20 is selected from: an alkyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N + (R21) 3 , wherein R21 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether, alkenyl ether, and -CY 2 -
- R22 in which Y is selected from H, CH3, C2H5, C3H7 and R22 is selected from an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and wherein at least one of R20 is a -CY 2 -R22; R17R17N-X-NR17R17 (V) , wherein :
- X is selected from -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 C(OH)HCH 2 -; and, R17 represents a group selected from: R17 and alkyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N + (R19)3 , wherein R19 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether, alkenyl ether, and -CY 2 - R18, in which Y is selected from H, CH3, C2H5, C3H7 and R18 is selected
- the heteroatom capable of coordinating to a transition metal may be pyridin-2-yl optionally substituted by -C0-C4-alkyl .
- the heteroatom donor group may be unsubstituted pyridinyl.
- R3 may be equal to R4 and be selected from -C(O)-O-CH3, -C (0) -O-CH2CH3, -C (0) -O-CH2C6H5 and CH2OH.
- At least one Rl or R2 is pyridin-2- ylmethyl and the other may be selected from -CH3, -
- the heteroatom capable of coordinating to a transition metal may be amino optionally substituted by -C0-C4-alkyl .
- the amino group may be substituted by two Cl-C4-alkyl groups.
- At least one of Rl or R2 may be dimethylamino and the other is selected from -CH3, -C2H5, -C3H7, -C4H9, C6H13, C8H17, C12H25, and C18H37.
- the heteroatom may be di C1-C4- alkyl amino.
- the ligand of formula III may be selected from 1,4,7, 10-tetrakis (pyridine-2ylmethyl) -1,4,7, 10- tetraazacyclododecane, N,N-bis (pyridin-2-yl-methyl) - bis (pyridin-2-yl) methylamine, N, N-bis (pyridin-2-yl- methyl-1, 1-bis (pyridin-2-yl) - 1- aminoethane, N, N, N' , N' -tetra (pyridin-2-yl-methyl) ethylenediamine, N- methyl-tris ( pyridin-2-ylmethyl) ethylene-1, 2-diamine; N-butyl-N, N ' , N ' -tris (pyridin-2-ylmethyl) ethylene-1 , 2- diamine; N-octyl-N, N ' , N ' -tris (pyridin-2- ylmethyl) ethylene-1, 2-
- Suitable catalysts include, mononuclear manganese complexes with optionally substituted terpyridine complexes, for examples as disclosed in US20040142843, a mononuclear manganese (III) complex with tris (2- (salicylideneamino) ethyl) amine .
- the aqueous solution is preferably not buffered.
- the aqueous solution may be substantially free from an inorganic buffer, e.g., carbonate, phosphate, and borate.
- the aqueous solution is not buffered other than by the organic sequestrant and hydrogen peroxide.
- the organic sequestrant and hydrogen peroxide may be considered to have some buffering capacity but this is not to be considered as buffering within the context of unbuffered embodiments of the present invention.
- a buffer is present, it is most preferably a carbonate buffer .
- the aqueous solution comprises from 0.01 to 10 g/1 of an organic sequestrant, the sequestrent selected from: an aminophosphonate sequestrant and a carboxylate sequestrant .
- the sequestrant is either an aminophosphonate sequestrant or a carboxylate sequestrant.
- the sequestrant is either an aminophosphonate sequestrant or an aminocarboxylate sequestrant.
- aminophosphonate sequestrants nitrilo trimethylene phosphonates, ethylene- diamine-N, N, N' , N' -tetra (methylene phosphonates) (Dequest 204) and diethylene-triamine-N, N, N' , N", N"- penta (methylenephosphonates) (Dequest 206), most preferably diethylene-triamine-N, N, N' , N",N"- penta (methylenephosphonates) .
- nitrilo trimethylene phosphonates ethylene- diamine-N, N, N' , N' -tetra (methylene phosphonates)
- Dequest 206 diethylene-triamine-N, N, N' , N", N"- penta (methylenephosphonates)
- aminocarboxylate sequestrants ethylenediaminetetraacetic acid (EDTA), N- hydroxyethylenediaminetetraacetic acid (HEDTA) , nitrilotriacetic acid (NTA) , N-hydroxyethylaminodiacetic acid, N-hydroxyethylaminodiacetic acid, glutamic diacetic acid, sodium iminodisuccinate, diethylenetriaminepentaacetic acid (DTPA), ethylenediamine-N, N' -disuccinic acid (EDDS), methylglycinediacetic acid (MGDA), and alanine-N, N-diacetic acid.
- a most preferred aminocarboxylate sequestrant is diethylenetriaminepentaacetic acid (DTPA) .
- the sequestrants may also be in the form of their salts, e.g., alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts salts.
- the sequestrant is in the free acid form, sodium or magnesium salt .
- carboxylate sequestrants are polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates .
- Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates .
- Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No.
- Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1, 439, 000.
- Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1, 1, 2, 2-ethane tetracarboxylates, 1, 1, 3, 3-propane tetracarboxylates and 1, 1, 2, 3-propane tetracarboxylates.
- Suitable water soluble organic salts are the homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
- Polymers of the latter type are disclosed in GB-A-I, 596, 756.
- Examples of such salts are polyacrylates of M. Wt. 2000 to 5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
- copolymeric polycarboxylate polymers which, formally at least, are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C1-C4 alkyl acrylic acid as second monomer.
- unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as first monomer
- an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C1-C4 alkyl acrylic acid as second monomer.
- Such polymers are available from BASF under the trade name Sokalan® CP5 (neutralised form), Sokalan® CP7, and Sokalan® CP45 (acidic form) .
- Most preferred sequestrants are Dequest 2066 or Dequest 2047.
- a bleach precursor may be used: Peracid may be added to a detergent product, but it is preferably formed in-situ from peroxide and a bleach precursor. A peracid may be formed by perhydrolysis of an acidic bleach precursor by the following reaction :
- the detergent composition used in the method of the present invention may include one or more bleach precursors.
- precursors selected form the group consisting of: sodium nonanoyloxybenzene sulphonate (SNOBS); nonanoyloxy aminocaproyloxy benzene sulphonate (NACOBS) ; sodium-4-benzoyloxy benzene sulphonate (SBOBS); N, N, N 1 N'- tetraacetyl ethylene diamine (TAED) ; sodium-l-methyl-2- benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-benzoloxy benzoate; 2- (N, N, N-trimethyl ammonium) ethyl sodium-4- sulphophenyl carbonate chloride (SPCC); trimethyl ammonium toluyloxy-benzene sulphonate; sodium 3, 5, 5-trimethyl hexanoyl-oxybenzene sulphonate (STHOBS) ; and substituted cationic nitriles; and mixtures thereof.
- SNOBS sodium
- peracid bleach precursors are known and amply described in literature, such as in the GB-A-O, 836, 988 ; GB- A-O, 864, 798; GB-A-O, 907, 356; GB-A-I, 003, 310 and GB-A- 1,519,351; DE-A-3, 337, 921 ; EP-A-O, 185,522; EP-A-O , 174 , 132 ; EP-A-O, 120, 591; and US-A-I , 246, 339; US-A-3,332, 882; US-A- 4,128,494; US-A-4, 412, 934 and US-A-4, 675, 393; and cationic i.e. quaternary ammonium substituted peroxyacid precursors are disclosed in US-A-4, 751,015 and US-A-4, 397, 757, in EP- A-O, 284, 292 and EP-A-O,
- the peracid forming reaction of peroxide and bleach precursor from the detergent may be obtained in the washing liquor inside the washing machine drum, or in an off-line mixing vessel.
- An advantage of the latter is that the peracid may be formed in a concentrated form at the desired pH and may be diluted with acidic water into the washing machine drum, thereby reducing the pH for the washing process resulting in better bleaching activity.
- the low environmental impact detergent product which can be used with the present invention preferably comprises bleach precursor in a peroxide: precursor ratio of between 1:2 and 25:1, more preferably between 2:1 and 10:1 on a molar basis.
- a peroxide generating cell comprising an electrochemical cell for the production of peroxide from tap water and air, and being suitable for use in said machine when the machine is in operation; whereby no added chemicals are needed to product hydrogen peroxide when the device is in operation.
- the hydrogen peroxide is preferably only added in the first step but may be present in the second step provided the initial pH levels are as defined above.
- the peroxide generating cell is preferably an electrochemical cell comprising one or more cathode and anode electrodes that are chargeable by a DC potential.
- the electrodes may for instance be in the form of plates or rods, preferably plates.
- the cathode is preferably a gas diffusion electrode.
- the cathode preferably comprises a catalyst bound to the cathode surface.
- the cathode may comprise conductive materials such as carbon (e.g. graphite, carbon nano-tubes and other forms of carbon) , metals or conductive polymers or combinations thereof.
- Preferred metal catalysts are transition metals, transition metal oxides or transition metal macrocycles. Preferred transition metals include gold, mercury and oxide covered metals such as nickel and cobalt.
- Preferred metal oxides include nickel oxide, cobalt oxide and spinels.
- Preferred transition metal macrocycles include: CoTsPc (phthalocyanine tetra- sulfonate) cobalt) and CoTMPP (tetramethoxyphenyl porphyrine) .
- the Anode is preferably a dimensionally stable anode, which is preferably constructed from conductive materials such as metals, carbon or conductive polymers or combinations thereof.
- transition metals are not preferred, in particular platinum, platinum alloys, platinum family metals, palladium, and silver. Also not preferred are perovskites and pyrochlores, such as lead ruthenate transition metal oxides, and macrocyclic FeTsPc (iron tetrasulfonato phthalocyanine) .
- the dimensions and specification of the peroxide generating cell are dependent on the intended use. If the peroxide is stored in a buffer tank inside the washing machine, a slow system producing peroxide e.g. overnight is suitable. However, when the peroxide is to be produced during the washing process, a fast producing system is required.
- the peroxide generating cell of the present invention preferably comprises a total cathode area of at least 10 cm 2 , more preferably at least 50 cm2, even more preferably at least 100 cm2 and at most 1000 cm 2 , more preferably at most 500 cm 2 , even more preferably at most 400 cm 2 , still more preferably at most 300 cm 2 ; the area being dependent on the demanded production rate.
- the surface area is preferably divided over between 1 and 25, more preferably between 1 and 10 cathode electrodes.
- the peroxide production rate is typically between 0.1 and 2000 mmol/h. The actual rate is dependent on amongst others the surface area of the cathode and the type of operation. In a system with a peroxide storage tank, a slow production rate is preferred, typically from 0.1 to 200 mmol/hr, while in a system where the peroxide is produced immediately during water intake, the production rate is preferably between 200 and 2000 mmol/hr.
- the efficiency of this type of peroxide generating cell is preferably from 50 to 100% at or just after the start of the peroxide production, typically from 60 to 95%.
- the total surface area of the anodes is between 10 and 100% of the total surface area of the cathodes.
- the electrodes are optionally separated by a semi-permeable membrane .
- the machine preferably also comprises a pH modifying device comprising an electrochemical cell comprising one or more cathode and anode electrodes for the production of acidic and alkaline water; whereby no added chemicals are needed to modify pH when the device is in operation.
- a pH modifying device comprising an electrochemical cell comprising one or more cathode and anode electrodes for the production of acidic and alkaline water; whereby no added chemicals are needed to modify pH when the device is in operation.
- the formulation used may contain a surfactant or a surfactant mixture.
- the use of surfactants helps to remove the waxy materials encountered in cotton.
- the surfactant may comprise one or more anionic, non-ionic, cationic, amphoteric, and zwitterionic surfactant, and - I i
- a surfactant is present in the range from 0.1 to 20 g/L, preferably 0.5 to 10 g/1. It is preferred that the surfactant is a non-ionic surfactant and most preferably biodegradable.
- the detergent may contain one or more optional cleaning agents, which include any agent suitable for enhancing the cleaning, appearance, condition and/or garment care.
- the optional cleaning agent may be present in the compositions of the invention in an amount of 0 to 20 wt.%, preferably 0.001 wt.% to 10 wt.%, more preferably 0.01 wt.% to 5 wt.% by weight of the total detergent composition.
- Some suitable optional cleaning agents include, but are not limited to antibacterial agents, colorants, perfumes, pro- perfumes, finishing aids, lime soap dispersants, composition malodour control agents, odour neutralisers, polymeric dye transfer inhibiting agents, crystal growth inhibitors, anti- tarnishing agents, anti-microbial agents, anti-oxidants, anti-redeposition agents, soil release polymers, thickeners, abrasives, corrosion inhibitors, suds stabilising polymers, process aids, fabric softening agents, optical brighteners, hydrotropes, suds or foam suppressors, suds or foam boosters, anti-static agents, dye fixatives, dye abrasion inhibitors, wrinkle reduction agents, wrinkle resistance agents, soil repellency agents, sunscreen agents, anti-fade agents, and mixtures thereof.
- the detergent may be dosed in any suitable format such as a liquid, gel, paste, tablet or sachet. In some cases granular formulations may be used although this is not preferred.
- the detergent is a non-aqueous product.
- Non-aqueous for the purpose of the present invention is meant to describe a product comprising less than 10 %, preferably less than 5 %, more preferably less than 3 % by weight of free water.
- the non-aqueous product may be a liquid, gel or paste or encapsulated in a sachet.
- the detergent may be dosed from a single container.
- the ingredients making up the detergent may be dosed from separate containers as described in EP-A-0419036.
- at least one ingredient from the detergent is dosed automatically.
- One advantage of a detergent may be that the reduced number and/or amount of ingredients enables a much smaller volume of detergent product. In practice this would mean that the consumer does not need to refill the containers as often or that the containers may be smaller, therefore making an automatic dosage system more feasible when using the device of the invention.
- the bleach precursor or activator catalyst
- the BC-I stain was obtained by CFT, Vlaardingen, Netherlands.
- the grass stain is prepared by rubbing fresh grass into cotton, after which it is brushed to get an evenly distributed stain.
- the Bandy Black Clay stain is prepared by rubbing soil mud into cotton, after which it is brushed to get an evenly distributed stain.
- Demineralised aqueous solution of 10 i ⁇ mol/1 hydrogen peroxide was made that contained either no buffer, carbonate buffer (0.3 g/1 Na 2 CO 3 ), Na-LAS/Lutensol A03 (each 0.4 g/1) + 0.3 g/1 Na 2 CO 3 , Lutensol A07 (0.8 g/1) + 0.3 g/1 Na 2 CO 3 .
- the appropriate amount of NaOH solution was added to either yield pH 10.5 or pH 11.0.
- the stains were first pre-treated at high pH using the above pre-treatment formulations, without catalyst for 20 minutes at 4O 0 C under mild agitation.
- the cloth/liquor (w/w) ratio was approximately 40.
- the pre-treatment step is done in the same composition (buffer, surfactant) as the 2 nd stage process with catalyst) .
- the pH in the 2 nd stage different (lower) .
- the cloths were then rinsed twice with phosphate buffer, dried and then measured for change in colour was measured with a Linotype-Hell scanner (ex Linotype) .
- the measured colour difference ( ⁇ E) between the washed cloth and the unwashed cloth is defined as follows:
- ⁇ E [ ( ⁇ L) 2 + ( ⁇ a) 2 + ( ⁇ b) 2 ] 1/2
- ⁇ L is a measure for the difference in darkness between the washed and unwashed test cloth
- ⁇ a and ⁇ b are measures for the difference in redness and yellowness respectively between both cloths.
- CIE Commission International de 1 'Eclairage
- BC-I cety-based monitor
- MeN4Py N,N-bis (pyridin-2-yl-methyl-l, 1-bis (pyridin-2-yl) - 1- aminoethane , hereafter referred to as MeN4Py, and the corresponding iron (II) complex, [Fe (MeN4py) Cl] Cl, were prepared as described in EP0909809. Note that this catalyst has been used in all experiments at 10 ⁇ M level
- the bleaching step (without pre-treatment) was done in the presence of 5 ⁇ M of [Mn 2 ( ⁇ -O) 3 (Me 3 tacn) 2 ] (PF 6 ) 2 at different pH's at 40 0 C for 30 min on BC-I and the SRI values, as defined above, were as follows:
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Abstract
A method of bleaching a fabric comprising the following steps : (i) a pretreatment step in which the fabric is treated with an the aqueous solution having a initial pH from 9 to 11.5 and comprising 0.5-50 mM hydrogen peroxide; followed by (ii) treatment with a preformed transition metal catalyst, the transition metal catalyst present in a concentration from 0.1 to 100 micromolar of an aqueous solution wherein the initial pH of this second step is from 7-11.
Description
A PROCESS FOR TREATING STAINS ON FABRIC
The present invention relates to a process for treating stains on fabric.
EP 0458397 discloses the use of manganese 1, 4, 7-Trimethyl- 1 , 4 , 7-triazacyclononane (Me3-TACN) complexes as bleaching and oxidation catalysts and use for paper/pulp bleaching and textile bleaching processes. 1, 4, 7-Trimethyl-l, 4, 7- triazacyclononane (Me3-TACN) has been used in dishwashing for automatic dishwashers, SUN™, and has also been used in a laundry detergent composition, OMO Power™.
United States Application 2001/0025695A1, Patt et al, discloses the use of PF6 ~ salts of 1, 2, -bis- (4, 7, -dimethyl- 1, 4, 7, -triazacyclonon-1-yl) -ethane and Me3-TACN (Me4-DTNE) .
United States Application 2002/010120 discloses the bleaching of substrates in an aqueous medium, the aqueous medium comprising a transition metal catalyst and hydrogen peroxide .
WO 2006/125517 discloses a method of catalytically treating a cellulose or starch substrate with a Mn(III) or Mn(IV) preformed transition metal catalyst salt and hydrogen peroxide in an aqueous solution. The preformed transition metal catalyst salt is described as having a non- coordinating counter ion and having a water solubility of at least 30 g/1 at 20 0C. Exemplified ligands of the catalysts described in WO 2006/125517 are 1, 4, 7-Trimethyl-l, 4, 7-
triazacyclononane (Mθ3-TACN) and 1, 2, -bis- (4, 7, -dimethyl- 1,4,7, -triazacyclonon-1-yl) -ethane (Me4-DTNE) .
An objective of the invention is to provide an improved stain pretreatment process which uses less chemicals, water etc. without sacrificing cleaning efficiency, especially for white fabrics and light coloured fabrics, relied upon by the modern consumer.
In one aspect the present invention provides a method of bleaching a fabric comprising the following steps: (i) a pretreatment step in which the fabric is treated with an the aqueous solution having a initial pH from 10.5 to 11.5 and comprising 0.5-50 mM (millimol/litre) hydrogen peroxide; followed by
(ii) treatment with a preformed transition metal catalyst, the transition metal catalyst present in a concentration from 0.1 to 100 micromolar of an aqueous solution wherein the initial pH of this second step is from 7-10.
Preferably the initial pH of the pretreatment step is 10.7-11.3 and more preferably 8-9.7.
Preferably the initial pH of the second step is 10.9-11.1 and more preferably 8.5-9.5.
The arrangement of the invention affords judicious use of a bleaching catalyst for effective cleaning of stains without the need for buffers, builders, chorine-based bleaching agents.
The method is particularly applicable to laundering machines that have capabilities to control the pH during the washing processes. The method is most particularly applicable to the bleaching of stains found on white garments or light coloured garments.
The preformed transition metal catalyst may be Fe (II) or Fe (III) or Mn (II) or Mn (III) or Mn(IV) . Preferred are Mn (III) or Mn (IV) .
The preformed transition metal catalyst salt may be a mononuclear Mn complex, or a dinuclear Mn(III) or Mn(IV) complex with at least one O2~ bridge.
The ligand of the catalyst may be a tridentate, tetradentate, pentadentate or hexadentate nitrogen and oxygen donor.
The manganese transition metal catalyst used may be non- deliquescent by using counter ions such as hexafluorophosphate, acetate, chloride, sulphate, nitrate, being most preferred.
The preformed transition metal catalyst may be a mononuclear or dinuclear complex of a Mn H-V transition metal catalyst, the ligand of the transition metal catalyst of formula (I) :
R N [ CR1 R9CR^R, wherein : Q = λ 2 3 4 ; p i s 3 or 4 ;
R is selected from: hydrogen, Cl-C6-alkyl, C2OH, ClCOOH, benzyl, and pyridin-2-ylmethyl or one of R is linked to the N of another Q via an ethylene bridge; Rl, R2, R3, and R4 are selected from: H, Cl-C4-alkyl, and Cl-C4-alkylhydroxy.
R may be selected from: hydrogen, CH3, C2H5, CH2CH2OH, benzyl and CH2COOH. R, Rl, R2, R3, and R4 may be selected from: H and Me.
The catalyst may be derived from a ligand selected from the group consisting 1, 4, 7-Trimethyl-l, 4, 7- triazacyclononane (Me3-TACN) , 1, 2, -bis- (4, 7, -dimethyl- 1, 4, 7, -triazacyclonon-1-yl) -ethane (Me4-DTNE) , 5,12- dimethyl-1, 5, 8, 12-tetraazabicyclo [6.6.2] hexadecane, 5, 12-dibenzyl-l, 5, 8, 12-tetraaza- bicyclo [ 6.6.2 ] hexadecane, .
The preformed catalyst may be an iron complex of a tetradentate, pentadentate or hexadentate nitrogen donor ligand, wherein the ligand is selected from the group consisting of:
wherein each R is selected from: hydrogen, F, Cl, Br, hydroxyl, Cl-C4-alkylO-, -NH-CO-H, -NH-CO-Cl-C4-alkyl,
-NH2, -NH-Cl-C4-alkyl, and Cl-C4-alkyl;
Rl and R2 are selected from Cl-C24-alkyl, C6-C10- aryl, and, a group containing a heteroatom capable of coordinating to a transition metal;
R3 and R4 are selected from hydrogen, C1-C8 alkyl, Cl-
C8-alkyl-O-Cl-C8-alkyl, Cl-C8-alkyl-O-C6-C10-aryl, C6-
C10-aryl, Cl-C8-hydroxyalkyl, and - (CH2) nC (O) OR5 wherein R5 is selected from: hydrogen, Cl-C4-alkyl, n is from 0 to 4, and mixtures thereof; and,
X is selected from C=O, -[C(R6)2]y~ wherein Y is from 0 to 3 each R6 is selected from hydrogen, hydroxyl, Cl-
C4-alkoxy and Cl-C4-alkyl;
R represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or -R4-R5,
each R4 represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and each R5 represents an optionally N-substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl;
R20 (IV) wherein each R20 is selected from: an alkyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N+(R21)3 , wherein R21 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether, alkenyl ether, and -CY2-
R22, in which Y is selected from H, CH3, C2H5, C3H7 and R22 is selected from an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and wherein at least one of R20 is a -CY2-R22;
R17R17N-X-NR17R17 (V) , wherein :
X is selected from -CH2CH2-, -CH2CH2CH2-, -CH2C(OH)HCH2-; and, R17 represents a group selected from: R17 and alkyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N+(R19)3 , wherein R19 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether, alkenyl ether, and -CY2- R18, in which Y is selected from H, CH3, C2H5, C3H7 and R18 is selected from an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and wherein at least two of R17 are -CY2-R18.
In Formula (II), the heteroatom capable of coordinating to a transition metal may be pyridin-2-yl optionally substituted by -C0-C4-alkyl . The heteroatom donor group may be unsubstituted pyridinyl. X may be C=O or C (OH) 2.
R3 may be equal to R4 and be selected from -C(O)-O-CH3, -C (0) -O-CH2CH3, -C (0) -O-CH2C6H5 and CH2OH.
At least one Rl or R2 (of formula II) is pyridin-2- ylmethyl and the other may be selected from -CH3, -
C2H5, -C3H7, -C4H9, C6H13, C8H17, C12H25, and C18H37.
In formula (II) the heteroatom capable of coordinating to a transition metal may be amino optionally substituted by -C0-C4-alkyl . The amino group may be substituted by two Cl-C4-alkyl groups. X may be C=O or C (OH) 2 and R3 = R4 may be selected from -C(0)-0-CH3, - C (0) -O-CH2CH3, -C (0) -O-CH2C6H5 and CH20H. At least one of Rl or R2 may be dimethylamino and the other is selected from -CH3, -C2H5, -C3H7, -C4H9, C6H13, C8H17, C12H25, and C18H37. The heteroatom may be di C1-C4- alkyl amino.
The ligand of formula III may be selected from 1,4,7, 10-tetrakis (pyridine-2ylmethyl) -1,4,7, 10- tetraazacyclododecane, N,N-bis (pyridin-2-yl-methyl) - bis (pyridin-2-yl) methylamine, N, N-bis (pyridin-2-yl- methyl-1, 1-bis (pyridin-2-yl) - 1- aminoethane, N, N, N' , N' -tetra (pyridin-2-yl-methyl) ethylenediamine, N- methyl-tris ( pyridin-2-ylmethyl) ethylene-1, 2-diamine; N-butyl-N, N ' , N ' -tris (pyridin-2-ylmethyl) ethylene-1 , 2- diamine; N-octyl-N, N ' , N ' -tris (pyridin-2- ylmethyl) ethylene-1, 2-diamine; N-dodecyl-N, N ' , N ' - tris (pyridin-2-ylmethyl) ethylene-1, 2-diamine; N- octadecyl-N, N ' , N ' -tris (pyridin-2-ylmethyl) ethylene-1, 2- diamine; N-methyl-N, N ' , N ' -tris (3-methyl-pyridin-2- ylmethyl) ethylene-1, 2-diamine; N-ethyl-N, N ' , N ' -tris (3- methyl-pyridin-2-ylmethyl) ethylene-1, 2-diamine; N- methyl-N, N ' , N ' -tris (5-methyl-pyridin-2- ylmethyl) ethylene-1 , 2 -diamine; N-ethyl-N, N',N'-tris(5- methyl-pyridin-2-ylmethyl) ethylene-1, 2-diamine; N- benzyl- N, N ' , N ' -tris (3-methyl-pyridin-2- ylmethyl) ethylene-1, 2-diamine; N-benzyl-N, N',N'-tris(5-
methyl-pyridin-2-ylmethyl) ethylene-1, 2-diamine; N- methyl-N,N' ,N' -tris (imidazol-2ylmethyl) - ethylenediamine; N-ethyl-N,N' ,N' -tris (imidazol- 2ylmethyl) -ethylenediamine; N, N' -dimethyl-N, N' - bis (imidazol-2-ylmethyl) -ethylenediamine; N-(l-propan- 2-ol) -N, N' ,N' -tris (imidazol-2ylmethyl) -ethylenediamine; N- (l-propan-2-ol) -N, N' ,N' -tris (1-methyl-imidazol- 2ylmethyl) -ethylenediamine; N, N-diethyl-N' , N",N"- tris (5-methyl-imidazol-4ylmethyl) -diethylenetriamine; N- (3-propan-l-ol) -N, N' ,N' -tris (l-methyl-imidazol-2- ylmethyl) -ethylenediamine; N-hexyl-N,N' , N' - tris (imidazol-2ylmethyl) -ethylenediamine; N-methyl- N, N' ,N' -tris (benzimidazol-2ylmethyl) -ethylenediamine; and, N- (3-propan-l-ol) methyl-N, N' , N' -tris (benzimidazol- 2ylmethyl) -ethylenediamine; 1, 4-bis (quinolin-2- ylmethyl) -7-octyl-l, 4, 7-triazacyclononane; 1, 4- bis (quinolin-2-ylmethyl) -7-ethyl-l, 4, 7- triazacyclononane; 1, 4-bis (quinolin-2-ylmethyl) -7- methyl-1, 4, 7-triazacyclononane; 1, 4-bis (pyridyl-2- methyl) -7-octyl-l, 4, 7-triazacyclononane; 1,4- bis (pyridyl-2-methyl) -7-ethyl-l, 4, 7-triazacyclononane; 1, 4-bis (pyridyl-2-methyl) -7-methyl-l, 4, 7- triazacyclononane; 1, 4-bis (pyrazol-1-ylmethyl) -7-octyl- 1,4, 7-triazacyclononane; 1, 4-bis (pyrazol-1-ylmethyl) -7- ethyl-1, 4, 7-triazacyclononane; 1, 4-bis (pyrazol-1- ylmethyl) -7-methyl-l, 4, 7-triazacyclononane, 3, 5- dimethylpyrazol-1-ylmethyl) -7-octyl-l, 4, 7- triazacyclononane; 3, 5-dimethylpyrazol-l-ylmethyl) -7- ethyl-1, 4, 7-triazacyclononane; 3, 5-dimethylpyrazol-l- ylmethyl) -7-methyl-l , 4 , 7-triazacyclononane; 1, 4-bis (1- methylimidazol-2-ylmethyl) -7-octyl-l, 4, 7-
triazacyclononane; 1, 4-bis ( 1 -methylimidazol-2- ylmethyl) -7-ethyl-l, 4, 7-triazacyclononane; 1, 4-bis (1- methylimidazol-2-ylmethyl) -7-methyl-l, 4, 7- triazacyclononane, 1,4, 7-tris (quinolin-2-ylmethyl) - 1 , 4 , 7-triazacyclononane; 1, 4, 7-tris (pyridin-2- ylmethyl) -1,4, 7-triazacyclononane .
Other suitable catalysts include, mononuclear manganese complexes with optionally substituted terpyridine complexes, for examples as disclosed in US20040142843, a mononuclear manganese (III) complex with tris (2- (salicylideneamino) ethyl) amine .
The aqueous solution is preferably not buffered. In this regard, the aqueous solution may be substantially free from an inorganic buffer, e.g., carbonate, phosphate, and borate. Most preferably, the aqueous solution is not buffered other than by the organic sequestrant and hydrogen peroxide. The organic sequestrant and hydrogen peroxide may be considered to have some buffering capacity but this is not to be considered as buffering within the context of unbuffered embodiments of the present invention.
If a buffer is present, it is most preferably a carbonate buffer .
Preferably, the aqueous solution comprises from 0.01 to 10 g/1 of an organic sequestrant, the sequestrent selected from: an aminophosphonate sequestrant and a carboxylate sequestrant .
The sequestrant is either an aminophosphonate sequestrant or a carboxylate sequestrant. Preferably, the sequestrant is either an aminophosphonate sequestrant or an aminocarboxylate sequestrant.
The following are preferred examples of aminophosphonate sequestrants nitrilo trimethylene phosphonates, ethylene- diamine-N, N, N' , N' -tetra (methylene phosphonates) (Dequest 204) and diethylene-triamine-N, N, N' , N", N"- penta (methylenephosphonates) (Dequest 206), most preferably diethylene-triamine-N, N, N' , N",N"- penta (methylenephosphonates) . One skilled in the art will be aware that that different types of each Dequest exist, e.g., as phosphonic acid or as sodium salts or any mixture thereof.
The following are preferred examples of aminocarboxylate sequestrants: ethylenediaminetetraacetic acid (EDTA), N- hydroxyethylenediaminetetraacetic acid (HEDTA) , nitrilotriacetic acid (NTA) , N-hydroxyethylaminodiacetic acid, N-hydroxyethylaminodiacetic acid, glutamic diacetic acid, sodium iminodisuccinate, diethylenetriaminepentaacetic acid (DTPA), ethylenediamine-N, N' -disuccinic acid (EDDS), methylglycinediacetic acid (MGDA), and alanine-N, N-diacetic acid. A most preferred aminocarboxylate sequestrant is diethylenetriaminepentaacetic acid (DTPA) .
The sequestrants may also be in the form of their salts, e.g., alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts salts. Preferably the
sequestrant is in the free acid form, sodium or magnesium salt .
Examples of carboxylate sequestrants are polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates . Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates . Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1, 1, 2, 2 -ethane tetracarboxylates, 1, 1, 3, 3-propane tetracarboxylates and 1, 1, 2, 3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1, 439, 000.
Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1, 1, 2, 2-ethane tetracarboxylates, 1, 1, 3, 3-propane tetracarboxylates and 1, 1, 2, 3-propane tetracarboxylates.
Other suitable water soluble organic salts are the homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two
carbon atoms. Polymers of the latter type are disclosed in GB-A-I, 596, 756. Examples of such salts are polyacrylates of M. Wt. 2000 to 5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
Also copolymeric polycarboxylate polymers which, formally at least, are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C1-C4 alkyl acrylic acid as second monomer. Such polymers are available from BASF under the trade name Sokalan® CP5 (neutralised form), Sokalan® CP7, and Sokalan® CP45 (acidic form) .
Most preferred sequestrants are Dequest 2066 or Dequest 2047.
A bleach precursor may be used: Peracid may be added to a detergent product, but it is preferably formed in-situ from peroxide and a bleach precursor. A peracid may be formed by perhydrolysis of an acidic bleach precursor by the following reaction :
O O
Il -OOH II R—C—X ►R—C-OOH +X"
Different types of precursors, such as e.g. cationic nitriles, have different reaction equations, but are also included in the scope of the present invention.
The detergent composition used in the method of the present invention may include one or more bleach precursors.
The most preferred are precursors selected form the group consisting of: sodium nonanoyloxybenzene sulphonate (SNOBS); nonanoyloxy aminocaproyloxy benzene sulphonate (NACOBS) ; sodium-4-benzoyloxy benzene sulphonate (SBOBS); N, N, N1N'- tetraacetyl ethylene diamine (TAED) ; sodium-l-methyl-2- benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-benzoloxy benzoate; 2- (N, N, N-trimethyl ammonium) ethyl sodium-4- sulphophenyl carbonate chloride (SPCC); trimethyl ammonium toluyloxy-benzene sulphonate; sodium 3, 5, 5-trimethyl hexanoyl-oxybenzene sulphonate (STHOBS) ; and substituted cationic nitriles; and mixtures thereof.
Further peracid bleach precursors are known and amply described in literature, such as in the GB-A-O, 836, 988 ; GB- A-O, 864, 798; GB-A-O, 907, 356; GB-A-I, 003, 310 and GB-A- 1,519,351; DE-A-3, 337, 921 ; EP-A-O, 185,522; EP-A-O , 174 , 132 ; EP-A-O, 120, 591; and US-A-I , 246, 339; US-A-3,332, 882; US-A- 4,128,494; US-A-4, 412, 934 and US-A-4, 675, 393; and cationic i.e. quaternary ammonium substituted peroxyacid precursors are disclosed in US-A-4, 751,015 and US-A-4, 397, 757, in EP- A-O, 284, 292 and EP-A-O, 331, 229.
The peracid forming reaction of peroxide and bleach precursor from the detergent may be obtained in the washing liquor inside the washing machine drum, or in an off-line mixing vessel. An advantage of the latter is that the peracid may be formed in a concentrated form at the desired pH and may be diluted with acidic water into the washing
machine drum, thereby reducing the pH for the washing process resulting in better bleaching activity.
The low environmental impact detergent product which can be used with the present invention preferably comprises bleach precursor in a peroxide: precursor ratio of between 1:2 and 25:1, more preferably between 2:1 and 10:1 on a molar basis.
Preferably the process is carried out in an automatic washing machine. A peroxide generating cell comprising an electrochemical cell for the production of peroxide from tap water and air, and being suitable for use in said machine when the machine is in operation; whereby no added chemicals are needed to product hydrogen peroxide when the device is in operation.
The hydrogen peroxide is preferably only added in the first step but may be present in the second step provided the initial pH levels are as defined above.
The peroxide generating cell is preferably an electrochemical cell comprising one or more cathode and anode electrodes that are chargeable by a DC potential. The electrodes may for instance be in the form of plates or rods, preferably plates. The cathode is preferably a gas diffusion electrode. The cathode preferably comprises a catalyst bound to the cathode surface. The cathode may comprise conductive materials such as carbon (e.g. graphite, carbon nano-tubes and other forms of carbon) , metals or conductive polymers or combinations thereof. Preferred metal catalysts are transition metals, transition metal oxides or transition metal macrocycles. Preferred transition
metals include gold, mercury and oxide covered metals such as nickel and cobalt. Preferred metal oxides include nickel oxide, cobalt oxide and spinels. Preferred transition metal macrocycles include: CoTsPc (phthalocyanine tetra- sulfonate) cobalt) and CoTMPP (tetramethoxyphenyl porphyrine) . The Anode is preferably a dimensionally stable anode, which is preferably constructed from conductive materials such as metals, carbon or conductive polymers or combinations thereof.
Some transition metals are not preferred, in particular platinum, platinum alloys, platinum family metals, palladium, and silver. Also not preferred are perovskites and pyrochlores, such as lead ruthenate transition metal oxides, and macrocyclic FeTsPc (iron tetrasulfonato phthalocyanine) .
The dimensions and specification of the peroxide generating cell are dependent on the intended use. If the peroxide is stored in a buffer tank inside the washing machine, a slow system producing peroxide e.g. overnight is suitable. However, when the peroxide is to be produced during the washing process, a fast producing system is required. The peroxide generating cell of the present invention preferably comprises a total cathode area of at least 10 cm2, more preferably at least 50 cm2, even more preferably at least 100 cm2 and at most 1000 cm2, more preferably at most 500 cm2, even more preferably at most 400 cm2, still more preferably at most 300 cm2; the area being dependent on the demanded production rate. The surface area is preferably divided over between 1 and 25, more preferably between 1 and
10 cathode electrodes. The peroxide production rate is typically between 0.1 and 2000 mmol/h. The actual rate is dependent on amongst others the surface area of the cathode and the type of operation. In a system with a peroxide storage tank, a slow production rate is preferred, typically from 0.1 to 200 mmol/hr, while in a system where the peroxide is produced immediately during water intake, the production rate is preferably between 200 and 2000 mmol/hr. The efficiency of this type of peroxide generating cell is preferably from 50 to 100% at or just after the start of the peroxide production, typically from 60 to 95%.
The total surface area of the anodes is between 10 and 100% of the total surface area of the cathodes.
The electrodes are optionally separated by a semi-permeable membrane .
The machine preferably also comprises a pH modifying device comprising an electrochemical cell comprising one or more cathode and anode electrodes for the production of acidic and alkaline water; whereby no added chemicals are needed to modify pH when the device is in operation.
Surfactant
The formulation used may contain a surfactant or a surfactant mixture. The use of surfactants, for example, helps to remove the waxy materials encountered in cotton. The surfactant may comprise one or more anionic, non-ionic, cationic, amphoteric, and zwitterionic surfactant, and
- I i
mixtures thereof. Further examples are given in Surface Active Agents and Detergents (VoI I and II by Schwartz, Perry and Berch) . A variety of such surfactants are also generally disclosed in US-A-3, 929, 678.
In this regard, it is preferred that a surfactant is present in the range from 0.1 to 20 g/L, preferably 0.5 to 10 g/1. It is preferred that the surfactant is a non-ionic surfactant and most preferably biodegradable.
Additional detergent ingredients may be used also, such as enzymes. Preferred enzymes include, but are not limited to proteases, cellulases, lipases, amylases, peroxidases. The detergent may contain one or more optional cleaning agents, which include any agent suitable for enhancing the cleaning, appearance, condition and/or garment care. Generally, the optional cleaning agent may be present in the compositions of the invention in an amount of 0 to 20 wt.%, preferably 0.001 wt.% to 10 wt.%, more preferably 0.01 wt.% to 5 wt.% by weight of the total detergent composition.
Some suitable optional cleaning agents include, but are not limited to antibacterial agents, colorants, perfumes, pro- perfumes, finishing aids, lime soap dispersants, composition malodour control agents, odour neutralisers, polymeric dye transfer inhibiting agents, crystal growth inhibitors, anti- tarnishing agents, anti-microbial agents, anti-oxidants, anti-redeposition agents, soil release polymers, thickeners, abrasives, corrosion inhibitors, suds stabilising polymers, process aids, fabric softening agents, optical brighteners, hydrotropes, suds or foam suppressors, suds or foam
boosters, anti-static agents, dye fixatives, dye abrasion inhibitors, wrinkle reduction agents, wrinkle resistance agents, soil repellency agents, sunscreen agents, anti-fade agents, and mixtures thereof.
The detergent may be dosed in any suitable format such as a liquid, gel, paste, tablet or sachet. In some cases granular formulations may be used although this is not preferred. In one preferred embodiment the detergent is a non-aqueous product. Non-aqueous for the purpose of the present invention is meant to describe a product comprising less than 10 %, preferably less than 5 %, more preferably less than 3 % by weight of free water. The non-aqueous product may be a liquid, gel or paste or encapsulated in a sachet.
It is desirable to equip washing machines with one or more detergent product containers so that the detergent product may be dosed automatically. The detergent may be dosed from a single container. Alternatively, the ingredients making up the detergent may be dosed from separate containers as described in EP-A-0419036. Thus in one preferred embodiment at least one ingredient from the detergent is dosed automatically. One advantage of a detergent may be that the reduced number and/or amount of ingredients enables a much smaller volume of detergent product. In practice this would mean that the consumer does not need to refill the containers as often or that the containers may be smaller, therefore making an automatic dosage system more feasible when using the device of the invention. When an automatic dosage system is applied, it is preferred that the bleach
precursor or activator (catalyst) is stored separately from the other components of the detergent product.
EXAMPLES
Below are non limiting examples of the invention, included by way of example only.
The BC-I stain was obtained by CFT, Vlaardingen, Netherlands.
The grass stain is prepared by rubbing fresh grass into cotton, after which it is brushed to get an evenly distributed stain.
The Bandy Black Clay stain is prepared by rubbing soil mud into cotton, after which it is brushed to get an evenly distributed stain.
Experimental Method:
Demineralised aqueous solution of 10 iπmol/1 hydrogen peroxide was made that contained either no buffer, carbonate buffer (0.3 g/1 Na2CO3), Na-LAS/Lutensol A03 (each 0.4 g/1) + 0.3 g/1 Na2CO3, Lutensol A07 (0.8 g/1) + 0.3 g/1 Na2CO3. The appropriate amount of NaOH solution was added to either yield pH 10.5 or pH 11.0.
The stains were first pre-treated at high pH using the above pre-treatment formulations, without catalyst for 20 minutes
at 4O0C under mild agitation. The cloth/liquor (w/w) ratio was approximately 40.
After 20 minutes the cloths were removed from the pre- treatment solutions, rinsed twice with demineralised water, dried and added to a fresh solution containing
a. 10 mmol/1 H2O2, 20 μM of catalyst at pH 8, 9. b. 10 mmol/1 H2O2, 20 μM of catalyst at pH 8, 9. c. 10 mmol/1 H2O2, 20 μM of catalyst at pH 8, 9. d. 10 mmol/1 H2O2, 20 μM of catalyst at pH 8, 9.
The cloths were then treated for another 10 minutes at 4O0C.
Note: Here, the pre-treatment step is done in the same composition (buffer, surfactant) as the 2nd stage process with catalyst) . However, the pH in the 2nd stage different (lower) .
The cloths were then rinsed twice with phosphate buffer, dried and then measured for change in colour was measured with a Linotype-Hell scanner (ex Linotype) . The change in colour (including bleaching) is expressed as the ΔE value versus white and the values in the tables are 100- ΔE; a higher SRI value means a cleaner cloth (100=white) . The measured colour difference (ΔE) between the washed cloth and the unwashed cloth is defined as follows:
ΔE = [ (ΔL) 2 + (Δa) 2 + (Δb) 2 ] 1/2
wherein ΔL is a measure for the difference in darkness between the washed and unwashed test cloth; Δa and Δb are measures for the difference in redness and yellowness respectively between both cloths. With regard to this colour measurement technique, reference is made to Commission International de 1 'Eclairage (CIE); Recommendation on Uniform Colour Spaces, colour difference equations, psychometric colour terms, supplement no 2 to CIE Publication, no 15, Colormetry, Bureau Central de Ia CIE, Paris 1978. The results are shown below in the tables and are listed.
Comparisons are in all cases made wherein the catalyst has been added at t=0 in the same solution as given above for the 2nd process (so between pH 8 and 10 with different formulations) .
Different stains were used: BC-I (tea-based monitor) , Curry oil, Bandy black clay and grass.
Below the results for different catalysts are given.
1. [Mn2 (μ-O) 3 (Me3tacn) 2] (PF6) 2
Mn2 ( -O) 3 ( 1 , 4 , 7 -t rime thy 1- 1 , 4 , 7 -triazacyclononane ) 2 ] PF6) 2 was prepared as published elsewhere (J. Chem. Soc, Dalton Trans, 353 (1996) ) .
Effect of pre-treatment process on BC-I stains
a. Pretreating the stain at pH 11 with carbonate buffer, and then adding catalyst at pH 9.6, yields 95 SRI. The reference at pH 9.5 gives 92 SRI. b. Pretreating the stain at pH 11 without buffer, and then adding catalyst at pH 7.1, yields 92 SRI. The reference at pH 8 gives 88 SRI. c. Pretreating the stain at pH 11 with Lutensol A07 and carbonate buffer, and then adding catalyst at pH 9.5, yields 95.5 SRI. The reference at pH 9.0 gives 93 SRI.
Effect of pre-treatment process on CBB stains
a. Pretreating the stain at pH 11 with Lutensol A07 and carbonate buffer, and then adding catalyst at pH 10, yields 88 SRI. The reference at pH 9.3 gives 82 SRI. b. Pretreating the stain at pH 11 with Na-LAS/Lutosol A03 in carbonate buffer, and then adding catalyst at pH 10, yields 88 SRI. The reference gives at pH 9.5 84 SRI.
Effect of pre-treatment process on grass stains
a. Pretreating the stain at pH 11 with Na-LAS/Lutosol A03 in carbonate buffer, and then adding catalyst at pH 8.6, yields 77 SRI. The reference at pH 8.5 gives 69 SRI. b. Pretreating the stain at pH 11 with Na-LAS/Lutosol A03 in carbonate buffer, and then adding catalyst at pH 9.1, yields 77 SRI. The reference at pH 9 gives 71 SRI. c. Pretreating the stain at pH 11 with Lutensol A07 in carbonate buffer, and then adding catalyst at pH 8.3, yields 76 SRI. The reference at pH 8.5 gives 68 SRI.
d. Pretreating the stain at pH 11 with Lutensol A07 in carbonate buffer, and then adding catalyst at pH 9.9, yields 78 SRI. The reference at pH 9.5 gives 69 SRI.
2. [Mn(Bcyclam)Cl2]
4, 11 -dimethyl- 1, 4, 8, 11-tetraazabicyclo [6.6.2] hexadecane , hereafter referred to as Bcyclam, and the corresponding manganese (II) complex, [Mn (Bcyclam) CI2] , were prepared as described in WO98/39098 and J.Am. Chem.Soc, 122, 2512 (2000) ) .
Effect of pre-treatment process on grass stains
a. Pretreating the stain at pH 10.5 with Na-LAS/Lutosol
A03 in carbonate buffer, and then adding catalyst at pH 8.2, yields 77 SRI. The reference at pH 8.3 gives 70 SRI. b. Pretreating the stain at pH 10.5 with Lutensol A07 in carbonate buffer, and then adding catalyst at pH 8.2, yields 74.5 SRI. The reference at pH 8.4 gives 68.5 SRI.
3. [Fe(N2py3o)Cl]Cl
Dimethyl 2, 4-di- (2-pyridyl) -3-methyl-7- (pyridin-2-ylmethyl) - 3,7-diaza-bicyclo[3.3.1]nonan-9-one-l,5-dicarboxylate (N2py3o) and the iron (II) complex thereof [Fe (N2py3o) Cl] Cl was prepared as described in WO0248301.
Effect of pre-treatment process on grass stains
a. Pretreating the stain at pH 11 with Na-LAS/Lutosol A03 in carbonate buffer, and then adding catalyst at pH 8, yields 78 SRI. The reference at pH 8.5 gives 68 SRI. b. Pretreating the stain at pH 11 with Lutensol A07 in carbonate buffer, and then adding catalyst at pH 8, yields 75 SRI. The reference at pH 8.4 gives 68 SRI.
4. [Fe(N2py2-amine)Cl]Cl
Dimethyl 2, 4-di- (2-pyridyl) -3-methyl-7-
( (dimethylamino) ethyl) -3,7-diaza-bicyclo[3.3.1]nonan-9-one- 1, 5-dicarboxylate (N2py2-amine) and the iron (II) complex thereof [Fe (N2py2-amine) Cl] Cl was prepared as described in WO 03/104379.
Effect of pre-treatment process on grass stains
a. Pretreating the stain at pH 10.5 with Na-LAS/Lutosol
A03 in carbonate buffer, and then adding catalyst at pH 8.1, yields 80 SRI. The reference at pH 8.4 gives 70 SRI. b. Pretreating the stain at pH 11 with Na-LAS/Lutosol A03 in carbonate buffer, and then adding catalyst at pH
9.4, yields 78 SRI. The reference at pH 9.1 gives 71 SRI. c. Pretreating the stain at pH 11 with Lutensol A07 in carbonate buffer, and then adding catalyst at pH 8, yields 77 SRI. The reference at pH 8.2 gives 70 SRI.
Effect of pre-treatment process on curry oil stains
a. Pretreating the stain at pH 10.5 in carbonate buffer, and then adding catalyst at pH 7.9, yields 57 SRI. The reference at pH 7.6 gives 47 SRI.
Pretreating the stain at pH 11 without buffer, and then adding catalyst at pH 5.4, yields 63 SRI. The reference at pH 7.5 gives 53 SRI.
5. [Fe(MeN4py)Cl]Cl
N,N-bis (pyridin-2-yl-methyl-l, 1-bis (pyridin-2-yl) - 1- aminoethane , hereafter referred to as MeN4Py, and the corresponding iron (II) complex, [Fe (MeN4py) Cl] Cl, were prepared as described in EP0909809. Note that this catalyst has been used in all experiments at 10 μM level
Effect of pre-treatment process on grass stains
a. Pretreating the stain at pH 10.5 with Na-LAS/Lutosol
A03 in carbonate buffer, and then adding catalyst at pH 8, yields 77 SRI. The reference at pH 8.6 gives 68 SRI. b. Pretreating the stain at pH 11 with Na-LAS/Lutosol A03 in carbonate buffer, and then adding catalyst at pH 9.2, yields 77 SRI. The reference at pH 9.2 gives 69 SRI.
Conclusions
The results are considered to be more than 95% different
(least significant difference) , when a difference in SRI of
at least 0.5 for BC-I; 2.8 for curry oil; 1.2 for carbon black clay; and 1.1 for the grass stain was observed. So all results given above show that the effect of pre- treatment without catalyst give a significant benefit compared to the single-stage process.
Comparative example to show Effect of increased pH on bleaching performance of [Mn2 (μ-O) 3 (Mβ3tacn) 2] (PF6) 2
The bleaching step (without pre-treatment) was done in the presence of 5 μM of [Mn2 (μ-O) 3 (Me3tacn) 2] (PF6) 2 at different pH's at 40 0C for 30 min on BC-I and the SRI values, as defined above, were as follows:
With Sodium Carbonate buffer (0.3 g/1) , no surfactant pH 8.0: 92.8 pH 10.2 95.5
No buffer, no surfactant pH 5.2 87.5 pH 9.9 94.5
Na-LAS/Lutensol A03 (each 0.4 g/1) + 0.3 g/1 Na2CO3 pH 7.8 92.9 pH 9.7 95.6
Lutensol A07 (0.8 g/1) + 0.3 g/1 Na2CO3. pH 8.0 93.6 pH 9.5 95.6
Conclusion
The results show the effect of pre-treatment without catalyst at a higher pH 9-11.5 gives a significant benefit compared to when carried out at low pH.
Claims
1. A method of bleaching a fabric comprising the following steps :
(i) a pretreatment step in which the fabric is treated with an the aqueous solution having a initial pH from 9 to 10.5 and comprising 0.5-50 mM (millimol/litre) hydrogen peroxide; followed by (ii) treatment with a preformed transition metal catalyst, the transition metal catalyst present in a concentration from 0.1 to 100 micromolar of an aqueous solution wherein the initial pH of this second step is from 7-10.
2. A method according to claim 1 wherein the preformed transition metal catalyst may be Fe (II) or Fe (III) or Mn (II) or Mn (III) or Mn(IV) .
3. A method according to any preceding claim wherein the ligand of the catalyst may be a tridentate, tetradentate, pentadentate or hexadentate nitrogen and oxygen donor
4. A method according to any preceding claim wherein the preformed transition metal catalyst may be a mononuclear or dinuclear complex of a Mn H-V transition metal catalyst, the ligand of the transition metal catalyst of formula (I) :
R is selected from: hydrogen, Cl-C6-alkyl, C2OH, ClCOOH, benzyl, and pyridin-2-ylmethyl or one of R is linked to the N of another Q via an ethylene bridge;
Rl, R2, R3, and R4 are selected from: H, Cl-C4-alkyl, and Cl-C4-alkylhydroxy.
5. The method according to claim 1 wherein the preformed catalyst is an iron complex of a tetradentate, pentadentate or hexadentate nitrogen donor ligand, wherein the ligand is selected from the group consisting of:
wherein each R is selected from: hydrogen, F, Cl, Br, hydroxyl, Cl-C4-alkylO-, -NH-CO-H, -NH-CO-Cl-C4-alkyl,
-NH2, -NH-Cl-C4-alkyl, and Cl-C4-alkyl;
Rl and R2 are selected from Cl-C24-alkyl, C6-C10-aryl, and, a group containing a heteroatom capable of coordinating to a transition metal;
R3 and R4 are selected from hydrogen, C1-C8 alkyl, Cl-
C8-alkyl-O-Cl-C8-alkyl, Cl-C8-alkyl-O-C6-C10-aryl, C6-
C10-aryl, Cl-C8-hydroxyalkyl, and - (CH2) nC (O) OR5 wherein R5 is selected from: hydrogen, Cl-C4-alkyl, n is from 0 to 4, and mixtures thereof; and, X is selected from C=O, -[C(R6)2]y~ wherein Y is from 0 to 3 each R6 is selected from hydrogen, hydroxyl, Cl- C4-alkoxy and Cl-C4-alkyl;
R3 represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or -R4-R5, each R4 represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and each R5 represents an optionally N-substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl;
R20 ;iv) wherein each R20 is selected from: an alkyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N+(R21)3 , wherein R21 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether, alkenyl ether, and -CY2- R22, in which Y is selected from H, CH3, C2H5, C3H7 and R22 is selected from an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and wherein at least one of R20 is a -CY2-R22;
R17R17N-X-NR17R17 (V) , wherein :
X is selected from -CH2CH2-, -CH2CH2CH2-, -CH2C(OH)HCH2-; and, R17 represents a group selected from: R17 and alkyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N+(R19)3 , wherein R19 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether, alkenyl ether, and -CY2- R18, in which Y is selected from H, CH3, C2H5, C3H7 and R18 is selected from an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and wherein at least two of R17 are -CY2-RI8.
6. A method according to any preceding claim wherein the pretreatment step is carried out for 1 - 120 mins .
7. A method according to any claim 6 wherein the pretreatment step is carried out for 5 - 60 mins.
8. A method according to claim 7 wherein the pretreatment step is carried out for 10 - 40 mins.
9. A method according to any preceding claim wherein the second step is carried out for 1 - 120 mins.
10. A method according to claim 9 wherein the second step is carried out for 5 -60 mins.
11. A method according to claim 10 wherein the second step is carried out for 10 - 40 mins.
12. A method according to any preceding claim wherein said method takes place in an automatic laundry washing machine.
13. A method according to claim 12 wherein the machine comprises a pH modulator for moderation of the pH of the method in at least one of the steps.
14. A method according to any of claims 12 or 13 wherein the machine comprises a hydrogen peroxide electrode .
15. A method according to any of claims 12-14 wherein the machine comprises a water treatment device.
16. A method according to 15 wherein the water treatment device comprises a flow through capacitor.
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EP08160343.3 | 2008-07-14 | ||
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2011060109A1 (en) * | 2009-11-11 | 2011-05-19 | The Procter & Gamble Company | Cleaning method |
WO2012101149A1 (en) | 2011-01-26 | 2012-08-02 | Novozymes A/S | Storage-stable enzyme granules |
WO2013092051A1 (en) | 2011-12-20 | 2013-06-27 | Unilever Plc | Liquid detergents comprising lipase and bleach catalyst |
WO2014070661A1 (en) * | 2012-10-29 | 2014-05-08 | Ashland Licensing And Intellectual Property Llc | Resin compositions |
WO2021097601A1 (en) * | 2019-11-18 | 2021-05-27 | Solvay Sa | Solid bleach particles |
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EP0172602A1 (en) * | 1984-06-06 | 1986-02-26 | Interox Chemicals Limited | Bleaching and washing compositions |
DE10200672A1 (en) * | 2001-01-10 | 2002-07-11 | Kao Corp | Bleach composition for use in e.g. detergent powders and liquids, comprises a peroxy bleaching agent, a metal-containing anionic bleach activator, and a cationic compound |
US20040038844A1 (en) * | 2000-03-01 | 2004-02-26 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Composition and method for bleaching a substrate |
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2009
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EP0172602A1 (en) * | 1984-06-06 | 1986-02-26 | Interox Chemicals Limited | Bleaching and washing compositions |
US20040038844A1 (en) * | 2000-03-01 | 2004-02-26 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Composition and method for bleaching a substrate |
DE10200672A1 (en) * | 2001-01-10 | 2002-07-11 | Kao Corp | Bleach composition for use in e.g. detergent powders and liquids, comprises a peroxy bleaching agent, a metal-containing anionic bleach activator, and a cationic compound |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2011060109A1 (en) * | 2009-11-11 | 2011-05-19 | The Procter & Gamble Company | Cleaning method |
US8449626B2 (en) | 2009-11-11 | 2013-05-28 | The Procter & Gamble Company | Cleaning method |
WO2012101149A1 (en) | 2011-01-26 | 2012-08-02 | Novozymes A/S | Storage-stable enzyme granules |
WO2013092051A1 (en) | 2011-12-20 | 2013-06-27 | Unilever Plc | Liquid detergents comprising lipase and bleach catalyst |
WO2014070661A1 (en) * | 2012-10-29 | 2014-05-08 | Ashland Licensing And Intellectual Property Llc | Resin compositions |
US9187616B2 (en) | 2012-10-29 | 2015-11-17 | Ashland Licensing And Intellectual Property Llc | Resin compositions |
WO2021097601A1 (en) * | 2019-11-18 | 2021-05-27 | Solvay Sa | Solid bleach particles |
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