EP0783035A2 - Système de blanchiment contenant des sels de Bis-et-tris-(mu-oxo)-di-manganèse complexé - Google Patents
Système de blanchiment contenant des sels de Bis-et-tris-(mu-oxo)-di-manganèse complexé Download PDFInfo
- Publication number
- EP0783035A2 EP0783035A2 EP96120743A EP96120743A EP0783035A2 EP 0783035 A2 EP0783035 A2 EP 0783035A2 EP 96120743 A EP96120743 A EP 96120743A EP 96120743 A EP96120743 A EP 96120743A EP 0783035 A2 EP0783035 A2 EP 0783035A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- alkyl
- bleaching agent
- bis
- agent systems
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011572 manganese Substances 0.000 title claims abstract description 20
- 150000003839 salts Chemical class 0.000 title claims abstract description 19
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 12
- 238000004061 bleaching Methods 0.000 title claims description 21
- 239000007844 bleaching agent Substances 0.000 claims abstract description 27
- 239000003446 ligand Substances 0.000 claims abstract description 20
- 239000012459 cleaning agent Substances 0.000 claims abstract description 11
- 150000001450 anions Chemical class 0.000 claims abstract description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 9
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000002252 acyl group Chemical group 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 44
- 239000003599 detergent Substances 0.000 claims description 14
- 239000012190 activator Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000007983 Tris buffer Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000005342 perphosphate group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims 1
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical class OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 22
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 48
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- -1 C5-C10-Cycloalkyl Chemical group 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 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 9
- 239000007800 oxidant agent Substances 0.000 description 9
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 9
- 125000006479 2-pyridyl methyl group Chemical group [H]C1=C([H])C([H])=C([H])C(=N1)C([H])([H])* 0.000 description 8
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 8
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 241001122767 Theaceae Species 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 3
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 3
- 235000021537 Beetroot Nutrition 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- JPMRGPPMXHGKRO-UHFFFAOYSA-N 2-(chloromethyl)pyridine hydrochloride Chemical compound Cl.ClCC1=CC=CC=N1 JPMRGPPMXHGKRO-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 235000021438 curry Nutrition 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 150000004966 inorganic peroxy acids Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- IFUQIEXEVCFFBW-UHFFFAOYSA-N n,n,n',n'-tetrakis(2-pyridin-2-ylethyl)butane-1,4-diamine Chemical compound C=1C=CC=NC=1CCN(CCC=1N=CC=CC=1)CCCCN(CCC=1N=CC=CC=1)CCC1=CC=CC=N1 IFUQIEXEVCFFBW-UHFFFAOYSA-N 0.000 description 2
- PAVSJKXXDLMPJI-UHFFFAOYSA-N n,n,n',n'-tetrakis(2-pyridin-2-ylethyl)propane-1,3-diamine Chemical compound C=1C=CC=NC=1CCN(CCC=1N=CC=CC=1)CCCN(CCC=1N=CC=CC=1)CCC1=CC=CC=N1 PAVSJKXXDLMPJI-UHFFFAOYSA-N 0.000 description 2
- ZODATTHCRVWTBI-UHFFFAOYSA-N n,n,n',n'-tetrakis(pyridin-2-ylmethyl)propane-1,3-diamine Chemical compound C=1C=CC=NC=1CN(CC=1N=CC=CC=1)CCCN(CC=1N=CC=CC=1)CC1=CC=CC=N1 ZODATTHCRVWTBI-UHFFFAOYSA-N 0.000 description 2
- OOTKJPZEEVPWCR-UHFFFAOYSA-N n-methyl-1-pyridin-2-ylmethanamine Chemical compound CNCC1=CC=CC=N1 OOTKJPZEEVPWCR-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000004967 organic peroxy acids Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- MIKSWWHQLZYKGU-UHFFFAOYSA-M sodium;2-benzoyloxybenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1OC(=O)C1=CC=CC=C1 MIKSWWHQLZYKGU-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical compound C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- RFQGAFQKNITSIA-UHFFFAOYSA-N 2-(carboxyamino)benzoic acid Chemical compound OC(=O)NC1=CC=CC=C1C(O)=O RFQGAFQKNITSIA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical class OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 1
- FAGGUIDTQQXDSJ-UHFFFAOYSA-N 3-benzoylazepan-2-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCNC1=O FAGGUIDTQQXDSJ-UHFFFAOYSA-N 0.000 description 1
- ZWJOGLACKJHHKM-UHFFFAOYSA-N 4-pyridin-2-ylbutane-1,3-diamine Chemical compound NC(CCN)CC1=NC=CC=C1 ZWJOGLACKJHHKM-UHFFFAOYSA-N 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 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
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 229910003177 MnII Inorganic materials 0.000 description 1
- 229910016887 MnIV Inorganic materials 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
- 239000004365 Protease Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
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- 239000008139 complexing agent Substances 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- JZBWUTVDIDNCMW-UHFFFAOYSA-L dipotassium;oxido sulfate Chemical compound [K+].[K+].[O-]OS([O-])(=O)=O JZBWUTVDIDNCMW-UHFFFAOYSA-L 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- BRDYCNFHFWUBCZ-UHFFFAOYSA-N dodecaneperoxoic acid Chemical compound CCCCCCCCCCCC(=O)OO BRDYCNFHFWUBCZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical class OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 150000004680 hydrogen peroxides Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- AHSBSUVHXDIAEY-UHFFFAOYSA-K manganese(iii) acetate Chemical compound [Mn+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AHSBSUVHXDIAEY-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 125000001402 nonanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003444 phase transfer catalyst Substances 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
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- NYCVCXMSZNOGDH-UHFFFAOYSA-N pyrrolidine-1-carboxylic acid Chemical class OC(=O)N1CCCC1 NYCVCXMSZNOGDH-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000020095 red wine Nutrition 0.000 description 1
- 230000000630 rising effect Effects 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
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003672 ureas Chemical class 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
Definitions
- Bleaches that release active oxygen are an essential part of modern washing and cleaning agents. Its main task is to remove stubborn stains such as tea, coffee, red wine or fruit juices from textile fibers or solid surfaces. This is done by oxidative destruction of the chromophoric system; At the same time, adhering microorganisms are killed and odorants neutralized.
- Hydrogen peroxide, organic or inorganic peracid are mostly used as bleaching agents.
- a persalt is usually used as a source of active oxygen in powdery products.
- Typical examples are sodium perborates or percarbonates or urea adducts.
- bleach activators are often added.
- Examples include tetraacetylethylenediamine (TAED), diacetyldioxohexahydrotriazine (DADHT), pentaacetylglycose (PAG), benzoyloxibenzenesulfonate (BOBS) and nonanoyloxibenzenesulfonate (NOBS).
- TAED tetraacetylethylenediamine
- DADHT diacetyldioxohexahydrotriazine
- PAG pentaacetylglycose
- BOBS benzoyloxibenzenesulfonate
- NOBS nonanoyloxibenzenesulfonate
- transition metals in free or complex form catalyze the decomposition of hydrogen peroxides.
- the effectiveness of the compounds described so far is unsatisfactory in most cases.
- the addition of metal salts leads to catalytic decomposition of the hydrogen peroxide, but no bleaching effect is observed. This is usually associated with damage to the textile fabric. The occurrence of free transition metals during the washing and cleaning process is therefore undesirable.
- the metal salt is used in complexed form, the corresponding complex must be stable to hydrolysis and oxidation during storage and under conditions of use in order to suppress these side effects.
- EP A 458 397 and 458 398 describes the use of macrocyclic polyamines as complex ligands in multinuclear, oxygen-bridged manganese complexes. In combination with oxidizing agents, especially on tea stains, these complexes show good bleaching properties.
- the difficult to access complex ligand of the triazacyclononane type has a disadvantage. It is only accessible in a multi-stage, by-product-rich manufacturing process. Similar complexes are described in EP 544 519, again the synthesis of the complex ligand is very complex and difficult to implement on an industrial scale.
- L is preferably a ligand of the formula II.
- R is preferably C 1 -C 4 -alkyl, in particular methyl.
- anion A are Cl - , Br - , J - , NO 3 - , ClO 4 - , NCS - , PF 6 - , RSO 3 - , RSO 4 - , SO 4 2- , BPh 4 - , OAc - .
- Preferred anions are PF 6 - , ClO 4 - , tosylate.
- the ligands of the formula III contained in these manganese complex salts are prepared by reacting 2- (chloromethyl) pyridinium chloride with an alkylenediamine in the presence of a phase transfer catalyst (see Synthesis, June 1992, p. 539-540) or in an analogous manner for the substituted other ligands of formula III.
- the ligands of the formula II are prepared in the same way by reacting 2- (chloromethyl) pyridinium chloride or analogous pyridinium compounds with an amine R-NH 2 .
- the manganese complex salts of the formula I are prepared in accordance with the information in Inorg. Chem.
- the metal complexes can either be added to the washing and cleaning agent in prefabricated form or generated in situ from the ligand and transition metal during the washing process.
- the bleaching catalysts are used in combination with an oxidizing agent.
- oxidizing agents that can be used are hydrogen peroxide, alkali metal perborates, percarbonates, perphosphates or persulfates. If the catalysts are used in powdery products, sodium perborate mono- or tetrahydrate, caroate in the form of the triple salt and sodium percarbonate, the latter in particular in coated form, are particularly preferred. These compounds can be used either with the catalysts alone or, in accordance with a preferred embodiment, additionally together with a bleach activator. This extends the range of applications and strengthens the germicidal properties of the formulation.
- Bleach activators are known from numerous patent applications. Examples of these are reactive esters and amides such as in GB 836,988, 864,798, 907,356, 1,003,310 and 1,519,351; EP 284,292, 331,229, 303,520, 185,522, 174,132, 120,591 and US 1,246,339, 3,332,882, 4,128,494, 4,412,934, 4,675,393, 4,751,015 and 4,397,757.
- organic peroxycarboxylic acids can also be used directly as oxidizing agents.
- Typical representatives are peroxibenzoic acid and substituted derivatives, aliphatic mono- and dicarboxylic acids such as pernonanoic acid, perlauric acid, 1,9-diperoxiazeldic acid and 1,12-dodecanediperic acid.
- N, N'-phthaloylaminoperoxycarboxylic acids such as N, N'-phthaloylaminoperoxihexanoic acid (PAP), 6-octylamino-6-oxoperoxihexanoic acid, monoperoxiphthalic acid and its salts, 2-alkylperoxi-1,4-butanedioic acids or 4,4'-sulphonylbisperoxiboesoes.
- composition of the bleaching agent system according to the invention can vary within wide limits and is generally between 0.0005 to 2% by weight, preferably 0.001 to 0.5% by weight of the bleaching catalyst described and 1 to 99.9995%, preferably 5 to 99.999 % of an oxidizing agent from the group of inorganic or organic peracids or persalt, and optionally 0 to 70%, preferably 10 to 60% of a bleach activator.
- the bleaching systems according to the invention are used in heavy-duty detergents, multi-component detergents (modular systems), stain salts, stain pretreatment agents, machine dishwashing detergents, cleaning agents for hard surfaces, disinfectants and denture cleaners.
- the catalysts also act as dye transfer inhibitors.
- the catalysts are normally added to the washing and cleaning agent in granular form.
- Inorganic salts such as sodium sulfate, chloride, phosphate or silicates can be used as granulation aids. In a preferred application form, they are incorporated into the activator granulate.
- inorganic or organic auxiliaries can be used for granulation, film-forming materials such as surfactants, fatty acids, celulose derivatives or polymers are preferred.
- the granules can additionally be provided with a coating, which on the one hand increases their storage stability and interactions with other detergent ingredients can be prevented during storage, but on the other hand their release kinetics can also be influenced.
- the bleach system according to the invention can be added to the washing and cleaning agents in the form of a powder or as granules.
- washing and cleaning agents normally also contain surface-active compounds such as anionic, nonionic, zwitterionic, amphoteric or cationic surfactants, builders, enzymes and additives.
- Surfactants can be of natural or synthetic origin and are e.g. in "Surface Active Agents and Detergents" Volumes I and II by Schwartz, Perry and Berch. Examples are alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, alpha-sulfofatty acid methyl esters, soaps and alkyl ether sulfonates. Nonionic surfactants such as alkyl polyglycol ethers, alkyl polyglucosides, glucamides, sugar esters and amine oxides can also be used.
- Important builder and cobuilder substances which can be used in combination with the bleaching system according to the invention are phosphates such as sodium tripolyphosphate, zeolites of the types A, X and P, alkali metal carbonates and bicarbonates, amorphous and crystalline silicates, in particular layered silicates such as SKS-6, 7, 9 or 10 from Hoechst AG or disilicates such as those sold by Akzo under the trade name Britesil ® .
- Organic carboxylic acids such as citric acid or amino acids can be used as co-builders, but also polymers of the polyacrylic acid type or copolymers of acrylic acid and maleic acid or their derivatives. Phosphonate or other complexing agents can also be added.
- Amylase, proteases, lipases, cellulases and peroxidases can be used as enzymes, cellulose ethers, silicones, bentonites, optical brighteners and perfume as further additives.
- N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine were dissolved in 30 ml of a mixture of ethanol and water (5: 1) and then Mn (acetate) 3 ⁇ 2H 2 O (0.96 g; 3.6 mmol) was added. Then was 2.2 g (20 mmol) sodium butyrate were added and then 2 ml HClO 4 (70%). A pH of 7.5 was established. Then 3 g (24.48 mmol) NaClO 4 were added and this mixture was stirred for 4 hours at room temperature.
- TAED tetraacetylethylene diamine
- Example 3 Washing tests in a Linitest device
- Example 3 The tests were carried out as described in Example 3. Instead of the test soil tea (BC-1), beetroot and curry on cotton (manufacturer laundry research Krefeld) were used. catalyst Beetroot ⁇ RE Curry ⁇ RE without 0 0 K1 + 2.0 + 0.6 K4 + 1.1 + 0.1 K2 + 4.0 + 0.9
- the bleaching results on the test soils beetroot and curry can also be significantly increased.
- the washing tests were carried out in the Linitest réelle at 40 ° C; Washing time 30 min. 1.5 g / l WMP were pre-dissolved in 200 ml water (15 ° dH) and 0.5 g / l sodium perborate monohydrate was added. Before the start of the washing tests, 0; 1.5; 3; 6; 12; 25 mg / l of the catalysts added. The washing tests were carried out analogously to Example 3. The table shows the reflectance differences ⁇ RE of the washes with and without a catalyst.
- Example 7 Influence of various oxidizing agents on the bleaching result
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Catalysts (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19600159A DE19600159A1 (de) | 1996-01-04 | 1996-01-04 | Bleichmittelsysteme enthaltend Bis- und Tris-(mu-oxo)-di-Mangan-Komplexsalze |
| DE19600159 | 1996-01-04 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0783035A2 true EP0783035A2 (fr) | 1997-07-09 |
| EP0783035A3 EP0783035A3 (fr) | 1998-02-25 |
| EP0783035B1 EP0783035B1 (fr) | 2003-09-24 |
Family
ID=7782152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96120743A Expired - Lifetime EP0783035B1 (fr) | 1996-01-04 | 1996-12-23 | Système de blanchiment contenant des sels de Bis-et-tris-(mu-oxo)-di-manganèse complexé |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5942152A (fr) |
| EP (1) | EP0783035B1 (fr) |
| JP (1) | JPH09194886A (fr) |
| AT (1) | ATE250660T1 (fr) |
| CA (1) | CA2194342A1 (fr) |
| DE (2) | DE19600159A1 (fr) |
| ES (1) | ES2207663T3 (fr) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0880579A2 (fr) * | 1996-02-16 | 1998-12-02 | Henkel Kommanditgesellschaft auf Aktien | Complexes de metaux de transition utilises comme activateurs pour composes peroxy |
| EP0927241A1 (fr) * | 1996-08-26 | 1999-07-07 | The Procter & Gamble Company | Regulation de l'activite de la cellulase par un terminateur |
| EP0909809A3 (fr) * | 1997-10-01 | 1999-07-21 | Unilever Plc | Activation de blanchiment |
| GB2386616A (en) * | 2002-03-21 | 2003-09-24 | Unilever Plc | Bleaching composition |
| WO2009141258A1 (fr) * | 2008-05-23 | 2009-11-26 | Henkel Ag & Co. Kgaa | Détergent préservant les textiles |
| WO2012000846A1 (fr) | 2010-06-28 | 2012-01-05 | Basf Se | Composition de blanchiment dépourvue de métal |
| WO2013060706A1 (fr) | 2011-10-25 | 2013-05-02 | Basf Se | Utilisation de copolymères d'acrylate comme agents anti-redéposition de la saleté et agents de libération de la saleté dans des processus de blanchisserie |
| WO2013060708A1 (fr) | 2011-10-25 | 2013-05-02 | Basf Se | Utilisation de copolymères en peigne ou séquencés comme agents anti-redéposition de la saleté et agents de libération de la saleté dans des processus de blanchisserie |
| WO2014154508A1 (fr) | 2013-03-27 | 2014-10-02 | Basf Se | Copolymères blocs comme agents de libération de la saleté dans des procédés de blanchisserie |
| WO2017186480A1 (fr) | 2016-04-26 | 2017-11-02 | Basf Se | Composition de blanchiment sans métal |
| US10214606B2 (en) | 2013-11-27 | 2019-02-26 | Basf Se | Random copolymers as soil release agents in laundry processes |
| EP3524347A1 (fr) | 2008-04-09 | 2019-08-14 | Basf Se | Utilisation de composés complexes hydrazides métalliques en tant que catalyseurs d'oxydation |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6274122B1 (en) * | 1999-01-07 | 2001-08-14 | Mclaughlin Gerald | Device and method using dry mixtures for whitening teeth |
| US20040131561A1 (en) * | 2001-03-14 | 2004-07-08 | Mclaughlin Gerald | Strips for treating teeth |
| JP2005194244A (ja) * | 2004-01-09 | 2005-07-21 | Shigenobu Yano | 亜鉛イオン蛍光センサー |
| WO2005087951A2 (fr) | 2004-03-05 | 2005-09-22 | Gen-Probe Incorporated | Reactifs, procedes et kits utilise dans la desactivation d'acides nucleiques |
| KR100647976B1 (ko) * | 2004-05-03 | 2006-11-23 | 애경산업(주) | 표백촉매로서 거대고리 망간 착화합물 및 이를 함유한표백제 및 표백세제 조성물 |
| US8946140B2 (en) * | 2009-05-14 | 2015-02-03 | Ecolab Usa Inc. | Compositions, systems and method for in situ generation of alkalinity |
| US10837949B1 (en) * | 2012-03-22 | 2020-11-17 | Piers Richard Warburton | Peracetic acid sensor with filter to remove hydrogen peroxide |
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- 1996-01-04 DE DE19600159A patent/DE19600159A1/de not_active Withdrawn
- 1996-12-23 ES ES96120743T patent/ES2207663T3/es not_active Expired - Lifetime
- 1996-12-23 DE DE59610733T patent/DE59610733D1/de not_active Expired - Lifetime
- 1996-12-23 EP EP96120743A patent/EP0783035B1/fr not_active Expired - Lifetime
- 1996-12-23 AT AT96120743T patent/ATE250660T1/de not_active IP Right Cessation
- 1996-12-27 JP JP8350981A patent/JPH09194886A/ja not_active Withdrawn
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0880579A2 (fr) * | 1996-02-16 | 1998-12-02 | Henkel Kommanditgesellschaft auf Aktien | Complexes de metaux de transition utilises comme activateurs pour composes peroxy |
| EP0927241A1 (fr) * | 1996-08-26 | 1999-07-07 | The Procter & Gamble Company | Regulation de l'activite de la cellulase par un terminateur |
| EP0909809A3 (fr) * | 1997-10-01 | 1999-07-21 | Unilever Plc | Activation de blanchiment |
| GB2386616A (en) * | 2002-03-21 | 2003-09-24 | Unilever Plc | Bleaching composition |
| EP3524347A1 (fr) | 2008-04-09 | 2019-08-14 | Basf Se | Utilisation de composés complexes hydrazides métalliques en tant que catalyseurs d'oxydation |
| WO2009141258A1 (fr) * | 2008-05-23 | 2009-11-26 | Henkel Ag & Co. Kgaa | Détergent préservant les textiles |
| WO2012000846A1 (fr) | 2010-06-28 | 2012-01-05 | Basf Se | Composition de blanchiment dépourvue de métal |
| WO2013060706A1 (fr) | 2011-10-25 | 2013-05-02 | Basf Se | Utilisation de copolymères d'acrylate comme agents anti-redéposition de la saleté et agents de libération de la saleté dans des processus de blanchisserie |
| WO2013060708A1 (fr) | 2011-10-25 | 2013-05-02 | Basf Se | Utilisation de copolymères en peigne ou séquencés comme agents anti-redéposition de la saleté et agents de libération de la saleté dans des processus de blanchisserie |
| WO2014154508A1 (fr) | 2013-03-27 | 2014-10-02 | Basf Se | Copolymères blocs comme agents de libération de la saleté dans des procédés de blanchisserie |
| US9790452B2 (en) | 2013-03-27 | 2017-10-17 | Basf Se | Block copolymers as soil release agents in laundry processes |
| US10214606B2 (en) | 2013-11-27 | 2019-02-26 | Basf Se | Random copolymers as soil release agents in laundry processes |
| WO2017186480A1 (fr) | 2016-04-26 | 2017-11-02 | Basf Se | Composition de blanchiment sans métal |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE250660T1 (de) | 2003-10-15 |
| EP0783035B1 (fr) | 2003-09-24 |
| DE59610733D1 (de) | 2003-10-30 |
| US5942152A (en) | 1999-08-24 |
| JPH09194886A (ja) | 1997-07-29 |
| ES2207663T3 (es) | 2004-06-01 |
| CA2194342A1 (fr) | 1997-07-05 |
| DE19600159A1 (de) | 1997-07-10 |
| EP0783035A3 (fr) | 1998-02-25 |
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