EP1445305B1 - Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren - Google Patents
Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren Download PDFInfo
- Publication number
- EP1445305B1 EP1445305B1 EP04001912A EP04001912A EP1445305B1 EP 1445305 B1 EP1445305 B1 EP 1445305B1 EP 04001912 A EP04001912 A EP 04001912A EP 04001912 A EP04001912 A EP 04001912A EP 1445305 B1 EP1445305 B1 EP 1445305B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bis
- weight
- pyridine
- bleaching
- acid
- 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.)
- Expired - Lifetime
Links
- 229910052723 transition metal Inorganic materials 0.000 title claims description 15
- 150000003624 transition metals Chemical class 0.000 title claims description 14
- 239000003054 catalyst Substances 0.000 title claims description 12
- 239000007844 bleaching agent Substances 0.000 title description 15
- 150000001875 compounds Chemical class 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 40
- -1 tetrafluoroborate Chemical group 0.000 claims description 38
- 238000004061 bleaching Methods 0.000 claims description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 239000003446 ligand Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 9
- 239000004753 textile Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical group 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical group [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 3
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical group [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 2
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 150000004967 organic peroxy acids Chemical class 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims 2
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims 1
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 26
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- 239000000460 chlorine Substances 0.000 description 21
- 239000011572 manganese Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 235000014113 dietary fatty acids Nutrition 0.000 description 13
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 12
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000012190 activator Substances 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 239000003945 anionic surfactant Substances 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000012459 cleaning agent Substances 0.000 description 9
- 150000002191 fatty alcohols Chemical class 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002736 nonionic surfactant Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 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 7
- 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 7
- 150000001298 alcohols Chemical class 0.000 description 6
- 238000004851 dishwashing Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 235000000346 sugar Nutrition 0.000 description 6
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 5
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
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- 239000004615 ingredient Substances 0.000 description 5
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- 239000003760 tallow Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 244000060011 Cocos nucifera Species 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011565 manganese chloride Substances 0.000 description 4
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- 159000000001 potassium salts Chemical class 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 108010084185 Cellulases Proteins 0.000 description 3
- 102000005575 Cellulases Human genes 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 150000001735 carboxylic acids Chemical class 0.000 description 3
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
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- PATMLLNMTPIUSY-UHFFFAOYSA-N phenoxysulfonyl 7-methyloctanoate Chemical compound CC(C)CCCCCC(=O)OS(=O)(=O)OC1=CC=CC=C1 PATMLLNMTPIUSY-UHFFFAOYSA-N 0.000 description 3
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- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical class COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 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
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000005474 octanoate group Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229940071089 sarcosinate Drugs 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 125000005624 silicic acid group Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- QSKQNALVHFTOQX-UHFFFAOYSA-M sodium nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O QSKQNALVHFTOQX-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007944 soluble tablet Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 235000019263 trisodium citrate Nutrition 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- the present invention relates to the use of certain transition metal complex compounds for enhancing the bleaching effect of peroxygen compounds in bleaching colored stains on textiles as well as on hard surfaces, as well as detergents and cleaners containing such complex compounds.
- Inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
- the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.
- the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators.
- bleach activators For this purpose, numerous compounds have been proposed, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles.
- NOBS sodium nonanoyloxybenzenesulfonate
- ISONOBS sodium isononanoyloxybenzenesulfonate
- acylated sugar derivatives such as pentaacetylglucose.
- WO 96/23859, WO 96/23860 and WO 96/23861 describe the use of corresponding Co (III) complexes in automatic dishwashing compositions.
- certain manganese complexes are known from EP 0 630 964 which, although they have no pronounced effect on bleach reinforcement of peroxygen compounds, do not discolor dyed textile fibers, they can cause the bleaching of soil or dye removed from the fiber in wash liquors.
- copper and cobalt complexes are known which can carry ligands from a variety of groups of substances and are to be used as bleaching and oxidation catalysts.
- WO 97/07191 proposes complexes of manganese, iron, cobalt, ruthenium and malenbdenum with salen-type ligands as activators for peroxygen compounds in hard surface cleaning solutions.
- EP 1 225 215 describes the use of transition metal complexes containing oxime ligands as a catalyst for peroxygen compounds.
- the present invention has the object of improving the oxidation and bleaching action of peroxygen compounds, especially inorganic peroxygen compounds, at low temperatures below 80 ° C. especially in the temperature range of about 10 ° C to 45 ° C, the goal.
- the required metal complexes should be easily accessible and easy to prepare.
- transition metal complexes with nitrogen-containing ligands contribute significantly to the cleaning performance against colored stains that are on textiles or on hard surfaces.
- transition metal complexes are used in detergents, bleaches, and cleaners containing peroxygen compounds, particularly in laundry and hard surface cleaners, particularly for utensils, and in solutions for bleaching colored stains.
- ligand L examples include pyridine, imidazole, picoline, imidazoline, pyrrole, pyrazole, triazole, hexamethyleneimine, piperidine, lutidines or similar nitrogen-containing heterocycles, which are unsubstituted or substituted by one or two C 1 -C 4 alkyl groups
- the halides such as chloride, bromide and iodide are used, but also nitrate, sulfate, perchlorate, ammonia and complex anions such as tetrafluoroborate and hexafluorophosphate or anions of organic C 1 -C 22 carboxylic acids such as citrates, acetates, propionates , Butyrates, hexanoates, octanoates, nonanoate and laurate.
- the anion ligands provide charge balance between the transition metal central atom and the ligand system.
- Particularly preferred complexes are compounds of the structure Fe (L) 2 X 2 or Mn (L) 2 X 2 such as bis (pyridine) dichloro-iron (II), bis (pyridine) dichloro-manganese (II), such as bis (morpholine) dichloro-iron (II), bis (morpholine) dichloro-manganese (II), bis (methylimidazole) dichloro-iron (II), bis (methylimidazole) dichloro-manganese (II), bis (ethylimidazole) dichloro-iron (II) , Bis (ethylimidazole) dichloro-manganese (II), bis (pyrazole) dichloro-manganese (II), bis (pyrazole) dichloro-manganese (II), bis (pyrazole) dichloro-iron (II), bis (pyridine) dibromoiron (II), bis (pyridine
- the peroxygen compound used are primarily alkali metal perborate mono- or tetrahydrate and / or alkali metal percarbonate, with sodium being the preferred alkali metal.
- alkali metal or ammonium peroxosulfates such as, for example, potassium peroxomonosulfate (technical name: Caroat® or Oxone®).
- concentration of these peroxygen compounds on the total formulation of detergents, bleaches and cleaners is 5 - 90%, preferably 10 - 70%.
- the amounts of peroxygen compounds are generally chosen so that between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen, are present in the solutions of the detergents and cleaners.
- bleach-enhancing Complex connection depends on the purpose of use. Depending on the desired degree of activation, it is used in amounts such that 0.01 mmol to 25 mmol, preferably 0.1 mmol to 2 mmol complex per mole of peroxygen compound are used, but in special cases, these limits can also be exceeded or fallen below.
- bleaching and cleaning agents are preferably 0.0025 to 0.25 wt .-%, in particular 0.01 to 0.5 wt .-% of the above-defined bleach-enhancing complex compound.
- washing, bleaching and cleaning agents may also contain hydrogen peroxide or organic-based oxidizing agents in the concentration range of 1 to 20%.
- hydrogen peroxide or organic-based oxidizing agents include all known peroxycarboxylic acids, e.g. Monoperoxyphthalic acid, dodecanediperoxyacid or phthalimidoperoxycarboxylic acids such as PAP and related systems or the amido peracids mentioned in EP-A-170386.
- bleaching here encompasses both the bleaching of dirt located on the textile surface and the bleaching of dirt located in the wash liquor and detached from the textile surface. The same applies analogously to the bleaching of soiling on hard surfaces. Other potential applications are in personal care, e.g. in the bleaching of hair and to improve the effectiveness of denture cleaners. Furthermore, the described metal complexes find use in commercial laundries, in wood and paper bleaching, bleaching of cotton and in disinfectants.
- the invention relates to a process for the purification of textiles as well as hard surfaces, in particular crockery, using said complex compounds together with peroxygen compounds in aqueous, optionally further detergent or detergent ingredients containing solution, and detergents and cleaners for hard surfaces, in particular detergents for dishes, those preferred for use in machine processes containing such complex compounds.
- the use according to the invention essentially consists in providing conditions for hard surfaces contaminated with colored soiling or, in the case of soiled textiles, conditions under which a peroxidic oxidizing agent and the complex compound of the formula (1) can react with one another, with the aim of obtaining more strongly oxidizing secondary products , Such conditions are especially present when the reactants meet in aqueous solution.
- This can be done by separately adding the peroxygen compound and the complex of formula (1) to the aqueous solution of the detergent and cleaner.
- the process according to the invention is particularly advantageously carried out using a detergent or hard surface cleaning agent which contains the complex compound of the formula (1) and, if appropriate, a peroxygen-containing oxidizing agent.
- the peroxygen compound may also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, when a non-oxygen detergent or cleaner is used.
- the washing and cleaning agents which may be in the form of granules, powdery or tablet-like solids, other shaped bodies, homogeneous solutions or suspensions, may contain, in principle, all known ingredients customary in such agents, as well as the said bleach-enhancing metal complex.
- the compositions may contain, in particular, builder substances, surface-active surfactants, peroxygen compounds, additional peroxygen activators or organic peracids, water-miscible organic solvents, sequestering agents, enzymes, and special additives with color- or fiber-sparing action.
- Other auxiliaries such as electrolytes, pH regulators, silver corrosion inhibitors, foam regulators, as well as dyes and fragrances are possible.
- a hard surface cleaning agent according to the invention may contain abrasive constituents, in particular quartz flours, wood flours, plastic flours, chalks and glass microspheres, and mixtures thereof.
- Abrasives are preferably not more than 20 wt .-%, in particular from 5 to 15 wt .-%, contained in the cleaning agents.
- the washing, bleaching and cleaning agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants in question.
- surfactants are present in detergent compositions according to the invention in proportions of preferably from 1 to 50% by weight, in particular from 3 to 30% by weight, whereas in hard-surface cleaners normally lower proportions, that is to say amounts of up to 20% by weight. , in particular up to 10 wt .-% and preferably in the range of 0.5 to 5 wt .-% are included.
- Dishwashing detergents typically use low-foam compounds.
- Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
- surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, olefinsulfonates, that is mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
- alkanesulfonates which are obtained from C 12 -C 18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- esters of alpha-sulfo fatty acids for example the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by sulfonating the methyl esters of fatty acids of vegetable and / or animal origin having 8 to 20 carbon atoms be prepared in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts.
- Suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof.
- Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 8 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
- alk (en) ylsulfates of said chain length which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis.
- 2,3-Alkyl sulfates prepared, for example, according to US Pat. Nos. 3,234,158 and 5,075,041 are suitable anionic surfactants.
- EO ethylene oxide
- the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 -C 18 fatty alcohol residues or mixtures of these.
- Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosinate).
- anionic surfactants are in particular soaps, for example in amounts of 0.2 to 5 wt .-%, into consideration.
- Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
- the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- Anionic surfactants are preferably present in detergents according to the invention in amounts of from 0.5 to 10% by weight and in particular in amounts of from 5 to 25% by weight.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position . or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
- alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
- the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO.
- the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
- the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G represents a glycose unit having 5 or 6 C atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4.
- polyhydroxy fatty acid amides of the formula (I) in the radical R 1 -CO for an aliphatic acyl radical having 6 to 22 carbon atoms
- R 2 for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
- [Z] for a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in R 3 is a linear or branched alkyl or alkenyl radical having 7 to 21 carbon atoms, R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 6 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or an aryl radical or a Oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1 -C 4 alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives this rest stands.
- [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to WO 95/07331, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
- nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.
- Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide and the fatty acid alkanolamides may also be suitable.
- hydroxyalkyl quats of the general structures (III) and (IV) are preferred.
- surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called “spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in WO 95/19953, WO 95/19954 and WO 95/19955. Other surfactant types may have dendrimeric structures.
- a detergent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
- Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates and polymeric alkali metal phosphates which may be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called Natriumhexametaphosphat and the corresponding potassium salts or mixtures of sodium and potassium salts.
- the water-insoluble, water-dispersible inorganic builder materials used are, in particular, crystalline or amorphous alkali aluminosilicates, in amounts of up to 50% by weight.
- the detergent grade crystalline sodium aluminosilicates particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X.
- Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.
- Suitable builder substances are also crystalline alkali metal silicates, which may be present alone or in a mixture with amorphous silicates.
- the alkali metal silicates useful as builders preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
- Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio of Na 2 O: SiO 2 , of 1: 2 to 1: 2.8.
- Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na 2 Si x O 2 ⁇ + 1 .
- YH 2 O is used, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4.
- Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
- both ⁇ - and ⁇ -sodium is preferably ⁇ -sodium silicates with a modulus from 1.9 to 3.2, according to Japanese Patent Application JP 04/238 809 or JP 04/260 610 are produced.
- amorphous silicates practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used.
- a crystalline sodium layer silicate with a modulus of 2 to 3 is used. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
- a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion®.
- alkali metal aluminosilicate in particular zeolite, is present as an additional builder substance, this is Weight ratio aluminosilicate to silicate, in each case based on anhydrous active substances, preferably 1:10 to 10: 1.
- the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
- Such builder substances are preferably contained in agents according to the invention in amounts of up to 60% by weight, in particular from 5 to 40% by weight.
- the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid.
- Polyphosphonic acids especially aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid can also be used.
- polymeric (poly) carboxylic acids in particular the polycarboxylates obtainable by oxidation of polysaccharides or dextrins, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality.
- the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, in each case based on the free acid.
- a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
- Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
- Also suitable are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
- the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
- the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
- Such polymers generally have a molecular weight between 1000 and 200,000.
- Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
- the organic builder substances can, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 wt .-% aqueous solutions are used. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
- organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1 to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular water-containing agents.
- Suitable water-soluble builder components in hard surface cleaners according to the invention are in principle all builders customarily used in detergents for dishwashing, for example the abovementioned alkali metal phosphates. Their amounts may be in the range of up to about 60 wt .-%, in particular 5 to 20 wt .-%, based on the total mean.
- water-soluble builder components in addition to polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the above-mentioned type of polycarboxylates, which act as co-builders in hard water regions, and naturally occurring hydroxycarboxylic acids, such as mono-, dihydroxysuccinic acid, alpha- Hydroxypropionic acid and gluconic acid.
- Preferred organic builder components include the salts of Citric acid, especially sodium citrate.
- sodium citrate anhydrous tri-sodium citrate and preferably trisodium citrate dihydrate are suitable. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
- the acids corresponding to the said co-builder salts may also be present.
- bleach activators that is to say compounds which release peroxocarboxylic acids under perhydrolysis conditions.
- Suitable are the usual bleach activators containing O- and / or N-acyl groups.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates , in particular nonanoyl or Isononanoyloxybenzolsulfonat (NOBS or ISONOBS) or their amido derivatives, such as in EP 170 386, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and also acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacety
- the enzymes optionally contained in the agents according to the invention include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT, Maxamyl®, Duramyl®, Purafectel OxAm, cellulases such as Celluzyme®, Carezyme®, K-AC® and / or those disclosed in International Patent Applications WO 96/34108 and WO 96/34092 known cellulases and / or lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
- proteases such as BLAP®, Optimase®, Opticlean®, Max
- the enzymes used may be adsorbed to carriers and / or embedded in encapsulants, as described for example in International Patent Applications WO 92/131347 or WO 94/23005, in order to protect them against premature inactivation. They are preferably present in detergents and cleaners according to the invention in amounts of up to 10% by weight, in particular from 0.05 to 5% by weight, enzymes which are particularly preferably stabilized against oxidative degradation being used.
- Machine dishwashing detergents according to the invention preferably comprise the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates.
- Alkali silicates may be present in amounts of up to 40% by weight. in particular 3 to 30 wt .-%, based on the total agent, be contained.
- the alkali carrier system preferably used in cleaning agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be present in an amount of up to 50% by weight, preferably 5 to 40% by weight.
- a further subject of the invention is a machine dishwashing composition containing from 15 to 65% by weight, in particular from 20 to 60% by weight of water-soluble builder component, from 5 to 25% by weight, in particular from 8 to 17% by weight.
- Oxygen-based bleaching agents respectively; based on the total agent, and 0.1 to 5 wt .-% of one or more of the cyclic sugar ketones defined above.
- Such an agent is preferably low alkaline, that is, its weight percent solution has a pH of 8 to 11.5, especially 9 to 11.
- inventive means for the automatic cleaning of dishes are 20 to 60 wt .-% of water-soluble organic builder, in particular alkali citrate, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.
- silver corrosion inhibitors can be used in dishwashing detergents according to the invention.
- Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, molybdenum, vanadium or cerium salts and / or complexes, as well as Salts and / or complexes of the metals present in the complexes suitable according to the invention with other than in formula (I) predetermined ligands.
- the agents foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-regulating compound, preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettklareamide and mixtures thereof and other other known commercially available foam inhibitors are added.
- a foam-regulating compound preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettklareamide and mixtures thereof and other other known commercially available foam inhibitors are added.
- the foam inhibitors in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
- Further optional ingredients in the compositions according to the invention are, for example, perfume oils.
- organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers.
- Such water-miscible solvents are preferably present in the detergents according to the invention not more than 20% by weight, in particular from 1 to 15% by weight.
- the compositions according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, Succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides.
- system- and environmentally compatible acids in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, Succinic acid, glutaric acid and / or adipic acid
- mineral acids in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides.
- pH regulators are preferably not more than 10% by weight, in particular from 0.5 to 6% by weight, in the compositions according to the invention.
- compositions according to the invention are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roller compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleach catalyst are to be expected, can be prepared.
- Solutions according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
- compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / l can also be achieved by using the builder components with at least a proportion of liquid mixture components in a first process stage while increasing the bulk density of this premix and subsequently - if desired after an intermediate drying - the other constituents of the agent, including the bleach catalyst, combined with the thus obtained premix.
- compositions according to the invention in tablet form, the procedure is preferably such that all ingredients are mixed together in a mixer and the mixture by means of conventional tablet presses, for example Eccentric or rotary presses, pressed with pressing pressures in the range of 200 ⁇ 10 5 Pa to 1500 ⁇ 10 5 Pa.
- a tablet thus produced has a weight of 1 to 5 g to 40 g, in particular from 20 g to 30 g, with a diameter from 3 to 5 mm to 40 mm.
- the bleaching performance of the compounds of the invention Cat 1 to Cat 5 was tested in comparison to the bleach activator TAED.
- 10 mg / l of the catalyst were dissolved in a wash liquor prepared by dissolving 2 g / l of a bleach-free basic detergent (WMP, WFK, Krefeld).
- WMP bleach-free basic detergent
- 1 g / l of sodium percarbonate (Degussa) the washing experiments were carried out in a Linitest apparatus (Heraeus) at 20 to 40 ° C. The washing time was 30 min, water hardness 18 ° dH.
- connection Remission difference (ddR%) 20 ° C 40 ° C BC-1 BC-4 BC-1 BC-4 Cat 1 3.6 1.5 5.7 3.0 Cat 2 3.8 2.9 4.5 3.6 Cat 3 3.8 1.4 8.1 3.9 Cat 4 2.8 1.6 7.0 3.7 TAED (V1) 2.5 1.1 4.0 2.4
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10304131A DE10304131A1 (de) | 2003-02-03 | 2003-02-03 | Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren |
DE10304131 | 2003-02-03 |
Publications (2)
Publication Number | Publication Date |
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EP1445305A1 EP1445305A1 (de) | 2004-08-11 |
EP1445305B1 true EP1445305B1 (de) | 2006-09-27 |
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EP04001912A Expired - Lifetime EP1445305B1 (de) | 2003-02-03 | 2004-01-29 | Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren |
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US (1) | US6875734B2 (es) |
EP (1) | EP1445305B1 (es) |
JP (1) | JP2004238623A (es) |
DE (2) | DE10304131A1 (es) |
ES (1) | ES2273103T3 (es) |
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DE102008045215A1 (de) | 2008-08-30 | 2010-03-04 | Clariant International Ltd. | Verwendung von Mangan-Oxalatenn als Bleichkatalysatoren |
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US9657435B2 (en) | 2010-06-28 | 2017-05-23 | Basf Se | Metal free bleaching composition |
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JP2015502414A (ja) | 2011-10-25 | 2015-01-22 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 洗濯プロセスにおける汚れ再付着防止剤および汚れ剥離剤としてのアクリレートコポリマーの使用 |
RU2014120925A (ru) | 2011-10-25 | 2015-12-10 | Басф Се | Применение гребенчатых или блок-сополимеров в качестве средств против повторного осаждения загрязнения и грязеотталкивающих средств в процессах стирки |
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- 2003-02-03 DE DE10304131A patent/DE10304131A1/de not_active Withdrawn
-
2004
- 2004-01-29 DE DE502004001553T patent/DE502004001553D1/de not_active Expired - Lifetime
- 2004-01-29 ES ES04001912T patent/ES2273103T3/es not_active Expired - Lifetime
- 2004-01-29 EP EP04001912A patent/EP1445305B1/de not_active Expired - Lifetime
- 2004-02-02 JP JP2004025638A patent/JP2004238623A/ja active Pending
- 2004-02-02 US US10/769,963 patent/US6875734B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE502004001553D1 (de) | 2006-11-09 |
ES2273103T3 (es) | 2007-05-01 |
US6875734B2 (en) | 2005-04-05 |
US20040198626A1 (en) | 2004-10-07 |
JP2004238623A (ja) | 2004-08-26 |
EP1445305A1 (de) | 2004-08-11 |
DE10304131A1 (de) | 2004-08-05 |
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