EP1105454A1 - Manganese complexes as catalysts for peroxygenated compounds to clean hard surfaces, especially dishes - Google Patents
Manganese complexes as catalysts for peroxygenated compounds to clean hard surfaces, especially dishesInfo
- Publication number
- EP1105454A1 EP1105454A1 EP99941530A EP99941530A EP1105454A1 EP 1105454 A1 EP1105454 A1 EP 1105454A1 EP 99941530 A EP99941530 A EP 99941530A EP 99941530 A EP99941530 A EP 99941530A EP 1105454 A1 EP1105454 A1 EP 1105454A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- hydrogen
- formula
- alkyl
- branched
- 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.)
- Withdrawn
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 43
- 150000002696 manganese Chemical class 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 title claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- -1 COOR1 Chemical group 0.000 claims abstract description 23
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012190 activator Substances 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 4
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical group 0.000 claims abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- 238000004061 bleaching Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 19
- 239000012459 cleaning agent Substances 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 claims description 13
- 239000007844 bleaching agent Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 3
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- KLYCPFXDDDMZNQ-UHFFFAOYSA-N Benzyne Chemical compound C1=CC#CC=C1 KLYCPFXDDDMZNQ-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000004685 tetrahydrates Chemical class 0.000 claims description 2
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims 1
- 150000004682 monohydrates Chemical class 0.000 claims 1
- 150000004967 organic peroxy acids Chemical class 0.000 claims 1
- 239000003599 detergent Substances 0.000 abstract description 8
- 238000004851 dishwashing Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 125000004429 atom Chemical group 0.000 abstract description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract 2
- 150000003254 radicals Chemical class 0.000 abstract 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 abstract 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 abstract 1
- XXJGBENTLXFVFI-UHFFFAOYSA-N 1-amino-methylene Chemical group N[CH2] XXJGBENTLXFVFI-UHFFFAOYSA-N 0.000 abstract 1
- GRHZLQBPAJAHDM-SPRQWYLLSA-N [(3as,4r,6ar)-2,3,3a,4,5,6a-hexahydrofuro[2,3-b]furan-4-yl] n-[(2s,4s,5s)-5-[[2-(2,6-dimethylphenoxy)acetyl]amino]-4-hydroxy-1,6-diphenylhexan-2-yl]carbamate Chemical group CC1=CC=CC(C)=C1OCC(=O)N[C@H]([C@@H](O)C[C@H](CC=1C=CC=CC=1)NC(=O)O[C@@H]1[C@@H]2CCO[C@@H]2OC1)CC1=CC=CC=C1 GRHZLQBPAJAHDM-SPRQWYLLSA-N 0.000 abstract 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 abstract 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical group O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 abstract 1
- 244000269722 Thea sinensis Species 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 235000013616 tea Nutrition 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 4
- 229940088598 enzyme Drugs 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000008233 hard water Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 3
- 102000013142 Amylases Human genes 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 108091005804 Peptidases Proteins 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000004365 Protease Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 235000019418 amylase Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 159000000001 potassium salts Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004367 Lipase Substances 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000005263 alkylenediamine group Chemical group 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
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- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 2
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- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 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 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- FFLHFURRPPIZTQ-UHFFFAOYSA-N (5-acetyloxy-2,5-dihydrofuran-2-yl) acetate Chemical compound CC(=O)OC1OC(OC(C)=O)C=C1 FFLHFURRPPIZTQ-UHFFFAOYSA-N 0.000 description 1
- ZQEOKONOFKQRIR-NUEKZKHPSA-N (5R,6R,7R)-3,5,6-triacetyl-3,5,6,7-tetrahydroxy-7-(hydroxymethyl)nonane-2,4,8-trione Chemical compound C(C)(=O)[C@@]([C@]([C@@](C(C(O)(C(C)=O)C(C)=O)=O)(O)C(C)=O)(O)C(C)=O)(O)CO ZQEOKONOFKQRIR-NUEKZKHPSA-N 0.000 description 1
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- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
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- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 108010020346 Polyglutamic Acid Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 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
- 244000300264 Spinacia oleracea Species 0.000 description 1
- 235000009337 Spinacia oleracea Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 235000006468 Thea sinensis Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 108090000637 alpha-Amylases Proteins 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 235000020279 black tea Nutrition 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 108010005400 cutinase Proteins 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 description 1
- AJFXNBUVIBKWBT-UHFFFAOYSA-N disodium;boric acid;hydrogen borate Chemical compound [Na+].[Na+].OB(O)O.OB(O)O.OB(O)O.OB([O-])[O-] AJFXNBUVIBKWBT-UHFFFAOYSA-N 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 239000003792 electrolyte 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
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 235000012209 glucono delta-lactone Nutrition 0.000 description 1
- 229960003681 gluconolactone Drugs 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000008427 organic disulfides Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000011837 pasties Nutrition 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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume 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
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003352 sequestering agent Substances 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
- 235000019982 sodium hexametaphosphate Nutrition 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
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000004753 textile Substances 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
- 150000003624 transition metals Chemical class 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles 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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/168—Organometallic compounds or orgometallic complexes
Definitions
- the present invention relates to the use of certain manganese complexes as catalysts for reactions with peroxygen compounds for bleaching colored stains on hard surfaces.
- Hard surface cleaners containing such catalysts are another subject of the invention.
- Inorganic peroxygen compounds especially 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 disinfection and bleaching purposes.
- the oxidizing effect of these substances in dilute solutions depends strongly on the temperature. For example, with H 2 O 2 or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for which numerous proposals have become known in the literature.
- N- or O-acyl compounds for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopamide and sulfuryl cyanuryl amides , in addition to carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetyl glucose.
- the bleaching effect of aqueous peroxide liquors can be increased to such an extent that even at temperatures around 60 ° C essentially the same effects occur as with the
- transition metal salts and complexes as so-called bleaching catalysts.
- From DE-A-19529904 and WO 97/07191 cleaning agents for dishes are already known which contain transition metal complexes of the salen type as an activator for peroxygen compounds. However, even these are not yet able to meet all requirements.
- manganese complexes of the formulas below have a significantly improved bleach-catalyzing effect on colored soils which are found on hard surfaces. If these complexes are added in catalytic amounts to a dishwashing detergent which contains a peroxygen compound and optionally TAED (N, N, N ', N'-tetraacetylethylenediamine), tea stains on porcelain at 45 ° C. are largely removed in the dishwasher. This also applies when using hard water, where it is known that the removal of tea deposits is more difficult to achieve than in soft water.
- TAED N, N, N ', N'-tetraacetylethylenediamine
- the invention accordingly relates to the use of manganese complexes of the formula (1) or (2)
- R 8 is hydrogen, CH 2 OH, CH 2 NH 2 or SO 3 M, where M is hydrogen, an alkali metal atom, ammonium or the cation of an organic amine,
- R 5 and R 6 are independently hydrogen, linear or branched CC 4 alkyl; linear or branched C 1 -C 8 alkylene-R 2 , in which R 2 is ORi, COORi or NR 3 R 4 , mean unsubstituted aryl or aryl which is substituted by cyano, halogen, ORi, COORi, nitro, linear or branched -C 8 -alkyl, NR 3 R 4 , wherein R 3 and R 4 independently of one another are hydrogen or linear or branched CC 2 -alkyl, or by -N ® R ⁇ R 3 R 4 , wherein R 1t R 3 and R 4 are the have the meanings given,
- R 7 independently of one another are hydrogen or -CC alkyl
- Zi and Z 2 independently of one another are hydrogen, hydroxy, dC 4 alkoxy or di (C 1 -C 4 alkyl) amino, and
- A stands for a charge-balancing anion ligand, as catalysts for reactions with peroxygen compounds in cleaning solutions for hard surfaces, in particular for dishes, wherein not all of the substituents Z 1f Z 2 , R 5 and R 6 in the compounds of the formula (1) may simultaneously be hydrogen if Y 1, 2-phenylene is.
- the preferred compounds according to formula (1) include those in which 7. ⁇ and / or Z 2 independently of one another denote hydrogen, hydroxyl, methoxy, ethoxy, dimethylamino or diethylamino.
- the preferred compounds of the formulas (1) and (2) also include those in which Y is ethylene, 1,2- or 1,3-propylene, 1-methyl-1,2-propylene, 2-methyl-1,2 propylene, 1,2-cyclohexylene or 1,2-phenylene. Particularly preferred meanings of Y are ethylene, 1,3-propylene, 2-methyl-1,2-propylene, 1,2-cyclohexylene or 1,2-phenylene.
- Y is a 1,2-cyclohexylene radical, this can be present in any of its stereoisomeric cis / trans forms.
- R 5 and R 6 independently of one another are preferably hydrogen, methyl, ethyl or unsubstituted phenyl, in particular hydrogen.
- the alkyl residues with 1 to 4 carbon atoms include in particular the methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl and tert-butyl group.
- Preferred meanings of ⁇ are methyl or especially hydrogen.
- R 7 preferably denotes hydrogen, methyl or ethyl, especially methyl.
- R 8 is preferably hydrogen.
- the charge-balancing anion ligand A in the compounds of the formulas (1) and (2) can be mono- or polyvalent, in which case it can neutralize a number of manganese atoms with the organic ligands mentioned. It is preferably a halide, in particular chloride, a hydroxide, hexafluorophosphate, perchlorate or the anion of a carboxylic acid, such as formate, acetate, benzoate or citrate.
- the compounds of the formula (1) or (2) used according to the invention are known or can be prepared by processes known in principle by the reaction of salicylaldehyde, which optionally carries the substituents Z 1 or Z 2 defined above, or two fused rings as in the compounds of the formula (2), with diamines H 2 NY-NH 2 and reaction of the salen ligand thus obtainable with manganese salts, as described, for example, in European patent application EP-A-630964.
- the compounds of the formula (1) or (2) can be used individually or in mixtures with two or more compounds of the formula (1) or (2). In addition, they can also be used together with one or more uncomplexed salen ligands, for example with those ligands which are contained in the compounds of the formula (1) or (2).
- the invention further relates to detergents for hard surfaces, in particular detergents for dishes, and preferably those for use in machine cleaning processes which contain one of the compounds of the formula (1) or (2) described above as a bleaching catalyst, and a process for cleaning hard surfaces Surfaces, especially of dishes, using such a bleaching catalyst.
- the use according to the invention essentially consists in creating, in the presence of a hard surface contaminated with colored soils, conditions under which a peroxide-containing oxidizing agent and the bleaching catalyst according to formula (1) or (2) can react with one another with the aim of producing secondary products with a stronger oxidizing action receive.
- Such conditions exist particularly when both reactants meet in aqueous solution. This can be done by separately adding the peroxygen compound and the bleaching catalyst to an optionally detergent-containing solution.
- the method according to the invention is particularly advantageously carried out using a cleaning agent according to the invention for hard surfaces, which contains the bleaching catalyst and an oxidizing agent containing peroxygen.
- the peroxygen compound can also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, if a peroxide-free cleaning agent is used.
- the conditions can be varied widely depending on the intended use. In addition to purely aqueous solutions, mixtures of water and suitable organic solvents are also suitable as the reaction medium.
- the amounts of peroxygen compounds used are generally selected so that the solutions contain between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5,000 ppm active oxygen.
- the amount of bleaching catalyst used also depends on the application. Depending on the desired degree of activation, 0.00001 mol to 0.025 mol, preferably 0.0001 mol to 0.02 mol, of activator are used per mol of peroxygen compound, but these limits can also be exceeded or fallen below in special cases.
- the invention further relates to a cleaning agent for hard surfaces, in particular for dishes, which contains 0.001% by weight to 1% by weight, in particular 0.005% by weight to 0.1% by weight, of a bleaching catalyst according to formula (1) or (2) in addition to the usual ingredients compatible with the bleaching catalyst.
- a bleaching catalyst according to formula (1) or (2) in addition to the usual ingredients compatible with the bleaching catalyst.
- the bleaching catalyst can be adsorbed on carriers in a manner known in principle and / or embedded in coating substances.
- the cleaning agents according to the invention which can be in the form of solids or suspensions in powder or tablet form, homogeneous solutions or suspensions, can, in addition to the bleaching catalyst used according to the invention, in principle contain all the known ingredients which are customary in such agents.
- the agents according to the invention can contain, in particular, builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as silver corrosion inhibitors, foam regulators, additional peroxygen activators as well as colorants and fragrances.
- a cleaning agent according to the invention for hard surfaces can also contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and micro-glass balls, and mixtures thereof.
- Abrasives are preferably not contained in the cleaning agents according to the invention in excess of 20% by weight, in particular from 5% by weight to 15% by weight.
- Another subject matter of the invention is a low-alkaline agent for machine cleaning of dishes, the 1% by weight solution of which has a pH of 8 to 11.5, preferably 9 to 10.5, containing 15% by weight to 60% by weight, in particular 30 %
- oxygen-based bleaching agent in each case based on the total agent comprising a bleaching catalyst according to formula (1) or (2), in particular in amounts of 0.005% by weight to 0.1% by weight.
- all builders commonly used in machine dishwashing detergents for example polymeric alkali metal phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts, are suitable as water-soluble builder components, in particular in such low-alkaline cleaning agents.
- examples include tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, sodium tripolyphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts and mixtures of sodium and potassium salts.
- Their amounts can range up to about 35% by weight, based on the total agent.
- Other possible water-soluble builder components are, for example, organic polymers of native or synthetic origin, especially polycarboxylates, which act as co-builders, particularly in hard water regions.
- polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are suitable.
- Commercial products are, for example, Sokalan® CP 5 and PA 30 from BASF.
- Polymers of native origin that can be used as co-builders include, for example, oxidized starch, as known, for example, from international patent application WO 94/05762, and polyamino acids such as polyglutamic acid or polyaspartic acid.
- Other possible builder components are naturally occurring hydroxycarboxylic acids such as mono- and di-hydroxy succinic acid, ⁇ -hydroxypropionic acid and gluconic acid.
- the salts of citric acid, in particular sodium citrate are suitable as builder components.
- Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
- the pH adjusted to the mean can also be the acids corresponding to the co-builder salts mentioned.
- Suitable bleaches based on oxygen are primarily alkali perborate or tetrahydrate and / or alkali percarbonate, with sodium being the preferred alkali metal.
- the use of sodium percarbonate has advantages in particular in cleaning agents for dishes, since it has a particularly favorable effect on the corrosion behavior on glasses.
- known peroxycarboxylic acids for example dodecanediperic acid or phthalimidopercarboxylic acids, which can optionally be substituted on the aromatic, can also be present.
- bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates, and magnesium salts such as magnesium sulfate may also be useful.
- bleach-activating active substances that is to say compounds which contain perbenzoic and / or peroxocarboxylic acids which are optionally substituted under perhydrolysis conditions, with 1 to 10 C atoms, especially 2 to 4 carbon atoms, can be used.
- bleach activators cited at the outset which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
- the low-alkaline machine dishware according to the invention preferably contains cleaning agents the usual alkali carriers such as alkali silicates, alkaicarbonates and / or alkali hydrogen carbonates.
- Alkali silicates can be used in amounts of up to 30% by weight. , based on the total agent.
- the use of the highly alkaline metasilicates as alkali carriers is preferably avoided entirely.
- the alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, which is contained in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight.
- the ratio of carbonate to bicarbonate used varies, but an excess of sodium bicarbonate is usually used, so that the weight ratio between bicarbonate and carbonate is generally 1: 1 to 15: 1.
- agents according to the invention 20% by weight to 40% by weight of water-soluble organic builder, in particular alkali citrate, 5% by weight to 15% by weight alkali carbonate and 20% by weight to 40% by weight alkali silicate are contained.
- surfactants in particular low-foaming nonionic surfactants, can also be added to the agents according to the invention, which serve to better detach fatty soils, as wetting agents and, if appropriate, as granulating aids in the course of the preparation of the cleaning agents.
- Their amount can be up to 10% by weight, in particular up to 5% by weight, and is preferably in the range from 0.5% by weight to 3% by weight.
- Extremely low-foaming compounds are usually used, in particular for use in machine dishwashing processes. These preferably include C 12 -C 8 alkyl polyethylene glycol polypropylene glycol ether, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
- surfactants from the family of glucamides such as, for example, alkyl-N-methyl-glucamides, in which the alkyl part preferably consists of a fatty alcohol with the C chain length C 6 -C 14 . It is partially advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides.
- the compounds of the formula (1) or (2) are generally used in amounts which are too low to provide protection against silver corrosion, so that silver corrosion inhibitors are additionally present in dishwashing detergents according to the invention can be used, the effect of which can be enhanced by the compounds of the formula (1) or (2).
- Preferred silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, optionally substituted benzotriazole, manganese, titanium, zirconium, hafnium, vanadium, cobalt or cerium salts and or complexes in which the metals mentioned are in one of the oxidation states II , III, IV, V or VI are present.
- the agents according to the invention can contain enzymes such as proteases, amylases, pullulanases, cutinases and lipases, for example proteases such as BLAP®, Optimase®, Opticiean®, Maxacal®, Maxapem®, Esperase® and / or Savinase®, amylases such as Termamyl® , Amylase-LT®, Maxamyl® and / or Duramyl®, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
- proteases such as BLAP®, Optimase®, Opticiean®, Maxacal®, Maxapem®, Esperase® and / or Savinase®
- amylases such as Termamyl® , Amylase-LT®, Maxamyl® and / or Duramyl®
- lipases such as Lipolase®, Lipomax®, Luma
- the enzymes which may be used, as described, for example, in international patent applications WO 92/11347 or WO 94/23005, can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation. They are preferably contained in the cleaning agents according to the invention not more than 2% by weight, in particular from 0.1% by weight to 1.2% by weight.
- the cleaning agents foam too much during use, they can contain up to 6% by weight, preferably about 0.5% to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica , Paraffin, paraffin-alcohol combinations, hydrophobized silica, the bis fatty acid amides and other other known commercially available defoamers.
- a foam-suppressing compound preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica , Paraffin, paraffin-alcohol combinations, hydrophobized silica, the bis fatty acid amides and other other known commercially available defoamers.
- Other optional ingredients in the agents according to the invention are, for example, perfume oils.
- the organic solvents which can be used in the agents according to the invention include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms , in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers derivable from the compound classes mentioned.
- Such water-miscible solvents are preferably not present in the cleaning agents according to the invention in excess of 20% by weight, in particular from 1% by weight to 15% by weight.
- the agents 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 contain mineral acids, especially sulfuric acid, or alkali hydrogen sulfates, or bases, especially ammonium or alkali hydroxides.
- Such pH regulators are preferably not contained in the agents according to the invention in excess of 10% by weight, in particular from 0.5% by weight to 6% by weight.
- the preparation of the solid compositions according to the invention is not difficult and can be carried out in a manner known in principle, for example by spray drying or granulation, the peroxygen compound and bleaching catalyst optionally being added separately later.
- Cleaning agents according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
- the agents according to the invention are preferably in the form of powdery, granular or tablet-like preparations which are known in a manner known per se, for example by mixing, granulating, roller compacting and / or by spray drying the thermally loadable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleaching catalyst can be expected to be produced.
- the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 ⁇ 10 5 Pa to 1 500 • 10 5 Pa pressed.
- a tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.
- Agents according to the invention can be produced 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 in a first process step by adding the builder components with at least a portion of liquid mixture components Increasing the bulk density of this premix is mixed and subsequently - if desired after an intermediate drying - the further constituents of the composition, including the bleaching catalyst, are combined with the premix obtained in this way.
- Agents for cleaning dishes according to the invention can be used both in household dishwashers and in commercial dishwashers. It is added by hand or using suitable dosing devices.
- the application concentrations in the cleaning liquor are generally about 1 to 8 g / l, preferably 2 to 5 g / l.
- a machine wash program is generally supplemented and ended by a few intermediate rinse cycles with clear water following the cleaning cycle and a rinse cycle with a customary rinse aid. After drying, when using the agents according to the invention, completely clean and hygienically perfect dishes are obtained. Examples:
- connections (108) and (109) have the following structure:
- Example 1 Soiling procedure: A tea infusion (12 g tea leaves / liter) is made from black tea (Twinings brand) and hard water (total hardness: 18 ° dH) with stirring at 99 ° C. Allow to infuse for five minutes and filter the tea. Then about 100 ml of tea are poured into a porcelain cup. The tea is left in the cups for 30 minutes. The cups are then emptied in three steps of approx. 35 ml. There is a waiting period of five minutes between the emptying steps. The completely empty cups are dried at 70 ° C for 60 minutes. Reini ⁇ un ⁇ sprozedere: The cups were cleaned in a Miele G-690 D dishwasher with the F ⁇ in program at 45 ° C using hard water.
- Amylase (0.8% active) 0.5
- Example 4 The procedure is as described in Example 1 of EP-A-630964, but instead of salicylaldehyde, an equivalent amount of the 1: 1 mixture of salicylaldehyde and 2-hydroxy-4-diethylamino-benzaldehyde and instead of ethylenediamine, an equivalent amount of 2-amino-2-methyl-3-aminopropane.
- the manganese complex is then formed as described there, and a mixture of the following 4 manganese complexes is obtained:
- Example 1 If the procedure described in Example 1 is followed, but an equivalent amount of this mixture is used as the catalyst, a good cleaning action is also obtained.
- Example 5 Another good cleaning effect is achieved if, instead of the mixture from Example 4, one is used which contains only the last two of the complexes listed. This mixture is accessible by purifying the mixture of the uncomplexed ligands from the first stage of the preparation according to Example 4.
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Abstract
Manganese complexes of formula (1) or (2) are used as activators for peroxygenated compounds in dishwashing detergents, wherein Y represents linear or branched alkylene of formula -C(R1)2]m, wherein m is a whole number ranging from 2-8 and the radicals R1 represent independently from each other hydrogen or C1-C4-alkyl, -CX=CX-, whereby X is cyano, linear or branched C1-C8 -alkyl or di-(linear or branched C1-C8 alkyl)-amino; -(CH2)q-NR1-(CH2)q-, wherein R1 has the meaning thus cited and q is 1, 2, 3 or 4 or stands for a 1,2-cyclohexylene or 1,2 phenyl radical of formula (a) or (b), wherein R8 represents hydrogen, CH2OH, CH2NH2 or SO3M, wherein M represents hydrogen, an alkaline metal atom, ammonium or the cation of an organic amine, R?5 and R6¿ represent independently from each other hydrogen, linear or branched C¿1?-C4 -lkyl; linear or branched C1-C8alkene-R2, wherein R2 is OR1, COOR1 or NR3R4, unsubstituted aryl or aryl that is substituted by cyano, halogen, OR1, COOR1, nitro, linear or branched C1-C8-alkyl, NR3R4, wherein R3 and R4 mean independently from each other hydrogen or linear or branched C1-C12-alkyl; or substituted by -N?oR¿1R3R4, wherein R1, R3, R4 have the meanings thus cited, the radicals R7 represent independently from each other hydrogen or C1-C4 alkyl, Z1 and Z2 represent independently from each other hydrogen, hydroxy, C1-C4 alkoxy or di-(C1-C4-alkyl)amino and A stands for a charge-equalising anion ligand.
Description
MANGANKOMPLEXE ALS KATALYSATOREN FÜR PERSAUERSTOFFVERBINDUNGEN ZUR REINIGUNG VON HARTEN OBERFLÄCHEN INSBESONDERE VON GESCHIRRMANGANE COMPLEXES AS CATALYSTS FOR PERCENTAGE COMPOUNDS FOR CLEANING HARD SURFACES, IN PARTICULAR DISHES
Die vorliegende Erfindung betrifft die Verwendung von bestimmten Mangankomplexen als Katalysatoren für Reaktionen mit Persauerstoffverbindungen zum Bleichen von gefärbten Anschmutzungen an harten Oberflächen. Reinigungsmittel für harte Oberflächen, die derartige Katalysatoren enthalten, stellen einen weiteren Erfindungsgegenstand dar.The present invention relates to the use of certain manganese complexes as catalysts for reactions with peroxygen compounds for bleaching colored stains on hard surfaces. Hard surface cleaners containing such catalysts are another subject of the invention.
Anorganische Persauerstoffverbindungen, insbesondere Wasserstoffperoxid und feste Persauerstoffverbindungen, die sich in Wasser unter Freisetzung von Wasserstoffperoxid lösen, wie Natriumperborat und Natriumcarbonat-Perhydrat, werden seit langem als Oxidationsmittel zu Desinfektions- und Bleichzwecken verwendet. Die Oxidationswirkung dieser Substanzen hängt in verdünnten Lösungen stark von der Temperatur ab. So erzielt man beispielsweise mit H2O2 oder Perborat in alkalischen Bleichflotten erst bei Temperaturen oberhalb von etwa 80° C eine ausreichend schnelle Bleiche verschmutzter Textilien. Bei niedrigeren Temperaturen kann die Oxidationswirkung der anorganischen Persauerstoffverbindungen durch Zusatz sogenannter Bleichaktivatoren verbessert werden, für die zahlreiche Vorschläge in der Literatur bekannt geworden sind. Es handelt sich vor allem um Verbindungen aus den Stoffklassen der N- oder O-Acylverbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Hydrotriazine, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, ausserdem um Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, Carbonsäureester, insbesondere Natrium-nonanoyloxy-benzolsulfonat, Natrium-isononanoyloxy-benzolsulfonat und acylierte Zuckerderivate, wie Pentaacetylgiukose. Durch Zusatz dieser Substanzen kann die Bleichwirkung wässriger Peroxidflotten so weit gesteigert werden, dass bereits bei Temperaturen um 60° C im wesentlichen die gleichen Wirkungen wie mit der Peroxidflotte allein bei 95° C eintreten.Inorganic peroxygen compounds, especially 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 disinfection and bleaching purposes. The oxidizing effect of these substances in dilute solutions depends strongly on the temperature. For example, with H 2 O 2 or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for which numerous proposals have become known in the literature. These are primarily compounds from the substance classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopamide and sulfuryl cyanuryl amides , in addition to carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetyl glucose. By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that even at temperatures around 60 ° C essentially the same effects occur as with the peroxide liquor alone at 95 ° C.
Auch diese Temperaturen sind für das manuelle Reinigen harter Oberflächen, beispielweise von Geschirr, noch zu hoch und werden normalerweise auch in maschinellen Geschirrspül- verfahren nicht immer erreicht. Im Bemühen um energiesparende Verfahren zum maschinellen Reinigen von Geschirr gewinnen in den letzten Jahren Anwendungstemperaturen von unterhalb 60° C, insbesondere unterhalb 50° C bis hinunter zur Kaltwassertemperatur, an Bedeutung.
Bei diesen niedrigen Temperaturen lässt die Wirkung der bisher bekannten Aktivatorverbindungen in der Regel erkennbar nach, besonders bei schwer bleichbaren Anschmutzungen, wie beispielsweise Teerückständen auf Porzellan oder Glas. Es hat deshalb nicht an Bestrebungen gefehlt, für diesen Temperaturbereich wirksamere Aktivatoren zu entwickeln, ohne dass bis heute ein überzeugender Erfolg zu verzeichnen gewesen wäre.These temperatures, too, are still too high for manual cleaning of hard surfaces, for example dishes, and are usually not always reached even in automatic dishwashing processes. In the past few years, application temperatures of below 60 ° C., in particular below 50 ° C., down to the cold water temperature have become increasingly important in the search for energy-saving methods for machine cleaning of dishes. At these low temperatures, the effect of the activator compounds known to date generally diminishes noticeably, particularly in the case of soiling which is difficult to bleach, such as, for example, tea residues on porcelain or glass. There has been no shortage of efforts to develop more effective activators for this temperature range without convincing success to date.
Ein Ansatzpunkt dazu könnte sich durch den Einsatz von Übergangsmetallsalzen und -komplexen als sogenannte Bleichkatalysatoren ergeben. Aus DE-A-19529904 und WO 97/07191 sind bereits Reinigungsmittel für Geschirr bekannt, die Übergangsmetallkomplexe vom Salen-Typ als Aktivator für Persauerstoffverbindungen enthalten. Auch diese vermögen jedoch noch nicht, allen Anforderungen gerecht zu werden.One starting point could be the use of transition metal salts and complexes as so-called bleaching catalysts. From DE-A-19529904 and WO 97/07191 cleaning agents for dishes are already known which contain transition metal complexes of the salen type as an activator for peroxygen compounds. However, even these are not yet able to meet all requirements.
Es wurde nun gefunden, dass überraschenderweise Mangankomplexe der nachstehenden Formeln eine deutlich verbesserte bleichkatalysierende Wirkung auf gefärbte Anschmutzungen haben, die sich an harten Oberflächen befinden. Werden diese Komplexe in katalytischen Mengen zu einem Geschirrspülmittel gegeben, das eine Persauerstoffverbindung und gegebenenfalls TAED (N,N,N',N'-Tetraacetylethylendiamin) enthält, so werden Teeanschmutzungen an Porzellan bei 45° C in der Geschirrspülmaschine weitgehend entfernt. Dies gilt auch bei Verwendung von Hartwasser, wo bekanntlich die Entfernung von Teebelag schwieriger zu erreichen ist als in Weichwasser.It has now been found that, surprisingly, manganese complexes of the formulas below have a significantly improved bleach-catalyzing effect on colored soils which are found on hard surfaces. If these complexes are added in catalytic amounts to a dishwashing detergent which contains a peroxygen compound and optionally TAED (N, N, N ', N'-tetraacetylethylenediamine), tea stains on porcelain at 45 ° C. are largely removed in the dishwasher. This also applies when using hard water, where it is known that the removal of tea deposits is more difficult to achieve than in soft water.
Gegenstand der Erfindung ist demgemäss die Verwendung von Mangankomplexen der Formel (1) oder (2)The invention accordingly relates to the use of manganese complexes of the formula (1) or (2)
oder
worin or wherein
Y lineares oder verzweigtes Alkylen der Formel -[C(R1)2]m bedeutet, wobei m eine ganze Zahl von 2 bis 8 bedeutet und R unabhängig voneinander Wasserstoff oder CrC4-Alkyl ist, -CX=CX-, worin X Cyano, lineares oder verzweigtes Cι-C8-alkyl oder Di-(lineares oder verzweigtes Cι-C8-alky)l-amino ist; -(CH2)q-NR1-(CH2)q-, worin Ri die angegebene Bedeutung hat und q 1 , 2, 3 oder 4 ist; oder einen 1 ,2-Cyclohexylen- oder 1 ,2- Phenylenrest der FormelY is linear or branched alkylene of the formula - [C (R 1 ) 2 ] m , where m is an integer from 2 to 8 and R is independently hydrogen or CrC 4 alkyl, -CX = CX-, where X is cyano , linear or branched C 1 -C 8 alkyl or di (linear or branched C 1 -C 8 alkyl) l-amino; - (CH 2 ) q-NR 1 - (CH 2 ) q-, wherein Ri has the meaning given and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene or 1,2-phenylene radical of the formula
worin R8 Wasserstoff , CH2OH, CH2NH2oder SO3M bedeutet, wobei M Wasserstoff, ein Alkalimetall Atom, Ammonium oder das Kation eines organischen Amins darstellt,wherein R 8 is hydrogen, CH 2 OH, CH 2 NH 2 or SO 3 M, where M is hydrogen, an alkali metal atom, ammonium or the cation of an organic amine,
R5 und R6 unabhängig voneinander Wasserstoff, lineares oder verzweigtes C C4-alkyl; lineares oder verzweigtes C1-C8-alkylene-R2, worin R2 ORi, COORi oder NR3R4ist, unsubstituiertes Aryl oder Aryl bedeuten, das substituiert ist durch Cyano, Halogen, ORi, COORi , Nitro, lineares oder verzweigtes Cι-C8-alkyl, NR3R4, worin R3 und R4 unabhängig voneinander Wasserstoff oder lineares oder verzweigtes C C 2-alkyl bedeuten, oder durch -N®RιR3R4, worin R1t R3 und R4 die angegebenen Bedeutungen besitzen,R 5 and R 6 are independently hydrogen, linear or branched CC 4 alkyl; linear or branched C 1 -C 8 alkylene-R 2 , in which R 2 is ORi, COORi or NR 3 R 4 , mean unsubstituted aryl or aryl which is substituted by cyano, halogen, ORi, COORi, nitro, linear or branched -C 8 -alkyl, NR 3 R 4 , wherein R 3 and R 4 independently of one another are hydrogen or linear or branched CC 2 -alkyl, or by -N ® RιR 3 R 4 , wherein R 1t R 3 and R 4 are the have the meanings given,
R7 unabhängig voneinander Wasserstoff oder Cι-C -Alkyl,R 7 independently of one another are hydrogen or -CC alkyl,
Zi und Z2 unabhängig voneinander Wasserstoff, Hydroxy, d-C4 Alkoxy oder Di-(C1-C4- alkyl)amino, undZi and Z 2 independently of one another are hydrogen, hydroxy, dC 4 alkoxy or di (C 1 -C 4 alkyl) amino, and
A für einen iadungsausgleichenden Anionliganden steht,
als Katalysatoren für Reaktionen mit Persauerstoffverbindungen in Reinigungslösungen für harte Oberflächen, insbesondere für Geschirr, wobei in den Verbindungen der Formel (1) nicht alle Substituenten Z1f Z2, R5 und R6 gleichzeitig Wasserstoff sein dürfen, wenn Y 1 ,2-Phenylen ist.A stands for a charge-balancing anion ligand, as catalysts for reactions with peroxygen compounds in cleaning solutions for hard surfaces, in particular for dishes, wherein not all of the substituents Z 1f Z 2 , R 5 and R 6 in the compounds of the formula (1) may simultaneously be hydrogen if Y 1, 2-phenylene is.
Zu den bevorzugten Verbindungen gemäss Formel (1 ) gehören solche, in denen 7.\ und/oder Z2 unabhängig voneinander Wasserstoff, Hydroxy, Methoxy, Ethoxy, Dimethylamino oder Diethylamino bedeuten.The preferred compounds according to formula (1) include those in which 7. \ and / or Z 2 independently of one another denote hydrogen, hydroxyl, methoxy, ethoxy, dimethylamino or diethylamino.
Zu den bevorzugten Verbindungen gemäss Formel (1) und (2) gehören ferner solche, in denen Y Ethylen, 1,2- oder 1,3-Propylen, 1-Methyl-1,2-propylen, 2-Methyl-1 ,2-propylen, 1,2- Cyclohexylen oder 1 ,2-Phenylen bedeutet. Besonders bevorzugte Bedeutungen von Y sind Ethylen, 1 ,3-Propylen, 2-Methyl-1,2-propylen, 1 ,2-Cyclohexylen oder 1,2-Phenylen.The preferred compounds of the formulas (1) and (2) also include those in which Y is ethylene, 1,2- or 1,3-propylene, 1-methyl-1,2-propylene, 2-methyl-1,2 propylene, 1,2-cyclohexylene or 1,2-phenylene. Particularly preferred meanings of Y are ethylene, 1,3-propylene, 2-methyl-1,2-propylene, 1,2-cyclohexylene or 1,2-phenylene.
Bedeutet Y einen 1 ,2-Cyclohexylenrest, so kann dieser in jeder seiner stereoisomeren cis/trans-Formen vorliegen.If Y is a 1,2-cyclohexylene radical, this can be present in any of its stereoisomeric cis / trans forms.
R5 und R6 bedeuten unabhängig voneinander vorzugsweise Wasserstoff, Methyl, Ethyl oder unsubstituiert.es Phenyl, insbesondere Wasserstoff.R 5 and R 6 independently of one another are preferably hydrogen, methyl, ethyl or unsubstituted phenyl, in particular hydrogen.
Zu den Alklresten mit 1 bis 4 C-Atomen gehören insbesondere die Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, sec-Butyl-, iso-Butyl- und tert-Butyl-Gruppe.The alkyl residues with 1 to 4 carbon atoms include in particular the methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl and tert-butyl group.
Bevorzugte Bedeutungen von ^ sind Methyl oder vor allem Wasserstoff.Preferred meanings of ^ are methyl or especially hydrogen.
R7 bedeutet vorzugsweise Wasserstoff, Methyl oder Ethyl, insbesondere Methyl.R 7 preferably denotes hydrogen, methyl or ethyl, especially methyl.
R8 bedeutet vorzugsweise Wasserstoff.R 8 is preferably hydrogen.
Der ladungsausgleichende Anionligand A in den Verbindungen der Formel (1 ) und (2) kann ein- oder mehrwertig sein, wobei er im letzteren Fall entsprechend mehrere Manganatome mit den genannten organischen Liganden neutralisieren kann. Vorzugsweise handelt es sich um ein Halogenid, insbesondere Chlorid, ein Hydroxid, Hexafluorophosphat, Perchlorat oder um das Anion einer Carbonsäure, wie Formiat, Acetat, Benzoat oder Citrat.
Die erfindungsgemäss verwendeten Verbindungen gemäss Formel (1 ) oder (2) sind bekannt oder können nach im Prinzip bekannten Verfahren durch die Reaktion von Salicylaldehyd, der gegebenenfalls die oben definierten Substituenten Z1 oder Z2 trägt oder zwei anellierte Ringe wie bei den Verbindungen der Formel (2) aufweist, mit Diaminen H2N-Y-NH2 und Umsetzung des so erhältlichen Salen-Liganden mit Mangansalzen hergestellt werden, wie dies zum Beispiel in der europäischen Patentanmeldung EP-A-630964 beschrieben worden ist.The charge-balancing anion ligand A in the compounds of the formulas (1) and (2) can be mono- or polyvalent, in which case it can neutralize a number of manganese atoms with the organic ligands mentioned. It is preferably a halide, in particular chloride, a hydroxide, hexafluorophosphate, perchlorate or the anion of a carboxylic acid, such as formate, acetate, benzoate or citrate. The compounds of the formula (1) or (2) used according to the invention are known or can be prepared by processes known in principle by the reaction of salicylaldehyde, which optionally carries the substituents Z 1 or Z 2 defined above, or two fused rings as in the compounds of the formula (2), with diamines H 2 NY-NH 2 and reaction of the salen ligand thus obtainable with manganese salts, as described, for example, in European patent application EP-A-630964.
Die Verbindungen der Formel (1) oder (2) können einzeln oder in Mischungen mit zwei oder mehreren Verbindungen der Formel (1) oder (2) eingesetzt werden. Ausserdem können sie auch zusammen mit einem oder mehreren nichtkomplexierten Salenliganden verwendet werden, beispielsweise mit solchen Liganden, die in den Verbindungen der Formel (1) oder (2) enthalten sind.The compounds of the formula (1) or (2) can be used individually or in mixtures with two or more compounds of the formula (1) or (2). In addition, they can also be used together with one or more uncomplexed salen ligands, for example with those ligands which are contained in the compounds of the formula (1) or (2).
Weiterhin betrifft die Erfindung Reinigungsmittel für harte Oberflächen insbesondere Reinigungsmittel für Geschirr und unter diesen vorzugsweise solche für den Einsatz in maschinellen Reinigungsverfahren, die eine der oben beschriebenen Verbindungen der Formel (1) oder (2) als Bleichkatalysator enthalten, und ein Verfahren zur Reinigung von harten Oberflächen, insbesondere von Geschirr, unter Einsatz eines derartigen Bleichkatalysators.The invention further relates to detergents for hard surfaces, in particular detergents for dishes, and preferably those for use in machine cleaning processes which contain one of the compounds of the formula (1) or (2) described above as a bleaching catalyst, and a process for cleaning hard surfaces Surfaces, especially of dishes, using such a bleaching catalyst.
Die erfindungsgemässe Verwendung besteht im wesentlichen darin, in Gegenwart einer mit gefärbten Anschmutzungen verunreinigten harten Oberfläche Bedingungen zu schaffen, unter denen ein peroxidhaltiges Oxidationsmittel und der Bleichkatalysator gemäss Formel (1) oder (2) miteinander reagieren können, mit dem Ziel stärker oxidierend wirkende Folgeprodukte zu erhalten. Solche Bedingungen liegen insbesondere dann vor, wenn beide Reaktionspartner in wässriger Lösung aufeinander treffen. Dies kann durch separate Zugabe der Persauerstoffverbindung und des Bleichkatalysators zu einer gegebenenfalls reinigungsmittelhaitigen Lösung geschehen. Besonders vorteilhaft wird das erfindungsgemässe Verfahren jedoch unter Verwendung eines erfindungsgemässen Reinigungsmittels für harte Oberflächen, das den Bleichkatalysator und ein persauerstoffhaltiges Oxidationsmittel enthält, durchgeführt. Die Persauerstoffverbindung kann auch separat, in Substanz oder als vorzugsweise wässrige Lösung oder Suspension, zur Lösung zugegeben werden, wenn ein peroxidfreies Reinigungsmittel verwendet wird.
Je nach Verwendungszweck können die Bedingungen weit variiert werden. So kommen neben rein wässrigen Lösungen auch Mischungen aus Wasser und geeigneten organischen Lösungsmitteln als Reaktionsmedium in Frage. Die Einsatzmengen an Persauerstoffverbindungen werden im allgemeinen so gewählt, dass in den Lösungen zwischen 10 ppm und 10 % Aktivsauerstoff, vorzugsweise zwischen 50 ppm und 5 000 ppm Aktivsauerstoff vorhanden sind. Auch die verwendete Menge an Bleichkatalysator hängt vom Anwendungszweck ab. Je nach gewünschtem Aktivierungsgrad werden 0,00001 Mol bis 0,025 Mol, vorzugsweise 0,0001 Mol bis 0,02 Mol Aktivator pro Mol Persauerstoffverbindung verwendet, doch können in besonderen Fällen diese Grenzen auch über- oder unterschritten werden.The use according to the invention essentially consists in creating, in the presence of a hard surface contaminated with colored soils, conditions under which a peroxide-containing oxidizing agent and the bleaching catalyst according to formula (1) or (2) can react with one another with the aim of producing secondary products with a stronger oxidizing action receive. Such conditions exist particularly when both reactants meet in aqueous solution. This can be done by separately adding the peroxygen compound and the bleaching catalyst to an optionally detergent-containing solution. However, the method according to the invention is particularly advantageously carried out using a cleaning agent according to the invention for hard surfaces, which contains the bleaching catalyst and an oxidizing agent containing peroxygen. The peroxygen compound can also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, if a peroxide-free cleaning agent is used. The conditions can be varied widely depending on the intended use. In addition to purely aqueous solutions, mixtures of water and suitable organic solvents are also suitable as the reaction medium. The amounts of peroxygen compounds used are generally selected so that the solutions contain between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5,000 ppm active oxygen. The amount of bleaching catalyst used also depends on the application. Depending on the desired degree of activation, 0.00001 mol to 0.025 mol, preferably 0.0001 mol to 0.02 mol, of activator are used per mol of peroxygen compound, but these limits can also be exceeded or fallen below in special cases.
Ein weiterer Gegenstand der Erfindung ist ein Reinigungsmittel für harte Oberflächen, insbesondere für Geschirr, welches 0,001 Gew. % bis 1 Gew. %, insbesondere 0,005 Gew. % bis 0,1 Gew. % eines Bleichkatalysators gemäss Formel (1) oder (2) neben üblichen, mit dem Bleichkatalysator verträglichen Inhaltsstoffen enthält. Der Bleichkatalysator kann in im Prinzip bekannter Weise an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein.The invention further relates to a cleaning agent for hard surfaces, in particular for dishes, which contains 0.001% by weight to 1% by weight, in particular 0.005% by weight to 0.1% by weight, of a bleaching catalyst according to formula (1) or (2) in addition to the usual ingredients compatible with the bleaching catalyst. The bleaching catalyst can be adsorbed on carriers in a manner known in principle and / or embedded in coating substances.
Die erfindungsgemässen Reinigungsmittel, die als pulver- oder tablettenförmige Feststoffe, homogene Lösungen oder Suspensionen vorliegen können, können ausser dem erfindungsgemäss verwendeten Bleichkatalysator im Prinzip alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten. Die erfindungsgemässen Mittel können insbesondere Buil- dersubstanzen, oberflächenaktive Tenside, Persauerstoffverbindungen, wassermischbare organische Lösungsmittel, Enzyme, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren und weitere Hilfsstoffe, wie Silberkorrosionsinhibitoren, Schaumregulatoren, zusätzliche Persauerstoff-Aktivatoren sowie Färb- und Duftstoffe enthalten.The cleaning agents according to the invention, which can be in the form of solids or suspensions in powder or tablet form, homogeneous solutions or suspensions, can, in addition to the bleaching catalyst used according to the invention, in principle contain all the known ingredients which are customary in such agents. The agents according to the invention can contain, in particular, builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as silver corrosion inhibitors, foam regulators, additional peroxygen activators as well as colorants and fragrances.
Ein erfindungsgemässes Reinigungsmittel für harte Oberflächen kann darüber hinaus abrasiv wirkende Bestandteile, insbesondere aus der Gruppe, umfassend Quarzmehle, Holzmehle, Kunststoffmehle, Kreiden und Mikroglaskugeln, sowie deren Gemische enthalten. Abrasivstoffe sind in den erfindungsgemässen Reinigungsmitteln vorzugsweise nicht über 20 Gew. %, insbesondere von 5 Gew. % bis 15 Gew. %, enthalten.
Ein weiterer Erfindungsgegenstand ist ein niederalkalisches Mittel zum maschinellen Reinigen von Geschirr, dessen 1 -gewichtsprozentige Lösung einen pH-Wert von 8 bis 11,5, vorzugsweise 9 bis 10,5 aufweist, enthaltend 15 Gew. % bis 60 Gew. %, insbesondere 30 Gew. % bis 50 Gew. % wasserlösliche Builderkomponente, 3 Gew. % bis 25 Gew. %, insbesondere 5 Gew. % bis 15 Gew. % Bleichmittel auf Sauerstoffbasis, jeweils bezogen auf das gesamte Mittel, welches einen Bleichkatalysator gemäss Formel (1) oder (2), insbesondere in Mengen von 0,005 Gew. % bis 0,1 Gew. %, enthält.A cleaning agent according to the invention for hard surfaces can also contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and micro-glass balls, and mixtures thereof. Abrasives are preferably not contained in the cleaning agents according to the invention in excess of 20% by weight, in particular from 5% by weight to 15% by weight. Another subject matter of the invention is a low-alkaline agent for machine cleaning of dishes, the 1% by weight solution of which has a pH of 8 to 11.5, preferably 9 to 10.5, containing 15% by weight to 60% by weight, in particular 30 % By weight to 50% by weight of water-soluble builder component, 3% by weight to 25% by weight, in particular 5% by weight to 15% by weight, oxygen-based bleaching agent, in each case based on the total agent comprising a bleaching catalyst according to formula (1) or (2), in particular in amounts of 0.005% by weight to 0.1% by weight.
Als wasserlösliche Builderkomponenten insbesondere in derartigen niederalkalischen Reinigungsmitteln kommen prinzipiell alle in maschinellen Geschirreinigungsmitteln üblicherweise eingesetzten Builder in Frage, zum Beispiel polymere Alkaliphosphate, die in Form ihrer alkalischen, neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können. Beispiele hierfür sind Tetranatriumdiphosphat, Dinatriumdihydrogendiphosphat, Pen- tanatriumtriphosphat, Natriumtripoiyphosphat, sogenanntes Natriumhexametaphosphat sowie die entsprechenden Kaliumsalze sowie Gemische aus Natrium- und Kaliumsalzen. Ihre Mengen können im Bereich von bis zu etwa 35 Gew. %, bezogen auf das gesamte Mittel liegen. Weitere mögliche wasserlösliche Builderkomponenten sind zum Beispiel organische Polymere nativen oder synthetischen Ursprungs, vor allem Polycarboxylate, die insbesondere in Hartwasserregionen als Co-Builder wirken.In principle, all builders commonly used in machine dishwashing detergents, for example polymeric alkali metal phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts, are suitable as water-soluble builder components, in particular in such low-alkaline cleaning agents. Examples include tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, sodium tripolyphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts and mixtures of sodium and potassium salts. Their amounts can range up to about 35% by weight, based on the total agent. Other possible water-soluble builder components are, for example, organic polymers of native or synthetic origin, especially polycarboxylates, which act as co-builders, particularly in hard water regions.
In Betracht kommen beispielsweise Polyacrylsäuren und Copolymere aus Maleinsäureanhydrid und Acrylsäure sowie die Natriumsalze dieser Polymersäuren. Handelsübliche Produkte sind zum Beispiel Sokalan® CP 5 und PA 30 der Firma BASF. Zu den als Co- Builder brauchbaren Polymeren nativen Ursprungs gehören beispielsweise oxidierte Stärke, wie zum Beispiel aus der internationalen Patentanmeldung WO 94/05762 bekannt, und Polyaminosäuren wie Polyglutaminsäure oder Polyasparaginsäure. Weitere mögliche Builderkomponenten sind natürlich vorkommende Hydroxycarbonsäuren wie zum Beispiel Mono- und Di-hydroxybernsteinsäure, α-Hydroxypropionsäure und Gluconsäure. Ausserdem kommen als Builderkomponente die Salze der Citronensäure, insbesondere Natriumeitrat in Frage. Als Natriumeitrat kommen wasserfreies Trinatriumcitrat und vorzugsweise Trinatiumcitratdihydrat in Betracht. Trinatriumcitratdihydrat kann als fein- oder grobkristallines Pulver eingesetzt werden. In Abhängigkeit vom letztlich in den erfindungsgemässen
Mitteln eingestellten pH-Wert können auch die zu den genannten Co-Builder-Salzen korrespondierenden Säuren vorliegen.For example, polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are suitable. Commercial products are, for example, Sokalan® CP 5 and PA 30 from BASF. Polymers of native origin that can be used as co-builders include, for example, oxidized starch, as known, for example, from international patent application WO 94/05762, and polyamino acids such as polyglutamic acid or polyaspartic acid. Other possible builder components are naturally occurring hydroxycarboxylic acids such as mono- and di-hydroxy succinic acid, α-hydroxypropionic acid and gluconic acid. In addition, the salts of citric acid, in particular sodium citrate, are suitable as builder components. Anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable as sodium citrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the ultimately in the The pH adjusted to the mean can also be the acids corresponding to the co-builder salts mentioned.
Als Bleichmittel auf Sauerstoffbasis kommen in erster Linie Alkaliperboratmono- beziehungsweise -tetrahydrat und/oder Alkalipercarbonat in Betracht, wobei Natrium das bevorzugte Alkalimetall ist. Der Einsatz von Natriumpercarbonat hat insbesondere in Reinigungsmitteln für Geschirr Vorteile, da es sich besonders günstig auf das Korrosionsverhalten an Gläsern auswirkt. Zusätzlich oder insbesondere alternativ können auch bekannte Peroxycarbonsäuren, zum Beispiel Dodecandipersäure oder Phthalimidopercarbonsäuren, die gegebenenfalls am Aromaten substituiert sein können, enthalten sein. Überdies kann auch der Zusatz geringer Mengen bekannter Bleichmittelstabilisatoren wie beispielsweise von Phosphonaten, Boraten beziehungsweise Metaboraten und Metasilikaten sowie Magnesiumsalzen wie Magnesiumsulfat zweckdienlich sein.Suitable bleaches based on oxygen are primarily alkali perborate or tetrahydrate and / or alkali percarbonate, with sodium being the preferred alkali metal. The use of sodium percarbonate has advantages in particular in cleaning agents for dishes, since it has a particularly favorable effect on the corrosion behavior on glasses. In addition or in particular as an alternative, known peroxycarboxylic acids, for example dodecanediperic acid or phthalimidopercarboxylic acids, which can optionally be substituted on the aromatic, can also be present. In addition, the addition of small amounts of known bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates, and magnesium salts such as magnesium sulfate may also be useful.
Zusätzlich zu den Bleichkatalysatoren gemäss Formel (1) oder (2) können weitere als bleichaktivierende Wirkstoffe bekannte Übergangsmetallsalze beziehungsweise -komplexe und/oder konventionelle Bleichaktivatoren, das heisst Verbindungen, die unter Perhydrolyse- bedingungen gegebenenfalls substituierte Perbenzo- und/oder Peroxocarbonsäuren mit 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen ergeben, eingesetzt werden. Geeignet sind die eingangs zitierten üblichen Bleichaktivatoren, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N,N-diacetyl-N,N- dimethyl-harnstoff (DDU), acylierte Triazinderivate, insbesondere 1 ,5-Diacetyl-2,4- dioxohexahydro-1 ,3,5-triazin (DADHT), acylierte Phenylsulfonate, insbesondere Nonanoyloxy- oder Isononanoyloxybenzolsulfonat, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat und 2,5-Diacetoxy-2,5-dihydrofuran sowie acetyliertes Sorbit und Mannit und acylierte Zuckerderivate, insbesondere Pentaacetylgiukose (PAG), Sucrosepolyacetat (SUPA), Pentaacetylfructose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton. Auch die aus der deutschen Patentanmeldung DE-A- 4443 177 bekannten Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden.In addition to the bleaching catalysts according to formula (1) or (2), other transition metal salts or complexes known as bleach-activating active substances and / or conventional bleach activators, that is to say compounds which contain perbenzoic and / or peroxocarboxylic acids which are optionally substituted under perhydrolysis conditions, with 1 to 10 C atoms, especially 2 to 4 carbon atoms, can be used. Suitable are the conventional bleach activators cited at the outset which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N, N-diacetyl-N, N-dimethylurea (DDU), acylated triazine derivatives, in particular 1, 5-diacetyl-2, 4-dioxohexahydro-1, 3,5-triazine (DADHT), acylated phenyl sulfonates, especially nonanoyloxy- or isononanoyloxybenzenesulfonate, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol acylated sugar derivatives, in particular pentaacetylgiucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone. The combinations of conventional bleach activators known from German patent application DE-A-4443 177 can also be used.
Vorzugsweise enthalten die erfindungsgemässen niederalkalischen maschinellen Geschirrei-
nigungsmittel die üblichen Alkaliträger wie zum Beispiel Alkalisilikate, Alkaicarbonate und/oder Alkalihydrogencarbonate. Zu den üblicherweise eingesetzten Alkaliträgern zählen Carbonate, Hydrogencarbonate und Alkalisilikate mit einem Molverhältnis SiO2 / M2O (M = Alkaliatom) von 1 ,5 : 1 bis 2,5 : 1. Alkalisilikate können dabei in Mengen von bis zu 30 Gew. %, bezogen auf das gesamte Mittel, enthalten sein. Auf den Einsatz der hoch alkalischen Metasilikate als Alkaliträger wird vorzugsweise ganz verzichtet. Das in den erfindungsgemässen Mitteln bevorzugt eingesetzte Alkaliträgersystem ist ein Gemisch aus Carbonat und Hydrogencarbonat, vorzugsweise Natriumcarbonat und -hydrogencarbonat, das in einer Menge von bis zu 60 Gew. %, vorzugsweise 10 Gew. % bis 40 Gew. %, enthalten ist. Je nachdem, welcher pH-Wert letztendlich gewünscht wird, variiert das Verhältnis von eingesetztem Carbonat zu eingesetztem Hydrogencarbonat, üblicherweise wird jedoch ein Überschuss an Natriumhydrogencarbonat eingesetzt, so dass das Gewichtsverhältnis zwischen Hydrogencarbonat und Carbonat im allgemeinen 1 : 1 bis 15 : 1 beträgt.The low-alkaline machine dishware according to the invention preferably contains cleaning agents the usual alkali carriers such as alkali silicates, alkaicarbonates and / or alkali hydrogen carbonates. The alkali carriers commonly used include carbonates, hydrogen carbonates and alkali silicates with a SiO 2 / M 2 O (M = alkali atom) molar ratio of 1.5: 1 to 2.5: 1. Alkali silicates can be used in amounts of up to 30% by weight. , based on the total agent. The use of the highly alkaline metasilicates as alkali carriers is preferably avoided entirely. The alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, which is contained in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight. Depending on which pH value is ultimately desired, the ratio of carbonate to bicarbonate used varies, but an excess of sodium bicarbonate is usually used, so that the weight ratio between bicarbonate and carbonate is generally 1: 1 to 15: 1.
In einer weiteren bevorzugten Ausführungsform erfindungsgemässer Mittel sind 20 Gew. % bis 40 Gew. % wasserlöslicher organischer Builder-, insbesondere Alkalicitrat, 5 Gew. % bis 15 Gew. % Alkalicarbonat und 20 Gew. % bis 40 Gew. % Alkalisilikat enthalten.In a further preferred embodiment of agents according to the invention, 20% by weight to 40% by weight of water-soluble organic builder, in particular alkali citrate, 5% by weight to 15% by weight alkali carbonate and 20% by weight to 40% by weight alkali silicate are contained.
Den erfindungsgemässen Mitteln können gegebenenfalls auch Tenside, insbesondere schwach schäumende nichtionische Tenside zugesetzt werden, die der besseren Ablösung fetthaltiger Anschmutzungen, als Netzmittel und gegebenfalls im Rahmen der Herstellung der Reigungsmittel als Granulierhilfsmittel dienen. Ihre Menge kann bis zu 10 Gew. %, insbesondere bis zu 5 Gew. % betragen und liegt vorzugsweise im Bereich von 0,5 Gew. % bis 3 Gew.-%. Üblicherweise werden insbesondere für den Einsatz in maschinellen Geschirrspülverfahren extrem schaumarme Verbindungen eingesetzt. Hierzu zählen vorzugsweise C12-Cι8-Alkylpolyethylenglykol-polypropylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Propylenoxideinheiten im Molekül. Man kann aber auch andere bekannt schaumarme nichtionische Tenside verwenden, wie zum Beispiel
glykol-polybutylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Butylenoxideinheiten im Molekül, endgruppenverschlossene Alkylpolyalkylenglykolmischether sowie die zwar schäumenden, aber ökologisch attraktiven C8-C14-Alkylpolyglucoside mit einem Polymerisierungsgrad von etwa 1 bis 4 und/oder C12-Cι4-Alkylpolyethylenglykole mit 3 bis 8 Ethylenoxideinheiten im Molekül. Ebenfalls geeignet sind Tenside aus der Familie der Glucamide wie zum Beispiel Alkyl-N-Methyl-Glucamide, in denen der Alkylteil bevorzugt aus
einem Fettalkohol mit der C-Kettenlänge C6-C14 besteht. Es ist teilweise vorteilhaft, wenn die beschriebenen Tenside als Gemische eingesetzt werden, zum Beispiel die Kombination Alkylpolyglykosid mitt Fettalkoholethoxylaten oder Glucamid mit Alkylpolyglykosiden.If appropriate, surfactants, in particular low-foaming nonionic surfactants, can also be added to the agents according to the invention, which serve to better detach fatty soils, as wetting agents and, if appropriate, as granulating aids in the course of the preparation of the cleaning agents. Their amount can be up to 10% by weight, in particular up to 5% by weight, and is preferably in the range from 0.5% by weight to 3% by weight. Extremely low-foaming compounds are usually used, in particular for use in machine dishwashing processes. These preferably include C 12 -C 8 alkyl polyethylene glycol polypropylene glycol ether, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. But you can also use other known low-foaming nonionic surfactants, such as Glycol-polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end-capped alkyl polyalkylene glycol mixed ethers and the foaming but ecologically attractive C 8 -C 14 -alkyl polyglucosides with a degree of polymerization of about 1 to 4 and / or C 12 -Cι 4 - Alkyl polyethylene glycols with 3 to 8 ethylene oxide units in the molecule. Also suitable are surfactants from the family of glucamides, such as, for example, alkyl-N-methyl-glucamides, in which the alkyl part preferably consists of a fatty alcohol with the C chain length C 6 -C 14 . It is partially advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides.
Obwohl Mangankomplexe bekanntermassen der Korrosion von Silber entgegenwirken können, werden die Verbindungen der Formel (1) oder (2) in der Regel in Mengen eingesetzt, die zu gering sind, um einen Silberkorrosionsschutz zu bewirken, so dass in erfindungsgemässen Reinigungsmitteln für Geschirr Silberkorrosionsinhibitoren noch zusätzlich eingesetzt werden können, deren Wirkung durch die Verbindungen gemäss Formel (1 ) oder (2) verstärkt werden kann. Bevorzugte Silberkorrosionsschutzmittel sind organische Disulfide, zweiwertige Phenole, dreiwertige Phenole, gegebenenfalls substituiertes Benzotriazol, Mangan-, Titan-, Zirkonium-, Hafnium-, Vanadium-, Cobalt- oder Cersalze und oder -komplexe, in denen die genannten Metalle in einer der Oxidationsstufen II, III, IV, V oder VI vorliegen.Although manganese complexes are known to counteract the corrosion of silver, the compounds of the formula (1) or (2) are generally used in amounts which are too low to provide protection against silver corrosion, so that silver corrosion inhibitors are additionally present in dishwashing detergents according to the invention can be used, the effect of which can be enhanced by the compounds of the formula (1) or (2). Preferred silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, optionally substituted benzotriazole, manganese, titanium, zirconium, hafnium, vanadium, cobalt or cerium salts and or complexes in which the metals mentioned are in one of the oxidation states II , III, IV, V or VI are present.
Zusätzlich können die erfindungsgemässen Mittel Enzyme wie Proteasen, Amylasen, Pullu- lanasen, Cutinasen und Lipasen enthalten, beispielsweise Proteasen wie BLAP®, Optimase®, Opticiean®, Maxacal®, Maxapem®, Esperase® und/oder Savinase®, Amylasen wie Termamyl®, Amylase-LT®, Maxamyl® und/oder Duramyl®, Lipasen wie Lipolase®, Lipomax®, Lumafast® und/oder Lipozym®. Die gegebenenfalls verwendeten Enzyme können, wie zum Beispiel in den internationalen Patentanmeldungen WO 92/11347 oder WO 94/23005 beschrieben, an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Sie sind in den erfindungsgemässen Reinigungsmitteln vorzugsweise nicht über 2 Gew. %, insbesondere von 0,1 Gew. % bis 1 ,2 Gew. %, enthalten.In addition, the agents according to the invention can contain enzymes such as proteases, amylases, pullulanases, cutinases and lipases, for example proteases such as BLAP®, Optimase®, Opticiean®, Maxacal®, Maxapem®, Esperase® and / or Savinase®, amylases such as Termamyl® , Amylase-LT®, Maxamyl® and / or Duramyl®, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®. The enzymes which may be used, as described, for example, in international patent applications WO 92/11347 or WO 94/23005, can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation. They are preferably contained in the cleaning agents according to the invention not more than 2% by weight, in particular from 0.1% by weight to 1.2% by weight.
Sofern die Reinigungsmittel bei der Anwendung zu stark schäumen, können ihnen noch bis zu 6 Gew. %, vorzugsweise etwa 0,5 Gew. % bis 4 Gew. % einer schaumunterdrückenden Verbindung, vorzugsweise aus der Gruppe der Silikonöle, Gemische aus Silikonöl und hydrophobierter Kieselsäure, Paraffin, Parafin-Alkohol-Kombinationen, hydrophobierter Kieselsäure, der Bisfettsäureamide und sonstiger weiterer bekannter im Handel erhältlicher Entschäumer zugesetzt werden. Weitere fakultative Inhaltsstoffe in den erfindungsgemässen Mitteln sind zum Beispiel Parfümöle.
Zu den in den erfindungsgemässen Mitteln, insbesondere wenn sie in flüssiger oder pastöser Form vorliegen, verwendbaren organischen Lösungsungsmitteln gehören Alkohole mit 1 bis 4 C-Atomen, insbesondere Methanol, Ethanol, Isopropanol und tert.-Butanol, Diole mit 2 bis 4 C-Atomen, insbesondere Ethylenglykol und Propylenglykol, sowie deren Gemische und die aus den genannten Verbindungsklassen ableitbaren Ether. Derartige wassermischbare Lösungmittel sind in den erfindungsgemässen Reinigungsmitteln vorzugsweise nicht über 20 Gew. %, insbesondere von 1 Gew. % bis 15 Gew.-%, vorhanden.If the cleaning agents foam too much during use, they can contain up to 6% by weight, preferably about 0.5% to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica , Paraffin, paraffin-alcohol combinations, hydrophobized silica, the bis fatty acid amides and other other known commercially available defoamers. Other optional ingredients in the agents according to the invention are, for example, perfume oils. The organic solvents which can be used in the agents according to the invention, in particular if they are in liquid or pasty form, include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms , in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers derivable from the compound classes mentioned. Such water-miscible solvents are preferably not present in the cleaning agents according to the invention in excess of 20% by weight, in particular from 1% by weight to 15% by weight.
Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können die erfindungsgemässen Mittel System- und umweltverträgliche Säuren, insbesondere Citronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure, oder Alkalihydrogensulfate, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind in den erfindungsgemässen Mitteln vorzugsweise nicht über 10 Gew. %, insbesondere von 0,5 Gew. % bis 6 Gew. %, enthalten.To set a desired pH value which does not result from the mixture of the other components, the agents 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 contain mineral acids, especially sulfuric acid, or alkali hydrogen sulfates, or bases, especially ammonium or alkali hydroxides. Such pH regulators are preferably not contained in the agents according to the invention in excess of 10% by weight, in particular from 0.5% by weight to 6% by weight.
Die Herstellung der erfindungsgemässen festen Mittel bereitet keine Schwierigkeiten und kann in im Prinzip bekannter Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei Persauerstoffverbindung und Bleichkatalysator gegebenfalls später getrennt zugesetzt werden.The preparation of the solid compositions according to the invention is not difficult and can be carried out in a manner known in principle, for example by spray drying or granulation, the peroxygen compound and bleaching catalyst optionally being added separately later.
Erfindungsgemässe Reinigungsmittel in Form wässriger oder sonstige übliche Lösungsmittel enthaltender Lösungen werden besonders vorteilhaft durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, hergestellt.Cleaning agents according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
Die erfindungsgemässen Mittel liegen vorzugsweise als pulverförmige, granuläre oder tablettenförmige Präparate vor, die in an sich bekannter Weise, beispielsweise durch Mischen, Granulieren, Walzenkompaktieren und/oder durch Sprühtrocknung der thermisch belastbaren Komponenten und Zumischen der empfindlicheren Komponenten, zu denen insbesondere Enzyme, Bleichmittel und der Bleichkatalysator zu rechnen sind, hergestellt werden können.
Zur Herstellung von erfindungsgemässen Reinigungsmitteln in Tablettenform geht man vorzugsweise derart vor, dass man alle Bestandteile in einem Mischer miteinander vermischt und das Gemisch mittels herkömmlicher Tablettenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Pressdrucken im Bereich von 200 • 105 Pa bis 1 500 • 105 Pa verpresst. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Biegefestigkeit von normalerweise über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 15 g bis 40 g, insbesondere von 20 g bis 30 g auf, bei einemn Durchmesser von 35 mm bis 40 mm.The agents according to the invention are preferably in the form of powdery, granular or tablet-like preparations which are known in a manner known per se, for example by mixing, granulating, roller compacting and / or by spray drying the thermally loadable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleaching catalyst can be expected to be produced. To produce cleaning agents according to the invention in tablet form, the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 · 10 5 Pa to 1 500 • 10 5 Pa pressed. In this way, unbreakable tablets are obtained which, under operating conditions, dissolve sufficiently quickly and have a flexural strength of normally more than 150 N. A tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.
Die Herstellung erfindungsgemässer Mittel in Form von nicht staubenden, lagerstabil rieselfähigen Pulvern und/oder Granulaten mit hohen Schüttdichten im Bereich von 800 bis 1000 g/l kann dadurch erfolgen, dass man in einer ersten Verfahrensstufe die Builder- Komponenten mit wenigstens einem Anteil flüssiger Mischungskomponenten unter Erhöhung der Schüttdichte dieses Vorgemisches vermischt und nachfolgend - gewünschten- falls nach einer Zwischentrocknung - die weiteren Bestandteile des Mittels, darunter den Bleichkatalysator, mit dem so gewonnenen Vorgemisch vereinigt.Agents according to the invention can be produced 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 in a first process step by adding the builder components with at least a portion of liquid mixture components Increasing the bulk density of this premix is mixed and subsequently - if desired after an intermediate drying - the further constituents of the composition, including the bleaching catalyst, are combined with the premix obtained in this way.
Erfindungsgemässe Mittel zur Reinigung von Geschirr können sowohl in Haushaltsgeschirrspülmaschinen wie in gewerblichen Spülmaschinen eingesetzt werden. Die Zugabe erfolgt von Hand oder mittels geeigneter Dosiervorrichtungen. Die Anwendungskonzentrationen in der Reinigungsflotte betragen in der Regel etwa 1 bis 8 g/l, vorzugsweise 2 bis 5 g/l.Agents for cleaning dishes according to the invention can be used both in household dishwashers and in commercial dishwashers. It is added by hand or using suitable dosing devices. The application concentrations in the cleaning liquor are generally about 1 to 8 g / l, preferably 2 to 5 g / l.
Ein maschinelles Spüiprogramm wird im allgemeinen durch einige auf den Reinigungsgang folgende Zwischenspülgänge mit klarem Wasser und einen Klarspülgang mit einem gebräuchlichen Klarspülmittel ergänzt und beendet. Nach dem Trocknen erhält man beim Einsatz erfindungsgemässer Mittel ein völlig sauberes und in hygienischer Hinsicht einwandfreies Geschirr.
Beispiele:A machine wash program is generally supplemented and ended by a few intermediate rinse cycles with clear water following the cleaning cycle and a rinse cycle with a customary rinse aid. After drying, when using the agents according to the invention, completely clean and hygienically perfect dishes are obtained. Examples:
Die folgenden Substanzen wurden getestet:The following substances have been tested:
Substanz Y Zi z2 Substance Y Zi z 2
(101) 1 ,2-Cyclohexylen -N(C2H5)2 -N(C2H5)2 (101) 1,2-Cyclohexylene -N (C 2 H 5 ) 2 -N (C 2 H 5 ) 2
(102) 1 ,2-Ethylen -N(C2H5)2 -N(C2H5)2 (102) 1, 2-Ethylene -N (C 2 H 5 ) 2 -N (C 2 H 5 ) 2
(103) 1 ,2-Ethylen -OH -OH(103) 1,2-Ethylene -OH -OH
(104) 1 ,2-Ethylen -N(CH3)2 -N(CH3)2 (104) 1, 2-Ethylene -N (CH 3 ) 2 -N (CH 3 ) 2
(105) 1 ,2-Ethylen -H -H(105) 1,2-ethylene -H -H
(106) 1 ,2-Ethylen -OCH3 -OCH3 (106) 1,2-ethylene -OCH 3 -OCH 3
(107) 1 ,3-Propylen -N(C2H5)2 -N(C2H5)2 (107) 1,3-propylene -N (C 2 H 5 ) 2 -N (C 2 H 5 ) 2
(108) 2-Methyl-1 ,2-propylen -N(C2H5)2 -OCH3(108) 2-methyl-1,2-propylene -N (C 2 H 5 ) 2 -OCH3
(109) 2-Methyl-1 ,2-propylen -N(C2H5)2 -H(109) 2-methyl-1,2-propylene -N (C 2 H 5 ) 2 -H
(110) 1 ,2-Phenylen OH OH(110) 1,2-phenylene OH OH
Die Verbindungen (108) und (109) haben folgende Struktur:
The connections (108) and (109) have the following structure:
Ausserdem wurden die folgenden Substanzen getestet:The following substances were also tested:
Substanz R7 Substance R 7
(111) 1 ,2-Cyclohexylen CH3 (111) 1,2-cyclohexylene CH 3
(112) 1,2-Ethylen CH3 (112) 1,2-ethylene CH 3
Beispiel 1 : Anschmutzunαsprozedere: Ein Teesud (12g Teeblätter/Liter) wird unter Rühren bei 99° C aus Schwarztee (Marke Twinings) und Hartwasser (Gesamthärte: 18° dH) hergestellt. Man lässt fünf Minuten ziehen und filtriert den Tee. Es werden dann ca. 100 ml Tee in eine Porzellantasse gegossen. Der Tee wird 30 Minuten in den Tassen stehen gelassen. Die Tassen werden anschliessend in drei Schritten von ca. 35 ml entleert. Zwischen den Entleerungsschritten wird jeweils fünf Minuten gewartet. Die völlig entleerten Tassen werden 60 Minuten bei 70° C getrocknet.
Reiniαunαsprozedere: Die Tassen wurden in einem Miele G-690 D Geschirrspüler mit dem Fθinprogramm bei 45°C unter Verwendung von Hartwasser gereinigt. Bei jedem Reinigungsprogramm wurden jeweils 12 mit Tee angeschmutzte Tassen gereinigt. Ausserdem befanden sich sechs Gläser mit Milchanschmutzungen, 24 saubere Teller und 60 g von einer Mischung verschiedener Lebensmittel (u. a. Spinat, Eier, Hackfleisch, Stärke)in der Maschine. Die Dosierung des Geschirrspülmittels war: 17.2 g einer phosphathaltigen Grundformulierung, 1.72g Natriumperborat-monohydrat, 0.8 g TAED und ggf. 50 ppm Katalysator (ppm bezogen auf das Metall). Nach der Reinigung wurde die Entfernung des Teebelags visuell auf einer Skala von 0 (=unverändert sehr starker Belag) bis 10 (=kein Belag) benotet. In Tabelle 1 werden die Noten für unsere Katalysatoren verglichen mit einer Referenz (nur TAED, kein Katalysator). Die in der Tabelle angegebenen Noten sind die Medianwerte aus mehreren Reinigungsprogrammen mit je 12 Tassen. Die Tabelle zeigt, dass die Noten für die erfindungsgemäss verwendeten Katalysatoren signifikant besser sind als der Referenzwert.Example 1: Soiling procedure: A tea infusion (12 g tea leaves / liter) is made from black tea (Twinings brand) and hard water (total hardness: 18 ° dH) with stirring at 99 ° C. Allow to infuse for five minutes and filter the tea. Then about 100 ml of tea are poured into a porcelain cup. The tea is left in the cups for 30 minutes. The cups are then emptied in three steps of approx. 35 ml. There is a waiting period of five minutes between the emptying steps. The completely empty cups are dried at 70 ° C for 60 minutes. Reiniαunαsprozedere: The cups were cleaned in a Miele G-690 D dishwasher with the Fθin program at 45 ° C using hard water. In each cleaning program, 12 cups soiled with tea were cleaned. There were also six glasses with milk soiling, 24 clean plates and 60 g of a mixture of different foods (including spinach, eggs, minced meat, starch) in the machine. The dosage of the dishwashing detergent was: 17.2 g of a basic formulation containing phosphate, 1.72 g of sodium perborate monohydrate, 0.8 g of TAED and possibly 50 ppm of catalyst (ppm based on the metal). After cleaning, the removal of the tea topping was assessed visually on a scale from 0 (= unchanged very thick deposit) to 10 (= no deposit). Table 1 compares the scores for our catalysts with a reference (TAED only, no catalyst). The notes given in the table are the median values from several cleaning programs with 12 cups each. The table shows that the marks for the catalysts used according to the invention are significantly better than the reference value.
Tabelle 1. Noten für die BelagsentfernungTable 1. Sheet removal marks
Ähnliche Ergebnisse erzielt man, wenn man das Geschirrspüimitte! folgender Zusammensetzung zusammen mit 50 ppm der in der obenstehenden Tabelle verwendeten Katalysatoren, 1.72g Natriumperborat-monohydrat und 0.8 g TAED verwendet.Similar results can be achieved if you put the dishwasher in the middle! following composition together with 50 ppm of the catalysts used in the table above, 1.72 g of sodium perborate monohydrate and 0.8 g of TAED.
Inhaltsstoff Gew.%Ingredient% by weight
Natriumtripolyphosphat 30Sodium tripolyphosphate 30
Natriumcarbonat 25Sodium carbonate 25
Hydratisiertes 2.0r Silikat 18.5Hydrated 2.0r silicate 18.5
Nichtionisches Tensid 2.5Nonionic surfactant 2.5
Polymer (60 % Acrylsäure, 20 % Maleinsäure, 20 % Ethylacrylat) 5Polymer (60% acrylic acid, 20% maleic acid, 20% ethyl acrylate) 5
Protease (4% aktiv) 1Protease (4% active) 1
Amylase (0.8% aktiv) 0.5Amylase (0.8% active) 0.5
Wasser, Natriumsulfat, etc. Rest bis 100%Water, sodium sulfate, etc. rest up to 100%
Beispiel 2:Example 2:
10.1 mg (30 μmol) Morin-Dihydrat wurde in 1000 ml einer Boraxpufferlösung (9 mmol Di- Natriumtetraborat/Liter, pH=9.4) gelöst. Bei t= 0 Min. wurde 295 mg (2.5 mmol) Natriumperborat-monohydrat und, je nach dem, 3.4 μmol Katalysator oder 137 mg (0.6
mmol) TAED zugegeben. Über einen Zeitraum von 30 Minuten wurde bei 27° C minütlich die Extinktion E der Lösung bei 400 nm gemessen. In Tabelle 2 sind die Werte für die prozentuale Entfärbung D(t), berechnet nach D(t)=[E(0)-E(t)]/E(0)*100, angegeben.10.1 mg (30 μmol) of morin dihydrate was dissolved in 1000 ml of a borax buffer solution (9 mmol disodium tetraborate / liter, pH = 9.4). At t = 0 min. 295 mg (2.5 mmol) sodium perborate monohydrate and, depending on the, 3.4 μmol catalyst or 137 mg (0.6 mmol) TAED added. The extinction E of the solution at 400 nm was measured every minute at 27 ° C. over a period of 30 minutes. Table 2 shows the values for the percent decolorization D (t), calculated according to D (t) = [E (0) -E (t)] / E (0) * 100.
Man erkennt, dass die Bleichwirkung in Lösung bei den Verbindungen (101) bis (104) besser ist als die von TAED, obwohl die Konzentration von TAED viel höher war. Ausserdem erkennt man, dass nach 30 Minuten eine bessere Entfärbung erreicht wird als mit der Verbindung M2.It can be seen that the bleaching action in solution for compounds (101) to (104) is better than that of TAED, although the concentration of TAED was much higher. You can also see that after 30 minutes a better decolorization is achieved than with the compound M2.
Beispiel 3: Arbeitet man wie im Beispiel 1 beschrieben, verwendet jedoch als Katalysator eine äquivalente Menge der Verbindung der FormelEXAMPLE 3 The procedure is as described in Example 1, but an equivalent amount of the compound of the formula is used as the catalyst
so erhält man ebenfalls eine gute Reinigungswirkung.
Beispiel 4: Man arbeitet wie im Beispiel 1 der EP-A-630964 beschrieben, setzt jedoch anstelle von Salicylaldehyd eine äquivalente Menge der 1:1 -Mischung von Salicylaldehyd und 2-Hydroxy-4-diethylamino-benzaldehyd und anstelle von Ethylendiamin eine äquivalente Menge von 2-Amino-2-methyl-3-aminopropan ein. Danach wird wie dort beschrieben der Mangankomplex gebildet.Man erhält eine Mischung der folgenden 4 Mangankomplexe: this also gives a good cleaning effect. Example 4: The procedure is as described in Example 1 of EP-A-630964, but instead of salicylaldehyde, an equivalent amount of the 1: 1 mixture of salicylaldehyde and 2-hydroxy-4-diethylamino-benzaldehyde and instead of ethylenediamine, an equivalent amount of 2-amino-2-methyl-3-aminopropane. The manganese complex is then formed as described there, and a mixture of the following 4 manganese complexes is obtained:
Arbeitet man wie im Beispiel 1 beschrieben, verwendet jedoch als Katalysator eine äquivalente Menge dieser Mischung, so erhält man ebenfalls eine gute Reinigungswirkung.If the procedure described in Example 1 is followed, but an equivalent amount of this mixture is used as the catalyst, a good cleaning action is also obtained.
Beispiel 5: Ebenfalls gute Reinigungswirkung erzielt man, wenn man statt der Mischung aus Beispiel 4 eine solche einsetzt, die lediglich die beiden letzten der aufgeführten Komplexe enthält. Diese Mischung ist durch Reinigung der Mischung der unkomplexierten Liganden aus der ersten Stufe der Herstellung gemäss Beispiel 4 zugänglich.
Example 5: Another good cleaning effect is achieved if, instead of the mixture from Example 4, one is used which contains only the last two of the complexes listed. This mixture is accessible by purifying the mixture of the uncomplexed ligands from the first stage of the preparation according to Example 4.
Claims
1. Verwendung von Mangankomplexen der Formel (1 ) oder (2)1. Use of manganese complexes of the formula (1) or (2)
oder or
wonn wonn
Y lineares oder verzweigtes Alkylen der Formel -[C(R1)2]m bedeutet, wobei m eine ganze Zahl von 2 bis 8 bedeutet und Ri unabhängig voneinander Wasserstoff oder d-C4-Alkyl ist, -CX=CX-, worin X Cyano, lineares oder verzweigtes d-Cβ-alkyl oder Di-(lineares oder verzweigtes Cι-Cβ-alkyl)-amino ist; -(CH2)q-NRr(CH2)q-, worin R^ die angegebene Bedeutung hat und q 1 , 2, 3 oder 4 ist; oder einen 1 ,2-Cyclohexylen- oder 1 ,2- Phenylenrest der FormelY is linear or branched alkylene of the formula - [C (R 1 ) 2 ] m , where m is an integer from 2 to 8 and R 1 is independently hydrogen or dC 4 alkyl, -CX = CX-, where X is cyano , linear or branched dC β -alkyl or di- (linear or branched Cι-C β -alkyl) -amino; - (CH 2 ) q -NRr (CH 2 ) q -, in which R ^ has the meaning given and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene or 1,2-phenylene radical of the formula
worin Ffe Wasserstoff, CH2OH, CH2NH2oder SO3M bedeutet, wobei M Wasserstoff, ein Alkalimetall Atom, Ammonium oder das Kation eines organischen Amins darstellt,
R5 und Rβ unabhängig voneinander Wasserstoff, lineares oder verzweigtes Cι-C -alkyl; lineares oder verzweigtes C1-C8-alkylene-R2) worin R2 OR1( COOR! oder NR3R4ist, unsubstituiertes Aryl oder Aryl bedeuten, das substituiert ist durch Cyano, Halogen, ORi, COORi, Nitro, lineares oder verzweigtes Ci-Cβ-alkyl, NR3R4, worin R3 und R unabhängig voneinander Wasserstoff oder lineares oder verzweigtes CrCι2-alkyl bedeuten; oder durch -NΘRιR3R4, worin Ri, R3 und R4 die angegebenen Bedeutungen besitzen,in which Ffe is hydrogen, CH 2 OH, CH 2 NH 2 or SO 3 M, where M is hydrogen, an alkali metal atom, ammonium or the cation of an organic amine, R 5 and R β are independently hydrogen, linear or branched C 1 -C 4 alkyl; linear or branched C 1 -C 8 -alkylene-R 2) where R 2 is OR 1 ( COOR ! or NR 3 R 4 , mean unsubstituted aryl or aryl which is substituted by cyano, halogen, ORi, COORi, nitro, linear or branched Ci-Cβ-alkyl, NR 3 R 4 , wherein R 3 and R independently of one another are hydrogen or linear or branched CrCι 2 alkyl; or by -N Θ RιR 3 R 4 , wherein R 1, R 3 and R 4 are the have the meanings given,
R7 unabhängig voneinander Wasserstoff oder Cι-C4-Alkyl,R 7 independently of one another are hydrogen or -CC 4 alkyl,
Z und Z2 unabhängig voneinander Wasserstoff, Hydroxy, Cι-C4 Alkoxy oder Di-(Cι-C4- alkyl)amino, undZ and Z 2 independently of one another are hydrogen, hydroxy, C 1 -C 4 alkoxy or di (C 1 -C 4 alkyl) amino, and
A für einen ladungsausgleichenden Anionliganden steht, als Katalysatoren für Reaktionen mit Persauerstoffverbindungen in Reinigungslösungen für harte Oberflächen, wobei in den Verbindungen der Formel (1) nicht alle Substituenten Z Z2,A stands for a charge-balancing anion ligand, as catalysts for reactions with peroxygen compounds in cleaning solutions for hard surfaces, not all of the substituents ZZ 2 in the compounds of the formula (1),
R5 und R6 gleichzeitig Wasserstoff sein dürfen, wenn Y 1 ,2-Phenylen ist.R 5 and R 6 may simultaneously be hydrogen if Y is 1,2-phenylene.
2. Verwendung von Komplexen der Formel (1 ) oder (2) als Katalysatoren für Reaktionen mit Persauerstoffverbindungen in Reinigungslösungen für Geschirr.2. Use of complexes of the formula (1) or (2) as catalysts for reactions with peroxygen compounds in cleaning solutions for dishes.
3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass in der Formel (1) Zt und Z2 unabhängig voneinander Wasserstoff, Hydroxy, Methoxy, Ethoxy, Dimethylamino oder Diethylamino bedeuten.3. Use according to claim 1 or 2, characterized in that in the formula (1) Z t and Z 2 independently of one another are hydrogen, hydroxyl, methoxy, ethoxy, dimethylamino or diethylamino.
4. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass in der Formel (1) und (2) Y Ethylen, 1,2- oder 1 ,3-Propylen, 1-Methyl-1,2-propylen, 2-Methyl-1 ,2- propylen, 1 ,2-Cyclohexylen oder 1,2-Phenylen bedeuten.4. Use according to one of claims 1 to 3, characterized in that in the formula (1) and (2) Y ethylene, 1,2- or 1,3-propylene, 1-methyl-1,2-propylene, 2nd -Methyl-1, 2-propylene, 1, 2-cyclohexylene or 1,2-phenylene.
5. Verwendung nach Anspruch 4, dadurch gekennzeichnet, dass Y Ethylen, 1 ,3-Propylen, 2- Methyl-1,2-propylen, 1 ,2-Cyclohexylen oder 1 ,2-Phenylen bedeuten.5. Use according to claim 4, characterized in that Y is ethylene, 1, 3-propylene, 2-methyl-1,2-propylene, 1, 2-cyclohexylene or 1, 2-phenylene.
6. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass in der Formel (1) und (2) R5 und R6 unabhängig voneinander Wasserstoff, Methyl, Ethyl oder unsubstituiertes Phenyl, insbesondere Wasserstoff, bedeuten.6. Use according to one of claims 1 to 5, characterized in that in the formula (1) and (2) R 5 and R 6 independently of one another are hydrogen, methyl, ethyl or unsubstituted phenyl, in particular hydrogen.
7. Verwendung nach Anspruch 1 , dadurch gekennzeichnet, dass in der Formel (2) R7 unabhängig voneinander Wasserstoff, Methyl oder Ethyl, insbesondere Methyl, bedeutet.
7. Use according to claim 1, characterized in that in the formula (2) R 7 independently of one another is hydrogen, methyl or ethyl, in particular methyl.
8. Verwendung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass der ladungsausgleichende Anionligand A in den Verbindungen der Formel (1 ) oder (2) Halogenid, Hydroxid, Hexafluorophosphat, Perchlorat oder das Anion einer organischen Carbonsäure ist.8. Use according to one of claims 1 to 7, characterized in that the charge-balancing anion ligand A in the compounds of formula (1) or (2) is halide, hydroxide, hexafluorophosphate, perchlorate or the anion of an organic carboxylic acid.
9. Verwendung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die zu aktivierende Persauerstoffverbindung aus der Gruppe, umfassend organische Persäuren, Wasserstoffperoxid, Perborat und Percarbonat sowie deren Gemische, ausgewählt wird.9. Use according to one of claims 1 to 8, characterized in that the peroxygen compound to be activated is selected from the group comprising organic peracids, hydrogen peroxide, perborate and percarbonate and mixtures thereof.
10. Verwendung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass man zusätzlich einen üblichen Bleichaktivator, insbesondere TAED, einsetzt.10. Use according to one of claims 1 to 9, characterized in that additionally a conventional bleach activator, in particular TAED, is used.
11. Verfahren zur Reinigung von harten Oberflächen, insbesondere von Geschirr, unter Einsatz einer Verbindung der Formel (1) oder (2).11. A method for cleaning hard surfaces, especially dishes, using a compound of formula (1) or (2).
12. Reinigungsmittel für harte Oberflächen, insbesondere für Geschirr, dadurch gekennzeichnet, dass es 0,001 Gew. % bis 1 Gew. %, insbesondere 0,005 Gew. % bis 0,1 Gew. % eines Bleichkatalysators gemäss Formel (1) oder (2) neben üblichen, mit dem Bleichkatalysator verträglichen Inhaltsstoffen enthält.12. Cleaning agent for hard surfaces, in particular for dishes, characterized in that it contains 0.001% by weight to 1% by weight, in particular 0.005% by weight to 0.1% by weight, of a bleaching catalyst according to formula (1) or (2) Contains usual ingredients compatible with the bleaching catalyst.
13. Reinigungsmittel gemäss Anspruch 12, dadurch gekennzeichnet, dass es zusätzlich TAED enthält.13. Cleaning agent according to claim 12, characterized in that it additionally contains TAED.
14. Niederalkalisches Mittel zum maschinellen Reinigen von Geschirr dessen 1 -gewichtsprozentige Lösung einen pH-Wert von 8 bis 11 ,5 aufweist, enthaltend 15 Gew. % bis 60 Gew. %, insbesondere 30 Gew. % bis 50 Gew. % wasserlösliche Builderkomponente, 3 Gew. % bis 25 Gew. %, insbesondere 5 Gew. % bis 15 Gew. % Bleichmittel auf Sauerstoffbasis, jeweils bezogen auf das gesamte Mittel, dadurch gekennzeichnet dass es einen Bleichkatalysator gemäss Formel (1 ) oder (2), insbesondere in Mengen von 0,005 Gew. % bis 0,1 Gew. %, enthält.14. Low-alkaline agent for machine cleaning of dishes whose 1% by weight solution has a pH of 8 to 11.5, containing 15% by weight to 60% by weight, in particular 30% by weight to 50% by weight, water-soluble builder component, 3% by weight to 25% by weight, in particular 5% by weight to 15% by weight, oxygen-based bleaching agent, in each case based on the total agent, characterized in that it is a bleaching catalyst according to formula (1) or (2), in particular in amounts from 0.005% by weight to 0.1% by weight.
15. Mittel nach einem der Ansprüche 12 bis 14, dadurch gekennzeichnet dass es als Bleichmittel Alkaliperboratmonohydrat, Alkaliperborattetrahydrat, Alkalipercarbonat und/oder
Peroxycarbonsäure enthält.
15. Agent according to one of claims 12 to 14, characterized in that it contains alkali perborate monohydrate, alkali perborate tetrahydrate, alkali percarbonate and / or as bleaching agent Peroxycarboxylic acid contains.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99941530A EP1105454A1 (en) | 1998-08-19 | 1999-08-06 | Manganese complexes as catalysts for peroxygenated compounds to clean hard surfaces, especially dishes |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98810811 | 1998-08-19 | ||
EP98810811 | 1998-08-19 | ||
PCT/EP1999/005699 WO2000011129A1 (en) | 1998-08-19 | 1999-08-06 | Manganese complexes as catalysts for peroxygenated compounds to clean hard surfaces, especially dishes |
EP99941530A EP1105454A1 (en) | 1998-08-19 | 1999-08-06 | Manganese complexes as catalysts for peroxygenated compounds to clean hard surfaces, especially dishes |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1105454A1 true EP1105454A1 (en) | 2001-06-13 |
Family
ID=8236267
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99941530A Withdrawn EP1105454A1 (en) | 1998-08-19 | 1999-08-06 | Manganese complexes as catalysts for peroxygenated compounds to clean hard surfaces, especially dishes |
Country Status (7)
Country | Link |
---|---|
US (2) | US6306808B1 (en) |
EP (1) | EP1105454A1 (en) |
JP (1) | JP2002523558A (en) |
KR (1) | KR20010072730A (en) |
AU (1) | AU5511099A (en) |
NO (1) | NO20010766L (en) |
WO (1) | WO2000011129A1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1159389B1 (en) * | 1999-03-08 | 2004-03-24 | Ciba Specialty Chemicals Holding Inc. | Washing and cleaning process |
JP2002538329A (en) * | 1999-03-08 | 2002-11-12 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Processing method of fiber material |
WO2000053574A1 (en) * | 1999-03-08 | 2000-09-14 | Ciba Specialty Chemicals Holding Inc. | Manganese complexes of salen ligands and the use thereof |
ATE315627T1 (en) | 1999-07-14 | 2006-02-15 | Ciba Sc Holding Ag | METAL COMPLEXES OF TRIPODAL LIGANDS |
US20050129978A1 (en) * | 2002-12-25 | 2005-06-16 | Semiconductor Energy Laboratory Co., Ltd. | Electroluminescent device and method of manufacturing thereof |
JP2007126776A (en) * | 2005-11-02 | 2007-05-24 | Nisshin Kagaku Kenkyusho:Kk | Method for treatment of waste paper pulp and deinking assistant |
GB0616444D0 (en) * | 2006-08-18 | 2006-09-27 | Reckitt Benckiser Nv | Detergent composition |
WO2009101588A2 (en) * | 2008-02-11 | 2009-08-20 | Ecolab Inc. | Use of activator complexes to enhance lower temperature cleaning in alkaline peroxide cleaning systems |
US20090325841A1 (en) * | 2008-02-11 | 2009-12-31 | Ecolab Inc. | Use of activator complexes to enhance lower temperature cleaning in alkaline peroxide cleaning systems |
EP2228426A1 (en) * | 2009-03-13 | 2010-09-15 | Rohm and Haas Company | Scale-reducing additive for automatic dishwashing systems |
US8946140B2 (en) * | 2009-05-14 | 2015-02-03 | Ecolab Usa Inc. | Compositions, systems and method for in situ generation of alkalinity |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0630964B1 (en) * | 1993-06-19 | 1998-08-05 | Ciba SC Holding AG | Inhibition of re-absorption of migrating dyes in the wash liquor |
ES2221665T3 (en) * | 1994-07-21 | 2005-01-01 | Ciba Specialty Chemicals Holding Inc. | COMPOSITION OF WHITENING OF FABRICS. |
GB9425296D0 (en) * | 1994-12-15 | 1995-02-15 | Ciba Geigy Ag | Inhibition of dye migration |
DE19529904A1 (en) * | 1995-08-15 | 1997-02-20 | Henkel Kgaa | Detergent with activator complexes for peroxygen compounds |
EP0876464A1 (en) * | 1995-10-19 | 1998-11-11 | Ciba SC Holding AG | Bleaching or washing composition |
DE69826951T2 (en) * | 1997-09-09 | 2006-02-23 | Ciba Speciality Chemicals Holding Inc. | Method of tissue care |
-
1999
- 1999-08-06 JP JP2000566386A patent/JP2002523558A/en active Pending
- 1999-08-06 US US09/763,017 patent/US6306808B1/en not_active Expired - Fee Related
- 1999-08-06 EP EP99941530A patent/EP1105454A1/en not_active Withdrawn
- 1999-08-06 KR KR1020017002043A patent/KR20010072730A/en not_active Application Discontinuation
- 1999-08-06 AU AU55110/99A patent/AU5511099A/en not_active Abandoned
- 1999-08-06 WO PCT/EP1999/005699 patent/WO2000011129A1/en not_active Application Discontinuation
-
2001
- 2001-02-15 NO NO20010766A patent/NO20010766L/en not_active Application Discontinuation
- 2001-08-31 US US09/943,657 patent/US20020058599A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
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See references of WO0011129A1 * |
Also Published As
Publication number | Publication date |
---|---|
US6306808B1 (en) | 2001-10-23 |
WO2000011129A1 (en) | 2000-03-02 |
US20020058599A1 (en) | 2002-05-16 |
JP2002523558A (en) | 2002-07-30 |
AU5511099A (en) | 2000-03-14 |
NO20010766D0 (en) | 2001-02-15 |
KR20010072730A (en) | 2001-07-31 |
NO20010766L (en) | 2001-04-05 |
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