EP2329001B1 - Bleichkatalysatormischungen bestehend aus mangansalzen und oxalsäure oder deren salze - Google Patents
Bleichkatalysatormischungen bestehend aus mangansalzen und oxalsäure oder deren salze Download PDFInfo
- Publication number
- EP2329001B1 EP2329001B1 EP09778106A EP09778106A EP2329001B1 EP 2329001 B1 EP2329001 B1 EP 2329001B1 EP 09778106 A EP09778106 A EP 09778106A EP 09778106 A EP09778106 A EP 09778106A EP 2329001 B1 EP2329001 B1 EP 2329001B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- manganese
- oxalic acid
- salts
- bleach activator
- weight
- 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.)
- Active
Links
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims description 75
- 239000000203 mixture Substances 0.000 title claims description 39
- 239000007844 bleaching agent Substances 0.000 title claims description 24
- 235000006408 oxalic acid Nutrition 0.000 title claims description 24
- 150000002696 manganese Chemical class 0.000 title claims description 8
- 239000003054 catalyst Substances 0.000 title description 8
- 150000003839 salts Chemical class 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000004851 dishwashing Methods 0.000 claims description 16
- 239000012190 activator Substances 0.000 claims description 15
- -1 manganese halides Chemical class 0.000 claims description 15
- 239000003599 detergent Substances 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 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 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical class [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical class [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical class [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004685 tetrahydrates Chemical class 0.000 claims description 2
- 150000004682 monohydrates Chemical class 0.000 claims 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims 1
- 229940039790 sodium oxalate Drugs 0.000 claims 1
- 238000004061 bleaching Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000012459 cleaning agent Substances 0.000 description 9
- 150000003751 zinc Chemical class 0.000 description 9
- 150000002697 manganese compounds Chemical class 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 241001122767 Theaceae Species 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229940088598 enzyme Drugs 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 102000013142 Amylases Human genes 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 3
- 235000019418 amylase Nutrition 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 159000000001 potassium salts Chemical class 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 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 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003826 tablet Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 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
- 102000035195 Peptidases Human genes 0.000 description 2
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 125000005263 alkylenediamine group Polymers 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 235000019421 lipase Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 229910052615 phyllosilicate Inorganic materials 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
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- 239000001509 sodium citrate Substances 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
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- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- 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
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- WLDGDTPNAKWAIR-UHFFFAOYSA-N 1,4,7-trimethyl-1,4,7-triazonane Chemical compound CN1CCN(C)CCN(C)CC1 WLDGDTPNAKWAIR-UHFFFAOYSA-N 0.000 description 1
- LYPVKWMHGFMDPD-UHFFFAOYSA-N 1,5-diacetyl-1,3,5-triazinane-2,4-dione Chemical compound CC(=O)N1CN(C(C)=O)C(=O)NC1=O LYPVKWMHGFMDPD-UHFFFAOYSA-N 0.000 description 1
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- TWDUKWCXYKWSKZ-UHFFFAOYSA-N 2-(7-methyloctanoyloxy)benzenesulfonic acid Chemical compound CC(C)CCCCCC(=O)OC1=CC=CC=C1S(O)(=O)=O TWDUKWCXYKWSKZ-UHFFFAOYSA-N 0.000 description 1
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- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 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
- 150000001412 amines 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
- RVEDSNKPFDBZRK-UHFFFAOYSA-N benzenesulfonyl dodecanoate;sodium Chemical compound [Na].CCCCCCCCCCCC(=O)OS(=O)(=O)C1=CC=CC=C1 RVEDSNKPFDBZRK-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 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
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 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
- 239000008139 complexing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 108010005400 cutinase Proteins 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000000249 desinfective effect Effects 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
- 238000010410 dusting Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 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
- 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
- 239000004519 grease Substances 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
- 239000008233 hard water Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000003446 ligand Substances 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
- 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
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical class [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910021527 natrosilite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000001402 nonanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002912 oxalic acid derivatives Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 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
- 239000002304 perfume Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 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
- 239000001488 sodium phosphate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007944 soluble tablet Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
- 229940038773 trisodium citrate Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 1
- 229940100530 zinc ricinoleate Drugs 0.000 description 1
- 229940006174 zinc valerate Drugs 0.000 description 1
- MXODCLTZTIFYDV-JHZYRPMRSA-L zinc;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Zn+2].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O.C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O MXODCLTZTIFYDV-JHZYRPMRSA-L 0.000 description 1
- YISPIDBWTUCKKH-UHFFFAOYSA-L zinc;4-methylbenzenesulfonate Chemical compound [Zn+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 YISPIDBWTUCKKH-UHFFFAOYSA-L 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
- BUDAIZWUWHWZPQ-UHFFFAOYSA-L zinc;pentanoate Chemical compound [Zn+2].CCCCC([O-])=O.CCCCC([O-])=O BUDAIZWUWHWZPQ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
Definitions
- the present invention relates to the use of certain manganese compounds in combination with oxalic acid or its derivatives for enhancing the bleaching effect of inorganic peroxygen compounds in bleaching colored stains on hard surfaces, and hard surface cleaners containing such combinations.
- Inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
- the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.
- the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine and acylated glycolurils, such as tetraacetylglycoluril, also carboxylic acid anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxybenzenesulfonate, sodium lauroyl-benzenesulfonate or decanoyloxybenzoic acid and acylated sugar derivatives, such as pentaacetylglucose, have become known in the literature.
- bleach activators for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine and acyl
- manganese / EDTA complexes as in EP 0 141 470 or manganese sulfate / picolinic acid mixtures, as in US 3,532,634 or manganese (II) or (III) salts in combination with carbonates ( EP 0 082 563 ), Fatty acids ( US 4,626,373 ), Phosphonates ( EP 0 072 166 ), Hydroxycarboxylic acids ( EP 0 237 111 ) or citric acid or its salts ( EP 0 157 483 ).
- De-C1 19909546 describes the use of Mn-ions in combination with oxalate complexing agents for improving the enzymatic oxidation in detergents and dishwashing detergents.
- W02001 / 045842 describes a bleach catalyst containing a macrocyclic organic ligand (TCAN), besides a water-insoluble Mn compound such as manganese oxide or manganese oxalate and a peroxide source.
- TCAN macrocyclic organic ligand
- the present invention has the improvement of the oxidation and bleaching action of inorganic peroxygen compounds in conjunction with Manganese compounds at low temperatures below 80 ° C, especially in the temperature range of about 15 to 45 ° C, the goal.
- manganese compounds in combination with a persalt and oxalic acid, their salts or derivatives have a significant contribution to the cleaning performance of the peroxygen compounds against colored stains on hard surfaces, especially when used in combination with under perhydrolysis conditions peroxycarboxylic acid releasing compounds.
- the invention relates to bleach catalyst mixtures as defined in claim 1, containing a manganese compound, oxalic acid, its salts or derivatives, and an inorganic Persaergesstoffitati.
- the manganese compounds are manganese salts in the +2 or +3 oxidation states selected from the group consisting of manganese halides, with the chlorides being preferred, manganese sulfates, manganese acetates, manganese acetylacetonates, and manganese nitrates.
- the oxalic acid can be used as the free acid, mono- or disalt of alkali or alkaline earth metals or ammonium salts.
- derivatives of oxalic acid can be used, wherein at least one acid function is not derivatized, besides oxalic acid derivatives are suitable which hydrolyze under washing conditions and release oxalic acid.
- a peracid substance compound in addition to a peracid substance compound, preferably 0.025 to 2.5% by weight, in particular 0.05 to 1.5% by weight of bleach-intensifying manganese compound and 0.025 to 2.5% by weight, in particular 0, 05 to 1.5 wt .-% of oxalic acid, their salts or derivatives.
- Suitable peroxygen compounds are hydrogen peroxide, but in the first place alkali perborate or tetrahydrate and / or alkali metal percarbonate, with sodium being the preferred alkali metal.
- the use of Sodium percarbonate has particular advantages in dishwashing detergents, as it has a particularly favorable effect on the corrosion behavior of glasses.
- the oxygen-based bleaching agent is therefore preferably an alkali percarbonate, especially sodium percarbonate.
- the amounts of peroxygen compounds used are generally chosen so that in the solutions between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm of active oxygen are present.
- bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
- the bleach formulation can be conventional bleach activators, that is, compounds which give perbenzoic acid optionally substituted under perhydrolysis conditions and / or peroxycarboxylic acids having 1 to 10 carbon atoms, especially 2 to 4 carbon atoms.
- bleach activators that is, compounds which give perbenzoic acid optionally substituted under perhydrolysis conditions and / or peroxycarboxylic acids having 1 to 10 carbon atoms, especially 2 to 4 carbon atoms.
- Suitable are the customary bleach activators cited at the outset which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates , in particular nonanoyl or Isononanoyloxybenzolsulfonat, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG), Pentaacetylfruktose, Te
- bleaching is understood to mean here both the bleaching of dirt located on the hard surface, in particular tea, and the bleaching of dirt removed from the hard surface in the dishwashing liquor.
- the main purpose of the use is to create conditions under which a peroxidic oxidizing agent and the combination of manganese salt and oxalic acid according to the invention can react with one another in the presence of a hard surface contaminated with colored stains, with the aim of obtaining more strongly oxidizing secondary products.
- Such conditions are especially present when the reactants meet in aqueous solution.
- This can be done by separately adding the peroxygen compound and the inventive combination of manganese salt and oxalic acid to an optionally detergent-containing solution.
- the method is particularly advantageous using a Hard surface cleaning agent containing the inventive combination of manganese salt and oxalic acid and a peroxygen-containing oxidizing agent.
- the peroxygen compound may also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, if a non-oxygenated cleaner is used.
- the cleaning agents which may be in the form of granules, powdery or tablet-like solids, other shaped bodies, homogeneous solutions or suspensions, may contain, in principle, all known ingredients customary in such agents, as well as the said bleach-enhancing active ingredient.
- the compositions may in particular contain builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic solvents, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as silver corrosion inhibitors, foam regulators, additional peroxygen activators and dyes and fragrances.
- a hard surface cleaner can contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and glass microspheres, and mixtures thereof.
- Abrasives are preferably not more than 20 wt .-%, in particular from 5 to 15 wt .-%, contained in the cleaning agents.
- An apparatus for machine dishwashing containing from 15 to 65% by weight, in particular from 20 to 60% by weight of water-soluble builder component, from 5 to 25% by weight, in particular from 8 to 17% by weight, of oxygen-based bleach, in each case to the total agent, and 0.05% to 1.5% by weight each of manganese salt and oxalic acid.
- Such an agent is particularly low alkaline, that is, its 1-weight percent solution has a pH of 8 to 11.5, preferably 9 to 11.
- Suitable water-soluble builder components in detergents are in principle all builders customarily employed in detergents for dishwashing, for example alkali phosphates which may be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Their amounts may be in the range of up to about 60 wt .-%, in particular 5 to 20 wt .-%, based on the total mean.
- water-soluble builder components besides polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the polycarboxylate type which act as co-builders, especially in hard water regions.
- organic polymers of the polycarboxylate type which act as co-builders, especially in hard water regions.
- examples include polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymeric acids.
- Commercially available products are, for example, Sokalan TM CP 5, CP 10 and PA 30 from BASF.
- co-builder polymers of native origin include oxidized starch and polyamino acids such as polyglutamic acid or polyaspartic acid.
- hydroxycarboxylic acids such as mono-, dihydroxysuccinic, alpha-hydroxypropionic and gluconic acid.
- Preferred organic builder components include the salts of citric acid, especially sodium citrate.
- sodium citrate anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
- the acids corresponding to the said co-builder salts may also be present.
- the enzymes optionally present in the compositions include proteases, amylases, pullulanases, cutinases and / or lipases, for example, proteases such as BLAP TM, Optimase TM, Opticlean TM, Maxacal TM, Maxapem TM, Durazym TM, Purafect TM OxP, Esperase TM and / or Savinase TM, amylases such as Termamyl TM, Amylase-LT TM, Maxamyl TM, Duramyl TM and / or lipases such as Lipolase TM, Lipomax TM, Lumafast TM and / or Lipozym TM.
- proteases such as BLAP TM, Optimase TM, Opticlean TM, Maxacal TM, Maxapem TM, Durazym TM, Purafect TM OxP, Esperase TM and / or Savinase TM
- the enzymes used may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the cleaning agents in amounts of up to 10% by weight, in particular from 0.05 to 5% by weight, particular preference being given to using enzymes which are stabilized against oxidative degradation.
- the machine dishwashing detergents preferably contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali metal bicarbonates.
- Alkali silicates may be present in amounts of up to 40% by weight. in particular from 3 to 30% by weight, based on the total agent.
- the alkali carrier system preferably used in the compositions is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be contained in an amount of up to 50% by weight, preferably 5 to 40% by weight.
- compositions 20 to 60% by weight of water-soluble organic builders, in particular alkali citrate, 3 to 20% by weight of alkali metal carbonate and 3 to 40% by weight of alkali metal disilicate are contained.
- Surfactants in particular anionic surfactants, zwitterionic surfactants and preferably weakly foaming nonionic surfactants may also be added to the compositions if appropriate, which serve to better remove greasy soilings, as wetting agents and, if appropriate, in the course of the preparation of the cleaning agents as granulation auxiliaries.
- Their amount can be up to 20 wt .-%, in particular up to 10 wt .-% and is preferably in the range of 0.5 to 5 wt .-%.
- extremely low-foam compounds are used in particular in detergents for use in automatic dishwashing processes.
- C 12 -C 18 -alkylpolyethylenglykol-polypropylene glycol ethers with in each case at to 8 mol ethylene oxide and propylene oxide units in the molecule.
- surfactants from the family of glucamides such as, for example, alkyl-N-methylglucamides, in which the alkyl moiety preferably originates from 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 presence of amine oxides, betaines and ethoxylated alkylamines is also possible.
- silverware inhibitors can be used in dishwashing detergents.
- Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, cobalt or cerium salts and / or complexes in which the abovementioned Metals depending on the metal in one of the oxidation states II, III, IV, V or VI.
- crystalline layered silicates and / or zinc salts are sold, for example, by the company Clariant under the trade name Na-SKS, z. Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, Magadiite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, makatite).
- Na-SKS-5 alpha -Na 2 Si 2 O 5
- Na-SKS-7 beta-Na 2 Si 2 O 5 , natrosilite
- Na-SKS-9 NaHSi 2 O 5 .H 2 O
- Na-SKS-10 NaHSi 2 O 5 .3H 2 O, kanemite
- Na-SKS-11 t-Na 2 Si 2 O 5
- Na-SKS-13 NaHSi 2 O 5
- Na-SKS-6 delta-Na 2 Si 2 O 5
- preferred automatic dishwashing or automatic dishwashing assistants have a weight fraction of the crystalline layered silicate of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0.4 to 10% by weight. -%, based in each case on the total weight of these funds.
- automatic dishwashing or dishwashing auxiliaries comprise at least one zinc salt selected from the group of organic zinc salts, preferably from the group of soluble organic zinc salts, more preferably from the group of soluble zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate , Zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesulfonate.
- group of organic zinc salts preferably from the group of soluble organic zinc salts, more preferably from the group of soluble zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate , Zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesulfonate.
- automatic dishwashing or automatic dishwashing aids in which the proportion by weight of the zinc salt relative to the total weight of this agent is 0.1 to 10% by weight, preferably 0.2 to 7% by weight and in particular 0, are preferred , 4 to 4 wt .-% and regardless of which zinc salts are used, in particular therefore irrespective of whether organic or inorganic zinc salts, soluble or non-soluble zinc salts or mixtures thereof are used.
- the cleaning agents may still 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, paraffins, paraffin-alcohol combinations, hydrophobized silica, the Bisfettklareamide, and other other known commercially available defoamer may be added.
- a foam-suppressing compound preferably from the group of silicone oils
- Mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the Bisfettklareamide, and other other known commercially available defoamer may be added.
- Other optional ingredients in the compositions are, for example, perfume oils.
- organic solvents which can be used in the compositions, in particular if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers.
- Such water-miscible solvents are preferably present in the detergents not more than 20% by weight, in particular from 1 to 15% by weight.
- the agents can system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also, mineral acids, in particular sulfuric acid or alkali metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
- acids in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid
- mineral acids in particular sulfuric acid or alkali metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
- pH regulators are preferably not more than 10% by weight, in particular from 0.5 to 6% by weight, in the compositions.
- the preparation of the solid agents presents no difficulties and may be carried out in a manner known in the art, for example by spray-drying or granulation, wherein peroxygen compound and bleach catalyst are optionally added separately later.
- Detergents in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
- compositions are preferably in the form of powdered, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roller compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the like Bleaching catalyst are expected to be produced.
- the procedure is preferably such that all ingredients are mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with pressing pressures in the range of 200 x 10 5 Pa to 1500x10 5 Pa pressed.
- a tablet thus produced has a weight of 15 to 40 g, in particular from 20 to 30 g, with a diameter of 35 to 40 mm.
- compositions in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 800 to 1000 g / l can be carried out by subjecting the builder components with at least a proportion of liquid mixture components in a first process step Increase the bulk density of this premix and subsequently - if desired, after an intermediate drying - the other constituents of the agent, including the bleach catalyst, combined with the thus obtained premix.
- Means for cleaning dishes can be used both in household dishwashers and in commercial dishwashers. The addition is carried out by hand or by means of suitable metering 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 terminated by a few rinses of clear water following a cleaning cycle and a rinse cycle with a common rinse aid. After drying, the use of compositions containing inventive lead activator mixtures gives a completely clean and hygienically perfect dishes.
- tea cups were immersed in a 70 ° C. hot tea solution 25 times. Then each of the tea solution was added to each tea cup and the cup dried in a drying oven.
- Table 1 test product rating V1 (cleaner) 37% V2 (cleaner + 100 mg Mn (III) acetate) 57% V3 (cleaner + 100 mg Mn (II) sulphate) 55% V4 (cleaner + 100 mg oxalic acid) 60% V5 (cleaner + 100 mg FeSO 4 + 100 mg oxalic acid) 53% V6 (cleaner + 100 mg Na-oxalate) 67% M1 (cleaner + 100 mg Mn (II) SO 4 + 100 mg oxalic acid) 98% M2 (cleaner + 100 mg Mn (II) acetate + 100 mg oxalic acid) 97% M3 (cleaner + 100 mg Mn (II) SO 4 + 100 mg Na-oxalate) 95% M4 (cleaner + 100 mg Mn (III) acetate + 100 mg oxalic acid) 95% M5 (cleaner + 50 mg Mn (II) SO 4 + 50 mg oxalic acid) 73% M6 (clean
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL09778106T PL2329001T3 (pl) | 2008-08-30 | 2009-08-26 | Mieszaniny katalizatorów bielenia składające się z soli manganu i kwasu szczawiowego lub jego soli |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102008045207A DE102008045207A1 (de) | 2008-08-30 | 2008-08-30 | Bleichkatalysatormischungen bestehend aus Mangansalzen und Oxalsäure oder deren Salze |
PCT/EP2009/006163 WO2010022919A1 (de) | 2008-08-30 | 2009-08-26 | Bleichkatalysatormischungen bestehend aus mangansalzen und oxalsäure oder deren salze |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2329001A1 EP2329001A1 (de) | 2011-06-08 |
EP2329001B1 true EP2329001B1 (de) | 2012-10-10 |
Family
ID=41226123
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09778106A Active EP2329001B1 (de) | 2008-08-30 | 2009-08-26 | Bleichkatalysatormischungen bestehend aus mangansalzen und oxalsäure oder deren salze |
Country Status (10)
Country | Link |
---|---|
US (1) | US20110146723A1 (pt) |
EP (1) | EP2329001B1 (pt) |
JP (1) | JP5469667B2 (pt) |
CN (1) | CN102131908B (pt) |
DE (1) | DE102008045207A1 (pt) |
DK (1) | DK2329001T3 (pt) |
ES (1) | ES2396414T3 (pt) |
PL (1) | PL2329001T3 (pt) |
PT (1) | PT2329001E (pt) |
WO (1) | WO2010022919A1 (pt) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008038376A1 (de) * | 2008-08-19 | 2010-02-25 | Clariant International Ltd. | Verfahren zur Herstellung von 3,7-Diaza-bicyclo[3.3.1]nonan-Verbindungen |
DE102008045215A1 (de) * | 2008-08-30 | 2010-03-04 | Clariant International Ltd. | Verwendung von Mangan-Oxalatenn als Bleichkatalysatoren |
DE102008064009A1 (de) | 2008-12-19 | 2010-06-24 | Clariant International Ltd. | Verfahren zur Herstellung von 3,7-Diaza-bicyclo[3.3.1]nonan-Metall-Komplexen |
CN105369581A (zh) * | 2015-11-04 | 2016-03-02 | 泉州市新宏化工贸易有限公司 | 一种棉织物练漂后除氧工艺及棉洁爽 |
US10329522B2 (en) | 2016-05-19 | 2019-06-25 | Ecolab Usa Inc. | Cleaning compositions for use with calcite-based stone |
DE102017004742A1 (de) * | 2017-05-17 | 2018-11-22 | Weylchem Wiesbaden Gmbh | Beschichtete Granulate, deren Verwendung und Wasch- und Reinigungsmittel enthaltend diese |
CN110055771B (zh) * | 2019-05-13 | 2022-01-25 | 乐象永续科技(杭州)有限公司 | 一种纺织材料的漂白和改性方法和用途 |
EP4296343A1 (en) | 2022-06-24 | 2023-12-27 | WeylChem Performance Products GmbH | Compositions comprising protonated triazacyclic compounds and manganese(ii) acetate, manufacturing thereof, and bleaching and cleaning agent comprising same |
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GB1182143A (en) | 1966-03-01 | 1970-02-25 | United States Borax Chem | Bleaching Compositions and Methods. |
US4414127A (en) * | 1981-07-06 | 1983-11-08 | Syntex (U.S.A.) Inc. | Contact lens cleaning solutions |
GR76237B (pt) | 1981-08-08 | 1984-08-04 | Procter & Gamble | |
US4481129A (en) | 1981-12-23 | 1984-11-06 | Lever Brothers Company | Bleach compositions |
GB8329762D0 (en) | 1983-11-08 | 1983-12-14 | Unilever Plc | Manganese adjuncts |
GB8405189D0 (en) | 1984-02-28 | 1984-04-04 | Interox Chemicals Ltd | Peroxide activation |
US4728455A (en) | 1986-03-07 | 1988-03-01 | Lever Brothers Company | Detergent bleach compositions, bleaching agents and bleach activators |
CN86103060A (zh) * | 1986-04-27 | 1987-04-22 | 刘能振 | 由高锰酸盐和还原性物质组成的漂白剂 |
DE4443177A1 (de) | 1994-12-05 | 1996-06-13 | Henkel Kgaa | Aktivatormischungen für anorganische Perverbindungen |
US6734155B1 (en) * | 1997-07-09 | 2004-05-11 | The Procter & Gamble Company | Cleaning compositions comprising an oxidoreductase |
EP1002041B1 (en) * | 1997-07-09 | 2003-03-05 | The Procter & Gamble Company | Cleaning compositions comprising an oxidoreductase |
JPH1143410A (ja) * | 1997-07-11 | 1999-02-16 | Lion Corp | カビ取り剤組成物 |
DE19758183A1 (de) * | 1997-12-30 | 1999-07-01 | Henkel Kgaa | Waschaktiver Formkörper mit spezifischer Oberfläche |
DE19909546C1 (de) * | 1999-03-04 | 2000-06-29 | Consortium Elektrochem Ind | Mehrkomponentensystem zur enzymkatalysierten Oxidation von Substraten sowie Verfahren zur enzymkatalysierten Oxidation |
JP2000282091A (ja) * | 1999-03-31 | 2000-10-10 | Lion Corp | 漂白活性化触媒および該化合物を含有する漂白剤組成物 |
GB9930422D0 (en) * | 1999-12-22 | 2000-02-16 | Unilever Plc | Bleach catalysts |
AT408987B (de) * | 2000-10-13 | 2002-04-25 | Thonhauser Gmbh Dipl Ing | Reinigungs- und desinfektionsmittel |
JP4186037B2 (ja) * | 2001-07-09 | 2008-11-26 | ライオン株式会社 | 漂白性組成物 |
AU2003205725A1 (en) * | 2002-02-28 | 2003-09-09 | Unilever N.V. | Bleach catalyst enhancement |
MXPA05000483A (es) * | 2002-07-11 | 2005-03-23 | Ciba Sc Holding Ag | Uso de compuestos complejos de metal como catalizadores de oxidacion. |
DE10304131A1 (de) | 2003-02-03 | 2004-08-05 | Clariant Gmbh | Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren |
DE10345273A1 (de) | 2003-09-30 | 2005-04-21 | Clariant Gmbh | Verwendung von Übergangsmetallkomplexen mit Lactamliganden als Bleichkatalysatoren |
DE502004010306D1 (de) * | 2003-10-31 | 2009-12-10 | Henkel Ag & Co Kgaa | Verpackungsverfahren |
GB0411304D0 (en) * | 2004-05-21 | 2004-06-23 | Fellows Adrian N | An antimicrobial composition |
DE102005027619A1 (de) * | 2005-06-15 | 2006-12-28 | Clariant Produkte (Deutschland) Gmbh | Verfahren zur Herstellung von 3,7-Diaza-bicyclo[3.3.1]nonan-Verbindungen |
DE102008038376A1 (de) * | 2008-08-19 | 2010-02-25 | Clariant International Ltd. | Verfahren zur Herstellung von 3,7-Diaza-bicyclo[3.3.1]nonan-Verbindungen |
DE102008045215A1 (de) * | 2008-08-30 | 2010-03-04 | Clariant International Ltd. | Verwendung von Mangan-Oxalatenn als Bleichkatalysatoren |
DE102008064009A1 (de) * | 2008-12-19 | 2010-06-24 | Clariant International Ltd. | Verfahren zur Herstellung von 3,7-Diaza-bicyclo[3.3.1]nonan-Metall-Komplexen |
-
2008
- 2008-08-30 DE DE102008045207A patent/DE102008045207A1/de not_active Withdrawn
-
2009
- 2009-08-26 EP EP09778106A patent/EP2329001B1/de active Active
- 2009-08-26 PT PT97781066T patent/PT2329001E/pt unknown
- 2009-08-26 CN CN2009801329174A patent/CN102131908B/zh active Active
- 2009-08-26 US US13/060,828 patent/US20110146723A1/en not_active Abandoned
- 2009-08-26 PL PL09778106T patent/PL2329001T3/pl unknown
- 2009-08-26 ES ES09778106T patent/ES2396414T3/es active Active
- 2009-08-26 JP JP2011524245A patent/JP5469667B2/ja not_active Expired - Fee Related
- 2009-08-26 WO PCT/EP2009/006163 patent/WO2010022919A1/de active Application Filing
- 2009-08-26 DK DK09778106.6T patent/DK2329001T3/da active
Also Published As
Publication number | Publication date |
---|---|
WO2010022919A1 (de) | 2010-03-04 |
CN102131908B (zh) | 2013-02-20 |
PT2329001E (pt) | 2013-01-24 |
EP2329001A1 (de) | 2011-06-08 |
JP5469667B2 (ja) | 2014-04-16 |
US20110146723A1 (en) | 2011-06-23 |
JP2012500871A (ja) | 2012-01-12 |
DE102008045207A1 (de) | 2010-03-04 |
ES2396414T3 (es) | 2013-02-21 |
DK2329001T3 (da) | 2013-01-28 |
CN102131908A (zh) | 2011-07-20 |
PL2329001T3 (pl) | 2013-03-29 |
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