EP2329001A1 - Bleach catalyst mixtures consisting of manganese salts and oxalic acid or the salts thereof - Google Patents
Bleach catalyst mixtures consisting of manganese salts and oxalic acid or the salts thereofInfo
- Publication number
- EP2329001A1 EP2329001A1 EP09778106A EP09778106A EP2329001A1 EP 2329001 A1 EP2329001 A1 EP 2329001A1 EP 09778106 A EP09778106 A EP 09778106A EP 09778106 A EP09778106 A EP 09778106A EP 2329001 A1 EP2329001 A1 EP 2329001A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- salts
- manganese
- oxalic acid
- weight
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 25
- 235000006408 oxalic acid Nutrition 0.000 title claims abstract description 21
- 150000003839 salts Chemical class 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 title claims description 32
- 150000002696 manganese Chemical class 0.000 title claims description 11
- 239000003054 catalyst Substances 0.000 title abstract description 10
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 12
- 239000003599 detergent Substances 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 13
- 239000012190 activator Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000012459 cleaning agent Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 3
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical class [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 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 2
- 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 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
- 150000001875 compounds Chemical class 0.000 abstract description 22
- 230000009471 action Effects 0.000 abstract description 3
- 238000004061 bleaching Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000004851 dishwashing Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- -1 cationic nitrile Chemical class 0.000 description 11
- 239000003513 alkali 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
- 150000003751 zinc Chemical class 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 241001122767 Theaceae Species 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 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
- 239000004615 ingredient Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 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
- 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
- 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 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
- 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
- 239000000969 carrier Substances 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
- 239000006260 foam Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese 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
- 150000002978 peroxides Chemical class 0.000 description 3
- 159000000001 potassium salts Chemical class 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000003826 tablet Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 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
- 239000000470 constituent Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 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
- 239000000843 powder Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 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
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 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
- 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
- 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
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- GZFRVDZZXXKIGR-UHFFFAOYSA-N 2-decanoyloxybenzoic acid Chemical compound CCCCCCCCCC(=O)OC1=CC=CC=C1C(O)=O GZFRVDZZXXKIGR-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 101000740449 Bacillus subtilis (strain 168) Biotin/lipoyl attachment protein Proteins 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- RKWGIWYCVPQPMF-UHFFFAOYSA-N Chloropropamide Chemical compound CCCNC(=O)NS(=O)(=O)C1=CC=C(Cl)C=C1 RKWGIWYCVPQPMF-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 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
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 108010083608 Durazym Proteins 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241001180747 Hottea Species 0.000 description 1
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- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 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
- 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
- 108010020346 Polyglutamic Acid Proteins 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
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 description 1
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect 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
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001342 alkaline earth metals 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
- 150000003863 ammonium salts 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
- 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
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 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
- 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
- 150000002334 glycols Chemical class 0.000 description 1
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 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
- 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
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Chemical class 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
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical class [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical class [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 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
- 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
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920005646 polycarboxylate 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
- 238000000926 separation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 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
- 235000019982 sodium hexametaphosphate Nutrition 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
- 239000008247 solid mixture 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
- 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
- 150000004685 tetrahydrates Chemical class 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
- 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 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
- Bleach catalyst mixtures consisting of manganese salts and oxalic acid or salts thereof
- the present invention relates to the use of certain manganese compounds in combination with oxalic acid or its derivatives for enhancing the bleaching action of, in particular, 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 depends on dilute
- 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 lauroylbenzenesulfonate 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 acylated glycolurils, such as tetraacetylglycoluril, also carb
- Transition metal salts and complexes as so-called bleach catalysts.
- the metal complexes provided that they ensure a good soil removal at all under the conditions of the purification process, are usually characterized by a complex synthesis and the associated high production costs of the complex ligand.
- manganese compounds which cause a certain bleaching efficiency under washing and cleaning conditions in combination with persalts.
- manganese / EDTA complexes as in EP 0 141 470 or manganese sulfate / picolinic acid mixtures, as in
- 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 0 C, especially in the temperature range of about 15 to 45 0 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 provides bleach catalyst mixtures containing a manganese compound and oxalic acid, their salts or derivatives.
- manganese compounds all manganese salts in the oxidation states +2 or +3 find use, for example, manganese halides, wherein the
- Chlorides are preferred, manganese sulfates, manganese salts of organic acids such as manganese acetates, manganese acetylacetonates, manganese nitrates, and manganese complexes, as described in EP 1 445 305 or EP 1 520 910.
- 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.
- detergents and cleaners according to the invention are 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% by weight containing oxalic acid, its 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 glycol loops, in particular tetraacetylglycoluril (TAGU), acylated thazine 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 invention relates to a process for the cleaning of hard surfaces, in particular dishes using in aqueous, optionally further detergent ingredients, especially peroxide-based oxidants containing solution, and cleaning agents for hard surfaces, especially detergents for dishes and among these preferably those for the Use in machine cleaning processes, the inventive combinations of manganese (II) or (III) salts and oxalic acid, their salts or derivatives.
- the use of the present invention consists in providing 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 process according to the invention is particularly advantageous using an inventive Hard surface cleaning agent containing the combination of manganese salt and oxalic acid of the present invention and optionally 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 according to the invention may in principle contain all known ingredients customary in such agents, as well as the said bleach-intensifying active substance.
- the compositions according to the invention may contain, in particular, 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 also dyes and fragrances.
- a hard surface cleaning agent according to the invention may contain abrasive constituents, 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 according to the invention.
- a further subject of the invention is a machine for cleaning dishes containing 15 to 65% by weight, in particular 20 to 60% by weight of water-soluble builder component, 5 to 25% by weight, in particular 8 to 17% by weight of bleach Oxygen basis, in each case based on the total agent, and in each case 0.05 to 1, 5 wt .-% 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 cleaning compositions according to the invention are in principle all builders customarily used in detergents for dishwashing, for example alkali phosphates which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
- water-soluble builder components in addition to polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the type of the polycarboxylates of native or synthetic origin, which act as co-builders, in particular in hard water regions.
- polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymeric acids are suitable.
- Commercially available products are, for example, Sokalan TM CP 5, CP 10 and PA 30 from BASF.
- suitable co-builder polymers of native origin include oxidized starch and polyamino acids such as polyglutamic acid or
- Polyaspartic acid Other possible builder components are naturally occurring hydroxycarboxylic acids such as mono-, dihydroxysuccinic, alpha-hydroxypropionic and gluconic acid.
- the preferred organic builder components include the salts of citric acid, especially sodium citrate.
- 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.
- the acids corresponding to the said co-builder salts may also be present.
- the enzymes optionally contained in agents according to the invention 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 detergents according to the invention 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 according to the invention preferably contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali metal bicarbonates.
- the alkali carriers commonly used include carbonates, bicarbonates and
- Alkalisilicates can in amounts of up to 40 wt .-%, in particular 3 to 30 wt .-%, based to be included on the entire medium.
- the alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be present in an amount of up to 50% by weight, preferably 5 to 40% by weight.
- agents are 20 to 60 wt .-% of water-soluble organic builder, in particular alkali, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.
- Surfactants in particular anionic surfactants, zwitterionic surfactants and, preferably, low-foaming nonionic surfactants may also be added to the compositions according to the invention, which serve as a wetting agent and optionally as part of the preparation of the cleaning agents as granulating aids for better separation of greasy soils.
- 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 2 -C 8 -alkylpolyethylene glycol polypropylene glycol ethers with in each case up to 8 mol of ethylene oxide and propylene oxide units in the molecule.
- One can also use other known low-foaming nonionic surfactants such as C 2 -C 8 alkyl polyethylene-polybutylene glycol ethers containing up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end-capped Alkylpolyalkylenglykolmischether and although foaming, but ecologically attractive Cs-Cu Alkylpolyglucosides having a degree of polymerization of about 1 to 4 and / or Ci 2 -Ci 4 -Alkylpolyethylenglykole with 3 to 8 ethylene 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 having the C chain length C 6 -Cu. 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.
- silver corrosion inhibitors can be used in dishwashing detergents according to the invention.
- Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, 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 Oi 7 -XH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 -XH 2 O, Makatite).
- 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 Oi 7 -XH 2 O
- 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 0 5
- Na-SKS-13 NaHSi 2 O 5
- Na-SKS-6 delta-Na 2 Si 2 0 5
- An overview of crystalline phyllosilicates can be found, for. For example, in the article published in "Soap-Oils-Fats-Waxes, Volume 116, No. 20/1990" on pages 805-808.
- 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 dishwasher detergents or dishwashing auxiliaries contain 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 for example in the presence of anionic surfactants, foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-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. Further optional ingredients in the compositions according to the invention are, for example, perfume oils.
- organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms , in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compound ethers.
- Such water-miscible solvents are preferably present in the detergents according to the invention not more than 20% by weight, in particular from 1 to 15% by weight.
- compositions according to the invention may contain 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 hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
- Such pH regulators are preferably not more than 10% by weight, in particular from 0.5 to 6% by weight, in the middle of the invention.
- compositions according to the invention presents no difficulties and can 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 according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
- compositions according to the invention are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleach catalyst are to be expected, can be prepared.
- the procedure is preferably such that all components are mixed together in a mixer and the mixture is compressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing pressures in the range from 200 ⁇ 10 5 Pa to 1500 ⁇ 10 5 Pa.
- Conditions of use sufficiently quickly soluble tablets with flexural strengths of normally over 150 N Preferably, such a tablet produced in such a way a weight of 15 to 40 g, in particular from 20 to 30 g, with a diameter of 35 to 40 mm.
- compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / l can be carried out by subjecting the builder components to at least a portion of liquid mixture components in a first process substep 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.
- Detergents according to the invention 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, when using agents according to the invention, a completely clean and hygienically perfect dishes are obtained.
Abstract
The invention relates to bleach catalysts containing a managanese compound and oxalic acid, or the salt or derivatives thereof. The presence of the oxalic acid reinforces the action of the manganese compound as a bleach catalyst.
Description
Bleichkatalysatormischungen bestehend aus Mangansalzen und Oxalsäure oder deren Salze Bleach catalyst mixtures consisting of manganese salts and oxalic acid or salts thereof
Die vorliegende Erfindung betrifft die Verwendung bestimmter Manganverbindungen in Kombination mit Oxalsäure oder deren Derivate zur Verstärkung der Bleichwirkung von insbesondere anorganischen Persauerstoffverbindungen beim Bleichen von gefärbten Anschmutzungen an harten Oberflächen, und Reinigungsmittel für harte Oberflächen, welche derartige Kombinationen enthalten.The present invention relates to the use of certain manganese compounds in combination with oxalic acid or its derivatives for enhancing the bleaching action of, in particular, inorganic peroxygen compounds in bleaching colored stains on hard surfaces, and hard surface cleaners containing such combinations.
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 verdünntenInorganic 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 depends on dilute
Lösungen stark von der Temperatur ab; so erzielt man beispielsweise mit HbO2 oder Perborat in alkalischen Bleichflotten erst bei Temperaturen oberhalb von etwa 80 0C eine ausreichend schnelle Bleiche verschmutzter Textilien. Bei niedrigeren Temperaturen kann die Oxidationswirkung der anorganischen Persauerstoffverbindungen durch Zusatz sogenannter Bleichaktivatoren verbessert werden, für die zahlreichen Vorschläge, vor allem aus den Stoffklassen der N- oder O-Acylverbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin und acylierte Glykolurile, wie Tetraacetylglykoluril, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, Carbonsäureester, insbesondere Natrium- nonanoyloxybenzolsulfonat, Natrium-lauroyl-benzolsulfonat oder Decanoyloxy- benzoesäure und acylierte Zuckerderivate, wie Pentaacetylglukose, in der Literatur bekannt geworden sind. In der neueren Literatur werden daneben eine Reihe von Nitrilderivaten, insbesondere kationische Nitrilquats für diesen Einsatzzweck beansprucht. Durch Zusatz dieser Substanzen kann dieSolutions strongly on the temperature; Thus, for example, with HbO 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 0 C, a sufficiently fast bleaching of soiled textiles. At lower temperatures, 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 lauroylbenzenesulfonate or decanoyloxybenzoic acid and acylated sugar derivatives, such as pentaacetylglucose, have become known in the literature. In addition, the recent literature claims a number of nitrile derivatives, in particular cationic nitrile quats, for this purpose. By adding these substances, the
Bleichwirkung wässriger Peroxidflotten so weit gesteigert werden, dass bereits bei Temperaturen um 60 0C im Wesentlichen die gleichen Wirkungen wie mit der Peroxidflotte allein bei 95 0C eintreten.
Im Bemühen um energiesparende Wasch- und Bleichverfahren gewinnen in den letzten Jahren Anwendungstemperaturen deutlich unterhalb 60 CC, insbesondere unterhalb 45 0C bis herunter zur Kaltwassertemperatur an Bedeutung.Bleaching effect of aqueous peroxide liquors are increased so much that even at temperatures around 60 0 C substantially the same effects as with the peroxide solution alone at 95 0 C. In the quest for energy-saving washing and bleaching process in recent years application temperatures well below 60 C C, especially below 45 0 C down to the cold water temperature in importance.
Bei diesen niedrigen Temperaturen lässt die Wirkung der bisher bekannten Aktivatorverbindungen in der Regel erkennbar nach. Es hat deshalb nicht an Bestrebungen gefehlt, für diesen Temperaturbereich wirksamere Systeme zu entwickeln, ohne dass bis heute ein überzeugender Erfolg zu verzeichnen gewesen wäre. Ein Ansatzpunkt dazu ergibt sich durch den Einsatz vonAt these low temperatures, the effect of the previously known activator compounds usually decreases noticeably. There has therefore been no lack of efforts to develop more effective systems for this temperature range, without that to date a convincing success would have been recorded. One starting point for this is the use of
Übergangsmetallsalzen und -komplexen, als sogenannte Bleichkatalysatoren. Die Metallkomplexe, sofern sie unter den Bedingungen des Reinigungsprozesses überhaupt eine gute Schmutzentfernung gewährleisten, sind meist durch eine aufwendige Synthese und damit verbunden hohe Herstellkosten des Komplexliganden gekennzeichnet.Transition metal salts and complexes, as so-called bleach catalysts. The metal complexes, provided that they ensure a good soil removal at all under the conditions of the purification process, are usually characterized by a complex synthesis and the associated high production costs of the complex ligand.
Weiterhin sind eine Reihe relativ einfacher Manganverbindungen beschrieben, die unter Wasch- und Reinigungsbedingungen in Kombination mit Persalzen eine gewisse Bleichwirksamkeit hervorrufen. Hierzu zählen Mangan/EDTA-Komplexe wie in EP 0 141 470 oder Mangansulfat/Picolinsäure-Mischungen, wie inFurthermore, a number of relatively simple manganese compounds are described, which cause a certain bleaching efficiency under washing and cleaning conditions in combination with persalts. These include manganese / EDTA complexes as in EP 0 141 470 or manganese sulfate / picolinic acid mixtures, as in
US 3,532,634 beansprucht oder aber Mangan(ll) oder (Ill)-Salze in Kombination mit Carbonaten (EP 0 082 563), Fettsäuren (US 4,626,373), Phosphonaten (EP 0 072 166), Hydroxycarbonsäuren (EP 0 237 111 ) oder Zitronensäure bzw. deren Salze (EP 0 157 483). Keine der genannten Kombinationen weist jedoch eine signifikante Reinigungsleistung an hartnäckigen Teeanschmutzungen auf harten Oberflächen auf. Weiterhin ist bekannt, dass Oxalat-Ionen einen positiven Effekt auf Mangan-katalysierte Epoxidationen in Gegenwart von Trimethyl-1 ,4,7- triazacyclononan ausüben, (T.H. Bennur et al., Journal of Molecular Catalysis A: Chemical 185 (2002) 71-80).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 their salts (EP 0 157 483). However, none of the above combinations has significant cleaning performance on stubborn tea stains on hard surfaces. Furthermore, it is known that oxalate ions have a positive effect on manganese-catalyzed epoxidations in the presence of trimethyl-1,4,7-triazacyclononane (TH Bennur et al., Journal of Molecular Catalysis A: Chemical 185 (2002) 71-). 80).
Die vorliegende Erfindung hat die Verbesserung der Oxidations- und Bleichwirkung anorganischer Persauerstoffverbindungen in Verbindung mit
Manganverbindungen bei niedrigen Temperaturen unterhalb von 80 0C, insbesondere im Temperaturbereich von ca. 15 bis 45 0C, zum Ziel.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 0 C, especially in the temperature range of about 15 to 45 0 C, the goal.
Es wurde nun gefunden, dass Manganverbindungen in Kombination mit einem Persalz und Oxalsäure, deren Salze oder Derivate einen deutlichen Beitrag zur Reinigungsleistung der Persauerstoffverbindungen gegenüber gefärbten Anschmutzungen an harten Oberflächen aufweisen, insbesondere wenn man sie in Kombination mit unter Perhydrolysebedingungen Peroxocarbonsäure abspaltenden Verbindungen einsetzt.It has now been found that 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.
Gegenstand der Erfindung sind Bleichkatalysatormischungen enthaltend eine Manganverbindung und Oxalsäure, deren Salze oder Derivate.The invention provides bleach catalyst mixtures containing a manganese compound and oxalic acid, their salts or derivatives.
Als Manganverbindungen können alle Mangansalze in den Oxidationsstufen +2 oder +3 Verwendung finden, beispielsweise Manganhalogenide, wobei dieAs manganese compounds, all manganese salts in the oxidation states +2 or +3 find use, for example, manganese halides, wherein the
Chloride bevorzugt sind, Mangansulfate, Mangansalze organischer Säuren wie Manganacetate, Manganacetylacetonate, Mangannitrate, sowie Mangankomplexe, wie sie in EP 1 445 305 oder EP 1 520 910 beschrieben sind. Die Oxalsäure kann als freie Säure, Mono- oder Disalz von Alkali- oder Erdalkalimetallen oder Ammoniumsalzen zum Einsatz kommen. Weiterhin können Derivate der Oxalsäure verwendet werden, wobei zumindest eine Säurefunktion nicht derivatisiert ist, daneben sind Oxalsäurederivate geeignet, die unter Waschbedingungen hydrolysieren und Oxalsäure freisetzen.Chlorides are preferred, manganese sulfates, manganese salts of organic acids such as manganese acetates, manganese acetylacetonates, manganese nitrates, and manganese complexes, as described in EP 1 445 305 or EP 1 520 910. The oxalic acid can be used as the free acid, mono- or disalt of alkali or alkaline earth metals or ammonium salts. Furthermore, 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.
In erfindungsgemäßen Wasch- und Reinigungsmitteln sind neben einerIn detergents and cleaners according to the invention are in addition to a
Persäurestoffverbindung vorzugsweise 0,025 bis 2,5 Gew.-%, insbesondere 0,05 bis 1 ,5 Gew.-% an bleichverstärkender Manganverbindung und 0,025 bis 2,5 Gew.-%, insbesondere 0,05 bis 1 ,5 Gew.-% an Oxalsäure, ihrer Salze oder Derivate enthalten.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% by weight containing oxalic acid, its salts or derivatives.
Als Persauerstoffverbindungen kommen Wasserstoffperoxid, in erster Linie aber 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. Das Bleichmittel auf Sauerstoffbasis ist deshalb vorzugsweise ein Alkalipercarbonat, insbesondere Natriumpercarbonat.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.
Die Einsatzmengen an Persauerstoffverbindungen werden im Allgemeinen so gewählt, dass in den Lösungen zwischen 10 ppm und 10 % Aktivsauerstoff, vorzugsweise zwischen 50 und 5000 ppm Aktivsauerstoff vorhanden sind.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.
Ein Zusatz geringer Mengen bekannter Bleichmittelstabilisatoren wie beispielsweise von Phosphonaten, Boraten beziehungsweise Metaboraten und Metasilikaten sowie Magnesiumsalzen wie Magnesiumsulfat kann zweckdienlich sein.Addition of small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
Zusätzlich zu erfindungsgemäßen Bleichkatalysatormischungen kann die Bleichmittelformulierung konventionelle Bleichaktivatoren, das heißt Verbindungen, die unter Perhydrolysebedingungen gegebenenfalls substituierte Perbenzoesäure 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 Glykoluhle, insbesondere Tetraacetylglykoluril (TAGU), acylierte Thazinderivate, insbesondere 1 ,5-Diacetyl- 2,4-dioxohexahydro-1 ,3,5-triazin (DADHT), acylierte Phenylsulfonate, insbesondere Nonanoyl- oder Isononanoyloxybenzolsulfonat, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat und 2,5-Diacetoxy-2,5- dihydrofuran sowie acetyliertes Sorbit und Mannit, und acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton. Auch die aus der deutschen Patentanmeldung DE 44 43 177 bekannten Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. In einer bevorzugten
Ausführungsform der erfindungsgemäßen Verwendung wird gleichzeitig mit der Manganverbindung, der Oxalsäure und der Wasserstoffperoxid-generierenden Verbindung auch eine derartige unter Perhydrolysebedingungen Peroxocarbonsäure abspaltende Verbindung verwendet. In einer bevorzugten Ausführungsform erfindungsgemäßer Mittel sind 1 bis 10 Gew.-%, insbesondere 2 bis 6 Gew.-% an derartiger unter Perhydrolysebedingungen Peroxocarbonsäure abspaltender Verbindung anwesend.In addition to bleach catalyst blends according to the invention, 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. 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. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycol loops, in particular tetraacetylglycoluril (TAGU), acylated thazine 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, Tetraacetylxylose and Octaacetyllactose and acetylated , optionally N-alkylated glucamine and gluconolactone. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. In a preferred Embodiment of the use according to the invention is used simultaneously with the manganese compound, the oxalic acid and the hydrogen peroxide-generating compound and such under perhydrolysis conditions peroxocarboxylic acid releasing compound. In a preferred embodiment of inventive agents, 1 to 10% by weight, in particular 2 to 6% by weight, of such compound releasing peroxycarboxylic acid under perhydrolysis conditions are present.
Unter dem Begriff der Bleiche wird hier sowohl das Bleichen von sich auf der harten Oberfläche befindendem Schmutz, insbesondere Tee, als auch das Bleichen von in der Geschirrspülflotte befindlichem, von der harten Oberfläche abgelöstem Schmutz verstanden.The term 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.
Weiterhin betrifft die Erfindung ein Verfahren zur Reinigung von harten Oberflächen, insbesondere von Geschirr unter Einsatz von in wässriger, gegebenenfalls weitere Reinigungsmittelbestandteile, insbesondere Oxidationsmittel auf Persauerstoffbasis, enthaltender Lösung, und Reinigungsmittel für harte Oberflächen, insbesondere Reinigungsmittel für Geschirr und unter diesen vorzugsweise solche für den Einsatz in maschinellen Reinigungsverfahren, die erfindungsgemäßen Kombinationen aus Mangan(ll) oder (III) salzen und Oxalsäure, deren Salze oder Derivate enthalten.Furthermore, the invention relates to a process for the cleaning of hard surfaces, in particular dishes using in aqueous, optionally further detergent ingredients, especially peroxide-based oxidants containing solution, and cleaning agents for hard surfaces, especially detergents for dishes and among these preferably those for the Use in machine cleaning processes, the inventive combinations of manganese (II) or (III) salts and oxalic acid, their salts or derivatives.
Die erfindungsgemäße Verwendung besteht im Wesentlichen darin, in Gegenwart einer mit gefärbten Anschmutzungen verunreinigten harten Oberfläche Bedingungen zu schaffen, unter denen ein peroxidisches Oxidationsmittel und die erfindungsgemäße Kombination aus Mangansalz und Oxalsäure miteinander reagieren können, mit dem Ziel, stärker oxidierend wirkende Folgeprodukte zu erhalten. Solche Bedingungen liegen insbesondere dann vor, wenn die Reaktionspartner in wässriger Lösung aufeinander treffen. Dies kann durch separate Zugabe der Persauerstoffverbindung und der erfindungsgemäßen Kombination aus Mangansalz und Oxalsäure zu einer gegebenenfalls reinigungsmittelhaltigen Lösung geschehen. Besonders vorteilhaft wird das erfindungsgemäße Verfahren jedoch unter Verwendung eines erfindungsgemäßen
Reinigungsmittels für harte Oberflächen, das die erfindungsgemäße Kombination aus Mangansalz und Oxalsäure und gegebenenfalls 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 persauerstofffreies Reinigungsmittel verwendet wird.Essentially, the use of the present invention consists in providing 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. However, the process according to the invention is particularly advantageous using an inventive Hard surface cleaning agent containing the combination of manganese salt and oxalic acid of the present invention and optionally 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.
Die erfindungsgemäßen Reinigungsmittel, die als Granulate, pulver- oder tablettenförmige Feststoffe, als sonstige Formkörper, homogene Lösungen oder Suspensionen vorliegen können, können außer dem genannten bleichverstärkenden Wirkstoff im Prinzip alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten. Die erfindungsgemäßen Mittel können insbesondere Buildersubstanzen, oberflächenaktive Tenside, Persauerstoffverbindungen, wassermischbare organische Lösungsmittel, 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 may be in the form of granules, pulverulent or tablet-like solids, other shaped articles, homogeneous solutions or suspensions, may in principle contain all known ingredients customary in such agents, as well as the said bleach-intensifying active substance. The compositions according to the invention may contain, in particular, 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 also dyes 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 bis 15 Gew.-%, enthalten.In addition, a hard surface cleaning agent according to the invention may contain abrasive constituents, 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 according to the invention.
Ein weiterer Erfindungsgegenstand ist ein Mittel zum maschinellen Reinigen von Geschirr, enthaltend 15 bis 65 Gew.-%, insbesondere 20 bis 60 Gew.-% wasserlösliche Builderkomponente, 5 bis 25 Gew.-%, insbesondere 8 bis 17 Gew.-% Bleichmittel auf Sauerstoffbasis, jeweils bezogen auf das gesamte Mittel, und jeweils 0,05 bis 1 ,5 Gew.-% Mangansalz und Oxalsäure enthalten. Ein derartiges Mittel ist insbesondere niederalkalisch, das heißt seine 1 -gewichtsprozentige Lösung weist einen pH-Wert von 8 bis 11 ,5, vorzugsweise 9 bis 11 auf.
Als wasserlösliche Builderkomponenten in erfindungsgemäßen Reinigungsmitteln kommen prinzipiell alle in Mitteln für die maschinelle Reinigung von Geschirr üblicherweise eingesetzten Builder in Frage, zum Beispiel Alkaliphosphate, die in Form ihrer alkalischen, neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können. Beispiele hierfür sind Trinatriumphosphat, Tetranathumdiphosphat, Dinatriumdihydrogendiphosphat, Pentanatriumtriphosphat, sogenanntes Natriumhexametaphosphat sowie die entsprechenden Kaliumsalze beziehungsweise Gemische aus Natrium- und Kaliumsalzen. Ihre Mengen können im Bereich von bis zu etwa 60 Gew.-%, insbesondere 5 bis 20 Gew.-%, bezogen auf das gesamte Mittel liegen. Weitere mögliche wasserlösliche Builderkomponenten sind neben Polyphosphonaten und Phosphonatalkylcarboxylaten zum Beispiel organische Polymere nativen oder synthetischen Ursprungs vom Typ der Polycarboxylate, die insbesondere in Hartwasserregionen als Co-Builder wirken. In Betracht kommen beispielsweise Polyacrylsäuren und Copolymere aus Maleinsäureanhydrid und Acrylsäure sowie die Natriumsalze dieser Polymersäuren. Handelsübliche Produkte sind zum Beispiel Sokalan™ CP 5, CP 10 und PA 30 der Firma BASF. Zu den als Co-Builder brauchbaren Polymeren nativen Ursprungs gehören beispielsweise oxidierte Stärke und Polyaminosäuren wie Polyglutaminsäure oderA further subject of the invention is a machine for cleaning dishes containing 15 to 65% by weight, in particular 20 to 60% by weight of water-soluble builder component, 5 to 25% by weight, in particular 8 to 17% by weight of bleach Oxygen basis, in each case based on the total agent, and in each case 0.05 to 1, 5 wt .-% 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 cleaning compositions according to the invention are in principle all builders customarily used in detergents for dishwashing, for example alkali phosphates which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetranathium 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. Further possible water-soluble builder components, in addition to polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the type of the polycarboxylates of native or synthetic origin, which act as co-builders, in particular in hard water regions. For example, polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymeric acids are suitable. Commercially available products are, for example, Sokalan ™ CP 5, CP 10 and PA 30 from BASF. Examples of suitable co-builder polymers of native origin include oxidized starch and polyamino acids such as polyglutamic acid or
Polyasparaginsäure. Weitere mögliche Builderkomponenten sind natürlich vorkommende Hydroxycarbonsäuren wie zum Beispiel Mono-, Dihydroxybernsteinsäure, alpha -Hydroxypropionsäure und Gluconsäure. Zu den bevorzugten organischen Builderkomponenten gehören die Salze der Citronensäure, insbesondere Natriumeitrat. Als Natriumeitrat kommen wasserfreies Trinatriumcitrat und vorzugsweise Trinatriumcitratdihydrat 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.Polyaspartic acid. Other possible builder components are naturally occurring hydroxycarboxylic acids such as mono-, dihydroxysuccinic, alpha-hydroxypropionic and gluconic acid. The preferred organic builder components include the salts of citric acid, especially sodium citrate. 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 pH value ultimately set in the agents according to the invention, the acids corresponding to the said co-builder salts may also be present.
Zu den in erfindungsgemäßen Mitteln gegebenenfalls enthaltenen Enzymen gehören Proteasen, Amylasen, Pullulanasen, Cutinasen und/oder Lipasen,
beispielsweise Proteasen wie BLAP™, Optimase™, Opticlean™, Maxacal™, Maxapem™, Durazym™, Purafect™ OxP, Esperase™ und/oder Savinase™, Amylasen wie Termamyl™, Amylase-LT™, Maxamyl™, Duramyl™ und/oder Lipasen wie Lipolase™, Lipomax™, Lumafast™ und/oder Lipozym™. Die verwendeten Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Sie sind in den erfindungsgemäßen Reinigungsmitteln vorzugsweise in Mengen bis zu 10 Gew.-%, insbesondere von 0,05 bis 5 Gew.-%, enthalten, wobei besonders bevorzugt gegen oxidativen Abbau stabilisierte Enzyme eingesetzt werden.The enzymes optionally contained in agents according to the invention include proteases, amylases, pullulanases, cutinases and / or lipases, for example, proteases such as BLAP ™, Optimase ™, Opticlean ™, Maxacal ™, Maxapem ™, Durazym ™, Purafect ™ OxP, Esperase ™ and / or Savinase ™, amylases such as Termamyl ™, Amylase-LT ™, Maxamyl ™, Duramyl ™ and / or lipases such as Lipolase ™, Lipomax ™, Lumafast ™ and / or Lipozym ™. The enzymes used may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the detergents according to the invention 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.
Vorzugsweise enthalten die erfindungsgemäßen maschinellen Geschirrreinigungsmittel die üblichen Alkaliträger wie zum Beispiel Alkalisilikate, Alkalicarbonate und/oder Alkalihydrogencarbonate. Zu den üblicherweise eingesetzten Alkaliträgern zählen Carbonate, Hydrogencarbonate undThe machine dishwashing detergents according to the invention preferably contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali metal bicarbonates. The alkali carriers commonly used include carbonates, bicarbonates and
Alkalisilikate mit einem Molverhältnis SiO2/M2O (M = Alkaliatom) von 1 : 1 bis 2,5 : 1. Alkalisilikate können dabei in Mengen von bis zu 40 Gew.-%, insbesondere 3 bis 30 Gew.-%, bezogen auf das gesamte Mittel, enthalten sein. 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 50 Gew.-%, vorzugsweise 5 bis 40 Gew.-%, enthalten sein kann.Alkali silicates with a molar ratio of SiO 2 / M 2 O (M = alkali metal) of 1: 1 to 2.5: 1. Alkalisilicates can in amounts of up to 40 wt .-%, in particular 3 to 30 wt .-%, based to be included on the entire medium. The alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be present in an amount of up to 50% by weight, preferably 5 to 40% by weight.
In einer weiteren Ausführungsform erfindungsgemäßer Mittel sind 20 bis 60 Gew.-% wasserlöslicher organischer Builder, insbesondere Alkalicitrat, 3 bis 20 Gew.-% Alkalicarbonat und 3 bis 40 Gew.-% Alkalidisilikat enthalten.In a further embodiment of the invention, agents are 20 to 60 wt .-% of water-soluble organic builder, in particular alkali, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.
Den erfindungsgemäßen Mitteln können gegebenenfalls auch Tenside, insbesondere Aniontenside, zwitterionische Tenside und vorzugsweise schwach schäumende nichtionische Tenside zugesetzt werden, die der besseren Ablösung fetthaltiger Anschmutzungen, als Netzmittel und gegebenenfalls im Rahmen der Herstellung der Reinigungsmittel als Granulierhilfsmittel dienen. Ihre Menge kann bis zu 20 Gew.-%, insbesondere bis zu 10 Gew.-% betragen und liegt
vorzugsweise im Bereich von 0,5 bis 5 Gew.-%. Üblicherweise werden insbesondere in Reinigungsmitteln für den Einsatz in maschinellen Geschirrspülverfahren extrem schaumarme Verbindungen eingesetzt. Hierzu zählen vorzugsweise Ci2-Ci8-Alkylpolyethylenglykol-polypropylenglykolether mit jeweils bei zu 8 Mol Ethylenoxid- und Propylenoxideinheiten im Molekül. Man kann aber auch andere bekannt schaumarme nichtionische Tenside verwenden, wie zum Beispiel Ci2-Ci8-Alkylpolyethylenglykol-polybutylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Butylenoxideinheiten im Molekül, endgruppenverschlossene Alkylpolyalkylenglykolmischether sowie die zwar schäumenden, aber ökologisch attraktiven Cs-Cu-Alkylpolyglucoside mit einem Polymerisierungsgrad von etwa 1 bis 4 und/oder Ci2-Ci4-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-Cu stammt. Es ist teilweise vorteilhaft, wenn die beschriebenen Tenside als Gemische eingesetzt werden, zum Beispiel die Kombination Alkylpolyglykosid mit Fettalkoholethoxylaten oder Glucamid mit Alkylpolyglykosiden. Auch die Anwesenheit von Aminoxiden, Betainen und ethoxlierten Alkylaminen ist möglich.Surfactants, in particular anionic surfactants, zwitterionic surfactants and, preferably, low-foaming nonionic surfactants may also be added to the compositions according to the invention, which serve as a wetting agent and optionally as part of the preparation of the cleaning agents as granulating aids for better separation of greasy soils. 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 .-%. Usually, extremely low-foam compounds are used in particular in detergents for use in automatic dishwashing processes. These include preferably C 2 -C 8 -alkylpolyethylene glycol polypropylene glycol ethers with in each case up to 8 mol of ethylene oxide and propylene oxide units in the molecule. One can also use other known low-foaming nonionic surfactants such as C 2 -C 8 alkyl polyethylene-polybutylene glycol ethers containing up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end-capped Alkylpolyalkylenglykolmischether and although foaming, but ecologically attractive Cs-Cu Alkylpolyglucosides having a degree of polymerization of about 1 to 4 and / or Ci 2 -Ci 4 -Alkylpolyethylenglykole 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-methylglucamides, in which the alkyl moiety preferably originates from a fatty alcohol having the C chain length C 6 -Cu. 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.
Um einen Silberkorrosionsschutz zu bewirken, können in erfindungsgemäßen Reinigungsmitteln für Geschirr Silberkorrosionsinhibitoren eingesetzt werden. Bevorzugte Silberkorrosionsschutzmittel sind organische Sulfide wie Cystin und Cystein, zwei- oder dreiwertige Phenole, gegebenenfalls alkyl- oder arylsubstituierte Triazole wie Benzotriazol, Isocyanursäure, Titan-, Zirkonium-, Hafnium-, Cobalt- oder Cersalze und/oder -komplexe, in denen die genannten Metalle je nach Metall in einer der Oxidationsstufen II, III, IV, V oder VI vorliegen.To effect silver corrosion protection, silver corrosion inhibitors can be used in dishwashing detergents according to the invention. Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, 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.
Um Glaskorrosion während des Spülganges zu verhindern, können in erfindungsgemäßen Reinigungsmitteln für Geschirr entsprechende Inhibitoren eingesetzt werden. Besonders vorteilhaft sind hier kristalline schichtförmige Silikate und/oder Zinksalze. Die kristallinen schichtförmigen Silikate werden beispielsweise von der Fa. Clariant unter dem Handelsnamen Na-SKS vertrieben, z. B. Na-SKS-1 (Na2Si22O45-XH2O, Kenyait), Na-SKS-2 (Na2Si14O29.xH2O,
Magadiit), Na-SKS-3 (Na2Si8Oi7-XH2O) oder Na-SKS-4 (Na2Si4O9-XH2O, Makatit). Von diesen eignen sich vor allem Na-SKS-5 (alpha -Na2Si2O5), Na-SKS-7 (beta - Na2Si2O5, Natrosilit), Na-SKS-9 (NaHSi2O5-H2O), Na-SKS-10 (NaHSi2O5.3H2O, Kanemit), Na-SKS-11 (t-Na2Si205) und Na-SKS-13 (NaHSi2O5), insbesondere aber Na-SKS-6 (delta-Na2Si205). Einen Überblick über kristalline Schichtsilikate findet sich z. B. in dem in "Seifen-Öle-Fette-Wachse, 116 Jahrgang, Nr. 20/1990" auf den Seiten 805-808 veröffentlichten Artikel.In order to prevent glass corrosion during the rinse, corresponding inhibitors can be used in dishwashing detergents according to the invention. Particularly advantageous here are crystalline layered silicates and / or zinc salts. The crystalline layered silicates 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 Oi 7 -XH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 -XH 2 O, Makatite). Of these, especially 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 0 5) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 (delta-Na 2 Si 2 0 5 ). An overview of crystalline phyllosilicates can be found, for. For example, in the article published in "Soap-Oils-Fats-Waxes, Volume 116, No. 20/1990" on pages 805-808.
Bevorzugte maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel weisen im Rahmen der vorliegenden Anmeldung einen Gewichtsanteil des kristallinen schichtförmigen Silikats von 0,1 bis 20 Gew.-%, vorzugsweise von 0,2 bis 15 Gew.-% und insbesondere von 0,4 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht dieser Mittel, auf.In the context of the present application, 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.
In einer weiteren bevorzugten Ausführungsform enthalten erfindungsgemäße maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel mindestens ein Zinksalz ausgewählt aus der Gruppe der organischen Zinksalze, vorzugsweise aus der Gruppe der löslichen organischen Zinksalze, besonders bevorzugt aus der Gruppe der löslichen Zinksalze monomerer oder polymerer organischer Säuren, insbesondere aus der Gruppe Zinkacetat, Zinkacetylacetonat, Zinkbenzoat, Zinkformiat, Zinklactat, Zinkgluconat, Zinkricinoleat, Zinkabietat, Zinkvalerat, Zink-p-toluolsulfonat.In a further preferred embodiment, automatic dishwasher detergents or dishwashing auxiliaries according to the invention contain 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.
Als bevorzugt gelten im Rahmen der vorliegenden Anmeldung dabei maschinelle Geschirrspülmittel oder maschinelle Geschirrspülhilfsmittel, bei denen der Gewichtsanteil des Zinksalz bezogen auf das Gesamtgewicht dieses Mittels 0,1 bis 10 Gew.-%, vorzugsweise 0,2 bis 7 Gew.-% und insbesondere 0,4 bis 4 Gew.-% beträgt und zwar unabhängig davon welche Zinksalze eingesetzt werden, insbesondere also unabhängig davon ob organische oder anorganische Zinksalze, lösliche oder nicht lösliche Zinksalze oder deren Mischungen eingesetzt werden.
Sofern die Reinigungsmittel, zum Beispiel bei Anwesenheit von Aniontensiden, bei der Anwendung zu stark schäumen, können ihnen noch bis zu 6 Gew.-%, vorzugsweise etwa 0,5 bis 4 Gew.-% einer schaumdrückenden Verbindung, vorzugsweise aus der Gruppe der Silikonöle, Gemische aus Silikonöl und hydrophobierter Kieselsäure, Paraffine, Paraffin-Alkohol-Kombinationen, hydrophobierter Kieselsäure, der Bisfettsäureamide, und sonstiger weiterer bekannter im Handel erhältliche Entschäumer zugesetzt werden. Weitere fakultative Inhaltsstoffe in den erfindungsgemäßen Mitteln sind zum Beispiel Parfümöle.For the purposes of the present application, 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. If the cleaning agents, for example in the presence of anionic surfactants, foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils , Mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the Bisfettsäureamide, and other other known commercially available defoamer may be added. Further optional ingredients in the compositions according to the invention are, for example, perfume oils.
Zu den in den erfindungsgemäßen Mitteln, insbesondere wenn sie in flüssiger oder pastöser Form vorliegen, verwendbaren organischen Lösungsmitteln 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 Lösungsmittel sind in den erfindungsgemäßen Reinigungsmitteln vorzugsweise nicht über 20 Gew.-%, insbesondere von 1 bis 15 Gew.-%, vorhanden.Among the organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms , in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compound ethers. Such water-miscible solvents are preferably present in the detergents according to the invention not more than 20% by weight, in particular from 1 to 15% by weight.
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 Mittein vorzugsweise nicht über 10 Gew.-%, insbesondere von 0,5 bis 6 Gew.-%, enthalten.In order to establish a desired pH, which does not naturally result from the mixture of the other components, the compositions according to the invention may contain 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 hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 10% by weight, in particular from 0.5 to 6% by weight, in the middle of the invention.
Die Herstellung der erfindungsgemäßen festen Mittel bietet keine Schwierigkeiten und kann in im Prinzip bekannter Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei Persauerstoffverbindung und Bleichkatalysator gegebenenfalls später getrennt zugesetzt werden.
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.The preparation of the solid compositions according to the invention presents no difficulties and can 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 according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
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.The compositions according to the invention are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleach catalyst are to be expected, can be prepared.
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 x105 Pa bis 1500x105 Pa verpresst.To prepare detergents according to the invention in tablet form, the procedure is preferably such that all components are mixed together in a mixer and the mixture is compressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing pressures in the range from 200 × 10 5 Pa to 1500 × 10 5 Pa.
Man erhält so problemlos bruchfeste und dennoch unterYou get so unbreakable and yet under
Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Biegefestigkeiten von normalerweise über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 15 bis 40 g, insbesondere von 20 bis 30 g auf, bei einem Durchmesser von 35 bis 40 mm.Conditions of use sufficiently quickly soluble tablets with flexural strengths of normally over 150 N. Preferably, such a tablet produced in such a way a weight of 15 to 40 g, in particular from 20 to 30 g, with a diameter of 35 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 Verfahrensteilstufe die Builder-Komponenten mit wenigstens einem Anteil flüssiger Mischungskomponenten unter Erhöhung der Schüttdichte dieses Vorgemisches vermischt und nachfolgend - gewünschtenfalls nach einer Zwischentrocknung - die weiteren Bestandteile des Mittels, darunter den Bleichkatalysator, mit dem so gewonnenen Vorgemisch vereinigt.
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.The preparation of compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / l can be carried out by subjecting the builder components to at least a portion of liquid mixture components in a first process substep 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. Detergents according to the invention 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.
Ein maschinelles Spülprogramm wird im Allgemeinen durch einige auf den Reinigungsgang folgende Zwischenspülgänge mit klarem Wasser und einem 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.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, when using agents according to the invention, a completely clean and hygienically perfect dishes are obtained.
BeispieleExamples
Beispiele 1 - 5Examples 1 - 5
Ein Reinigungsmittel (V1 ), enthaltend 44 Gew.-Teile Natriumtripolyphosphat,A cleaning agent (V1) containing 44 parts by weight of sodium tripolyphosphate,
30 Gew.-Teile Natriumcarbonat, 10 Gew.-% Schichtsilikat SKS-6, 10 Gew.-Teile Natriumperboratmonohydrat, jeweils 1 ,5 Gew.-Teil Protease- und Amylase- Granulat, 3 Gew.-Teile nichtionisches Tensid sowie 2 Gew.-Teile N.N.N'N'-Tetraacetylethylendiamin (TAED) in Granulatform und Reinigungsmittel gemäß der Erfindung (M 1 bis M6), die ansonsten wie V1 zusammengesetzt waren, aber erfindungsgemäße Mischungen aus Mangansalzen und Oxalsäure enthielten, wurden auf ihre Tee-entfernenden Eigenschaften geprüft. In V 2-6 sind weitere nicht erfindungsgemäße Mischungen als Vergleichsbeispiele aufgeführt.30 parts by weight of sodium carbonate, 10 wt .-% phyllosilicate SKS-6, 10 parts by weight of sodium perborate monohydrate, in each case 1, 5 parts by weight of protease and amylase granules, 3 parts by weight of nonionic surfactant and 2 wt. Parts of NNN'N'-tetraacetylethylenediamine (TAED) in granular form and detergents according to the invention (M 1 to M6), otherwise compounded as V 1 but containing blends of manganese salts and oxalic acid according to the invention, were tested for their tea-removing properties , In V 2-6 other non-inventive mixtures are listed as comparative examples.
Zur Herstellung standardisierter Teebeläge wurden Teetassen in eine 70 CC warme Teelösung 25-mal eingetaucht. Anschließend wurde jeweils etwas der Teelösung in jede Teetasse gegeben und die Tasse im Trockenschrank getrocknet.
Die Spülversuche wurden in einer Geschirrspülmaschine Miele G 688 SC bei 45 0C unter Verwendung von Wasser der Wasserhärte 21 °dH in Gegenwart von 100 g IKW Testschmutz durchgeführt. Die Belagsentfernung wurde anschließend visuell auf einer Skala von 0 (= unverändert sehr starker Belag) bis 100 % (= kein Belag) benotet.To prepare standardized tea coverings, tea cups were immersed in a 70 C 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. The rinsing tests were carried out in a dishwasher Miele G 688 SC at 45 0 C using water of water hardness 21 ° dH in the presence of 100 g of IKW test soil. The pad removal was then graded visually on a scale from 0 (= very strong pad) to 100% (= no pad).
Tabelle 1 :Table 1 :
Die in der Tabelle 1 angegebene Bewertung der erfindungsgemäßen Mittel M1 bis M6 liegen signifikant besser als der Wert für das Vergleichsprodukt V1 sowie der Vergleichsversuche V2-6. The evaluation of the inventive agents M1 to M6 given in Table 1 are significantly better than the value for the comparative product V1 and the comparative experiments V2-6.
Man erkennt, dass durch die erfindungsgemäße Verwendung eine signifikant bessere Bleichwirkung erreicht werden kann als durch den konventionellen Bleichaktivator TAED alleine.It can be seen that a significantly better bleaching effect can be achieved by the use according to the invention than by the conventional bleach activator TAED alone.
Im Wesentlichen gleiche Ergebnisse wurden erhalten, wenn man das Natriumperborat durch Natriumpercarbonat ersetzte. Im Wesentlichen gleiche Ergebnisse wurden auch erhalten, wenn an Stelle der Oxalsäure Na-Oxalat eingesetzt wurde.
Substantially similar results were obtained when replacing the sodium perborate with sodium percarbonate. Substantially similar results were also obtained when Na oxalate was substituted for the oxalic acid.
Claims
1. Bleichaktivatormischungen enthaltend eine Manganverbindung und Oxalsäure, deren Salze oder Derivate.1. Bleach activator mixtures containing a manganese compound and oxalic acid, their salts or derivatives.
2. Bleichaktivatormischung nach Anspruch 1 enthaltend ein anorganisches Mangansalz als Manganverbindung.2. bleach activator mixture according to claim 1 containing an inorganic manganese salt as manganese compound.
3. Wasch- und Reinigungsmittel enthaltend eine Bleichaktivatormischung nach Anspruch 1.3. washing and cleaning agent containing a bleach activator mixture according to claim 1.
4. Wasch- und Reinigungsmittel enthaltend 0,025 bis 2,5 Gew.-% einer Manganverbindung und 0,05 bis 1 ,5 Gew.-5 Oxalsäure, deren Salze oder Derivate.4. detergents and cleaning agents containing 0.025 to 2.5 wt .-% of a manganese compound and 0.05 to 1, 5 wt .- 5 oxalic acid, their salts or derivatives.
5. Reinigungsmittel für harte Oberflächen enthaltend eine Bleichaktivatormischung nach Anspruch 1.5. A hard surface cleaner comprising a bleach activator mixture according to claim 1.
6. Bleichmittel enthaltend eine Bleichaktivatormischung nach Anspruch 1.6. bleaching agent containing a bleach activator mixture according to claim 1.
7. Wasch- und Reinigungsmittel enthaltend, 10 bis 30 % Na-Percarbonat,7. Washing and cleaning compositions containing 10 to 30% Na percarbonate,
2 bis 6 % TAED, 0,25 bis 0,75 % eines Mangan (II) oder (III) salzes und 0,25 bis 0,75 % Oxalsäure oder Natriumoxalat. 2 to 6% TAED, 0.25 to 0.75% of a manganese (II) or (III) salt and 0.25 to 0.75% oxalic acid or sodium oxalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL09778106T PL2329001T3 (en) | 2008-08-30 | 2009-08-26 | Bleach catalyst mixtures consisting of manganese salts and oxalic acid or the salts thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102008045207A DE102008045207A1 (en) | 2008-08-30 | 2008-08-30 | Bleach catalyst mixtures consisting of manganese salts and oxalic acid or salts thereof |
| PCT/EP2009/006163 WO2010022919A1 (en) | 2008-08-30 | 2009-08-26 | Bleach catalyst mixtures consisting of manganese salts and oxalic acid or the salts thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2329001A1 true EP2329001A1 (en) | 2011-06-08 |
| EP2329001B1 EP2329001B1 (en) | 2012-10-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP09778106A Active EP2329001B1 (en) | 2008-08-30 | 2009-08-26 | Bleach catalyst mixtures consisting of manganese salts and oxalic acid or the salts thereof |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20110146723A1 (en) |
| EP (1) | EP2329001B1 (en) |
| JP (1) | JP5469667B2 (en) |
| CN (1) | CN102131908B (en) |
| DE (1) | DE102008045207A1 (en) |
| DK (1) | DK2329001T3 (en) |
| ES (1) | ES2396414T3 (en) |
| PL (1) | PL2329001T3 (en) |
| PT (1) | PT2329001E (en) |
| WO (1) | WO2010022919A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102008038376A1 (en) * | 2008-08-19 | 2010-02-25 | Clariant International Ltd. | Process for the preparation of 3,7-diazabicyclo [3.3.1] nonane compounds |
| DE102008045215A1 (en) * | 2008-08-30 | 2010-03-04 | Clariant International Ltd. | Use of manganese oxalates as bleaching catalysts |
| DE102008064009A1 (en) | 2008-12-19 | 2010-06-24 | Clariant International Ltd. | Process for the preparation of 3,7-diaza-bicyclo [3.3.1] nonane-metal complexes |
| CN105369581A (en) * | 2015-11-04 | 2016-03-02 | 泉州市新宏化工贸易有限公司 | Deoxygenization technology adopted after cotton fabric scouring and bleaching and cotton cleaning agent |
| BR112018073540B1 (en) | 2016-05-19 | 2023-04-25 | Ecolab Usa Inc | METHOD FOR CLEANING A CALCITE STONE SURFACE, COMPOSITION AND USE |
| DE102017004742A1 (en) * | 2017-05-17 | 2018-11-22 | Weylchem Wiesbaden Gmbh | Coated granules, their use and detergents and cleaning agents containing them |
| CN110055771B (en) * | 2019-05-13 | 2022-01-25 | 乐象永续科技（杭州）有限公司 | Textile material bleaching and modifying method and use |
| 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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| CN86103060A (en) * | 1986-04-27 | 1987-04-22 | 刘能振 | The bleaching agent of forming by permanganate and reducing substances |
| DE4443177A1 (en) | 1994-12-05 | 1996-06-13 | Henkel Kgaa | Activator mixtures for inorganic per compounds |
| US6734155B1 (en) * | 1997-07-09 | 2004-05-11 | The Procter & Gamble Company | Cleaning compositions comprising an oxidoreductase |
| WO1999002640A1 (en) * | 1997-07-09 | 1999-01-21 | The Procter & Gamble Company | Cleaning compositions comprising an oxidoreductase |
| JPH1143410A (en) * | 1997-07-11 | 1999-02-16 | Lion Corp | Mold-removing agent composition |
| DE19758183A1 (en) * | 1997-12-30 | 1999-07-01 | Henkel Kgaa | Washable molded body with a specific surface |
| DE19909546C1 (en) * | 1999-03-04 | 2000-06-29 | Consortium Elektrochem Ind | Enzymatic oxidation system, e.g. for lignin oxidation, bleaching, chemical synthesis or waste water treatment, comprises a manganese oxidase, an oxidizing agent and manganese ions |
| JP2000282091A (en) * | 1999-03-31 | 2000-10-10 | Lion Corp | Bleaching activating catalyst and bleaching agent composition containing the same compound |
| GB9930422D0 (en) * | 1999-12-22 | 2000-02-16 | Unilever Plc | Bleach catalysts |
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| DE102008038376A1 (en) * | 2008-08-19 | 2010-02-25 | Clariant International Ltd. | Process for the preparation of 3,7-diazabicyclo [3.3.1] nonane compounds |
| DE102008045215A1 (en) * | 2008-08-30 | 2010-03-04 | Clariant International Ltd. | Use of manganese oxalates as bleaching catalysts |
| DE102008064009A1 (en) * | 2008-12-19 | 2010-06-24 | Clariant International Ltd. | Process for the preparation of 3,7-diaza-bicyclo [3.3.1] nonane-metal complexes |
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- 2008-08-30 DE DE102008045207A patent/DE102008045207A1/en not_active Withdrawn
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2009
- 2009-08-26 CN CN2009801329174A patent/CN102131908B/en active Active
- 2009-08-26 ES ES09778106T patent/ES2396414T3/en active Active
- 2009-08-26 WO PCT/EP2009/006163 patent/WO2010022919A1/en active Application Filing
- 2009-08-26 PT PT97781066T patent/PT2329001E/en unknown
- 2009-08-26 PL PL09778106T patent/PL2329001T3/en unknown
- 2009-08-26 JP JP2011524245A patent/JP5469667B2/en not_active Expired - Fee Related
- 2009-08-26 US US13/060,828 patent/US20110146723A1/en not_active Abandoned
- 2009-08-26 DK DK09778106.6T patent/DK2329001T3/en active
- 2009-08-26 EP EP09778106A patent/EP2329001B1/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| PL2329001T3 (en) | 2013-03-29 |
| WO2010022919A1 (en) | 2010-03-04 |
| US20110146723A1 (en) | 2011-06-23 |
| EP2329001B1 (en) | 2012-10-10 |
| DE102008045207A1 (en) | 2010-03-04 |
| JP2012500871A (en) | 2012-01-12 |
| ES2396414T3 (en) | 2013-02-21 |
| PT2329001E (en) | 2013-01-24 |
| CN102131908A (en) | 2011-07-20 |
| CN102131908B (en) | 2013-02-20 |
| JP5469667B2 (en) | 2014-04-16 |
| DK2329001T3 (en) | 2013-01-28 |
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