EP2329000B1 - Utilisation d'oxalates de manganèse comme catalyseur de blanchiment - Google Patents
Utilisation d'oxalates de manganèse comme catalyseur de blanchiment Download PDFInfo
- Publication number
- EP2329000B1 EP2329000B1 EP09778105A EP09778105A EP2329000B1 EP 2329000 B1 EP2329000 B1 EP 2329000B1 EP 09778105 A EP09778105 A EP 09778105A EP 09778105 A EP09778105 A EP 09778105A EP 2329000 B1 EP2329000 B1 EP 2329000B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- manganese
- weight
- oxalate
- acid
- bleaching
- 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.)
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Links
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical class [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 title claims abstract description 22
- 239000007844 bleaching agent Substances 0.000 title claims description 16
- 239000003054 catalyst Substances 0.000 title claims description 10
- 239000003599 detergent Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 24
- 238000004061 bleaching Methods 0.000 claims description 17
- 238000004851 dishwashing Methods 0.000 claims description 16
- -1 alkali metal percarbonate Chemical class 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
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- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
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- 150000001340 alkali metals Chemical class 0.000 claims description 4
- HDJUVFZHZGPHCQ-UHFFFAOYSA-L manganese(2+);oxalate;dihydrate Chemical compound O.O.[Mn+2].[O-]C(=O)C([O-])=O HDJUVFZHZGPHCQ-UHFFFAOYSA-L 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
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- VCPHCCYQFNKUJS-UHFFFAOYSA-L manganese(2+) oxalate trihydrate Chemical compound O.O.O.[Mn+2].[O-]C(=O)C([O-])=O VCPHCCYQFNKUJS-UHFFFAOYSA-L 0.000 claims description 2
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- RVEDSNKPFDBZRK-UHFFFAOYSA-N benzenesulfonyl dodecanoate;sodium Chemical compound [Na].CCCCCCCCCCCC(=O)OS(=O)(=O)C1=CC=CC=C1 RVEDSNKPFDBZRK-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 244000309464 bull Species 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
- 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
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 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
- 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
- 238000011038 discontinuous diafiltration by volume reduction Methods 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
- 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
- 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
- 239000003205 fragrance Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 235000012209 glucono delta-lactone Nutrition 0.000 description 1
- 229960003681 gluconolactone Drugs 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical class [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- AHSBSUVHXDIAEY-UHFFFAOYSA-K manganese(iii) acetate Chemical compound [Mn+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AHSBSUVHXDIAEY-UHFFFAOYSA-K 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910021527 natrosilite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000001402 nonanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- ZHMWXTKEPYYIEZ-UHFFFAOYSA-N oxalic acid;trihydrate Chemical compound O.O.O.OC(=O)C(O)=O ZHMWXTKEPYYIEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 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
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- QSKQNALVHFTOQX-UHFFFAOYSA-M sodium nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O QSKQNALVHFTOQX-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000007944 soluble tablet Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 1
- 229940100530 zinc ricinoleate Drugs 0.000 description 1
- 229940006174 zinc valerate Drugs 0.000 description 1
- MXODCLTZTIFYDV-JHZYRPMRSA-L zinc;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Zn+2].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O.C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O MXODCLTZTIFYDV-JHZYRPMRSA-L 0.000 description 1
- YISPIDBWTUCKKH-UHFFFAOYSA-L zinc;4-methylbenzenesulfonate Chemical compound [Zn+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 YISPIDBWTUCKKH-UHFFFAOYSA-L 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
- BUDAIZWUWHWZPQ-UHFFFAOYSA-L zinc;pentanoate Chemical compound [Zn+2].CCCCC([O-])=O.CCCCC([O-])=O BUDAIZWUWHWZPQ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/391—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
Definitions
- the present invention relates to the use of manganese oxalates in detergents on hard surfaces as bleach catalysts for enhancing the bleaching effect of inorganic peroxygen compounds in bleaching colored stains on hard surfaces.
- Inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
- the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.
- the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine and acylated glycolurils, such as tetraacetylglycoluril, also carboxylic acid anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxybenzenesulfonate, sodium lauroyl-benzenesulfonate or decanoyloxybenzoic acid and acylated sugar derivatives, such as pentaacetylglucose, have become known in the literature.
- bleach activators for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine and acyl
- manganese / EDTA complexes as in EP 0 141 470 or manganese sulfate / picolinic acid mixtures, as in US 3,532,634 or manganese (II) or (III) salts in combination with carbonates ( EP 0 082 563 ), Fatty acids ( US 4,626,373 ), Phosphonates ( EP 0 072 166 ), Hydroxycarboxylic acids ( EP 0 237 111 ) or citric acid or its salts ( EP 0 157 483 ).
- the invention relates to the use of manganese oxalates as bleach catalysts in cleaning agents, as defined in claim 1.
- Manganese oxalates can be prepared in a manner known per se by reacting manganese salts with oxalic acid in water. Examples include in A. Huizing et al., Mat. Res. Bull. Vol. 12, pp. 605-6166, 1977 and Donkova et al., Thermochimica Acta, Vol. 421, pp. 141-149, 2004 ,
- both the white manganese (II) oxalate dihydrate and the pink manganese (II) oxalate trihydrate are suitable. Although they have only a very low water solubility, these compounds surprisingly show a good bleaching performance in combination with inorganic peroxygen compounds.
- manganese (II) sulfate manganese (II) acetate
- manganese (III) acetate or manganese (II) chloride better storage stability in alkaline detergent and cleaner formulations.
- the manganese oxalates according to the invention are more volume-effective bleach catalysts, which is advantageous, in particular, when used in machine dishwashing detergent tablets.
- the cleaning agents preferably contain from 0.025 to 2.5% by weight, in particular from 0.05 to 1.5% by weight, of bleach-intensifying manganese oxalates.
- the manganese oxalates may also be combined with oxalic acid, thereby increasing their water solubility.
- the manganese oxalate: oxalic acid ratio in this case may correspond to 1: 0 to 1: 5 parts by weight.
- 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, since 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 ppm 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.
- bleach activators that is to say compounds which give perbenzoic acid which is optionally substituted under perhydrolysis conditions and / or peroxycarboxylic acids having 1 to 10 C atoms, in particular 2 to 4 C atoms.
- Suitable are the customary bleach activators cited at the outset which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates , in particular nonanoyl or Isononanoyloxybenzolsulfonat, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG), Pentaacetylfruktose, Te
- bleaching is understood to mean here both the bleaching of dirt located on the hard surface, in particular tea, and the bleaching of dirt removed from the hard surface in the dishwashing liquor.
- the use of the present invention is to create conditions on a hard surface contaminated with colored stains, under which a peroxidic oxidizing agent and the manganese oxalates can react with each other, 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 manganese oxalate to an optionally detergent-containing solution.
- the inventive method is particularly advantageous using a Hard surface cleaning agent containing a manganese oxalate 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 which may be in the form of granules, powdered or tablet-form solids, other shaped bodies, homogeneous solutions or suspensions, may contain, in principle, all known ingredients customary in such agents, as well as the said manganese oxalate.
- the compositions may in particular contain builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic solvents, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as silver corrosion inhibitors, foam regulators, additional peroxygen activators and dyes and fragrances.
- a hard surface cleaner can contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and glass microspheres, and mixtures thereof.
- Abrasives are preferably not more than 20 wt .-%, in particular from 5 to 15 wt .-%, contained in the cleaning agents.
- An apparatus for machine dishwashing may contain from 15 to 65% by weight, especially from 20 to 60% by weight of water-soluble builder component, from 5 to 25% by weight, especially from 8 to 17% by weight of oxygen-based bleach, in each case to the total agent, and each containing 0.05 to 1.5 wt .-% manganese oxalate.
- 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.
- alkali phosphates which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
- alkali phosphates which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
- examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
- Their amounts may be in the range of up to about 60 wt .-%, in particular 5 to 20 wt .-%, based on the total mean.
- water-soluble builder components 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.
- 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.
- co-builder polymers of native origin include oxidized starch and polyamino acids such as polyglutamic acid or polyaspartic acid.
- hydroxycarboxylic acids such as mono-, dihydroxysuccinic, alpha-hydroxypropionic and gluconic acid.
- Preferred organic builder components include the salts of citric acid, especially sodium citrate.
- sodium citrate anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
- the acids corresponding to the said co-builder salts may also be present.
- the enzymes optionally present in the compositions include proteases, amylases, pullulanases, cutinases and / or lipases, for example proteases such as BLAP TM, Optimase TM, Opticlean TM, Maxacal TM, Maxapem TM, Durazym TM, Purafect TM OxP, Esperase TM and / or Savinase TM, amylases such as Termamyl TM, Amylase-LT TM, Maxamyl TM, Duramyl TM and / or Lipases such as Lipolase TM, Lipomax TM, Lumafast TM and / or Lipozym TM.
- proteases such as BLAP TM, Optimase TM, Opticlean TM, Maxacal TM, Maxapem TM, Durazym TM, Purafect TM OxP, Esperase TM and / or Savinase TM
- the enzymes used may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the cleaning agents in amounts of up to 10% by weight, in particular from 0.05 to 5% by weight, particular preference being given to using enzymes which are stabilized against oxidative degradation.
- the machine dishwashing detergents preferably contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali metal bicarbonates.
- Alkali silicates may be present in amounts of up to 40% by weight. in particular from 3 to 30% by weight, based on the total agent.
- the alkali carrier system preferably used in the compositions is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be contained in an amount of up to 50% by weight, preferably 5 to 40% by weight.
- a further agent 20 to 60 wt .-% of water-soluble organic builder in particular alkali citrate, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.
- Surfactants in particular anionic surfactants, zwitterionic surfactants and preferably weakly foaming nonionic surfactants may also be added to the compositions if appropriate, which serve to better remove greasy soilings, as wetting agents and, if appropriate, in the course of the preparation of the cleaning agents as granulation auxiliaries.
- Their amount can be up to 20 wt .-%, in particular up to 10 wt .-% and is preferably in the range of 0.5 to 5 wt .-%.
- extremely low-foam compounds are used in particular in detergents for use in automatic dishwashing processes.
- C 12 -C 18 -Alkylpolyethylenglykol-polypropylene glycol ethers each with at 8 mol ethylene oxide and propylene oxide in the molecule.
- you can also use other known low-foam nonionic surfactants such as C 12 -C 18 alkylpolyethylene glycol polybutylenglykolether with up to 8 moles of ethylene oxide and butylene oxide in the molecule, end phenomenonver totale Alkylpolyalkylenglykolmischether and the foaming, but ecologically attractive C 8 -C 14 - Alkylpolyglucoside having a degree of polymerization of about 1 to 4 and / or C 12 -C 14 alkyl polyethylene glycols having 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 with the C chain length C 6 -C 14 . It is partially advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides. The presence of amine oxides, betaines and ethoxylated alkylamines is also possible.
- silverware inhibitors can be used in dishwashing detergents.
- Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, Hafhium-, cobalt or cerium salts and / or complexes, in which Metals depending on the metal in one of the oxidation states II, III, IV, V or VI.
- crystalline layered silicates and / or zinc salts are sold, for example, by the company Clariant under the trade name Na-SKS, z. Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, makatite).
- Na-SKS-5 alpha -Na 2 Si 2 O 5
- Na-SKS-7 beta-Na 2 Si 2 O 5 , natrosilite
- Na-SKS-9 NaHSi 2 O 5 .H 2 O
- Na-SKS-10 NaHSi 2 O 5 .3H 2 O, Kanemite
- Na-SKS-11 t-Na 2 Si 2 O 5
- Na-SKS-13 NaHSi 2 O 5
- Na-SKS-6 delta-Na 2 Si 2 O 5
- preferred automatic dishwashing or automatic dishwashing assistants have a weight fraction of the crystalline layered silicate of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0.4 to 10% by weight. -%, based in each case on the total weight of these funds.
- automatic dishwashing or dishwashing auxiliaries comprise at least one zinc salt selected from the group of organic zinc salts, preferably from the group of soluble organic zinc salts, more preferably from the group of soluble zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate , Zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesulfonate.
- group of organic zinc salts preferably from the group of soluble organic zinc salts, more preferably from the group of soluble zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate , Zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesulfonate.
- automatic dishwashing or automatic dishwashing aids in which the proportion by weight of the zinc salt relative to the total weight of this agent is 0.1 to 10% by weight, preferably 0.2 to 7% by weight and in particular 0, are preferred , 4 to 4 wt .-% and regardless of which zinc salts are used, in particular therefore irrespective of whether organic or inorganic zinc salts, soluble or non-soluble zinc salts or mixtures thereof are used.
- the cleaning agents may still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils , Mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, bis-fatty acid amides, and other other known commercially available defoamers.
- a foam-suppressing compound preferably from the group of silicone oils , Mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, bis-fatty acid amides, and other other known commercially available defoamers.
- Other optional ingredients in the compositions are, for example, perfume oils.
- organic solvents which can be used in the compositions, in particular if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers.
- Such water-miscible solvents are preferably present in the detergents not more than 20% by weight, in particular from 1 to 15% by weight.
- the agents can system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also, mineral acids, in particular sulfuric acid or alkali metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
- acids in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid
- mineral acids in particular sulfuric acid or alkali metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
- pH regulators are preferably not more than 10% by weight, in particular from 0.5 to 6% by weight, in the compositions.
- the preparation of the solid agents presents no difficulties and may be carried out in a manner known in the art, for example by spray-drying or granulation, wherein peroxygen compound and bleach catalyst are optionally added separately later.
- Detergents in the form of aqueous or other conventional solvent-containing solutions are particularly advantageous simple mixing of the ingredients that can be added in bulk or as a solution in an automatic mixer made.
- compositions are preferably in the form of powdered, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roller compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the like Bleaching catalyst are expected to be produced.
- the procedure is preferably such that all ingredients are mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with pressing pressures in the range of 200x10 5 Pa to 1500x10 5 Pa pressed.
- a tablet thus produced has a weight of 15 to 40 g, in particular from 20 to 30 g, with a diameter of 35 to 40 mm.
- compositions in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 800 to 1000 g / l can be effected by subjecting the builder components with at least a proportion of liquid mixture components in a first process step Increase the bulk density of this premix and subsequently - if desired, after an intermediate drying - the other constituents of the agent, including the bleach catalyst, combined with the thus obtained premix.
- Means for cleaning dishes can be used both in household dishwashers and in commercial dishwashers become. The addition is done 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.
- V 2 and V3 other non-inventive manganese salts or mixtures consisting of manganese salts and oxalic acid are listed as comparative examples.
- tea cups were immersed in a 70 ° C. hot tea solution 25 times. Then each of the tea solution was added to each tea cup and the cup dried in a drying oven.
- Table 1 test product rating V1 (cleaner) 37% V2 (cleaner + 100 mg Mn (II) sulphate) 55% V3 (cleaner + 50 mg Mn (II) SO 4 + 50 mg oxalic acid) 73% M1 (cleaner + 100 mg Mn (II) oxalate dihydrate) 80% M2 (cleaner + 100 mg Mn (III) oxalate trihydrate) 78% M3 (cleaner + 50 mg Mn (II) oxalate dihydrate) 65%
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
Claims (9)
- Utilisation d'oxalates de manganèse dans des produits de nettoyage pour surfaces dures, en tant que catalyseurs de blanchiment, pour l'accentuation de l'action de blanchiment de composés peroxygénés inorganiques dans le blanchiment de salissures colorées.
- Utilisation selon la revendication 1, caractérisée en ce que l'oxalate de manganèse est un oxalate de manganèse(II) dihydraté ou un oxalate de manganèse (II) trihydraté.
- Utilisation selon la revendication 1 ou 2, caractérisée en ce que les composés peroxygénés inorganiques sont un perborate de métal alcalin mono- ou tétrahydraté et/ou un percarbonate de métal alcalin.
- Utilisation selon la revendication 3, caractérisée en ce que le métal alcalin est le sodium.
- Utilisation selon la revendication 1, caractérisée en ce qu'on utilise en outre de l'acide oxalique libre.
- Utilisation selon une ou plusieurs des revendications 1 à 5, caractérisée en ce qu'on utilise en outre de la tétraacétylènediamine.
- Utilisation selon une ou plusieurs des revendications 1 à 6, caractérisée en ce que le produit de nettoyage pour surfaces dures contient le composé peroxygéné et 0,025 à 2,5 % en poids d'oxalate de manganèse.
- Utilisation selon la revendication 7, caractérisée en ce que le produit de nettoyage pour surfaces dures contient le composé peroxygéné et 0,05 à 1,5 % en poids d'oxalate de manganèse.
- Utilisation selon une ou plusieurs des revendications 1 à 8, caractérisée en ce que le produit de nettoyage pour surfaces dures est un produit de lavage de la vaisselle.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL09778105T PL2329000T3 (pl) | 2008-08-30 | 2009-08-26 | Zastosowanie szczawianów manganu jako katalizatorów bielenia |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102008045215A DE102008045215A1 (de) | 2008-08-30 | 2008-08-30 | Verwendung von Mangan-Oxalatenn als Bleichkatalysatoren |
PCT/EP2009/006162 WO2010022918A1 (fr) | 2008-08-30 | 2009-08-26 | Utilisation d'oxalates de manganèse comme catalyseur de blanchiment |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2329000A1 EP2329000A1 (fr) | 2011-06-08 |
EP2329000B1 true EP2329000B1 (fr) | 2012-07-18 |
Family
ID=41216482
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP09778105A Active EP2329000B1 (fr) | 2008-08-30 | 2009-08-26 | Utilisation d'oxalates de manganèse comme catalyseur de blanchiment |
Country Status (10)
Country | Link |
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US (1) | US8927478B2 (fr) |
EP (1) | EP2329000B1 (fr) |
JP (1) | JP5667055B2 (fr) |
CN (1) | CN102131909B (fr) |
DE (1) | DE102008045215A1 (fr) |
DK (1) | DK2329000T3 (fr) |
ES (1) | ES2388234T3 (fr) |
PL (1) | PL2329000T3 (fr) |
PT (1) | PT2329000E (fr) |
WO (1) | WO2010022918A1 (fr) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102008038376A1 (de) * | 2008-08-19 | 2010-02-25 | Clariant International Ltd. | Verfahren zur Herstellung von 3,7-Diaza-bicyclo[3.3.1]nonan-Verbindungen |
DE102008045207A1 (de) * | 2008-08-30 | 2010-03-04 | Clariant International Limited | Bleichkatalysatormischungen bestehend aus Mangansalzen und Oxalsäure oder deren Salze |
DE102008064009A1 (de) | 2008-12-19 | 2010-06-24 | Clariant International Ltd. | Verfahren zur Herstellung von 3,7-Diaza-bicyclo[3.3.1]nonan-Metall-Komplexen |
GB201014328D0 (en) * | 2010-08-27 | 2010-10-13 | Reckitt Benckiser Nv | Detergent composition comprising manganese-oxalate |
GB201218415D0 (en) * | 2012-10-15 | 2012-11-28 | Reckitt & Colman Overseas | Ultrasonic method of cleaning |
MX2015015054A (es) * | 2013-05-02 | 2016-02-25 | Ecolab Usa Inc | Composicion de detergente concentrado para la remocion mejorada de almidon en las aplicaciones de lavavajillas. |
JP6254693B2 (ja) | 2013-10-24 | 2017-12-27 | エコラボ ユーエスエー インコーポレイティド | 表面から汚れを除去する組成物及び方法 |
DE102013019269A1 (de) | 2013-11-15 | 2015-06-03 | Weylchem Switzerland Ag | Geschirrspülmittel sowie dessen Verwendung |
US20180216041A1 (en) | 2015-07-06 | 2018-08-02 | Ecolab Usa Inc. | Stain removal through novel oxidizer and chelant combination |
US10414972B2 (en) | 2015-10-30 | 2019-09-17 | Halliburton Energy Services, Inc. | Peroxide containing formation conditioning and pressure generating composition and method |
RU2696990C2 (ru) * | 2017-12-26 | 2019-08-08 | Общество с ограниченной ответственностью "АНГАРА ДЕВЕЛОПМЕНТ" (ООО "АНГАРА ДЕВЕЛОПМЕНТ") | Раствор для очистки поверхности от отложений различной природы |
EP4008765A1 (fr) | 2020-12-07 | 2022-06-08 | WeylChem Performance Products GmbH | Compositions comprenant des composés triazacycliques protonés et agent de blanchiment et agent de nettoyage les contenant |
EP4296343A1 (fr) | 2022-06-24 | 2023-12-27 | WeylChem Performance Products GmbH | Compositions comprenant des composés triazacycliques protonés et de l'acétate de manganèse(ii), leur fabrication, et agent de blanchiment et de nettoyage les comprenant |
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GB1182143A (en) | 1966-03-01 | 1970-02-25 | United States Borax Chem | Bleaching Compositions and Methods. |
US4414127A (en) | 1981-07-06 | 1983-11-08 | Syntex (U.S.A.) Inc. | Contact lens cleaning solutions |
GR76237B (fr) | 1981-08-08 | 1984-08-04 | Procter & Gamble | |
US4481129A (en) | 1981-12-23 | 1984-11-06 | Lever Brothers Company | Bleach compositions |
GB8329762D0 (en) | 1983-11-08 | 1983-12-14 | Unilever Plc | Manganese adjuncts |
GB8405189D0 (en) | 1984-02-28 | 1984-04-04 | Interox Chemicals Ltd | Peroxide activation |
US4728455A (en) | 1986-03-07 | 1988-03-01 | Lever Brothers Company | Detergent bleach compositions, bleaching agents and bleach activators |
US5106523A (en) * | 1989-06-16 | 1992-04-21 | The Clorox Company | Thickened acidic liquid composition with amine fwa useful as a bleaching agent vehicle |
JP2602563B2 (ja) * | 1989-12-15 | 1997-04-23 | 花王株式会社 | 液体酸素系漂白剤組成物 |
WO1995034628A1 (fr) | 1994-06-13 | 1995-12-21 | Unilever N.V. | Activation de blanchiment |
DE4443177A1 (de) | 1994-12-05 | 1996-06-13 | Henkel Kgaa | Aktivatormischungen für anorganische Perverbindungen |
EP1002041B1 (fr) * | 1997-07-09 | 2003-03-05 | The Procter & Gamble Company | Compositions de lavage/nettoyage contenant une oxydoreductase |
US6734155B1 (en) * | 1997-07-09 | 2004-05-11 | The Procter & Gamble Company | Cleaning compositions comprising an oxidoreductase |
CA2248476A1 (fr) | 1997-10-01 | 1999-04-01 | Unilever Plc | Activation du blanchiment |
DE19909546C1 (de) * | 1999-03-04 | 2000-06-29 | Consortium Elektrochem Ind | Mehrkomponentensystem zur enzymkatalysierten Oxidation von Substraten sowie Verfahren zur enzymkatalysierten Oxidation |
US7183291B2 (en) * | 1999-04-29 | 2007-02-27 | Council Of Scientific And Industrial Research | Method for the treatment of malaria by the use of primaquine derivative N1-(3-ethylidinotetrahydrofuran-2-one)-N4- (6-methoxy-8-quinolinyl)-1,4-pentanediamine as gametocytocidal agent |
GB9930422D0 (en) * | 1999-12-22 | 2000-02-16 | Unilever Plc | Bleach catalysts |
GB0030673D0 (en) | 2000-12-15 | 2001-01-31 | Unilever Plc | Ligand and complex for catalytically bleaching a substrate |
GB0104980D0 (en) | 2001-02-28 | 2001-04-18 | Unilever Plc | Liquid cleaning compositions and their use |
BR0306912A (pt) | 2002-02-28 | 2004-11-09 | Unilever Nv | Composição de branqueamento, e, processo para o branqueamento de uma mancha |
RU2004139079A (ru) | 2002-06-06 | 2005-11-20 | Унилевер Н.В. (NL) | Лиганд и комплекс для каталитического обесцвечивания субстрата |
DE10304131A1 (de) | 2003-02-03 | 2004-08-05 | Clariant Gmbh | Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren |
DE60321832D1 (de) * | 2003-05-07 | 2008-08-07 | Ciba Holding Inc | Bleichzusammensetzung und bleichwaschmittelzusammensetzung |
DE10345273A1 (de) | 2003-09-30 | 2005-04-21 | Clariant Gmbh | Verwendung von Übergangsmetallkomplexen mit Lactamliganden als Bleichkatalysatoren |
GB0411304D0 (en) | 2004-05-21 | 2004-06-23 | Fellows Adrian N | An antimicrobial composition |
US7285522B2 (en) * | 2004-08-25 | 2007-10-23 | The Clorox Company | Bleaching with improved whitening |
DE102005027619A1 (de) | 2005-06-15 | 2006-12-28 | Clariant Produkte (Deutschland) Gmbh | Verfahren zur Herstellung von 3,7-Diaza-bicyclo[3.3.1]nonan-Verbindungen |
DE102008045207A1 (de) | 2008-08-30 | 2010-03-04 | Clariant International Limited | Bleichkatalysatormischungen bestehend aus Mangansalzen und Oxalsäure oder deren Salze |
-
2008
- 2008-08-30 DE DE102008045215A patent/DE102008045215A1/de not_active Withdrawn
-
2009
- 2009-08-26 WO PCT/EP2009/006162 patent/WO2010022918A1/fr active Application Filing
- 2009-08-26 CN CN2009801330379A patent/CN102131909B/zh active Active
- 2009-08-26 JP JP2011524244A patent/JP5667055B2/ja not_active Expired - Fee Related
- 2009-08-26 US US13/060,836 patent/US8927478B2/en active Active
- 2009-08-26 DK DK09778105.8T patent/DK2329000T3/da active
- 2009-08-26 ES ES09778105T patent/ES2388234T3/es active Active
- 2009-08-26 PL PL09778105T patent/PL2329000T3/pl unknown
- 2009-08-26 PT PT09778105T patent/PT2329000E/pt unknown
- 2009-08-26 EP EP09778105A patent/EP2329000B1/fr active Active
Also Published As
Publication number | Publication date |
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DE102008045215A1 (de) | 2010-03-04 |
PL2329000T3 (pl) | 2012-12-31 |
ES2388234T3 (es) | 2012-10-11 |
US8927478B2 (en) | 2015-01-06 |
CN102131909A (zh) | 2011-07-20 |
EP2329000A1 (fr) | 2011-06-08 |
CN102131909B (zh) | 2013-02-13 |
US20110166055A1 (en) | 2011-07-07 |
JP2012500870A (ja) | 2012-01-12 |
DK2329000T3 (da) | 2012-10-15 |
PT2329000E (pt) | 2012-09-17 |
WO2010022918A1 (fr) | 2010-03-04 |
JP5667055B2 (ja) | 2015-02-12 |
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