EP3409753A1 - Enhanced bleaching during washing and cleaning - Google Patents
Enhanced bleaching during washing and cleaning Download PDFInfo
- Publication number
- EP3409753A1 EP3409753A1 EP18172235.6A EP18172235A EP3409753A1 EP 3409753 A1 EP3409753 A1 EP 3409753A1 EP 18172235 A EP18172235 A EP 18172235A EP 3409753 A1 EP3409753 A1 EP 3409753A1
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- European Patent Office
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- liquor
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- 238000004061 bleaching Methods 0.000 title claims abstract description 19
- 238000004140 cleaning Methods 0.000 title claims abstract description 16
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- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 240000000851 Vaccinium corymbosum Species 0.000 description 1
- 235000003095 Vaccinium corymbosum Nutrition 0.000 description 1
- 235000017537 Vaccinium myrtillus Nutrition 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 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
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000005011 alkyl ether group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 108090000637 alpha-Amylases Proteins 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 150000008064 anhydrides 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
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 235000021014 blueberries Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 108010005400 cutinase Proteins 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 108010002430 hemicellulase Proteins 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical class COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- PATMLLNMTPIUSY-UHFFFAOYSA-N phenoxysulfonyl 7-methyloctanoate Chemical compound CC(C)CCCCCC(=O)OS(=O)(=O)OC1=CC=CC=C1 PATMLLNMTPIUSY-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 235000019419 proteases Nutrition 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- QSKQNALVHFTOQX-UHFFFAOYSA-M sodium nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O QSKQNALVHFTOQX-UHFFFAOYSA-M 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- CVYDEWKUJFCYJO-UHFFFAOYSA-M sodium;docosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O CVYDEWKUJFCYJO-UHFFFAOYSA-M 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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
- C11D3/02—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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
Definitions
- the present invention relates to the use of certain polyoxometallates for the activation of molecular oxygen in connection with the bleaching of soils when washing textiles, as well as washing and cleaning processes in which such polyoxometalates are used.
- 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 alkali 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 addition of so-called bleach activators which are able to provide peroxycarboxylic under the abovementioned perhydrolysis and for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example several times acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic anhydrides, in particular phthalic anhydride and alkylsuccinic anhydrides, carboxylic esters, in particular sodium nonanoyloxybenzenesulphonate, sodium isononanoyloxy Benzenesulfonate,
- bleaching agents which contain peroxygen compounds and polyoxometalates as bleach catalysts, wherein in the polyoxometalates Mo, W, Nn, Ta and / or V must be present and in addition transition metals of the 2nd and 8th subgroup may be included.
- the international patent application WO 99/28426 A1 relates to compositions which contain a bleaching agent and as a bleach catalyst a Keggin, Dawson or Finke polyoxocobaltate.
- the international patent application WO 00/39264 A1 relates to a bleaching process using a bleaching composition containing a polyoxometalate and air as the primary source of oxygen atoms.
- the object of the present invention is to improve the oxidation and bleaching action of liquors used in washing textiles or cleaning hard surfaces, especially at low temperatures in the range of about 10 ° C to 45 ° C.
- M early transition metals comprising the elements of groups 3 to 6 of the Periodic Table, in particular Groups 5 and 6 and preferably V, Cr, Mo, and W, which may optionally have been proportionally substituted by later transition metals compris
- a second subject of the invention is the use of these polyoxometalates for enhancing the cleaning performance of detergents or cleaners in aqueous, especially surfactant-containing liquor in the presence of a gaseous phase which is present in addition to the liquid phase of the liquor and molecular oxygen, in particular atmospheric oxygen.
- bleaching stains is to be understood in its broadest sense and includes both the bleaching of colored stains on the fabric, the bleaching of stained debris located in the wash liquor, and the staining of the stained fabric removed from the fabric the oxidative destruction of textile dyes found in the wash liquor, which detach themselves under the washing conditions of textiles before they can be applied to differently colored textiles.
- the polyoxometalate is preferably selected from the group comprising Na 5 [IMo 6 O 24 ] .3H 2 O, K 5 [SiW 11 VO 40 ] .12H 2 O, Na 5 PMo 10 V 2 O 40 and mixtures of at least two of these.
- the use according to the invention consists of creating conditions under which the molecular oxygen provided, in particular via the dosage form air, and the said polyoxometalate can react with one another, with the aim of obtaining more strongly oxidizing secondary products.
- Such conditions are particularly present when the polyoxometalate is present in an aqueous system and in addition to the liquid phase of this aqueous system, a gaseous phase, for example air, is present, which contains molecular oxygen. This can penetrate through the interface to the liquid phase in the aqueous system and form there or at the said interface with the polyoxometalate a more oxidizing secondary product.
- a gaseous phase for example air
- the formation of the more highly oxidative secondary product may be enhanced and / or accelerated by the use of a gas phase having a higher concentration of molecular oxygen and / or a gas phase containing molecular oxygen under increased pressure if desired. If a gas phase which is not present at normal pressure or the usual ambient pressure is used, a pressure of up to 100 bar, in particular in the range of 10 bar to 80 bar, is preferred.
- the liquor containing the polyoxometalate may contain customary constituents of detergents or cleaning agents which originate in the customary manner from the introduction of such agents into the liquor.
- the washing or cleaning agents used in the preparation of the liquor can be free from peroxygen compounds. If desired, the formation of the more strongly oxidizing secondary product can be accelerated, starting from an optionally washing or cleaning agent-containing liquor containing so much H 2 O 2 or in water H 2 O 2- supplying substance that their concentration (calculated as H 2 O 2 ) in the liquor is from 0.01 mmol / l to 0.5 mmol / l, in particular from 0.06 mmol / l to 0.12 mmol / l.
- the reaction with the polyoxometalate consumes the H 2 O 2 or the substance which delivers H 2 O 2 in water, but does not have to be replaced since it has a more oxidizing secondary product after its reaction with stains to be bleached in the sense of a molecular cycle Oxygen is newly formed.
- the washing or cleaning agent used in addition to the polyoxometalate in the liquor is therefore free of peroxygen compounds or contains only so much of H 2 O 2 or in water H 2 O 2 -lautnder substance that their concentration (calculated as H 2 O 2 ) in the liquor 0.01 mmol / l to 0.5 mmol / l, in particular 0.06 mmol / l to 0.12 mmol / l.
- the concentration ranges given above therefore refer to the calculated by the total amount of added agent releasable H 2 O 2 .
- Further objects of the invention are a process for washing laundry and a process for cleaning hard surfaces, comprising the process steps of (a) providing an aqueous liquor containing said polyoxometalate, and (b) contacting said liquor with textiles to be washed or hard surfaces to be cleaned in the presence of a gaseous phase which is present in addition to the liquid phase of the aqueous liquor and contains molecular oxygen, in particular atmospheric oxygen.
- a gaseous phase which is present in addition to the liquid phase of the aqueous liquor and contains molecular oxygen, in particular atmospheric oxygen.
- the contact between the aqueous liquor and the object to be washed or cleaned at temperatures ranging from 20 ° C to 95 ° C, in particular from 30 ° C to 60 ° C, ago.
- the process steps (a) and (b) need not be carried out one after the other, but result on introduction of the material to be cleaned into the machine and subsequent flushing of an agent containing the polyoxometalate with water at the same time.
- the object to be washed or cleaned remains in contact with the aqueous liquor for a period of from 15 minutes to 2.5 hours, especially from 45 minutes to 1.5 hours.
- the methods according to the invention can be carried out manually or with the aid of conventional devices, for example washing machines or dishwashers.
- the amounts of polyxoxometalate used are chosen such that their concentration in the liquor preferably ranges from 0.05 ⁇ mol / l to 5 ⁇ m / l, in particular 0.1 ⁇ mol / l to 0.12 ⁇ mol / l lies.
- concentrations of H 2 O 2 or water H 2 O 2 -derfernderder substance in the fleet also apply to preferred embodiments of the inventive method.
- the liquor used in the context of the invention preferably has a pH in the range from pH 6 to pH 14, in particular from pH 8.5 to pH 12.
- Detergents and cleaners which may be in the form of particularly pulverulent solids, in densified particle form, as homogeneous solutions or as suspensions or dispersions, may contain, in principle, all known ingredients common in such agents besides the bleach-enhancing compound used in accordance with the invention.
- solid compositions which can be used in the context of the present invention are usually 0.0005 wt .-% to 4 wt .-%, preferably 0.00076 wt .-% to 0.4 wt .-%, and In particular, 0.0015 wt .-% to 0.01 wt .-% of polyoxometalate defined above.
- liquid agents which can be used in the context of the present invention, usually 0.0005 wt .-% to 6 wt .-%, preferably 0.0006 wt .-% to 0.54 wt .-%, and in particular from 0.001% to 0.013% by weight of polyoxometalate as defined above.
- the detergents and cleaning agents may in particular contain builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, grayness inhibitors, color transfer inhibitors, foam regulators and dyes and fragrances.
- Suitable peroxygen compounds which may additionally be present are, in particular, inorganic peroxygen compounds such as hydrogen peroxide and inorganic salts which release hydrogen peroxide under the conditions of use, such as perborate, percarbonate and / or persilicate, and hydrogen peroxide inclusion compounds, such as H 2 O 2 -urea adducts.
- Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle.
- the peroxygen compounds can be added as such or in the form of these containing agents, which may in principle contain all conventional detergent or cleaner ingredients, to the Waschavynger cleaning solution. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. If a washing or cleaning agent used in the invention contains peroxygen compounds, these are preferably in amounts of 0.1 wt .-% to 50 wt .-%, in particular from 5 wt .-% to 20 wt .-% and particularly preferred from 7% to 17%, and most preferably from 8% to 15%, by weight.
- the agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof come into question.
- Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups.
- ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
- Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
- Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form.
- Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation.
- Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.
- Such surfactants are present in the detergents used in the invention in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, while means for cleaning hard surfaces , in particular of tableware, preferably 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight of surfactants.
- An agent used in the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
- the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid, sugar acids and carboxymethylinulines, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris ( methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), lysine tetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and poly
- the relative average molecular weight (here and hereinafter: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50 000 g / mol to 120 000 g / mol, in each case based on the free acid.
- a particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 g / mol to 100,000 g / mol.
- Suitable, though less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in wherein the proportion of the acid is at least 50 wt .-%.
- vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene
- the proportion of the acid is at least 50 wt .-%.
- water-soluble organic builders it is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer.
- the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) -acrylic acid.
- the second acidic monomer or its salt can be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred.
- the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol.
- Preferred polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate.
- the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2 , 5: 1 lies.
- the second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted.
- Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight.
- % preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate.
- This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Particularly preferred is sucrose.
- the use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer.
- terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol.
- Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
- the organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
- organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.
- Suitable water-soluble inorganic builder materials are, in particular, polyphosphates, preferably sodium triphosphate.
- water-insoluble inorganic builder materials are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25 wt .-%, preferably from 3 wt .-% to 20 wt .-% and in particular in amounts of 5 wt .-% to 15 wt. -% used.
- the detergent-grade crystalline sodium aluminosilicates particularly zeolite A, zeolite P, and zeolite MAP, and optionally zeolite X, are preferred.
- Amounts near the above upper limit are preferably used in solid, particulate agents.
- suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
- Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.
- water-soluble inorganic builder materials may be included.
- polyphosphates such as sodium triphosphate
- these include in particular the water-soluble crystalline and / or amorphous alkali metal silicate builders.
- Such water-soluble inorganic builder materials are preferably included in detergents in amounts of from 1% to 20%, and more preferably from 5% to 15%, by weight.
- the alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be amorphous or crystalline.
- Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
- the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na 2 Si x O used 2x + 1 ⁇ y H 2 O in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
- Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
- both ⁇ - and ⁇ -sodium disilicates are preferred.
- amorphous alkali metal silicates practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used.
- a crystalline sodium layer silicate is used with a modulus of 2 to 3, as it can be prepared from sand and soda.
- Sodium silicates with a modulus in the range 1.9 to 3.5 are used in another embodiment of the compositions.
- a granular compound of alkali metal silicate and alkali carbonate as it is commercially available, for example, under the name Nabion® 15.
- Machine dishwashing detergents are preferably of low alkaline content and contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates.
- Alkali silicates may be used in amounts of up to 30% by weight. %, based on the total mean.
- the use of the highly alkaline metasilicates as alkali carriers is preferably completely dispensed with.
- the alkali carrier system used with preference is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which is present in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight.
- the ratio of carbonate used and bicarbonate used varies, but usually an excess of sodium bicarbonate is used, so that the weight ratio of bicarbonate to carbonate is generally from 1: 1 to 15: 1.
- Suitable enzymes contained in the compositions are, in particular, those from the class of proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, lipase and / or or cellulase is particularly preferred.
- the proportion is preferably 0.2 wt .-% to 1.5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%.
- the enzymes can be adsorbed in a customary manner on carriers and / or embedded in coating substances or incorporated as concentrated, as anhydrous liquid formulations.
- Suitable gravel inhibitors or soil release agents are cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose.
- cellulose ethers such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose.
- sodium carboxymethylcellulose and mixtures thereof with methylcellulose are used.
- Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units.
- the proportion of graying inhibitors and / or soil-release active ingredients is generally not more than 2 wt .-% and is preferably 0.5 wt .-% to 1.5 wt .-%, each based on the agent.
- optical brighteners for textiles made of cellulose fibers include derivatives of diaminostilbenedisulfonic acid or alkali metal salts thereof.
- salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or similarly constructed compounds which are suitable instead of the morpholino group carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group.
- brighteners of the substituted 4,4'-distyryl-diphenyl type may be present, for example, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl.
- mixtures of brighteners can be used.
- brighteners of the 1,3-diaryl-2-pyrazolines type for example 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of similar construction are particularly suitable.
- the content of the composition in optical brighteners or brightener mixtures is generally not more than 1 wt .-%, preferably 0.05 wt .-% to 0.5 wt .-%.
- the customary foam regulators which can be used in the compositions include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanated or otherwise rendered hydrophobic.
- the polysiloxanes can consist of both linear compounds as well as crosslinked polysiloxane resins and mixtures thereof.
- Further antifoams are paraffin hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each having 12 to 22 carbon atoms.
- the proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight.
- 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 present in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight, based in each case on the composition.
- 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 hydrogensulfates, or bases, in particular ammonium or alkali metal hydroxides, contain.
- Such pH regulators are preferably contained in the compositions not more than 10% by weight, in particular from 0.5% by weight to 6% by weight.
- compositions 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.
- the synthesis was carried out analogously to the procedure under a) using adjusted amounts of sodium metavanadate (2.44 g in 10 ml of water) and sodium molybdate dihydrate (12.1 g in 20 ml of water). 3.5 g of 10-molybdo-2-vanadophosphoric acid were obtained.
- the synthesis was carried out analogously to the procedure under a) using adjusted amounts of sodium metavanadate (3.66 g in 20 ml of water) and sodium molybdate dihydrate (5.45 g in 15 ml of water). 0.72 g of 9-molybdo-3-vanadophosphoric acid was obtained.
- the molybdovanadophosphoric acid prepared in 2 b) was converted by ion exchange through the ion exchange resin Amberlite IR-120 in sodium form
- the textile sample was swirled for 30 seconds in 50 ml of demineralized water to the Rinse off washing solution.
- the evaluation of the stain removal performance was carried out on the dried textile samples via color difference measurement according to the L * a * b * values and the Y values calculated therefrom as a measure of the brightness.
- the following table shows the Y values that resulted after washing.
- the experiments were repeated without the addition of Na 5 [IMo 6 O 24 ], and replacing this active substance with the same amount of Mn-Me 3 TACN, which resulted in values also given in Table 1.
- the Y values when using the active substance according to the invention in the presence of air are greater than those in the presence of nitrogen; they are also larger than those resulting from its replacement by a known bleach catalyst or when using only the detergent, which corresponds to a higher whiteness and thus improved stain removal.
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Abstract
Die Oxidations- und Bleichleistung beim Waschen von Textilien und beim Reinigen harter Oberflächen, insbesondere bei niedrigen Temperaturen sollte verbessert werden. Dies gelang im Wesentlichen durch den Einsatz bestimmter Polyoxometallate.The oxidation and bleaching performance of washing textiles and cleaning hard surfaces, especially at low temperatures, should be improved. This was achieved mainly by the use of certain polyoxometalates.
Description
Die vorliegende Erfindung betrifft die Verwendung von bestimmten Polyoxometallaten zur Aktivierung von molekularem Sauerstoff in Zusammenhang mit dem Bleichen von Anschmutzungen beim Waschen von Textilien, sowie Wasch- und Reinigungsverfahren, bei denen derartige Polyoxometallate eingesetzt werden.The present invention relates to the use of certain polyoxometallates for the activation of molecular oxygen in connection with the bleaching of soils when washing textiles, as well as washing and cleaning processes in which such polyoxometalates are used.
Anorganische Persauerstoffverbindungen, insbesondere Wasserstoffperoxid und feste Persauerstoffverbindungen, die sich in Wasser unter Freisetzung von Wasserstoffperoxid lösen, wie Natriumperborat und Natriumcarbonat-Perhydrat, werden seit langem als Oxidationsmittel zu Desinfektions- und Bleichzwecken verwendet. Die Oxidationswirkung dieser Substanzen hängt in verdünnten Lösungen stark von der Temperatur ab; so erzielt man beispielsweise mit H2O2 oder Alkaliperborat in alkalischen Bleichflotten erst bei Temperaturen oberhalb von etwa 80 °C eine ausreichend schnelle Bleiche verschmutzter Textilien. Bei niedrigeren Temperaturen kann die Oxidationswirkung der anorganischen Persauerstoffverbindungen durch Zusatz sogenannter Bleichaktivatoren verbessert werden, die in der Lage sind, unter den angesprochenen Perhydrolysebedingungen Peroxocarbonsäuren zu liefern und für die zahlreiche Vorschläge, vor allem aus den Stoffklassen der N- oder O-Acylverbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Hydrotriazine, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid und Alkylbernsteinsäureanhydride, Carbonsäureester, insbesondere Natriumnonanoyloxy-benzolsulfonat, Natrium-isononanoyloxy-benzolsulfonat, O-acylierte Zuckerderivate, wie Pentaacetylglukose, und N-acylierte Lactame, wie N-Benzoylcaprolactam, in der Literatur bekannt geworden sind. Durch Zusatz dieser Substanzen kann die Bleichwirkung wäßriger Peroxidflotten so weit gesteigert werden, daß bereits bei Temperaturen um 60 °C im Wesentlichen die gleichen Wirkungen wie mit der Peroxidflotte allein bei 95 °C eintreten.Inorganic peroxygen compounds, 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 alkali perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by addition of so-called bleach activators which are able to provide peroxycarboxylic under the abovementioned perhydrolysis and for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example several times acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic anhydrides, in particular phthalic anhydride and alkylsuccinic anhydrides, carboxylic esters, in particular sodium nonanoyloxybenzenesulphonate, sodium isononanoyloxy Benzenesulfonate, O-acylated sugar derivatives, such as pentaacetyl glucose, and N-acylated lactams, such as N-benzoyl-caprolactam, have become known in the literature. By adding these substances, the bleaching action of aqueous peroxide liquors can be increased so much that even at temperatures around 60 ° C substantially the same effects as with the peroxide solution alone at 95 ° C occur.
Im Bemühen um energiesparende Wasch- und Bleichverfahren gewinnen in den letzten Jahren Anwendungstemperaturen deutlich unterhalb 60 °C, insbesondere unterhalb 45 °C bis herunter zur Kaltwassertemperatur an Bedeutung.In the search for energy-saving washing and bleaching processes in recent years application temperatures well below 60 ° C, especially below 45 ° C down to the cold water temperature in importance.
Bei niedrigen Temperaturen läßt die Wirkung der bisher bekannten Aktivatorverbindungen in der Regel erkennbar nach.At low temperatures, the effect of the previously known activator compounds usually decreases noticeably.
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10-Molybdo-2-vanadophosphorsäure und ihre Herstellung sind in
Die vorliegende Erfindung hat die Verbesserung der Oxidations- und Bleichwirkung von beim Waschen von Textilien oder beim Reinigen harter Oberflächen eingesetzter Flotten, insbesondere bei niedrigen Temperaturen im Bereich von ca. 10 °C bis 45 °C, zum Ziel.The object of the present invention is to improve the oxidation and bleaching action of liquors used in washing textiles or cleaning hard surfaces, especially at low temperatures in the range of about 10 ° C to 45 ° C.
Gegenstand der Erfindung ist die Verwendung von Polyoxometallaten, ausgewählt aus der Gruppe umfassend umfassend oxometallische Polyeder-Basiseinheiten MOx mit x = 5 oder 6, in denen M frühe Übergangsmetalle umfassend die Elemente der Gruppen 3 bis 6 des Periodensystems, insbesondere der Gruppen 5 und 6 und vorzugsweise V, Cr, Mo, und W repräsentiert, die gegebenenfalls anteilig durch spätere Übergangsmetalle umfassend die Elemente der Gruppen 3 bis 12, insbesondere der Gruppen 5 bis 10 des Periodensystems substituiert worden sein können, wobei die oxometallischen Polyeder um ein zentrales Heteroatom aus der Gruppe umfassend die Elemente der Gruppen 13 bis 17, insbesondere von Gruppe 14 bis 16 des Periodensystems herum zu einem Cluster angeordnet sein können, und deren Mischungen, zur Aktivierung von molekularem Sauerstoff, insbesondere Luftsauerstoff, beim Waschen von Textilien oder Reinigen harter Oberflächen. Ein zweiter Gegenstand der Erfindung ist die Verwendung von diesen Polyoxometallaten zur Verstärkung der Reinigungsleistung von Wasch- oder Reinigungsmitteln in wässriger, insbesondere tensidhaltiger Flotte in Anwesenheit einer gasförmigen Phase, die neben der flüssigen Phase der Flotte vorliegt und molekularen Sauerstoff, insbesondere Luftsauerstoff, enthält.The invention relates to the use of polyoxometalates selected from the group comprising oxometallic polyhedron base units MO x with x = 5 or 6, in which M early transition metals comprising the elements of groups 3 to 6 of the Periodic Table, in particular Groups 5 and 6 and preferably V, Cr, Mo, and W, which may optionally have been proportionally substituted by later transition metals comprising the elements of groups 3 to 12, in particular of groups 5 to 10 of the periodic table, wherein the oxometallic polyhedra is a central heteroatom from the Group comprising the elements of groups 13 to 17, in particular from group 14 to 16 of the periodic table can be arranged to form a cluster, and mixtures thereof for the activation of molecular oxygen, in particular atmospheric oxygen, when washing textiles or cleaning hard surfaces. A second subject of the invention is the use of these polyoxometalates for enhancing the cleaning performance of detergents or cleaners in aqueous, especially surfactant-containing liquor in the presence of a gaseous phase which is present in addition to the liquid phase of the liquor and molecular oxygen, in particular atmospheric oxygen.
Ein weiterer Gegenstand der Erfindung ist die Verwendung von Polyoxometallaten, ausgewählt aus der Gruppe umfassend umfassend oxometallische Polyeder-Basiseinheiten MOx mit x = 5 oder 6, in denen M frühe Übergangsmetalle umfassend die Elemente der Gruppen 3 bis 6 des Periodensystems, insbesondere der Gruppen 5 und 6 und vorzugsweise V, Cr, Mo, und W repräsentiert, die gegebenenfalls anteilig durch spätere Übergangsmetalle umfassend die Elemente der Gruppen 3 bis 12, insbesondere der Gruppen 5 bis 10 des Periodensystems substituiert worden sein können, wobei die oxometallischen Polyeder um ein zentrales Heteroatom aus der Gruppe umfassend die Elemente der Gruppen 13 bis 17, insbesondere von Gruppe 14 bis 16 des Periodensystems herum zu einem Cluster angeordnet sein können, und deren Mischungen, zum Bleichen von Farbanschmutzungen beim Waschen von Textilien in wässriger, insbesondere tensidhaltiger, Flotte, oder in wässrigen, insbesondere tensidhaltigen, Reinigungslösungen für harte Oberflächen, insbesondere für Geschirr, zum Bleichen von gefärbten Anschmutzungen, insbesondere von Tee, in Anwesenheit einer gasförmigen Phase, die neben der flüssigen Phase der Flotte vorliegt und molekularen Sauerstoff, insbesondere Luftsauerstoff, enthält. Die Formulierung "Bleichen von Anschmutzungen" ist dabei in ihrer weitesten Bedeutung zu verstehen und umfaßt sowohl das Bleichen von sich auf dem Textil befindendem gefärbten Schmutz, das Bleichen von in der Waschflotte befindlichem, vom Textil abgelösten gefärbten Schmutz als auch das oxidative Zerstören von sich in der Waschflotte befindenden Textilfarben, die sich unter den Waschbedingungen von Textilien ablösen, bevor sie auf andersfarbige Textilien aufziehen können.Another object of the invention is the use of polyoxometalates selected from the group comprising comprising oxometallic polyhedron base units MO x with x = 5 or 6, in which M early transition metals comprising the elements of groups 3 to 6 of the Periodic Table, in particular groups and 6 and preferably V, Cr, Mo, and W, which may optionally have been proportionally substituted by later transition metals comprising the elements of groups 3 to 12, in particular of groups 5 to 10 of the Periodic Table, wherein the oxometallic polyhedra is a central heteroatom from the group comprising the elements of groups 13 to 17, in particular from group 14 to 16 of the periodic table, to a cluster, and mixtures thereof, for bleaching color stains in the washing of textiles in aqueous, in particular surfactant, liquor, or in aqueous, in particular surfactant-containing, cleaning solutions f r hard surfaces, in particular for tableware, for bleaching colored stains, especially tea, in the presence of a gaseous phase present in addition to the liquid phase of the fleet and containing molecular oxygen, in particular atmospheric oxygen. The phrase "bleaching stains" is to be understood in its broadest sense and includes both the bleaching of colored stains on the fabric, the bleaching of stained debris located in the wash liquor, and the staining of the stained fabric removed from the fabric the oxidative destruction of textile dyes found in the wash liquor, which detach themselves under the washing conditions of textiles before they can be applied to differently colored textiles.
Das Polyoxometallat wird vorzugsweise ausgewählt aus der Gruppe umfassend Na5[IMo6O24] · 3 H2O, K5[SiW11VO40] · 12 H2O, Na5PMo10V2O40 und Mischungen aus mindestens zweien von diesen.The polyoxometalate is preferably selected from the group comprising Na 5 [IMo 6 O 24 ] .3H 2 O, K 5 [SiW 11 VO 40 ] .12H 2 O, Na 5 PMo 10 V 2 O 40 and mixtures of at least two of these.
Die erfindungsgemäße Verwendung besteht im wesentlichen darin, Bedingungen zu schaffen, unter denen der insbesondere über die Darreichungsform Luft bereitgestellte molekulare Sauerstoff und das genannte Polyoxometallat miteinander reagieren können, mit dem Ziel, stärker oxidierend wirkende Folgeprodukte zu erhalten. Solche Bedingungen liegen insbesondere dann vor, wenn das Polyoxometallat in einem wäßrigen System vorliegt und neben der flüssigen Phase dieses wäßrigen Systems eine gasförmige Phase, beispielsweise Luft, vorliegt, die molekularen Sauerstoff enthält. Dieser kann durch die Grenzfläche zur flüssigen Phase in das wäßrige System eindringen und dort oder an der genannten Grenzfläche mit dem Polyoxometallat ein stärker oxidierendes Folgeprodukt bilden. Mittels Durchmischung der flüssigen und der gasförmigen Phase kann die Bildung des stärker oxidierenden Folgeprodukts noch verstärkt werden. Der Einsatz unter Umgebungsdruck und -temperatur stehender Luft ist möglich. Allerdings kann die Bildung des stärker oxidierenden Folgeprodukts durch den Einsatz einer eine höhere Konzentration an molekularem Sauerstoff aufweisenden Gasphase und/oder einer molekularen Sauerstoff enthaltenenden Gasphase unter erhöhtem Druck gewünschtenfalls verstärkt und/oder beschleunigt werden. Wenn eine nicht bei Normaldruck oder üblichem Umgebungsdruck vorliegende Gasphase eingesetzt wird, ist ein Druck bis 100 bar, insbesondere im Bereich von 10 bar bis 80 bar, bevorzugt. Die das Polyoxometallat enthaltende Flotte kann daneben übliche Bestandteile von Wasch- oder Reinigungsmitteln enthalten, die in üblicher Weise aus dem Einbringen von derartigen Mitteln in die Flotte stammen. Da die bleichende Wirkung der Flotte durch das Zusammenwirken des genannten Polyoxometallats mit molekularem Sauerstoff verstärkt wird, können die bei der Zubereitung der Flotte zum Einsatz kommenden Wasch- oder Reinigungsmittel frei von Persauerstoffverbindungen sein. Gewünschtenfalls kann die Bildung des stärker oxidierenden Folgeprodukts beschleunigt werden, wenn man von einer gegebenenfalls wasch- oder reinigungsmittelhaltigen Flotte ausgeht, die soviel an H2O2 oder in Wasser H2O2-liefernder Substanz enthält, dass deren Konzentration (berechnet als H2O2) in der Flotte 0,01 mmol/l bis 0,5 mmol/l, insbesondere 0,06 mmol/l bis 0,12 mmol/l beträgt. Durch die Reaktion mit dem Polyoxometallat wird das H2O2 oder die in Wasser H2O2-liefernde Substanz verbraucht, muss aber nicht ersetzt werden, da stärker oxidierendes Folgeprodukt nach dessen Abreaktion mit zu bleichenden Anschmutzungen im Sinne eines Kreislaufs mit Hilfe von molekularem Sauerstoff neu gebildet wird. In bevorzugten Ausführungsformen der Erfindung ist das neben dem Polyoxometallat in der Flotte eingesetzte Wasch- oder Reinigungsmittel daher frei von Persauerstoffverbindungen oder enthält nur so viel an H2O2 oder in Wasser H2O2-liefernder Substanz, dass deren Konzentration (berechnet als H2O2) in der Flotte 0,01 mmol/l bis 0,5 mmol/l, insbesondere 0,06 mmol/l bis 0,12 mmol/l beträgt. Da sich die eingesetzte Persauerstoffverbindung nicht zur Gänze gleichzeitig löst und das H2O2 in der Flotte wie geschildert abreagieren kann, ist der Versuch, die Konzentration des H2O2 in der zum Waschen oder Reinigen eingesetzten Flotte zu messen, wenig zweckmäßig; die vorstehend angegeben Konzentrationsbereiche beziehen sich daher auf die rechnerisch aus der Gesamtmenge von zugegebenem Mittel freisetzbares H2O2.Essentially, the use according to the invention consists of creating conditions under which the molecular oxygen provided, in particular via the dosage form air, and the said polyoxometalate can react with one another, with the aim of obtaining more strongly oxidizing secondary products. Such conditions are particularly present when the polyoxometalate is present in an aqueous system and in addition to the liquid phase of this aqueous system, a gaseous phase, for example air, is present, which contains molecular oxygen. This can penetrate through the interface to the liquid phase in the aqueous system and form there or at the said interface with the polyoxometalate a more oxidizing secondary product. By mixing the liquid and the gaseous phase, the formation of the more strongly oxidizing secondary product can be enhanced. The use under ambient pressure and temperature of standing air is possible. However, the formation of the more highly oxidative secondary product may be enhanced and / or accelerated by the use of a gas phase having a higher concentration of molecular oxygen and / or a gas phase containing molecular oxygen under increased pressure if desired. If a gas phase which is not present at normal pressure or the usual ambient pressure is used, a pressure of up to 100 bar, in particular in the range of 10 bar to 80 bar, is preferred. In addition, the liquor containing the polyoxometalate may contain customary constituents of detergents or cleaning agents which originate in the customary manner from the introduction of such agents into the liquor. Since the bleaching effect of the liquor is enhanced by the interaction of said polyoxometalate with molecular oxygen, the washing or cleaning agents used in the preparation of the liquor can be free from peroxygen compounds. If desired, the formation of the more strongly oxidizing secondary product can be accelerated, starting from an optionally washing or cleaning agent-containing liquor containing so much H 2 O 2 or in water H 2 O 2- supplying substance that their concentration (calculated as H 2 O 2 ) in the liquor is from 0.01 mmol / l to 0.5 mmol / l, in particular from 0.06 mmol / l to 0.12 mmol / l. The reaction with the polyoxometalate consumes the H 2 O 2 or the substance which delivers H 2 O 2 in water, but does not have to be replaced since it has a more oxidizing secondary product after its reaction with stains to be bleached in the sense of a molecular cycle Oxygen is newly formed. In preferred embodiments of the invention, the washing or cleaning agent used in addition to the polyoxometalate in the liquor is therefore free of peroxygen compounds or contains only so much of H 2 O 2 or in water H 2 O 2 -liefernder substance that their concentration (calculated as H 2 O 2 ) in the liquor 0.01 mmol / l to 0.5 mmol / l, in particular 0.06 mmol / l to 0.12 mmol / l. Since the peroxygen compound used does not completely dissolve at the same time and the H 2 O 2 in the liquor can react as described above, the attempt to measure the concentration of H 2 O 2 in the liquor used for washing or cleaning is not very expedient; the concentration ranges given above therefore refer to the calculated by the total amount of added agent releasable H 2 O 2 .
Weitere Gegenstände der Erfindung sind ein Verfahren zum Waschen von Wäsche und ein Verfahren zum Reinigen harter Oberflächen, umfassend die Verfahrensschritte (a) Bereitstellen einer wäßrigen Flotte, enthaltend das genannte Polyoxometallat, und (b) In-Kontakt-Bringen dieser Flotte mit zu waschenden Textilien oder zu reinigenden harten Oberflächen in Anwesenheit einer gasförmigen Phase, die neben der flüssigen Phase der wässrigen Flotte vorliegt und molekularen Sauerstoff, insbesondere Luftsauerstoff, enthält. Vorzugsweise stellt man den Kontakt zwischen der wäßrigen Flotte und dem zu waschenden oder zu reinigenden Gegenstand bei Temperaturen im Bereich von 20 °C bis 95 °C, insbesondere von 30 °C bis 60 °C, her. Insbesondere bei maschineller Anwendung müssen die Verfahrensschrite (a) und (b) nicht nacheinander ausgeführt werden, sondern ergeben sich bei Einbringen des zu reinigenden Gutes in die Maschine und anschließendes Einspülen eines Mittels, welches das Polyoxometallat enthält, mit Wasser gleichzeitig. Vorzugsweise bleibt der zu waschende oder zu reinigende Gegenstand über einen Zeitraum von 15 Minuten bis 2,5 Stunden, insbesondere von 45 Minuten bis 1,5 Stunden, mit der wäßrigen Flotte in Kontakt. Die erfindungsgemäßen Verfahren können manuell oder mit Hilfe üblicher Vorrichtungen, beispielsweise Waschmaschinen oder Geschirrspülmaschinen, ausgeführt werden. Im Rahmen einer erfindungsgemäßen Verwendung und eines erfindungsgemäßen Verfahrens werden die Einsatzmengen an Polyxoxometallat so gewählt, dass dessen Konzentration in der Flotte vorzugsweise im Bereich von 0,05 µmol/l bis 5 µm/l, insbesondere 0,1 µmol/l bis 0,12 µmol/l liegt. Die oben genannten Konzentrationen an H2O2 oder in Wasser H2O2-liefernder Substanz in der Flotte gelten auch für bevorzugte Ausführungsformen der erfindungsgemäßen Verfahren.Further objects of the invention are a process for washing laundry and a process for cleaning hard surfaces, comprising the process steps of (a) providing an aqueous liquor containing said polyoxometalate, and (b) contacting said liquor with textiles to be washed or hard surfaces to be cleaned in the presence of a gaseous phase which is present in addition to the liquid phase of the aqueous liquor and contains molecular oxygen, in particular atmospheric oxygen. Preferably, the contact between the aqueous liquor and the object to be washed or cleaned at temperatures ranging from 20 ° C to 95 ° C, in particular from 30 ° C to 60 ° C, ago. In particular when used mechanically, the process steps (a) and (b) need not be carried out one after the other, but result on introduction of the material to be cleaned into the machine and subsequent flushing of an agent containing the polyoxometalate with water at the same time. Preferably, the object to be washed or cleaned remains in contact with the aqueous liquor for a period of from 15 minutes to 2.5 hours, especially from 45 minutes to 1.5 hours. The methods according to the invention can be carried out manually or with the aid of conventional devices, for example washing machines or dishwashers. In the context of a use according to the invention and a method according to the invention, the amounts of polyxoxometalate used are chosen such that their concentration in the liquor preferably ranges from 0.05 μmol / l to 5 μm / l, in particular 0.1 μmol / l to 0.12 μmol / l lies. The abovementioned concentrations of H 2 O 2 or water H 2 O 2 -derfernderder substance in the fleet also apply to preferred embodiments of the inventive method.
Die im Rahmen der Erfindung zum Einsatz kommende Flotte weist vorzugsweise einen pH-Wert im Bereich von pH 6 bis pH 14, insbesondere von pH 8,5 bis pH 12 auf.The liquor used in the context of the invention preferably has a pH in the range from pH 6 to pH 14, in particular from pH 8.5 to pH 12.
Wasch- und Reinigungsmittel, die als insbesondere pulverförmige Feststoffe, in nachverdichteter Teilchenform, als homogene Lösungen oder als Suspensionen beziehungsweise Dispersionen vorliegen können, können außer der erfindungsgemäß verwendeten bleichverstärkenden Verbindung im Prinzip alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten. In festen Mitteln, die im Rahmen der vorliegenden Erfindung eingesetzt werden können, sind in der Regel 0,0005 Gew.-% bis 4 Gew.-%, vorzugsweise 0,00076 Gew.-% bis 0,4 Gew.-%, und insbesondere 0,0015 Gew.-% bis 0,01 Gew.-% an oben definiertem Polyoxometallat enthalten. Vorzugsweise sind in flüssigen Mitteln, die im Rahmen der vorliegenden Erfindung eingesetzt werden können, in der Regel 0,0005 Gew.-% bis 6 Gew.-%, vorzugsweise 0,0006 Gew.-% bis 0,54 Gew.-%, und insbesondere 0,001 Gew.-% bis 0,013 Gew.-% an oben definiertem Polyoxometallat enthalten. Die Wasch- und Reinigungsmittel können insbesondere Buildersubstanzen, oberflächenaktive Tenside, wassermischbare organische Lösungsmittel, Enzyme, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren und weitere Hilfsstoffe, wie optische Aufheller, Vergrauungsinhibitoren, Farbübertragungsinhibitoren, Schaumregulatoren sowie Farb- und Duftstoffe enthalten.Detergents and cleaners, which may be in the form of particularly pulverulent solids, in densified particle form, as homogeneous solutions or as suspensions or dispersions, may contain, in principle, all known ingredients common in such agents besides the bleach-enhancing compound used in accordance with the invention. In solid compositions which can be used in the context of the present invention, are usually 0.0005 wt .-% to 4 wt .-%, preferably 0.00076 wt .-% to 0.4 wt .-%, and In particular, 0.0015 wt .-% to 0.01 wt .-% of polyoxometalate defined above. Preferably, in liquid agents which can be used in the context of the present invention, usually 0.0005 wt .-% to 6 wt .-%, preferably 0.0006 wt .-% to 0.54 wt .-%, and in particular from 0.001% to 0.013% by weight of polyoxometalate as defined above. The detergents and cleaning agents may in particular contain builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, grayness inhibitors, color transfer inhibitors, foam regulators and dyes and fragrances.
Als gegebenenfalls zusätzlich vorhandene geeignete Persauerstoffverbindungen kommen insbesondere anorganische Persauerstoffverbindungen wie Wasserstoffperoxid und unter den Einsatzbedingungen Wasserstoffperoxid abgebende anorganische Salze, wie Perborat, Percarbonat und/oder Persilikat, und Wasserstoffperoxid-Einschlußverbindungen, wie H2O2-Harnstoffaddukte, in Betracht. Wasserstoffperoxid kann dabei auch mit Hilfe eines enzymatischen Systems, das heißt einer Oxidase und ihres Substrats, erzeugt werden. Sofern feste Persauerstoffverbindungen eingesetzt werden sollen, können diese in Form von Pulvern oder Granulaten verwendet werden, die auch in im Prinzip bekannter Weise umhüllt sein können. Die Persauerstoffverbindungen können als solche oder in Form diese enthaltender Mittel, die prinzipiell alle üblichen Wasch- oder Reinigungsmittelbestandteile enthalten können, zu der Waschbeziehungsweise Reinigungslauge zugegeben werden. Besonders bevorzugt wird Alkalipercarbonat, Alkaliperborat-Monohydrat oder Wasserstoffperoxid in Form wäßriger Lösungen, die 3 Gew.-% bis 10 Gew.-% Wasserstoffperoxid enthalten, eingesetzt. Falls ein im Rahmen der Erfindung eingesetztes Wasch- oder Reinigungsmittel Persauerstoffverbindungen enthält, sind diese vorzugsweise in Mengen von 0,1 Gew.-% bis 50 Gew.-%, insbesondere von 5 Gew.-% bis 20 Gew.-% und besonders bevorzugt von 7 Gew.-% bis 17 Gew.-% und äußerst bevorzugt 8 Gew.-% bis 15 Gew.-% vorhanden.Suitable peroxygen compounds which may additionally be present are, in particular, inorganic peroxygen compounds such as hydrogen peroxide and inorganic salts which release hydrogen peroxide under the conditions of use, such as perborate, percarbonate and / or persilicate, and hydrogen peroxide inclusion compounds, such as H 2 O 2 -urea adducts. Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. The peroxygen compounds can be added as such or in the form of these containing agents, which may in principle contain all conventional detergent or cleaner ingredients, to the Waschbeziehungsweise cleaning solution. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. If a washing or cleaning agent used in the invention contains peroxygen compounds, these are preferably in amounts of 0.1 wt .-% to 50 wt .-%, in particular from 5 wt .-% to 20 wt .-% and particularly preferred from 7% to 17%, and most preferably from 8% to 15%, by weight.
Die Mittel können ein oder mehrere Tenside enthalten, wobei insbesondere anionische Tenside, nichtionische Tenside und deren Gemische in Frage kommen. Geeignete nichtionische Tenside sind insbesondere Alkylglykoside und Ethoxylierungs- und/oder Propoxylierungsprodukte von Alkylglykosiden oder linearen oder verzweigten Alkoholen mit jeweils 12 bis 18 C-Atomen im Alkylteil und 3 bis 20, vorzugsweise 4 bis 10 Alkylethergruppen. Weiterhin sind entsprechende Ethoxylierungs- und/oder Propoxylierungsprodukte von N-Alkyl-aminen, vicinalen Diolen, Fettsäureestern und Fettsäureamiden, die hinsichtlich des Alkylteils den genannten langkettigen Alkoholderivaten entsprechen, sowie von Alkylphenolen mit 5 bis 12 C-Atomen im Alkylrest brauchbar.The agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof come into question. Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
Geeignete anionische Tenside sind insbesondere Seifen und solche, die Sulfat- oder SulfonatGruppen mit bevorzugt Alkaliionen als Kationen enthalten. Verwendbare Seifen sind bevorzugt die Alkalisalze der gesättigten oder ungesättigten Fettsäuren mit 12 bis 18 C-Atomen. Derartige Fettsäuren können auch in nicht vollständig neutralisierter Form eingesetzt werden. Zu den brauchbaren Tensiden des Sulfat-Typs gehören die Salze der Schwefelsäurehalbester von Fettalkoholen mit 12 bis 18 C-Atomen und die Sulfatierungsprodukte der genannten nichtionischen Tenside mit niedrigem Ethoxylierungsgrad. Zu den verwendbaren Tensiden vom Sulfonat-Typ gehören lineare Alkylbenzolsulfonate mit 9 bis 14 C-Atomen im Alkylteil, Alkansulfonate mit 12 bis 18 C-Atomen, sowie Olefinsulfonate mit 12 bis 18 C-Atomen, die bei der Umsetzung entsprechender Monoolefine mit Schwefeltrioxid entstehen, sowie alpha-Sulfofettsäureester, die bei der Sulfonierung von Fettsäuremethyl- oder -ethylestern entstehen.Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form. Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation. Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.
Derartige Tenside sind in den im Rahmen der Erfindung eingesetzten Waschmitteln in Mengenanteilen von vorzugsweise 5 Gew.-% bis 50 Gew.-%, insbesondere von 8 Gew.-% bis 30 Gew.-%, enthalten, während Mittel zur Reinigung von harten Oberflächen, insbesondere von Geschirr vorzugsweise 0,1 Gew.-% bis 20 Gew.-%, insbesondere 0,2 Gew.-% bis 5 Gew.-% Tenside, enthalten.Such surfactants are present in the detergents used in the invention in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, while means for cleaning hard surfaces , in particular of tableware, preferably 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight of surfactants.
Ein im Rahmen der Erfindung eingesetztes Mittel enthält vorzugsweise mindestens einen wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder. Zu den wasserlöslichen organischen Buildersubstanzen gehören Polycarbonsäuren, insbesondere Citronensäure, Zuckersäuren und Carboxymethylinuline, monomere und polymere Aminopolycarbonsäuren, insbesondere Glycindiessigsäure, Methylglycindiessigsäure, Nitrilotriessigsäure, Iminodisuccinate wie Ethylendiamin-N,N'-dibernsteinsäure und Hydroxyiminodisuccinate, Ethylendiamintetraessigsäure sowie Polyasparaginsäure, Polyphosphonsäuren, insbesondere Aminotris-(methylenphosphonsäure), Ethylendiamintetrakis(methylenphosphonsäure), Lysintetra(methylenphosphosäure) und 1-Hydroxyethan-1,1-diphosphonsäure, polymere Hydroxyverbindungen wie Dextrin sowie polymere (Poly-)carbonsäuren, insbesondere durch Oxidation von Polysacchariden zugängliche Polycarboxylate, polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Die relative mittlere Molekülmasse (hier und im Folgenden: Gewichtsmittel) der Homopolymeren ungesättiger Carbonsäuren liegt im allgemeinen zwischen 5 000 g/mol und 200 000 g/mol, die der Copolymeren zwischen 2 000 g/mol und 200 000 g/mol, vorzugsweise 50 000 g/mol bis 120 000 g/mol, jeweils bezogen auf freie Säure. Ein besonders bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative mittlere Molekülmasse von 50 000 g/mol bis 100 000 g/mol auf. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinylethern, wie Vinylmethylethern, Vinylester, Ethylen, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. Als wasserlösliche organische Buildersubstanzen können auch Terpolymere eingesetzt werden, die als Monomere zwei ungesättigte Säuren und/oder deren Salze sowie als drittes Monomer Vinylalkohol und/ oder ein Vinylalkohol-Derivat oder ein Kohlenhydrat enthalten. Das erste saure Monomer beziehungsweise dessen Salz leitet sich von einer monoethylenisch ungesättigten C3-C8-Carbonsäure und vorzugsweise von einer C3-C4-Monocarbonsäure, insbesondere von (Meth)-acrylsäure ab. Das zweite saure Monomer beziehungsweise dessen Salz kann ein Derivat einer C4-C8-Dicarbonsäure sein, wobei Maleinsäure besonders bevorzugt ist. Die dritte monomere Einheit wird in diesem Fall von Vinylalkohol und/oder vorzugsweise einem veresterten Vinylalkohol gebildet. Insbesondere sind Vinylalkohol-Derivate bevorzugt, welche einen Ester aus kurzkettigen Carbonsäuren, beispielsweise von C1-C4-Carbonsäuren, mit Vinylalkohol darstellen. Bevorzugte Polymere enthalten dabei 60 Gew.-% bis 95 Gew.-%, insbesondere 70 Gew.-% bis 90 Gew.-% (Meth)acrylsäure bzw. (Meth)acrylat, besonders bevorzugt Acrylsäure bzw. Acrylat, und Maleinsäure bzw. Maleinat sowie 5 Gew.-% bis 40 Gew.-%, vorzugsweise 10 Gew.-% bis 30 Gew.-% Vinylalkohol und/oder Vinylacetat. Ganz besonders bevorzugt sind dabei Polymere, in denen das Gewichtsverhältnis von (Meth)acrylsäure beziehungsweise (Meth)acrylat zu Maleinsäure beziehungsweise Maleinat zwischen 1:1 und 4:1, vorzugsweise zwischen 2:1 und 3:1 und insbesondere 2:1 und 2,5:1 liegt. Dabei sind sowohl die Mengen als auch die Gewichtsverhältnisse auf die Säuren bezogen. Das zweite saure Monomer beziehungsweise dessen Salz kann auch ein Derivat einer Allylsulfonsäure sein, die in 2-Stellung mit einem Alkylrest, vorzugsweise mit einem C1-C4-Alkylrest, oder einem aromatischen Rest, der sich vorzugsweise von Benzol oder Benzol-Derivaten ableitet, substituiert ist. Bevorzugte Terpolymere enthalten dabei 40 Gew.-% bis 60 Gew.-%, insbesondere 45 bis 55 Gew.-% (Meth)acrylsäure beziehungsweise (Meth)acrylat, besonders bevorzugt Acrylsäure beziehungsweise Acrylat, 10 Gew.-% bis 30 Gew.-%, vorzugsweise 15 Gew.-% bis 25 Gew.-% Methallylsulfonsäure bzw. Methallylsulfonat und als drittes Monomer 15 Gew.-% bis 40 Gew.-%, vorzugsweise 20 Gew.-% bis 40 Gew.-% eines Kohlenhydrats. Dieses Kohlenhydrat kann dabei beispielsweise ein Mono-, Di-, Oligo- oder Polysaccharid sein, wobei Mono-, Di- oder Oligosaccharide bevorzugt sind. Besonders bevorzugt ist Saccharose. Durch den Einsatz des dritten Monomers werden vermutlich Sollbruchstellen in das Polymer eingebaut, die für die gute biologische Abbaubarkeit des Polymers verantwortlich sind. Diese Terpolymere weisen im Allgemeinen eine relative mittlere Molekülmasse zwischen 1 000 g/mol und 200 000 g/mol, vorzugsweise zwischen 200 g/mol und 50 000 g/mol auf. Weitere bevorzugte Copolymere sind solche, die als Monomere Acrolein und Acrylsäure/Acrylsäuresalze beziehungsweise Vinylacetat aufweisen. Die organischen Buildersubstanzen können, insbesondere zur Herstellung flüssiger Mittel, in Form wäßriger Lösungen, vorzugsweise in Form 30- bis 50-gewichtsprozentiger wäßriger Lösungen eingesetzt werden. Alle genannten Säuren werden in der Regel in Form ihrer wasserlöslichen Salze, insbesondere ihre Alkalisalze, eingesetzt.An agent used in the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid, sugar acids and carboxymethylinulines, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris ( methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), lysine tetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by oxidation of polysaccharides accessible polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and Mixed polymers of these, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The relative average molecular weight (here and hereinafter: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50 000 g / mol to 120 000 g / mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 g / mol to 100,000 g / mol. Suitable, though less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in wherein the proportion of the acid is at least 50 wt .-%. As water-soluble organic builders, it is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) -acrylic acid. The second acidic monomer or its salt can be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C 1 -C 4 carboxylic acids, with vinyl alcohol. Preferred polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particular preference is given to polymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2 , 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Particularly preferred is sucrose. The use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
Derartige organische Buildersubstanzen können gewünschtenfalls in Mengen bis zu 40 Gew.-%, insbesondere bis zu 25 Gew.-% und vorzugsweise von 1 Gew.-% bis 8 Gew.-% enthalten sein. Mengen nahe der genannten Obergrenze werden vorzugsweise in pastenförmigen oder flüssigen, insbesondere wasserhaltigen, Mitteln eingesetzt.If desired, such organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.
Als wasserlösliche anorganische Buildermaterialien kommen insbesondere Polyphosphate, vorzugsweise Natriumtriphosphat, in Betracht. Als wasserunlösliche anorganische Buildermaterialien werden insbesondere kristalline oder amorphe, wasserdispergierbare Alkalialumosilikate, in Mengen nicht über 25 Gew.-%, vorzugsweise von 3 Gew.-% bis 20 Gew.-% und insbesondere in Mengen von 5 Gew.-% bis 15 Gew.-% eingesetzt. Unter diesen sind die kristallinen Natriumalumosilikate in Waschmittelqualität, insbesondere Zeolith A, Zeolith P sowie Zeolith MAP und gegebenenfalls Zeolith X, bevorzugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, teilchenförmigen Mitteln eingesetzt. Geeignete Alumosilikate weisen insbesondere keine Teilchen mit einer Korngröße über 30 µm auf und bestehen vorzugsweise zu wenigstens 80 Gew.-% aus Teilchen mit einer Größe unter 10 µm. Ihr Calciumbindevermögen liegt in der Regel im Bereich von 100 bis 200 mg CaO pro Gramm.Suitable water-soluble inorganic builder materials are, in particular, polyphosphates, preferably sodium triphosphate. As water-insoluble inorganic builder materials are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25 wt .-%, preferably from 3 wt .-% to 20 wt .-% and in particular in amounts of 5 wt .-% to 15 wt. -% used. Among these, the detergent-grade crystalline sodium aluminosilicates, particularly zeolite A, zeolite P, and zeolite MAP, and optionally zeolite X, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.
Zusätzlich oder alternativ zum genannten wasserunlöslichen Alumosilikat und Alkalicarbonat können weitere wasserlösliche anorganische Buildermaterialien enthalten sein. Zu diesen gehören neben den Polyphosphaten wie Natriumtriphosphat insbesondere die wasserlöslichen kristallinen und/oder amorphen Alkalisilikat-Builder. Derartige wasserlösliche anorganische Buildermaterialien sind in Mitteln vorzugsweise in Mengen von 1 Gew.-% bis 20 Gew.-%, insbesondere von 5 Gew.-% bis 15 Gew.-% enthalten. Die als Buildermaterialien brauchbaren Alkalisilikate weisen vorzugsweise ein molares Verhältnis von Alkalioxid zu SiO2 unter 0,95, insbesondere von 1:1,1 bis 1:12 auf und können amorph oder kristallin vorliegen. Bevorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsilikate, mit einem molaren Verhältnis Na2O:SiO2 von 1:2 bis 1:2,8. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugsweise kristalline Schichtsilikate der allgemeinen Formel Na2SixO2x+1 · y H2O eingesetzt, in der x, das sogenannte Modul, eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Bevorzugte kristalline Schichtsilikate sind solche, bei denen x in der genannten allgemeinen Formel die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ-Natriumdisilikate (Na2Si2O5 · y H2O) bevorzugt. Auch aus amorphen Alkalisilikaten hergestellte, praktisch wasserfreie kristalline Alkalisilikate der obengenannten allgemeinen Formel, in der x eine Zahl von 1,9 bis 2,1 bedeutet, können eingesetzt werden. Weiter bevorzugt wird ein kristallines Natriumschichtsilikat mit einem Modul von 2 bis 3 eingesetzt, wie es aus Sand und Soda hergestellt werden kann. Natriumsilikate mit einem Modul im Bereich von 1,9 bis 3,5 werden in einer weiteren Ausführungsform der Mittel eingesetzt. In einer bevorzugten Ausgestaltung setzt man ein granulares Compound aus Alkalisilikat und Alkalicarbonat ein, wie es zum Beispiel unter dem Namen Nabion® 15 im Handel erhältlich ist.In addition to or as an alternative to said water-insoluble aluminosilicate and alkali carbonate, further water-soluble inorganic builder materials may be included. In addition to the polyphosphates, such as sodium triphosphate, these include in particular the water-soluble crystalline and / or amorphous alkali metal silicate builders. Such water-soluble inorganic builder materials are preferably included in detergents in amounts of from 1% to 20%, and more preferably from 5% to 15%, by weight. The alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be amorphous or crystalline. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na 2 Si x O used 2x + 1 · y H 2 O in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na 2 Si 2 O 5 .yH 2 O) are preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used. More preferably, a crystalline sodium layer silicate is used with a modulus of 2 to 3, as it can be prepared from sand and soda. Sodium silicates with a modulus in the range 1.9 to 3.5 are used in another embodiment of the compositions. In a preferred One uses a granular compound of alkali metal silicate and alkali carbonate, as it is commercially available, for example, under the name Nabion® 15.
Maschinelle Geschirreinigungsmittel sind vorzugsweise niederalkalisch und enthalten die üblichen Alkaliträger wie zum Beispiel Alkalisilikate, Alkalicarbonate und/oder Alkalihydrogencarbonate. Zu den üblicherweise eingesetzten Alkaliträgern zählen Carbonate, Hydrogencarbonate und Alkalisilikate mit einem Molverhältnis SiO2/M2O (M = Alkaliatom) von 1,5 : 1 bis 2,5 : 1. Alkalisilikate können dabei in Mengen von bis zu 30 Gew.-%, bezogen auf das gesamte Mittel, enthalten sein. Auf den Einsatz der hoch alkalischen Metasilikate als Alkaliträger wird vorzugsweise ganz verzichtet. Das bevorzugt eingesetzte Alkaliträgersystem ist ein Gemisch aus Carbonat und Hydrogencarbonat, vorzugsweise Natriumcarbonat und -hydrogencarbonat, das in einer Menge von bis zu 60 Gew.-%, vorzugsweise 10 Gew.-% bis 40 Gew.-%, enthalten ist. Je nachdem, welcher pH-Wert letztendlich gewünscht wird, variiert das Verhältnis von eingesetztem Carbonat und eingesetztem Hydrogencarbonat, üblicherweise wird jedoch ein Überschuß an Natriumhydrogencarbonat eingesetzt, so daß das Gewichtsverhältnis zwischen Hydrogencarbonat und Carbonat im allgemeinen 1 : 1 bis 15 : 1 beträgt.Machine dishwashing detergents are preferably of low alkaline content and contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates. The alkali carriers used conventionally include carbonates, bicarbonates and alkali silicates having a molar ratio of SiO 2 / M 2 O (M = alkali atom) of from 1.5: 1 to 2.5: 1. Alkali silicates may be used in amounts of up to 30% by weight. %, based on the total mean. The use of the highly alkaline metasilicates as alkali carriers is preferably completely dispensed with. The alkali carrier system used with preference is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which is present in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight. Depending on which pH is ultimately desired, the ratio of carbonate used and bicarbonate used varies, but usually an excess of sodium bicarbonate is used, so that the weight ratio of bicarbonate to carbonate is generally from 1: 1 to 15: 1.
In einer weiteren Ausführungsform der Mittel zur Reinigung von Geschirr sind in diesen 20 Gew.-% bis 40 Gew.-% wasserlöslicher organischer Builder, insbesondere Alkalicitrat, 5 Gew.-% bis 15 Gew.-% Alkalicarbonat und 20 Gew.-% bis 40 Gew.-% Alkalidisilikat enthalten.In a further embodiment of the means for cleaning crockery in these 20 wt .-% to 40 wt .-% of water-soluble organic builder, in particular alkali citrate, 5 wt .-% to 15 wt .-% alkali carbonate and 20 wt .-% bis 40 wt .-% Alkalidisilikat included.
Als in den Mitteln gegebenenfalls enthaltene Enzyme kommen insbesondere solche aus der Klasse der Proteasen, Lipasen, Cutinasen, Amylasen, Pullulanasen, Xylanasen, Hemicellulasen, Cellulasen, Peroxidasen sowie Oxidasen beziehungsweise deren Gemische in Frage, wobei der Einsatz von Protease, Amylase, Lipase und/oder Cellulase besonders bevorzugt ist. Der Anteil beträgt vorzugsweise 0,2 Gew.-% bis 1,5 Gew.-%, insbesondere 0,5 Gew.-% bis 1 Gew.-%. Die Enzyme können in üblicher Weise an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein oder als konzentrierte, möglichst wasserfreie Flüssigformulierungen eingearbeitet werden.Suitable enzymes contained in the compositions are, in particular, those from the class of proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, lipase and / or or cellulase is particularly preferred. The proportion is preferably 0.2 wt .-% to 1.5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%. The enzymes can be adsorbed in a customary manner on carriers and / or embedded in coating substances or incorporated as concentrated, as anhydrous liquid formulations.
Geeignete Vergrauungsinhibitoren beziehungsweise soil-release-Wirkstoffe sind Celluloseether, wie Carboxymethylcellulose, Methylcellulose, Hydroxyalkylcellulosen und Cellulosemischether, wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose und Methyl-Carboxymethylcellulose. Vorzugsweise werden Natrium-Carboxymethylcellulose und deren Gemische mit Methylcellulose eingesetzt. Zu den üblicherweise eingesetzten Soil-release-Wirkstoffen gehören Copolyester, die Dicarbonsäureeinheiten, Alkylenglykoleinheiten und Polyalkylenglykoleinheiten enthalten. Der Anteil an Vergrauungsinhibitoren und/oder soil-release-Wirkstoffen liegt im allgemeinen nicht über 2 Gew.-% und beträgt vorzugsweise 0,5 Gew.-% bis 1,5 Gew.-%, jeweils bezogen aud das Mittel.Suitable gravel inhibitors or soil release agents are cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose. Preferably, sodium carboxymethylcellulose and mixtures thereof with methylcellulose are used. Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. The proportion of graying inhibitors and / or soil-release active ingredients is generally not more than 2 wt .-% and is preferably 0.5 wt .-% to 1.5 wt .-%, each based on the agent.
Als optische Aufheller für insbesondere Textilien aus Cellulosefasern (zum Beispiel Baumwolle) können beispielsweise Derivate der Diaminostilbendisulfonsäure beziehungsweise deren Alkalimetallsalze enthalten sein. Geeignet sind zum Beispiel Salze der 4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)-stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholinogruppe eine Diethanolaminogruppe, eine Methylaminogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ des substituierten 4,4'-Distyryl-diphenyl anwesend sein, zum Beispiel 4,4'-Bis-(4-chlor-3-sulfostyryl)-diphenyl. Auch Gemische von Aufhellern können verwendet werden. Für Polyamidfasern eignen sich besonders gut Aufheller vom Typ der 1,3-Diaryl-2-pyrazoline, beispielsweise 1-(p-Sulfoamoylphenyl)-3-(p-chlorphenyl)-2-pyrazolin sowie gleichartig aufgebaute Verbindungen. Der Gehalt des Mittels an optischen Aufhellern beziehungsweise Aufhellergemischen liegt im allgemeinen nicht über 1 Gew.-%, vorzugsweise 0,05 Gew.-% bis 0,5 Gew.-%.Examples of optical brighteners for textiles made of cellulose fibers (for example cotton) include derivatives of diaminostilbenedisulfonic acid or alkali metal salts thereof. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or similarly constructed compounds which are suitable instead of the morpholino group, carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Further, brighteners of the substituted 4,4'-distyryl-diphenyl type may be present, for example, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl. Also, mixtures of brighteners can be used. For polyamide fibers, brighteners of the 1,3-diaryl-2-pyrazolines type, for example 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of similar construction are particularly suitable. The content of the composition in optical brighteners or brightener mixtures is generally not more than 1 wt .-%, preferably 0.05 wt .-% to 0.5 wt .-%.
Zu den in den Mitteln einsetzbaren üblichen Schaumregulatoren gehören beispielsweise Polysiloxan-Kieselsäure-Gemische, wobei die darin enthaltene feinteilige Kieselsäure vorzugsweise silaniert oder anderweitig hydrophobiert ist. Die Polysiloxane können sowohl aus linearen Verbindungen wie auch aus vernetzten Polysiloxan-Harzen sowie aus deren Gemischen bestehen. Weitere Entschäumer sind Paraffinkohlenwasserstoffe, insbesondere Mikroparaffine und Paraffinwachse, deren Schmelzpunkt oberhalb 40 °C liegt, gesättigte Fettsäuren beziehungsweise Seifen mit insbesondere 20 bis 22 C-Atomen, zum Beispiel Natriumbehenat, und Alkalisalze von Phosphorsäuremono- und/oder -dialkylestern, in denen die Alkylketten jeweils 12 bis 22 C-Atome aufweisen. Unter diesen wird bevorzugt Natriummonoalkylphosphat und/oder -dialkylphosphat mit C16- bis C18-Alkylgruppen eingesetzt. Der Anteil der Schaumregulatoren kann vorzugsweise 0,2 Gew.-% bis 2 Gew.-% betragen.The customary foam regulators which can be used in the compositions include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanated or otherwise rendered hydrophobic. The polysiloxanes can consist of both linear compounds as well as crosslinked polysiloxane resins and mixtures thereof. Further antifoams are paraffin hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each having 12 to 22 carbon atoms. Among these, preference is given to using sodium monoalkyl phosphate and / or dialkyl phosphate having C 16 - to C 18 -alkyl groups. The proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight.
Zu den in den 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 in Mengen von vorzugsweise nicht über 20 Gew.-%, insbesondere von 1 Gew.-% bis 15 Gew.-%, jeweils bezogen auf das Mittel, vorhanden.Among the 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 present in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight, based in each case on the composition.
Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können die 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 Mitteln vorzugsweise nicht über 10 Gew.-%, insbesondere von 0,5 Gew.-% bis 6 Gew.-%, enthalten.To establish a desired, by the mixture of the other components not automatically resulting pH, 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 hydrogensulfates, or bases, in particular ammonium or alkali metal hydroxides, contain. Such pH regulators are preferably contained in the compositions not more than 10% by weight, in particular from 0.5% by weight to 6% by weight.
Die Herstellung fester Mittel bietet keine Schwierigkeiten und kann in im Prinzip bekannter Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei das Polyoxometallat gegebenenfalls später getrennt zugesetzt werden kann.The preparation of solid agents presents no difficulties and may be carried out in a manner known in the art, for example by spray-drying or granulation, the polyoxometalate optionally being able to be added separately later.
Mittel 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.Compositions 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.
1,35 g Na2MoO4 · 2 H2O und 0,2 g NalO3 wurden in jeweils 1 ml heißem destillierten Wasser (≈ 95 °C) gelöst. Anschließend wurden tropfenweise 0,62 ml 12 N HCl-Lösung zur Natriummolybdatlösung gegeben und die Natriumperiodatlösung mit der Natriummolybdatlösung vereinigt. Die Mischung wurde bei 85 °C auf etwa 1,3 ml eingeengt und anschließend auf Raumtemperatur abgekühlt. Die ausgefallenen farblosen plättchenartigen Kristalle wurden abzentrifugiert, drei Mal mit 5 bis 10 ml Ethanol gewaschenund für einige Stunden bei 60 °C im Trockenschrank getrocknet. Man erhielt 9 g Na5[IMo6O24] · 3 H2O.1.35 g of Na 2 MoO 4 .2H 2 O and 0.2 g of NalO 3 were dissolved in each 1 ml of hot distilled water (≈ 95 ° C). Then 0.62 ml of 12N HCl solution was added dropwise to the sodium molybdate solution and the sodium periodate solution was combined with the sodium molybdate solution. The mixture was concentrated to about 1.3 ml at 85 ° C and then cooled to room temperature. The precipitated colorless platelet-like crystals were centrifuged off, washed three times with 5 to 10 ml of ethanol and dried for a few hours at 60 ° C in a drying oven. 9 g of Na 5 [IMo 6 O 24 ] .3H 2 O were obtained.
Zu einer Lösung von 0,61 g Natriummetavanadat in 10 ml kochendem Wasser wurden 0,71 g in 5 ml Wasser gelöstem Natriumhydrogenphosphat zugegeben. Die Lösung wurde mit 0,5 ml konzentrierter Schwefelsäure angesäuert und zu der nun rot gefärbten Lösung 13,3 g in 20 ml Wasser gelöstes Natriummolybdat-Dihydrat gegeben. Unter starkem Rühren wurden 8,5 ml konzentrierter Schwefelsäure langsam zugegeben, wodurch sich der rote Farbton der Lösung etwas aufhellte. Nach dem Abkühlen auf 25 °C wurde die Heteropolysäure 4 Mal mit jeweils 10 ml Diethylether extrahiert. Während der Extraktion bildete sich ein Dreiphasensystem aus, in dessen mittlerer Schicht sich das Heteropolyetherat befand. Die mittleren Phasen wurden isoliert und bei 60 °C getrocknet. Das entstandene Produkt wurde aus 5 ml Wasser umkristallisiert und an der Luft getrocknet. Man erhielt 2,8 g 11-Molybdo-1-vanadophosphorsäure.To a solution of 0.61 g of sodium metavanadate in 10 ml of boiling water was added 0.71 g of sodium hydrogenphosphate dissolved in 5 ml of water. The solution was acidified with 0.5 ml of concentrated sulfuric acid and added to the now red-colored solution 13.3 g dissolved in 20 ml of water sodium molybdate dihydrate. With vigorous stirring, 8.5 ml of concentrated sulfuric acid was added slowly, which somewhat lightened the red color of the solution. After cooling to 25 ° C, the heteropolyacid was extracted 4 times with 10 ml of diethyl ether. During the extraction, a three-phase system was formed, in the middle layer of which the heteropolyetherate was located. The middle phases were isolated and dried at 60 ° C. The resulting product was recrystallized from 5 ml of water and dried in air. 2.8 g of 11-molybdo-1-vanadophosphoric acid were obtained.
Die Synthese erfolgte analog zum Vorgehen unter a) unter Einsatz angepasster Mengen an Natriummetavanadat (2,44 g in 10 ml Wasser) und Natriummolybdat-Dihydrat (12,1 g in 20 ml Wasser). Man erhielt 3,5 g 10-Molybdo-2-vanadophosphorsäure.The synthesis was carried out analogously to the procedure under a) using adjusted amounts of sodium metavanadate (2.44 g in 10 ml of water) and sodium molybdate dihydrate (12.1 g in 20 ml of water). 3.5 g of 10-molybdo-2-vanadophosphoric acid were obtained.
Die Synthese erfolgte analog zum Vorgehen unter a) unter Einsatz angepasster Mengen an Natriummetavanadat (3,66 g in 20 ml Wasser) und Natriummolybdat-Dihydrat (5,45 g in 15 ml Wasser). Man erhielt 0,72 g 9-Molybdo-3-vanadophosphorsäure.The synthesis was carried out analogously to the procedure under a) using adjusted amounts of sodium metavanadate (3.66 g in 20 ml of water) and sodium molybdate dihydrate (5.45 g in 15 ml of water). 0.72 g of 9-molybdo-3-vanadophosphoric acid was obtained.
Die in 2 b) hergestellte Molybdovanadophosphorsäure wurde durch lonenaustausch über das lonenaustauscherharz Amberlite IR-120 in Natriumform überführtThe molybdovanadophosphoric acid prepared in 2 b) was converted by ion exchange through the ion exchange resin Amberlite IR-120 in sodium form
16,5 ml 4 M HCl-Lösung wurden innerhalb von 10 min in Schritten von 1 ml zu einer stark gerührten (≈ 750 rpm) Lösung von 18,2 g Na2WO4 · 2 H2O (0,55 mmol) in 30 ml destilliertem Wasser gegeben. Anschließend wurde eine Lösung von 1,1 g Na2SiO3 (5 mmol) in 10 ml destilliertem Wasser hinzugefügt und etwa 4 mL 4 M HCl-Lösung zugegeben, um einen pH-Wert von 5 bis 6 zu erreichen. Die Lösung wurde für 100 min gerührt und der pH-Wert währenddessen durch Zugabe von weiterer 4 M HCl-Lösung konstant bei 5 bis 6 gehalten. 9 g KCl wurden anschließend der Lösung zugesetzt und die Lösung manuell für 15 min gerührt. Der weiße Niederschlag aus K8[β2-SiW11O39] · 14 H2O wurde abfiltriert und einige Stunden bei 60 °C im Trockenschrank getrocknet.16.5 ml of 4 M HCl solution were added over 10 min in 1 ml increments to a vigorously stirred (~ 750 rpm) solution of 18.2 g Na 2 WO 4 .2H 2 O (0.55 mmol) 30 ml of distilled water. Subsequently, a solution of 1.1 g of Na 2 SiO 3 (5 mmol) in 10 mL of distilled water was added and about 4 mL of 4 M HCl solution added to reach a pH of 5 to 6. The solution was stirred for 100 min while maintaining the pH constant at 5-6 by adding further 4M HCl solution. 9 g of KCl were then added to the solution and the solution was stirred manually for 15 min. The white precipitate of K 8 [β 2 -SiW 11 O 39 ] · 14 H 2 O was filtered off and dried for a few hours at 60 ° C in a drying oven.
Zu einer Lösung von 0,25 g VOSO4 · 5 H2O in 3 ml Pufferlösung (Essigsäure-Acetatpuffer mit einem pH-Wert von ca. 4,7) wurden 2,4 g K8[β2-SiW11O39] · 14 H2O zugegeben, die Lösung wurde auf 60 °C erhitzt und innerhalb von 3 min wurden 0,75 g KCl hinzugefügt. Die Lösung wurde über Nacht im Kühlschrank bei ca. 5 °C aufbewahrt, und am nächsten Tag wurde der schwarze Niederschlag abfiltriert. Das Filtrat wurde erneut über Nacht im Kühlschrank bei ca. 5 °C aufbewahrt, und am nächsten Tag wurde der zusätzlich ausgefallene schwarze Niederschlag ebenfalls abfiltriert. Nach dem zweiten Filtriervorgang wurde die Lösung für 2 h in ein Eisbad gestellt, wodurch zusätzliche Mengen an Produkt als dunkelvioletter Feststoff auskristallisierten. Man erhielt insgesamt 1,6 g K5[SiW11VO40].To a solution of 0.25 g VOSO 4 .5H 2 O in 3 ml buffer solution (acetic acid acetate buffer with a pH of about 4.7) 2.4 g K 8 [β 2 -SiW 11 O 39 ] · 14 H 2 O was added, the solution was heated to 60 ° C and within 3 min 0.75 g KCl was added. The solution was stored in the refrigerator at about 5 ° C overnight, and the black precipitate was filtered off the next day. The filtrate was again stored overnight in the refrigerator at about 5 ° C, and the next day the additionally precipitated black precipitate was also filtered off. After the second filtration, the solution was placed in an ice bath for 2 hours, whereby additional amounts of product crystallized out as a dark purple solid. A total of 1.6 g of K 5 [SiW 11 VO 40 ] was obtained.
15 ml jeweils einer wässrigen Lösung, enthaltend 0,6 g/l eines bleichmittelfreien Waschmittels, 2 µmol/l Na5[IMo6O24] sowie die in der nachfolgenden Tabelle 1 angegebene Konzentration [mmol/l] an H2O2, und ein mit einer standardisierten Heidelbeer-Anschmutzung versehenes Baumwollläppchen wurden in einen Glaseinsatz überführt und dieser in einen Autoklaven eingesetzt. Der Autoklav wurde verschlossen, mit 80 bar an synthetischer Luft oder Stickstoff beaufschlagt, auf Dichtigkeit überprüft, in eine auf 40 °C vortemperierte Heizmanschette eingesetzt und für 1 Stunde bei dieser Temperatur gehalten. Nach Abkühlen des Autoklaven im Wasserbad und Ablassen des Drucks wurde die Textilprobe für 30 Sekunden in 50 ml vollentsalztem Wasser geschwenkt, um die Waschlösung abzuspülen. Die Auswertung der Fleckentfernungsleistung erfolgte an den getrockneten Textilproben über Farbabstandsmessung gemäß der L*a*b* -Werte und die daraus berechneten Y-Werte als Maß für die Helligkeit. Die folgende Tabelle zeigt die Y-Werte, die sich nach dem Waschen ergaben. Zum Vergleich wurden die Versuche ohne den Zusatz von Na5[IMo6O24], und unter Ersatz dieses Wirkstoffs durch die gleiche Menge an Mn-Me3TACN wiederholt, was zu ebenfalls in Tabelle 1 angegebenen Werten führte.
Die Y-Werte bei Einsatz des erfindungswesentlichen Wirkstoffs in Anwesenheit von Luft sind größer als diejenigen bei Anwesenheit von Stickstoff; sie sind außerdem größer als diejenigen, die sich bei seinem Ersatz durch einen bekannten Bleichkatalysator oder beim Einsatz nur des Waschmittels ergeben, was einem höheren Weißgrad und somit einer verbesserten Fleckentfernung entspricht.The Y values when using the active substance according to the invention in the presence of air are greater than those in the presence of nitrogen; they are also larger than those resulting from its replacement by a known bleach catalyst or when using only the detergent, which corresponds to a higher whiteness and thus improved stain removal.
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Citations (7)
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WO1997007886A1 (en) | 1995-08-22 | 1997-03-06 | Hoechst Research & Technology Deutschland Gmbh & Co. Kg | Manganiferous polyoxometalates, synthesis and use thereof |
EP0761809A2 (en) | 1995-08-22 | 1997-03-12 | Hoechst Aktiengesellschaft | Bleaching composition comprising polyoxometalates bleach catalyst |
WO1999028426A1 (en) | 1997-12-03 | 1999-06-10 | U.S. Borax Inc. | Bleaching compositions |
WO2000039264A1 (en) | 1998-12-23 | 2000-07-06 | Unilever Plc | Bleaching with polyoxometalates and air or molecular oxygen |
US20030191040A1 (en) * | 2002-03-28 | 2003-10-09 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Liquid cleaning compositions and their use |
RO122728B1 (en) * | 2007-07-31 | 2009-12-30 | Universitatea "Aurel Vlaicu" Din Arad | Environmental friendly process for bleaching natural fibres by catalytic oxidation with polyoxometalates |
US20160213003A1 (en) * | 2013-09-07 | 2016-07-28 | Ningbo Yuchen Enviroclean Tech Co., Ltd. | Application of polyoxometalate in preparation of disinfectant for sterilizing and removing formaldehyde |
-
2017
- 2017-06-01 DE DE102017209335.8A patent/DE102017209335A1/en not_active Withdrawn
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2018
- 2018-05-15 EP EP18172235.6A patent/EP3409753B1/en active Active
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WO1997007886A1 (en) | 1995-08-22 | 1997-03-06 | Hoechst Research & Technology Deutschland Gmbh & Co. Kg | Manganiferous polyoxometalates, synthesis and use thereof |
EP0761809A2 (en) | 1995-08-22 | 1997-03-12 | Hoechst Aktiengesellschaft | Bleaching composition comprising polyoxometalates bleach catalyst |
WO1999028426A1 (en) | 1997-12-03 | 1999-06-10 | U.S. Borax Inc. | Bleaching compositions |
WO2000039264A1 (en) | 1998-12-23 | 2000-07-06 | Unilever Plc | Bleaching with polyoxometalates and air or molecular oxygen |
US20030191040A1 (en) * | 2002-03-28 | 2003-10-09 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Liquid cleaning compositions and their use |
RO122728B1 (en) * | 2007-07-31 | 2009-12-30 | Universitatea "Aurel Vlaicu" Din Arad | Environmental friendly process for bleaching natural fibres by catalytic oxidation with polyoxometalates |
US20160213003A1 (en) * | 2013-09-07 | 2016-07-28 | Ningbo Yuchen Enviroclean Tech Co., Ltd. | Application of polyoxometalate in preparation of disinfectant for sterilizing and removing formaldehyde |
Non-Patent Citations (2)
Title |
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DATABASE WPI Week 201036, Derwent World Patents Index; AN 2010-G08162, XP002785850 * |
G.A. TSIGDINOS; C-J. HALLADA, INORG. CHEM., vol. 7, no. 1068, pages 437 - 441 |
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