EP3409753A1 - Renforcement de l'effet de blanchiment lors du lavage et du nettoyage - Google Patents

Renforcement de l'effet de blanchiment lors du lavage et du nettoyage Download PDF

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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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groups
group
periodic table
elements
liquor
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EP18172235.6A
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German (de)
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EP3409753B1 (fr
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Andre Haetzelt
Adam Dzierbinski
Peter HAUSOUL
Regina Palkovits
Sean Jung
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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EP18172235.6A 2017-06-01 2018-05-15 Renforcement de l'effet de blanchiment lors du lavage et du nettoyage Active EP3409753B1 (fr)

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DE102017209335.8A DE102017209335A1 (de) 2017-06-01 2017-06-01 Bleichverstärkung beim Waschen und Reinigen

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EP3409753A1 true EP3409753A1 (fr) 2018-12-05
EP3409753B1 EP3409753B1 (fr) 2020-04-22

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997007886A1 (fr) 1995-08-22 1997-03-06 Hoechst Research & Technology Deutschland Gmbh & Co. Kg Polyoxymetallates contenant du manganese, leur synthese et leur utilisation
EP0761809A2 (fr) 1995-08-22 1997-03-12 Hoechst Aktiengesellschaft Composition de blanchiment contenant des polyoxométalates comme catalyseurs de blanchiment
WO1999028426A1 (fr) 1997-12-03 1999-06-10 U.S. Borax Inc. Compositions de blanchiment
WO2000039264A1 (fr) 1998-12-23 2000-07-06 Unilever Plc Blanchiment a l'aide de polyoxometalates et d'air ou d'oxygene moleculaire
US20030191040A1 (en) * 2002-03-28 2003-10-09 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Liquid cleaning compositions and their use
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