EP3409757B1 - Composition detergente blanchissante - Google Patents

Composition detergente blanchissante Download PDF

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Publication number
EP3409757B1
EP3409757B1 EP18172292.7A EP18172292A EP3409757B1 EP 3409757 B1 EP3409757 B1 EP 3409757B1 EP 18172292 A EP18172292 A EP 18172292A EP 3409757 B1 EP3409757 B1 EP 3409757B1
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weight
acid
alkali
bleaching
liquor
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EP18172292.7A
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German (de)
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EP3409757A1 (fr
Inventor
Nadine BLUHM
Andre Haetzelt
Sean Jung
Adam Dzierbinski
Peter HAUSOUL
Regina Palkovits
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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • the present invention relates to the use of certain polyoxometalates for activating peroxygen compounds in connection with the bleaching of soiling when washing textiles, as well as detergents and cleaning agents which contain such polyoxometalates.
  • Inorganic peroxygen compounds in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the release of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidizing effect of these substances in dilute solutions depends strongly on the temperature; for example, with H 2 O 2 or alkali perborate in alkaline bleaching liquors, sufficiently rapid bleaching of soiled textiles is only achieved at temperatures above about 80 ° C.
  • bleach activators which are capable of delivering peroxocarboxylic acids under the perhydrolysis conditions mentioned and for which numerous proposals, especially from the classes of N- or O-acyl compounds, for example several times acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulphurylamides and cyanurates, also carboxylic acid anhydrides, especially sodium anhydride anhydrides, especially sodium anhydride anhydrides, sodium anhydride anhydrides, especially sodium anhydride anhydrides, especially sodium anhydride anhydrides, especially sodium anhydride anhydride, especially benz
  • bleaches which contain peroxygen compounds and polyoxometalates as bleach catalysts, the polyoxometalates having to contain Mo, W, Nn, Ta and / or V and transition metals of the 2nd and 8th subgroups.
  • the international patent application WO 99/28426 A1 relates to compositions containing a bleaching active ingredient and, as a bleaching catalyst, a polyoxocobaltate with a Keggin, Dawson or Finke structure.
  • 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 patent application US 2003/0191040 A1 relates to a liquid cleaning composition containing a proteolytic enzyme and a primary stabilizer therefor, which composition further comprises a polyoxometalate.
  • the liquid cleaning composition can further contain a bleaching agent or bleaching system.
  • the patent application US 2010/0035786 A1 relates to an alkaline, aqueous formulation for combination with peroxide for cleaning a microelectronic component, the formulation comprising: (a) water, (b) at least one metal ion-free base in sufficient quantity to produce a final formulation with an alkaline pH, (c) 0.01 to 5% by weight (expressed as% SiO 2 ) of at least one water-soluble metal ion-free silicate corrosion inhibitor, (d) 0.01 to 10% by weight of at least one metal chelating agent and (e) more than 0 to 2.0% by weight of at least one oxometalate.
  • the present invention aims to improve the oxidation and bleaching action of inorganic peroxygen compounds, in particular at low temperatures in the range from approx. 10 ° C. to 45 ° C.
  • the invention relates to the use of H 5 [PMo 10 V 2 O 40 ] and / or its alkali or ammonium salts for bleaching colored stains when washing textiles, in particular in an aqueous, surfactant-containing liquor.
  • Said polyoxometalate can be anhydrous or contain water of crystallization and can be used according to the invention.
  • the invention also relates to the use of a combination of peroxygen compound and said polyoxometalate in, in particular, aqueous, surfactant-containing cleaning solutions for hard surfaces, in particular for dishes, for bleaching colored soiling, for example tea.
  • bleaching is understood to mean both the bleaching of dirt on the hard surface, in particular tea, and the bleaching of dirt in the dishwashing liquor that has been detached from the hard surface.
  • the use according to the invention consists essentially in creating conditions under which the peroxygen compound and the aforementioned polyoxometalate can react with one another, with the aim of obtaining secondary products with a more strongly oxidizing effect.
  • Such conditions are particularly present when the reactants meet in an aqueous system. This can be done by adding the peroxygen compound and the polyoxometalate separately to a liquor that may contain a detergent or cleaning agent. However, it is particularly advantageously carried out using a washing or cleaning agent which contains the polyoxometalate and a peroxidic oxidizing agent.
  • the peroxygen compound can also be added separately, in bulk or as a preferably aqueous solution or suspension, to the aqueous system if a detergent or cleaning agent free from peroxygen compounds is used. Depending on the intended use, the conditions can be varied widely. In addition to purely aqueous solutions, mixtures of water and suitable organic solvents can also be used as the reaction medium.
  • the invention further relates to a process for washing laundry, comprising the process steps (a) providing an aqueous liquor containing H 2 O 2 or a particularly inorganic peroxygen compound which provides H 2 O 2 in water and the polyoxometalate mentioned, and (b) Bringing this liquor into contact with textiles to be washed.
  • the contact between the aqueous liquor and the object to be washed or cleaned is preferably established at temperatures in the range from 20.degree. C. to 80.degree. C., in particular from 40.degree. C. to 60.degree.
  • the object to be washed preferably remains for a period of 20 minutes to 120 minutes, in particular 30 minutes up to 90 minutes, in contact with the aqueous liquor.
  • the methods according to the invention can be carried out manually or with the aid of conventional devices, for example washing machines.
  • the amounts of peroxygen compounds used are generally chosen so that between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm active oxygen are present;
  • the concentration of the polyoxometalate in the liquor is preferably from 0.00005 g / l to 0.5 g / l, in particular from 0.005 g / l to 0.05 g / l.
  • a combination of peroxygen compound and the polyoxometalate mentioned is preferably used for bleaching soiling, in particular tea, when washing textiles, in particular in an aqueous, surfactant-containing liquor.
  • bleaching of soiling is to be understood in its broadest sense and includes both the bleaching of colored soil on the textile, the bleaching of colored soil in the wash liquor that has been detached from the textile and the oxidative destruction of itself the textile dyes in the wash liquor that detach from textiles under the washing conditions before they can be absorbed onto textiles of different colors.
  • the use according to the invention for bleaching colored stains can be realized particularly easily by introducing the polyoxometalate into an aqueous liquor, preferably containing surfactants, which also contains peroxygen compound and the textile to be cleaned or the object to be cleaned with a hard surface, the order of introduction of polyoxometalate, peroxygen compound and textile or object with a hard surface, or a preferably surfactant-containing aqueous liquor which contains the polyoxometalate and peroxygen compound is applied to the textile to be cleaned or the hard surface to be cleaned.
  • the polyoxometalate is preferably used as a component of a washing or cleaning agent, which particularly preferably also contains the peroxygen compound.
  • Solid agents preferably contain from 0.001% by weight to 45% by weight, in particular from 0.085% by weight to 5% by weight, of such polyoxometalate.
  • Liquid agents preferably contain from 0.0011% by weight to 85% by weight, in particular 0.11% by weight to 8.5% by weight, of such polyoxometalate.
  • the detergents and cleaning agents which can be in particular powdery solids, in compacted particle form, as homogeneous solutions or as suspensions or dispersions, in addition to the bleach-enhancing compound and preferably peroxygen compound used according to the invention, can in principle contain all known ingredients that are customary in such agents.
  • the detergents and cleaning agents according to the invention can in particular contain builders, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators, additional peroxygen activators and dyes and fragrances .
  • Suitable organic or inorganic peroxygen compounds are organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, in particular inorganic peroxygen compounds such as hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the cleaning conditions, such as perborate, percarbonate and / or persilicate -Inclusion compounds such as H 2 O 2 urea adducts, into consideration. Hydrogen peroxide can also be generated with the help of an enzymatic system, i.e. an oxidase and its substrate.
  • solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be coated in a manner known in principle.
  • the peroxygen compounds can be added to the washing or cleaning liquor as such or in the form of agents containing them, which can in principle contain all customary detergent or cleaning agent constituents.
  • Alkali percarbonate, alkali perborate monohydrate or hydrogen peroxide in the form of aqueous solutions which contain 3% by weight to 10% by weight hydrogen peroxide are particularly preferably used.
  • the detergent or cleaning agent contains peroxygen compounds, these are preferably in amounts from 0.1% by weight to 50% by weight, in particular from 5% by weight to 20% by weight and particularly preferably from 7% by weight % to 17% by weight, and most preferably 8% to 15% by weight.
  • peroxocarboxylic acid-supplying compounds can also be used under perhydrolysis conditions, although the bleach-improving effect of the polyoxometalate also occurs in their absence.
  • Compounds which produce perbenzoic acid and / or aliphatic peroxocarboxylic acids having 1 to 12 carbon atoms, in particular 2 to 4 carbon atoms, which may be substituted under perhydrolysis conditions, alone or in mixtures, can be used as compounds which produce peroxocarboxylic acid under perhydrolysis conditions.
  • the bleach activators cited at the beginning, the O- and / or N-acyl groups, in particular the number of carbon atoms mentioned, are suitable and / or carry optionally substituted benzoyl groups.
  • Polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N- are preferred Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or isononanoyl or lauroyloxybenzenesulfonate (NOBS or iso-
  • bleach-activating compounds such as, for example, nitriles, from which perimidic acids are formed, may be present.
  • nitriles such as, for example, nitriles, from which perimidic acids are formed
  • R 1 stands for -H, -CH 3 , a C 2-24 -alkyl or -alkenyl radical, a substituted C 1-24 -alkyl or C 2-24 -alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH 2 , -CN and -N (+) -CH 2 -CN, an alkyl or alkenylaryl radical with a C 1-24 -alkyl group, or for a substituted alkyl or alkenylaryl radical with at least one, preferably two, optionally substituted C 1-24 -alkyl group (s) and optional
  • Oxygen-transferring sulfonimines and / or acylhydrazones can also be used.
  • the presence of other bleach-catalyzing transition metal complexes is also possible. These are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes.
  • Both inorganic and organic compounds are suitable as ligands in the transition metal complexes, including, in addition to carboxylates, especially compounds with primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole , Triazole, 2,2'-bispyridylamine, tris- (2-pyridylmethyl) amine, 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl -1,5,9-triazacyclododecane, (bis - ((1-methylimidazol-2-yl) methyl)) - (2-pyridylmethyl) amine, N, N '- (bis- (1-methylimidazole-2- yl) methyl) ethylenediamine, N-bis- (2-benzimidazoly
  • the inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic, and among these in particular monodentate or bidentate ligands. These include in particular the halides, such as fluoride, chloride, bromide and iodide, and the (NO 2 ) group, that is to say a nitro ligand or a nitrito ligand.
  • the (NO 2 ) - group can also be bound to a transition metal in a chelating manner, or it can bridge two transition metal atoms asymmetrically or ⁇ 1 -O-.
  • the transition metal complexes to be used in the activator system according to the invention can also carry further ligands, as a rule of a simpler structure, in particular monovalent or polyvalent anion ligands.
  • ligands for example, nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, perchlorate and complex anions such as hexafluorophosphate are possible.
  • the anion ligands are intended to balance the charge between the central transition metal atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible.
  • Such ligands in particular can also have a bridging effect, so that polynuclear complexes are formed.
  • both metal atoms in the complex do not have to be the same. It is also possible to use binuclear complexes in which the two central transition metal atoms have different oxidation numbers. If anion ligands are missing or the The presence of anion ligands does not lead to charge equalization in the complex, anionic counterions are present in the transition metal complex compounds which neutralize the cationic transition metal complex.
  • anionic counterions include, in particular, nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, benzoate, citrate or oxalate.
  • transition metal complex compounds examples include Mn (IV) 2 ( ⁇ -O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) -di-hexafluorophosphate, [N, N'-bis [( 2-hydroxy-5-vinylphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-nitrophenyl) methylene] -1, 2-diaminocyclohexane] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-phenylenediamine] manganese (III) acetate, [N, N ' -Bis [(2-hydroxyphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxyphenyl) chloride,
  • the washing and cleaning agents can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof.
  • Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Soaps that can be used are preferably the alkali salts of saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized.
  • the sulfate-type surfactants which can be used include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation.
  • the sulfonate-type surfactants that can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are formed when corresponding monoolefins are reacted with sulfur trioxide, as well as alpha-sulfo fatty acid esters, which are formed during the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are contained in the cleaning agents or detergents in proportions of preferably 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight, while the cleaning agents or detergents for cleaning hard surfaces, in particular of dishes, preferably 0.1 wt% to 20 wt%, in particular 0.2 wt% to 5 wt% surfactants.
  • the cleaning or washing agent 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 carboxymethyl inulins, monomeric and polymeric aminopolycarboxylic acids, in particular glycine diacetic acid, methyl glycine diacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediaminoacetic acid, methylenediamineacetic acid, especially ethylenediaminosuccinic acid, and, in particular, ethylenediaminosuccinic 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 polycarboxy
  • the relative average molecular weight (here and below: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, that of the copolymers between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, each 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, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid makes up at least 50% by weight.
  • vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene
  • the acid makes up at least 50% by weight.
  • Terpolymers which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as a third monomer can also be used as water-soluble organic builder substances.
  • 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, maleic acid being particularly preferred.
  • the third monomeric unit is formed by vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which represent an ester of short-chain carboxylic acids, for example of C 1 -C 4 carboxylic acids, with vinyl alcohol are particularly preferred.
  • Preferred polymers here contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and also 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, vinyl alcohol and / or vinyl acetate.
  • 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, are very particularly preferred , 5: 1. 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 40% by weight to 60% by weight, in particular 45 to 55% by weight (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight %, preferably 15% by weight to 25% by weight of methallylsulfonic acid or methallylsulfonate and, as the third monomer, 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate.
  • This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Sucrose is particularly preferred.
  • 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 acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • the organic builder substances can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions, in particular for the production of liquid agents. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali salts.
  • Such organic builder substances can, if desired, 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 upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, detergents and cleaning agents.
  • Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate.
  • the water-insoluble inorganic builder materials used are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25% by weight, preferably from 3% by weight to 20% by weight and in particular in amounts from 5% by weight to 15% by weight. -% used.
  • the crystalline sodium aluminosilicates in detergent quality in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite X, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions.
  • Suitable aluminosilicates have in particular no particles with a grain size of more than 30 ⁇ m and preferably at least 80% by weight of particles with a size of less than 10 ⁇ m.
  • Their calcium binding capacity is usually in the range of 100 to 200 mg CaO per gram.
  • water-soluble inorganic builder materials can be contained.
  • polyphosphates such as sodium triphosphate
  • these include in particular the water-soluble crystalline and / or amorphous alkali silicate builders.
  • Such water-soluble inorganic builder materials are contained in detergents and cleaning agents preferably in amounts of from 1% by weight to 20% by weight, in particular from 5% by weight to 15% by weight.
  • the alkali metal silicates which can be used as builder materials preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • the crystalline silicates used alone or in a mixture with amorphous silicates are preferably crystalline sheet silicates of the general formula Na 2 Si x O 2x + 1 y H 2 O, in which x, the so-called module, is a number 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 sheet silicates are those in which x in the general formula mentioned assumes the values 2 or 3.
  • both ß- and ⁇ -sodium disitics are preferred.
  • Virtually anhydrous crystalline alkali silicates of the abovementioned general formula, in which x is a number from 1.9 to 2.1, which are produced from amorphous alkali silicates, can also be used in detergents and cleaning agents.
  • a crystalline layered sodium silicate with a module of 2 to 3, as can be produced from sand and soda is used.
  • Sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further embodiment of the washing and cleaning agents.
  • a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.
  • Machine dishwashing detergents are preferably lower alkaline and contain the usual alkali carriers such as alkali silicates, alkali carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates can be used in amounts of up to 30 wt. %, based on the total agent, be included.
  • the use of the highly alkaline metasilicates as alkali carriers is preferably not used at all.
  • the alkali carrier system preferably used in cleaning agents is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight.
  • the ratio of carbonate and hydrogen carbonate used varies depending on which pH value is ultimately desired, but an excess of sodium hydrogen carbonate is usually used, so that the weight ratio between hydrogen carbonate and carbonate is generally 1: 1 to 15: 1.
  • water-soluble organic builders in particular alkali citrate, 5% by weight to 15% by weight alkali metal carbonate and 20% by weight to 40 wt .-% alkali disilicate contain.
  • the enzymes that may be contained in the detergents and cleaning agents 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 cellulase is particularly preferred.
  • the proportion is preferably 0.2% by weight to 1.5% by weight, in particular 0.5% by weight to 1% by weight.
  • the enzymes can be adsorbed on carrier substances in the usual way and / or embedded in coating substances or incorporated as concentrated liquid formulations which are as water-free as possible.
  • Suitable graying inhibitors or soil release active ingredients are cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed cellulose ethers such as methyl hydroxyethyl cellulose, methylhydroxypropyl cellulose and methyl carboxymethyl cellulose. Sodium carboxymethyl cellulose and mixtures thereof with methyl cellulose are preferably used.
  • the soil release active ingredients usually used include copolyesters which contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units.
  • the proportion of graying inhibitors and / or soil release active ingredients in the detergents and cleaning agents is generally not more than 2% by weight and is preferably 0.5% by weight to 1.5% by weight.
  • derivatives of diaminostilbene disulfonic acid or alkali metal salts thereof can be included as optical brighteners for textiles made of cellulose fibers (for example cotton).
  • salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or similarly structured compounds 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 can be present, for example 4,4'-bis- (4-chloro-3-sulfostyryl) -diphenyl. Mixtures of brighteners can also be used.
  • Brighteners of the 1,3-diaryl-2-pyrazoline type for example 1- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and similarly structured compounds are particularly suitable for polyamide fibers.
  • the content of optical brighteners or brightener mixtures in the agent is in generally not more than 1% by weight, preferably 0.05% by weight to 0.5% by weight. In a preferred embodiment of the invention, the agent is free from such active ingredients.
  • the customary foam regulators that can be used in washing and cleaning agents include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanized or otherwise hydrophobized.
  • the polysiloxanes can consist of both linear compounds and crosslinked polysiloxane resins and mixtures thereof.
  • Further defoamers are paraffinic hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C, saturated fatty acids or soaps with in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali salts of phosphoric acid mono- and / or dialkyl esters, in which the alkyl chains each have 12 to 22 carbon atoms.
  • sodium monoalkyl phosphate and / or dialkyl phosphate having C 16 to C 18 alkyl groups is preferably used.
  • the proportion of foam regulators can preferably be 0.2% by weight to 2% by weight.
  • the organic solvents that can be used in detergents and cleaning agents include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 C. Atoms, in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers which can be derived from the mentioned classes of compounds.
  • Such water-miscible solvents are present in the washing and cleaning agents in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight.
  • the agents according to the invention can contain acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides.
  • acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides.
  • Such pH regulators are contained in the agents according to the invention preferably not more than 10% by weight, in particular from 0.5% by weight to 6% by weight.
  • the production of the solid detergents and cleaning agents presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, the peroxygen compound and bleach catalyst optionally being added later separately.
  • the detergents and cleaning agents in the form of aqueous solutions or solutions containing other customary solvents are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • the detergents and cleaning agents are preferably in the form of powdery, granular or tablet-like preparations, which are prepared in a manner known per se, for example by mixing, granulating, roller compacting and / or by spray drying the thermally loadable components and admixing the more sensitive components, to which in particular enzymes, Bleach and the bleach-activating system are expected to be produced.
  • a method having an extrusion step is preferred.
  • the preferred procedure is to mix all the ingredients together in a mixer and then apply the mixture using conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 ⁇ 10 5 Pa to 1,500 ⁇ 10 5 Pa pressed.
  • a tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm up to 40 mm.
  • the detergents and cleaning agents in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 800 g / l to 1000 g / l can also be carried out by using the builder components in a first process stage mixed with at least one portion of liquid mixture components to increase the bulk density of this premix and subsequently - if desired after intermediate drying - the other ingredients of the agent, including the performance-enhancing active ingredient or the performance-enhancing active ingredient combination, combined with the premix thus obtained.
  • the Y values when using the active ingredient essential to the invention are greater than those which are obtained when using only the detergent, which corresponds to a higher degree of whiteness and thus to improved stain removal.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (9)

  1. Utilisation d'une association d'un composé peroxygéné et de H5[PMo10V2O40] et/ou de ses sels alcalins ou d'ammonium pour blanchir des taches de couleur lors du lavage de textiles, en particulier dans un bain aqueux contenant un tensioactif, ou en particulier dans des solutions nettoyantes aqueuses contenant un tensioactif pour des surfaces dures, en particulier pour de la vaisselle, pour blanchir des taches colorées, en particulier de thé.
  2. Utilisation selon la revendication 1, caractérisée en ce qu'un agent détergent ou nettoyant est utilisé, lequel contient du H5[PMo10V2O40] et/ou ses sels alcalins ou d'ammonium.
  3. Utilisation selon la revendication 2, caractérisée en ce que l'agent contient 0,001 % à 45 % en poids, en particulier 0,085 % à 5 % en poids, de H5[PMo10V2O40] et/ou de ses sels alcalins ou d'ammonium.
  4. Utilisation selon la revendication 2, caractérisée en ce que l'agent est liquide et contient 0,0011 % à 85 % en poids, en particulier 0,11 % à 8,5 % en poids, de H5[PMo10V2O40] et/ou de ses sels alcalins ou d'ammonium.
  5. Utilisation selon l'une des revendications 2 ou 3, caractérisée en ce que l'agent contient un composé peroxygéné en des quantités de 0,1 % à 50 % en poids, en particulier de 5 % à 20 % en poids.
  6. Utilisation selon l'une des revendications 1 à 5, caractérisée en ce que le composé peroxygéné est inorganique.
  7. Procédé de lavage du linge, comprenant les étapes de procédé de (a) mise à disposition d'un bain aqueux contenant du H2O2 ou un composé peroxygéné en particulier inorganique libérant du H2O2 dans l'eau et du H5[PMo10V2O40] et/ou ses sels alcalins ou d'ammonium, et de (b) mise en contact de ce bain avec des textiles à laver.
  8. Procédé selon la revendication 7, caractérisé en ce que le contact entre le bain aqueux et l'article à laver est réalisé à des températures comprises entre 20 °C et 80 °C, en particulier entre 40 °C et 60 °C.
  9. Procédé selon la revendication 7 ou 8, caractérisé en ce que l'article à laver reste en contact avec le bain aqueux pendant une période de 20 à 120 minutes, en particulier de 30 à 90 minutes.
EP18172292.7A 2017-06-01 2018-05-15 Composition detergente blanchissante Active EP3409757B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102017209332.3A DE102017209332A1 (de) 2017-06-01 2017-06-01 Bleichendes Wasch- oder Reinigungsmittel

Publications (2)

Publication Number Publication Date
EP3409757A1 EP3409757A1 (fr) 2018-12-05
EP3409757B1 true EP3409757B1 (fr) 2020-08-19

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EP (1) EP3409757B1 (fr)
DE (1) DE102017209332A1 (fr)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19530787A1 (de) 1995-08-22 1997-02-27 Hoechst Ag Mangan enthaltende Polyoxometallate, Synthese und Verwendung
DE19530786A1 (de) 1995-08-22 1997-02-27 Hoechst Ag Bleichmittelzusammensetzung enthaltend Polyoxometallate als Bleichkatalysator
GB9725614D0 (en) 1997-12-03 1998-02-04 United States Borax Inc Bleaching compositions
US6074437A (en) 1998-12-23 2000-06-13 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Bleaching with polyoxometalates and air or molecular oxygen
GB0207430D0 (en) * 2002-03-28 2002-05-08 Unilever Plc Liquid cleaning compositionsand their use
MY145938A (en) * 2007-02-14 2012-05-31 Avantor Performance Mat Inc Peroxide activated oxometalate based formulations for removal of etch residue
RO122728B1 (ro) * 2007-07-31 2009-12-30 Universitatea "Aurel Vlaicu" Din Arad Procedeu ecologic de albire a fibrelor naturale prin oxidare catalitică, cu polioxometalaţi
CN103503921B (zh) * 2013-09-07 2015-04-22 宁波市雨辰环保科技有限公司 多聚金属氧酸盐在制备用于杀菌或去除甲醛的消毒剂中的应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
DE102017209332A1 (de) 2018-12-06
EP3409757A1 (fr) 2018-12-05

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