EP2737042B1 - Lessive ou produit de nettoyage présentant un composé médiateur activable électrochimiquement - Google Patents

Lessive ou produit de nettoyage présentant un composé médiateur activable électrochimiquement Download PDF

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Publication number
EP2737042B1
EP2737042B1 EP12740133.9A EP12740133A EP2737042B1 EP 2737042 B1 EP2737042 B1 EP 2737042B1 EP 12740133 A EP12740133 A EP 12740133A EP 2737042 B1 EP2737042 B1 EP 2737042B1
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Prior art keywords
acid
mediator compound
washing
weight
compound
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German (de)
English (en)
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EP2737042A1 (fr
EP2737042B2 (fr
Inventor
Mareile Job
Peter Schmiedel
Erik BRÜCKNER
Guido Grundmeier
Markus Voigt
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/395—Bleaching agents
    • C11D3/3951—Bleaching agents combined with specific additives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3955—Organic bleaching agents
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/46—Specific cleaning or washing processes applying energy, e.g. irradiation

Definitions

  • the present invention relates to the use of certain organic mediator compounds for enhancing the cleaning performance of detergents and cleaners against soiling, washing or cleaning processes using bleach-active species generated from the mediator compound, and detergents and cleaners containing the mediator compound.
  • Inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators which are able to provide peroxycarboxylic acids under the abovementioned perhydrolysis conditions and for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example reactive Esters, polyacylated alkylenediamines, in particular N, N, N ', N'-tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic anhydrides, in particular, phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate (NOBS), sodium isononanoyl
  • transition metal compounds in particular transition metal complexes, for increasing the oxidation power of peroxygen compounds or atmospheric oxygen in detergents and cleaners has also been proposed on various occasions.
  • the transition metal compounds proposed for this purpose include, for example, manganese, iron, cobalt, ruthenium or molybdenum-salene complexes, manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, manganese, iron, cobalt, Ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, and manganese complexes with polyazacycloalkane ligands, such as TACN.
  • a disadvantage of such metal complexes is that they either do not have sufficient bleaching performance, in particular at low temperature, or, if the bleaching performance is adequate, undesirably damage the colors of the material to be washed or cleaned and possibly even of the material itself, for example the textile fibers, can come.
  • bleaching-active species can be produced from organic mediator compounds by means of electrolysis, which have an excellent bleaching-enhancing effect and enhance the cleaning performance of detergents and cleaners, in particular with respect to bleachable stains.
  • an object of the invention is the use of a bleaching-active species produced electrolytically by a redox reaction from an organic mediator compound for enhancing the cleaning performance of detergents and cleaners, especially bleachable and / or proteinaceous soils, in aqueous, especially surfactant-containing, liquor characterized in that the mediator compound emits an electron in the preparation of bleaching-active species.
  • Mediator compounds which can be used according to the invention are organic compounds which are known in aqueous system, preferably in aqueous solution, can be electrolytically oxidized.
  • they are aliphatic, cycloaliphatic, aromatic or araliphatic compounds optionally containing heteroatoms, which is a group N-OH
  • N-OR is a nitroxyl radical NO ⁇ and / or a group NO - with a counter cation M + or 1 ⁇ 2 M 2+ , where R is an alkyl group having preferably 1 to 4 C atoms and M is hydrogen, an alkali metal or an alkaline earth metal, to which, for example, hydroxamic acids such as N-hydroxyphthalimide, N-hydroxyheteroaromatics such as 1-hydroxyindole, 1-hydroxybenzimidazole and 1-hydroxybenzotriazole, radicals sterically hindered N-hydroxy compounds such as (2,2,6,6-tetramethylpiperidin-1-yl) oxyl,
  • the preparation of the bleaching-active species can be carried out in a simple manner by subjecting an aqueous system containing the mediator compound to an electrical potential difference applied between at least two electrodes so that the mediator compound gives off an electron.
  • an electrical potential difference applied between at least two electrodes so that the mediator compound gives off an electron.
  • the potential difference is preferably from 0.2 V to 5 V, in particular from 1 V to 3 V.
  • the mediator compound preferably forms from the bleaching-active species by reaction with the soiling, so that a reversible redox system is present.
  • the mediator compound in particular when using a conventional dispensing device, passes an electrolysis device before it enters the chamber of a washing machine or dishwashing machine, in particular in aqueous solution or slurry flows through an electrolysis cell which is in the feed line can be mounted inside or outside the machine.
  • other active ingredients such as enzymes, unaffected perform their performance, and only later by switching on the electrolysis device to start the bleaching effect.
  • the electrolysis device is installed inside a washing or dishwashing machine in the flooded area of the washing or cleaning room, in a drum washing machine preferably outside the washing drum.
  • the device may be a permanently installed component of the washing machine or dishwashing machine or a separate component.
  • the electrolysis device designed in particular as an electrolysis cell is embodied in a further embodiment of the invention as a separate device separate from a washing machine or dishwashing machine, which device is operated with its own power source, for example a battery (e-bleach-ball).
  • Another embodiment of the invention is to integrate the electrolyzer in an additional water cycle within the machine.
  • the electrodes of the electrolyzer can contact the electrolyte (wash liquor, or service water supplied) containing the organic mediator compound, for example, when the e-bleach ball is in contact during the Washing process is located in the washing drum of a washing machine.
  • Further objects of the invention are a method for washing textiles and a method for cleaning hard surfaces, in particular for machine cleaning of dishes, using a bleaching-active species produced electrolytically by a redox reaction from an organic mediator compound, which is characterized in that the mediator compound emits an electron in the preparation of the bleaching-active species.
  • the activity of the bleach if desired, depending on the degree of contamination or tissue, can be easily modified by controlling the current intensity.
  • the current intensity In the case of textile washing processes, there is no damage to the textile treated in this way, which exceeds that which occurs when conventional means are used.
  • the concentration of the mediator compound in the aqueous washing or cleaning liquor is 0.05 mmol / l to 5 mmol / l, in particular 0.1 mmol / l to 2 mmol / l.
  • the use according to the invention and the process according to the invention are in each case preferably carried out at temperatures in the range from 10 ° C. to 95 ° C., in particular from 20 ° C. to 40 ° C.
  • the use according to the invention and the method according to the invention are in each case preferably carried out at pH values in the range from pH 2 to pH 12, in particular from pH 4 to pH 11.
  • the use according to the invention or the method according to the invention can be realized particularly simply by the use of a washing or cleaning agent which contains the mediator compound.
  • a washing or cleaning agent which contains the mediator compound.
  • Detergents for cleaning textiles and agents for cleaning hard surfaces, especially dishwashing detergents and among these preferably those for machine use, the 0.1 wt .-% to 10 wt .-% of an organic MediatorENS by means of electrolysis by a redox reaction can be converted into a bleaching-active species and in the production of the bleaching-active species releases an electron, in addition to conventional compatible ingredients, in particular a surfactant, are therefore further objects of the invention.
  • an agent according to the invention may additionally contain, in particular, peroxygen-containing bleaching agent.
  • peroxygen-containing bleaching agent is that it is possible to dispense with bleach as well as with conventional bleach activator, so that, as a result, a smaller amount of detergent or cleaning agent has to be used per wash cycle or cleaning cycle.
  • An agent according to the invention is therefore in a preferred embodiment free of bleach and conventional bleach activator.
  • agents according to the invention 0.5 wt .-% to 5 wt .-% of the mediator compound.
  • a bleaching as well as a bleach-free application if down-regulated for the latter case, the current to zero.
  • the consumer therefore needs to wash insensitive, usually white and from sensitive, usually colored textiles only a single detergent.
  • compositions according to the invention which can be in the form of homogeneous solutions or suspensions in particular as pulverulent solids, in densified particle form, may contain, in principle, all known ingredients customary in such agents, apart from the mediator compound to be used according to the invention.
  • the agents according to the invention may in particular be builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, dye transfer inhibitors, grayness inhibitors, wrinkle-reducing polymeric agents and polymer preservatives, bleaching agents, bleach activators, and other adjuvants, such as optical brighteners, foam regulators, dyes and fragrances.
  • compositions of the invention may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic and / or amphoteric surfactants may be included.
  • 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, alkanesulfonates 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 cleaning or washing agents according to the invention in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, while the disinfectant according to the invention as well as inventive cleaning agent preferably 0.1 wt .-% to 20 wt .-%, in particular 0.2 wt .-% to 5 wt .-% surfactants.
  • the cationic surfactants have customary anions in the charge balance necessary type and number, which can be selected in addition to, for example halides also from the anionic surfactants.
  • the cationic surfactants used are hydroxyalkyltrialkylammonium compounds, in particular C 12-18 -alkyl (hydroxyethyl) dimethylammonium compounds, and preferably their halides, in particular chlorides.
  • An agent according to the invention preferably contains 0.5% by weight to 25% by weight, in particular 1% by weight to 15% by weight, of cationic surfactant.
  • An agent according to 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 and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diene diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by oxidation of polysaccharides or dextrins accessible polycarboxylates, and / or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain polymerized small amounts of
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, each based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
  • 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 may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Such polymers generally have a molecular weight between 1,000 and 200,000.
  • 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 paste-form or liquid, in particular water-containing, agents according to the invention.
  • Suitable water-soluble inorganic builder materials are, in particular, polymeric alkali metal phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used.
  • detergent grade crystalline sodium aluminosilicates especially zeolite A, P and optionally X. 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 usually in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention 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 may be present in amorphous or crystalline form.
  • 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 .beta.- and ⁇ -Natriumdisitikate (Na 2 Si 2 O 5 ⁇ y H 2 O) is preferred.
  • compositions according to the invention can be prepared from amorphous alkali silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used in inventive compositions.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.
  • the weight ratio is aluminosilicate to silicate, in each case based on anhydrous active substances, preferably 1:10 to 10: 1.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
  • Builder substances are preferably present in the detergents or cleaners according to the invention in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
  • the water-soluble builder block contains at least 2 of components b), c), d) and e) in amounts greater than 0% by weight.
  • component a in a preferred embodiment of the composition according to the invention, 15% by weight to 25% by weight of alkali carbonate, which may at least partly be replaced by alkali metal hydrogencarbonate, and up to 5% by weight, in particular 0.5% by weight. % to 2.5% by weight of citric acid and / or alkali citrate.
  • component a) 5% by weight to 25% by weight, in particular 5% by weight to 15% by weight, are used.
  • component b) in a preferred embodiment of the composition according to the invention, 1% by weight to 5% by weight of alkali metal silicate with a modulus in the range from 1.8 to 2.5 are contained.
  • agents according to the invention contain from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate.
  • Phosphonic acids are also understood as meaning optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids).
  • They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, for example dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane 1,1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediamine tetrakis (methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.
  • dimethylaminomethane diphosphonic acid 3-aminopropane-1-hydroxy-1,1-diphosphonic acid
  • 1-amino-1-phenylmethane diphosphonic acid 1-hydroxyethane 1,1-diphosphonic acid
  • amino-tris methylenephosphonic acid
  • alkali metal phosphate in particular trisodium polyphosphate, are contained.
  • Alkaliphosphat is the summary term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and pass on Madrell's salt.
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt of density 2.33 gcm -3 , has a melting point of 253 ° (decomposition to form (KPO 3 ) x , potassium polyphosphate) and is slightly soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 mol.
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4. Condensation of NaH 2 PO 4 or KH 2 PO 4 results in higher mol.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates.
  • pentasodium triphosphate is phosphoric acid with sodium carbonate solution or sodium hydroxide in the Stoichiometric ratio to the reaction and dehydrated the solution by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps).
  • Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade.
  • the potassium polyphosphates are widely used in the washing and cleaning industry.
  • sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • agents according to the invention contain from 1.5% by weight to 5% by weight of polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid.
  • polymeric polycarboxylate in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid.
  • homopolymers of acrylic acid particularly preferred are those having an average molecular weight in the range from 5,000 D to 15,000 D (PA standard).
  • Suitable enzymes which can be used in the compositions are, in addition to the abovementioned oxidase, those from the class of the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof, for example proteases such as BLAP®, Optimase®, Opticlean ®, Maxacal ®, Maxapem ®, Alcalase ®, Esperase ®, Savinase ®, Durazym ® and / or Purafect ® OxP, amylases such as Termamyl ®, Amylase - LT ®, Maxamyl ®, Duramyl ® and / or Purafect ® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, cellulases such as Cellu
  • fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents.
  • the optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are in the washing, cleaning and disinfecting agents according to the invention preferably in amounts up to 10 wt .-%, in particular from 0.2 wt .-% to 2 wt .-%, with particular preference against oxidative degradation stabilized enzymes are used.
  • the agent contains 5% by weight to 50% by weight, in particular 8-30% by weight of anionic and / or nonionic surfactant, up to 60% by weight, in particular 5-40% by weight.
  • peroxygen compounds which may be omitted in intended for use in the method according to the invention preferably but in particular organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic Salts, such as perborate, percarbonate and / or persilicate, into consideration.
  • Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate.
  • 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. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions which contain 3% by weight to 10% by weight of hydrogen peroxide. If desired, peroxygen compounds in amounts of up to 50% by weight, in particular from 5% by weight to 30% by weight, are present in detergents or cleaners according to the invention.
  • bleach activators which form peroxycarboxylic acids or peroxoimidic acids under perhydrolysis conditions and / or customary bleach-activating transition metal complexes can be used.
  • the optional, especially in amounts of 0.5 wt .-% to 6 wt .-%, present component of the bleach activators includes the commonly used N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfuryl amides and cyanurates, in addition to carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl-phenolsulfonat, and acylated sugar derivatives, in particular pentaacet
  • the bleach activators may have been coated or granulated in a known manner with coating substances to avoid interaction with the per compounds, with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine having mean particle sizes of 0.01 mm to 0.8 mm, granulated 1.5- diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or particulate form trialkylammonium acetonitrile is particularly preferred.
  • Such bleach activators are preferably contained in detergents or cleaners in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
  • organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms , in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compound ethers.
  • Such water-miscible solvents are preferably present in the detergents according to the invention not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • the compositions according to the invention can contain system- and environmentally compatible 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 bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight, in the compositions according to the invention.
  • Soil release polymers are, for example, nonionic or cationic cellulose derivatives.
  • the particularly polyester-active soil release polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol.
  • Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR 11 -) a OH, also known as polymeric Diol H- (O- (CHR 11 -) a ) b OH may be present.
  • Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 11 denotes hydrogen
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
  • the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140.
  • the molecular weight or the maximum molecular weight distribution of preferred soil release polyester is in the range from 250 to 100,000, in particular from 500 to 50,000 Residual Ph underlying acid is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof.
  • acids having at least two carboxyl groups may be included in the soil release-capable polyester.
  • alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
  • Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000.
  • these polyesters may also be end developmentver consideration, with alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids in question as end groups.
  • polymers of ethylene terephthalate and polyethylene terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5,000 and the molar ratio of ethylene terephthalate to polyethylene terephthalate is 50:50 to 90:10 are used alone or in combination with cellulose derivatives.
  • Polyvinylpyrrolidones polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers belong to the color transfer inhibitors which are suitable for use in laundry detergents according to the invention.
  • the inventive compositions for use in the textile laundry may contain anti-crease agents, since textile fabrics, in particular of rayon, wool, cotton and their mixtures, may tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction.
  • anti-crease agents since textile fabrics, in particular of rayon, wool, cotton and their mixtures, may tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction.
  • These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • Graying inhibitors have the task of keeping suspended from the hard surface and in particular from the textile fiber suspended dirt in the fleet.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.
  • the agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl).
  • Mixtures of the aforementioned optical brightener can be used.
  • foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
  • silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, optionally alkyl or aminoalkyl-substituted triazoles such as benzotriazole and cobalt, manganese, titanium, zirconium, hafnium, vanadium or cerium salts and / or complexes in which the said metals in one of the oxidation states II, III, IV, V or VI.
  • compositions according to the invention presents no difficulties and can be carried out in a manner known in principle, for example by spray-drying or granulation.
  • a process comprising an extrusion step is preferred.
  • Detergents, cleaners or disinfectants 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. In a preferred embodiment of means for the particular machine cleaning of dishes, these are tablet-shaped.

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Claims (11)

  1. Agent de lavage ou de nettoyage, caractérisé en ce qu'il contient de 0,1 à 10 % en poids d'un composé médiateur organique qui peut être converti en une espèce décolorante active au moyen d'une électrolyse par réaction d'oxydoréduction, caractérisé en ce que le composé médiateur cède un électron lors de la production des espèces décolorantes actives.
  2. Agent selon la revendication 1, caractérisé en ce qu'il contient de 0,5 % en poids à 5 % en poids du composé médiateur et/ou est exempt d'agents décolorants et d'activateur de décoloration classique.
  3. Utilisation d'une espèce décolorante active générée par voie électrolytique par une réaction d'oxydoréduction d'un composé médiateur organique pour renforcer le pouvoir nettoyant des agents de lavage et de nettoyage dans un bain aqueux, plus particulièrement contenant un tensioactif, caractérisé en ce que le composé médiateur cède un électron lors de la production des espèces décolorantes actives.
  4. Procédé de lavage de textiles ou de nettoyage de surfaces dures, en particulier de nettoyage de la vaisselle en machine, par l'utilisation d'une espèce décolorante active générée par voie électrolytique par une réaction d'oxydoréduction d'un composé médiateur organique, caractérisé en ce que le composé médiateur cède un électron lors de la fabrication de l'espèce décolorante active.
  5. Procédé selon la revendication 4, caractérisé en ce que le bain contenant le composé médiateur est électrolysé de façon continue ou en une ou plusieurs fois pendant des intervalles de temps déterminés, en particulier de 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes ou 60 minutes.
  6. Procédé selon la revendication 4, caractérisé en ce que, avant d'entrer dans la chambre d'une machine à laver, en particulier lors de l'utilisation d'un dispositif d'incorporation classique, le composé médiateur passe par un dispositif d'électrolyse, en particulier traverse une cellule électrolytique dans une solution aqueuse ou une suspension.
  7. Procédé selon la revendication 4 ou 5, caractérisé en ce que le dispositif d'électrolyse, conçu notamment sous la forme d'une cellule d'électrolyse, est conçu sous la forme d'un dispositif qui est séparé d'une machine à laver ou d'un lave-vaisselle et qui est alimenté par sa propre source d'alimentation en courant.
  8. Utilisation selon la revendication 3 ou procédé selon l'une des revendications 4 à 7, caractérisé en ce que la concentration du composé médiateur dans le bain de lavage ou de nettoyage aqueux est de 0,05 mmol/l à 5 mmol/l, notamment de 0,1 mmol/l à 2 mmol/l.
  9. Utilisation ou procédé selon l'une des revendications 3 à 8, caractérisé en ce qu'il est mis en oeuvre à des valeurs de pH dans la gamme de pH 2 à pH 12, en particulier de pH 4 à pH 11.
  10. Agent, utilisation ou procédé selon l'une des revendications 1 à 9, caractérisé en ce que le composé médiateur organique forme un système redox réversible en solution aqueuse.
  11. Agent, utilisation ou procédé selon l'une des revendications 1 à 10, caractérisé en ce que le composé médiateur organique est un composé aliphatique, cycloaliphatique, aromatique ou araliphatique, contenant éventuellement un hétéroatome, qui comporte un groupe N-OH, N-OR, un radical nitroxyle N-O· et/ou un groupe N-O- comportant un contre-cation M+ ou 1/2 M2+, R étant un groupe alkyle ayant notamment de 1 à 4 atomes de carbone et M étant l'hydrogène, un métal alcalin ou un métal alcalino-terreux, notamment un acide hydroxamique, tel que le N-hydroxyphtalimide, un N-hydroxyhétéroaromate tel que le 1-hydroxyindole, le 1-hydroxybenzimidazole et le 1-hydroxybenzotriazole, un radical d'un composé N-hydroxy à empêchement stérique tel que le (2,2,6,6-tétraméthylpipéridin-1-yl)oxyle, et une oxymidocétone que l'acide violurique et l'acide N,N'-diméthylviolurique.
EP12740133.9A 2011-07-29 2012-07-24 Procédé de lavage ou de nettoyage avec un composé médiateur activable électrochimiquement Active EP2737042B2 (fr)

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DE102011080099A DE102011080099A1 (de) 2011-07-29 2011-07-29 Wasch- oder Reinigungsmittel mit elektrochemisch aktivierbarer Mediatorverbindung
PCT/EP2012/064491 WO2013017476A1 (fr) 2011-07-29 2012-07-24 Lessive ou produit de nettoyage présentant un composé médiateur activable électrochimiquement

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DE102014213311A1 (de) 2014-07-09 2016-01-14 Henkel Ag & Co. Kgaa Neuartiges Waschverfahren mit elektrochemisch aktivierbarer Mediatorverbindung
DE102014109623B4 (de) * 2014-07-09 2023-01-05 Miele & Cie. Kg Verfahren zum Betreiben eines wasserführenden elektrischen Gerät sowie wasserführendes elektrisches Gerät
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DE102011080099A1 (de) 2013-01-31
US10435649B2 (en) 2019-10-08
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PL2737042T5 (pl) 2023-01-09
WO2013017476A1 (fr) 2013-02-07
US20140143959A1 (en) 2014-05-29
ES2664834T3 (es) 2018-04-23
PL2737042T3 (pl) 2018-08-31
ES2664834T5 (es) 2022-05-20
KR102046861B1 (ko) 2019-11-20
EP2737042B2 (fr) 2022-04-06

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