EP3409753B1 - 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

Info

Publication number
EP3409753B1
EP3409753B1 EP18172235.6A EP18172235A EP3409753B1 EP 3409753 B1 EP3409753 B1 EP 3409753B1 EP 18172235 A EP18172235 A EP 18172235A EP 3409753 B1 EP3409753 B1 EP 3409753B1
Authority
EP
European Patent Office
Prior art keywords
liquor
weight
mmol
cleaning
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP18172235.6A
Other languages
German (de)
English (en)
Other versions
EP3409753A1 (fr
Inventor
Andre Haetzelt
Adam Dzierbinski
Peter HAUSOUL
Regina Palkovits
Sean Jung
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3409753A1 publication Critical patent/EP3409753A1/fr
Application granted granted Critical
Publication of EP3409753B1 publication Critical patent/EP3409753B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2

Definitions

  • the present invention relates to the use of certain polyoxometalates for activating molecular oxygen in connection with the bleaching of soils when washing textiles, and to washing and cleaning processes in which such polyoxometalates are used.
  • Inorganic peroxygen compounds especially 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 disinfection 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 quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by the addition of so-called bleach activators, which are able to deliver peroxocarboxylic acids under the perhydrolysis conditions mentioned and for which numerous suggestions, especially from the substance classes of the 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, sulfurylamides and cyanurononoyl anonoyl anonoyl anoxides, especially sodium phthalic acid anhydride, benzenesulfonate, O-acylated sugar derivatives, such as pentaacetyl glucose, and N-acylated lactams, such as N
  • Bleaching agents which contain peroxygen compounds and polyoxometalates as bleaching catalysts, whereby the polyoxometalates must contain Mo, W, Nn, Ta and / or V and may additionally contain transition metals of the 2nd and 8th subgroups.
  • the international patent application WO 99/28426 A1 relates to compositions containing a bleaching agent 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 polyoxometalates NaWO 4 , H 4 SiW 12 O 40 , H 3 PW 12 O 40 , ⁇ - and ⁇ -K 8 SiW 11 O 39 , ⁇ -Na 10 SiW 9 O34, ⁇ -K 7 PW 11 O 39 are specifically disclosed , K 7 SiVMnW 10 O 39 , K 8 [P 2 CuW 17 O 62 H 2 ], K 8 [P 2 CuW 17 O 62 H 2 ], K 10 [ ⁇ -2-P 2 W 17 O 61 ], Cs 5 NbSiW 11 O 40 , K 5 (NbO 2 ) SiW 11 O 39 , ((CH 3 ) 3 NH) 4 (NbO 2 ) PW 11 O 39 , K 7 Mo 2 VSiW 9 O 40 , K 7 VMnSi
  • the patent RO 122728 B1 discloses a bleaching process for natural fibers, the fibers being treated with the sodium salt of 10-molybdo-2-vanadophosphoric acid in a first step. After heating, cooling and filtering, the fibers are treated in the next step with an alkaline solution containing H 2 O 2 .
  • the present invention aims to improve the oxidation and bleaching effect of liquors used in washing textiles or cleaning hard surfaces, in particular at low temperatures in the range from approximately 10 ° C. to 45 ° C.
  • the invention relates to the use of polyoxometalates 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 from at least two of these, for the activation of molecular oxygen, in particular atmospheric oxygen, when washing textiles or cleaning hard surfaces.
  • a second object of the invention is the use of these polyoxometalates to enhance the cleaning performance of detergents or cleaning agents in aqueous, in particular surfactant-containing, liquor in the presence of a gaseous phase which is present in addition to the liquid phase of the liquor and contains molecular oxygen, in particular atmospheric oxygen.
  • Another object of the invention is the use of polyoxometalates 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, for bleaching color stains when washing textiles in aqueous, in particular surfactant-containing, liquor, or in aqueous, in particular surfactant-containing, cleaning solutions for hard surfaces, in particular for dishes, for bleaching colored stains, in particular tea, in the presence of a gaseous phase which is present in addition to the liquid phase of the liquor and contains molecular oxygen, in particular atmospheric oxygen.
  • polyoxometalates 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, for bleaching color stains when washing textiles in
  • bleaching of soiling is to be understood in its broadest meaning and includes both the bleaching of colored dirt present on the textile, the bleaching of colored dirt present in the wash liquor and detached from the textile, and also the oxidative destruction of textile dyes in the wash liquor, which detach from textiles under the washing conditions before they can be drawn onto textiles of a different color.
  • the use according to the invention essentially consists in creating conditions under which the molecular oxygen provided in particular via the dosage form air and the polyoxometalate mentioned can react with one another with the aim of obtaining secondary products having a stronger oxidizing action.
  • Such conditions exist in particular when the polyoxometalate is present in an aqueous system and in addition to the liquid phase of this aqueous system there is a gaseous phase, for example air, which contains molecular oxygen.
  • a gaseous phase for example air
  • This can penetrate into the aqueous system through the interface with the liquid phase and form a more oxidizing secondary product there or at the interface mentioned with the polyoxometalate.
  • the formation of the more oxidizing secondary product can be increased.
  • the use of air at ambient pressure and temperature is possible.
  • the formation of the more oxidizing secondary product can, if desired, be increased and / or accelerated by using a gas phase having a higher concentration of molecular oxygen and / or a gas phase containing molecular oxygen under increased pressure.
  • a gas phase which is not present at normal pressure or normal ambient pressure is used, a pressure up to 100 bar, in particular in the range from 10 bar to 80 bar, is preferred.
  • the liquor containing the polyoxometalate can also contain the usual constituents of detergents or cleaning agents which, in the usual way, originate from the introduction of such agents into the liquor.
  • the detergents or cleaning agents used in the preparation of the liquor can be free of peroxygen compounds. If desired, the formation of the more oxidizing secondary product can be accelerated if one starts from a liquor which may contain detergents or cleaning agents and which contains so much H 2 O 2 or H 2 O 2 -supplying substance that its concentration (calculated as H 2 O 2 ) in the liquor is 0.01 mmol / l to 0.5 mmol / l, in particular 0.06 mmol / l to 0.12 mmol / l.
  • the reaction with the polyoxometalate consumes the H 2 O 2 or the substance which supplies H 2 O 2 in water, but does not have to be replaced, since the more strongly oxidizing secondary product after its reaction with soils to be bleached in the sense of a cycle with the aid of molecular Oxygen is regenerated.
  • the detergent or cleaning agent used in the liquor in addition to the polyoxometalate is therefore free of peroxygen compounds or contains only so much H 2 O 2 or H 2 O 2 -supplying substance in water that its concentration (calculated as H 2 O 2 ) in the liquor is 0.01 mmol / l to 0.5 mmol / l, in particular 0.06 mmol / l to 0.12 mmol / l.
  • the peroxygen compound used does not completely dissolve at the same time and the H 2 O 2 in the liquor can react as described, the attempt to measure the concentration of H 2 O 2 in the liquor used for washing or cleaning is not very useful; the concentration ranges given above therefore relate to the H 2 O 2 that can be arithmetically released from the total amount of added agent.
  • the invention further relates to a method for washing laundry and a method for cleaning hard surfaces, comprising the process steps (a) providing an aqueous liquor containing said polyoxometalate, and (b) bringing this liquor into contact 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.
  • the contact between the aqueous liquor and the object to be washed or cleaned is preferably established at temperatures in the range from 20 ° C. to 95 ° C., in particular from 30 ° C. to 60 ° C.
  • process steps (a) and (b) do not have to be carried out in succession, but rather occur simultaneously when the product to be cleaned is introduced into the machine and then an agent which contains the polyoxometalate is rinsed in with water.
  • the object to be washed or cleaned preferably remains in contact with the aqueous liquor over a period of 15 minutes to 2.5 hours, in particular 45 minutes to 1.5 hours.
  • the methods according to the invention can be carried out manually or using conventional devices, for example washing machines or dishwashers.
  • the amounts of polyxoxometalate used are selected such that their concentration in the liquor is preferably in the range from 0.05 ⁇ mol / l to 5 ⁇ m / l, in particular 0.1 ⁇ mol / l to 0.12 ⁇ mol / l.
  • concentrations of H 2 O 2 or in water in the liquor supplying H 2 O 2 also apply to preferred embodiments of the process according to the invention.
  • 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 cleaning agents which can be present in particular as powdery solids, in post-compacted particle form, as homogeneous solutions or as suspensions or dispersions, can, in addition to the bleach-boosting compound used according to the invention, in principle contain all known ingredients which are customary in such agents.
  • Solid agents which can be used in the context of the present invention are generally 0.0005% by weight to 4% by weight, preferably 0.00076% by weight to 0.4% by weight, and contain in particular 0.0015% by weight to 0.01% by weight of the polyoxometalate defined above.
  • liquid compositions which can be used in the context of the present invention, preference is given to 0.0005% by weight to 6% by weight, preferably 0.0006% by weight to 0.54% by weight, and in particular contain 0.001% by weight to 0.013% by weight of the polyoxometalate defined above.
  • the detergents and cleaning agents can contain, in particular, builder substances, 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 and colorants and fragrances.
  • Suitable peroxygen compounds which may additionally be present are in particular inorganic peroxygen compounds such as hydrogen peroxide and inorganic salts which give off 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 generated using an enzymatic system, i.e. 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 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 which, in principle, can contain all the usual washing or cleaning agent components.
  • Alkali percarbonate, alkali perborate monohydrate or hydrogen peroxide is particularly preferably used in the form of aqueous solutions which contain 3% by weight to 10% by weight of hydrogen peroxide.
  • a washing or cleaning agent used in the context of the invention contains peroxygen compounds, these are preferably in amounts of from 0.1% by weight to 50% by weight, in particular from 5% by weight to 20% by weight, and are particularly preferred from 7% by weight to 17% by weight and most preferably 8% by weight to 15% by weight.
  • the 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.
  • Usable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized.
  • the surfactants of the sulfate type 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 surfactants of the sulfonate type which can be used include linear alkylbenzenesulfonates with 9 to 14 C atoms in the alkyl part, alkanesulfonates with 12 to 18 C atoms, and olefin sulfonates with 12 to 18 C atoms which are formed in the reaction of corresponding monoolefins with sulfur trioxide, as well as alpha-sulfofatty acid esters, which arise in 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% by weight to 50% by weight, in particular 8% by weight to 30% by weight, while detergents for cleaning hard surfaces , in particular of dishes, 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 context of 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 carboxymethylinulins, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-dyuccinodiacetic acid and ethylenediaminodiacetic acid, methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), lysine tetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular polycarboxylates, polymeric acrylic acids,
  • 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, each based on 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 which the proportion of acid is at least 50 wt .-%.
  • Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as 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, maleic acid being particularly preferred.
  • the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C 1 -C 4 -carboxylic acids, with vinyl alcohol are particularly preferred.
  • Preferred polymers contain 60% by weight to 95% by weight, in particular 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 .-% vinyl alcohol and / or vinyl acetate.
  • Polymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleinate 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 lies. Both the amounts and the weight ratios are based on the acids.
  • the second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which, in the 2-position, has an alkyl radical, preferably 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 of (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.
  • the use of the third monomer presumably creates predetermined breaking points in 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 acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • the organic builder substances can be used, in particular for the production 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.
  • 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. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents.
  • Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate.
  • crystalline or amorphous, water-dispersible alkali alumosilicates are used as water-insoluble inorganic builder materials, in amounts of not more than 25% by weight, preferably from 3% by weight to 20% by weight and in particular in amounts of 5% by weight to 15% by weight. -% used.
  • the detergent-grade crystalline sodium aluminosilicates in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite X, are preferred. Amounts close to the above upper limit are preferably used in solid, particulate compositions.
  • Suitable aluminosilicates in particular have no particles with a grain size above 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m.
  • Your 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 preferably contained in amounts of from 1% by weight to 20% by weight, in particular from 5% by weight to 15% by weight.
  • the alkali silicates that can be used 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 can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8.
  • Crystalline phyllosilicates of the general formula Na 2 Si x O 2x + 1 .yH 2 O, in which x, the so-called modulus, is a number of 1, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates. 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
  • both ⁇ - and ⁇ -sodium disitikates Na 2 Si 2 O 5 .y H 2 O
  • Sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further embodiment of the agent.
  • a granular compound of alkali silicate and alkali carbonate as is commercially available, for example, under the name Nabion® 15.
  • Machine dishwashing detergents are preferably low 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% by weight. %, based on the total, may be included.
  • the use of the highly alkaline metasilicates as alkali carriers is preferably avoided entirely.
  • the alkali carrier system used with preference is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, which is contained in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight.
  • the ratio of carbonate and bicarbonate used varies, but an excess of sodium bicarbonate is usually used, so that the weight ratio between bicarbonate and carbonate is generally 1: 1 to 15: 1.
  • these contain 20% by weight to 40% by weight of water-soluble organic builders, in particular alkali citrate, 5% by weight to 15% by weight of alkali carbonate and 20% by weight to Contain 40 wt .-% alkali disilicate.
  • Enzymes which may be present in the 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 onto carrier substances in a conventional manner and / or embedded in coating substances or incorporated as concentrated liquid formulations which are as anhydrous 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, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Sodium carboxymethyl cellulose and mixtures thereof with methyl cellulose are preferably 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% by weight and is preferably 0.5% by weight to 1.5% by weight, in each case based on the composition.
  • Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts can be present as optical brighteners for textiles made in particular from cellulose fibers (for example cotton).
  • 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 compounds of the same structure are suitable Instead of the morpholino group, wear a diethanolamino group, a methylamino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted 4,4'-distyryl-diphenyl type may also 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 compounds of the same structure are particularly suitable for polyamide fibers.
  • the content of optical brighteners or brightener mixtures in the agent is generally not more than 1% by weight, preferably 0.05% by weight to 0.5% by weight.
  • the usual foam regulators which can be used in the compositions include, for example, polysiloxane-silica mixtures, the fine-particle 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 paraffin 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 C atoms, for example sodium behenate, and alkali metal 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 with 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 which can be used in the compositions include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers which can be derived from the compound classes mentioned.
  • 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 be 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, especially sulfuric acid or alkali hydrogen sulfates, or bases, especially ammonium or alkali hydroxides, contain.
  • Such pH regulators are preferably not contained in the agents above 10% by weight, in particular from 0.5% by weight to 6% by weight.
  • Agents 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 to an automatic mixer.
  • the synthesis was carried out analogously to the procedure under a) using adapted 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 adapted amounts of sodium metavanadate (3.66 g in 20 ml water) and sodium molybdate dihydrate (5.45 g in 15 ml water). 0.72 g of 9-molybdo-3-vanadophosphoric acid was obtained.
  • the molybdovanadophosphoric acid prepared in 2 b) was converted into sodium form by ion exchange via the ion exchange resin Amberlite IR-120
  • the Y values when using the active substance essential to the invention in the presence of air are greater than those in the presence of nitrogen; they are also larger than those which result when it is replaced by a known bleaching catalyst or when only the detergent is used, which corresponds to a higher degree of whiteness and thus improved stain removal.

Claims (9)

  1. Utilisation de polyoxométallates, choisis dans le groupe comprenant Na5[IMo6O24] • 3H2O, K5[SiW11VO40] • 12H2O, Na5PMo10V2O40 et des mélanges d'au moins deux d'entre eux, pour renforcer le pouvoir nettoyant d'agents de lavage ou de nettoyage dans un bain aqueux, en particulier contenant des tensioactifs, en présence d'une phase gazeuse qui est présente en plus de la phase liquide du bain et qui contient de l'oxygène moléculaire, en particulier de l'oxygène atmosphérique.
  2. Utilisation de polyoxométallates, choisis dans le groupe comprenant Na5[IMo6O24] • 3H2O, K5[SiW11VO40] • 12H2O, Na5PMo10V2O40 et des mélanges d'au moins deux d'entre eux, pour blanchir des taches colorées lors du lavage de textiles dans un bain aqueux, en particulier contenant des tensioactifs, ou dans des solutions nettoyantes aqueuses, en particulier contenant des tensioactifs, destinées à des surfaces dures, en particulier à de la vaisselle, pour blanchir des taches colorées, en particulier de thé, en présence d'une phase gazeuse qui est présente en plus de la phase liquide du bain et qui contient de l'oxygène moléculaire, en particulier de l'oxygène atmosphérique.
  3. Utilisation de polyoxométallates, choisis dans le groupe comprenant Na5[IMo6O24] • 3H2O, K5[SiW11VO40] • 12H2O, Na5PMo10V2O40 et des mélanges d'au moins deux d'entre eux, pour activer de l'oxygène moléculaire, en particulier de l'oxygène atmosphérique, lors du lavage de textiles ou du nettoyage de surfaces dures.
  4. Utilisation selon l'une des revendications 1 à 3, caractérisée en ce que, en plus du polyoxométallate, un agent de lavage ou de nettoyage exempt de composés peroxygénés est utilisé.
  5. Utilisation selon l'une des revendications 1 à 3, caractérisée en ce que, en plus du polyoxométallate, un agent de lavage ou de nettoyage est utilisé, lequel contient une quantité suffisante de H2O2 ou d'une substance libérant de l'H2O2 dans l'eau pour que sa concentration (exprimée en H2O2) dans le bain soit de 0,01 mmol/l à 0,5 mmol/l, en particulier de 0,06 mmol/l à 0,12 mmol/l.
  6. Procédé de lavage du linge, comprenant les étapes de procédé de (a) mise à disposition d'un bain aqueux contenant un polyoxométallate, choisi dans le groupe comprenant Na5[IMo6O24] • 3H2O, K5[SiW11VO40] • 12H2O, Na5PMo10V2O40 et des mélanges d'au moins deux d'entre eux, et de (b) mise en contact de ce bain avec des textiles à laver en présence d'une phase gazeuse qui est présente en plus de la phase liquide du bain aqueux et qui contient de l'oxygène moléculaire, en particulier de l'oxygène atmosphérique.
  7. Procédé de nettoyage de surfaces dures, comprenant les étapes de procédé de (a) mise à disposition d'un bain aqueux contenant un polyoxométallate, choisi dans le groupe comprenant Na5[IMo6O24] • 3H2O, K5[SiW11VO40] • 12H2O, Na5PMo10V2O40 et des mélanges d'au moins deux d'entre eux, et de (b) mise en contact de ce bain avec une surface dure à nettoyer en présence d'une phase gazeuse qui est présente en plus de la phase liquide du bain et qui contient de l'oxygène moléculaire, en particulier de l'oxygène atmosphérique.
  8. Procédé selon la revendication 6 ou 7, caractérisé en ce que le contact entre le bain aqueux et l'objet à laver ou à nettoyer se produit à des températures comprises entre 20 °C et 95 °C, en particulier entre 30 °C et 60 °C, et/ou en ce que l'objet à laver ou à nettoyer reste en contact avec le bain pendant une durée de 15 minutes à 2,5 heures, en particulier de 45 minutes à 1,5 heure.
  9. Procédé selon l'une des revendications 6 à 8, caractérisé en ce qu'une quantité suffisante de H2O2 ou d'une substance libérant de l'H2O2 dans l'eau est introduite dans le bain pour que sa concentration (exprimée en H2O2) soit de 0,01 mmol/l à 0,5 mmol/l, en particulier de 0,06 mmol/l à 0,12 mmol/l.
EP18172235.6A 2017-06-01 2018-05-15 Renforcement de l'effet de blanchiment lors du lavage et du nettoyage Active EP3409753B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102017209335.8A DE102017209335A1 (de) 2017-06-01 2017-06-01 Bleichverstärkung beim Waschen und Reinigen

Publications (2)

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

Family

ID=62167173

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18172235.6A Active EP3409753B1 (fr) 2017-06-01 2018-05-15 Renforcement de l'effet de blanchiment lors du lavage et du nettoyage

Country Status (2)

Country Link
EP (1) EP3409753B1 (fr)
DE (1) DE102017209335A1 (fr)

Family Cites Families (7)

* 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
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
EP3409753A1 (fr) 2018-12-05
DE102017209335A1 (de) 2018-12-06

Similar Documents

Publication Publication Date Title
EP2440641B1 (fr) Dioxyde de manganèse nanoparticulaire
DE102009001692A1 (de) Wasch- oder Reinigungsmittel mit gegebenenfalls in situ erzeugtem bleichverstärkendem Übergangsmetallkomplex
DE102009001691A1 (de) Wasch- oder Reinigungsmittel mit gegebenenfalls in situ erzeugtem bleichverstärkendem Übergangsmetallkomplex
EP2714877B1 (fr) Systèmes activateurs pour composés peroxygénés
DE19616767A1 (de) Bleichaktivatoren für Wasch- und Reinigungsmittel
EP2737042B1 (fr) Lessive ou produit de nettoyage présentant un composé médiateur activable électrochimiquement
EP1749084B1 (fr) Combinaison de renforcement d'agents de blanchiment a utiliser dans des produits de lavage et de nettoyage
EP2440644B1 (fr) Agent de blanchiment non agressif
EP3409753B1 (fr) Renforcement de l'effet de blanchiment lors du lavage et du nettoyage
EP3406698A1 (fr) Composition de blanchiment pour lavage ou nettoyage comprenant un précurseur d'oxaziridine
EP3415593B1 (fr) Renforcement de l'effet de blanchiment lors du lavage et du nettoyage
WO2008015074A1 (fr) Agent de lavage ou de nettoyage comprenant des particules de substance active blanchissante de taille optimisée
EP3409757B1 (fr) Composition detergente blanchissante
DE19619646A1 (de) Stabilisierung von Alkalipercarbonat
EP4061918B1 (fr) Activateur de blanchiment ayant un groupe cationique et produit détergent ou nettoyant le contenant
WO2017102475A1 (fr) Acylhydrazones comprenant des groupes pyridine
EP3440181B1 (fr) Acylhydrazones possédant des groupes n-méthylpipéridine
EP3289056B1 (fr) Utilisation des produits de lavage et de nettoyage contenant de la sulfobétaïne
DE102020203397A1 (de) Leistungsverstärkung beim Waschen und Reinigen
EP3409756A1 (fr) Composition detergente blanchissante
DE102014219228A1 (de) Proteinhaltige Waschmittel
EP0866116A2 (fr) Bisacylacetal dérivés comme activateurs de blanchiment pour les compositions détergentes à lessive
DE19858661A1 (de) Bisdiacylacetale als Bleichaktivatoren für Wasch- und Reinigungsmittel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180515

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20200110

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502018001238

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1260071

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200515

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200422

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200822

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200722

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200824

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200723

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200722

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502018001238

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200531

26N No opposition filed

Effective date: 20210125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200515

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200515

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200531

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210531

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20220520

Year of fee payment: 5

Ref country code: FR

Payment date: 20220525

Year of fee payment: 5

Ref country code: DE

Payment date: 20220519

Year of fee payment: 5

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502018001238

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20230515

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20231201

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230515