EP0850292B2 - Produit detergent inhibant le transfert de couleurs - Google Patents

Produit detergent inhibant le transfert de couleurs Download PDF

Info

Publication number
EP0850292B2
EP0850292B2 EP96924815A EP96924815A EP0850292B2 EP 0850292 B2 EP0850292 B2 EP 0850292B2 EP 96924815 A EP96924815 A EP 96924815A EP 96924815 A EP96924815 A EP 96924815A EP 0850292 B2 EP0850292 B2 EP 0850292B2
Authority
EP
European Patent Office
Prior art keywords
weight
detergent
laundry
polyvinyl pyrrolidone
active oxygen
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.)
Expired - Lifetime
Application number
EP96924815A
Other languages
German (de)
English (en)
Other versions
EP0850292B1 (fr
EP0850292A1 (fr
Inventor
Peter Sandkühler
Winfried Pochandke
Eduard Smulders
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7766057&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0850292(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0850292A1 publication Critical patent/EP0850292A1/fr
Publication of EP0850292B1 publication Critical patent/EP0850292B1/fr
Application granted granted Critical
Publication of EP0850292B2 publication Critical patent/EP0850292B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the invention relates to a detergent for use in washing processes for coloreds containing color transfer inhibitor and bleach and bleach activator, a process for washing colored laundry, a process for preventing hue changes and inhibiting color transfer, and the use of said laundry detergents in such processes.
  • Detergents for use in household washing processes for coloreds are as a rule free of bleaching agents in order to avoid the oxidative damage to the textile dyes.
  • color detergents are as a rule free of bleaching agents in order to avoid the oxidative damage to the textile dyes.
  • the use of bleach systems that is combinations of active oxygen compounds with peroxycarboxylic acid peeling off bleach activators, in laundry detergents extremely desirable because the cleaning effect of the detergent is increased by the bleaching effect on laundry dirt and the bleach can also act graying, germicidal and odor-repellent so that their use additionally increases hygiene during washing.
  • Color detergents normally contain agents for color transfer inhibition in order to prevent the discoloration of laundry parts, that is, a transfer of dyes that have been detached from the coloreds and get into the wash liquor, on different colored textiles. It is believed that such dye transfer inhibiting agents complex and stabilize the dyes in the wash liquor.
  • Polyvinylpyrrolidone is known to be one of the most effective color transfer inhibitors.
  • the European patent application EP 0 508 034 A1 discloses granular detergents which contain surfactant, builder, polyvinylpyrrolidone having molecular weights of 5,000 to 22,000 and up to 15% by weight of inorganic filler salt and which result in polyvinylpyrrolidone concentrations of 5 mg / l to 500 mg / l in the wash solution may contain peroxygen bleach and bleach activator.
  • the not pre-published European patent application EP 0 717 103 A2 relates to laundry detergents containing from 5% to 90% by weight of anionic and / or nonionic surfactant, from 5% to 70% by weight of builder, from 0.1% to 30% by weight of peroxygen compound and 0.005 wt .-% to 2 wt .-% of a manganese-containing complex, wherein the agent additionally polyvinylpyrrolidone in amounts of 0.05 wt .-% to 5 wt .-% have.
  • Another object of the invention is a process for washing colored laundry, alone or in combination with white laundry, in aqueous, surfactant-containing liquor using such agent or all its individual components, which is characterized in that the wash liquor at least temporarily a concentration of Polyvinylpyrrolidone in the range of 0.01 g / l to 1 g / l, in particular from 0.05 g / l to 0.2 g / l, and an active oxygen concentration in the range of 0.01 g / l to 0.2 g / l, in particular from 0.03 g / l to 0.15 g / l.
  • a modification of such a method consists in a method for preventing hue changes and inhibiting the color transfer to white or other colored laundry when washing colored laundry, alone or in combination with white laundry, in aqueous, surfactant-containing liquor, which is characterized in that Wash liquor at least temporarily a concentration of polyvinylpyrrolidone in the range of 0.01 g / l to 1 g / l, in particular from 0.05 g / l to 0.2 g / l, and a concentration of active oxygen in the range of 0.01 g / l to 0.2 g / l, in particular from 0.03 g / l to 0.15 g / l.
  • the concentrations of polyvinylpyrrolidone and active oxygen in the wash liquor are maintained for a period of from 5 minutes to 90 minutes, more preferably from 10 minutes to 70 minutes.
  • the said processes are carried out so that the wash liquor has a temperature of up to 60 ° C, in particular in the range of 30 ° C to 60 ° C.
  • the components can also be metered individually into the liquor, which is preferably present in a household washing machine.
  • Color transfer inhibiting polyvinylpyrrolidone may be in inventive compositions which are liquid, pasty or solid, which in non-exhaustive list both powdery and compacted, extruded and tableted agents are to be understood, preferably in amounts of 0.1 wt .-% to 5 wt .-%, in particular 0.4 wt .-% to 2.5 wt .-% contain. It preferably has a molecular weight in the range of 5,000 to 4,000,000, in particular in the range of 10,000 to 100,000.
  • Active oxygen-based bleaches are preferably present in the composition according to the invention in amounts of 5% by weight to 25% by weight, in particular 6% by weight to 15% by weight.
  • Suitable bleaching agents include the peroxygen compounds commonly used in detergents, such as hydrogen peroxide and perborate, which may be in the form of tetra- or monohydrate, percarbonate, per-pyrophosphate and persilicate, which are present as alkali salts, usually as sodium salts.
  • hydrogen peroxide, alkali metal perborate monohydrate and / or alkali metal percarbonate is used.
  • peroxycarboxylic acid releasing bleach activator is preferably present in the inventive compositions in amounts of 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 7 wt .-%.
  • Such bleach activators include the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, as described, for example, in US Pat German patent applications DE 14 67 582 or DE 43 38 920 Hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and lactams, such as those from the international Patent Application WO 95/00626 known N-acyl-valerolactam or the example of the international Patent Applications WO 94/27970 .
  • N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N
  • WO 94/28103 and WO 94/28105 known N-acyl-caprolactams, in addition carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonat, and acylated sugar derivatives, especially pentaacetylglucose.
  • carboxylic acid anhydrides in particular phthalic anhydride
  • carboxylic acid esters in particular sodium isononanoyl-phenolsulfonat
  • acylated sugar derivatives especially pentaacetylglucose.
  • the bleach activator is preferably selected from the aliphatic, cycloaliphatic or aromatic peroxocarboxylic acid which is linear or branched under perhydrolysis conditions and has compounds which split off from 2 to 12 carbon atoms and mixtures thereof.
  • the bleach activators in particular for use in solid or powdery agents, may have been coated or granulated in a known manner with shell substances to avoid interaction with the per compounds, with granular tetraacetylethylenediamine having mean particle sizes of 0.01 mm to 0.9 mm with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine 0.8 mm, as for example according to the European patent EP 037 026 and / or granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as described in the German patent DD 255 884 is particularly preferred.
  • compositions are not limited, but since the agents according to the invention are those for use in washing processes for coloreds, they are preferably free from optical brighteners.
  • Surfactants in particular anionic and / or nonionic surfactants, are described in US Pat agents according to the invention in amounts of from 8% by weight to 30% by weight, in particular 12% by weight to 24% by weight, it being to be noted that the amount of nonionic surfactant exceeds the stated upper limit of 8 Wt .-%, based on the total mean, does not exceed.
  • Suitable nonionic surfactants include the alkoxylates, especially the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
  • the degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 14 and in particular between 6 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
  • Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates.
  • alkoxylates in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof.
  • suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part usable.
  • the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters as described in the international Patent Application WO 90/13533 as well as fatty acid polyhydroxyamides, as prepared according to the methods of U.S. Pat. Nos. 1,985,424 .
  • Nonionic surfactants of the so-called alkylpolyglycoside type which are suitable for incorporation in the agents according to the invention are compounds of the general formula (G) n -OR 1 , in which R 1 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is one Number between 1 and 10 mean.
  • the glycoside component (G) n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomermaschinesgrad.
  • the degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4.
  • Preferred monomer building block is glucose because of its good availability.
  • the alkyl or alkenyl moiety R 1 of the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can be used to prepare useful glycosides. Also useful in this case are the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and also mixtures thereof.
  • Nonionic surfactant is preferably contained in an agent according to the invention in amounts of from 2% by weight to 8% by weight, in particular from 3% by weight to 7% by weight.
  • compositions according to the invention may instead or additionally comprise further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably up to 22% by weight, in particular from 7% by weight to 18% by weight, in each case based on the total Means, included.
  • Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation.
  • alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • a conventional sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
  • alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases Such alkyl and / or alkenyl sulfates are preferably present in the compositions according to the invention in amounts of from 7% by weight to 18% by weight, in particular from 8% by weight to 15% by weight.
  • Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates.
  • ether sulfates preferably contain from 1 to 30, in particular from 2 to 10, ethylene glycol groups per molecule.
  • Suitable anionic surfactants of the sulfonate type include the ⁇ -sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids.
  • nonionic surfactant and synthetic anionic surfactant are present, their weight ratio in the composition according to the invention is preferably from 1: 8 to 1: 2, in particular from 1: 6 to 1: 3.
  • soaps saturated fatty acid soaps, as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, derived soaps are suitable.
  • those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C 12 -C 18 fatty acid soaps and up to 50% by weight of unsaturated soaps, for example, oleic acid soap.
  • soap is included in amounts up to 5% by weight, especially from 0.1% to 2% by weight.
  • higher amounts of soap of usually up to 15 wt .-% may be included.
  • compositions of the invention often include soil release agents known as soil release agents.
  • soil release agents include copolyesters which contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units and which, because of their chemical similarity to polyester fibers, are particularly effective for washing textiles of this material but can also exhibit the desired effect on fabrics of other materials.
  • Dirt-releasing copolyesters of the type mentioned as well as their use in detergents have been known for a long time.
  • German Offenlegungsschrift DT describes 16 17 141 a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers.
  • German patent application DT 22 00 911 relates to detergents containing nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate.
  • German Offenlegungsschrift DT 22 53 063 are called acidic textile finishing agents containing a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol.
  • European patent EP 185 427 For example, methyl or ethyl group-endcapped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and laundry detergents containing such soil release polymer are known.
  • the European patent EP 241 984 relates to a polyester which in addition to oxyethylene groups and terephthalic acid units also contains substituted ethylene units and glycerol units.
  • Such soil-release polyesters are preferably present in agents according to the invention in amounts of from 0.25% by weight to 5% by weight, in particular from 0.5% by weight to 1.5% by weight.
  • compositions of the invention include water-soluble and / or water-insoluble builders, in particular selected from alkali metal aluminosilicate, crystalline or amorphous alkali metal silicate, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof.
  • An agent according to the invention preferably contains from 20% by weight to 45% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders.
  • the water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and the polymeric (poly) carbon acids, in particular the polycarboxylates of the international, which are obtainable by oxidation of polysaccharides Patent Application WO 93/16110 , polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances copolymerized without carboxylic acid functionality.
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, 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.
  • vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene
  • Preferred terpolymers contain 60 wt .-% to 95 wt .-%, in particular 70 wt .-% to 90 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate.
  • polymers may also be a derivative of an allylsulfonic acid as a monomer, which is substituted in position 2 with an alkyl radical, preferably with a C 1 -C 4 alkyl radical, or an aromatic radical which is derived preferably from benzene or benzene derivatives is.
  • Preferred polymers then contain 40 wt .-% to 60 wt .-%, in particular 45 to 55 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10 wt .-% to 30 wt.
  • % preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate.
  • This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
  • terpolymers can be prepared in particular by methods which are described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 are generally described, and generally have a molecular weight between 1000 and 200,000, preferably between 200 and 50,000 and in particular between 3000 and 10,000. All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts, and 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.
  • Such organic builders are preferably in amounts up to 15 wt .-%, in particular to to 12 wt .-% and particularly preferably from 2 wt .-% to 10 wt .-%. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.
  • Water-insoluble, water-dispersible, crystalline or amorphous alkali metal aluminosilicates in amounts of up to 35% by weight, preferably from 10% by weight to 30% by weight, and in liquid agents, in particular from 5% by weight, are used as inorganic builder materials 20 wt .-%, used.
  • the detergent-grade crystalline alkali metal aluminosilicates particularly zeolite A, zeolite P and optionally zeolite X, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Their calcium binding capacity which according to the data of German patent DE 24 12 837 can be determined ranges from 100 to 200 mg Ca0 per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline or amorphous alkali silicates which may be present alone or in a mixture with one another.
  • the alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali oxide to SiO 2 of from 1: 1.1 to 1:12.
  • 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.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil (R) .
  • Those with a molar ratio Na 2 O: SiO 2 of 1: 1.9 to 1: 2.8 can be prepared by the process of European patent application EP 0 425 427 getting produced.
  • the crystalline silicates crystalline layer silicates corresponding to general formula are preferably Na 2 Si x O 2x + 1 ⁇ yH 2 O used in the x, the so-called module is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula, for example, in the European Patent Application EP 0 164 514 described.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both ⁇ - and Sodium disilicates (Na 2 Si 2 O 5 .yH 2 O) are preferred.
  • Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5 are used in a further preferred embodiment of detergents according to the invention which contain a polymer according to the invention.
  • the content of alkali metal silicates, in particular in the case of solid compositions according to the invention, is preferably 5% by weight to 30% by weight and in particular 7% by weight to 20% by weight, based on anhydrous active substance.
  • alkali metal aluminosilicate in particular zeolite
  • the content of alkali metal silicate is preferably from 5% by weight to 20% by weight and in particular from 7% by weight to 15% by weight, based on anhydrous active substance.
  • the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 1: 2 to 2: 1.
  • the agents may contain other ingredients common in detergents.
  • these optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, grayness inhibitors, for example cellulose ethers, foam inhibitors, for example organopolysiloxanes or paraffins, and solvents and dyes and fragrances.
  • Solvents which are used in particular in liquid agents according to the invention are, in addition to water, preferably those which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether.
  • lower alcohols for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether.
  • Suitable optionally contained enzymes are in particular those from the class of proteases, lipases, cutinases, amylases, pullulanases, cellulases, hemicellulases, oxidases and peroxidases and mixtures thereof.
  • derived from fungi or bacterial strains enzymatic agents are used. They can be obtained in a known manner by fermentation processes from suitable microorganisms.
  • Proteases are commercially available, for example, under the names BLAP (R), Savinase (R), Esperase (R), Maxatase (R), Optimase.RTM (R), Alcalase (R), Durazym (R) or Maxapem (R) are available.
  • the lipase which can be used can be obtained, for example, from Humicola lanuginosa, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species.
  • Suitable lipases are known, for example, under the names Lipolase (R) , Lipozyme (R) , Lipomax (R) , Amano (R) lipase, Toyo-Jozo (R) lipase, Meito (R) lipase and Diosynth (R) . Lipase commercially available.
  • Suitable amylases are, for example, commercially available under the names Maxamyl (R) , Duramyl (R) and Termamyl (R) .
  • the usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5.
  • Such cellulases are for example from the German Offenlegungsschriften DE 31 17 250 . DE 32 07 825 . DE 32 07 847 . DE 33 22 950 or the European patent applications EP 265 832 . EP 269 977 . EP 270 974 . EP 273 125 such as EP 339,550 known.
  • Commercially available cellulases are Celluzyme (R) and Carezyme (R) from Novo Nordisk and KAC (R) from Kao.
  • usual enzyme stabilizers include amino alcohols, such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, such as from the European patent applications EP 376,705 and EP 378,261 Boric acid or alkali borates, boric acid-carboxylic acid combinations, such as from the European patent application EP 451 924 known, boric acid esters, such as from the international Patent Application WO 93/11215 or the European patent application EP 511 456 known boronic acid derivatives, such as from the European patent application EP 583 536 known, calcium salts, for example from the European patent EP 28,865 known Ca-formic acid combination, magnesium salts, such as from the European patent application EP 378 262 known, and / or sulfur-containing reducing agents, such as from the European patent applications EP 080 748 or EP 080 223 known.
  • amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof
  • lower carboxylic acids
  • Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances, such as in the German Offenlegungsschrift DE 34 36 194 , the European patent applications EP 262 588 . EP 301 414 . EP 309 931 or the European patent specification EP 150 386 described.
  • an agent according to the invention may contain graying inhibitors.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the graying of the fibers.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, 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.
  • particulate compositions according to the invention can be carried out in the simplest manner by mixing the individual particles in a conventional mixer, in particular a drum, roller, belt or free-fall mixer, whereby optional other pulverulent constituents and, if desired, also liquid or liquefied constituents, to which in particular nonionic surfactants , but also colorants and fragrances may be added by spraying. It is preferred to convert the thermally loadable components in a manner known in principle by spray-drying an aqueous slurry into a particulate product and, if appropriate, to mix this with thermally sensitive constituents, to which in particular the bleaching agents are to be expected.
  • a conventional mixer in particular a drum, roller, belt or free-fall mixer
  • Granular high-density detergents according to the invention may preferably be prepared according to the method of International Patent Application WO 91/02047 getting produced. This is the strand-like compression of a homogeneous premix of detergent ingredients via hole-forming, which preferably have an opening width of 0.5 mm to 5 mm, followed by comminuting the extrudate and subsequent treatment in a Rondier réelle, which leads to substantially uniformly spherical products. Granular particles having bulk densities of generally 700 g / l to 1050 g / l are obtained by the compacting extrusion step. These may be complete washing or cleaning agents or components of such agents, which are completed by admixing usually not co-extrudable further components, such as solid or formulated foam regulators or enzymes in solid form.
  • a powdered detergent ( BW ) of the composition given in Table 1 below was used alone and after addition of 1.2% by weight of polyvinylpyrrolidone having an average molar mass of about 40,000 ( V1 ), 8% by weight perborate monohydrate and 2 %
  • TAED 0.2% by weight of polyvinylpyrrolidone and 8% by weight of perborate monohydrate ( V3 ) and 1.2% by weight of polyvinylpyrrolidone, 8% by weight of perborate monohydrate and 2% by weight of TAED ( M1 ) on the ability to prevent "staining" (transfer of textile dye from dyed textile to white textile in the common wash).
  • Table 1 Composition [% by weight] BW Na dodecylbenzenesulfonate 13 Nonionic surfactant a) 1 Nonionic surfactant b) 5 Soap 2 citric acid 3 polymeric polycarboxylate 4 Zeolite Na-A 38 sodium silicate 1 sodium 13 Water and sodium sulfate on 100 a) 5-fold ethoxylated C 16/18 fatty alcohol b) 7-ethoxylated C 12/18 fatty alcohol Bleeding [dE] after washing at 40 ° C dyed textile BW V1 V2 V3 M1 Jeans, dark brown 16.1 14.4 16.2 13.7 12.6 Jeans, blackberry 12.6 5.7 12.8 4.6 4.3 Corduroy pants, red 7.1 4.7 6.9 5.5 4.8 Bleeding [dE] after washing at 60 ° C dyed textile BW V1 V2 V3 M1 Sweatshirt, dark green 13.5 14.8 14.9 13.1 11.9 Jeans, blackberry 21.1 9.6 22.7 9.4 9.4 Bath towel,

Landscapes

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

Claims (15)

  1. Produit détergent inhibant le transfert de couleurs, contenant un agent tensioactif, de la polyvinylpyrrolidone, un agent de blanchiment à base d'oxygène actif et un activateur du blanchiment dégageant de l'acide peroxycarboxylique dans des conditions de perhydrolyse, caractérisé en ce qu'il contient de 8 % en poids à 30 % en poids d'agent tensioactif, dont de l'agent tensioactif non ionique en des quantités jusqu'à 8 % en poids, et le rapport pondéral de l'activateur de blanchiment à la polyvinylpyrrolidone se situe en dessous de 5, ledit produit détergent ne présentant pas la composition suivante : LAS - C45 AS 7 C24 AS - TAS - 45E7 7 25E3 - Glucamide - Zéolithe MAP 38 Na SKS-6 5 Citrate 10 Carbonate 7 Silicate (dans le rapport 2,0) - PC3 14 PB1 - PB4 - TAED 2,5 Protéase (Alcalase®) 2,0 Amylase (Termamyl®) 0,4 Lipase (lipolyse®) 0,4 PVP 1,0 PVNO - PVPVI - MnPC - EDTMP 0,1 CMC 0,8 Agent antimousse Eclaircissant optique 1 - Eclaircissant optique 2 0,2 Eclaircissant optique 3 - Humidité, sulfates et analogues 6,6 100
    avec les significations suivantes
    LAS alkyl(en C12)benzènesulfonate linéaire
    AS alkylsulfate de sodium
    TAS alcool de suif-sulfate de sodium
    45E7 alcool primaire en C14-C15 condensé avec une moyenne de 7 mol d'oxyde d'éthylène
    25E3 alcool primaire en C12-C15 condensé avec une moyenne de 3 mol d'oxyde d'éthylène
    PC3 percarbonate
    PB 1 perborate monohydraté
    PB4 perborate tétrahydraté
    TAED tétra-acétyléthylènediamine
    PVP polyvinylpyrrolidone
    PVNO N-oxyde de polyvinylpyridine
    PVPVI copolymère de polyvinylpyrrolidone- polyvinylimidazole
    MnPC phtalocyaninetétrasulfonate de manganèse
    EDTMP éthylènediamine-tétraméthylène-phosphonate
    CMC carboxyméthylcellulose
    Figure imgb0005
     Eclaircissant optique 1 : R = un groupe diéthanolamino et R2 = un groupe SO3Na
    Eclaircissant optique 2 : R = un groupe morpholino et R2 = un groupe SO3Na
    Eclaircissant optique 3 : R = un groupe anilino, R2 = un groupe SO3Na ou un atome d'hydrogène.
  2. Produit selon la revendication 1,
    caractérisé en ce que
    le rapport pondéral de l'activateur de blanchiment à la polyvinyl pyrrolidone est inférieur à 4 et est en particulier compris entre 0,5 et 3,5.
  3. Produit selon la revendication 1 ou 2,
    caractérisé en ce qu'
    il contient de 0,1 % en poids à 5 % en poids, en particulier de 0,4 % en poids à 2,5 % en poids de polyvinylpyrrolidone.
  4. Produit selon l'une quelconque des revendications 1 à 3,
    caractérisé en ce que
    la polyvinylpyrrolidone présente une masse molaire entre 5000 et 4 millions, en particulier entre 10 000 et 100 000.
  5. Produit selon l'une quelconque des revendications 1 à 4,
    caractérisé en ce qu'
    il contient de 5 % en poids à 25 % en poids, en particulier de 6 % à 15 % en poids d'agent de blanchiment à base d'oxygène actif.
  6. Produit selon l'une quelconque des revendications 1 à 5,
    caractérisé en ce que
    l'agent de blanchiment à base d'oxygène actif est choisi parmi le peroxyde d'hydrogène, un perborate de métal alcalin monohydraté, un perborate de métal alcalin et leurs mélanges.
  7. Produit selon l'une quelconque des revendications 2 à 6,
    caractérisé en ce qu'
    il contient de 0,5 % en poids à 10 % en poids, en particulier de 1 % en poids à 7 % en poids d'activateur de blanchiment.
  8. Produit selon l'une quelconque des revendications 2 à 7,
    caractérisé en ce que
    l'activateur de blanchiment est choisi parmi les composés et leurs mélanges dégageant dans les conditions de la perhydrolyse, des acides peroxocarboxyliques, aliphatiques, cycloaliphatiques ou aromatiques, linéaires ou à chaîne ramifiée, ayant de 2 à 12 atomes de C.
  9. Produit selon l'une quelconque des revendications 1 à 8,
    caractérisé en ce qu'
    il est dépourvu d'éclaircissants optiques.
  10. Procédé de lavage de lessive colorée, seul ou en combinaison avec de la lessive blanche, dans un bain aqueux contenant un agent tensioactif, avec utilisation d'un produit selon l'une des revendications 1 à 9 ou l'ensemble de leurs divers composants dans les rapports pondéraux mentionnés,
    caractérisé en ce que
    le bain de lavage présente au moins temporairement une concentration en polyvinylpyrrolidone comprise entre 0,01 g/l et 1 g/l, en particulier entre 0,05 g/l et 0,2 g/l, et une concentration d'oxygène actif comprise entre 0,01 g/l et 0,2 g/l, en particulier entre 0,03 g/l et 0,15 g/l.
  11. Procédé d'inhibition des modifications de nuances de couleur et d'inhibition du transfert de couleurs sur la lessive blanche ou d'une autre couleur lors du lavage d'une lessive colorée, selon une combinaison avec une lessive blanche, dans un bain aqueux contenant un agent tensioactif avec utilisation d'un produit selon l'une des revendications 1 à 9 ou de l'ensemble de ses divers composants dans les rapports pondéraux mentionnés,
    caractérisé en ce que
    le bain de lavage présente au moins temporairement une concentration en polyvinylpyrrolidone comprise entre 0,01 g/l et 1 g/l, et en particulier entre 0,05 g/l et 0,2 g/l, et une concentration en oxygène actif comprise entre 0,01 g/l et 0,2 g/l, en particulier entre 0,03 g/l et 0,15 g/l.
  12. Procédé selon la revendication 10 ou 11,
    caractérisé en ce que
    la concentration en polyvinyl pyrrolidone et en oxygène actif est maintenue pendant un intervalle de 5 minutes à 90 minutes, en particulier de 10 minutes à 70 minutes.
  13. Procédé selon l'une quelconque des revendications 10 à 12,
    caractérisé en ce que
    l'action de l'oxygène actif est renforcée par la formation in situ d'acide peroxocarboxylique dans le bain de lavage constitué d'agents de blanchiments à base d'oxygène actif et d'activateur de blanchiment.
  14. Procédé selon l'une quelconque des revendications 10 à 13,
    caractérisé en ce que
    le bain de lavage présente une température allant jusqu'à 60°C, en particulier comprise entre 30 et 60°C.
  15. Utilisation d'un produit selon l'une des revendications 1 à 9,
    dans un procédé de lavage de lessive colorée, ou d'inhibition des modifications de nuances de couleur ou d'inhibition du transfert de couleur sur la lessive blanche ou d'une autre couleur lors du lavage d'une lessive colorée.
EP96924815A 1995-07-07 1996-06-29 Produit detergent inhibant le transfert de couleurs Expired - Lifetime EP0850292B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19524451 1995-07-07
DE19524451A DE19524451A1 (de) 1995-07-07 1995-07-07 Farbübertragungsinhibierendes Waschmittel
PCT/EP1996/002847 WO1997003166A1 (fr) 1995-07-07 1996-06-29 Produit detergent inhibant le transfert de couleurs

Publications (3)

Publication Number Publication Date
EP0850292A1 EP0850292A1 (fr) 1998-07-01
EP0850292B1 EP0850292B1 (fr) 2001-04-11
EP0850292B2 true EP0850292B2 (fr) 2010-12-29

Family

ID=7766057

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96924815A Expired - Lifetime EP0850292B2 (fr) 1995-07-07 1996-06-29 Produit detergent inhibant le transfert de couleurs

Country Status (5)

Country Link
EP (1) EP0850292B2 (fr)
AT (1) ATE200513T1 (fr)
DE (2) DE19524451A1 (fr)
ES (1) ES2156285T5 (fr)
WO (1) WO1997003166A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0229146D0 (en) 2002-12-13 2003-01-15 Unilever Plc Polymers and laundry detergent compositions containing them
GB0229147D0 (en) 2002-12-13 2003-01-15 Unilever Plc Polymers and laundry detergent compositions containing them

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3535516A1 (de) † 1985-10-04 1987-04-09 Fritz Buchner Tablettenfoermiges wasch- und reinigungsmittel, verfahren zu seiner herstellung und seine verwendung
EP0265257A2 (fr) † 1986-10-24 1988-04-27 Unilever Plc Composition détergente
EP0508034A1 (fr) † 1991-04-12 1992-10-14 The Procter & Gamble Company Composition détergente contenant des polyvinylpyrrolidones
EP0540784A1 (fr) † 1991-11-06 1993-05-12 The Procter & Gamble Company Compositions empêchant le transfert de colorant
US5259994A (en) † 1992-08-03 1993-11-09 The Procter & Gamble Company Particulate laundry detergent compositions with polyvinyl pyrollidone
WO1995002675A1 (fr) † 1993-07-12 1995-01-26 Novo Nordisk A/S Composition detersive comprenant deux cellulases
WO1995017496A1 (fr) † 1993-12-21 1995-06-29 The Procter & Gamble Company Compositions inhibant le transfert de colorant et contenant de la protease
WO1995027028A1 (fr) † 1994-03-31 1995-10-12 The Procter & Gamble Company Compositions detergentes

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69327654T2 (de) * 1993-11-11 2000-08-31 The Procter & Gamble Company, Cincinnati Beim Waschen weichmachende Zusammensetzungen
GB9425296D0 (en) * 1994-12-15 1995-02-15 Ciba Geigy Ag Inhibition of dye migration

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3535516A1 (de) † 1985-10-04 1987-04-09 Fritz Buchner Tablettenfoermiges wasch- und reinigungsmittel, verfahren zu seiner herstellung und seine verwendung
EP0265257A2 (fr) † 1986-10-24 1988-04-27 Unilever Plc Composition détergente
EP0508034A1 (fr) † 1991-04-12 1992-10-14 The Procter & Gamble Company Composition détergente contenant des polyvinylpyrrolidones
EP0540784A1 (fr) † 1991-11-06 1993-05-12 The Procter & Gamble Company Compositions empêchant le transfert de colorant
US5259994A (en) † 1992-08-03 1993-11-09 The Procter & Gamble Company Particulate laundry detergent compositions with polyvinyl pyrollidone
WO1995002675A1 (fr) † 1993-07-12 1995-01-26 Novo Nordisk A/S Composition detersive comprenant deux cellulases
WO1995017496A1 (fr) † 1993-12-21 1995-06-29 The Procter & Gamble Company Compositions inhibant le transfert de colorant et contenant de la protease
WO1995027028A1 (fr) † 1994-03-31 1995-10-12 The Procter & Gamble Company Compositions detergentes

Also Published As

Publication number Publication date
WO1997003166A1 (fr) 1997-01-30
EP0850292B1 (fr) 2001-04-11
ES2156285T3 (es) 2001-06-16
DE59606783D1 (de) 2001-05-17
ES2156285T5 (es) 2011-04-25
EP0850292A1 (fr) 1998-07-01
ATE200513T1 (de) 2001-04-15
DE19524451A1 (de) 1997-01-09

Similar Documents

Publication Publication Date Title
EP0767830B1 (fr) Production de granules d'enzymes multiples
EP0759947B1 (fr) Polyesters facilitant le lavage
EP3810742B1 (fr) Carbamates de xylose utilisés comme agents antisalissures
EP4100498B1 (fr) Dérivés de chitosane en tant qu'agents anti-salissures
EP3049508B1 (fr) Carbamates de cellulose utilisés comme principes actifs ayant la capacité de dissoudre les saletés
DE4440956A1 (de) Schmutzabweisendes Waschmittel mit bestimmter Tensidkombination
EP1888732B1 (fr) Renforcement du pouvoir detersif de detergents par l'intermediaire d'un polymere
EP1592763B2 (fr) Detergent contenant un agent de blanchiment et un derive de cellulose facilitant l'elimination des salissures sur les textiles en coton
EP3280788B1 (fr) Détergents et produits de nettoyage à principe actif polymère
EP1592765B1 (fr) Augmentation de la puissance de nettoyage de produits de lavage a l'aide d'un derive cellulosique et d'un polymere hygroscopique
EP0698079B1 (fr) Produits de lavage et de nettoyage contenant une lipase
EP0822973B1 (fr) Detergents contenant de la cellulase
DE10037126A1 (de) Cellulasehaltiges Waschmittel
EP3083918B1 (fr) Copolymères comprenant des groupes siloxane, utilisés comme agents antisalissures
EP0767829B1 (fr) Production des granules d'enzymes multiples et leur utilisation
EP0850292B2 (fr) Produit detergent inhibant le transfert de couleurs
DE102015004400A1 (de) Wasch- und Reinigungsmittel mit polymerem Wirkstoff
EP0944701A1 (fr) Polymeres facilitant le lavage, agissant sur le coton
EP3004312B1 (fr) Substances actives polymères contenant des groupes sulfonates améliorant le pouvoir lavant primaire
EP0753046B1 (fr) Detergent a base de lipases
DE19804656A1 (de) Cellulasehaltiges Waschmittel
DE102004063766A1 (de) Verwendung von polyglykolether-modifiziertem Polysaccharid als schmutzablösevermögender Waschmittelzusatz
EP3227423B1 (fr) Compositions détergentes comprenant un agent actif polymère
DE10112136A1 (de) Verhinderung von Textilschäden beim Waschen
DE10062008B4 (de) Farbschonendes Waschmittel

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

17P Request for examination filed

Effective date: 19971219

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE ES FR IT NL

17Q First examination report despatched

Effective date: 19981023

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE ES FR IT NL

REF Corresponds to:

Ref document number: 200513

Country of ref document: AT

Date of ref document: 20010415

Kind code of ref document: T

ET Fr: translation filed
REF Corresponds to:

Ref document number: 59606783

Country of ref document: DE

Date of ref document: 20010517

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2156285

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed
PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: UNILEVER N.V.

Effective date: 20020110

NLR1 Nl: opposition has been filed with the epo

Opponent name: UNILEVER N.V.

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: UNILEVER N.V.

Effective date: 20020110

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20070228

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

Ref country code: FR

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

Effective date: 20060630

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: HENKEL AG & CO. KGAA

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: HENKEL AG & CO. KGAA

Effective date: 20080611

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: UNILEVER N.V.

Effective date: 20020110

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20101229

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AT BE DE ES FR IT NL

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Ref document number: 2156285

Country of ref document: ES

Kind code of ref document: T5

Effective date: 20110425

REG Reference to a national code

Ref country code: FR

Ref legal event code: RN

Effective date: 20121112

REG Reference to a national code

Ref country code: FR

Ref legal event code: D3

Effective date: 20130123

PGRI Patent reinstated in contracting state [announced from national office to epo]

Ref country code: FR

Effective date: 20130123

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

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

Ref country code: ES

Payment date: 20150626

Year of fee payment: 20

Ref country code: DE

Payment date: 20150619

Year of fee payment: 20

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

Ref country code: AT

Payment date: 20150619

Year of fee payment: 20

Ref country code: FR

Payment date: 20150619

Year of fee payment: 20

Ref country code: NL

Payment date: 20150618

Year of fee payment: 20

Ref country code: BE

Payment date: 20150618

Year of fee payment: 20

Ref country code: IT

Payment date: 20150622

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59606783

Country of ref document: DE

Ref country code: NL

Ref legal event code: MK

Effective date: 20160628

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK07

Ref document number: 200513

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160629

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20161006

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

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20160630