EP0888449B1 - Detergent et nettoyant solide a masse volumique apparente elevee contenant des tensioactifs et des adjuvants, et compose approprie - Google Patents

Detergent et nettoyant solide a masse volumique apparente elevee contenant des tensioactifs et des adjuvants, et compose approprie Download PDF

Info

Publication number
EP0888449B1
EP0888449B1 EP97907093A EP97907093A EP0888449B1 EP 0888449 B1 EP0888449 B1 EP 0888449B1 EP 97907093 A EP97907093 A EP 97907093A EP 97907093 A EP97907093 A EP 97907093A EP 0888449 B1 EP0888449 B1 EP 0888449B1
Authority
EP
European Patent Office
Prior art keywords
weight
zeolite
detergent
alkyl
water
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.)
Revoked
Application number
EP97907093A
Other languages
German (de)
English (en)
Other versions
EP0888449A1 (fr
Inventor
Katrin Burmeister
Roswitha Pawelczyk
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=7788887&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0888449(B1) "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 EP0888449A1 publication Critical patent/EP0888449A1/fr
Application granted granted Critical
Publication of EP0888449B1 publication Critical patent/EP0888449B1/fr
Anticipated expiration legal-status Critical
Revoked 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D3/08—Silicates
    • 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
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to a solid detergent and builder-containing detergent and cleaning agent with a high bulk density or compound therefor, which contains water-soluble silicate and zeolite as a builder and C 9 -C 13 alkylbenzenesulfonates and C 8 -C 22 alkyl sulfates as anionic surfactants.
  • zeolite in particular, are used as inorganic builder substances Zeolite NaA and Zeolite P, and alkali silicates used.
  • inorganic builder substances Zeolite NaA and Zeolite P
  • alkali silicates used.
  • mixtures of zeolite with alkali silicates and alkali carbonates are used and organic builders, such as polymeric carboxylates.
  • EP-A-0 291 869 describes combinations of builders from zeolite, aminoalkane polyphosphonate and / or polymeric polycarboxylate and 1-hydroxyethane-1,1-diphosphonate (HEDP), with certain weight ratios of the last three components a synergism regarding the change in the training of Show fiber incrustations.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • crystalline, layered sodium silicates as a builder is described, for example, in European patent application EP-A-164 514, which discloses a builder combination which mainly contains crystalline sheet silicates of the formula (I) NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • layered silicates can be used as water softeners both separately and in detergents and cleaning agents together with other builders such as phosphates, zeolite, other silicates, phosphonates and polycarboxylates.
  • EP-A-0 405 122 a builder combination is used described for a textile detergent which is a mixture of zeolite and crystalline Contains layered sodium silicate in a ratio of 4: 1 to 1: 4.
  • the zeolites are used in the production of detergents at the same time their absorbency, i.e. the adsorption capacity by acting as a carrier material for some surfactants, e.g. nonionic surfactants.
  • zeolites are replaced by the water-soluble silicates in products containing large amounts of sticky substances, for example alkylbenzenesulfonates, this leads to increased stickiness.
  • the alkyl benzene sulfonates can be replaced, for example, by the fatty alkyl sulfates.
  • Japanese patent application JP-A-4036398 discloses high bulk density detergent compositions in which zeolite is completely replaced by crystalline layered sodium silicate and a mixture of an alkylbenzenesulfonate and a fatty alkyl sulfate is used.
  • Examples 3 and 8 describe compositions of 20% by weight ⁇ -Na 2 Si 2 O 5 , 10% by weight of a C 10 -C 14 alkylbenzenesulfonate and 10% by weight of a C 12 alkyl sulfate.
  • the fatty alkyl sulfates have the disadvantage that they have a lower solubility than the alkyl benzene sulfonates and in particular the C 12 -C 14 fatty alkyl sulfates foam very strongly.
  • zeolite is necessary to process the surfactants in the spray tower can.
  • the tower powder Solid removed, so that correspondingly smaller amounts of surfactant are incorporated can.
  • the surfactants must then partly as separate additional components Detergent can be added.
  • solid and liquid Detergent raw materials in particular anionic surfactants, builder substances, alkalizing agents and liquid nonionic surfactants and optionally water or aqueous solutions of the preceding, with simultaneous or subsequent shaping and If necessary, drying can be combined by first all solid Components mixed together and then the liquid components be added, an additive to improve the dissolution behavior from the group of fatty alkyl sulfates, olefin sulfonates, alkyl aromatic sulfonates and Mixtures of these after mixing the solid ingredients in the process is introduced.
  • Both organic and inorganic come as builder substances Substances into consideration, e.g. Zeolites, layered silicates, and polymers Polycarboxylates.
  • the agents described contain up to 50% by weight of zeolite.
  • German patent application DE-A-195 25 378 describes a method for Manufacture of readily soluble washing and cleaning agents with bulk density above 600 g / l, in which zeolite is completely or partially dispensed with.
  • a Compound made by powdered alkali metal carbonate, or alkali metal silicate a mixture thereof is agglomerated using an aqueous preparation.
  • This aqueous preparation contains, inter alia, one or more anionic surfactants, advantageously Alkylbenzenesulfonates and / or alk (en) ylsulfates.
  • the compound can be added later liquid ingredients, especially nonionic surfactants are treated.
  • the washing or cleaning agent then contains the compound, between 0 and 30% by weight of zeolite and is produced by granulation, roller compaction, extrusion or mixing.
  • the present invention had the object of a powdery washing and see To provide cleaning agents that are easy to manufacture and that are easy to use.
  • S. 3a availability i.e. good powder properties, e.g. low stickiness and good Solubility, the zeolite at least partially by a water-soluble silicate can be replaced.
  • the present invention relates to a solid detergent and builder-containing washing and cleaning agent with a high bulk density or compound therefor, this agent being an anionic surfactant from 0.1% by weight to 10% by weight of C 9 -C 13 alkylbenzenesulfonates and 10% by weight to 50% by weight of C 8 -C 22 alkyl sulfates and as a builder contains 10% by weight to 45% by weight of water-soluble silicates and up to 30% by weight of zeolite.
  • the weight percentages given here relate to the total funds.
  • the total of the ingredients adds up to 100% by weight.
  • the water-soluble alkali silicates contained according to the invention can be amorphous, X-ray 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: 1.8 to 1: 3.5.
  • Such crystalline layered silicates are described, for example, in European patent application 164 514.
  • Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3.
  • M represents sodium
  • x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 • yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in the international patent application WO-A-91/08171.
  • the content of water-soluble alkali silicates in the agents is preferably 10% by weight to 40% by weight and in particular 10% by weight to 35% by weight, based on the anhydrous active substance.
  • the agents according to the invention contain C 8 -C 22 alkyl sulfates as further substances, which are preferably contained in an amount of 12 wt.% To 30 wt.% In the agent according to the invention.
  • Particularly suitable C 8 -C 22 alkyl sulfates are the sulfuric acid monoesters of the fatty alcohols, in particular the C 6 -C 18 fatty alcohols, such as lauryl, myristyl, cetyl or stearyl alcohol or the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil may also contain proportions of unsaturated alcohols, for example oleyl alcohol.
  • Preferred mixtures are those in which the proportion of the alkyl radicals is 15 to 40% by weight on C 12 , 5 to 15% by weight on C 14 , 15 to 25% by weight on C 16 , 30 to 60% by weight on C 18 and less than 1% by weight on C 10 are distributed.
  • alkylbenzenesulfonates are preferably present in the agent according to the invention in an amount of 0.5 wt.% To 5 wt.
  • Preferred alkylbenzenesulfonates are those cuts which contain large amounts of C 12 -alkylbenzenesulfonate.
  • the C 8 -C 22 alkyl sulfates and the C 9 -C 13 alkyl benzene sulfonates are present in a weight ratio of 20: 1 to 2: 1, in particular 10: 1 to 2: 1, in the agent according to the invention.
  • the detergents and cleaning agents according to the invention can be used as further ingredients other builders and surfactants and others, usually in such agents have contained substances.
  • the agent according to the invention can also contain zeolites as optional builder substances.
  • Zeolite A for example, but also zeolite are suitable X and zeolite P and mixtures of A, X and / or P.
  • Zeolite is preferably from A type in detergent quality.
  • Mixtures of zeolite NaA are also suitable and NaX, the proportion of the zeolite NaX in such mixtures expediently is below 30%. They have practically no particles larger than 30 ⁇ m and exist preferably at least 80% of particles smaller than 10 microns in size.
  • Suitable Zeolites have an average particle size of less than 10 ⁇ m (measurement method: Eisenhofer diffraction; Average volume distribution), preferably between 1.5 and 4.5 ⁇ m, in particular between 2.0 and 4.0 ⁇ m.
  • Your calcium binding capacity is in the range from 100 to 200 mg CaO / g.
  • the zeolite generally has a water content of 17 up to 25% by weight, preferably 18 to 22, in particular 20 to 22% by weight.
  • the salary the average of finely divided, in particular crystalline, hydrated zeolite preferably 0.5 to 30 wt .-%, based on anhydrous active substance.
  • the weight ratio of water-soluble silicates to zeolite between 1: 0.01 and 1: 1.5.
  • Polymeric carboxylates or polymeric carboxylic acids can also be used as additional builders be included. These polymeric carboxylates or carboxylic acids can in the invention Detergent is present in an amount of 1 to 15 wt .-%.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 800 to 150,000 (based on acid).
  • Suitable copolymers Polycarboxylates are especially those of acrylic acid with methacrylic acid and Acrylic acid or methacrylic acid with maleic acid.
  • Have proven to be particularly suitable Copolymers of acrylic acid with maleic acid have proven to be 50 to 90% by weight of acrylic acid and contain 50 to 10% by weight of maleic acid.
  • Their relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and especially 50,000 to 100,000.
  • the (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution are used, 20 to 55% by weight aqueous solutions being preferred.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 1 to 12 % By weight, in particular 2 to 10% by weight.
  • biodegradable terpolymers for example those those according to DE-A-43 00 772 as monomers salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as according to DE-C-42 21 381 Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those described in the German patent applications DE-A-43 03 320 and P 44 17 734.8 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • Further usable organic builders are, for example, those preferred in Form of their sodium salts used polycarboxylic acids, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acid, aminocarboxylic acid, nitrilotriacetic acid (NTA), as long as there is no objection to such use for ecological reasons is, and mixtures of these.
  • Preferred salts are the salts of the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Suitable anionic surfactants agent C of the invention can -Alkylpolyglykolethersulfonate 6 -C 18, C 6 -C 18 -Fettklareestersulfonate, C 6 -C 18 -Fettalkylethersulfate, olefin sulfonates, glycerol ether, Glycerol ether sulfates, alkenyl sulfates, Hydroxymischethersulfate, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, amide acids, C 6 -C 18 fatty acid amide ether sulfates, C 6 -C 18 alkyl (ether) carboxylates, fatty acid isethionates, NC 6 -C 16 acyl sarcosinates, NC 6 -C 18 acyl taurides, C 6 -C 18 - Contain alkyl
  • soaps can be contained in the agents according to the invention, in particular saturated fatty acid soaps, the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut-, Palm kernel or tallow fatty acids, derived soap mixtures, are suitable.
  • the further surfactants and the soaps can be used in a total amount of 1 to 15 % By weight, in particular 1 to 10% by weight, alone or in any mixtures in the agents according to the invention are present.
  • the total surfactant content is in the Agents according to the invention preferably over 20 wt .-%.
  • the agent according to the invention can also contain nonionic surfactants in an amount of 1 to 25% by weight, preferably 2% by weight to 20% by weight.
  • the preferred nonionic surfactants are liquid, alkoxylated, preferably ethoxylated, especially primary alcohols with preferably 8 to 18 carbon atoms (alkyl polyglycol ether) and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or in 2- Position may be methyl branched, or may contain linear and methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms for example from coconut oil, tallow oil or oleyl alcohol, which can have an average of 2 to 8 EO units per mole of alcohol, are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO units or 7 EO units, C 9 -C 11 alcohols with 3 EO units, 5 EO units or 7 EO units and mixtures of these this, such as mixtures of C 12 -C 14 alcohol with 3 EO units and C 12 -C 18 alcohol with 5 EO units.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol alkoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • the agent according to the invention can be alkyl polyglycosides, Fatty acid alkyl esters; Contain amine oxides and polyhydroxy fatty acid amides.
  • Structure breakers can be used as further components. Structure breakers are usually used to improve the processability of funds. Suitable structure breakers are particularly ethoxylated C 8 -C 18 fatty alcohols with 20 to 45 EO, preferably tallow fatty alcohols with 30 and 40 EO, polyethylene glycol or polypropylene glycol, sulfates and / or disulfates of polyethylene glycol or polypropylene glycol, sulfosuccinates and / or disulfosuccinates of polyethylene glycol or polypropylene glycol or mixtures of these.
  • the nonionic surfactants and the structure breakers can be used in a ratio of nonionic surfactant to structure breaker of 1: 1 to 15: 1.
  • the detergents produced according to the invention preferably contain peroxy bleaching agents and in particular peroxy bleaching agents in combination with bleach activators.
  • peroxy bleaching agents sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid.
  • the detergents preferably contain 5 to 25% by weight and in particular 10 to 20% by weight of bleaching agent, sodium percarbonate and / or sodium perborate monohydrate being preferably used.
  • bleach activators can be incorporated into the preparations which form organic peracids with H 2 O 2 .
  • these are N- or O-acyl compounds, for example multi-acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanuric acid hydrides, and also carboxylic acid hydrides , Carboxylic acid esters, especially sodium isonanoyloxybenzenesulfonate, and acylated sugar derivatives, especially pentaacetyl glucose.
  • N- or O-acyl compounds for example multi-acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular
  • the bleach activator can be coated with coating substances in a known manner or, if necessary with the aid of auxiliaries, granulated or extruded / pelletized and, if desired, contain further additives, for example dye.
  • Such granules preferably contain over 70% by weight, in particular from 90% by weight to 99% by weight, of bleach activator.
  • a bleach activator is preferably used which forms peracetic acid under the washing conditions.
  • TAED tetraacetylethylenediamine
  • DADHT 1,5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • Extruded TAED which contains 70 70% by weight of TAED, 15 to 25% by weight of C 12-18 fatty alcohol sulfate and 2 to 6% by weight of soda can also be used.
  • the content of bleach activators in the detergents containing bleach is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Suitable ingredients of the agents according to the invention are water-soluble inorganic salts such as bicarbonates, carbonates or mixtures thereof; in particular alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously 5 and 15% by weight.
  • the other detergent ingredients include foam inhibitors, optical brighteners, enzymes, fabric softening agents, colors and fragrances.
  • Neutral salts can also be found in an amount up to 20 wt .-% may be contained, their proportion is preferably ⁇ 10 wt .-%.
  • the agent can contain additional graying inhibitors in an amount of 0.1 to 5 % By weight, based on the composition.
  • additional graying inhibitors are Suitable water-soluble colloids mostly organic, for example soluble starch preparations and Z.
  • Enzymes come from the class of proteases, lipases or lipolytic acting enzymes, amylases, cellulases or mixtures thereof in question. Particularly good are suitable from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens Active ingredients. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and Celiulase or from cellulase and Lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest.
  • lipolytic enzymes are the well-known cutinases. Peroxidases too or oxidases have been found to be suitable in some cases.
  • the enzymes can adsorbed on carriers and / or embedded in coating substances to counter them to protect premature decomposition.
  • the proportion of enzymes, enzyme mixtures or Enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 % By weight.
  • the stabilizers come in particular for peroxygen compounds and enzymes Salts, such as neutral sodium salts, of polyphosphonic acids, especially of 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DETPMP diethylenetriaminepentamethylenephosphonic acid
  • ethylenediaminetetramethylenephosphonic acid ethylenediaminetetramethylenephosphonic acid.
  • the phosphonates can be in Amounts of up to 1.5% by weight are used, but preference is given to these additives dispensed with, so that the detergents according to the invention have a mathematical calculation Have phosphorus content of 0%.
  • the agents can contain enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1 wt .-% sodium formate can be used.
  • proteases those with soluble calcium seeds and a calcium content of preferably about 1.2 % By weight, based on the enzyme, are stabilized.
  • boron compounds for example boric acid, boron oxide, borax and others Alkali metal borates.
  • Suitable foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica as well as paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica.
  • Can with advantage mixtures of different foam inhibitors can also be used, e.g. those made of silicone oil, Paraffin oil or waxing.
  • the foam inhibitors are preferably attached to a granular, water-soluble or dispersible carrier substance bound.
  • the powder detergents can be used as optical brighteners, for example derivatives of Contain diaminostilbenedisulfonic acid or its alkali metal salts, which are good in dispersions Have it incorporated (see below).
  • the maximum amount of brightener in the invention Average is 0.5 wt .-%, preferably amounts from 0.02 to 0.25 wt .-% used.
  • Another object of the present invention relates to the production of detergents and cleaning agents containing surfactants and builders which contain 0.1% by weight to 10% by weight of C 9 -C 13 alkylbenzenesulfonate and 10% by weight to 50 % By weight of C 8 -C 22 alkyl sulfate as anionic surfactants and 10 to 45% by weight of water-soluble silicates and 0 to 30% by weight of zeolite as a builder, in which a premix is prepared from solid and liquid detergent constituents and this Premix is then pressed.
  • liquid non-ionic substances in particular come as liquid detergent components Surfactants into consideration.
  • the combination of the solid and liquid detergent raw materials under simultaneous or subsequent shaping and, if desired, drying can be carried out according to all known Processes in which washing and cleaning agents with a high bulk density, i.e. with a bulk density above 500 g / l, preferably above 600 g / l and in particular between 700 and 1,000 g / l, are carried out.
  • Examples of such known and preferred processes are granulation processes, in which either contain the solid ingredients of a detergent or cleaning agent spray-dried washing and cleaning agent or a mixture of spray-dried and non-spray-dried ingredients of washing and Detergents, if necessary including the additive, in a quick running mixer compacted and simultaneously in this mixer or after it in a further device, for example in a fluidized bed, with the liquid Components are mixed or applied.
  • a premix is first is made from detergent ingredients.
  • This solid, preferably homogeneous premix is with the addition of a plasticizer and / or lubricant over hole shapes with opening widths the predetermined granule dimension at high pressures between 25 and 200 bar extruded.
  • the strand is immediately after exiting the hole shape cut to the predetermined granule dimension by means of a cutting device.
  • the application of the high working pressure causes the premix to be plasticized in the formation of granules and provides the cutting ability of the freshly extruded strands for sure.
  • the premix consists at least partly of solid, preferably finely divided usual ingredients of detergents and cleaning agents, where appropriate liquid components are mixed.
  • the solid ingredients can go through Spray drying obtained tower powders, but also agglomerates, the selected one Mixture components as pure substances that mix with each other in the finely divided state will be, as well as mixtures of these. Subsequently, if necessary added the liquid ingredients and then the one selected according to the invention Plasticizers and / or lubricants mixed. As a plasticizer and / or lubricant aqueous solutions of polymeric polycarboxylates as well as highly concentrated anionic surfactant pastes and nonionic surfactants are preferred. For a detailed description of the Process and the appropriate ingredients of the premix and the appropriate Plasticizer and / or lubricant is based on the disclosure of the international Patent application WO 91/02047 referenced.
  • the liquid Nonionic surfactants also as a liquid component or as a plasticizer and / or Lubricants can be added to the solid premix or they are an ingredient a solid mixture component of the premix, this solid Mixture component can consist of a carrier bead, which with a solution or a dispersion was applied.
  • the addition of the liquid component, that is not bound to a carrier bead, can at any point in the process to Example in the production of the premix, but also in the processing of the plasticized Premix, but before passing through the hole shape (perforated nozzle plate) respectively.
  • Kneaders of any configuration are preferably used as the homogenizing device, For example, 2-screw kneaders can be selected.
  • the intensive mixing process can itself lead to a desired temperature increase. Moderately elevated temperatures of, for example, 60 to 70 ° C are usually not exceeded.
  • the premix preferably fed continuously to a 2-screw kneader (extruder), the Housing and its extruder pelletizing head to the predetermined extrusion temperature tempered, for example heated to 40 to 60 ° C. Under the action of shear the extruder screws, the premix is plasticized at pressures of 25 to 200 bar, in the form of fine strands through the perforated nozzle plate in the extruder head and finally the extrudate, preferably in a rotating knife, in reduced spherical to cylindrical granules.
  • the hole diameter in the Perforated nozzle plate and the strand cut length are based on the selected granulate dimension Voted.
  • the production of Granules of a substantially uniformly predeterminable particle size in which individual the absolute particle sizes to be adapted to the intended application can.
  • particle diameters up to at most 0.8 cm are preferred.
  • Important embodiments see the production of uniform granules Diameters in the millimeter range, for example in the range from 0.5 to 5 mm and especially in the range of 0.8 to 3 mm.
  • the length / diameter ratio of the In an important embodiment, the chopped off primary granulate lies in Range from 1: 1 to about 3: 1.
  • the still plastic, moist To supply primary granulate to a further shaping processing step be there edges present on the raw granulate are rounded, so that ultimately spherical or at least approximately spherical granules can be obtained.
  • small amounts of dry powder for example, can be used at this stage Zeolite powder such as zeolite NaA powder can also be used. This shape can be used in standard rounding machines, for example in rotary machines with rotating Bottom disc.
  • the granules are then preferably one Drying step, for example a fluidized bed dryer, supplied.
  • Tablets can, for example, be produced in such a way that the builder substances, in particular the water-soluble alkali silicates and possibly all other components mixed together in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses, hydraulic presses or rotary presses with pressures in the range from 1 to 300 bar, advantageously in the range from about 5 to 200 bar and in particular between 10 and 150 bar.
  • the compression is preferably carried out without the addition of water.
  • the premixes provided for compression however, by mixing the individual ingredients, which are at least partially in Pre-assembled form as a granular compound.
  • a tablet produced in this way preferably has a weight from 10 to 120 g, in particular from 20 to 100 g, the diameter of the Tablets is usually less than 100 mm.
  • the Diameter / height ratio of the tablets should be optimized so that a as little abrasion as possible on the vertical walls of the tabletting apparatus (higher Diameter / low height) with sufficient stability and not too large Surface (small diameter / high height) is guaranteed.
  • Preferred diameter / height ratios the cylindrical compacts are about 0.5: 1 to 10: 1, especially at 1: 1 to 8: 1.
  • dry powders of this type are zeolite NaA powder, but also precipitated or pyrogenic silica, as for example as Aerosil® or Sipernat® (products from Degussa) in Are commercially available. Highly concentrated, at least 90, are also preferred % By weight alcohol sulfate powder which is essentially, i.e. at least 90% particles exist with a particle size smaller than 100 microns. In particular are Mixtures of zeolite and alcohol sulfate powder are preferred.
  • the washing and cleaning agents can be produced uniformly from extrudates, which have the above-mentioned ingredients.
  • the finished funds can, however also from a mixture of several different solids, in particular several various granules, of which, for example, the Powdered washing and cleaning agents according to the invention the main ingredient form.
  • the bleach, the bleach activator, the enzymes and Dyes and fragrances are subsequently added to the extrudates. It is preferred that the bleach, the bleach activator and the enzymes are each in compacted granular form, for example as extrudates produced separately, by means of a kneader of the configuration described above or via a pellet press be obtained.
  • the mixture was homogenized for 2 minutes and then in a twin-screw extruder fed, its housing including the extruder pelletizing head was tempered to 45 ° C.
  • the premix was plasticized under the shear action of the extruder screws and then extruded at a pressure of 120 bar through the extruder perforated die plates into fine strands with a diameter of 1.2 mm, which were chopped into approximately spherical granules using a knock-out knife . (Length / diameter ratio about 1, hot cut).
  • the product obtained was rounded off for about 1 minute in a commercially available rounding machine of the type Marumerizer® with the addition of small amounts of zeolite NaA and then dried at a supply air temperature of 70 ° C. in a fluidized bed dryer until an exhaust air temperature of 53 ° C. was reached.
  • Example 1 (comparison)
  • Example 2 composition End product 1 Premix 1 End product 2
  • Premix 2 Premix 2 C 11 -C 13 alkyl benzene sulfonate 1.00 1.19 C 12-18 fatty alcohol sulfate 17.77 21.26 16.77 20.05 C 12-18 fatty alcohol x 7 EO 3.55 4.24 3.55 4.24 optical brightener 0.04 0.05 0.04 0.05 Perfume 0.36 0.36
  • Zeolite 3.15 3.15 Na perborate monohydrate 17.53 20.96 17.53 20.96 TAED 7.00 7.00

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 (11)

  1. Produit de lavage et de nettoyage solide renfermant des agents tensio-actifs et des adjuvants, et ayant une densité apparente élevée, ou composition destinée à cette fonction, caractérisé en ce qu'
    il renferme d'une part, en tant qu'agent tensio-actif anionique 0,1 à 10 % en poids d'alkylbenzenesulfonate en C9-C13, et 10 à 50 % en poids d'alkylsulfate en C8-C22, l'alkylsulfate en C8-C22 et l'alkylbenzenesulfonate en C9-C13 étant présents dans des rapports compris entre 20:1 à 2:1, et d'autre part, en tant qu'adjuvant, 10 à 45 % en poids de silicates solubles dans l'eau et jusqu'à 30 % en poids de zéolithe.
  2. Produit selon la revendication 1,
    caractérisé en ce que
    les silicates solubles dans l'eau et la zéolithe sont présents dans un rapport pondéral de 1:0,01 à 1:1,5.
  3. Produit selon l'une quelconque des revendications 1 et 2,
    caractérisé en ce qu'
    il renferme des agents tensio-actifs non-ioniques en quantité de 1 à 25 % en poids.
  4. Produit selon l'une quelconque des revendications 1 à 3,
    caractérisé en ce qu'
    il renferme entre 5 et 25 % en poids d'agent de blanchiment.
  5. Produit selon l'une quelconque des revendications 1 à 4,
    caractérisé en ce qu'
    il renferme des enzymes de la classe des protéases, des lipases, des amylases, des cellulases ou de leur mélange en quantité de 0,1 et 5 % en poids, sous forme de granulats.
  6. Procédé de préparation d'un produit de lavage et de nettoyage solide renfermant des agents tensio-actifs et des adjuvants et ayant une densité apparente élevée, ou composition destinée à cette fonction,
    caractérisé en ce que le produit renferme, d'une part en tant qu'agent tensio-actif anionique 0,1 à 10 % en poids d' alkylbenzenesulfonate en C9-C13, et 10 à 50 % en poids d'alkylsulfate en C8-C22, l'alkylsulfate en C8-C22 et l'alkylbenzenesulfonate en C9-C13 étant présents dans des rapports compris entre 20:1 à 2:1, et d'autre part, en tant qu'adjuvant, 10 à 45 % en poids de silicates solubles dans l'eau et 0 à 30 % en poids de zéolithe, les composants liquides et solides étant mélangés en un prémélange homogène puis comprimés.
  7. Procédé selon la revendication 6,
    caractérisé en ce que
    l'on comprime le prémélange sous des pressions élevées comprises entre 25 et 200 bars sous la forme d'un cordon, par des orifices de formage ayant une largeur correspondant à la dimension prédéterminée des granulats en y ajoutant un plastifiant et / ou un lubrifiant, et, directement après sa sortie de l'orifice de formage, on découpe le cordon au moyen d'un dispositif de découpe en granulats de dimension prédéterminée.
  8. Procédé selon la revendication 6,
    caractérisé en ce que
    l'on comprime le prémélange sous la forme de comprimés.
  9. Procédé selon l'une quelconque des revendications 6 à 8,
    caractérisé en ce qu'
    on met en oeuvre des agents tensio-actifs non ioniques en tant que constituant liquide.
  10. Procédé selon l'une quelconque des revendications 6 à 9,
    caractérisé en ce qu'
    on met en oeuvre des agents tensio-actifs anioniques sous forme solide ou liquide à pâteuse.
  11. Procédé selon l'une quelconque des revendications 6 à 10,
    caractérisé en ce qu'
    on ajuste la densité apparente du produit entre 600 et 1000 g/l.
EP97907093A 1996-03-21 1997-03-12 Detergent et nettoyant solide a masse volumique apparente elevee contenant des tensioactifs et des adjuvants, et compose approprie Revoked EP0888449B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19611013 1996-03-21
DE19611013A DE19611013A1 (de) 1996-03-21 1996-03-21 Festes Tensid- und Builder-haltiges Wasch- oder Reinigungsmittel mit hohem Schüttgewicht oder Compound hierfür
PCT/EP1997/001241 WO1997034994A1 (fr) 1996-03-21 1997-03-12 Detergent et nettoyant solide a masse volumique apparente elevee contenant des tensioactifs et des adjuvants, et compose approprie

Publications (2)

Publication Number Publication Date
EP0888449A1 EP0888449A1 (fr) 1999-01-07
EP0888449B1 true EP0888449B1 (fr) 2001-12-05

Family

ID=7788887

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97907093A Revoked EP0888449B1 (fr) 1996-03-21 1997-03-12 Detergent et nettoyant solide a masse volumique apparente elevee contenant des tensioactifs et des adjuvants, et compose approprie

Country Status (5)

Country Link
EP (1) EP0888449B1 (fr)
AT (1) ATE210179T1 (fr)
DE (2) DE19611013A1 (fr)
ES (1) ES2169357T3 (fr)
WO (1) WO1997034994A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7910538B2 (en) 2008-06-04 2011-03-22 The Procter & Gamble Company Detergent composition

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5961663A (en) * 1997-05-29 1999-10-05 Colgate-Palmolive Co. Microwave-dried amorphous alkali metal silicate powders and their use as builders in detergent compositions
EP0971028A1 (fr) * 1998-07-10 2000-01-12 The Procter & Gamble Company Comprimé détergent à caractéristiques de dissolution et mécaniques améliorées
EP0971029B1 (fr) * 1998-07-10 2005-02-16 The Procter & Gamble Company Comprimé détergent ayant des caractéristiques mécaniques et des propriétés de dissolution élevées
US6559115B1 (en) * 1998-07-10 2003-05-06 The Procter & Gamble Company Detergent tablet with high mechanical and dissolution characteristics
DE19903290A1 (de) * 1999-01-28 2000-08-03 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit definiertem Aniontensidverhalten
DE19911570A1 (de) * 1999-03-16 2000-09-28 Henkel Kgaa Aniontensid-Granulate
WO2001025391A1 (fr) * 1999-10-06 2001-04-12 The Procter & Gamble Company Comprime detergent presentant des caracteristiques dissolvantes et mecaniques puissantes
DE10031619A1 (de) * 2000-06-29 2002-01-10 Cognis Deutschland Gmbh Tensidgranulate mit verbesserter Auflösegeschwindigkeit
DE102015002877A1 (de) * 2015-03-09 2016-09-15 Henkel Ag & Co. Kgaa Granulares Wasch- oder Reinigungsmittel mit verbesserter Lösegeschwindigkeit
US11767495B2 (en) * 2020-03-13 2023-09-26 YFY Consumer Products, Co. Systems and methods for manufacturing solid granules

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0436398A (ja) * 1990-06-01 1992-02-06 Lion Corp 高嵩密度粒状洗剤組成物
DE4125178A1 (de) * 1991-07-30 1993-02-04 Henkel Kgaa Pulverfoermige aniontensidzubereitung
DE19525378A1 (de) * 1995-07-12 1997-01-16 Henkel Kgaa Amorphes Alkalisilicat-Compound

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7910538B2 (en) 2008-06-04 2011-03-22 The Procter & Gamble Company Detergent composition

Also Published As

Publication number Publication date
ATE210179T1 (de) 2001-12-15
EP0888449A1 (fr) 1999-01-07
WO1997034994A1 (fr) 1997-09-25
DE19611013A1 (de) 1997-09-25
ES2169357T3 (es) 2002-07-01
DE59705671D1 (de) 2002-01-17

Similar Documents

Publication Publication Date Title
EP0746599B1 (fr) Produit de lavage a adjuvants au silicate amorphes
EP0523099B1 (fr) Procede pour la fabrication d'agents de lavage et de nettoyage
EP0815196B1 (fr) Procede de fabrication d'un detergent ou nettoyant en poudre
EP1043389B1 (fr) Comprimés détergents contenant un desintégrant granulaire
EP0720644B1 (fr) Melanges detergents et produits de lavage ou de nettoyage a proprietes ameliorees de dissolution
EP0888449B1 (fr) Detergent et nettoyant solide a masse volumique apparente elevee contenant des tensioactifs et des adjuvants, et compose approprie
DE19723028A1 (de) Hilfsmittelgranulat für wasch- und reinigungsaktive Formkörper
EP0814152A2 (fr) Procédé de préparation des détergents solides
EP0839178B1 (fr) Compose amorphe de silicate alcalin
EP0793708B1 (fr) Procede de preparation par extrusion d' agents de lavage ou de nettoyage contenant des adjuvants de lavage hydrosolubles
EP1167509B1 (fr) Granules d'agent tensio-actif a vitesse de decomposition amelioree
DE19723616A1 (de) Granulares Waschmittel
DE19624415A1 (de) Verfahren zur Herstellung von festen Wasch- oder Reinigungsmitteln
DE19622443A1 (de) Granulare Waschmittel, enthaltend optischen Aufheller
EP0746601A1 (fr) Produit detergent ou nettoyant granulaire
DE4320358A1 (de) Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate
WO2000037595A1 (fr) Compactat contenant des agents renforçateurs a base de silicates
EP0711338A1 (fr) Procede de fabrication d'un produit extrude a activite detergente ou nettoyante
DE4325308A1 (de) Feste waschaktive Zubereitung mit verbessertem Einspülverhalten
EP0937132A2 (fr) Procede de fabrication d'agents de lavage et de nettoyage
DE19752388A1 (de) Verfahren zur Herstellung von Wasch- und Reinigungsmitteln mit hoher Schüttdichte
WO1997018290A1 (fr) Procede de preparation de detergents et de nettoyants granulaires ou constituants utilises pour les preparer
DE19807807A1 (de) Pulverförmiges bis granulares 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

17P Request for examination filed

Effective date: 19980912

AK Designated contracting states

Kind code of ref document: A1

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

RIN1 Information on inventor provided before grant (corrected)

Inventor name: PAWELCZYK, ROSWITHA

Inventor name: BURMEISTER, KATRIN

17Q First examination report despatched

Effective date: 19991006

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: 210179

Country of ref document: AT

Date of ref document: 20011215

Kind code of ref document: T

REF Corresponds to:

Ref document number: 59705671

Country of ref document: DE

Date of ref document: 20020117

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2169357

Country of ref document: ES

Kind code of ref document: T3

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 PLC

Effective date: 20020904

NLR1 Nl: opposition has been filed with the epo

Opponent name: UNILEVER PLC

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

Free format text: ORIGINAL CODE: EPIDOS OBSO

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

Ref country code: FR

Payment date: 20030310

Year of fee payment: 7

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

Ref country code: AT

Payment date: 20030312

Year of fee payment: 7

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

Ref country code: DE

Payment date: 20030320

Year of fee payment: 7

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

Ref country code: BE

Payment date: 20030522

Year of fee payment: 7

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

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

Free format text: STATUS: PATENT REVOKED

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

Ref country code: NL

Payment date: 20040310

Year of fee payment: 8

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

Ref country code: ES

Payment date: 20040318

Year of fee payment: 8

27W Patent revoked

Effective date: 20031127

NLR2 Nl: decision of opposition

Effective date: 20031127

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

Free format text: ORIGINAL CODE: 0009299OPPO