EP1144567B1 - Waschmitteltablette - Google Patents

Waschmitteltablette Download PDF

Info

Publication number
EP1144567B1
EP1144567B1 EP99933807A EP99933807A EP1144567B1 EP 1144567 B1 EP1144567 B1 EP 1144567B1 EP 99933807 A EP99933807 A EP 99933807A EP 99933807 A EP99933807 A EP 99933807A EP 1144567 B1 EP1144567 B1 EP 1144567B1
Authority
EP
European Patent Office
Prior art keywords
phase
detergent tablet
mould
adhesive
detergent
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
EP99933807A
Other languages
English (en)
French (fr)
Other versions
EP1144567A2 (de
EP1144567A3 (de
Inventor
Christopher James Binder
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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=26314048&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1144567(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from GBGB9815525.2A external-priority patent/GB9815525D0/en
Priority claimed from GB9818720A external-priority patent/GB2340842A/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP1144567A2 publication Critical patent/EP1144567A2/de
Publication of EP1144567A3 publication Critical patent/EP1144567A3/de
Application granted granted Critical
Publication of EP1144567B1 publication Critical patent/EP1144567B1/de
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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0086—Laundry tablets
    • 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
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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 present invention relates to multi-phase detergent tablets.
  • it relates to multi-phase detergent tablets having improved robustness and product integrity together with excellent dissolution characteristics.
  • detergent compositions in tablet form are known in the art. It is understood that detergent compositions in tablet form hold several advantages over detergent compositions in particulate form, such as ease of dosing, handling, transportation and storage.
  • Detergent tablets are most commonly prepared by pre-mixing components of a detergent composition and forming the pre-mixed detergent components into a tablet using any suitable equipment, preferably a tablet press. Tablets are typically formed by compression of the components of the detergent composition so that the tablets produced are sufficiently robust to be able to withstand handling and transportation without sustaining damage. In addition to being robust, tablets must also dissolve sufficiently fast so that the detergent components are released into the wash water as soon as possible at the beginning of the wash cycle.
  • the present invention therefore seeks to find a balance between tablet robustness and tablet dissolution.
  • Multi-phase detergent tablets described in the prior art are prepared by compressing a first composition in a tablet press to form a substantially planar first layer. A further detergent composition is then delivered to the tablet press on top of the first layer. This second composition is then compressed to form another substantially planar second layer.
  • the first layer is generally subjected to more than one compression as it is also compressed during the compression of the second composition.
  • the first and second compression forces are in the same order of magnitude. The Applicant has found that where this is the case, because the compression force must be sufficient to bind the first and second compositions together, the force used in both the first and second compression steps must be in the range of from about 4,000 to about 20,000 kg (assuming a tablet cross-section of about 10 cm 2 ).
  • GB-A-2,320,254 discloses a tablet prepared by selecting from a base particle mixture a low porosity portion, adding to this portion a liquid non-ionic surfactant or hydrocarbon oil, mixing the resulting treated particles with the rest of the particles and tabletting the whole.
  • EP 481,547 A1 discloses a multi-phase detergent tablet comprising an inner layer, a barrier layer and an outer layer. The tablet releases sequentially ingredients contained in the outer layer and ingredients contained in the inner layer.
  • the present invention therefore provides multi-phase detergent tablets for use in automatic dishwashing, laundry, and which have improved integrity and robustness together with excellent dissolution characteristics.
  • a multi-phase detergent tablet for use in a washing machine, the tablet comprising a first phase in the form of a shaped body having at least one mould in the surface thereof wherein the first phase is in adhesive contact with one or more second phases contained within the mould, at least one second phase being in the form of a compressed particulate solid incorporating adhesive which is liquid a 28°C and having an average porosity of less than 0.15 ml/g, preferably less than 0.13 ml/g and more preferably less than 0.11 ml/g as measured by mercury porosimetry.
  • Porosity can be measured by known methods including image analysis, mercury porosimetry, determination and comparison of volume and mass, determination and comparison of surface area and diameter, gas chromatography, x-ray small angle scattering and displacement methods.
  • the method of measuring porosity used herein is the mercury porosimetry method, average porosity being defined as the total intrusion volume of the particulate solid (prior to introduction of the liquid adhesive) for pore volumes below 30 ⁇ m.
  • the compressed particulate solid has an average porosity of less than 0.09 ml/g, more preferably less than 0.07 ml/g and especially less than 0.05 ml/g.
  • the adhesive is liquid at or close to ambient temperatures (28°C, more preferably 25°C and above). It is also preferred herein to use adhesives that are water-frangible or water-sensitive, for example, adhesives based on water-soluble or water-emulsifiable polymers. It will also be understood that water and other solvent-based adhesives, for example, adhesives comprising aqueous polymeric solutions or emulsions, are also suitable for use herein. However, the preferred adhesives are either water-free or are used in conjunction with a water-sink (for example, anhydrous builder salts) in order to minimise the free moisture content of the final tablet compositions which is preferably less than about 1% by weight.
  • a water-sink for example, anhydrous builder salts
  • the liquid adhesive is incorporated by post-addition, preferably as a spray-on, to the particulate solid prior to compression.
  • the level of liquid adhesive is preferably from 0.1% to 3%, more preferably from 0.5% to 1.5% by weight of the second phase particulate solid.
  • the first phase also takes the form of a compressed particulate solid, the average porosity of which is greater than that of the second phase particulate solid by at least 10%, preferably at least 30%, and more preferably at least 60%, this being valuable for optimum adhesion.
  • the average porosity of the first phase is at least 0.1 ml/g, preferably at least 0.12 ml/g, more preferably at least 0.14 ml/g, especially at least 0.16 ml/g and more especially at least 0.18 ml/g as measured by mercury porosimetry.
  • Preferred adhesives for use herein are selected from water-soluble poly(C 2 -C 4 )-alkylene oxide polymers and copolymers, poly(C 2 -C 4 )-alkoxylated nonionic surfactants, aqueous polymeric solutions and emulsions, and mixtures thereof.
  • highly preferred from the viewpoint of optimum product integrity, robustness and dissolution characteristics are the polyethylene glycols having an average molecular weight in the range from 200 to 700, preferably from 250 to 600, although polyethylene glycols of a somewhat higher average molecular weight, for example up to 900, can be used if the detergent tablet is prepared at a temperature slightly above ambient, for example up to 28°C.
  • a multi-phase detergent tablet for use in a washing machine, the tablet comprising a first phase in the form of a shaped body having at least one mould in the surface thereof wherein the first phase is in adhesive contact with one or more second phases contained within the mould, at least one second phase being in the form of a compressed particulate solid incorporating liquid adhesive selected from polyethylene glycols having an average molecular weight in the range from 200 to 700.
  • the detergent tablets herein comprise at least one first phase in adhesive contact with one or more second phases (sometimes referred to herein as 'optional subsequent phases').
  • the first phase is a compressed shaped body prepared at an applied compression pressure of at least 250 kg/cm 2 , preferably at least 350 kg/cm 2 (3.43 kN/cm 2 or 34.3 MPa), more preferably from 400 to 2000 kg/cm 2 , and especially from 600 to 1200 kg/cm 2 (compression pressure herein is the applied force divided by the cross-sectional area of the tablet in a plane transverse to the applied force - in effect, the transverse cross-sectional area of the die of the rotary press).
  • the second phase is preferably formed at a compression pressure of less than 350 kg/cm 2 , preferably in the range from 40 kg/cm 2 to 300 kg/cm 2 and more preferably from 70 to 270 kg/cm 2 .
  • the first phase is formed by compression at a pressure greater than that applied to the second phase.
  • the compression pressures applied to the first and second phases will generally be in a ratio of at least 1.2:1, preferably at least 2:1, more preferably at least 4:1.
  • Post-addition preferably takes the form of a spray-on of the liquid adhesive to the particulate solid and normally will take place as a final step shortly before compression, preferably within 1 day, and more preferably within 12 hours.
  • a multi-phase detergent tablet for use in a washing machine, the tablet comprising a first phase in the form of a shaped body having at least one mould in the surface thereof wherein the first phase is in adhesive contact with one or more second phases, at least one second phase contained within the mould being in the form of a compressed particulate solid incorporating adhesive which is liquid at 28°C and wherein the liquid adhesive is incorporated by post-addition, preferably as a spray-on, to the particulate solid prior to compression.
  • the tablets of the invention will preferably have a CBS of at least 8kg, preferably greater than 10kg, more preferably greater than 12kg, and especially greater than 14kg, CBS being measured per the US Consumer Product Safety Commission Test Specification.
  • the first and second phases herein are in a relatively high weight ratio to one another, for example at least about 6:1, preferably at least about 10:1; also that the tablet composition contain one or more detergent actives (for example enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents etc) which is predominantly concentrated in the second phase, for example, at least 50%, preferably at least 60%, especially 80% by weight of the active (based on the total weight of the active in tablet) is in the second phase of the tablet.
  • detergent actives for example enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents etc
  • compositions are optimum for tablet strength, dissolution, cleaning, and pH regulation characteristics providing, for example, tablet compositions capable of dissolving in the wash liquor so as to deliver at least 50%, preferably at least 60%, and more preferably at least 80% by weight of the detergent active to the wash liquor within 10, 5, 4 or even 3 minutes of the start of the wash process.
  • the time within which the multi-phase tablet or a phase thereof or a detergent active component dissolves is determined according to DIN 44990 using a dishwashing machine available from Bosch on the normal 65°C washing program with water hardness at 18°H using a minimum of six replicates or a sufficient number to ensure reproducibility.
  • the multi-phase detergent tablet of the present invention comprises a first phase, a second and optional subsequent phases.
  • the first phase is in the form of a shaped body of detergent composition comprising one or more detergent components as described below.
  • Preferred detergent components include, builder, bleach, enzymes and surfactant.
  • the components of the detergent composition are mixed together by, for example admixing dry components or spraying-on liquid components.
  • the components are then formed into a first phase using any suitable equipment, but preferably by compression, for example in a tablet press.
  • the first phase can be prepared by extrusion, casting.
  • the first phase is prepared such that it comprises at least one mould in the surface of the shaped body.
  • the mould is created using a specially designed tablet press wherein the surface of the punch that contacts the detergent composition is shaped such that when it contacts and presses the detergent composition it presses a mould, or multiple moulds into the first phase of the multi-phase detergent tablet.
  • the mould will have an inwardly concave or generally concave surface to provide improved adhesion to the second phase.
  • the tablets of the invention also include one or more additional phases prepared from a composition or compositions which comprise one or more detergent components as described below.
  • At least one phase (herein referred to as a second phase) preferably takes the form of a particulate solid (which term encompasses powders, granules, agglomerates, and other particulate solids including mixtures thereof with liquid binders, meltable solids, spray-ons) compressed into/within the one or more moulds of the first phase of the detergent tablet such that the second phase itself takes the form of a shaped body.
  • Preferred detergent components include builders, colourants, binders, surfactants, disrupting agents and enzymes, in particular amylase and protease enzymes.
  • the second and optional subsequent phases comprise a disrupting agent that may be selected from either a disintegrating agent or an effervescent agent.
  • Suitable disintegrating agents include agents that swell on contact with water or facilitate water influx and/or efflux by forming channels in the detergent tablet. Any known disintegrating or effervescing agent suitable for use in laundry or dishwashing applications is envisaged for use herein.
  • Suitable disintegrating agent include starch, starch derivatives such as Arbocel (tradename), Vivapur (tradename) both available from Rettenmaier, Nymcel (tradename) available from Metsa-serla , alginates, acetate trihydrate, burkeite, monohydrated carbonate formula Na 2 CO 3 .H 2 O, hydrated STPP with a phase I content of at least about 40%, carboxymethylcellulose (CMC), CMC-based polymers, sodium acetate, aluminium oxide.
  • Suitable effervescing agents are those that produce a gas on contact with water. Suitable effervesing agents may be oxygen, nitrogen dioxide or carbon dioxide evolving species.
  • effervescent agents may be selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate in combination with inorganic acids such as sulphamic acid and/or carboxylic acids such as citric, malic and maleic acid and mixtures thereof
  • the components of the detergent composition are mixed together by for example premixing dry components and admixing, preferably by spray-on, the adhesive and other liquid components.
  • the components of the second and optional subsequent phases are then compressed to form one or more layers or are fed into and retained within the mould provided by the first phase.
  • the tablets of the present invention comprises two phases; a first and a second phase.
  • the first phase will comprise, one mould and the second phase will normally consist of a single detergent active composition.
  • the first phase may comprise more than one mould and the second phase may be prepared from more than one detergent active composition.
  • the second phase may comprise more than one detergent active composition contained within one mould. It is also envisaged that several detergent active compositions are contained in separate moulds. In this way potentially chemically sensitive detergent components can be separated in order to avoid any loss in performance caused by components reacting together and potentially becoming inactive or exhausted.
  • the first, second and/or optional subsequent phases may comprise a binder.
  • the binder is selected from the group consisting of organic polymers, for example polyethylene and/or polypropylene glycols having an average molecular weight of from 1000 to 12000, especially those of molecular weight 4000, 6000 and 9000, polyvinyl pyrolindone (PVP), especially PVP of molecular weight 90 000, polyacrylates, sugars and sugar derivatives, starch and starch derivatives, for example hydroxy propyl methyl cellulose (HPMC) and carboxy methyl cellulose (CMC); and inorganic polymers, such as hexametaphosphate.
  • PVP polyvinyl pyrolindone
  • HPMC hydroxy propyl methyl cellulose
  • CMC carboxy methyl cellulose
  • inorganic polymers such as hexametaphosphate.
  • the polyethyleneglycol binders are highly preferred herein.
  • the combination of liquid adhesive and binder is particularly valuable from the viewpoint of providing
  • the first phase weighs greater than 5g. More preferably the first phase weighs from 10g to 30g, even more preferably from 15g to 25g and most preferably form 18g to 24g.
  • the second and optional subsequent phases weigh less than 4g. More preferably the second and/or optional subsequent phases weigh between 1g and 3.5g, most preferably from 1.3g to 2.5g.
  • an advantage of the present invention is that because a lower compression force is used heat, force or chemically sensitive detergent components can be incorporated into the detergent tablet without sustaining the consequential loss in performance usually encountered when incorporating such components into tablets.
  • Yet another advantage of the present invention is the ability to prepare a multi-phase detergent tablet wherein one phase can be designed to dissolve, preferably significantly before another phase.
  • the second and optional subsequent phase(s) dissolves before the first phase.
  • the first phase dissolves in from 5 to 20 minutes, more preferably from 10 to 15 minutes and the second and/or optional subsequent phases dissolve in less than 5 minutes, more preferably less than 4.5 minutes, most preferably less than 4 minutes.
  • the time in which the first, second and/or optional subsequent phase dissolve are independent from each other.
  • differential dissolution of the phases is achieved.
  • a particular benefit of being able to achieve differential dissolution of the multi-phase detergent tablet is that a component that is chemically inactivated by the presence of another component can be separated into a different phase.
  • the component that is inactivated is preferably located in the second and optional subsequent phase(s).
  • the multi-phase detergent tablets are prepared using any suitable tabletting equipment.
  • the tablets are prepared by compression in a tablet press capable of preparing a tablet comprising a mould.
  • the first phase is prepared using a specially designed tablet press.
  • the punch(es) of this tablet press are modified so that the surface of the punch that contacts the detergent composition has a convex surface.
  • a first detergent composition is delivered into the die of the tablet press and the punch is lowered to contact and then compress the detergent composition to form a first phase.
  • the first detergent composition is compressed using an applied pressure of at least 250 kg/cm 2 , preferably between 350 and 2000 kg/cm 2 , more preferably 500 to 1500 kg/cm 2 , most preferably 600 to 1200 kg/cm 2 .
  • the punch is then elevated, exposing the first phase containing a mould.
  • a second and optional subsequent detergent composition(s) is then delivered into the mould.
  • the specially designed tablet press punch is then lowered a second time to lightly compress the second and optional subsequent detergent composition(s) to form the second and optional subsequent phase(s).
  • the optional subsequent phase is prepared in an optional subsequent compression step substantially similar to the second compression step described above.
  • the second and optional subsequent detergent composition(s) is compressed at a pressure of preferably less than 350 kg/cm 2 , more preferably from 40 to 300 kg/cm 2 , most preferably from 70 to 270 kg/cm 2 .
  • the punch is elevated a second time and the multi-phase detergent tablet is ejected from the tablet press.
  • Multi-layer tablets without moulds can be prepared in a similar manner except using a tablet punch having a planar surface.
  • the first and second and or optional subsequent phases of the multi-phase detergent tablet described herein are prepared by compression of one or more compositions comprising detergent active components.
  • the compositions used in any of these phases may include a variety of different detergent components including builder compounds, surfactants, enzymes, bleaching agents, alkalinity sources, colourants, perfume, lime soap dispersants, organic polymeric compounds including polymeric dye transfer inhibiting agents, crystal growth inhibitors, heavy metal ion sequestrants, metal ion salts, enzyme stabilisers, corrosion inhibitors, suds suppressors, solvents, fabric softening agents, optical brighteners and hydrotropes.
  • the proportions of these active components are given by weight of the corresponding composition of active detergent components, unless specified otherwise.
  • Highly preferred detergent components of the first phase include a builder compound, a surfactant, an enzyme and a bleaching agent.
  • Highly preferred detergent components of the second phase include builder, enzymes and disrupting agent.
  • Builders suitable for use herein include water-soluble builders such as citrates, carbonates and polyphosphates and partially water-soluble or insoluble builders such as crystalline layered silicates (EP-A-0164514 and EP-A-0293640) and aluminosilicates inclusive of Zeolites A, B, P, X, HS and MAP.
  • the builder is typically present at a level of from about 1% to about 80% by weight, preferably from about 10% to about 70% by weight, most preferably from about 20% to about 60% by weight of composition.
  • Surfactants suitable herein include anionic surfactants such as alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkyl glyceryl sulfonates, alkyl and alkenyl sulphonates, alkyl ethoxy carboxylates, N-acyl sarcosinates, N-acyl taurates and alkyl succinates and sulfosuccinates, wherein the alkyl, alkenyl or acyl moiety is C 5 -C 20 , preferably C 10 -C 18 linear or branched; cationic surfactants such as choline esters (US-A-4228042, US-A-4239660 and US-A-4260529) and mono C 6 -C 16 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups;
  • Surfactants suitable herein are disclosed, for example, in US-A-3,929,678 , US-A- 4,259,217, EP-A-0414 549, WO-A-93/08876 and WO-A-93/08874.
  • Surfactants are typically present at a level of from about 0.2% to about 30% by weight, more preferably from about 0.5% to about 10% by weight, most preferably from about 1% to about 5% by weight of composition.
  • Enzymes suitable herein include bacterial and fungal cellulases such as Carezyme and Celluzyme (Novo Nordisk A/S); peroxidases; lipases such as Amano-P (Amano Pharmaceutical Co.), M1 Lipase R and Lipomax R (Gist-Brocades) and Lipolase R and Lipolase Ultra R (Novo); cutinases; proteases such as Esperase R , Alcalase R , Durazym R and Savinase R (Novo) and Maxatase R , Maxacal R , Properase R and Maxapem R (Gist-Brocades); and ⁇ and ⁇ amylases such as Purafect Ox Am R (Genencor) and Termamyl R , Ban R , Fungamyl R , Duramyl R , and Natalase R (Novo); and mixtures thereof. Enzymes are preferably added herein as prills, granulates, or cogranulates at
  • Bleaching agents suitable herein include chlorine and oxygen bleaches, especially inorganic perhydrate salts such as sodium perborate mono-and tetrahydrates and sodium percarbonate optionally coated to provide controlled rate of release (see, for example, GB-A-1466799 on sulfate/carbonate coatings), preformed organic peroxyacids and mixtures thereof with organic peroxyacid bleach precursors and/or transition metal-containing bleach catalysts (especially manganese or cobalt).
  • Inorganic perhydrate salts are typically incorporated at levels in the range from about 1% to about 40% by weight, preferably from about 2% to about 30% by weight and more preferably from abut 5% to about 25% by weight of composition.
  • Peroxyacid bleach precursors preferred for use herein include precursors of perbenzoic acid and substituted perbenzoic acid; cationic peroxyacid precursors; peracetic acid precursors such as TAED, sodium acetoxybenzene sulfonate and pentaacetylglucose; pemonanoic acid precursors such as sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate (iso-NOBS) and sodium nonanoyloxybenzene sulfonate (NOBS); amide substituted alkyl peroxyacid precursors (EP-A-0170386); and benzoxazin peroxyacid precursors (EP-A-0332294 and EP-A-0482807).
  • Bleach precursors are typically incorporated at levels in the range from about 0.5% to about 25%, preferably from about 1% to about 10% by weight of composition while the preformed organic peroxyacids themselves are typically incorporated at levels in the range from 0.5% to 25% by weight, more preferably from 1% to 10% by weight of composition.
  • Bleach catalysts preferred for use herein include the manganese triazacyclononane and related complexes (US-A-4246612, US-A-5227084); Co, Cu, Mn and Fe bispyridylamine and related complexes (US-A-5114611); and pentamine acetate cobalt(III) and related complexes(US-A-4810410).
  • suitable components herein include organic polymers having dispersant, anti-redeposition, soil release or other detergency properties invention in levels of from about 0.1% to about 30%, preferably from about 0.5% to about 15%, most preferably from about 1% to about 10% by weight of composition.
  • Preferred anti-redeposition polymers herein include acrylic acid containing polymers such as Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 (BASF GmbH), Acusol 45N, 480N, 460N (Rohm and Haas), acrylic acid/maleic acid copolymers such as Sokalan CP5 and acrylic/methacrylic copolymers.
  • Preferred soil release polymers herein include alkyl and hydroxyalkyl celluloses (US-A-4,000,093), polyoxyethylenes, polyoxypropylenes and copolymers thereof, and nonionic and anionic polymers based on terephthalate esters of ethylene glycol, propylene glycol and mixtures thereof.
  • Heavy metal sequestrants and crystal growth inhibitors are suitable for use herein in levels generally from about 0.005% to about 20%, preferably from about 0.1% to about 10%, more preferably from about 0.25% to about 7.5% and most preferably from about 0.5% to about 5% by weight of composition, for example diethylenetriamine penta (methylene phosphonate), ethylenediamine tetra(methylene phosphonate) hexamethylenediamine tetra(methylene phosphonate), ethylene diphosphonate, hydroxy-ethylene-1,1-diphosphonate, nitrilotriacetate, ethylenediaminotetracetate, ethylenediamine-N,N'-disuccinate in their salt and free acid forms.
  • diethylenetriamine penta methylene phosphonate
  • ethylene diphosphonate hydroxy-ethylene-1,1
  • compositions herein can contain a corrosion inhibitor such as organic silver coating agents in levels of from about 0.05% to about 10%, preferably from about 0.1% to about 5% by weight of composition (especially paraffins such as Winog 70 sold by Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibitor compounds (for example benzotriazole and benzimadazole - see GB-A-1137741) and Mn(II) compounds, particularly Mn(II) salts of organic ligands in levels of from about 0.005% to about 5%, preferably from about 0.01% to about 1%, more preferably from about 0.02% to about 0.4% by weight of the composition.
  • a corrosion inhibitor such as organic silver coating agents in levels of from about 0.05% to about 10%, preferably from about 0.1% to about 5% by weight of composition (especially paraffins such as Winog 70 sold by Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibitor compounds (for example benzotriazole and benzimadazole - see GB-A-11
  • Suitable components herein include colourants, water-soluble bismuth compounds such as bismuth acetate and bismuth citrate at levels of from about 0.01% to about 5%, enzyme stabilizers such as calcium ion, boric acid, propylene glycol and chlorine bleach scavengers at levels of from about 0.01% to about 6%, lime soap dispersants (see WO-A-93/08877), suds suppressors (see WO-93/08876 and EP-A-0705324), polymeric dye transfer inhibiting agents, optical brighteners, perfumes, fillers and clay and cationic fabric softeners.
  • enzyme stabilizers such as calcium ion, boric acid, propylene glycol and chlorine bleach scavengers at levels of from about 0.01% to about 6%
  • lime soap dispersants see WO-A-93/08877
  • suds suppressors see WO-93/08876 and EP-A-0705324
  • polymeric dye transfer inhibiting agents such as optical bright
  • the detergent tablets herein are preferably formulated to have a not unduly high pH, preferably a pH in 1% solution in distilled water of from about 8.0 to about 12.5, more preferably from about 9.0 to about 11.8, most preferably from about 9.5 to about 11.5.
  • a preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, silverware, metallic items, cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a the herein described compositions.
  • an effective amount is meant from 8g to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods.
  • the detergent tablets are from 15g to 40g in weight, more preferably from 20g to 35g in weight.
  • Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of the herein described compositions.
  • an effective amount is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
  • a dispensing device is employed in the washing method.
  • the dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.
  • the device may possess a number of openings through which the product may pass.
  • the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product.
  • the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.
  • Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle.
  • the dispensing device may be a flexible container, such as a bag or pouch.
  • the bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in EP-A-0018678.
  • it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in EP-A-0011500, EP-A-0011501, EP-A-0011502, and EP-A-0011968.
  • a convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
  • the multi-phase tablet compositions are prepared as follows.
  • the detergent active composition of phase 1 is prepared by admixing the granular and liquid components and is then passed into the die of a conventional rotary press.
  • the phase 1 particulate compositions have a mean particle size of from about 520-570 ⁇ m, with about 5% passing a 150 ⁇ m sieve and about 30% passing a 250 ⁇ m sieve.
  • the rotary press includes a punch suitably shaped for forming the mould.
  • the cross-section of the die is approximately 30x38 mm.
  • the composition is then subjected to to a compression force of 940 kg/cm 2 and the punch is then elevated exposing the first phase of the tablet containing the mould in its upper surface.
  • the detergent active composition of phase 2 is prepared in similar manner, except that the liquid adhesive, PEG 400, is added as a final step by spray-on onto the particulate mixture, and the composition is then passed into the die.
  • the phase 2 particulate compositions have a mean particle size of from about 430-470 ⁇ m, with about 5% passing a 150 ⁇ m sieve and about 35% passing a 250 ⁇ m sieve.
  • the particulate active composition is then subjected to a compression force of 170 kg/cm 2 , the punch is elevated, and the multi-phase tablet ejected from the tablet press.
  • the resulting tablets dissolve or disintegrate in a washing machine as described above within 12 minutes, phase 2 of the tablets dissolving within 5 minutes.
  • the tablets provide excellent dissolution and cleaning characteristics together with good tablet integrity, inter-phase adhesion and strength.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (13)

  1. Mehrphasige Detergenstablette zur Verwendung in einer Waschmaschine, wobei die Tablette umfasst: eine erste Phase in Form eines geformten Körpers mit mindestens einer Vertiefung in dessen Oberfläche, wobei die erste Phase in Haftkontakt mit einer oder mehreren zweiten Phasen steht, mindestens eine zweite Phase, welche innerhalb der Vertiefung enthalten ist, welche in Form eines komprimierten teilchenförmigen Feststoffs vorliegt, beinhaltend Haftmittel, das bei 28°C flüssig ist, und mit einer durschnittlichen Porosität von weniger als 0,15 ml/g, gemessen durch Quecksilber-Porosimetrie.
  2. Mehrphasige Detergenstablette nach Anspruch 1, wobei das Haftmittel bei 25°C und darüber flüssig ist und gewählt ist aus der Gruppe, bestehend aus wasserlöslichen Poly(C2-C4)-alkylenoxidpolymeren und -copolymeren, Poly(C2-C4)-alkoxylierten nichtionischen Tensiden, wässrigen polymeren Lösungen und Emulsionen und Mischungen hiervon.
  3. Mehrphasige Detergenstablette nach Anspruch 1 oder 2, wobei das Haftmittel gewählt ist aus Polyethylenglykolen mit einem durchschnittlichen Molekulargewicht im Bereich von 200 bis 700.
  4. Mehrphasige Detergenstablette zur Verwendung in einer Waschmaschine, wobei die Tablette umfasst: eine erste Phase in Form eines geformten Körpers mit mindestens einer Vertiefung in dessen Oberfläche, wobei die erste Phase in Haftkontakt mit einer oder mehreren zweiten Phasen steht, mindestens eine zweite Phase, welche innerhalb der Vertiefung enthalten ist, die in Form eines komprimierten teilchenförmigen Feststoffs vorliegt, beinhaltend ein Haftmittel, das bei 28°C flüssig ist, gewählt aus Polyethylenglykolen mit einem durchschnittlichen Molekulargewicht im Bereich von 200 bis 700.
  5. Mehrphasige Detergenstablette nach mindestens einem der Ansprüche 1 bis 4, wobei die erste und/oder zweite Phase zusätzlich ein Bindemittel umfasst, gewählt aus der Gruppe, bestehend aus Zucker und Zuckerderivaten, Stärke und Stärkederivaten, anorganischen und organischen Polymeren.
  6. Mehrphasige Detergenstablette nach Anspruch 5, wobei das Bindemittel gewählt ist aus Polyethylenglykolen mit einem durchschnittlichen Molekulargewicht im Bereich von 1.000 bis 12.000.
  7. Mehrphasige Detergenstablette nach mindestens einem der Ansprüche 1 bis 4, wobei das flüssige Haftmittel durch nachträgliche Zugabe eingebracht ist, vorzugsweise als eine Aufsprühung auf den teilchenförmigen Feststoff vor der Komprimierung.
  8. Mehrphasige Detergenstablette zur Verwendung in einer Waschmaschine, wobei die Tablette umfasst: eine erste Phase in Form eines geformten Körpers mit mindestens einer Vertiefung in dessen Oberfläche, wobei die erste Phase in Haftkontakt mit einer oder mehreren zweiten Phasen steht, mindestens eine zweite Phase, welche innerhalb der Vertiefung enthalten ist, welche in Form eines komprimierten teilchenförmigen Feststoffs vorliegt, beinhaltend Haftmittel, das bei 28°C flüssig ist, und wobei das flüssige Haftmittel durch nachträgliche Zugabe eingebracht ist, vorzugsweise als Aufsprühung auf den teilchenförmigen Feststoff vor der Komprimierung.
  9. Mehrphasige Detergenstablette nach mindestens einem der Ansprüche 1 bis 6, wobei die erste Phase in Form eines geformten Körpers vorliegt, gebildet durch Komprimieren bei einem Druck von größer als demjenigen der zweiten Phase.
  10. Mehrphasige Detergenstablette nach mindestens einem der Ansprüche 1 bis 7, wobei die zweite Phase bei einem Druck von weniger als 350 kg/cm2 komprimiert ist.
  11. Mehrphasige Detergenstablette nach mindestens einem der Ansprüche 1 bis 8, wobei die erste Phase bei einem Druck von mindestens 350 kg/cm2 komprimiert ist.
  12. Mehrphasige Detergenstablette nach mindestens einem der Ansprüche 1 bis 9, wobei
    a) die erste Phase in Form eines geformten Körpers mit mindestens einer Vertiefung darin vorliegt; und
    b) die zweite Phase in Form eines innerhalb der Vertiefung komprimierten teilchenförmigen Feststoffs vorliegt.
  13. Mehrphasige Detergenstablette nach mindestens einem der Ansprüche 1 bis 10, wobei die zweite Phase zusätzlich ein Disruptionsmittel umfasst.
EP99933807A 1998-07-17 1999-07-09 Waschmitteltablette Revoked EP1144567B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GBGB9815525.2A GB9815525D0 (en) 1998-07-17 1998-07-17 Detergent tablet
GB9815525 1998-07-17
GB9818720A GB2340842A (en) 1998-08-28 1998-08-28 Detergent tablet
GB9818720 1998-08-28
PCT/US1999/015490 WO2000004116A2 (en) 1998-07-17 1999-07-09 Detergent tablet

Publications (3)

Publication Number Publication Date
EP1144567A2 EP1144567A2 (de) 2001-10-17
EP1144567A3 EP1144567A3 (de) 2001-11-07
EP1144567B1 true EP1144567B1 (de) 2004-09-22

Family

ID=26314048

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99933807A Revoked EP1144567B1 (de) 1998-07-17 1999-07-09 Waschmitteltablette

Country Status (11)

Country Link
EP (1) EP1144567B1 (de)
JP (1) JP2002520475A (de)
AT (1) ATE277166T1 (de)
AU (1) AU4978599A (de)
BR (1) BR9912150A (de)
CA (1) CA2337401C (de)
DE (1) DE69920517T2 (de)
ES (1) ES2224681T3 (de)
HK (1) HK1041899A1 (de)
TR (1) TR200100095T2 (de)
WO (1) WO2000004116A2 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2089501A1 (de) * 2006-10-27 2009-08-19 Henkel AG & Co. KGaA Wasch- oder reinigungsmittelformkörper
EP2097503A1 (de) * 2006-10-27 2009-09-09 Henkel AG & Co. KGaA Wasch- oder reinigungsmittelformkörper

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE212660T1 (de) * 1998-07-17 2002-02-15 Procter & Gamble Waschmitteltablette
IES990573A2 (en) * 1998-07-17 2000-03-08 Procter & Gamble Detergent tablet
DE29911484U1 (de) * 1998-07-17 2000-02-24 Procter & Gamble Reinigungsmitteltablette
DK0979864T3 (da) * 1998-07-17 2002-04-22 Procter & Gamble Fremgangsmåde til fremstilling af detergenttabletter
DE19856214C1 (de) † 1998-12-05 2000-03-09 Henkel Kgaa Punkttablette
AU3159300A (en) * 1999-03-03 2000-09-21 Henkel Kommanditgesellschaft Auf Aktien Method of preparing multi-phase moulded detergent and/or cleaning agent articles
GB0003592D0 (en) * 2000-02-17 2000-04-05 Procter & Gamble Detergent tablet
DE10010760A1 (de) * 2000-03-04 2001-09-20 Henkel Kgaa Mehrphasige Wasch- und Reinigungsmittelformkörper mit nicht-gepreßten Anteilen
GB0015350D0 (en) † 2000-06-23 2000-08-16 Reckitt Benckiser Nv Improvements in or relating to compositions
DE10061421A1 (de) * 2000-12-09 2002-06-20 Henkel Kgaa Verfahren zur Herstellung geklebter Formkörper

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5133892A (en) * 1990-10-17 1992-07-28 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing detergent tablets
GB9114184D0 (en) * 1991-07-01 1991-08-21 Unilever Plc Detergent composition
GB2320254A (en) * 1996-12-12 1998-06-17 Procter & Gamble Process for making tabletted detergent compositions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2089501A1 (de) * 2006-10-27 2009-08-19 Henkel AG & Co. KGaA Wasch- oder reinigungsmittelformkörper
EP2097503A1 (de) * 2006-10-27 2009-09-09 Henkel AG & Co. KGaA Wasch- oder reinigungsmittelformkörper

Also Published As

Publication number Publication date
ES2224681T3 (es) 2005-03-01
WO2000004116A3 (en) 2001-08-16
JP2002520475A (ja) 2002-07-09
TR200100095T2 (tr) 2001-12-21
DE69920517T2 (de) 2005-11-10
AU4978599A (en) 2000-02-07
EP1144567A2 (de) 2001-10-17
HK1041899A1 (zh) 2002-07-26
CA2337401A1 (en) 2000-01-27
DE69920517D1 (de) 2004-10-28
WO2000004116A2 (en) 2000-01-27
ATE277166T1 (de) 2004-10-15
BR9912150A (pt) 2001-04-10
CA2337401C (en) 2005-10-11
EP1144567A3 (de) 2001-11-07

Similar Documents

Publication Publication Date Title
EP1144585B1 (de) Waschmitteltablette
US6686328B1 (en) Detergent tablet
US6770616B1 (en) Detergent tablet
US20020160930A1 (en) Detergent tablet
JP2002520481A (ja) 洗剤タブレット
JP2001512177A (ja) 錠剤型洗剤
EP1144567B1 (de) Waschmitteltablette
EP1378563B1 (de) Waschmittelzusammensetzung
US6974789B1 (en) Detergent tablet
JP2002520478A (ja) 洗剤タブレット
CA2298842A1 (en) A process for the production of a dishwasher detergent shaped body
CA2337408C (en) A multi-phase detergent tablet
CA2362955C (en) Multi-phase detergent tablet
WO2002033038A2 (en) Detergent tablet
JP2002523615A (ja) 洗剤タブレット
CA2455703C (en) A multi-phase detergent tablet
CA2357800A1 (en) Detergent tablets comprising a pectate lyase
GB2340842A (en) Detergent tablet
CA2510479A1 (en) A multi-phase detergent tablet
MXPA01007413A (en) Detergent tablet

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

PUAK Availability of information related to the publication of the international search report

Free format text: ORIGINAL CODE: 0009015

17P Request for examination filed

Effective date: 20010115

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

XX Miscellaneous (additional remarks)

Free format text: DERZEIT SIND DIE WIPO-PUBLIKATIONSDATEN A3 NICHT VERFUEGBAR.

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20030731

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: 7C 11D 3/37 B

Ipc: 7C 11D 17/00 A

RIC1 Information provided on ipc code assigned before grant

Ipc: 7C 11D 3/37 B

Ipc: 7C 11D 17/00 A

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU NL PT SE

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

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

Ref country code: LI

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

Effective date: 20040922

Ref country code: FI

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

Effective date: 20040922

Ref country code: CH

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

Effective date: 20040922

Ref country code: BE

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

Effective date: 20040922

Ref country code: AT

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

Effective date: 20040922

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

XX Miscellaneous (additional remarks)

Free format text: DERZEIT SIND DIE WIPO-PUBLIKATIONSDATEN A3 NICHT VERFUEGBAR.

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69920517

Country of ref document: DE

Date of ref document: 20041028

Kind code of ref document: P

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

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

Ref country code: GR

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

Effective date: 20041222

Ref country code: DK

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

Effective date: 20041222

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20040922

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2224681

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLAQ Examination of admissibility of opposition: information related to despatch of communication + time limit deleted

Free format text: ORIGINAL CODE: EPIDOSDOPE2

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAQ Examination of admissibility of opposition: information related to despatch of communication + time limit deleted

Free format text: ORIGINAL CODE: EPIDOSDOPE2

PLAR Examination of admissibility of opposition: information related to receipt of reply deleted

Free format text: ORIGINAL CODE: EPIDOSDOPE4

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

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

Ref country code: LU

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

Effective date: 20050709

Ref country code: CY

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

Effective date: 20050709

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

Ref country code: IE

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

Effective date: 20050711

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: HENKEL KGAA

Effective date: 20050622

ET Fr: translation filed
NLR1 Nl: opposition has been filed with the epo

Opponent name: HENKEL KGAA

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

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

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

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

Ref country code: PT

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

Effective date: 20050222

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: HENKEL AG & CO. KGAA

Effective date: 20050622

NLR1 Nl: opposition has been filed with the epo

Opponent name: HENKEL AG & CO. KGAA

REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1041899

Country of ref document: HK

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

APAN Information on closure of appeal procedure modified

Free format text: ORIGINAL CODE: EPIDOSCNOA9O

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

Ref country code: FR

Payment date: 20090708

Year of fee payment: 11

Ref country code: ES

Payment date: 20090713

Year of fee payment: 11

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: SE

Payment date: 20090708

Year of fee payment: 11

Ref country code: NL

Payment date: 20090722

Year of fee payment: 11

Ref country code: GB

Payment date: 20090612

Year of fee payment: 11

Ref country code: DE

Payment date: 20090730

Year of fee payment: 11

27W Patent revoked

Effective date: 20091002

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Effective date: 20091002

NLR2 Nl: decision of opposition

Effective date: 20091002

REG Reference to a national code

Ref country code: SE

Ref legal event code: ECNC

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

Ref country code: IT

Payment date: 20090725

Year of fee payment: 11