[go: up one dir, main page]

EP1907294B1 - Systeme d'emballage pour produit de lavage ou de nettoyage - Google Patents

Systeme d'emballage pour produit de lavage ou de nettoyage Download PDF

Info

Publication number
EP1907294B1
EP1907294B1 EP06723958A EP06723958A EP1907294B1 EP 1907294 B1 EP1907294 B1 EP 1907294B1 EP 06723958 A EP06723958 A EP 06723958A EP 06723958 A EP06723958 A EP 06723958A EP 1907294 B1 EP1907294 B1 EP 1907294B1
Authority
EP
European Patent Office
Prior art keywords
packaging system
water
insoluble
washing
sachets
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.)
Not-in-force
Application number
EP06723958A
Other languages
German (de)
English (en)
Other versions
EP1907294A1 (fr
Inventor
Christian Nitsch
Wolfgang Barthel
Ulrich Pegelow
Pavel Gentschev
Ulf Arno Timmann
Salvatore Fileccia
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL06723958T priority Critical patent/PL1907294T3/pl
Publication of EP1907294A1 publication Critical patent/EP1907294A1/fr
Application granted granted Critical
Publication of EP1907294B1 publication Critical patent/EP1907294B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D77/00—Packages formed by enclosing articles or materials in preformed containers, e.g. boxes, cartons, sacks or bags
    • B65D77/04—Articles or materials enclosed in two or more containers disposed one within another
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions

Definitions

  • the present application is a packaging system for detergents or cleaning agents, in particular a packaging system for pre-portioned dosage units of detergents or cleaners.
  • Detergents or cleaners are now available to the consumer in a variety of forms.
  • this offer also includes, for example, detergent concentrates in the form of extruded or tabletted compositions.
  • These fixed, concentrated or compressed forms of supply are characterized by a reduced volume per dosing unit and thus reduce the costs for packaging and transport.
  • the washing or cleaning agent tablets additionally meet the consumer's desire for simple dosing.
  • the corresponding means are comprehensively described in the prior art.
  • compacted detergents or cleaners also have a number of disadvantages.
  • Especially tableted supply forms are characterized by their high compression often by a delayed disintegration and thus a delayed release of their ingredients.
  • solid or liquid detergents or cleaners which have a water-soluble or water-dispersible packaging are increasingly being described in recent years. These agents are characterized as the tablets by a simplified dosage, since they can be dosed together with the outer packaging in the washing machine or dishwasher, but on the other hand they also allow the preparation of liquid or powdered detergents or cleaners, which compared to the Kompaktaten characterized by a better resolution and faster effectiveness.
  • the EP 1 314 654 A2 (Unilever) a dome-shaped pouch with a receiving chamber containing a liquid.
  • EP 1 256 623 A1 Subject of the European application EP 1 256 623 A1 (Procter & Gamble) is a kit of at least two bags of different composition and optics. The bags are separate and not as a compact single product.
  • EP 1 516 918 A2 (Procter & Gamble) a container, which is preferably provided with a viewing window and contains a group, for example, in terms of their color or shape of different dosage units.
  • German patent application DE 102 54 313 A1 (Henkel) describes water-soluble film envelopes for the packaging of detergent tablets.
  • the object of the present application was to provide an optimized packaging system for dosing units of detergents or cleaners.
  • This packaging system should, in particular, be characterized by improved storage stability the influence of chemical and physical influences on the dosing units. Furthermore, the amount of packaging material used should be largely reduced while maintaining the stability of the metering units.
  • This object has been achieved by a packaging system which comprises a combination of water-insoluble packaging systems which surround each other.
  • the consumer opens the water-insoluble bag of the secondary packaging system, removes one of the (n)> 2 water-insoluble bags from the primary packaging system and can then turn one of the (x)> 2 detergent or dosing units remove.
  • the water-insoluble bags of the first packaging system and / or the second packaging system are preferably closed prior to use by the consumer.
  • the washing or makesstoffdosierüen contained in the water-insoluble bag of the primary packaging system are preferably not separated from each other by further packaging means and are preferably in contact with each other
  • washing or cleaning agent dosing units are understood as meaning portions of washing or cleaning agents which are suitable for carrying out a cleaning process, preferably a machine dishwashing process or a mechanical textile cleaning process.
  • washing or cleaning agent dosing units are metering units for automatic dishwashing
  • these dosing units preferably have a weight above 5 g, preferably between 10 and 40 g, more preferably between 15 and 30 g and in particular between 15 and 25 g.
  • the volume of these metering units is preferably less than 50 ml, preferably between 10 and 40 ml, more preferably between 15 and 30 ml and in particular between 15 and 25 ml.
  • the washing or cleaning agent dosing units are dosing units for textile cleaning
  • these dosing units preferably have a weight above 10 g, preferably between 20 and 100 g, more preferably between 30 and 90 g and in particular between 40 and 80 g.
  • the volume of these dispensing units is preferably less than 120 ml, preferably between 20 and 100 ml, more preferably between 30 and 90 ml and in particular between 40 and 80 ml.
  • a packaging system characterized in that the water-insoluble bags of the primary packaging system each contain a number (x)> 3, preferably (x)> 4, particularly preferably (x)> 5 detergent or detergent dosing units, is therefore a preferred subject of the present application ,
  • the primary packaging system consists of a number (n)> 3, preferably (n)> 4, particularly preferably (n)> 5 water-insoluble bags.
  • the water-insoluble bags of the primary packaging system may be identical in terms of their dimensions or their filling, of course they may differ both in terms of their dimensions and in terms of their filling.
  • a preferred embodiment of the packaging system according to the invention is characterized in that the water-insoluble bags of the primary packaging system differ in their filling volumes by less than 50% by volume, preferably by less than 30% by volume and in particular by less than 10% by volume.
  • a further preferred embodiment of the packaging system according to the invention is characterized in that the number (n) of water-insoluble bags of the primary packaging system and the number (x) of the washing or cleaning contained in each of these bags Do not differentiate starsstoffdosierüen by more than 3, preferably not more than 2 and in particular not more than 1.
  • Packaging systems according to the invention characterized in that the primary and / or secondary packaging system has a moisture vapor transmission rate of 0.1 g / m 2 / day to less than 20 g / m 2 day when the packaging system is at 23 ° C and a relative humidity Stored equilibrium moisture content of 85%, are characterized by an improved storage stability of detergent or makesstoffdosierüen and are therefore preferred.
  • the packaging system according to the invention is suitable for stabilizing the washing and cleaning agent dosing units contained in a chemical and physical view.
  • the packaging system not only protects the active substances contained in the washing or cleaning agent dosing units from premature chemical decomposition but also protects the washing or cleaning agent dosing units from breakage or leakage.
  • the stabilization of the washing or cleaning agent dosing units against chemical or physical decomposition can be further improved by deliberately influencing the gas atmosphere within the primary and secondary packaging systems.
  • Packaging processes for detergents or cleaning agents are usually carried out in the ambient atmosphere.
  • the gas enclosed in the packaging therefore corresponds in its composition to the composition of the air or differs only slightly from it.
  • the primary packaging system is not filled with the secondary packaging system with a gas which has a different composition from the ambient air.
  • both the primary and the secondary packaging system are filled with a gas which differs in composition from the composition of the ambient air, but still the composition of the gas in the primary packaging system of the composition of the gas in different from the secondary packaging system.
  • Packaging systems characterized in that at least one water-insoluble bag of the primary packaging system and / or the water-insoluble bag of the secondary packaging system is filled with a gas which has a different composition from the ambient air, are preferred.
  • the primary (s) and / or secondary (s) packaging system (s) is filled with a gas that a volume fraction of nitrogen above 80 vol.%, Preferably above 85 vol.%, Particularly preferred above 90 vol.% And in particular above 95 vol.% Has.
  • the chemical and physical stability of the detergent dosing units may also be increased by the degree of filling of the primary and secondary packaging systems and / or by the gas pressure of the gas trapped in the primary and secondary packaging systems ,
  • the primary and secondary packaging systems have different fill levels.
  • the primary packaging system has a higher degree of filling than the secondary packaging system. So it is inventively preferred that the primary packaging system has a degree of filling above 80 vol .-%, preferably above 85 vol.% And in particular above 90 vol .-%, while the degree of filling of the secondary packaging system less than 75 vol .-%, preferably less than 70% by volume and in particular less than 60% by volume.
  • At least one of the packaging systems has a degree of filling above 95% by volume, preferably above 97% by volume and in particular above 99% by volume, very particularly preferably of 100% by volume.
  • a degree of filling can be realized, for example, by vacuum-sealing the water-insoluble bags of the primary packaging system and / or of the secondary packaging system.
  • Packaging systems characterized in that at least one water-insoluble bag of the primary packaging system and / or the water-insoluble bag of the secondary packaging system is vacuum-sealed, are preferred according to the invention.
  • the stability of the washing or cleaning agent dosing units contained in the packaging system according to the invention can be increased by inflating the water-insoluble bags of the primary packaging system and / or the secondary packaging system.
  • Packaging systems characterized in that at least one water-insoluble bag of the primary packaging system and / or the water-insoluble bag of the secondary packaging system is inflated, are preferred according to the invention.
  • the above filling level according to the invention relates both to the dosing units contained in the respective packaging system and to the gas contained in the respective packaging system.
  • Below the maximum filling level of a packaging system (100 vol .-%) is understood to mean the volume of a packaging system, which exceeds the packaging material of the respective packaging system undergoes a reversible or irreversible stretching.
  • the packaging system according to the invention comprises two surrounding water-insoluble bags.
  • bag while bag-like containers are referred to, which are distinguished from conventional packaging cartons, for example, by flexible, that is foldable or rollable side walls.
  • Particularly preferred packaging systems according to the invention are characterized in that at least one of the water-insoluble bags of the primary packaging system and / or the water-insoluble bag of the secondary packaging system is a stand-up bag, block bottom bag, gusseted bag or a flow pack.
  • the washing or cleaning agent dosing units packaged in the packaging system according to the invention are "single-dose units, ie detergent or detergent portions suitable for carrying out a single cleaning process, preferably a machine dishwashing process or a mechanical textile cleaning process
  • the remaining dosing units remain in the packaging system until the next use operation, in order to protect the dosing units remaining in the packaging system, the primary packaging system and / or the secondary packaging system is preferably provided with a resealable opening.
  • Packaging systems according to the invention characterized in that at least one of the water-insoluble bags of the primary packaging system and / or the water-insoluble bags of the secondary packaging system has a reclosable opening, are therefore preferred according to the invention.
  • the packaging system according to the invention is basically suitable for all washing or cleaning agent dosing units known to the person skilled in the art.
  • a portioned amount of detergent or cleaning agent which is suitable for carrying out a washing or cleaning operation, for example in a dishwasher or a textile washing machine, and which consumes itself in the course of this washing or cleaning cycle is referred to as the washing or cleaning agent dosing unit.
  • Typical automatic dishwashing dosage units have a volume of between 12 and 40 ml, preferably between 14 and 30 ml and in particular between 16 and 25 ml.
  • the preparation of the washing or cleaning agent dosing units can be carried out by the methods and methods known to the person skilled in the art.
  • the particularly preferred metering units also include the water-soluble containers, in particular deep-drawn or injection-molded containers, and the water-soluble film bags.
  • the washing or cleaning agent dosing units packaged in accordance with the invention are a compressed molding, preferably a washing or cleaning agent tablet.
  • particulate premixes are compacted in a so-called matrix between two punches to form a solid compressed product.
  • This process hereinafter referred to as tabletting, is divided into four sections: dosing, compaction, plastic deformation and ejection.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • ⁇ is the diametrical fracture stress (DFS) in Pa
  • P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article
  • D is the molded article diameter in meters and t the height of the moldings.
  • the tablets can also in the context of the present invention, multi-phase, in particular multi-layered, ausgestalten.
  • the moldings can be made in a predetermined spatial form and predetermined size.
  • the training as a blackboard the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.
  • This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
  • the spatial form of another embodiment of the moldings is adapted in their dimensions of Ein Schlauerhunt of commercial household washing machines or the dosing of commercial dishwashers, so that the moldings can be metered without dosing directly into the dispenser, where they dissolve during the Ein réellevorgangs, or from where they are released during the cleaning process.
  • the detergent tablets have a cavity.
  • This cavity may be a trough or alternatively a breakthrough.
  • Breakthroughs are in this case those cavities which extend through the shaped body and consequently have at least two, preferably exactly two openings on the surface of the shaped body. In this case, such breakthroughs are preferred, whose openings connect two opposite sides of the molding together.
  • the resulting shaped bodies can also be referred to as ring shaped bodies or as ring tablets.
  • the wells or apertures described above are filled in a preferred embodiment.
  • solids are just as suitable as liquids or solidifying melts.
  • the troughs or apertures may also be filled with one of the deep-drawn or injection-molded containers described below.
  • Particular preference is given to washing or cleaning agent tablets whose filled wells are closed with a water-soluble or water-dispersible film which is preferably adhesive with the detergent or cleaning product tablet.
  • washing or take-offsmitteldosierüen comprise a compressed molding and an adhering to this molded body water-soluble film.
  • multiphase dosing units which include not only a solid, for example, a flowable composition, preferably a liquid or a gel, and in water completely are soluble.
  • a flowable composition preferably a liquid or a gel
  • dosing units combine the advantages of pre-dosed detergent portions with the advantages of flowable, easily soluble detergents.
  • washing or cleaning agent dosing units based on the total weight of the washing or cleaning substances contained more than 4 wt.%, Preferably more than 6 wt.% And in particular more than 8 wt .-% sodium percarbonate contain, wherein the washing or craftsstoffdosierüen preferably comprise a compressed molding and adhering to this molded body water-soluble film.
  • packaging systems characterized in that the detergent or makesstoffdosierikien based on the total weight of the washing or cleaning active substances contained 0.5 to 8 wt .-%, preferably 1 to 7 and especially 2 to 6 wt.%
  • Nonionic surfactants contain, wherein the washing or makesstoffdosierikien preferably comprise a compressed molding and adhering to this molded body water-soluble film.
  • thermoformed containers or thermoformed bodies are those containers which are obtained by deep-drawing a first film-like wrapping material.
  • the deep drawing is preferably carried out by bringing the wrapping material over a receiving trough located in a die forming the deep-drawing tray and shaping the wrapping material into this receiving trough by the action of pressure and / or vacuum.
  • the shell material may be pre-treated before or during the molding by the action of heat and / or solvent and / or conditioning by relative to ambient conditions changed relative humidity and / or temperatures.
  • the pressure action can be carried out by two parts of a tool, which behave as positive and negative to each other and deform a spent between these tools film when squeezed.
  • the action of compressed air and / or the weight of the film and / or the weight of an active substance applied to the upper side of the film is also suitable as pressure forces.
  • the deep-drawn shell materials are preferably fixed after deep drawing by using a vacuum within the receiving wells and in their achieved by the deep-drawing process space shape.
  • the vacuum is preferably applied continuously from deep drawing to filling until sealing and in particular until the separation of the receiving chambers.
  • a discontinuous vacuum for example, for deep drawing of the receiving chambers and (after an interruption) before and during the filling of the receiving chambers, possible.
  • the continuous or discontinuous vacuum can vary in its thickness and, for example, take higher values at the beginning of the process (during deep drawing of the film) than at its end (during filling or sealing or singulation).
  • the shell material can be pre-treated by the action of heat before or during the molding into the receiving troughs of the matrices.
  • the shell material preferably a water-soluble or water-dispersible polymer film, is heated to temperatures above 60 ° C. for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0.4 to 2 seconds. preferably above 80 ° C, more preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C.
  • the dies used and the receiving troughs located in these dies are preferably carried out at temperatures below 20 ° C, preferably below 15 ° C, more preferably at temperatures between 2 and 14 ° C and in particular at temperatures between 4 and 12 ° C.
  • the cooling takes place continuously from the beginning of the deep-drawing process to the sealing and separation of the receiving chambers. Cooling fluids, preferably water, which are circulated in special cooling lines within the matrix, are particularly suitable for cooling.
  • This cooling as well as the previously described continuous or discontinuous application of a vacuum has the advantage of preventing shrinkage of the deep-drawn containers after deep drawing, whereby not only the appearance of the process product is improved, but also at the same time the discharge of the filled into the receiving chambers means the edge of the receiving chamber, for example in the sealing areas of the chamber, is avoided. Problems with the sealing of the filled chambers are thus avoided.
  • the deep drawing process can be between methods in which the shell material is guided horizontally in a forming station and from there in a horizontal manner for filling and / or sealing and / or separating and methods in which the shell material over a continuous circumferential Matrizenformwalze (optionally optionally with a counter-guided Patrizenformwalze, which lead the forming upper punches to the cavities of Matrizenformwalze) differ.
  • the first-mentioned process variant of the flat bed process is to operate both continuously and discontinuously, the process variant using a molding roll is usually continuous. All of the mentioned deep drawing methods are suitable for the production of the inventively preferred means.
  • the receiving troughs located in the matrices can be arranged "in series" or staggered.
  • thermoforming bodies can have one, two, three or more receiving chambers. These receiving chambers can be arranged side by side and / or one above the other in the deep-drawn part.
  • the individual receiving chambers of the thermoforming bodies are filled with different agents. It is preferred in particular to fill at least one receiving chamber of a thermoformed body with a liquid, while at least one further receiving chamber of this thermoformed body is filled with a solid
  • the washing or cleaning agent dosing units packaged in accordance with the invention are filled injection-molded containers.
  • Injection molding refers to the forming of a molding material such that the mass contained in a mass cylinder for more than one injection molding plastically softens under heat and flows under pressure through a nozzle into the cavity of a previously closed tool. The method is mainly applied to non-hardenable molding compounds which solidify in the tool by cooling. Injection molding is a very economical modern process for producing non-cutting shaped articles and is particularly suitable for automated mass production.
  • thermoplastic molding compounds are heated to liquefaction (up to 180 ° C) and injected under high pressure (up to 140 MPa) in closed, two-piece, that is from Gesenk (earlier Die) and core (formerly male) existing, preferably water-cooled molds, where they cool and solidify.
  • Suitable molding compositions are water-soluble polymers, for example the abovementioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.
  • Packaging systems preferred according to the invention are characterized in that the washing or cleaning agent dosing units are filled water-soluble or water-dispersible containers, preferably filled deep-drawn or injection-molded containers.
  • the agents according to the invention described above contain washing- and cleaning-active substances, preferably washing and cleaning-active substances from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids, fragrances and perfume carriers.
  • the builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
  • crystalline layer-form silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, where especially preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • Washing or cleaning agents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi x O 2x + 1 .yH 2 O of from 0.1 to 20% by weight of from 0.2 to 15% by weight and in particular from 0.4 to 10% by weight, based in each case on the total weight of these agents.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
  • the alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
  • Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which one
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • phosphates are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • the sodium potassium tripolyphosphates are also preferably used according to the invention.
  • phosphates are used as detergents or cleaning agents in the context of the present application
  • preferred agents comprise these phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium) Potassium tripolyphosphate), in amounts of from 5 to 80% by weight, preferably from 15 to 75% by weight, in particular from 20 to 70% by weight, based in each case on the weight of the washing or cleaning agent.
  • alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • alkali metal carbonates in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt.%, Preferably below 6 wt .-%, more preferably below 4 % By weight and in particular below 2% by weight, in each case based on the total weight of the washing or cleaning agent.
  • Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
  • compositions which, based on the weight of the washing or cleaning agent, are less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate (s) and / or hydrogencarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of detergents or cleaners to (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • the group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.
  • washing or cleaning agents in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
  • Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C9-11 alcohol containing 7 EO, C 13-15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactants consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • C 16-20 alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 -alcohol preferably a C 18 -alcohol
  • at least 12 mol preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • surfactants are further used which contain one or more tallow fatty alcohols with 20 to 30 EO in combination with a silicone defoamer.
  • Nonionic surfactants which have a melting point above room temperature.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa ⁇ s, preferably above 35 Pa ⁇ s and in particular above 40 Pa ⁇ s. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
  • the nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 Wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • nonionic surfactants of the general formula in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3, CH (CH 3 ) 2 and the indices w, x, y, z independently stand for integers from 1 to 6.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from - CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are suitable.
  • nonionic surfactants having a C 9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.
  • These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • R 1 is -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A"'O) z -R 2 , in the
  • R 1 and R 2 independently represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 alkyl or alkenyl radical;
  • A, A ', A "and A"' independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and
  • w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.
  • end-capped poly (oxyalkylated) nonionic surfactants which are of the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 in addition to a radical R 1 which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, where x is between 1 and 90, preferably between 40 and 80, and especially between 40 and 60.
  • surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 , in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
  • anionic surfactants are part of automatic dishwasher detergents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Machine dishwashing detergents which do not contain anionic surfactants are particularly preferred.
  • the group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners.
  • the washing or cleaning-active polymers for example the rinse aid polymers and / or polymers which act as softeners.
  • cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.
  • “Cationic polymers” in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCl designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • amphoteric polymers further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt.%, in each case based on the total weight of the automatic dishwashing agent is.
  • Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.
  • sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.
  • R 1 (R 2 ) C C (R 3 ) COOH in which R 1 to R 3 independently of one another are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.
  • Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds.
  • the content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer.
  • the sulfonic acid groups may be wholly or partly in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions.
  • metal ions preferably alkali metal ions and especially sodium ions.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the bleaching agents are a particularly preferred washing or cleaning substance.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP)] , o-Carboxybenzamidoperoxycaproic acid, N-Nonenylamidoperadipic Acid and N-Nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-Diperoxycarboxylic acid, 1,9-Di
  • chlorine or bromine releasing substances can be used.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • washing or cleaning agents which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight of bleaching agent, preferably Sodium percarbonate, included.
  • the active oxygen content of the washing or cleaning agents, in particular the automatic dishwashing agents in each case based on the total weight of the composition, preferably between 0.4 and 10 wt.%, Particularly preferably between 0.5 and 8 wt .-% and in particular between 0 , 6 and 5% by weight.
  • Particularly preferred compositions have an active oxygen content above 0.3 wt .-%, preferably above 0.7 wt .-%, more preferably above 0.8 wt .-% and in particular above 1.0 wt .-% to.
  • Bleach activators are used in laundry detergents or cleaners, for example, to achieve an improved bleaching effect when cleaned at temperatures of 60 ° C and below.
  • As bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.
  • TAED tetraacet
  • bleach catalysts can also be used.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt.%, In particular of 0.0025 wt. -% to 1 wt .-% and particularly preferably from 0.01% by weight to 0.25% by weight, based in each case on the total weight of the bleach activator-containing agents. But in special cases, more bleach activator can be used.
  • detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly.
  • Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • enzymes and / or enzyme preparations preferably solid protease preparations and / or amylase preparations, in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 4.5% by weight, and in particular from 0.4 to 4 wt.%, Each based on the total enzyme-containing agent used.
  • Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes.
  • the glass corrosion inhibitor used is at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • the content of cleaning agents to zinc salt is preferably between 0.1 to 5 wt.%, Preferably between 0.2 to 4 wt .-% and in particular between 0.4 to 3 wt .-%, or Content of zinc in oxidised form (calculated as Zn 2+ ) between 0.01 to 1 wt.%, Preferably between 0.02 and 0.5 wt.% And in particular between 0.04 and 0.2 wt.% , in each case based on the total weight of the glass corrosion inhibitor-containing agent.
  • disintegration aids so-called disintegrants
  • tablet disintegrants or disintegrants auxiliaries which ensure the rapid disintegration of tablets into water or gastric juice and for the release of the drugs in resorbable form.
  • Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
  • gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.
  • the gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water.
  • the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas.
  • Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • Acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts.
  • organic acidifying agents preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent.
  • Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.
  • perfume oils or perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • the detergents and cleaners may contain further ingredients which further improve the performance and / or aesthetic properties of these compositions.
  • Preferred agents contain one or more of the group of electrolytes, pH adjusters, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids , Phobic and impregnating agents, swelling and anti-slip agents and UV absorbers.

Landscapes

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

Claims (12)

  1. Système d'emballage pour des unités de dosage d'agent de lavage ou de nettoyage, comprenant
    a) un système d'emballage primaire sous forme d'un nombre (n) > 2 de sachets insolubles dans l'eau, chacun de ces sachets contenant un nombre (x) > 2 d'unités de dosage d'agent de lavage ou de nettoyage ; ainsi que
    b) un système d'emballage secondaire sous forme d'un sachet insoluble dans l'eau, qui contient les (n) sachets insolubles dans l'eau du système d'emballage primaire, caractérisé en ce que
    - les sachets insolubles dans l'eau du système d'emballage primaire et/ou le sachet insoluble dans l'eau du système d'emballage secondaire est/sont gonflé(s) ou
    - les sachets insolubles dans l'eau du système d'emballage primaire et/ou le sachet insoluble dans l'eau du système d'emballage secondaire est/sont scellés sous vide.
  2. Système d'emballage selon la revendication 1, caractérisé en ce qu'il s'agit, pour les unités de dosage d'agent de lavage ou de nettoyage de sachets remplis, solubles ou dispersibles dans l'eau.
  3. Système d'emballage selon la revendication 1, caractérisé en ce que les unités de dosage d'agent de lavage ou de nettoyage comprennent un corps façonné comprimé et une feuille soluble dans l'eau liée par adhérence à ce corps façonné.
  4. Système d'emballage selon l'une quelconque des revendications 1 à 3, caractérisé en ce que les unités de dosage d'agent de lavage ou de nettoyage, par rapport au poids total des substances actives en lavage ou en nettoyage contenues contiennent plus de 4% en poids, de préférence plus de 6% en poids et en particulier plus de 8% en poids de percarbonate de sodium.
  5. Système d'emballage selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les unités de dosage d'agent de lavage ou de nettoyage, par rapport au poids total des substances actives en lavage ou en nettoyage contenues contiennent 0,5 à 8% en poids, de préférence 1 à 7% en poids et en particulier 2 à 6% en poids d'agents tensioactifs non ioniques.
  6. Système d'emballage selon l'une quelconque des revendications 1 à 5, caractérisé en ce que les sachets insolubles dans l'eau du système d'emballage primaire contiennent à chaque fois un nombre (x) > 3, de préférence (x) > 4, de manière particulièrement préférée (x) > 5 d'unités de dosage d'agent de lavage ou de nettoyage.
  7. Système d'emballage selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le système d'emballage primaire est constitué par un nombre (n) > 3, de préférence (n) > 4, de manière particulièrement préférée (n)
    > 5 sachets insolubles dans l'eau.
  8. Système d'emballage selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le nombre (n) de sachets insolubles dans l'eau du système d'emballage primaire et le nombre (x) d'unités de dosage d'agent de lavage ou de nettoyage contenues dans chacun de ces sachets ne se distinguent pas de plus de 3, de préférence pas de plus de 2 et en particulier pas de plus de 1.
  9. Système d'emballage selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le système d'emballage primaire et/ou secondaire présente(nt) une vitesse de perméation de la vapeur d'humidité de 0,1 g/m2/jour à moins de 20 g/m2/jour, lorsque le système d'emballage est entreposé à 23°C et à une humidité relative à l'équilibre de 85%.
  10. Système d'emballage selon l'une quelconque des revendications 1 à 9, caractérisé en ce qu'au moins un sachet insoluble dans l'eau du système d'emballage primaire et/ou le sachet insoluble dans l'eau du système d'emballage secondaire est rempli avec un gaz, qui présente une composition différente de celle de l'air environnant.
  11. Système d'emballage selon l'une quelconque des revendications 1 à 9, caractérisé en ce qu'il s'agit, pour au moins un des sachets insolubles dans l'eau du système d'emballage primaire et/ou pour le sachet insoluble dans l'eau du système d'emballage secondaire, d'un sachet à fond plat, d'un sachet à fond carré , d'un sachet à soufflets ou d'un sac thermo-soudé, lorsque les sachets insolubles dans l'eau du système d'emballage primaire et/ou le sachet insoluble dans l'eau du système d'emballage secondaire est/sont gonflé(s).
  12. Système d'emballage selon l'une quelconque des revendications 1 à 10, caractérisé en ce qu'au moins un des sachets insolubles dans l'eau du système d'emballage primaire et/ou le sachet insoluble dans l'eau du système d'emballage secondaire présente une ouverture refermable lorsque les sachets insolubles dans l'eau du système d'emballage primaire et/ou le sachet insoluble dans l'eau du système d'emballage secondaire est/sont gonflé(s).
EP06723958A 2005-04-27 2006-04-01 Systeme d'emballage pour produit de lavage ou de nettoyage Not-in-force EP1907294B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL06723958T PL1907294T3 (pl) 2005-04-27 2006-04-01 Układ opakowaniowy do środków piorących lub czyszczących

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005025690A DE102005025690B4 (de) 2005-04-27 2005-04-27 Verpackungssystem für Wasch-oder Reinigungsmittel
PCT/EP2006/002999 WO2006114185A1 (fr) 2005-04-27 2006-04-01 Systeme d'emballage pour produit de lavage ou de nettoyage

Publications (2)

Publication Number Publication Date
EP1907294A1 EP1907294A1 (fr) 2008-04-09
EP1907294B1 true EP1907294B1 (fr) 2012-01-11

Family

ID=36579830

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06723958A Not-in-force EP1907294B1 (fr) 2005-04-27 2006-04-01 Systeme d'emballage pour produit de lavage ou de nettoyage

Country Status (7)

Country Link
US (1) US20080261851A1 (fr)
EP (1) EP1907294B1 (fr)
AT (1) ATE541028T1 (fr)
DE (1) DE102005025690B4 (fr)
ES (1) ES2377880T3 (fr)
PL (1) PL1907294T3 (fr)
WO (1) WO2006114185A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2412707T5 (es) * 2009-06-19 2023-06-12 Procter & Gamble Composición detergente líquida para lavado de vajillas a mano
ES2412684T3 (es) * 2009-06-19 2013-07-12 The Procter & Gamble Company Composición detergente de lavado de vajillas a mano líquida
US20140308162A1 (en) 2013-04-15 2014-10-16 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US8871699B2 (en) 2012-09-13 2014-10-28 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US20160200501A1 (en) 2015-01-14 2016-07-14 Monosol, Llc Web of cleaning products having a modified internal atmosphere and method of manufacture
EP3858966A1 (fr) * 2020-02-03 2021-08-04 The Procter & Gamble Company Emballage sous vide pour des partions de détergent unitisées

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2234655A (en) * 1939-04-26 1941-03-11 Ivers Lee Co Multiple package
CH593839A5 (fr) * 1976-02-19 1977-12-15 Sig Schweiz Industrieges
DE3326249A1 (de) * 1983-07-21 1985-01-31 Henkel Kgaa Wasch-, spuel- oder reinigungsmittelverpackung
US4933100A (en) * 1988-01-19 1990-06-12 Colgate-Palmolive Co. Built synthetic organic detergent composition patties and processes for washing laundry therewith
MA22576A1 (fr) * 1991-04-02 1993-04-01 Rhone Poulenc Agrochimie Systeme de conteneurisation .
DE4408718A1 (de) * 1994-03-15 1995-09-21 Henkel Kgaa Bruch- und lagerstabile, polyfunktionelle Reinigungstabletten, Verfahren zu ihrer Herstellung und ihre Verwendung
JPH0920311A (ja) * 1995-06-30 1997-01-21 Kyoraku Co Ltd 包装体およびその製造方法
DE19852936A1 (de) * 1998-01-24 1999-08-12 Henkel Kgaa Verpackung für tablettenförmige Gegenstände
GB9906175D0 (en) * 1999-03-17 1999-05-12 Unilever Plc A water soluble package
FR2793220B1 (fr) * 1999-05-04 2001-06-01 Oreal Ensemble pour la mise en contact extemporanee d'au moins deux elements, utilisation d'un tel ensemble et procede de traitement
GB2361707A (en) * 2000-04-28 2001-10-31 Procter & Gamble Pouched compositions
DE10025187A1 (de) 2000-05-20 2001-07-19 Henkel Kgaa Verpackung für tablettenförmige Gegenstände
DE10026551A1 (de) 2000-05-27 2001-11-08 Henkel Kgaa Verpackung für tablettenförmige Gegenstände
DE10108153A1 (de) * 2000-09-28 2002-10-24 Henkel Kgaa Muldentabletten und Verfahren zu ihrer Herstellung
PT1504994E (pt) * 2000-11-27 2007-10-17 Procter & Gamble Processo para a realização de bolsas solúveis em água
GB2374580B (en) * 2001-04-20 2003-07-16 Reckitt Benckiser Water-soluble containers
EP1724206A3 (fr) * 2001-05-08 2007-03-07 The Procter and Gamble Company Kit de sachets solubles ou dispersables dans l'eau
EP1396440A1 (fr) 2002-09-05 2004-03-10 The Procter & Gamble Company Produit emballé comprenant des poches flexibles remplies de liquide
DE10254313A1 (de) 2002-11-21 2004-06-09 Henkel Kgaa Verfahren zur Herstellung befüllter Wasch- und Reinigungsmittelformkörper
DE10336796B4 (de) * 2003-08-08 2005-05-19 Henkel Kgaa Wasch- oder Reinigungsmittel
US7325688B1 (en) * 2003-09-26 2008-02-05 Gowan Milling Company, L.L.C. Pressurized water-soluble pouch

Also Published As

Publication number Publication date
DE102005025690A1 (de) 2006-11-09
ATE541028T1 (de) 2012-01-15
WO2006114185A1 (fr) 2006-11-02
PL1907294T3 (pl) 2012-06-29
EP1907294A1 (fr) 2008-04-09
ES2377880T3 (es) 2012-04-02
DE102005025690B4 (de) 2007-02-01
US20080261851A1 (en) 2008-10-23

Similar Documents

Publication Publication Date Title
EP2220205B1 (fr) Produit de nettoyage
DE19944416A1 (de) Klarspülmittel
EP2225357B1 (fr) Composition détergente
EP1586631A2 (fr) Corps creux compartimentés comprenant une dose d' un produit de lavage, de mnettoyage ou de rincage
EP1740689A1 (fr) Procedes pour la production de detergents et de nettoyants
EP3599274B1 (fr) Poche d'agent de nettoyage multiphase
DE102005048182A1 (de) Faserguss-Verpackung mit Innenbeutel
DE10032612A1 (de) Klarspülmittel II
DE10066035B4 (de) Kompartiment-Hohlkörper
EP1907294B1 (fr) Systeme d'emballage pour produit de lavage ou de nettoyage
EP1213344A2 (fr) Composition de lavage ou de rinçage de vaiselle à la machine contenant un agent détruisant les mauvaises odeurs
DE19959875A1 (de) Preßverfahren für mehrphasige Formkörper
DE102004039472A1 (de) Verfahren zur Herstellung portionierter Wasch- oder Reinigungsmittel
EP1434714A1 (fr) Corps creux a compartiments et son procede de production
EP1434848A1 (fr) Produits de lavage, rin age ou nettoyage en portions dans des contenants souples solubles dans l'eau
EP1922401B1 (fr) Detergent ou nettoyant
DE10244802A1 (de) Pralle Waschmittelformkörper
DE10305799B4 (de) Verfahren zur Herstellung eines blasgeformten Waschmittelkörpers
DE10121017B4 (de) Gel-Tablette
EP4067469A1 (fr) Détergent
EP1210404B1 (fr) Composantes de detergent comprenant des matieres solides a fines particules
DE19957504A1 (de) Reinigungsmittelkomponente
WO2004031034A1 (fr) Corps formes de lessive retrecis
DE102005045440A1 (de) Portionierte Wasch- oder Reinigungsmittelzusammensetzung
DE10145618B4 (de) Portionierte Wasch-, Spül- oder 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: 20070810

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HENKEL AG & CO. KGAA

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20081029

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 502006010842

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: B65D0077040000

Ipc: C11D0017040000

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: C11D 17/04 20060101AFI20110809BHEP

Ipc: C11D 17/00 20060101ALI20110809BHEP

Ipc: B65D 77/04 20060101ALI20110809BHEP

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 BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 541028

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502006010842

Country of ref document: DE

Effective date: 20120315

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2377880

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20120402

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20120111

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

Ref country code: SI

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

Effective date: 20120111

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20120111

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

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

Ref country code: BG

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

Effective date: 20120411

Ref country code: LT

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

Effective date: 20120111

Ref country code: IS

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

Effective date: 20120511

Ref country code: NL

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

Effective date: 20120111

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

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

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: 20120111

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: 20120412

Ref country code: PT

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

Effective date: 20120511

Ref country code: LV

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

Effective date: 20120111

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

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: 20120111

BERE Be: lapsed

Owner name: HENKEL A.G. & CO. KGAA

Effective date: 20120430

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

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: 20120111

Ref country code: EE

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

Effective date: 20120111

Ref country code: RO

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

Effective date: 20120111

Ref country code: IE

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: 20120111

Ref country code: SE

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

Effective date: 20120111

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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

Ref country code: MC

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

Effective date: 20120430

Ref country code: SK

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

Effective date: 20120111

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26N No opposition filed

Effective date: 20121012

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

Effective date: 20120411

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 NON-PAYMENT OF DUE FEES

Effective date: 20120430

Ref country code: GB

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

Effective date: 20120411

Ref country code: BE

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

Effective date: 20120430

Ref country code: CH

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

Effective date: 20120430

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502006010842

Country of ref document: DE

Effective date: 20121012

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 541028

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120401

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

Ref country code: AT

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

Effective date: 20120401

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

Ref country code: TR

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

Effective date: 20120111

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

Ref country code: CZ

Payment date: 20140313

Year of fee payment: 9

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: 20120401

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

Ref country code: ES

Payment date: 20140311

Year of fee payment: 9

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

Ref country code: HU

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: 20060401

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

Ref country code: DE

Payment date: 20140417

Year of fee payment: 9

Ref country code: IT

Payment date: 20140422

Year of fee payment: 9

Ref country code: FR

Payment date: 20140409

Year of fee payment: 9

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

Ref country code: PL

Payment date: 20140313

Year of fee payment: 9

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

Ref country code: CZ

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

Effective date: 20150401

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502006010842

Country of ref document: DE

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

Ref country code: DE

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

Effective date: 20151103

Ref country code: IT

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

Effective date: 20150401

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20151231

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

Ref country code: FR

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

Effective date: 20150430

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20160602

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

Ref country code: ES

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

Effective date: 20150402

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

Ref country code: PL

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

Effective date: 20150401