EP1453941B1 - Bloc hydrosoluble comprenant un detergent a lessive liquide en couches - Google Patents

Bloc hydrosoluble comprenant un detergent a lessive liquide en couches Download PDF

Info

Publication number
EP1453941B1
EP1453941B1 EP02792755A EP02792755A EP1453941B1 EP 1453941 B1 EP1453941 B1 EP 1453941B1 EP 02792755 A EP02792755 A EP 02792755A EP 02792755 A EP02792755 A EP 02792755A EP 1453941 B1 EP1453941 B1 EP 1453941B1
Authority
EP
European Patent Office
Prior art keywords
water
package
composition
component
surfactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02792755A
Other languages
German (de)
English (en)
Other versions
EP1453941A1 (fr
Inventor
Feng-Lung Unilever Research U.S. Inc. HSU
Neeraj Unilever R & D Vlaardingen GUPTA
Kwang Ho Unilever Research U.S. Inc LEE
John Leslie Unilever R & D Port Sunlight STOREY
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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 Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP1453941A1 publication Critical patent/EP1453941A1/fr
Application granted granted Critical
Publication of EP1453941B1 publication Critical patent/EP1453941B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D17/043—Liquid or thixotropic (gel) compositions

Definitions

  • a water-soluble single-use package comprising a layered liquid detergent in the water-soluble body portion and a process of its preparation.
  • Detergent compositions are provided in many forms, of which granular and liquid compositions are the most prevalent. More recently, unit dose forms of detergent have been proposed in the form of compressed tablets of detergent powder or water-soluble packages, which are consumed during a single cleaning application. The unit dose forms are preferred by some consumers, in that the dose is pre-measured and, consequently, the unit dose form is faster, easier and less messy to use. Water-soluble packages filled with liquid detergent composition are desired especially by consumers who are used to liquid detergents.
  • EP 116422, EP 175485, GB 1247189, WO 99/47635, and Ginn disclose dual layer liquid cleaning compositions in a bottle or a water insoluble package.
  • the layers are achieved by employing an electrolyte, which when added to an aqueous surfactant solution, forces the separation of the surfactant from the aqueous phase.
  • electrolyte which when added to an aqueous surfactant solution, forces the separation of the surfactant from the aqueous phase.
  • the phenomenon of separating an organic component from an aqueous layer, by the addition of a salt (electrolyte) is known as "salting out.”
  • the salt increases the ionic character of water and drives the organic, less polar, component away.
  • the present invention includes a layered liquid detergent composition in a water-soluble single use package, the composition comprising at least two layers, with a surfactant and an organic electrolyte distributed within the layers.
  • the preferred inventive compositions include water, yet the water-soluble package remains intact on storage.
  • any particular upper concentration can be associated with any particular lower concentration.
  • Water-soluble body as used herein means soluble in cold water, i.e. soluble at 5°C and above.
  • Organic cation as used herein means a non-metal, positively charged ionic entity.
  • Organic electrolyte as used herein means an electrolyte containing an organic cation.
  • Transparent as used herein includes both transparent and translucent and means that an ingredient, or a mixture, or a phase, or a composition, or a package according to the invention preferably has a transmittance of more than 25%, more preferably more than 30%, most preferably more than 40%, optimally more than 50% in the visible part of the spectrum (approx. 410-800 nm).
  • absorbency may be measured as less than 0.6 (approximately equivalent to 25% transmitting) or by having transmittance greater than 25% wherein % transmittance equals: 1/10 absorbancy x 100%.
  • % transmittance equals: 1/10 absorbancy x 100%.
  • composition or "liquid detergent composition” as used herein means the final detergent composition (i.e., the detergent composition itself, but not the water-soluble body), including at least two layers.
  • the at least two layers comprise between them a surfactant and an organic electrolyte.
  • the package is preferably made of a clear, sealable, cold water soluble film such as polyvinyl alcohol. Thickness could range from 25 to 100 ⁇ m, more preferably from 35 to 80 ⁇ m, most preferably from 45 to 55 ⁇ m. Other materials from which the package can be made include but are not limited to methyl hydroxy propyl cellulose and polyethylene oxide. Polyvinyl alcohol is preferred due to its ready availability and low cost.
  • One supplier of polyvinyl alcohol film is Monosol Inc. European suppliers of suitable films include but are not limited to Monosol supplied by Monosol Inc. or PT supplied by Aicello or K-series supplied by Kurary or Hydrafilm supplied by Rainier Specialty polymers ltd, or QSA series by Polymer Films, Inc.
  • the water-soluble film of the base wall is the same material as that used to make the body wall. Both thermoforming and cold forming (e.g., with water) are possible.
  • the essential ingredients of the inventive laundry compositions are surfactant and organic electrolyte.
  • compositions of the invention contain one or more surface active agents (surfactants) selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic surfactants or mixtures thereof.
  • surfactants selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic surfactants or mixtures thereof.
  • the preferred surfactant detergents for use in the present invention are mixtures of anionic and nonionic surfactants although it is to be understood that any surfactant may be used alone or in combination with any other surfactant or surfactants.
  • the surfactant should comprise at least 5%, e.g., 5% to 80%, preferably at least 10% to 80%, more preferably 15% to 40%; even more preferably 15% to 35% of the composition.
  • Nonionic synthetic organic detergents which can be used with the invention, alone or in combination with other surfactants, are described below. Nonionic surfactants are typically included.
  • Nonionics surfactants are nonionic surfactants whch are pourable liquids, gels or pastes at 25°C.
  • Nonionic detergent surfactants normally have molecular weights of from about 300 to about 11,000. Mixtures of different nonionic detergent surfactants may also be used, provided the mixture is a liquid gel or paste at 25°C.
  • the composition may comprise one or more nonionic surfactants which are solid at 25°C. These dissolved and/or dispersed in either or both liquid layers.
  • nonionic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature).
  • suitable nonionic surfactants are those disclosed in U.S. Pat. Nos. 4,316,812 and 3,630,929 and applicants' published European specification EP-A-225,654.
  • the nonionic detergents are polyalkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic polyalkoxy group to a lipophilic moiety.
  • a preferred class of nonionic detergent is the alkoxylated alkanols wherein the alkanol is of 9 to 18 carbon atoms and wherein the number of moles of alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 12. Of such materials it is preferred to employ those wherein the alkanol is a fatty alcohol of 9 to 11 or 12 to 15 carbon atoms and which contain from 5 to 8 or 5 to 9 alkoxy groups per mole.
  • Nonionics are represented by the commercially well- known class of nonionics sold under the trademark Plurafac®.
  • the Plurafacs® are the reaction products of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include C 13 - C 15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide, C 13 - C 15 fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide, C 13 - C 15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide, or mixtures of any of the above.
  • a particularly preferred group of glycoside surfactants for use in the practice of this invention includes those of the formula above in which R is a monovalent organic radical (linear or branched) containing from about 6 to about 1 8(especially from about 8 to about 18) carbon atoms; y is zero; z is glucose or a moiety derived therefrom; x is a number having an average value of from 1 to about 4 (preferably from about 1 to 4).
  • Nonionic surfactants particularly useful for this application include, but are not limited to: alcohol ethoxylates (e.g. Neodol® 25-9 from Shell Chemical Co.), alkyl phenol ethoxylates (e.g. Tergitol® NP-9 from Union Carbide Corp.), alkylpolyglucosides (e.g. Glucapon® 600CS from Henkel Corp.), polyoxyethylenated polyoxypropylene glycols (e.g. Pluronic® L-65 from BASF Corp.), sorbitol esters (e.g. Emsorb® 2515 from Henkel Corp.), polyoxyethylenated sorbitol esters (e.g.
  • Emsorb® 6900 from Henkel Corp.
  • alkanolamides e.g. Alkamide® DC212/SE from Rhone-Poulenc Co.
  • N-alkypyrrolidones e.g. Surfadone® LP-100 from ISP Technologies Inc.
  • Mixtures of two or more of the nonionic surfactants can be used.
  • the preferred anionic surface active agents are the alkali metal, ammonium or alkanolamide salts of higher alkyl benzene sulfonates and alkali metal, ammonium or alkanolamide salts of higher alkyl sulfonates.
  • Preferred higher alkyl sulfonates are those in which the alkyl groups contain 8 to 26 carbon atoms, preferably 12 to 22 carbon atoms and more preferably 14 to 18 carbon atoms.
  • the alkyl group in the alkyl benzene sulfonate preferably contains 8 to 16 carbon atoms and more preferably 10 to 15 carbon atoms.
  • a particularly preferred alkyl benzene sulfonate is the sodium or potassium dodecyl benzene sulfonate, e.g. sodium linear dodecyl benzene sulfonate.
  • the alkyl substituent is preferably linear, i.e. normal alkyl, however, branched chain alkyl sulfonates can be employed, although they are not as good with respect to biodegradability.
  • the alkane, i.e. alkyl, substituent may be terminally sulfonated or may be joined, for example, to the carbon atom of the chain, i.e. may be a secondary sulfonate. It is understood in the art that the substituent may be joined to any carbon on the alkyl chain.
  • the higher alkyl sulfonates can be used as the alkali metal salts, such as sodium and potassium.
  • the preferred salts are the sodium salts.
  • the preferred alkyl sulfonates are the C 10 to C 18 primary normal alkyl sodium and potassium sulfonates, with the C 10 to C 15 primary normal alkyl sulfonate salt being more preferred.
  • normal alkyl and branched chain alkyl sulfates e.g., primary alkyl sulfates
  • anionic component e.g., sodium sulfate
  • the higher alkyl polyether sulfates used in accordance with the present invention can be normal or branched chain alkyl and contain lower alkoxy groups which can contain two or three carbon atoms.
  • the normal higher alkyl polyether sulfates are preferred in that they have a higher degree of biodegradability than the branched chain alkyl and the lower poly alkoxy groups are preferably ethoxy groups.
  • the preferred higher alkyl poly ethoxy sulfates used in accordance with the present invention are represented by the formula: R'--O(CH 2 CH 2 O) p --SO 3 M, where R' is C 8 to C 20 alkyl, preferably C 10 to C 18 and more preferably C 12 to C 15 ; p is 2 to 8, preferably 2 to 6, and more preferably 2 to 4;and M is an alkali metal, such as sodium and potassium, or an ammonium cation.
  • the sodium and potassium salts are preferred.
  • a preferred higher alkyl poly ethoxylated sulfate is the sodium salt of a triethoxy C 12 to C 15 alcohol sulfate having the formula: C 12-15 --O--(CH 2 CH 2 O) 3 --SO 3 Na
  • alkyl ethoxy sulfates examples include C 12-15 normal or primary alkyl triethoxy sulfate, sodium salt; n-decyl diethoxy sulfate, sodium salt; C 12 primary alkyl diethoxy sulfate, ammonium salt; C 12 primary alkyl triethoxy sulfate, sodium salt: C 15 primary alkyl tetraethoxy sulfate, sodium salt, mixed C 14-15 normal primary alkyl mixed tri- and tetraethoxy sulfate, sodium salt; stearyl pentaethoxy sulfate, sodium salt; and mixed C 10-18 normal primary alkyl triethoxy sulfate, potassium salt.
  • the normal alkyl ethoxy sulfates are readily biodegradable and are preferred.
  • the alkyl poly-lower alkoxy sulfates can be used in mixtures with each other and/or in mixtures with the above discussed higher alkyl benzene, alkyl sulfonates, or alkyl sulfates.
  • the alkali metal higher alkyl poly ethoxy sulfate can be used with the alkylbenzene sulfonate and/or with an alkyl sulfonate or sulfonate, in an amount of 0 to 70%, preferably 10 to 50% and more preferably 10 to 20% by weight of entire composition.
  • Anionic surfactants particularly useful for this application include, but are not limited to: linear alkyl benzene sulfonates (e.g. Vista® C-500 from Vista Chemical Co.), alkyl sulfates (e.g. Polystep® B-5 from Stepan Co.), polyoxyethylenated alkyl sulfates (e.g. Standapol® ES-3 from Stepan Co.), alpha olefin sulfonates (e.g. Witconate® AOS from Witco Corp.), alpha sulfo methyl esters (e.g. Alpha-Step® MC-48 from Stepan Co.), alkyl ether sulfates and isethionates (e.g. Jordapon® Cl from PPG Industries Inc.).
  • linear alkyl benzene sulfonates e.g. Vista® C-500 from Vista Chemical Co.
  • alkyl sulfates e.g. Polystep
  • Anionic surfactants may be added pre-neutralized or, preferably, may be formed in situ, by neutralizing a precursor acid (fatty acid in the case of soaps). Further, the anionic precursor or fatty acid should be over-neutralised (i.e. there should be an excess of the alkaline material used to form the counter-ion). Further still, it is preferable to use the organic counter-ion used for the organic electrolyte. Preferably, monoethanolamine salt of the anionic precursor acid is employed.
  • cationic surfactants are known in the art, and almost any cationic surfactant having at least one long chain alkyl group of about 10 to 24 carbon atoms is suitable in the present invention. Such compounds are described in "Cationic Surfactants", Jungermann, 1970, incorporated by reference.
  • Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be a straight chain or a branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g. carboxylate, sulfonate, sulfate.
  • an anionic water-solubilizing group e.g. carboxylate, sulfonate, sulfate.
  • Examples of compounds falling within this definition are sodium 3(dodecylamino)propionate, sodium 3-(dodecylamino)propane-1-sulfonate, sodium 2-(dodecylamino)ethyl sulfate, sodium 2-(dimethylamino)octadecanoate, disodium 3-(N- carboxymethyldodecylamino)propane 1-sulfonate, disodium octadecylimminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N, N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine.
  • Sodium 3-(dodecylamino)propane-1-sulfonate is preferred.
  • zwitterionic surfactants which may be used are set forth in U.S. Pat. No. 4,062,647, hereby incorporated by reference.
  • the surfactant in the laundry compositions of the invention is anionic and/or nonionic, especially linear alkylbenzene sulfonate, alkyl ether sulfate, alcohol ethoxylates and mixtures thereof.
  • mixtures of anionic and nonionc surfactants are especially preferred, for optimum greasy stain and particulate soil removal.
  • the most effective mixtures employ anionic to nonionic ratio of from 10: 1 to 1:10, preferably from 5:1 to 1:5, most preferably from 3:1 to 1:3.
  • nonionic surfactants are employed, in the absence of, or lower levels of, anionic surfactants, alone or in combination with cationic surfactants and/or antifoams.
  • an electrolyte containing an organic cation results in formulations which may contain more water, yet by virtue of much reduced water activity level, without damaging the water-soluble package, resulting in more cost-effective product. Higher amounts of water are also advantageous to accommodate hydrophilic functional ingredients. Furthermore, the use of organic electrolyte resulted in improved transparency of the compositions, compared to the same compositions containing an inorganic electrolyte (i.e., inorganic cation). In addition, organic electrolytes decrease the potential for surfactant crystallizing out during storage.
  • Electrolyte may be pre-formed or formed in situ.
  • organic electrolytes suitable for use in the present invention meet both of the following criteria:
  • Preferred electrolytes are selected from the group consisting of monoethanolamine, triethanolamine, and ammonium oxide salts of citrate, carbonate, bicarbonate, borate and sulfate.
  • Monoethanolamine salt is the most effective.
  • Monoethanolamine citrate, monoethanolamine carbonate and monoethanolamine borate are the most preferred, due to their ability to also function as builders and/or buffering agents in the detergent composition.
  • Monoethanolamine citrate is optimum, due to its optimum ability to salt out a surfactant and/or reduce the water activity.
  • the liquid detergent composition of the invention generally includes from 1 to 50%, more preferably from 5 to 40%, most preferably from 5 to 35%, and optimally from 10 to 30% of the organic electrolyte, in order to attain a stable layered composition, at optimum cost.
  • concentration of electrolyte to create a two-layered composition depends on the surfactant concentration, the water amount and the identity of the electrolyte.
  • the concentration needed may be predicted by calculating the ionic strength of the electrolyte at a particular concentration. It has been found as part of the present invention that the preferred electrolytes and preferred concentrations are those that have a calculated ionic strength of at least 4.2, preferably at least 4.4, more preferably at least 5.
  • the liquid laundry detergent according to the invention comprises at least two layers. Both layers are preferably isotropic (a single phase when viewed macroscopically), after standing still for at least 24 hours at 20°C. "Isotropic" is used herein to describe each layer of the inventive composition, since the composition overall contains at least two layers and thus could not be isotropic overall.
  • compositions comprise two layers, with the top layer containing majority, preferably all, of the surfactant, and the bottom layer containing the majority, preferably all, of the electrolyte.
  • compositions of the resultant layers do not necessarily correspond with the compositions of the respective layers prior to their being combined into a single composition. This is because of reaction between ingredients, in particular the acidic ingredients and the basic ingredients (e.g., monoethanolamine) and also, because of possible migration of material between the two layers, or emulsification of some of the layers within each other. Consequently, it is to be understood that the composition of the components as herein described pertains to the compositions prior to their being combined into a single composition. By virtue of employing a surfactant and an organic electrolyte in the amounts as herein described (and optional ingredients, including those described below), the composition separates into at least two layers, wherein the composition of the layers may differ from the composition of the initial components.
  • a surfactant and an organic electrolyte in the amounts as herein described (and optional ingredients, including those described below)
  • the ranges of the surfactant, electrolyte, and water content within the respective components or layers are as follows (% by weight of the relevant component): Surfactant Electrolyte Total Water Surfactant Component or Layer General 5-100 0-15 0-60 Preferred 10-70 0-5 1-40 Most Preferred 20-60 0-1 5-30 Optimum 20-55 0-1 5-25 Electrolyte Component or Layer General 0-5 1-100 0-90 Preferred 0-1 5-95 10-60 Most Preferred 0-1 10-60 20-70 Optimum 0-1 15-40 20-50
  • the volume ratio of the two components in the final composition is generally in the range of from 10:90 to 90:10, more preferably from 20:80 to 80:20, most preferably from 70:30 to 30:70, and optimally from 40:60 to 60:40, in order to provide the most pleasing appearance and optimum cleaning benefits.
  • the resulting layers have the volume ratios in the same ranges as described above (but the layer ratio may not be the same as the component ratio). More than two layers may be present.
  • the additional layer may be a capsule, dispersion or emulsion layer, as described below under Optional Ingredients.
  • a surfactant component may include both highly polar and highly non-polar ingredients, which might separate into more than one organic-rich layer.
  • the preferred laundry composition may include one or more well-known laundry ingredients, such as builders (from 0.1 to 20%), anti-redeposition agents, fluorescent dyes, perfumes, soil-release polymers, colorant, enzymes, buffering agents, antifoam agents, UV-absorber, etc. Electrolytes may serve as builders in the composition, yet additional builders may be present.
  • a particularly preferred optional ingredient is water.
  • the liquid detergent compositions of the invention may (but do not have to) contain significant amounts of water. Relatively high water amount is beneficial, in order to incorporate hydrophilic ingredients into the composition.
  • the layered composition is attained which may contain high amounts of water, yet the water present in the composition does not dissolve the water-soluble package enveloping the composition.
  • the liquid detergent composition of the invention generally includes from 0 to 70% of total (free and bound) water, more preferably from 5 to 50%, most preferably from 10 to 50%, and optimally from 25 to 40%, in order to obtain clarity and ease of the dispersion of the composition during use (% by weight of the composition). Yet, by virtue of employing the electrolyte as taught herein the water activity of the inventive compositions is generally low: typically less than 0.94, preferably less than 0.93, more preferably less than 0.9, optimally less than 0.8. in order to obtain compositions which contain optimum amounts of water, yet may be stored safely in a water-soluble package.
  • Water activity is the ratio of the vapor pressure of a solution to that of pure water. It is related to the inverse of the relative humidity of the atmosphere above the sample at equilibrium.
  • Apparatus Aqualab CX-2 Water Activity meter; Sample containers; Transfer pipets Water Activity Standards and Values: Lithium chloride (LiCl) 0.113 +/- 0.003 Magnesium chloride (MgCl2) 0.328 +/- 0.002 Sodium chloride (NaCl) 0.753 +/- 0.001 Potassium chloride (KCl) 0.843 +/- 0.003 Potassium sulfate (K2SO4) 0.973 +/- 0.005 Deionized water 1.000 +/- 0.003
  • hydrotrope which prevents liquid crystal formation.
  • the hydrotrope is typically included in the surfactant layer. The addition of the hydrotrope thus aids the clarity/transparency of the composition.
  • Suitable hydrotropes include but are not limited to propylene glycol, ethanol, salts of benzene sulphonate, toluene sulphonate, xylene sulphonate or cumene sulphonate.
  • Suitable salts include but are not limited to sodium, potassium, ammonium, monoethanolamine, triethanolamine.
  • the hydrotrope is selected from the group consisting of propylene glycol, xylene sulfonate, ethanol, and urea to provide optimum performance.
  • the amount of the hydrotrope is generally in the range of from 0 to 30%, preferably from 0.5 to 20%, most preferably from 1 to 15%.
  • a dye in order to create a composition with visually appealing colored layer or layers.
  • a dye is an organic molecule and so will partition into the organic (surfactant) layer. It is possible, although less usual that a dye may partition into the electrolyte layer.
  • Suitable dyes include but are not limited to:
  • the Azo and Pyrene families of dyes are suitable for inclusion into an electrolyte layer (i.e. these dyes will likely partition into the electrolyte layer-but may do so along with the surfactant layer).
  • One of the preferred embodiments is to include both a dye that will partition into a surfactant layer and a dye that will partition into an electrolyte layer, in order to provide a 2-colored composition.
  • the inventive compositions generally include from 0.0001 to 1%, more preferably from 0.0005 to 0.1 %, most preferably from 0.0001 to 0.1 % of the dye, in order to provide a pleasing appearance (% by weight of the composition).
  • the liquid compositions may include encapsulated ingredients, preferably in the form of transparent or colored capsules or an emulsion, or a dispersion. These capsules, emulsion, or dispersion, may be distributed in one or more layers of the inventive compositions, or may be present as an additional layer.
  • Preferred ingredients to be encapsulated are enzymes, bleaches, colorants, perfumes, and mixtures thereof to minimize the damage to these ingredients from water or surfactant, or alkaline ingredients, and/or to enhance the appearance of the product.
  • Preferred inventive compositions comprise from 0.5 to 20%, more preferably from 0.1 to 10%, most preferably from 0.3 to 6%, and optimally from 0.5 to 5%, in order to attain optimum performance and/or appearance (% by weight of the composition).
  • the pH of the inventive compositions is generally in the range of from 2.5 to 12.5, preferably in the range of from 4 to 10, most preferably from 6 to 9, in order to attain optimum laundry cleaning.
  • the composition of the components employed for making the inventive layered composition is as follows: Ingredients of component 1 (% by weight of the component): Anionic Surfactant 0 to 30% Non-ionic Surfactant 5 to 60 % Cationic Surfactant 0 to 5% Fatty Acid 0 to 20% Monoethanolamine 0 to 20% Propylene Glycol 5 to 30% Perfume 0 to 3.0% Phosphonate 0 to 2% Protease 0.1 to 2.0% Cellulase 0.01 to 0.5% Lipase 0 to 0.5% Anti-dye transfer polymers 0 to 1.0% Anti redeposition polymers 0 to 1.0 % water 0 to 20% Colorant To suitable color Silicone Antifoam 0 to 2.0 % Ingredients of component 2 (% by weight of the component): Citric Acid 30 to 60 % Monoethanolamine 10 to 60 % Water 5 to 70% Phosphonate 0 to 2.0% Carbonate 0 to 20% Bi-carbonate
  • the packages of the invention may be prepared from polyvinyl alcohol film, or other suitable material, which is filled, then sealed, preferably heat-sealed or water-sealed.
  • the packages may be filled in any suitable way.
  • the liquid detergent composition is pre-mixed (both components) and filled in the same manner as a single phase composition would be.
  • the composition may also be filled component by component.
  • the package may take many shapes as viewed in a plan view, such as rectangular, square, triangle, round, etc.
  • the package is in a polyhedral shape (e.g., tetrahedron or a pyramid).
  • the package is mixed with water (e.g., inside a laundry machine), in order to dissolve the body and to release the contents of the package.
  • water e.g., inside a laundry machine
  • Raw Material % Supplier Surfactant component Sodium Xylene Sulfonate 1.7 Stepan Co.
  • the product was a stable-two-layered liquid. 25 grams of each component were added into a polyvinyl alcohol pouch made of 75.6 microns thickness of polyvinyl alcohol film ex.
  • the pouch was stable for at least 3 weeks, with no visible impact on the film. Two transparent layers were visible in the pouch and separated easily after shaking.
  • the composition contained no water.
  • Component 1 (70% of total volume of the composition) % by weight of component
  • Anionic surfactant Linear Alkyl Benzene Sulphonate C12
  • Nonionic surfactant C12-15 7 ethylene oxide 60.00
  • Monopropylene Glycol 6.69 Monoethanolamine 3.81 Perfume 1.00 Phosphonate 0.50
  • Protease 1.00 Poly (vinylpyrrolidone) 0.30 Water 6.20 Colourant (acid dye) 0.00012 Silicone antifoam 0.50
  • Component 2 (30% of total volume of the composition) Citric Acid 33.02 Monoethanolamine 31.98 Water 35.00 Ionic strength, for component 2 10.32
  • Example 3 The two components each of Examples 3 and 4 were respectively dosed at 25ml per each package sealed by VFFS (vertical form film system), the package being formed of MONOSOL T film.
  • VFFS vertical form film system
  • compositions of Examples 3 and 4 showed superior clarity, separation between the layers and storage stability over several weeks at room temperature, as evidenced by lack of precipitation.
  • the packages were filled and sealed by HFFS (horizontal form film system) with no difference in performance.

Landscapes

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

Claims (20)

  1. Conditionnement de détergent de blanchissage destiné à l'utilisation dans une application de blanchissage unique, le conditionnement comprenant :
    (a) un corps hydrosoluble ;
    (b) une composition de détergent de blanchissage liquide contenue à l'intérieur du corps hydrosoluble pour libération par la dissolution du corps hydrosoluble, la composition comprenant :
    au moins deux phases, lesdites au moins deux phases comprenant au total :
    entre environ 10 et environ 90 % en poids de la composition d'un agent tensio-actif détergent ; et
    entre environ 1 et environ 50 % en poids de la composition d'un électrolyte organique.
  2. Conditionnement selon la revendication 1, dans lequel la composition comprend en outre au moins environ 10 % d'eau au total.
  3. Conditionnement selon la revendication 2, dans lequel l'activité de l'eau de la composition est inférieure à environ 0,94.
  4. Conditionnement selon la revendication 1, dans lequel la composition comprend en outre entre environ 25 % et environ 70 % d'eau, et dans lequel l'activité de l'eau de la composition est inférieure à environ 0,94.
  5. Conditionnement selon la revendication 1, dans lequel la composition comprend en outre un hydrotrope.
  6. Conditionnement selon la revendication 1, dans lequel la composition comprend en outre un colorant.
  7. Conditionnement selon la revendication 1, dans lequel la composition comprend en outre de l'eau et où la force ionique de l'électrolyte est au moins environ 4,4.
  8. Conditionnement selon la revendication 1, dans lequel l'agent tensio-actif détergent dans la composition comprend un mélange d'un agent tensio-actif anionique et non ionique.
  9. Conditionnement selon la revendication 8, dans lequel le rapport de l'agent tensio-actif anionique sur l'agent tensio-actif non ionique est entre environ 10 : 1 et environ 1 : 10.
  10. Conditionnement selon la revendication 1, dans lequel le rapport en volume de la première phase sur la seconde phase est entre environ 10 : 90 et environ 90 : 10.
  11. Conditionnement selon la revendication 1, dans lequel le corps hydrosoluble est transparent.
  12. Conditionnement selon la revendication 1, dans lequel le conditionnement est sous la forme d'un tétraèdre.
  13. Conditionnement selon la revendication 1, comprenant en outre une troisième phase.
  14. Conditionnement selon la revendication 13, dans lequel la troisième phase est une phase de capsules ou d'émulsion.
  15. Conditionnement de détergent de blanchissage destiné à l'utilisation dans une application de blanchissage unique, le conditionnement comprenant :
    (a) un corps hydrosoluble ;
    (b) une composition de détergent de blanchissage liquide contenue à l'intérieur du corps hydrosoluble pour libération par la dissolution du corps hydrosoluble, la composition comprenant au moins deux composants :
    (b1) un premier composant comprenant :
    (b11) entre environ 5 % et environ 100 % en poids du premier composant d'un agent tensio-actif détergent ;
    (b12) entre environ 0 et environ 60 % en poids du premier composant d'eau totale ;
    (b13) entre environ 0 et environ 15 % en poids du premier composant d'un électrolyte organique ;
    (b2) un second composant comprenant :
    (b21) entre environ 1 % et environ 100 % en poids du second composant d'un électrolyte organique ;
    (b22) entre environ 0 et environ 90 % en poids du second composant d'eau totale ;
    (b23) entre environ 0 % et environ 5 % en poids du second composant d'un agent tensio-actif détergent.
  16. Conditionnement selon la revendication 15, dans lequel la force ionique de l'électrolyte est au moins 4,4.
  17. Conditionnement selon la revendication 15, dans lequel la composition comprend en outre un hydrotrope dans le premier composant.
  18. Conditionnement selon la revendication 15, dans lequel la composition est transparente.
  19. Conditionnement selon la revendication 18, dans lequel le corps hydrosoluble est transparent.
  20. Procédé de fabrication d'un conditionnement de détergent de blanchissage comprenant une composition de détergent liquide multicouche destinée à l'utilisation dans une application de blanchissage unique, le procédé comprenant :
    (a) la préparation d'une composition de détergent comprenant au moins deux composants détergents liquides :
    (a1) un premier composant comprenant :
    (a11) entre environ 5 % et environ 100 %, en poids du premier composant d'un agent tensio-actif détergent ;
    (a12) entre environ 0 et environ 60 %, en poids du premier composant d'eau totale ;
    (a13) entre environ 0 et environ 15 %, en poids du premier composant d'un électrolyte organique ;
    (a2) un second composant comprenant :
    (a21) entre environ 1 % et environ 100 %, en poids du second composant d'un électrolyte organique ;
    (a22) entre environ 0 et environ 90 %, en poids du second composant d'eau totale ;
    (a23) entre environ 0 % et environ 5 %, en poids du second composant d'un agent tensio-actif détergent.
    (b) le remplissage du corps hydrosoluble avec la composition de détergent.
EP02792755A 2001-12-14 2002-11-12 Bloc hydrosoluble comprenant un detergent a lessive liquide en couches Expired - Lifetime EP1453941B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US2046201A 2001-12-14 2001-12-14
US20462 2001-12-14
PCT/EP2002/012624 WO2003052040A1 (fr) 2001-12-14 2002-11-12 Bloc hydrosoluble comprenant un detergent a lessive liquide en couches

Publications (2)

Publication Number Publication Date
EP1453941A1 EP1453941A1 (fr) 2004-09-08
EP1453941B1 true EP1453941B1 (fr) 2005-06-29

Family

ID=21798744

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02792755A Expired - Lifetime EP1453941B1 (fr) 2001-12-14 2002-11-12 Bloc hydrosoluble comprenant un detergent a lessive liquide en couches

Country Status (6)

Country Link
EP (1) EP1453941B1 (fr)
AT (1) ATE298784T1 (fr)
AU (1) AU2002358498A1 (fr)
DE (1) DE60204914T2 (fr)
ES (1) ES2244828T3 (fr)
WO (1) WO2003052040A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014152547A2 (fr) * 2013-03-14 2014-09-25 Novozymes A/S Poche de détergent comportant un film enzymatique soluble dans l'eau
CN109266467A (zh) * 2018-08-20 2019-01-25 四川建元天地环保科技有限公司 有机电解液在产品表面去污的用途

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9006169B2 (en) 2005-06-03 2015-04-14 The Procter & Gamble Company Personal care compositions with improved hyposensitivity
ES2563631T3 (es) 2004-07-02 2016-03-15 The Procter & Gamble Company Composiciones de higiene personal con hiposensibilidad mejorada
CA2608882C (fr) * 2005-06-01 2011-05-10 The Procter & Gamble Company Sachet hydrosoluble contenant un liquide
ES2363525T5 (es) * 2006-05-09 2015-03-23 The Procter & Gamble Company Bolsa que contiene líquido soluble en agua
EP2404988B1 (fr) 2010-07-07 2018-01-24 Dalli-Werke GmbH & Co. KG Composition d'application locale en pré-traitement de taches sur du linge
MA40028A (fr) 2014-04-22 2017-03-01 The Sun Products Corp Compositions détergentes en doses unitaires
EP3574078A4 (fr) * 2017-01-27 2020-08-19 Henkel IP & Holding GmbH Compositions de doses unitaires stables à teneur élevée en eau
EP3363888A1 (fr) * 2017-02-21 2018-08-22 The Procter & Gamble Company Utilisation d'une composition détergente liquide pour le lavage afin de réduire au minimum les effets défavorables lors d'une exposition accidentelle à des contenus d'articles de dose unitaire solubles dans l'eau

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU55174A1 (fr) * 1967-12-28 1969-08-08 Unilever Nv
DE19951635A1 (de) * 1999-10-26 2001-05-17 Henkel Kgaa Wäßriges mehrphasiges Reinigungsmittel

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014152547A2 (fr) * 2013-03-14 2014-09-25 Novozymes A/S Poche de détergent comportant un film enzymatique soluble dans l'eau
WO2014152547A3 (fr) * 2013-03-14 2014-11-20 Novozymes A/S Poche de détergent comportant un film enzymatique soluble dans l'eau
US11028352B2 (en) 2013-03-14 2021-06-08 Novozymes A/S Detergent pouch with enzymatic water-soluble film
CN109266467A (zh) * 2018-08-20 2019-01-25 四川建元天地环保科技有限公司 有机电解液在产品表面去污的用途

Also Published As

Publication number Publication date
ATE298784T1 (de) 2005-07-15
DE60204914T2 (de) 2006-04-27
EP1453941A1 (fr) 2004-09-08
WO2003052040A1 (fr) 2003-06-26
ES2244828T3 (es) 2005-12-16
AU2002358498A1 (en) 2003-06-30
DE60204914D1 (de) 2005-08-04

Similar Documents

Publication Publication Date Title
EP1453942B1 (fr) Emballage hydrosoluble a couches multiples de couleur distincte de detergeant a lessive liquide
EP1367118B1 (fr) Détergent lessiviel liquide à couche d'émulsion
US6037319A (en) Water-soluble packets containing liquid cleaning concentrates
US4886615A (en) Hydroxy polycarboxylic acid built non-aqueous liquid cleaning composition and method for use, and package therefor
US6972278B2 (en) Laundry detergent gel with suspended particles
EP1453941B1 (fr) Bloc hydrosoluble comprenant un detergent a lessive liquide en couches
EP3101104B1 (fr) Composition de detergent liquide compacte pour blanchisserie
EP3101102B2 (fr) Composition de detergent liquide compacte pour blanchisserie
AU2015303029A1 (en) Detergent
EP1319707B1 (fr) Poche contenant une composition pour le lavage du linge
ZA200501216B (en) Gel laundry detergent and/or pre-treater composition
EP1539916B1 (fr) Gel detergent a lessive et/ou agent de pre-traitement qui, une fois distribuees, s'accumulent
EP1539914A1 (fr) Detergent a lessive liquide ou en gel
US20030139316A1 (en) Layered liquid laundry detergent with colored bottom layer
US20230374424A1 (en) Laundry detergent composition
EP1453945A1 (fr) Emballage soluble dans l'eau avec un detergent a lessive liquide en couches
EP1453944B1 (fr) Sac polyedre hydrosoluble contenant un detergent lessiviel liquide en couches
JP2005171020A (ja) 容器入り漂白洗浄剤製品
JP2003160800A (ja) 容器入り合成洗剤

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: 20040409

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 IE IT LI LU MC NL PT SE SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

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

Owner name: UNILEVER PLC

Owner name: UNILEVER N.V.

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 IE IT LI LU MC NL PT SE SK TR

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050629

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: 20050629

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: 20050629

Ref country code: CZ

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

Effective date: 20050629

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: 20050629

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: 20050629

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: 20050629

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: 20050629

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 60204914

Country of ref document: DE

Date of ref document: 20050804

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

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: 20050929

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: 20050929

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: 20050929

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: 20050929

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: 20051112

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: 20051114

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: 20051130

Ref country code: LU

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

Effective date: 20051130

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051207

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2244828

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

ET Fr: translation filed
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

26N No opposition filed

Effective date: 20060330

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

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

Ref country code: NL

Payment date: 20201125

Year of fee payment: 19

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

Ref country code: FR

Payment date: 20201120

Year of fee payment: 19

Ref country code: IT

Payment date: 20201120

Year of fee payment: 19

Ref country code: GB

Payment date: 20201120

Year of fee payment: 19

Ref country code: DE

Payment date: 20201119

Year of fee payment: 19

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

Ref country code: BE

Payment date: 20201125

Year of fee payment: 19

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

Ref country code: ES

Payment date: 20210122

Year of fee payment: 19

REG Reference to a national code

Ref country code: NL

Ref legal event code: PD

Owner name: UNILEVER IP HOLDINGS B.V.; NL

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), ASSIGNMENT; FORMER OWNER NAME: UNILEVER N.V.

Effective date: 20210413

REG Reference to a national code

Ref country code: BE

Ref legal event code: PD

Owner name: UNILEVER IP HOLDINGS B.V.; NL

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), ASSIGNMENT; FORMER OWNER NAME: UNILEVER N.V.

Effective date: 20210607

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60204914

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20211201

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

Effective date: 20211112

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

Ref country code: BE

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

Effective date: 20211130

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20211130

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

Ref country code: NL

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

Effective date: 20211201

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

Ref country code: GB

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

Effective date: 20211112

Ref country code: DE

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

Effective date: 20220601

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: 20211130

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

Ref country code: IT

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

Effective date: 20211112

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20230210

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: 20211113