EP2099889B1 - Compositions de lavage du linge - Google Patents

Compositions de lavage du linge Download PDF

Info

Publication number
EP2099889B1
EP2099889B1 EP07847562A EP07847562A EP2099889B1 EP 2099889 B1 EP2099889 B1 EP 2099889B1 EP 07847562 A EP07847562 A EP 07847562A EP 07847562 A EP07847562 A EP 07847562A EP 2099889 B1 EP2099889 B1 EP 2099889B1
Authority
EP
European Patent Office
Prior art keywords
agents
alginate
bead
beads
benefit agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP07847562A
Other languages
German (de)
English (en)
Other versions
EP2099889A1 (fr
Inventor
Stuart Anthony Barnett
Andrew Philip Parker
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=38171329&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2099889(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP07847562A priority Critical patent/EP2099889B1/fr
Publication of EP2099889A1 publication Critical patent/EP2099889A1/fr
Application granted granted Critical
Publication of EP2099889B1 publication Critical patent/EP2099889B1/fr
Revoked 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

  • This invention relates to a gelled alginate bead. More particularly, the invention is directed to a gelled alginate bead comprising a certain ratio of D-mannuronate (M) to L-guluronate (G) residues, and to a process for making said bead.
  • the invention further relates to laundry treatment compositions comprising the beads of the invention and to the use of said beads to slowly release benefit agents.
  • Encapsulation or immobilisation of active materials is a well known technique which can offer advantages such as the stabilisation/protection of active materials that are otherwise unstable or reactive.
  • Alginates are known as encapsulation materials.
  • Alginates are linear polysaccharides made up from ⁇ -1,4 linked D-mannuronate (M) residues and its C-5 epimer ⁇ -1,4 linked L-guluronate (G) residues.
  • the alginates have a block polymeric arrangement of these M and G residues along the linear chain.
  • the arrangement of these blocks can be described as being blocks of repeating M residues, repeating G residues, or alternating M and G residues.
  • the ratio of D-mannuronate (M) to L-guluronate (G) residues present in the alginate is known as the M:G ratio.
  • EP 1 632 560 A1 disclose microcapsules for use in a liquid detergent composition.
  • the microcapsules have a core and a polyanion-polycation complex shell wherein the polyanion is capable of gelling in the presence of calcium.
  • the shell acts as a membrane and protects the core, or actives contained in the core from the surrounding medium.
  • the preferred polyanion is alginate having a M:G ratio of at least 1:1; higher M ratios (such as 1.1:1, and 2:1) being more preferred.
  • WO 00/46337 (Quest International B.V. ) relates to a liquid detergent composition containing greater than 5% by weight of surfactant and an encapsulate containing greater than 10% by weight of active material and a cross-linked anionic gum.
  • the anionic gum can be an alginate, and the active material can be a fragrance.
  • the active materials are substantively insoluble in water and/or sufficiently large (having a molecular weight of at least 5000) to be retained by the alginate.
  • WO97/14780 discloses encapsulated bleach particles comprising a galled polymer coating, such as an alginate.
  • laundry detergents and conditioners for example powders and liquids
  • formulations especially laundry detergents and conditioners (for example powders and liquids) are usually set up to dispense all of their ingredients into water at the start of the wash/rinse process.
  • the present invention therefore provides a gelled alginate bead, comprising a benefit agent.
  • the bead provides both slow release and retention beyond the main wash stage process of the benefit agent.
  • this invention is directed to a gelled alginate bead comprising:-
  • this invention is directed to a laundry treatment composition
  • a laundry treatment composition comprising the beads of the invention and at least one further laundry ingredient.
  • the laundry treatment composition may be a main wash composition, or a composition used in one or more of the rinse cycles of the laundry process.
  • Another aspect of the invention relates to the use of a gelled alginate bead comprising:-
  • a yet further aspect of the present invention relates to a method of treating fabrics with a wash liquor comprising a fabric benefit agent, said fabric benefit agent provided for by one or more beads of the invention, wherein the fabric benefit agent is slowly released during the wash process.
  • a general process for the formation of the gelled alginate beads comprises the following steps:-
  • An alternative process for the formation of the gelled alginate beads comprises the steps:-
  • the beads of the present invention provide numerous advantages in use. For example, they can be used as a carrier to enable the slow release of benefit agents over a longer period of time. This is particularly useful if the benefit agent offers improved benefits when it is present in a substantial proportion of the wash process (i.e. in the main wash and at least one of the rinse stages).
  • benefit agents may be lubricants, mild reducing agents, or sequestrants.
  • Another advantage of the present invention is that it allows release of the benefit agent to occur after the laundry process is finished.
  • perfumes, or antimicrobial agents are particularly useful as the benefit agents; the delayed release of perfume is perceived as a consumer plus, as perfume smell thus lasts longer past the laundry process; and the delayed release of an antimicrobial agent may help neutralise the bacteria that cause malodour on clothes.
  • a further advantage of the present invention is the provision for the slow release of water soluble benefit agents into the wash liquor.
  • the term “comprising” means including, made up of, composed of, consisting and/or consisting essentially of.
  • “Slow release” used interchangeably herein with “gradual” or “controlled” release means that the chosen benefit agent is released in a delayed fashion.
  • concentration of the benefit agent present in an aqueous medium for example a laundry wash/rinse liquor
  • Such automatic delayed release of benefit agent is distinct from manual addition of additional benefit agent portions, as this is not an automatic, continual release of benefit agent.
  • the benefit agent comprised therein is continually released over a period of time until total release of benefit agent is achieved.
  • the alginate bead when used in a laundry wash process, will either:-
  • gelled used herein, is understood to mean that the anionic alginate species has formed a cross-linked network with the cationic species.
  • the invention provides gelled alginate beads.
  • the shape of the beads comes will naturally arise from the chosen process of manufacture.
  • the beads are generally and preferably in a spherical form.
  • the gelled alginate beads can be thought of as a cross-linked alginate/cation matrix network encapsulating one or more benefit agents.
  • the gelled alginate beads are classed as 'matrix' encapsulates, and preferably do not take the form of a core/shell encapsulate whereby the core contains the benefit agent which is surrounded by a protective wall or barrier material.
  • the gelled alginate beads can be prepared via several routes. Examples of these routes include:-
  • the cationic species form the gelled cross-linked matrix with the alginate.
  • the cationic species may be any cationic species capable of forming a gelled network with alginate. However, metal cations are preferred. Preferred cationic species are those that arise in solution from divalent or polyvalent metal salts. In a preferred embodiment, the cationic species is calcium in the salt form of calcium chloride.
  • Alginate is the general name for alginic acid and its salts. Alginates are linear polysaccharides made up from ⁇ -1,4 linked D-mannuronate (M) residues and its C-5 epimer, ⁇ -1,4 linked L-guluronate (G) residues. The alginates have a block polymeric arrangement of these M and G residues along the linear chain. The arrangement of these blocks can be described as being blocks of repeating M residues, repeating G residues, or alternating M and G residues.
  • the ratio of mannuronate to guluronate residues present in the alginate is well known in the art as the M:G ratio.
  • the M:G ratio of the alginate can vary due to the source or growth conditions of the alginate.
  • One common alginate source is brown seaweed (Phaeophyceae).
  • the M:G ratio of the alginate used in the present invention is from 0.1:1 to less than 1:1, for example 0.1:1 to 0.99:1. This means that the alginates used herein contain a greater number of G residues than M residues.
  • the M:G ratio is preferably 0.1:1 to 0.8:1, more preferably from 0.2:1 to 0.8:1.
  • Certain embodiments of the beads of the present invention comprises alginate having an M:G ratio of from 0.25 to 0.75. Suitable sources for these alginates are those obtained from the fronds and stipes of Laminaria hyperborea.
  • the gelled alginate beads comprise alginate with a M:G as defined above.
  • Preferably all of the alginate present in the bead has the aforementioned M:G ratios.
  • the molecular weight of the alginate can be between 1,000 to 3,000,000 Daltons.
  • the alginate is used in the form of a sodium salt.
  • Suitable alginates with the desired M:G ratio are available under the "Manugel” trade name from International Speciality Products, for example “Manugel GMB”; “Protonal” from FMC Biopolymer; and, “Satialgine”, “Cecalgum” and “Algogel” from Texturant Systems.
  • the beads of the invention comprise a benefit agent.
  • the beads described herein can be used to deliver water-soluble and water-insoluble benefit agents or combinations thereof.
  • the benefit agent is water soluble.
  • water soluble is meant that the benefit agent dissolves in water to an extent of at least 90% by weight in water at 25°C.
  • the beads of the present invention are particularly advantageous for delayed release of benefit agents that are highly water soluble.
  • the inclusion level of the benefit agent(s) in the beads is dependant on the amount that is required to achieve the benefit required, the release profile of the agent(s) and the calcium level.
  • the inclusion level would be between 0.00001g and 0.2g per gram of alginate (0.001% to 20% by weight).
  • the inclusion level could be as high as 0.6g per gram of alginate (60% by weight).
  • the benefit agent preferably has a molecular weight below 5000 Daltons, more preferably below 4000 Daltons.
  • any benefit agent is applicable to the present invention.
  • the benefit agent is a fabric benefit agent, for laundry purposes.
  • the fabric benefit agent is selected from the group consisting of:- chlorine/oxygen scavengers, antioxidants, sequestrants, perfumes, antimicrobial agents, antibacterial agents, antifungal agents, lubricants, UV absorbers, shading dyes, fluorescent whitening agents, dispersants, anti-redeposition agents, soil release agents, enzymes (for removing fuzz or pills or preventing staining), dye transfer inhibitors, dye sequestrants, dye fixers, softeners, or crystal growth inhibitors.
  • the fabric benefit agent may also be a mixture of two or more of the aforementioned benefit agents.
  • the fabric benefit agent is selected from the group consisting of:- mild reducing agents, sequestrants, perfumes, fluorescent whitening agents, shading dyes, antimicrobial agents or mixtures thereof.
  • millild reducing agent refers to one with a redox potential of between 0 and -800mV in reference to a normal hydrogen electrode.
  • Sequestrants useful as benefit agents in the current invention include: ethylenediaminedisuccinate ("Octaquest (Trade Mark) E30", Octel Performance Chemicals), tetrasodium iminidisuccinate ("Baypure (Trade Mark) CX", Bayer), ethylenediaminetetra(methylene phosphonate ("Dequest (Trade Mark) 2047", Solutia), tetrasodium etidronate (“Turpinal (Trade Mark) 4NP”, Solutia).
  • the sequestrant is ethylenediaminedisuccinate.
  • An alternative embodiment includes both sequestrant and mild reducing agent as benefit agents in the bead.
  • the sequestrant and reducing agent are present in the alginate matrix in equal proportions.
  • the perfume if present, preferably has a molecular weight of from 50 to 500 Daltons.
  • the perfume suitably has a boiling point of from 30 to 500°C.
  • the beads may optionally further comprise a coloured material if required for aesthetic purposes.
  • the size of the beads, measured by the diameter of the beads is from 0.005 to 10mm.
  • the beads may be in a dried state or can be in a swollen state.
  • a swollen state is meant fully hydrated, for example when they are subjected to a liquid, generally water in laundry processes.
  • the bead sizes disclosed herein can apply to beads in a dry state or in a swollen state.
  • the bead size can by varied easily in the chosen process of manufacture.
  • the diameter of the tube that the alginate-benefit agent mixture is passed through can be varied to produce larger or smaller droplets as required.
  • very small bead diameters are preferred. Such bead diameters are in the range of from 0.005 to 0.2mm, preferably from 0.01 to 0.15mm, more preferably from 0.025 to 0.1mm.
  • these beads are designed to be small enough to deposit onto a fabric garment, with the fibres present in the fabric garment acting as a fishing net which scoops up the small beads. The small beads then can slowly release the fabric benefit agent after the laundering process (i.e. during storage or wear of the fabric).
  • Fabric benefit agents particularly useful in this system are fragrances (including perfume and perfume mixtures) and anti-microbial materials.
  • the beads of the invention may have larger diameters, for example, in the range of from 0.2mm to 10mm. In such an embodiment, preferably the beads have a diameter in the range of from 0.2 to 5mm, more preferably from 0.3 to 3mm.
  • Laundry treatment composition is herein described to include main wash and rinse products.
  • the laundry treatment compositions are main wash laundry detergent compositions.
  • they are rinse only compositions, for example rinse conditioners.
  • the laundry treatment composition is to be used in the main wash cycle, i.e. as a laundry detergent composition, then it may take the form of an isotropic liquid, a surfactant-structured liquid, a granular, spray-dried or dry-blended powder, a tablet, a paste, a molded solid or any other laundry detergent form known to those skilled in the art.
  • the laundry treatment composition will comprise one or more detersive surfactants.
  • the laundry treatment composition may take the form of a rinse added product, for example, a rinse conditioner.
  • the beads incorporated within the laundry treatment composition are of a large enough size (for example from 0.2mm to 10mm) to be retained in the drum of the washing machine between either the main wash-rinse cycle step or rinse-rinse cycle steps, depending on at what stage the laundry composition is added.
  • the alginate beads may be incorporated into an existing product as an adjunct.
  • Typical dosage levels of the gelled alginate beads in a laundry wash or rinse liquor is from 0.01 to 3.0g/l.
  • the gelled alginate beads of the invention will generally be used in conjunction with a textile compatible carrier in a laundry treatment composition.
  • the textile compatible carrier may also provide benefits in addition to those provided by the gelled alginate beads, e.g. softening, cleaning etc.
  • the carrier may be a detergent-active compound or a textile softener or conditioning compound or other suitable detergent or textile treatment agent. Many of these fall within the more general definition 'surfactant' as used herein.
  • the surfactant may comprise the entire carrier or other, non-surfactant carrier materials may be present.
  • the textile-compatible carrier In a washing process, as part of a conventional textile washing product, such as a detergent composition, the textile-compatible carrier will typically be a detergent-active compound. Whereas, if the textile treatment product is a rinse conditioner, the textile-compatible carrier will be a textile softening and/or conditioning compound. These are described in further detail below.
  • Liquid compositions may also include an agent which produces a pearlescent appearance, e.g. an organic pearlising compound such as ethylene glycol distearate, or inorganic pearlising pigments such as microfine mica or titanium dioxide (TiO 2 ) coated mica.
  • an agent which produces a pearlescent appearance e.g. an organic pearlising compound such as ethylene glycol distearate, or inorganic pearlising pigments such as microfine mica or titanium dioxide (TiO 2 ) coated mica.
  • Liquid compositions may be in the form of emulsions or emulsion precursors thereof.
  • the textile-compatible carrier may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.
  • the preferred textile-compatible carriers that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
  • Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkylsulphates, particularly C 8 -C 15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 6 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
  • Cationic surfactants that may be used include quaternary ammonium salts of the general formula R 1 R 2 R 3 R 4 N + X - wherein the R groups are independently hydrocarbyl chains of C 1 -C 22 length, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising cation (for example, compounds in which R 1 is a C 8 -C 22 alkyl group, preferably a C 8 -C 10 or C 12 -C 14 alkyl group, R 2 is a methyl group, and R 3 and R 4 , which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters) and pyridinium salts.
  • R 1 is a C 8 -C 22 alkyl group, preferably a C 8 -C 10 or C 12 -C 14 alkyl group
  • R 2 is a methyl group
  • the total quantity of detergent surfactant in the composition is suitably from 0.1 to 60 wt% e.g. 0.5-55 wt%, such as 5-50wt%.
  • the quantity of anionic surfactant (when present) is in the range of from 1 to 50% by weight of the total composition. More preferably, the quantity of anionic surfactant is in the range of from 3 to 35% by weight, e.g. 5 to 30% by weight.
  • the quantity of nonionic surfactant (when present) is in the range of from 2 to 25% by weight, more preferably from 5 to 20% by weight.
  • Amphoteric surfactants may also be used, for example amine oxides or betaines.
  • the laundry detergent compositions may suitably contain from 10 to 70%, preferably from 15 to 70% by weight, of detergency builder.
  • the quantity of builder is in the range of from 15 to 50% by weight.
  • the detergent composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate.
  • the aluminosilicate may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50%.
  • Aluminosilicates are materials having the general formula: 0.8-1.5 M 20 . Al 2 O 3 . 0.8-6 SiO 2 where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • phosphate builders may be used.
  • the textile-compatible carrier will be a textile softening and/or conditioning compound (hereinafter referred to as "textile softening compound”), which may be a cationic or nonionic compound.
  • textile softening compound may be water insoluble quaternary ammonium compounds.
  • the compounds may be present in amounts of up to 8% by weight (based on the total amount of the composition) in which case the compositions are considered dilute, or at levels from 8% to about 50% by weight, in which case the compositions are considered concentrates.
  • compositions suitable for delivery during the rinse cycle may also be delivered to the textile in the tumble dryer if used in a suitable form.
  • another product form is a composition (for example, a paste) suitable for coating onto, and delivery from, a substrate e.g. a flexible sheet or sponge or a suitable dispenser during a tumble dryer cycle.
  • Suitable cationic textile softening compounds are substantially water-insoluble quaternary ammonium materials comprising a single alkyl or alkenyl long chain having an average chain length greater than or equal to C 20 . More preferably, softening compounds comprise a polar head group and two alkyl or alkenyl chains having an average chain length greater than or equal to C 14 . Preferably the textile softening compounds have two, long-chain, alkyl or alkenyl chains each having an average chain length greater than or equal to C 16 .
  • the long chain alkyl or alkenyl groups have a chain length of C 18 or above. It is preferred if the long chain alkyl or alkenyl groups of the textile softening compound are predominantly linear.
  • Quaternary ammonium compounds having two long-chain aliphatic groups for example, distearyldimethyl ammonium chloride and di(hardened tallow alkyl) dimethyl ammonium chloride, are widely used in commercially available rinse conditioner compositions. Other examples of these cationic compounds are to be found in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch. Any of the conventional types of such compounds may be used in the compositions of the present invention.
  • the textile softening compounds are preferably compounds that provide excellent softening, and are characterised by a chain melting L ⁇ to L ⁇ transition temperature greater than 25°C, preferably greater than 35°C, most preferably greater than 45°C.
  • This L ⁇ to L ⁇ transition can be measured by DSC as defined in " Handbook of Lipid Bilayers", D Marsh, CRC Press, Boca Raton, Florida, 1990 (pages 137 and 337 ).
  • Substantially water-insoluble textile softening compounds are defined as textile softening compounds having a solubility of less than 1 x 10 -3 wt. % in demineralised water at 20°C.
  • the textile softening compounds have a solubility of less than 1 x 10 -4 wt. %, more preferably less than 1 x 10 -3 to 1 x 10 -6 wt . %.
  • cationic textile softening compounds that are water-insoluble quaternary ammonium materials having two C 12-22 alkyl or alkenyl groups connected to the molecule via at least one ester link, preferably two ester links.
  • Di(tallowoxyloxyethyl) dimethyl ammonium chloride and/or its hardened tallow analogue are especially preferred of the compounds of this type.
  • Other preferred materials include 1,2-bis(hardened tallowoyloxy)-3-trimethylammonium propane chloride. Their methods of preparation are, for example, described in US 4 137 180 (Lever Brothers Co). Preferably these materials comprise small amounts of the corresponding monoester as described in US 4 137 180 , for example, 1-hardened tallowoyloxy-2-hydroxy-3-trimethylammonium propane chloride.
  • cationic softening agents are alkyl pyridinium salts and substituted imidazoline species. Also useful are primary, secondary and tertiary amines and the condensation products of fatty acids with alkylpolyamines.
  • compositions may alternatively or additionally contain water-soluble cationic textile softeners, as described in GB 2 039 556B (Unilever ).
  • compositions may comprise a cationic textile softening compound and an oil, for example as disclosed in EP-A-0829531 .
  • compositions may alternatively or additionally contain nonionic textile softening agents such as lanolin and derivatives thereof.
  • Lecithins are also suitable softening compounds.
  • Nonionic softeners include L ⁇ phase forming sugar esters (as described in M Hato et al Langmuir 12, 1659, 1666, (1996 )) and related materials such as glycerol monostearate or sorbitan esters. Often these materials are used in conjunction with cationic materials to assist deposition (see, for example, GB 2 202 244 ). Silicones are used in a similar way as a co-softener with a cationic softener in rinse treatments (see, for example, GB 1 549 180 ).
  • compositions may also suitably contain a nonionic stabilising agent.
  • Suitable nonionic stabilising agents are linear C 8 to C 22 alcohols alkoxylated with 10 to 20 moles of alkylene oxide, C 10 to C 20 alcohols, or mixtures thereof.
  • the nonionic stabilising agent is a linear C 8 to C 22 alcohol alkoxylated with 10 to 20 moles of alkylene oxide.
  • the level of nonionic stabiliser is within the range from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, most preferably from 1 to 4% by weight.
  • the mole ratio of the quaternary ammonium compound and/or other cationic softening agent to the nonionic stabilising agent is suitably within the range from 40:1 to about 1:1, preferably within the range from 18:1 to about 3:1.
  • the composition can also contain fatty acids, for example C 8 to C 24 alkyl or alkenyl monocarboxylic acids or polymers thereof.
  • fatty acids for example C 8 to C 24 alkyl or alkenyl monocarboxylic acids or polymers thereof.
  • saturated fatty acids are used, in particular, hardened tallow C 16 to C 18 fatty acids.
  • the fatty acid is non-saponified, more preferably the fatty acid is free, for example oleic acid, lauric acid or tallow fatty acid.
  • the level of fatty acid material is preferably more than 0.1% by weight, more preferably more than 0.2% by weight.
  • Concentrated compositions may comprise from 0.5 to 20% by weight of fatty acid, more preferably 1% to 10% by weight.
  • the weight ratio of quaternary ammonium material or other cationic softening agent to fatty acid material is preferably from 10:1 to 1:10.
  • compositions according to the invention may comprise soil release polymers such as block copolymers of polyethylene oxide and terephthalate.
  • emulsifiers for example, sodium chloride or calcium chloride
  • electrolytes for example, sodium chloride or calcium chloride
  • pH buffering agents for example, sodium chloride or calcium chloride
  • perfumes preferably from 0.1 to 5% by weight
  • Further optional ingredients include non-aqueous solvents, perfume carriers, colourants, hydrotropes, antifoaming agents, enzymes and opacifiers.
  • Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof.
  • compositions may comprise one or more of anti-shrinking agents, anti-wrinkle agents, anti-spotting agents, germicides, fungicides, antioxidants, UV absorbers (sunscreens), dye fixatives, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids.
  • anti-shrinking agents anti-wrinkle agents
  • anti-spotting agents germicides, fungicides, antioxidants
  • UV absorbers unsunscreens
  • dye fixatives anti-corrosion agents
  • drape imparting agents antistatic agents and ironing aids.
  • the alginate (4.5g) and benefit agent (sodium thiosulphate pentahydrate, 4.5g) were dissolved in demin water (200ml) and mixed until homogeneous. The solution was then pumped via narrow bore (0.6mm internal diameter) tubing and allowed to drip into a solution of calcium chloride (3.5g/l, 500ml) from a height of approximately 20cm with slow continuous stirring via a magnetic stirrer.
  • the gelled alginate beads were filtered through a 0.5mm sieve and dried between multiple sheets of absorbent paper. The beads were then transferred to a large flat glass dish and dried at 70°C until all the beads had collapsed down to form irregular beads of ⁇ 1mm.
  • Gelled alginate beads comprising sodium thiosulphate (a mild reducing agent known in laundry) were prepared as follows:
  • ManugelTM GMB 4.5g was dissolved in 200ml demin water and dripped into 500ml of calcium chloride (3.5g/l). The beads were then filtered and dried. The final weight allowed the amount of calcium incorporated into the beads to be calculated. From this the level of thiosulphate could also be calculated for examples 2 and 3.
  • ManucolTM DH sodium alginate, M:G ratio 2.33 ex. International Speciality Products
  • ManucolTM DH was replaced with ManugelTM GMB, M:G ratio 0.43.
  • Iodiometric spectroscopy was used to measure the rate of release of thiosulphate over time.
  • Table 1 shows the difference in release rate of the two granules: Table 1 Showing the percentage of thiosulphate released (by measuring absorbance) from the beads during a 1 hr process Time (min) Abs. @ 45nm for Manugel DH (example 2) % Thiosulphate released Abs.
  • gelled alginate beads as prepared in example 3 were used in the following experiment.
  • Three loads were prepared comprising equal amounts of undyed non-fluorescent woven and knitted cotton (50x50cm in size, 1.25kg of each fabric type).
  • Wash 2 had 0.2g of sodium thiosulphate pentahydrate added to the main wash and to each of the four rinse stages during the fill process.
  • Wash 3 had 3.3g of gelled alginate beads added into the main wash (expected to deliver 1g of sodium thiosulphate pentahydrate across the wash).
  • the liquor samples were allowed to cool to room temperature.
  • the pH was measured and then adjusted to pH 7 with 1.0N hydrochloric acid.
  • the residual powder was then removed from the samples by filtration through a 0.45 ⁇ m cellulose filter.

Landscapes

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

Claims (13)

  1. Bille d'alginate gélifiée, comprenant :
    (a) de l'alginate avec un rapport D-mannuronate (M) : L-guluronate (G) de 0,1:1 à moins de 1:1 ;
    (b) une ou plusieurs espèces cationiques, de préférence un cation de métal divalent ou polyvalent ; et
    (c) un ou plusieurs agents bénéfiques.
  2. Bille selon la revendication 1, dans laquelle l'alginate a un rapport M:G de 0,1:1 à 0,8:1, de préférence de 0,2:1 à 0,8:1.
  3. Bille selon la revendication 1 ou la revendication 2, dans laquelle l'espèce cationique est un cation métallique divalent ou polyvalent.
  4. Bille selon la revendication 3, dans laquelle l'espèce cationique est un cation métallique divalent, de préférence le calcium.
  5. Bille selon la revendication 4, dans laquelle l'agent bénéfique est un agent bénéfique pour tissu.
  6. Bille selon la revendication 5, dans laquelle l'agent bénéfique pour tissu est choisi dans le groupe constitué par les fixateurs de chlore/ oxygène, les antioxydants, les agents séquestrants, les parfums, les agents antimicrobiens, les agents antibactériens, les agents antifongiques, les lubrifiants, les agents anti-UV, les teintes de nuançage, les agents blanchissants fluorescents, les dispersants, les agents antiredéposition, les agents anti-salissures, les enzymes pour éliminer la poussière ou les bouloches ou empêcher le dégorgement, les inhibiteurs de transfert de teinte, des séquestrants de teinte, des fixateurs de teinte, les adoucissants, les inhibiteurs de croissance cristalline, ou leurs mélanges.
  7. Bille selon la revendication 5, dans laquelle l'agent bénéfique pour tissu est choisi dans le groupe constitué par : les agents réducteurs modérés, les séquestrants, les parfums, les agents blanchissants fluorescents, les teintes de nuançage, les agents antimicrobiens ou leurs mélanges.
  8. Bille selon l'une quelconque des revendications précédentes, dans laquelle l'agent bénéfique est soluble dans l'eau.
  9. Bille selon l'une quelconque des revendications précédentes, dans laquelle la bille a un diamètre de 0,005 à 10 mm une fois gonflée.
  10. Bille selon la revendication 9, dans laquelle la bille a un diamètre de 0,005 à 0,2 mm une fois gonflée.
  11. Composition de traitement du linge comprenant les billes selon l'une quelconque des revendications 1 à 10 et au moins un ingrédient supplémentaire pour le linge, de préférence un vecteur compatible avec le textile.
  12. Utilisation d'une bille d'alginate gélifiée comprenant :
    (a) un alginate avec un rapport M:G de 0,1:1 à moins de 1:1 ;
    (b) une ou plusieurs espèces cationiques, de préférence un cation métallique monovalent ou polyvalent ; et
    (c) un ou plusieurs agents bénéfiques,
    dans un processus pour la libération lente dudit agent bénéfique dans un milieu aqueux, de préférence une lessive pour le lavage du linge.
  13. Procédé de traitement de tissus avec une lessive de lavage comprenant un agent bénéfique pour le tissu, ledit agent bénéfique pour le tissu étant formé par une ou plusieurs billes selon les revendications 1 à 10, où l'agent bénéfique pour le tissu est libéré lentement pendant le processus de lavage.
EP07847562A 2007-01-12 2007-11-30 Compositions de lavage du linge Revoked EP2099889B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07847562A EP2099889B1 (fr) 2007-01-12 2007-11-30 Compositions de lavage du linge

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07100459 2007-01-12
EP07847562A EP2099889B1 (fr) 2007-01-12 2007-11-30 Compositions de lavage du linge
PCT/EP2007/063046 WO2008083877A1 (fr) 2007-01-12 2007-11-30 Compositions de lavage du linge

Publications (2)

Publication Number Publication Date
EP2099889A1 EP2099889A1 (fr) 2009-09-16
EP2099889B1 true EP2099889B1 (fr) 2010-07-14

Family

ID=38171329

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07847562A Revoked EP2099889B1 (fr) 2007-01-12 2007-11-30 Compositions de lavage du linge

Country Status (8)

Country Link
EP (1) EP2099889B1 (fr)
CN (1) CN101578358B (fr)
AT (1) ATE474035T1 (fr)
BR (1) BRPI0720918A2 (fr)
DE (1) DE602007007816D1 (fr)
ES (1) ES2349267T3 (fr)
WO (1) WO2008083877A1 (fr)
ZA (1) ZA200903763B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2932956A1 (fr) 2014-04-14 2015-10-21 Symrise AG Capsules avec chargement d'actives haut

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0914211A2 (pt) * 2008-07-09 2015-11-03 Unilever Nv processo de produção do grânulo de alginato, grânulo de alginato obtido, uso do mesmo e, composição detergente para a lavagem de tecidos
EP4367211A1 (fr) * 2021-07-08 2024-05-15 Unilever IP Holdings B.V. Composition pour réduire les mauvaises odeurs

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4056085B2 (ja) * 1995-10-16 2008-03-05 ユニリーバー・ナームローゼ・ベンノートシヤープ 被包した漂白粒子
CN1153814A (zh) * 1996-01-02 1997-07-09 河南省华豫科技实业总公司 布料雨中晴洗涤剂及其生产方法
WO2000046337A1 (fr) * 1999-02-02 2000-08-10 Quest International B.V. Composition detergente
GB2356202A (en) * 1999-09-23 2001-05-16 Reckitt Benckiser Use of algins in combating hard water, scale and the like
GB0115761D0 (en) * 2001-06-28 2001-08-22 Quest Int Capsules
CN100519716C (zh) * 2004-05-31 2009-07-29 华中师范大学 软膜纸香皂及其生产方法和装置
EP1632560B1 (fr) * 2004-08-23 2011-01-05 The Procter & Gamble Company Microcapsules
GB0514716D0 (en) * 2005-07-19 2005-08-24 Unilever Plc Process to form fabric softening particle,particle obtained and its use

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2932956A1 (fr) 2014-04-14 2015-10-21 Symrise AG Capsules avec chargement d'actives haut

Also Published As

Publication number Publication date
DE602007007816D1 (de) 2010-08-26
CN101578358B (zh) 2012-05-23
BRPI0720918A2 (pt) 2014-03-25
ATE474035T1 (de) 2010-07-15
WO2008083877A1 (fr) 2008-07-17
EP2099889A1 (fr) 2009-09-16
CN101578358A (zh) 2009-11-11
ZA200903763B (en) 2010-08-25
ES2349267T3 (es) 2010-12-29

Similar Documents

Publication Publication Date Title
EP2297288B1 (fr) Compositions de lavage
JP6698176B2 (ja) 封入体を含む洗剤組成物
WO2003038028A2 (fr) Detergent ou nettoyant dispersible sensiblement exempt de sediments
EP2294169B1 (fr) Compositions de traitement du linge
EP2007860B1 (fr) Formule de traitement de tissu comprenant un agent de rinçage
JP2011524457A (ja) 洗濯組成物
DE102008047361A1 (de) Textilspülmittel
CA3006853A1 (fr) Article sous forme de dose unitaire hydrosoluble
EP2366008B1 (fr) Compositions de lessive
EP2099889B1 (fr) Compositions de lavage du linge
DK163308B (da) Stofbloedgoerende kraftigt virkende flydende rensemiddel indeholdende bentonit
EP2046927A1 (fr) Esterquats contenant des groupes oh pour rendements améliorés de substances odorantes
EP3580315B1 (fr) Adjuvant pour composition de lavage
EP2190964B1 (fr) Améliorations relatives à des compositions de traitement des tissus comprenant des séquestrants et des dispersants
CN110114452B (zh) 洗衣漂洗助剂组合物
US6555516B1 (en) Laundry product
DE10062585A1 (de) Teilchenförmiges Additiv für Wasch- und Reinigungsmittel
US20060052271A1 (en) Fabric laundering
CN102149804B (zh) 氨纶直接染料
ZA200503287B (en) Method of laundering coloured fabrics
GB2357294A (en) Fabric treatment composition
CN102165054B (zh) 阳离子异噻唑鎓染料
JPH0280496A (ja) 織物柔軟特性を有する洗剤組成物
DE102004015376A1 (de) Verwendung von Silizium-haltigen Verbindungen zur Behandlung von textilen Flächengebilden
EP1238051A1 (fr) Procede de traitement de tissu

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: 20090528

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 MT NL PL PT RO SE SI SK TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

DAX Request for extension of the european patent (deleted)
GRAC Information related to communication of intention to grant a patent modified

Free format text: ORIGINAL CODE: EPIDOSCIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Owner name: UNILEVER N.V.

Owner name: UNILEVER PLC

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 MT NL PL PT RO SE SI SK TR

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

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602007007816

Country of ref document: DE

Date of ref document: 20100826

Kind code of ref document: P

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20100714

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20100714

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Effective date: 20101216

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

Effective date: 20100714

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: 20100714

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: 20100714

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: 20100714

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: 20100714

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: 20101115

Ref country code: PL

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: 20100714

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: 20101114

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: 20100714

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: 20101014

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

Ref country code: DE

Payment date: 20101126

Year of fee payment: 4

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

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: 20100714

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: 20101015

Ref country code: BE

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

Effective date: 20100714

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: 20100714

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

Ref country code: TR

Payment date: 20101105

Year of fee payment: 4

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

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: 20100714

26 Opposition filed

Opponent name: HENKEL AG & CO. KGAA

Effective date: 20110414

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

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: 20100714

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: 20100714

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: 20100714

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: 20100714

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

Free format text: ORIGINAL CODE: EPIDOSNOBS2

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: 20101130

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602007007816

Country of ref document: DE

Effective date: 20110414

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

Free format text: ORIGINAL CODE: EPIDOSCOBS2

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: 20101130

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

Free format text: ORIGINAL CODE: EPIDOSNOBS3

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

Ref country code: MT

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: 20100714

Ref country code: IT

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

Effective date: 20101130

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

Ref country code: IT

Payment date: 20101130

Year of fee payment: 4

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

Ref country code: ES

Payment date: 20111124

Year of fee payment: 5

Ref country code: FR

Payment date: 20111128

Year of fee payment: 5

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

REG Reference to a national code

Ref country code: DE

Ref legal event code: R064

Ref document number: 602007007816

Country of ref document: DE

Ref country code: DE

Ref legal event code: R103

Ref document number: 602007007816

Country of ref document: DE

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

Ref country code: CH

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

Effective date: 20111130

Ref country code: LI

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

Effective date: 20111130

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: 20101130

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: 20110115

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

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

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20120729

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

Effective date: 20120729

REG Reference to a national code

Ref country code: DE

Ref legal event code: R107

Ref document number: 602007007816

Country of ref document: DE

Effective date: 20130124