Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
  • B29C63/0047—Preventing air-inclusions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
  • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
  • B32B17/10165—Functional features of the laminated safety glass or glazing
  • B32B17/10321—Laminated safety glass or glazing containing liquid layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/0038—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving application of liquid to the layers prior to lamination, e.g. wet laminating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
  • B29C63/48—Preparation of the surfaces
  • B29C2063/483—Preparation of the surfaces by applying a liquid
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
  • B29C63/02—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/406—Bright, glossy, shiny surface
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/412—Transparent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2405/00—Adhesive articles, e.g. adhesive tapes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/0007—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality
  • B32B37/003—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality to avoid air inclusion
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/30—Aspects of methods for coating glass not covered above
  • C03C2218/355—Temporary coating
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
  • Y10T156/10—Methods of surface bonding and/or assembly therefor
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249994—Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
  • Y10T428/249995—Constituent is in liquid form

Definitions

• the present invention relates to substrates which are, occasionally or permanently, at temperatures below 0 ° C., especially transparent.
• anti-ice for preserving transparency
• hydrophobic hydrophilic
• antifouling-self-cleaning photocatalytic
• reflecting light or heat radiation colored at least in part
• electroconductive-heating semi -conductor
• antistatic electroluminescent
• the coating formation process is adapted to ensure the desired adhesion and mechanical strength and, in particular, as little scratchability as possible or self-healing ability of the coating scratches, when the substrate is transparent. .
• the coating is regenerated when necessary.
• one or more functions can be provided by an adhesive film, having the advantage of the ease of its replacement by an identical film or carrying different functions.
• a method may consist in interposing a sufficient quantity of a liquid, in particular water mixed with a surfactant, to allow all the bubbles to be expelled by applying pressure to the film, for example its central part. towards its periphery, by means of a squeegee.
• the object of the invention is therefore to provide a method of assembling a flexible film to a substrate that guarantees a perfect interface between the two and, in particular, the absence of trapped air bubbles and the formation of frosted.
• the subject of the invention is a process for adhesion of a flexible film to a substrate, comprising the interposition between film and substrate of a sufficient quantity of a liquid, so that no bubbles trapped between the film and the substrate after the film has been applied to the substrate by means of a squeegee, characterized in that the liquid does not freeze at a substrate temperature below 0 ° C., especially at most -5 0 C and in particular at most -1O 0 C, and also at least -25 0 C, occasionally or permanently.
• the substrate is freed from any particles that are adhered to, cleaned and wiped, prior to the interposition of a sufficient amount of a liquid between film and substrate.
• the face of the flexible film to be adhered to the substrate is wetted with said sufficient amount of a liquid.
• Any suitable liquid deposition techniques such as flow coating, spraying, spray or the like may be employed.
• the face of the flexible film to be adhered to the substrate comprises an adhesive layer optionally provided with a protective film to be removed before the setting adhesion on the substrate.
• an adhesive can be integrated with the liquid interposed between film and substrate.
• the adhesives can be chosen from:
• thermoplastic polymers heated thermoplastic polymers to obtain a liquid having the appropriate viscosity to be deposited and then cooled to obtain a solid (polyethylene, ethylene-vinyl acetate copolymer, polyamide, polyester, etc.);
• adhesives in the form of ready-to-use films epoxy, phenolic, nitrile rubber, polyamide, polyvinyl butyral, polyvinyl chloride, ethylene-carboxylic acid copolymer;
• - pressure-sensitive adhesives do not change their physical state before and after application, remain permanently deformable and have a certain stickiness at ambient temperature: tackified elastomers (natural rubber - latex), ethylene-acetate copolymer vinyl, thermoplastic elastomer (polyurethane ...), styrene - diene block copolymer (styrene - butadiene - styrene, styrene - isoprene - styrene), polyaryl arylate), silicones;
• - elastomers natural rubber, styrene - butadiene rubber, polychloroprene, neoprene, nitrile rubber, butyl rubber;
• Inorganic adhesives soluble silicates with different silica - alkali proportions. According to preferred embodiments of the method of the invention:
• the face of the flexible film opposite that to be adhered to the substrate is wetted with an effective amount of liquid so that the squeegee slides easily on the film during the operation of applying the film to the substrate;
• the face of the flexible film opposite to that to be adhered to the substrate is provided with a protective film to be removed after adhesion of the flexible film to the substrate; this protective film is particularly likely to be wet to facilitate the sliding of the squeegee as indicated above;
• the liquid interposed between the film and the substrate comprises an effective amount of an antifreeze compound lowering the crystallization temperature such as a salt, in particular KCl, NaCl or equivalent in solution and / or alcohol and / or a polymer, copolymer, prepolymer or hydrophilic oligomer suitable, optionally in water, and optionally one or more surfactants.
• an antifreeze compound lowering the crystallization temperature such as a salt, in particular KCl, NaCl or equivalent in solution and / or alcohol and / or a polymer, copolymer, prepolymer or hydrophilic oligomer suitable, optionally in water, and optionally one or more surfactants.
• alcohols are particularly used ethanol, isopropanol.
• hydrophilic polymers, copolymers, prepolymers or oligomers constituting the interposed liquid are especially based on polyvinylpyrrolidone of the poly (n-vinyl-2-pyrrolidone) or poly (1-vinylpyrrolidone) type, polyvinylpyrridine of the poly (n-vinyl-2 pyridine) type. ), poly type
• poly (N ', N-hydroxyacrylamide) polyacrylamide polyacrylamide
• polyvinylacetate polyacrylonitrile
• polyvinylalcohol polyacrylonitrile
• polyacrolein polyethylene glycol
• polypropylene glycol polyoxyethylene.
• the copolymers are based on at least one of the monomers constituting these polymers.
• surfactants there may be mentioned compounds comprising a lipophilic part Y, which may be a linear, branched or unsaturated aliphatic chain or an aromatic or alkylaromatic chain, and an ionic hydrophilic head or not.
• anionic surfactants Y - CO 2 M + ; Y - OSO 3 M + ; Y - SO 3 M + ; dodecylbenzene sulfonate; alkyl sufonate; fatty acid and sulphonated fatty acid ester; alkylarylsulfonate; cationic surfactants: Y - (R) n NH + ( 4-n ), X " ; Y - R 4 N + , X " ; alkyltrimethylammonium; alkylbenzyldimethylammonium; imidazolinium salts; amine salts;
• Y - OR Y - OH; Y - CO 2 R; Y - CONHR; Y - (CH 2 CH 2 ⁇ - O) n -; polyol; alcohol; acid; ester; polyethoxylated fatty alcohol.
• Another object of the invention is constituted by a substrate and flexible film in mutual adhesion obtained with the interposition of a sufficient quantity of a liquid in the absence of any imprisoned bubble, characterized by the persistent absence of frost in case of displacement of the substrate and the film in an atmosphere where their temperature will be below 0 ° C., respectively at most -5 ° C. and -10 ° C., from an atmosphere with a temperature at least equal to 0, preferably between 10 and 35, in particular 15 and 30 and in particular 23 and 27 0 C and residual moisture of at least 25%.
• the substrate and flexible film form a transparent assembly.
• the substrate is made of glass or a plastic material such as polycarbonate, polypropylene, poly (methyl methacrylate), ethylene / vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate, polyurethane, polyvinyl butyral , cycloolefinic copolymer such as ethylene / norbornene or ethylene / cyclopentadiene, polycarbonate / polyester copolymer, ionomer resin such as ethylene / polyamine-neutralized (meth) acrylic acid copolymer and the like, alone or in mixtures.
• a plastic material such as polycarbonate, polypropylene, poly (methyl methacrylate), ethylene / vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate, polyurethane, polyvinyl butyral , cycloolefinic copolymer such as
• the film is anti-freeze and / or hydrophobic and / or hydrophilic and / or antifouling-self-cleaning (photocatalytic) and / or reflecting light or heat radiation, antisolar, low-emissive, and / or colored at least in part and / or electroconductive-heating and / or semiconductor and / or antistatic and / or electroluminescent;
• the film is anti-icing and, when at a temperature of at most -1 0 ° C., respectively -15 ° C. and -20 ° C., it is placed in an atmosphere at a temperature of at least 0, preferably between 10 and 35, in particular 15 and 30 and in particular 23 and 27 ° C.
• the film is based on a support made of polyamide, polyester, polyolefin such as polyethylene, polypropylene, cellulose, polystyrene, ethylene / vinyl acetate copolymer, polyvinyl alcohol, polyvinyl chloride, poly (terephthalate), ethylene), poly (methyl methacrylate), polycarbonate, polyvinylburyral, polyurethane, polyvinylpyrrolidone, polyvinylpyrridine, poly-2-hydroxyethylacrylate polyacrylate), polyacrylamide, polyvinyl acetate, polyacrylonitrile, polyacrolein, polyethylene glycol, polyoxyethylene; it may also be a copolymer or a mixture based on at least one of the polymers mentioned above; -
• the film is anti-icing in that it comprises an antifreeze compound
• the antifreeze compound As the antifreeze compound, the same as described above can be used for said interposed liquid. However, it is sought a durability of the anti-frost function of the film, which may require improving the mechanical strength of the layer incorporating the antifreeze compound, particularly when it is likely to be subjected to occasional mechanical contact, or
• the antifreeze compound may be crosslinked and / or combined with at least one compound that is physically interacting with it and / or dispersed in a solid, inorganic, for example, or mixed matrix of the ORMOCER (Organically Modified Ceramics) type. ).
• the anti-icing function can be integrated in the film itself or in a coating formed on the support of the film.
• the invention furthermore relates to a glazing unit comprising a substrate and flexible film as described above, as well as possibly other transparent sheets to which they are connected via adhesive layer (s) interlayer (s) or gas blade (s). From this glazing, said flexible film advantageously constitutes an outer face, thus functionalized.
• the glazing consists in particular of a monolithic glazing, laminated, multiple, insulating, vacuum.
• Such multiple glazing, insulating comprises for example two or three sheets of monolithic or laminated glass, separated two by two by a gas blade.
• the interest may be the thermal insulation of a refrigerated chamber vis-à-vis the outside atmosphere (a store .).
• This thermal insulation is obtained alternately by a vacuum glazing comprising at least two sheets of monolithic or laminated glass separated by a vacuum or a gas blade at reduced pressure. These two sheets may be associated with a third of which they are separated by a gas strip at reduced pressure or not.
• Such structures may comprise one or more low-emissive layers reflecting the heat radiated from outside the refrigerated enclosure.
• the thermal conductivity of its barrier that is to say all the elements through which the various sheets of monolithic or laminated glass constituent are held together and spaced two by two, is at most 1, 46 W / mK
• the polycarbonate film is provided with an adhesive layer oriented towards the insulating glazing unit, to which the film is fixed with the interposition of a liquid specified below.
• the polycarbonate film is coated, on the side opposite to that of the adhesive layer, with an anti-ice adsorbent layer forming a three-dimensional polymeric network based on polyvinylpyrrolidone and polyurethane.
• the thickness of the anti-icing layer is equal to 14.5 ⁇ m.
• Tests are carried out on doors installed on refrigerated sales cabinets in which a temperature of -25.5 ° C is maintained. The temperature measured on the inside of the door is -22 ° C. The furniture is placed in an atmosphere at a temperature of 25 ° C. and 60% residual humidity.
• the cabinet door is opened 10 min before the film is laid to prevent frosting on the glass.
• the inner face of the door is wetted with a sprayer filled with a washing composition (soapy water).
• the glass is scraped off with a scraper to remove any particles that are stuck, then with a rubber squeegee to wipe off the water. There must be no more frost on the door. If necessary wipe the edges with a cloth.
• the protective film of the adhesive is removed from the polycarbonate film and the liquid indicated in the table below is sprayed onto the adhesive.
• the liquid between the glass and the film is removed.
• the center of the glazing is scraped outwards. If necessary, cut the film so as to leave a game of a few mm between the amounts of the door and the film to promote the evacuation of the liquid.
• the table below shows the presence or absence of frost at different times after closing the door, as well as bubbles between the glass and the film.
• Mir is a detergent composition marketed by Henkel.
• Triton X is a mixture of polyethoxylated octylphenols (nonionic surfactant) marketed by Union Carbide.
• PEG 200 is a polyethylene glycol marketed by Merck (Art 807483).
• This table illustrates the possibility of reducing the formation of frost to prevent it, and thus obtain a permanent absence of frost.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
• Geochemistry & Mineralogy (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Combustion & Propulsion (AREA)
• Laminated Bodies (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Lining Or Joining Of Plastics Or The Like (AREA)

Applications Claiming Priority (2)

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• 2005
  • 2005-01-31 FR FR0550271A patent/FR2881422B1/fr not_active Expired - Fee Related
• 2006
  • 2006-01-30 CN CNA2006800036473A patent/CN101111369A/zh active Pending
  • 2006-01-30 WO PCT/FR2006/050073 patent/WO2006079763A2/fr active Application Filing
  • 2006-01-30 JP JP2007552704A patent/JP5160900B2/ja not_active Expired - Fee Related
  • 2006-01-30 US US11/815,049 patent/US20080138603A1/en not_active Abandoned
  • 2006-01-30 KR KR1020077017455A patent/KR101362793B1/ko not_active IP Right Cessation
  • 2006-01-30 KR KR1020127029734A patent/KR101364041B1/ko not_active IP Right Cessation
  • 2006-01-30 KR KR1020127029728A patent/KR101364233B1/ko not_active IP Right Cessation
  • 2006-01-30 BR BRPI0607050-7A patent/BRPI0607050A2/pt active Search and Examination
  • 2006-01-30 EP EP06709457A patent/EP1843895A2/fr not_active Withdrawn
  • 2006-01-30 CA CA 2595977 patent/CA2595977C/fr not_active Expired - Fee Related
  • 2006-01-30 MX MX2007008994A patent/MX2007008994A/es active IP Right Grant
• 2010
  • 2010-01-21 US US12/690,967 patent/US8057615B2/en not_active Expired - Fee Related

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