Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
  • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
  • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
  • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
  • C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
  • C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
  • C04B24/42—Organo-silicon compounds
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
  • C04B28/04—Portland cements
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/00482—Coating or impregnation materials
  • C04B2111/00517—Coating or impregnation materials for masonry
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/20—Resistance against chemical, physical or biological attack
  • C04B2111/2038—Resistance against physical degradation
  • C04B2111/2076—Discolouring resistant materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/20—Resistance against chemical, physical or biological attack
  • C04B2111/2092—Resistance against biological degradation
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/20—Resistance against chemical, physical or biological attack
  • C04B2111/21—Efflorescence resistance
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/20—Resistance against chemical, physical or biological attack
  • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials

Definitions

• the present invention relates to a new coating, particularly monolayer, in the field of construction, as well as its manufacturing process and its use for coating and treating surfaces (exterior or interior) of buildings, especially facades.
• plaster, or mortar, used in facades allow the waterproofing and decoration of the outer walls (usually vertical or inclined).
• waterproofing prevents water from reaching the support (this also implies that the coating must not crack, must adhere to the support, etc.).
• the decoration includes, in particular, dressage (planing action), color and appearance (eg smooth, trowel, scraped, structured, washed, etc.).
• coatings there are different types of coatings (in particular coated monolayers or deposited in several different layers with generally separated functionalities, coatings of essentially mineral or organic type, etc.), each type of coating having specific properties and the choice of the coating generally operating according to different criteria (cost, function (s) sought, manipulation (manual or mechanical application), media to be coated, mode of application, geographical location, climatic conditions, height of the building, etc. ).
• monolayer plaster lies in the fact that it alone (in one or possibly several passes according to the particular aspect sought) ensures the functions of waterproofing and decoration, unlike other so-called "traditional" coatings for which, in order to obtain the same result, it is necessary to superimpose layers of different compositions with, in particular, more or less long drying times between these layers.
• Mono coating can be used alone as a surface coating and does not need to be completed by a layer of another coating to be operational, even if the application of other layers is not prohibited so far.
• the monolayer coating allows a quick laying and providing the desired functions in a single product, its formulation is more complex than other coatings; in addition, like other coatings, its performance in terms of water resistance or hydrophobicity is not always sufficient to avoid alterations (particularly aesthetic or potentially visible) over time (especially for mineral coatings), such as differences in hues, due in particular to carbonation or bleaching phenomena and / or due to crazing phenomena and / or drying differentiated according to the locations, etc., or even biofouling (fungi, etc.). .), mineral (dust, %), and / or organic (smoke, soot, ...), or the proliferation of plant formations, etc.
• the present invention has sought to develop an improved coating for waterproofing and decorating building surfaces, in particular an improved aesthetic longevity coating having and providing increased and durable water resistance to said surfaces (and allowing to limit, as the case may be, visible alterations such as differences in hues and / or soiling and / or proliferation of plant formations), without this improvement being to the detriment of the other properties of the coating, this coating being particularly suitable for the market new or renovated, convenient to handle and to install according to common methods.
• coating comprising is meant “coating whose initial constituent (s) are -- or “coating formed from ", the coating after mixing including with water and / or after application on a surface in the form of a cream or a hardened layer in which certain constituents have optionally reacted.
• This coating (or mortar) according to the invention is preferably a mineral coating (that is to say in which the binder, in particular, is essentially - at least 95% and usually 100% - mineral), or may be optionally a organic coating (in which, for example, the binder is essentially based on organic resin (s)).
• a mineral coating that is to say in which the binder, in particular, is essentially - at least 95% and usually 100% - mineral
• the binder is essentially based on organic resin (s)
• it comprises (or is formed or prepared from) a mixture of components (basic mixture), which mixture may be chosen optionally from coating compositions or existing mortars commonly used to coat facades (especially for thermal insulation from the outside).
• this mixture of components comprises at least one binder and aggregates.
• the binder plays in particular on the adhesion, the cohesion and the resistance of the coating, and can be mineral and / or organic; it is generally formed of at least (or consisting of) cement (in particular Portland cement, especially white or gray, etc.) and / or plaster, and may also comprise lime (in particular aerial or hydraulic) and / or one or more organic resins (for example acrylic or styrene type, etc.). It is generally added to the mixture in the form of a powder, of particle size distributed in particular between 0 and 200 ⁇ m.
• the level of binder in the coating composition according to the invention is generally between 5 and 30% by weight relative to the composition of the coating ready to tempering (that is to say before adding water this composition is then conventionally in the form of a powder mixture).
• Aggregates play in particular on the thickness, the hardness, the final appearance and the permeability of the coating, and are generally formed of siliceous, calcareous and / or silico-calcareous sands, generally presenting a granulometry between 100 .mu.m and 5 mm, in particular between 100 .mu.m and 3 mm.
• the level of aggregates in the composition of the ready-to-mix coating is generally between 60 and 90% by weight.
• the base mixture or the composition of the coating may also comprise components called fillers, generally in the form of a powder, particle size in particular between 0 and 120 microns, these fillers being generally limestone or siliceous.
• the level of fillers in the composition of the ready-to-mix coating is generally between 0 and 30% by weight, the total sum of binder and fillers generally being between 5 and 60% by weight.
• the mixture may further comprise lightening fillers, for example expanded vermiculite and / or expanded perlite and / or glass expanded and / or expanded polystyrene, or even plant fibers, etc., these fillers having optionally a particle size distributed generally between 0 and 3 mm.
• the level of leaching loads in the composition of the plaster ready to tempering is generally between 0 and 10% by weight.
• additives or adjuvants conferring particular properties for example rheological agents, water-retaining agents, air-entraining agents, thickening agents, biocidal protective agents, dispersing agents, debulking agents, pigments (in particular mineral pigments), fibers (in the case of fiber coatings) of reinforcing or rheological functionality, accelerators and / or retarders, and / or other agents for improving the taking, hardening, stability of the coating after application, and / or playing on the color, the implementation of the coating, etc.
• the level of these additives and adjuvants in the composition of the ready-to-mix coating generally does not exceed the order of 10% by weight, and is most often between 0.1 and 10% by weight.
• the polysiloxane having at least one amine function mentioned according to the invention is an adjuvant or additive that can be conveniently added to the mixture already formed (it can be added to a pre-existing mixture) or can be add during the manufacture of the mixture or the coating (ready to mix or mixed with water) from the various constituents mentioned above.
• the level of adjuvant (s) in the form of polysiloxane (s) having at least one amine function in the composition of the ready-to-mix coating is preferably at least 0.1% by weight, and in most cases does not exceed not (is less than or equal to) 1% by weight; generally this level of polysiloxane (s) having at least one amine function is of the order of 0.1 to 0.5% by weight of the composition of the coating ready to tempering.
• the polysiloxane mentioned according to the invention has a main chain formed of an alternation of silicon-oxygen atoms on which groups, in particular organic groups (organopolysiloxane), bind (on the silicon atoms), at least one of these groups incorporating at least one amine group (or function) according to the invention (this amine group optionally contributing to couplings, connections, bindings, crosslinking, in particular in the final coating and / or in a mixture in the matrix cement).
• This polysiloxane is in particular part of the silicone oils. It is in particular a copolymer (in particular bi-or ter-polymer) formed of a repetition of different units (or siloxanes) (in particular a repetition of two or three different types of units or siloxanes, of which at least one includes an amino group).
• the polysiloxane according to the invention advantageously has a long main chain formed of a number n of units (or repeating units or siloxanes) which can reach several thousands, in particular greater than 15, in particular between 40 and 3000, this polysiloxane being in particular a linear or non-cyclic polysiloxane (chain optionally branched, but not closed, "acyclic" and / or not having a ring) .
• the coating according to the invention may also comprise a cyclic polysiloxane, especially in combination with a linear and / or acyclic polysiloxane (and in a generally lower proportion).
• the polysiloxane according to the invention is a polyalkylsiloxane (having at least one amino function (or group)), the alkyl groups carried by the silicon atoms in the main chain being chosen especially from the alkyl groups (or radicals) whose main chain has from 1 to 12, preferably from 1 to 6, carbon atoms, the majority of these alkyl groups being generally and advantageously methyl groups.
• the polysiloxane is also terminating (s) (tri) alkylsiloxy, in particular trimethylsiloxy.
• the polysiloxane according to the invention has at least one amino group or in particular aminoalkyl, in particular of -R-NH 2 or -R-NH-R'-NH 2 type in which R and R 'are chosen from groups ( or radicals) alkyls whose main chain has from 1 to 6 carbon atoms, this group being attached to a silicon atom, in particular non-terminal but internal to the main chain.
• the coating comprises, as polysiloxane (s), at least one preferentially linear and / or acyclic amino-functional polydimethylsiloxane, for example a dipolymer or polysiloxane such as dimethyl, methyl (aminoethylaminoisobutyl) siloxane with trimethylsiloxy termination, viscosity for example between 150 and 4000 cP and having a number n of units for example between 150 and 2000.
• polysiloxane s
• at least one preferentially linear and / or acyclic amino-functional polydimethylsiloxane for example a dipolymer or polysiloxane such as dimethyl, methyl (aminoethylaminoisobutyl) siloxane with trimethylsiloxy termination, viscosity for example between 150 and 4000 cP and having a number n of units for example between 150 and 2000.
• the coating according to the invention may optionally comprise, as adjuvants, several different polysiloxane (s) having at least one amine function.
• the coating according to the invention comprises other adjuvants of different formulation but may also contribute to improving the water resistance and longevity (particularly aesthetic) of the coated, for example from the family of silanes, and / or additional adjuvants with water-repellent effect, for example zinc stearate, sodium oleate, etc.
• the coating according to the invention is in the form of powder in its ready-to-mix form, before adding water to obtain a creamy texture ready to be applied.
• the mixing ratio (or added water) is generally of the order of 15 to 40 parts by weight (per 100 parts by weight of the ready-to-mix composition formed of the powder mixture). Note that the present invention relates to the plaster in its form ready to spoil as well as in its form mixed with water.
• the coating according to the invention is a monolayer coating, providing in particular in one or two passes the desired hydrophobicity / water repellency and decoration functions. It can be used as a facing coating intended to be attached (projected, applied, etc.) to a surface (or support), such as a wall or facade surface of a building, to give it aesthetics and protection.
• a surface or support
• the surface or the support receiving the coating may be made of different materials such as concrete or blocks, brick, cement, lime cement, masonry, glass wool or rock, etc.
• the coating according to the invention used in particular as a final layer, provides both the required aesthetic effect (color, etc.) and the functions sought for this type of coating, such as waterproofing and adhesion to the substrate. , mechanical strength (flexural, compressive, impact, cracking, etc.), resistance to temperature changes, freezing, ultraviolet, water vapor permeability, ease of implementation, and eventual training. It offers from the outset, without the need for a treatment or additional layer, a greatly improved protection against the penetration of water, the water in contact with this coating evacuating flowing along the coating, and effectively fights against the appearance of alterations (soils, plant formations, bleaching due to carbonation, crazing, drying spectra, etc.).
• the coating shows a particularly effective effect with respect to water resistance, the water not absorbing but evacuating into drops on the surface of the coating layer, this effect " beading "significant and improved resulting in particular by a contact angle (of a drop of water on the surface of a layer of said hardened coating) greater than 140 ° and / or by a stall angle (of a drop of water on the surface of a layer of said hardened coating) less than 30 °.
• the contact angle mentioned is measured by depositing a drop of distilled water of 8 ⁇ l using a micropipette on the surface of a smooth layer of hardened plaster (10 mm thick), then measuring by the top of the drop using a microscope the diameter of the drop (2 measurements per drop), this value of diameter to deduce the contact angle of the drop with the surface.
• the stall angle mentioned is measured by randomly depositing ten drops of 48 ⁇ l distilled water (in all) on the surface of a layer of hardened plaster positioned on a flat plate, then tilting the plate with a constant speed (in particular of the order of 0.257seconds) and noting to what degree of inclination the drop falls.
• the present invention also covers a coating characterized in that the contact angle of a drop of water on the surface of a layer of said cured coating is greater than 140 ° and / or such that the stall angle of a drop of water on the surface of a layer of said cured coating is less than 30 °.
• the present invention also relates to a method of manufacturing a coating according to the invention, wherein the other components of the composition of the coating are added at least one polysiloxane having at least one amine function.
• the polysiloxane may be added to the other components of the coating composition in the ready-to-mix formulation or in the ready-to-deposit coating after addition of water. Preferably, it is added to the powder coating composition by being previously adsorbed on at least one of the solid components of the composition.
• the method according to the invention thus preferably comprises a prior step of adsorbing the polysiloxane, initially in liquid form (the polysiloxane corresponding in particular to a silicone oil) to the surface of a component of the coating capable of trapping ( in particular by physisorption) said polysiloxane before incorporation into the coating composition.
• This adsorption is done in particular on a silicon-based component and / or even on a limestone component, in particular on all or part of the aggregates of the coating composition, for example by mixing the polysiloxane in liquid form with said granules.
• the mixture obtained incorporating the polysiloxane is then added, if appropriate, to the other components of the coating composition, the polysiloxane optionally being salted out in the final composition obtained.
• the coating according to the invention is advantageously preserved in the form of a powder (for example in a bag of coating ready to be spoiled) before its use.
• the coating Prior to its deposition on a support, the coating is normally mixed with water and then deposited on a surface, for example a building facade.
• the surface or support to receive the coating is generally clean, healthy (not at risk of fragmenting or crumbling), dusted and dry. If necessary, it may have been previously treated (for example pickled, ragréée, washed, provided with renformis, caulking, etc.) for example to equalize the surface, to make it suitable for receiving the coating according to the invention, to seal cracks, participate in the insulation of the support, etc.
• the coating can be made by any method to obtain the desired thickness and appearance, for example by spreading the chosen coating or by projecting it with a compressed air device, etc.
• the application of the coating can be made if necessary in one or more (depending for example the desired thickness, etc.) passes, applied fees on charges or if necessary dried before deposit of the next.
• the drying of the coating according to the invention is advantageously uniform even if the support varies, thus avoiding color differences of the hardened coating.
• reinforcing reinforcements for example in the form of reinforcing fiber grids
• the latter may be incorporated in a layer (where appropriate one of the passes) of coated, still fresh, deposited on the laying surface.
• the coating or mortar may be cleaned, for example with water before drying or brushed after drying.
• the appearance conferred by the coating may be smooth or not, no additional treatment or addition of a finishing coating or additional film is necessary (the coating may however be provided with additional decorations such as paints, moldings, stamping or structuring, etc.)
• the coating produced can be left bare, can be colored in the mass (due to the presence of pigments in the coating), can also be structured (with particular surface effects), for example by striation, stamping, shoeing , creation of ribs, etc. especially at the level of the coating.
• the thickness of the final coating (after deposition and, depending on the desired appearance, possible scraping, etc.) is generally of the order of 8 to 20 mm, in particular of 10 to 15 mm approximately.
• the drying and optional reaction (crosslinking, hardening) of the coating or of certain components of the coating is generally carried out at ambient temperature (in particular between 5 and 35 ° C.).
• the present invention also relates to a support (or structure or substrate), such as a wall or building facade, coated, at least in part, with the coating according to the invention.
• the coating composition according to the invention and the reference composition are formed from the same basic mixture consisting of an approved mortar as defined in the EN 196-1 standard, said mortar being based on cement and sand (including aggregates).
• the reference coating and the coating according to the invention different in that in the reference coating, the previous base mixture is completed by 2 parts by weight of zinc stearate (per 1000 parts by weight of the base mixture ) as an additive with water-repellent effect, while in the coating according to the invention the base mixture is completed by 2 parts by weight (per 1000 parts by weight of the base mixture) of an aminofunctional polydimethylsiloxane of viscosity included between 200 and 40OcP (number of siloxane units of the order of 160) and having an amine number of the order of 0.15%.
• the contact angle of a drop of water measured for the coating according to the invention is greater than 165 ° whereas it varies between 95 and 105 ° for the reference coating; and for 3 tests carried out, each time on 10 drops, the stall angle varies between 10 and 30 ° (the vast majority of the measurements being less than 20 °) for the coating according to the invention, whereas in the case of the reference coating, no drop having moved or fallen even for an angle greater than 90, this angle could not be evaluated (and is considered greater than 90 °). It is clear that in the case of the coating according to the invention, the water slides on the surface of the coating and is easily removed, while it tends to penetrate into the reference coating.
• the coatings according to the invention can be used in particular as facade coatings on the vertical or inclined external walls of buildings, etc.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Structural Engineering (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Paints Or Removers (AREA)
• Finishing Walls (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Laminated Bodies (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)

Applications Claiming Priority (2)

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• 2007
  • 2007-09-21 FR FR0757762A patent/FR2921359B1/fr active Active
• 2008
  • 2008-08-07 RU RU2010115773/03A patent/RU2010115773A/ru unknown
  • 2008-08-07 BR BRPI0816489-4A2A patent/BRPI0816489A2/pt not_active Application Discontinuation
  • 2008-08-07 EP EP08832009A patent/EP2193110A1/de not_active Withdrawn
  • 2008-08-07 WO PCT/FR2008/051474 patent/WO2009037409A1/fr active Application Filing
  • 2008-08-07 CN CN200880108087.7A patent/CN101801890B/zh not_active Expired - Fee Related
  • 2008-09-17 AR ARP080104034A patent/AR068462A1/es not_active Application Discontinuation

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