Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond

Definitions

• the present invention relates to a process for preparing a transparent polymeric material comprising a thermoplastic polycarbonate and surface-modified inorganic nanoparticles, as well as to a transparent polymeric material obtained by said process.
• automotive glazing not only transparent outer bodywork such as for example rear windows, custodes, side windows, glazed roofs, headlamps or lights, but also elements transparent interior interiors such as dashboard windows, dials or screens.
• Opt lens is understood to mean lenses that adapt in particular to a spectacle frame, whose function is to protect the eye and / or to correct vision, these lenses being chosen from among afocal, unifocal, bifocal and trifocal lenses. and progressive.
• Polycarbonate has advantages that make it particularly interesting for the optics including excellent transparency, excellent impact resistance, a high refractive index and a great lightness. On the other hand, it has the main weaknesses of not being very rigid and being very sensitive to scratches and abrasion.
• these mineral nanoparticles are incorporated directly into the polymer used in the molten state.
• the nanometric dimension of the mineral nanoparticles inevitably induces a phenomenon of aggregation of said nanoparticles when they are mixed in a thermoplastic polycarbonate matrix in the molten state.
• the polymer material obtained from this process exhibits a loss of transparency, as well as a coloration, in particular a yellowing, which makes its use difficult in the fields of optics.
• the incorporation of mineral nanoparticles can induce a degradation of the mechanical properties of the polymer material, such as, for example, impact resistance.
• thermoplastic polycarbonate matrix in order to improve the quality of the interface between the nanoparticles and the thermoplastic polycarbonate matrix and thus improve the mechanical and optical properties of the polymeric material, it is known from EP 1 767 562 a process for the preparation of transparent polymeric materials. comprising a thermoplastic polycarbonate and surface-modified mineral nanoparticles.
• This process consists in grafting, on the surface of the mineral nanoparticles, a monomer of the thermoplastic polycarbonate matrix by an aliphatic ether bond, then polymerizing in situ said monomer to form the thermoplastic polycarbonate matrix.
• the surface modification of said mineral nanoparticles is inseparable from the thermoplastic polycarbonate matrix.
• this method involves the use of a specific reactor for the polymerization of the thermoplastic polycarbonate matrix, this use being relatively restrictive.
• the object of the present invention is to overcome the disadvantages of the solutions of the state of the art by offering in particular a method of preparation of a transparent polymer material easily industrializable while preserving, or even improving, the optical and mechanical properties of the polymer material obtained by said process.
• the solution according to the present invention is to provide a method for preparing a transparent polymeric material comprising the following steps: i. obtaining composite nanoparticles comprising mineral nanoparticles coated with at least one monomer and / or at least one polymer capable of promoting physicochemical interactions at the interface between the mineral nanoparticles and a thermoplastic polycarbonate matrix, said mineral nanoparticles being modified at the surface by said monomer and / or said polymer:
• the preparation method according to the present invention makes it possible to significantly improve the cohesion of the mineral nanoparticles thus modified with the thermoplastic polycarbonate matrix, and to disperse said nanoparticles homogeneously in said matrix.
• the coupling agent advantageously allows the monomer and / or the polymer to be bonded via the surface of the mineral nanoparticles when said monomer and / or said polymer can not in particular be bonded directly to said surface.
• the surface modifications of the inorganic nanoparticles of the type adsorption or creation of physical or chemical interactions of the hydrogen bonding or van der Waals type, by the monomer and / or the polymer are preferably carried out directly on the surface of said nanoparticles, or in other terms without a coupling agent.
• the surface modification of the mineral nanoparticles can be advantageously achieved by creating a covalent bond between, on the one hand, the mineral nanoparticles and the coupling agent and d on the other hand, between the coupling agent and the monomer and / or the polymer.
• the surface modification of the mineral nanoparticles can be achieved by creating a covalent bond directly between the mineral nanoparticles and the monomer and / or the polymer, or by direct adsorption of the monomer and / or the polymer on the surface of said mineral nanoparticles.
• the said polymer when the surface of the mineral nanoparticles is modified by a polymer, the said polymer can be obtained by polymerization of the monomer which is specific to it (so-called in situ polymerization). , whether or not there is a coupling agent.
• step i the monomer of step i is grafted onto the surface of the mineral nanoparticles, and then it is polymerized.
• said polymerization requires the presence of an initiator capable of generating free radicals under the effect of actinic or thermal radiation.
• a coupling agent according to the invention in particular via the organosilane
• the latter is first grafted to the surface of the mineral nanoparticles.
• the monomer is grafted onto the surface of the mineral nanoparticles via said organosilane, or in other words, the monomer is typically grafted to said organosilane.
• the monomer is polymerized.
• the surface modification is direct, that is to say without a coupling agent, the monomer is grafted directly onto the surface of the mineral nanoparticles, and then it is polymerized.
• the surface of the mineral nanoparticles is modified by a monomer according to the invention, said monomer is not necessarily polymerized.
• the mineral nanoparticles are at least partially coated with said monomer as such.
• the composite nanoparticles obtained in step i may advantageously comprise at most 60% by weight of organic coating, preferably between 5 and 50% by weight of organic coating.
• organic coating means the organic layer formed around the mineral nanoparticles, said layer being obtained from the monomer and / or the polymer, and optionally the coupling agent.
• transparent polymeric material means a material through which an image is observed without significant loss of contrast.
• molten state refers to a state in which the thermoplastic polycarbonate matrix of step ii is in a malleable state.
• This malleable state well known to those skilled in the art, can be conventionally achieved when said matrix is heated to a temperature above the glass transition temperature, or softening temperature, of the thermoplastic polycarbonate.
• the expression "between a value x and a value y" means that the values x and y are included in this range of values.
• the physicochemical interactions at the interface between the mineral nanoparticles and the thermoplastic polycarbonate matrix can be advantageously favored when the monomer on the surface composite nanoparticles is in particular styrene, methyl methacrylate, butyl acrylate, bisphenol A, phosgene, diphenyl carbonate and / or acrylamide.
• Bisphenol A such as phosgene or diphenyl carbonate, are well known monomers of polycarbonate.
• the polymer on the surface of the composite nanoparticles is in particular polystyrene, polycarbonate, polymethyl methacrylate, butyl polyacrylate and / or polyacrylamide, and more particularly a styrene copolymer, of the monomer polycarbonate, methyl methacrylate, butyl acrylate, bisphenol A and / or acrylamide.
• the functional group of the organosilane is a functional group capable of reacting radically, and thus being able to create a covalent bond by a radical addition mechanism in the presence of an initiator, said initiator being able to generate free radicals under the effect of actinic or thermal radiation.
• the reactive functional group may be advantageously chosen from an acrylate, methacrylate, vinyl, allylic or alkenyl group, and preferably a vinyl group.
• the organosilane according to the present invention may further comprise a hydrolysable functional group.
• This functional group notably makes it possible to form covalent bonds on the surface of the mineral nanoparticles, and more particularly it makes it possible to form covalent bonds with the hydroxyl groups that may be present on the surface of said nanoparticles.
• the hydrolysable functional group may be linear or branched and selected from a carboxy and alkoxy group, preferably a C 1 -C 6 group . Mention may in particular be made of an ethoxy or methoxy group.
• an organosilane By way of example of an organosilane according to the present invention, mention may be made of vinyltrimethoxysilane or methacryloxypropyltrimethoxysilane.
• the inorganic nanoparticles according to the present invention typically have at least one of their nanoscale dimensions (10 9 meters).
• the term "dimension” is understood to mean the number-average size of all the nanoparticles of a given population, this dimension being conventionally determined by methods that are well known to those skilled in the art. According to these methods for determining the size of the nanoparticles, the size of the nanoparticles according to the present invention refers either to the Stokes diameter (if the method used is that of centrifugation sedimentation and X-ray analysis), or to the diffusion diameter.
• the method used is that of the light scattering by laser granulometry
• either to the diffraction diameter if the method used is that of the diffraction of the light by laser granulometry
• the width (I) of the nanoparticles defined as the smallest dimension of nanoparticles if the method used is that of microscopic analysis, such as SEM (Scanning Electron Microscopy) or TEM (Transmission Electron Microscopy)
• the results obtained must satisfy the nanoscale size condition of the nanoparticles of the invention according to at least one of the four methods mentioned above, preferably at least two of these methods. preferably at least three of these methods, and even more preferably, these four methods.
• the size of the mineral nanoparticles according to the invention is in particular at most 400 nm, preferably at most 300 nm, and more preferably at most 100 nm.
• the size of the mineral nanoparticles is between 0.1 and 80 nm, more preferably between 10 and 70 nm, and for example equal to 40 nm.
• the inorganic nanoparticles according to the present invention may be advantageously chosen from nanoparticles of alkaline earth metal carbonates, alkaline earth metal sulfates, metal oxides, metalloid oxides and / or siloxanes.
• the nanoparticles of alkaline earth metal carbonates may be calcium carbonate nanoparticles, those of alkaline earth metal sulfates of barium sulphate nanoparticles, or of metal oxides of alumina nanoparticles, zinc oxide, or titanium dioxide, those of metalloid oxides of silicon dioxide nanoparticles and those of siloxanes of silsesquioxane nanoparticles, and more particularly nanoparticles of Trisilanolphenyl Polyhedral SilSesquioxane (TP-POSS).
• TP-POSS Trisilanolphenyl Polyhedral SilSesquioxane
• the preferred mineral nanoparticles of this list are nanoparticles of calcium carbonate and alumina.
• the mixture of step ii may be carried out using an extruder.
• this mixing process is not limiting and any other method well known to those skilled in the art can be used.
• Another object of the present invention is a transparent polymeric material obtained by the method of preparation defined above.
• the transparent polymeric material thus has rigidity with optimized transparency, very good resistance to abrasion as well as impact, and yellowing-like coloration that is substantially non-existent.
• the transparent polymer material may comprise at most 15% by weight of mineral nanoparticles.
• This maximum quantity makes it possible, on the one hand, to limit the problems of rheology during the mixing of the composite nanoparticles in the thermoplastic polycarbonate matrix of step ii, and, on the other hand, to limit the cost of the polymer material, while having satisfactory transparency.
• the transparent polymer material may comprise at most 10% by weight of mineral nanoparticles, preferably at most 5% by weight of mineral nanoparticles, and more preferably a quantity of the order of
• Another object of the present invention is the use of said transparent polymer material for the manufacture of optical articles such as in particular automotive glazing, optical sighting instrumentation lens, helmet visor or ophthalmic lens.
• the thickness of the optical articles may be at most 15 mm, preferably between 0.1 and 5 mm, and more preferably between 0.5 and 4 mm.
• the optical article can be made from said transparent polymer material by any forming method well known to those skilled in the art, such as thermoforming, extrusion, calendering, spinning, injection molding, injection-compression or blow molding, the optical article retaining all the mechanical and optical properties of said polymeric material. More particularly, since the mixture of step ii can be carried out using an extruder, the rod at the exit of the extruder is granulated and then shaped by extrusion, injection or injection-compression to obtain the optical article. .
• Another object of the present invention is the use of mineral nanoparticles which have been at least partially coated with at least one monomer and / or at least one polymer capable of promoting physicochemical interactions at the interface between the mineral nanoparticles and a thermoplastic polycarbonate matrix, said mineral nanoparticles being surface-modified by said monomer and / or said polymer either directly or via a coupling agent chosen from a chlorosilane or an organosilane comprising a functional group capable of radical reaction, for the preparation of transparent polymer materials.
• the mineral nanoparticles and the polycarbonate used in the examples which follow were steamed under vacuum at 120 ° C. for at least 12 hours.
• Preparation process P1 modification of the surface of mineral nanoparticles by a monomer or a polymer in the presence of a coupling agent
• step i is carried out in the presence of a coupling agent (agC).
• First Variant V1 of Process P1 Grafting Bisphenol A or Polycarbonate on the Surface of Mineral Nanoparticles in the Presence of Chlorosilane
• 20 g of mineral nanoparticles are mixed in 600 g of chloroform at 60 ° C. under an inert atmosphere.
• An excess of chlorosilane is added to said mixture and allowed to react for 2 hours until excess chlorosilane has evaporated. Silane-grafted inorganic nanoparticles are thus obtained.
• the temperature is then raised to 130 0 C in order to evaporate the solvent.
• the mineral nanoparticles thus modified are washed with chloroform by Soxhlet extraction for 16 hours and then dried at 80 ° C. in an oven for 24 hours.
• Al-agC-PC composite nanoparticles corresponding to nanoparticles of alumina coated with polycarbonate
• Al-agC-BPA composite nanoparticles corresponding to alumina nanoparticles coated with Bisphenol A monomer, or in other words Bisphenol A, and CC-agC-PC composite nanoparticles, corresponding to coated calcium carbonate nanoparticles of polycarbonate.
• Second Variant V2 of Process P1 Grafting a Styrene Monomer on the Surface of Mineral Nanoparticles in the Presence of an Organosilane, and then Polymerization of the Monomer
• a second variant V2 of step i of P1 the grafting of a styrene monomer is carried out on the surface of the mineral nanoparticles, and then the polymerization of said monomer in the presence of an initiator capable of generating free radicals under effect of heat.
• 20 g of mineral nanoparticles are mixed in 300 g of ethanol
• silane-grafted inorganic nanoparticles are washed and recovered by centrifugation in ethanol.
• the polymerization of the monomer takes place in a non-aqueous medium and is carried out under air in an Erlenmeyer flask equipped with a condenser.
• the silane-grafted inorganic nanoparticles are first dispersed in tetrahydrofuran (THF), and then the mixture is heated to a temperature of 70 ° C. and stirred.
• THF tetrahydrofuran
• benzoyl peroxide is added to said mixture as an initiator and the styrene monomer.
• the mixture is allowed to react for 9 hours to polymerize the monomer (polymerization in situ).
• the mineral nanoparticles thus modified are then washed with soxhlet and then dried for 24 hours at 80 ° C.
• step i of the method P1 After the first or the second variant of step i of the method P1, said step i is followed by a mixing step (step ii) of the composite nanoparticles with a polycarbonate matrix at a temperature of the order of 270-290 0 C. the mixture of step ii is carried out using an extruder of the type
• the different transparent polymer materials MP obtained according to the first preparation method P1 comprise 1% by mass of mineral nanoparticles.
• Preparation process P2 modification of the surface of mineral nanoparticles by a monomer or a polymer without the presence of a coupling agent
• step i is carried out without the presence of a coupling agent.
• the inorganic nanoparticles are dispersed in chloroform and a solution containing polymethylmethacrylate dissolved in chloroform is added.
• the mass of polymer used is equal to the mass of mineral nanoparticles to be treated.
• the mixture is stirred at room temperature for 48 hours to adsorb said polymer directly to the surface of the mineral nanoparticles.
• the mineral nanoparticles thus modified are recovered by centrifugation and then washed several times with chloroform before being baked at 80 ° C. for 12 hours.
• the Al-PMMA composite nanoparticles are then obtained according to the first variant V1 of step i of the process P2 corresponding to alumina nanoparticles coated with polymethyl methacrylate.
• the grafting of a methyl methacrylate monomer is carried out on the surface of the mineral nanoparticles, and then the polymerization of said monomer in the presence of an initiator capable of generating free radicals under the effect of ultraviolet radiation.
• the lamp used is a Fisher Bioblock UV lamp with a wavelength of 365 nm and a power of 30 W.
• the crystallizer is placed about 5 cm from the lamp. The mixture is kept under stirring and under an inert atmosphere during the irradiation.
• the mineral nanoparticles thus modified are washed with ethanol by centrifugation several times.
• the modified mineral nanoparticles are dispersed in THF, centrifuged several times and baked at 80 ° C. for 12 hours.
• the composite nanoparticles Al-mPMMA are thus obtained, according to the second variant V2 of step i of the process P2, corresponding to alumina nanoparticles coated with polymethyl methacrylate obtained from the in situ polymerization of the methyl methacrylate monomer.
• step i of the process P2 After the first or the second variant of step i of the process P2, said step i is followed by a mixing step (step ii) of the composite nanoparticles with a polycarbonate matrix under the same conditions as the method P1.
• the different transparent polymer materials MP obtained according to the second preparation method P2 comprise 1% by mass of mineral nanoparticles.
• "reference" polymeric materials MR are also prepared as follows: a first MR1 reference material is prepared solely from polycarbonate as such, a second MR2 reference material is prepared by direct incorporation of nanoparticles alumina-type minerals, in a polycarbonate matrix under the conditions of step ii, and a third MR3 reference material is prepared by direct incorporation of calcium carbonate-type mineral nanoparticles into a polycarbonate matrix under the conditions of the step ii.
• the MR2 and MR3 polymer materials comprise 1% by weight of mineral nanoparticles.
• the origin of the various constituents mentioned in the preparation processes P1 and P2 or in the processes for obtaining the polymeric materials MR1 to MR3 is as follows: the polycarbonate of step i is a thermoplastic polycarbonate marketed by Acros-Organics under the reference Polycarbonate resin (CAS No. 24936-68-3), the polycarbonate matrix of step ii and the polycarbonate of the preparation reference polymer materials are a thermoplastic polycarbonate marketed by the company Bayer under the reference Makrolon A12647, Bisphenol A is marketed by the company Acros-Organics, under the reference 4,4'-lsopropylidenediphenol
• the styrene monomer is marketed by the company Acros-Organics, under the reference Styrene (CAS No. 100-42-5), the methyl methacrylate monomer is marketed by the company Aldrich, under the reference Methyl methacrylate,
• polymethyl methacrylate is marketed by Arkema, under the reference Altuglas, the alumina nanoparticles have a size of 13 nm, and are marketed by the company Degussa, under the reference Aeroxide AIUC, calcium carbonate nanoparticles are precipitated calcium carbonate particles having a size of 70 nm, marketed by Solvay under the Socal ® reference 31, the chlorosilane is sold by the company Acros- Organics, under the reference Silicon (IV) chloride (CAS No.
• vinyltrimethoxysilane is marketed by Dow Corning, under the reference Z-6300
• the benzophenone is marketed by the company Acros-Organics, under the reference Benzophenone (CAS No. 119-61 -9)
• the benzoyl peroxide is marketed by the company Acros-Organics, under the reference Benzoyl peroxide
• the size of the Socal ® 31 nanoparticles as that of the Aeroxide AIuC nanoparticles are determined by MET with a magnification of 40000 over twenty photos by first dispersing these nanoparticles in ethanol, then placing them on a copper grid, and finally covering them with a transparent amorphous polymer film.
• a width I, or number average size equal to 70 nm for Socal ® nanoparticles 31, and equal to 13 nm for Aeroxide AIUC nanoparticles.
• the mechanical and optical properties studied for the materials obtained are respectively the flexural modulus and the light transmission.
• the flexural modulus measurements are made on specimens in the form of dumbbell-type test pieces with a thickness of 4 mm, corresponding to the ISO 527-2 type 1 A.
• dumbbells are obtained from the granules of the polymeric materials MR and MP shaped using an injection molding machine of SANDRETTO SERIE OTTO A.T.
• the flexural modulus characterizes the stiffness of the polymeric material. The higher the flexural modulus, the better the rigidity of the material. It is determined according to ISO 178, using an ADAMEL LHOMARGY DY 26 universal electromechanical press, driven by TestWorks software.
• the light transmission measurements are carried out on specimens in the form of a dumbbell-type test piece with a thickness of 4 mm, in accordance with the ISO 527-2 type 1A standard, under the same conditions as for the measurements of the mechanical properties.
• the light transmission characterizes the transparency of the polymer material. The higher the light transmission, the better the transparency of said material.
• the transmission spectrum of the sample is determined by the products of the spectral distribution of the illuminant used, and according to the type of observation chosen.
• the illuminant used is the D65 reproducing daylight and the observation chosen is at 2 °.
• the transparent polymer materials MP1, MP2 and MP4 on the one hand, and MP5 on the other hand clearly have a flexural modulus together with an optimized light transmission with respect to the respective polymeric materials MR2 and MR3 .
• the flexural modulus of the transparent polymeric materials MP3 and MP7 has significantly increased for a satisfactory light transmission, compared to the polymeric materials MR2 and MR3.
• the transparent polymeric material MP6 has a satisfactory light transmission and a flexural modulus.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
• Nanotechnology (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Physics & Mathematics (AREA)
• Manufacturing & Machinery (AREA)
• Composite Materials (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• General Physics & Mathematics (AREA)
• Crystallography & Structural Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Graft Or Block Polymers (AREA)
• Polymerisation Methods In General (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Oxygen, Ozone, And Oxides In General (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=39276272

Family Applications (1)

Country Status (8)

Families Citing this family (22)

Family Cites Families (21)

• 2007
  • 2007-12-13 FR FR0759810A patent/FR2925059B1/fr not_active Expired - Fee Related
• 2008
  • 2008-12-09 WO PCT/EP2008/067076 patent/WO2009074554A1/fr active Application Filing
  • 2008-12-09 JP JP2010546228A patent/JP5734667B2/ja not_active Expired - Fee Related
  • 2008-12-09 EP EP08859213A patent/EP2220144A1/fr not_active Withdrawn
  • 2008-12-09 CN CN2008801203059A patent/CN101896538B/zh not_active Expired - Fee Related
  • 2008-12-09 KR KR1020107015550A patent/KR101623865B1/ko active IP Right Grant
  • 2008-12-09 BR BRPI0820889A patent/BRPI0820889B1/pt not_active IP Right Cessation
  • 2008-12-09 US US12/744,529 patent/US9163125B2/en not_active Expired - Fee Related

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events