Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
  • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
  • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
  • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
  • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
  • D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/5033—Amines aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

• the present invention relates to the field of composite materials based on reinforcing fibers and thermoset resins in particular to composite materials based on thermoset resins comprising a rheology regulating agent, having a thermoplastic behavior and which can be transformed into threads which can be woven or knitted.
• a composite material according to the invention consists of an organic matrix and an inorganic or organic reinforcement which can be in the form of fibers or textiles.
• the organic matrix can be a thermoset material as described below.
• a thermoset material is defined as being formed of polymer chains of variable length linked together by covalent bonds so as to form a three-dimensional network.
• Thermosetting materials can be obtained, for example, by reacting a thermosetting resin such as an epoxy with an amine type hardener.
• Thermoset materials have many properties allowing their use as structural adhesives or as a matrix for composite materials or in applications for the protection of electronic components.
• the reinforcing fiber which may include several thousand filaments, improves the mechanical characteristics of the composite structure. It can be composed of glass, carbon, aramid or any other organic or inorganic material providing the desired characteristics.
• Epoxy materials have a high crosslinking density, which gives them a high glass transition temperature (Tg), which gives the material excellent thermomechanical properties.
• Tg glass transition temperature
• Tg glass transition temperature
• stage B The making of composites by techniques usual presents difficulties such as the management of stage B.
• the process usually used by those skilled in the art goes through a step of wetting the fibers with epoxy resin with a loss of material due to the observed drop phenomenon, phenomenon directly related to the low cohesion of the liquid resin.
• This wetting step is followed by a pre-baking step to bring the thermoset resin to an intermediate conversion called stage B allowing easier handling.
• stage B an intermediate conversion
• These different processes are for example described in the work of Maurice Reyne “Composites Technology” HERMES edition, 1998.
• the Applicant has just found that specific formulations based on thermosetting materials and rheology regulating agents can be transformed into filaments or wicks and can be woven or knitted together with organic or inorganic fibers.
• the formulations of the invention comprise a thermosetting resin and a block copolymer having at least one block miscible with said resin, for example consisting mainly of methyl methacrylate units, used as a rheology control agent and at least one non-block miscible.
• These materials can be made by dissolving the copolymer in the thermosetting resin followed by the addition of the hardener. This dissolution can for example be carried out by the extrusion technique.
• the extrusion technique also allows the production of filaments which can be transformed into wicks.
• the first object of the invention is an organic fiber composed of a thermosetting resin and of a rheology control agent which can be obtained by extrusion, for example from a formulation based on thermosetting materials and rheology regulating agents.
• Another object of the invention is a fabric or knitted fabric obtained according to the following method: a. Weaving or knitting the filaments or fibers of the invention with glass or carbon fibers or any other type of organic and inorganic material. b.
• thermoset composites Realization of the desired structures with the semi-product obtained in a according to usual techniques for implementing semi-products for thermoset composites, such as draping, molding, or the production of sandwich systems. vs. Reaction of the formulation to obtain a composite material, according to the usual techniques for using thermoset composite materials, such as hot forming.
• the formulation of the invention comprises: - from 10 to 99% by weight of the total weight of the formulation of at least one thermosetting resin (I) - from 1 to 80% by weight of the total weight of the formulation of an agent rheology control system (II) comprising for example at least one block copolymer chosen from SBM, BM and MBM block copolymers in which:> each block is linked to the other by means of a covalent bond or of a or several intermediate molecules linked to one of the blocks by a covalent bond and to the other block by another covalent bond,> M is a polymer miscible with the thermosetting resin, for example a homopolymer of methyl methacrylate or a copolymer ( obtained by the polymerization of a mixture of monomers comprising at least 50% by weight of methyl methacrylate) comprising at least 50% by weight of methyl methacrylate,> B is a polymer incompatible with thermosetting resin and with blo c M and its glass transition temperature (Tg) is lower than the
• thermoset material it is defined as being formed of polymer chains of variable length linked together by covalent bonds so as to form a three-dimensional network.
• cyanoacrylates bismaleimides and epoxy resins crosslinked with a hardener.
• thermosetting formulations of bismaleimide type are for example: methylenedianiline + benzophenone dianhydride + nadic imide methylenedianiline + benzophenone dianhydride + phenylacetylene methylenedianiline + maleic anhydride + maleimide.
• the thermoset material advantageously comes from the reaction of a thermosetting epoxy resin and a hardener. It is also defined as any product of the reaction of an oligomer carrying oxirane functions and a hardener. Due to the reactions involved in the reaction of these epoxy resins, a crosslinked material corresponding to a network is obtained. more or less dense three-dimensional depending on the basic characteristics of the resins and hardeners used.
• epoxy resin hereinafter designated by E, means any organic compound having at least two functions of the oxirane type, polymerizable by ring opening.
• epoxy resins designates all the usual epoxy resins which are liquid at room temperature (23 ° C.) or at a higher temperature. These epoxy resins can be monomeric or polymeric on the one hand, aliphatic, cycloaliphatic, heterocyclic or aromatic on the other hand.
• epoxy resins examples include the diglycidyl ether of resorcinol, the diglycidyl ether of bisphenol A, the triglycidyl p-amino phenol, the diglycidyl ether of bromo-bisphenol F, the triglycidyl ether of m-amino phenol, tetraglycidyl methylene dianiline, triglycidyl ether of (trihydroxyphenyl) methane, polyglycidyl ethers of phenol formaldehyde novolac, polyglycidyl ethers of orthocresol novolac and tetraglycidyl ethers of tetraphenyl ethane.
• Epoxy resins having at least one aromatic ring are also preferred, such as the bisphenol A diglycidyl ethers.
• hardeners are used epoxy resins which react at room temperature or at temperatures above temperature. room.
• Acid anhydrides including succinic anhydride, ⁇ Aromatic or aliphatic polyamines, including diamino diphenyl sulphone (DDS) or methylene dianiline or 4 , 4'-Methylenebis- (3-chloro-2,6-diethylaniline) (MCDEA), • Dicyandiamide and its derivatives.
• Imidazoles • Polycarboxylic acids • Polyphenols.
• rheology control agent is understood to mean a compound which, mixed with the thermosetting material, allows the latter to be able to be transformed by all the techniques for using thermoplastics while retaining the ability to react to form a thermosetting material.
• a block copolymer chosen from among the SBM, BM or MBM block copolymers will be chosen in which:> each block is linked to the other by means of a covalent bond or of one or more intermediate molecules linked to the one of the blocks by a covalent bond and to the other block by another covalent bond,> M is a polymer miscible with the thermosetting resin.
• M consists of methyl methacrylate monomers or contains at least 20% by mass of methyl methacrylate, preferably at least 50% by mass of methyl methacrylate.
• the other monomers constituting the block M can be acrylic monomers or not, be reactive or not.
• reactive monomer is meant: a chemical group capable of reacting with the oxirane functions of the epoxy molecules or with the chemical groups of the hardener.
• reactive functions mention may be made of: oxirane functions, amine functions, carboxy functions.
• the reactive monomer can be (meth) acrylic acid or any other hydrolyzable monomer leading to these acids.
• the other monomers which may constitute the block M non-limiting examples that may be mentioned are glycidyl methacrylate, tert-butyl methacrylate.
• the Tg of B is less than 0 ° C and preferably less than -40 ° C.
• the monomer used to synthesize the elastomeric block B can be a diene chosen from butadiene, isoprene, 2,3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, 2-phenyl-1, 3 butadiene.
• B is advantageously chosen from poly (dienes), in particular poly (butadiene), poly (isoprene) and their random copolymers, or also from poly (dienes) partially or completely hydrogenated.
• polybutadienes those with the lowest Tg are advantageously used, for example polybutadiene-1, 4 of Tg (around -90 ° C) lower than that of polybutadiene-1, 2 (around 0 ° C).
• B blocks can also be hydrogenated. This hydrogenation is carried out according to the usual techniques.
• the monomer used to synthesize the elastomeric block B can also be an alkyl (meth) acrylate.
• Tg are indicated in parentheses after the monomer used: ethyl pacrylate (-24 ° C), butyl acrylate (-45 ° C), 2-ethylhexyl acrylate (-60 ° C), hydroxyethyl acrylate (-15 ° C) and 2-ethylhexyl methacrylate (-10 ° C).
• butyl acrylate is used.
• the acrylates of B are different from those of block M to respect the condition of incompatible B and M.
• the blocks B consist mainly of polybutadiene-1, 4.
• thermosetting resin is incompatible with the thermosetting resin and with the block M and its glass transition temperature Tg is lower than the temperature of use of the thermosetting material,> S is incompatible with the thermosetting resin, and the block B and its Tg or its temperature
• the melting point Tf is greater than the Tg of B.
• the Tg or the Tf of S is advantageously greater than 23 ° C. and preferably greater than 50 ° C.
• blocks S that may be mentioned are those which derive from vinyl aromatic compounds such as styrene, ⁇ -methyl styrene, vinyltoluene, and those which derive from alkyl esters of acrylic and / or methacrylic acids having from 1 to 18 atoms. carbon in the alkyl chain.
• the SBM, BM or MBM copolymer has a weight-average molar mass which can be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 and 200,000 g / mol.
• a weight-average molar mass which can be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 and 200,000 g / mol.
• its composition will be: between 10 and 80% and preferably between 15 and 70%.
• For B between 2 and 80% and preferably between 5 and 70%.
• S between 10 and 88% and preferably between 15 and 85%.
• the block copolymers used in the composition of the present invention can be produced, for example, by anionic polymerization according to the methods described in patent applications EP 524,054 and EP 749,987 or also by controlled radical polymerization.
• the proportion of rheological agent is from 10 to 60% for respectively 90 to 40% of thermosetting resin.
• the rheology control agent comprises at least one SBM block copolymer and at least one SB block copolymer. It advantageously comprises between 5 and 80% of SB diblock for respectively from 95 to 20% of SBM triblock.
• the SB diblock the S and B blocks are incompatible and they consist of the same monomers and possibly comonomers as the S blocks and the B blocks of the SBM triblock.
• the blocks S and B can be identical or different from the other blocks S and B present in the other block copolymers of the impact modifier in the thermoset material.
• the dibloc SB has a mass-average molar mass which can be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 and 200,000 g / mol.
• the SB diblock advantageously consists of a mass fraction of B of between 5 and 95% and preferably between 5 and 60%.
• the advantage of these compositions is that it is not necessary to purify the SBM at the end of its synthesis. Indeed, SBMs are generally prepared from SBs and the reaction often leads to a mixture of SBs and SBMs which are then separated in order to have SBMs.
• part of the SBM can be replaced by an SB diblock. This part can be up to 70% by weight of the SBM.
• the SBM triblock can be replaced with an MSBSM or MBSBM pentabloc.
• They can be prepared by anionic polymerization like the di or triblocks mentioned above but using a difunctional initiator.
• the number-average molar mass of these pentablocs is in the same intervals as that of the SBM triblocks.
• the proportion of the two blocks M together, of the two blocks B or S together is in the same intervals as the proportions of S, B and M in the SBM triblock.
• the formulations of the invention can be prepared by mixing the thermosetting resin not yet crosslinked using a conventional mixing device. We can use all thermoplastic techniques to achieve a homogeneous mixture between the thermosetting resin and the control agent such as extrusion.
• the product obtained will be in the form of a filament or wick.
• the material thus obtained unreacted or partially reacted may thus be in the form of a manipulable rubber material.
• This implementation will be done at a temperature where the reaction kinetics of the thermosetting material is slow.
• step [c] during implementation in the form of a finished object and by simply increasing the temperature, the thermosetting resin will be transformed into thermoset material.
• the rubber material during the reaction may, depending on the nature of the resin (II) and of the agent (I) used, return to the liquid state or remain in the rubber state. It is obvious that this invention can be applied to a reactive liquid resin which can form, after reaction, a linear or branched polymer exhibiting a thermoplastic behavior.
• the finished objects of the invention can be used in various applications, such as in the fields of sport, industry, automobile, electronics, aeronautics. Cooking conditions: These are the usual conditions. It would not depart from the scope of the invention to add in the formulation the usual additives, such as thermoplastics such as polyethersulfones, polysulfones, polyetherimides, polyphenylene ethers, liquid elastomers or impact-modifiers of the core-shell type .
• thermoplastics such as polyethersulfones, polysulfones, polyetherimides, polyphenylene ethers, liquid elastomers or impact-modifiers of the core-shell type .
• Hardener it is an amine hardener which is an aromatic diamine, 4,4'-Methylenebis- (3-chloro-2,6-diethylaniline) sold by the company Lonza under the commercial reference LONZACURE M-DEA. This product is characterized by a melting point between 87 ° C and 90 ° C and a molar mass of 310 g / mol.
• SBM1 it is a triblock copolymer SBM in which S is polystyrene, B is polybutadiene and M is polymethyl methacrylate.
• SBM1 contains 22% by mass fraction of polystyrene, 9% by mass fraction of polybutadiene and 69% by mass of polymethyl methacrylate, obtained by anionic polymerization successively of a polystyrene block of average molar mass by mass 7,000 g / mol, d '' a polybutadiene block with a mass of 11,000 g / mol and a polymethyl methacrylate block with a average molar mass of 84,000 g / mol
• This product was prepared according to the procedure described in EP 524-054 and in EP 749-987.
• SBM2 it is a triblock SBM copolymer in which S is polystyrene, B is polybutadiene and M is PMMA containing 12% by mass fraction of polystyrene, 18% by mass fraction of polybutadiene and 70% by mass of polymethacrylate of methyl, obtained by anionic polymerization successively of a polystyrene block of average molar mass by mass 14,000 g / mol, of a polybutadiene block of mass 22,000 g / mol and of a polymethyl methacrylate block of average molar mass in mass 85,000 g / mol.
• This product was prepared according to the procedure described in EP 524-054 and in EP 749-987. This product has three glass transitions, one of -90 ° C, the other of 95 ° C and the third of 130 ° C.
• Cooking conditions The mixes are cooked for 2 hours at 220 ° C. Measurement of the main mechanical relaxation temperature. Ta by thermomechanical analysis: The measurement of Ta was carried out by dynamic mechanical analysis on the post-cooked samples using a Rheometrics device (Rheometrics Solid Analyzer RSAII). The samples of parallelepiped shape (1 * 2.5 * 34mm 3 ) are subjected to a temperature sweep between 50 and 250 ° C at a traction frequency of 1 Hz. The glass transition temperature is taken at the maximum of tan ⁇ .
• Example 1 (according to the invention) An epoxy precursor DGEBA from the company DOW with a mass of 383 g / mol is mixed with stoichiometry with an amine hardener MDEA. This mixing is carried out in a Werner 40 type twin screw extruder with the addition of 40% of SBM1. The rod obtained having a diameter of 1 mm is wound at the extruder outlet. This rod is co-woven with a glass fiber from the company Owens Corning of tex 1200 having a size of type 121 A - RX. The glass to formulation ratio is 1.5. The co-woven fabric obtained is easy to handle and has no drop phenomenon. The co-woven fabric obtained is placed in a press for 2 hours at 220 ° C. After cooling, the Tg obtained is 165 ° C and the T obtained is 172 ° C. The composite material obtained shows no swelling in toluene.
• Example 2 (according to the invention) An epoxy precursor DGEBA from the company DOW with a mass of 383 g / mol is mixed with stoichiometry with an amine hardener MDEA. This mixing is carried out in a Werner 40 type twin screw extruder with the addition of 40% SBM2. The rod obtained having a diameter of 1 mm is wound at the extruder outlet. This rod is co-woven with a glass fiber from the company Owens Corning of tex 1200 having a size of type 121 A - RX. The Glass to formulation ratio is 1.5. The co-woven fabric obtained is easy to handle and has no drop phenomenon. The co-woven fabric obtained is placed in a press for 2 hours at 220 ° C. After cooling the Tg obtained is 164.8 ° C and the Ta obtained is 171.5 ° C. The composite material obtained shows no swelling in toluene.
• Example 3 (comparative) An epoxy precursor DGEBA from the company DOW with a mass of 383 g / mol is mixed with stoichiometry with an amine hardener MDEA. This mixture is produced in a Werner 40 type twin screw extruder with the addition of 40% SBS finaclear 520 from the company ATOFINA. The material leaving the extruder cannot be granulated because it has no resistance in the molten state.
• Example 4 (comparative) An epoxy precursor DGEBA from the company DOW with a mass of 383 g / mol is mixed with stoichiometry with an amine hardener MDEA. This mixture is produced in a Werner 40 type twin screw extruder with the addition of 40% D320 from the company ATOFINA. The material leaving the extruder cannot be granulated because it has no resistance in the molten state.
• Example 5 (according to the invention) An epoxy precursor DGEBA from the company DOW with a mass of 383 g / mol is mixed with stoichiometry with an amine hardener MDEA. This mixing is carried out in a Werner 40 type twin screw extruder with the addition of 40% SBM2. The rod obtained having a diameter of 1 mm is wound at the extruder outlet. This rod is woven to form a fabric of mixture SBM - DGEBA - MDEA (mixture A). This fabric is then placed on a glass fabric to form a sandwich A / glass fabric / A. This sandwich is then placed in a press for 2 hours at 220 ° C.
• SBM - DGEBA - MDEA mixture A
• Example 6 A DGEBA epoxy precursor from the company DOW with a mass of 383 g / mol is mixed with stoichiometry with an amine hardener MDEA. This mixture is produced in a Werner 40 type twin screw extruder with the addition of 20% SBM2. The rod obtained having a diameter of 1 mm is wound at the extruder outlet. This rod is co-woven with a fiberglass from the company Owens Corning of tex 1 00 having a size of type 121 A - RX. The Glass to formulation ratio is 1.5. The co-woven fabric obtained is easy to handle and has no drop phenomenon. The co-woven fabric obtained is placed in a press for 2 hours at 220 ° C. After cooling, the Tg obtained is 164.8 ° C and the T obtained is 171.7 ° C. The composite material obtained shows no swelling in toluene.
• Example 7 A DGEBA epoxy precursor from the company DOW with a mass of 383 g / mol is mixed with stoichiometry with an amine hardener MDEA. This mixing is carried out in a Werner 40 type twin screw extruder with the addition of 80% SBM2. The rod obtained having a diameter of 1 mm is wound at the extruder outlet. This rod is co-woven with a glass fiber from the company Owens Corning of tex 1200 having a size of type 121 A - RX. The Glass to formulation ratio is 1.5. The co-woven fabric obtained is easy to handle and has no drop phenomenon. The co-woven fabric obtained is placed in a press for 2 hours at 220 ° C. After cooling, the Tg obtained is 164.8 ° C and the T obtained is 160 ° C. The composite material obtained shows no swelling in toluene.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Textile Engineering (AREA)
• Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Reinforced Plastic Materials (AREA)
• Epoxy Resins (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Artificial Filaments (AREA)
• Woven Fabrics (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Chemical Treatment Of Fibers During Manufacturing Processes (AREA)

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• 2003
  • 2003-11-25 FR FR0313805A patent/FR2862655B1/fr not_active Expired - Fee Related
• 2004
  • 2004-11-25 DE DE602004007820T patent/DE602004007820T2/de not_active Expired - Lifetime
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