Classifications

• • 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
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/28—Shaping operations therefor
  • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
  • B29C70/32—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core on a rotating mould, former or core
• • 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
  • B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
  • B29C53/80—Component parts, details or accessories; Auxiliary operations
  • B29C53/8008—Component parts, details or accessories; Auxiliary operations specially adapted for winding and joining
  • B29C53/8066—Impregnating
• • 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
  • B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
  • B29C53/56—Winding and joining, e.g. winding spirally
  • B29C53/58—Winding and joining, e.g. winding spirally helically
  • B29C53/60—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels
  • B29C53/62—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels rotatable about the winding axis
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2101/00—Use of unspecified macromolecular compounds as moulding material
  • B29K2101/12—Thermoplastic materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2309/00—Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
  • B29K2309/08—Glass

Definitions

• the present invention relates to a body of revolution formed from at least one organic thermoplastic material reinforced by continuous glass strands wound around the axis of the body.
• the ribbon is generally obtained from continuous mixed yarns consisting of glass filaments and filaments of intimately mixed thermoplastic organic material, the most common version of these yarns, sold under the trade name TWINTEX® by the company SAINT-GOBAIN VETROTEX FRANCE, with a weight ratio, in percentages, of 60 or 75 for glass and 40 or 25 for organic thermoplastic material. If the previous process and the products obtained are efficient, they have certain limits or constraints in use: constraint of additional heating and pressure operations on the tube for uniform deposition of the ribbon, necessary addition of an internal coating ("liner ») For food applications or an external coating for better resistance to abrasion, the range of products obtained is small and not very flexible.
• the purpose of the present invention is to overcome the aforementioned drawbacks, and in particular to propose a more varied range of products which can for example have differentiated reinforcement rates on the same product, or whose rate is adapted "to order" without disturbances important, in particular with regard to the process or the devices employed.
• At least a first heated composite strip is introduced into at least one die
• At least one molten material is introduced simultaneously into said die in contact with said first composite strip, so as to obtain at least one second composite strip,
• the present invention also relates to a device for manufacturing a body of revolution, comprising:
• the invention also relates to a composite body of revolution, in particular obtained by the above method.
• This body has at least one zone formed only by winding a composite strip, this zone having, as the case may be, a modular reinforcement rate (s) (or differentiated or adjustable or variable reinforcement rate (s)), in particular a rate of varying reinforcement (s) along the axis of revolution and or along the thickness of the body of revolution, and / or this zone having a reduced rate of reinforcement, in particular compared to the rate of reinforcement (s) of the starting composite product (s) or of the first composite strip used (for example a reinforcement ratio of less than 75% by weight for a first strip having a reinforcement ratio of 75% or a reinforcement ratio of less than 60% by weight for a first strip having a reinforcement ratio of 60%) and / or a reduced reinforcement rate compared to that of the reinforced zones obtained by winding in the current bodies of revolution (for example a reinforcement rate representing less than 60% by
• the sheathing of the composite strip with a second material has multiple advantages: by reducing the ratio of the reinforcement material rate to the organic material rate of the strip wound on the rotating support, it allows more homogeneous deposition and better holding of said strip without requiring heating or the application of additional pressure on the deposited strip; by appropriately choosing the sheathing material, it avoids the subsequent addition of an internal coating (for example for food applications) or an external coating (for example an anti-corrosion coating); more generally, by the choice of the sheathing material, it is possible to impart additional properties to the body of revolution (anti-UV properties, sealing, anti-corrosion, etc.); it allows the reinforcement rate to be continuously adjusted by varying the amount of sheathing material delivered online (during the manufacture of the body) and thus makes it possible to obtain bodies having differentiated reinforcement rates from a starting product which may advantageously not vary.
• the process and the products according to the invention therefore have the advantage of being modular and this without changing the starting materials.
• the method according to the invention is easy and quick to implement, and is economical.
• the body according to the invention also has, at least in its zone obtained by winding, perfect cohesion between the different elements making it up (or even if necessary perfect continuity of the organic parts), the union between the different elements being sufficiently intimate to guarantee a particularly satisfactory lifetime and resistance.
• the first composite strip comprises at least one reinforcing material (glass, carbon, aramid, etc.) and at least one thermoplastic organic material.
• the reinforcing material preferably glass
• the son or filaments of reinforcing material are advantageously linked together by the thermoplastic organic material, itself preferably in the form of son and / or filaments, and / or by other reinforcing son and / or filaments (case of bands of woven or crossed reinforcements).
• the strip is obtained from composite threads formed of reinforcing filaments (preferably glass filaments) and filaments of at least one thermoplastic organic material, these different filaments being advantageously intimately mixed, the intimate structure of these wires facilitating the impregnation of glass fibers by the thermoplastic material, in particular making it possible to form a consolidated band (that is to say having a cohesion and an integrity which make it possible to handle it without damage) very homogeneous.
• reinforcing filaments preferably glass filaments
• filaments of at least one thermoplastic organic material these different filaments being advantageously intimately mixed, the intimate structure of these wires facilitating the impregnation of glass fibers by the thermoplastic material, in particular making it possible to form a consolidated band (that is to say having a cohesion and an integrity which make it possible to handle it without damage) very homogeneous.
• Advantageous composite yarns can be obtained according to a direct process such as that described in patents EP 0 367 661, WO 98/01751 or EP 0 599 695, the yarns according to this process having the advantage of having an excellent cost index -mixing inducing an excellent distribution of the glass strands in the thermoplastic material as explained in patent application WO00 / 24566.
• the first composite strip generally has a width of 1 to 10 cm approximately and can be essentially flat or have a more complex cross-sectional shape where each portion is comparable to a strip.
• the strip may be flexible, in particular capable of being wound when the strip is substantially flat, or more or less rigid.
• the use of a composite ribbon rather than a composite yarn has many advantages, in particular in terms of the distribution of the glass filaments in the thermoplastic material within the final product and convenience of implementation.
• the first strip when it enters the die has not only longitudinal continuity but also transverse continuity, in particular has a void volume rate of less than 5% (or even less than 3%, or even less than 0.5% ).
• the void volume rate can be measured in a known manner using a micrographic method of the image analysis type, or calculated using a formula as explained in patent application WO / 00/24566.
• the first composite strip comprises at least one organic thermoplastic material, called the first material, this material being for example chosen from polyolefins, in particular polyethylene (PE), polypropylene (PP), polyesters, in particular polyethylene terephthalate, polybutylene terephthalate, elastomers, especially an ethylene propylene polymer (EPDM), or polyvinyl chloride (PVC), or polyamides, etc. some of these materials (in particular polyethylene) have the advantage of being chemically inert and compatible from a food point of view, of being able to withstand very low temperatures and of having a low cost price.
• PE polyethylene
• PP polypropylene
• polyesters in particular polyethylene terephthalate, polybutylene terephthalate, elastomers, especially an ethylene propylene polymer (EPDM), or polyvinyl chloride (PVC), or polyamides, etc.
• EPDM ethylene propylene polymer
• PVC polyvinyl chloride
• the first strip is generally formed from continuous composite yarns extracted from winding (s) and assembled in a parallel (or substantially parallel) manner in at least one ply, and / or possibly from ply (s) of woven composite yarns or crossed.
• the sheet of wires (or if necessary at least one of the sheets) is introduced into a zone where it is heated to a temperature reaching at least that of melting.
• the sheet of heated son passes through an impregnation device to distribute evenly the first molten thermoplastic material and impregnate the reinforcing fibers therewith.
• a strip having a transverse continuity is thus obtained, this strip possibly being able to undergo an additional or joint step of impregnation, of conformation in order to obtain the desired profile.
• a step of regulating the tension of the wires can be provided (for example during their gathering in sheet (s) or bundle (s) or before their gathering) and / or the wires can be freed of all static electricity, by example before the passage of the tablecloth in the heating zone.
• the method according to the invention may include a step of forming the first strip as mentioned above or use one or more strips already formed, the strip or strips being in this latter case heated (and possibly shaped to a particular profile) in a step prior to heating to a temperature reaching at least that of melting the first thermoplastic material, before introduction into the die.
• the method according to the invention uses only as starting material composite yarns and thus comprises a prior step of forming the strip as seen above.
• the first composite strip or the strip obtained at the outlet of the impregnation device as explained above is advantageously maintained at temperature at a temperature close to the melting temperature of the first thermoplastic material (or at a malleability temperature of the first thermoplastic material) up to the die or to the winding means (such as the laying head) of the second strip mentioned according to the invention.
• the first strip is introduced into at least one die also supplied with a molten material called the second material (or dilution material or sheathing material).
• This second material can be identical or different from the first organic material forming the strip. It can also be a composite material. It can have specific properties or include additives or fillers giving it specific properties (for example sawdust to give a wood appearance, an additive improving resistance to hydrocarbons, it can also be loaded with talc, glass fibers, short or long, etc.).
• the second material comprises at least one organic or plastic material, advantageously thermoplastic, for example a polyolefin (in particular polyethylene or polypropylene) or polyvinyl chloride, or may optionally comprise a thermosetting material such as a polyurethane, or an elastomer, for example a SEBS modified polypropylene (styrene ethylene butadiene styrene).
• thermoplastic for example a polyolefin (in particular polyethylene or polypropylene) or polyvinyl chloride
• a thermosetting material such as a polyurethane
• elastomer for example a SEBS modified polypropylene (styrene ethylene butadiene styrene).
• the second material is chosen to be identical or similar or chemically compatible with the first material (so that there is good adhesion, or even continuity, between the two materials) forming the first strip, this second material possibly being able to be loaded with additives such as those mentioned above (sawdust, glass fibers, talc, etc.).
• the second strip formed thus preferably comprises a rate of reinforcing material of between 0 and 74% by weight of the strip, and preferably between 1 and 60% by weight, or even between 5 and 55% by weight (the threads used generally having a reinforcement rate of 60 or 75% by weight), over at least a certain part of its length, this rate can also vary depending on the length of the strip.
• the application of the second material also allows better consolidation of the first strip, the second strip obtained being somehow formed of at least one second material reinforced by at least one first composite strip.
• the second material adheres to the first strip in a particularly satisfactory manner (or even, when it is in particular the same material, fuses with the first material of the first tape), and this for different materials.
• the second strip thus advantageously comprises at least a first strip of continuous reinforcing fibers arranged in a substantially parallel and contiguous manner joined together by at least one first thermoplastic material, and at least one second material in intimate contact with said first strip. As indicated above, when the first material and the second are identical, the two materials are perfectly fused within the body of revolution obtained.
• the second material introduced into the die can come, for example, from an extrusion device. It is possible to perfectly control the quantity of material that one wants to add as well as the shape that one wants to give to the second strip, this shape being able to be imparted in particular by the die (and possibly by a device for additional conformation).
• the first strip can be deformed when it is introduced into the die then playing the role of a shaping device and coated with the second material, or simply be coated with the second material completing the shape imparted by the die (and possibly pass through an additional shaping device).
• the die allows both the positioning of the first strip and the calibration (or conformation) of the section of the second strip.
• the first strip (or the first strips if there are several introduced into one or more dies) can also be coated with several identical or different materials feeding the die (or if necessary several dies in series or in parallel), this fashion which further widens the range of products obtained.
• the sheathing material can vary from one strip to another, as well as within each strip, the different strips then being wound on, the support in rotation.
• by varying the supply of the various materials it is therefore possible not only to obtain bodies having different reinforcement rates, but also variable mixtures of materials along the axis of revolution and / or the thickness.
• the second strip (or the second strips when there are several) formed in the process according to the invention can advantageously be wound directly on a mandrel (the desired properties being possibly present in situ in the strip wound according to the invention), but it is not excluded to wind it on a tube or liner intended to form an integral part of the body of revolution or on a support such as a foam bar, and / or to add an external coating to the winding obtained, this coating being able to be applied for example in the form of a film or of a strip which is wound, etc.
• the second strip according to the invention can also be wound on a support already coated with a first winding (in the form for example of an organic strip). It is also not necessary (although not excluded) to heat and / or apply pressure to the second strip during its winding.
• the second strip can be wound by forming contiguous turns, spaced or overlapping each other at least in part.
• the winding of the strip (s) can be made more or less transversely, and generally done helically, the angle of the strip relative to the axis of the body being able to change according to the position along the axis and being imparted by the laying head depending in particular on the desired mechanical properties as mentioned later .
• Each support turn can see the deposit of one or more turns, over all or part of the length of the support, the next turn can see changing the orientation of the following turn (s). We can thus obtain structures with very dense windings, wraps, or loose windings like nets.
• the present invention also relates to a device for implementing the method described above.
• This device notably comprises one or more means for forming a composite strip or one or more means for delivering (and / or entraining) and for heating (and possibly impregnating and / or shaping) a sheet or strip already formed.
• these means may in particular include:
• At least one device for impregnating the heated bundle so as to obtain a strip for example a densified and laminated strip of flattened shape
• one or more means for maintaining the strip at temperature at least up to the die are provided.
• the device can also include a creel from which are spools of threads and at least one roller ensuring the guidance of the threads.
• the means for assembling the wires in the form of at least one bundle of parallel wires can for example consist of a plate with eyelets and / or a comb whose teeth allow parallel alignment of the wires according to regular spaces.
• one or more means for regulating the tension of the threads can be provided, for example upstream of the gathering means.
• an anti-static device can be provided, for example upstream of the heating means.
• the device comprises one or more heating means constituted by one or more ovens, for example of the infrared type, preferably operating with lamps regulated in power as a function of the temperature of the strip, this kind of oven having the advantage of being both efficient on the plan energetic and easy to regulate.
• the impregnation device may for example comprise three members arranged in a triangle and between which the beam travels, the height of separation of the members being adapted to establish an appropriate pressure on the surface of the bundle.
• the members can be cylinders (or bars) heating, and rotating or fixed.
• each cylinder may include a blade for scraping the molten thermoplastic material deposited on the cylinder after passage of the bundle.
• the impregnation device can also act as a shaping device or be followed by one or more additional shaping devices, so as to transform the bundle of wires or the strip formed into at least one strip of selected section.
• This shaping device can for example comprise a heating die, and / or rollers between which the bundle of wires or the strip circulates respectively.
• a device for example of conformation, can also ensure the centering of the ply, before in particular forming the strip, and comprise for example a lower roller and an upper roller of suitable shape (for example of hyperboloid shape or provided with flanges) and rotating in opposite directions, the ply of wires being concentrated around the central axis of travel during its passage between the two rollers to deliver a bundle of contiguous wires.
• suitable shape for example of hyperboloid shape or provided with flanges
• the device according to the invention also comprises at least one die, called sheathing die, preferably calibrated to the section of the second strip which it is desired to obtain, and into which at least one first strip and at least one can be introduced simultaneously.
• second molten material in contact with the strip so as to obtain a second strip consisting of at least a second material reinforced by at least a first strip.
• the device according to the invention comprises upstream of said die or this die itself comprises means for positioning and / or shaping of at least one strip for bringing it into contact with at least one second material.
• Said die can also include means for bringing the second material into contact with the strip by applying an overpressure to it.
• the second material (or the second materials when there are several) can come into contact with the first strip through different channels in the die.
• the amount of second material (s) delivered (s) may be different at different points in the section of the strip, for example more material may be deposited on one face of the first strip than on another, thus leading to a decentralization of the reinforcing material within the second band formed.
• the device according to the invention comprises at least one extruder providing at least one second molten material in the sheathing sector (s).
• the device according to the invention also comprises one or more winding means, these means comprising for example a laying head which positions the strip and facilitates its positioning.
• the laying head can be mobile and controlled in rotation; it can for example be formed of rotating or fixed rollers, self-cleaning and ensuring for example the centering of the strip, as described later with reference to the figures.
• the sheathing sector mentioned according to the invention (or at least one of the sheathing sectors when there are several) is located at the outlet of the above-mentioned laying head and before the support on which the second tape should be wound up.
• the device can also include one or more means (for example a hot air blowing nozzle) to heat at least in surface the strip in an area close to the support rotating around its axis or downstream of the contact zone between the strip and the support and / or one or more means for applying local pressure (for example in the form of at least one rotary roller) on the part of the external peripheral surface of the support coated with the strip , for example in an area immediately downstream of the previous heating area.
• the rotating support may for example be a mandrel, this mandrel being able to be heated or not, or a tube (or a solid insert or a part to be consolidated) which may or may not be part of the body of revolution obtained.
• the various elements of the device according to the invention can be fixed or mobile (in translation and / or in rotation).
• the body of revolution according to the invention is generally hollow, and comprises, in its wall, at least one reinforcement material in continuous form, generally wound helically around the (longitudinal) axis of revolution of the body, and at least a thermoplastic organic material (in which the reinforcing material is generally embedded).
• the continuous reinforcing thread (s) embedded in the organic material can form, for example, for at least part of them, an angle of the order of 15 ° with the axis of said body, or according to another advantageous mode an angle between 50 and 55 ° with the axis of said body, this arrangement making it possible to increase the axial and circumferential resistance of the body to the pressure exerted by a circulating fluid or contained inside for the same quantity of glass strands used.
• At least part of the continuous reinforcing threads embedded in the organic thermoplastic material form an angle close to 90 ° with the axis of the body and other continuous reinforcing threads are embedded in organic matter by being arranged longitudinally along the axis of the body.
• the wall of the body of revolution according to the invention is essentially or even entirely formed by the second wound strip.
• the invention also relates to a structure, for example a composite pipe, formed of the body of revolution defined above and coated for example with one or more finishing layers (by winding, co-extrusion, etc.), in particular made of thermoplastic organic material and / or provided with complementary elements (such as end caps, joined for example by welding or gluing, or at least one liner, etc.).
• a structure for example a composite pipe, formed of the body of revolution defined above and coated for example with one or more finishing layers (by winding, co-extrusion, etc.), in particular made of thermoplastic organic material and / or provided with complementary elements (such as end caps, joined for example by welding or gluing, or at least one liner, etc.).
• the body or structure according to the invention is particularly suitable for containing and / or conveying pressurized fluids.
• Other advantages and characteristics will now be described with reference to the attached figure showing a schematic view of a device for manufacturing a body of revolution according to the invention.
• the device shown allows the manufacture of a body of revolution 1 according to the invention formed by winding around a mandrel 2 of a composite strip 3 formed of a first strip 4 formed of reinforcing filaments arranged in parallel and contiguous and joined together by a first thermoplastic material, this strip being embedded in a second plastic material in intimate contact with said strip.
• the strip is formed from composite son 5 such as son sold by the company SAINT GOBAI N VETROTEX FRANCE under the trade name Twintex ® and manufactured for example by the process described in EP 0599695, these son being constituted by glass filaments and filaments of a thermoplastic organic material, of polyolefin or polyester type, intimately mixed together.
• composite son 5 such as son sold by the company SAINT GOBAI N VETROTEX FRANCE under the trade name Twintex ® and manufactured for example by the process described in EP 0599695, these son being constituted by glass filaments and filaments of a thermoplastic organic material, of polyolefin or polyester type, intimately mixed together.
• These wires are unwound from windings 6 arranged on a creel (not shown).
• This creel can be for example such as that described in patent application WO 00/24566.
• These wires are then assembled in parallel using one or more devices (symbolically represented by 7) such as one or more comb (s) and / or plate (s) with eyelets and / or roller (s) grooves and / or embarrassment (s), etc.
• One or more voltage regulation and / or movement detection and / or anti-static means may also be provided, for example at the level of the creel and / or at one or different points of the path before the strip is formed.
• the device according to the invention may comprise the sequence of means described under the reference 75 in patent application WO00 / 24566 between the creel and the first oven 8.
• the wires gathered in a parallel and contiguous manner pass through a first oven or a first series of infrared ovens 8 where they are heated to a temperature reaching at least that of melting the first thermoplastic material, then the sheet of heated son passes through an impregnation device 9 which by flattening the sheet allows obtain a first strip or ribbon by evacuating the air contained between the wires to densify the material and by completely embedding the glass filaments in the thermoplastic material.
• the impregnation device 9 is for example constituted three heating cylinders parallel to each other and arranged in a triangle, the upper cylinder being adjustable in height so that the strip is more or less flattened.
• the first heated strip thus formed is maintained at temperature, by passing through a second oven or a second series of ovens 10, up to the laying head 11, this head advantageously being pivotable so as to be able to change the angle of deposition of the ribbon.
• This head can for example be that described under the reference 71 in patent application WO00 / 24566.
• the first strip is introduced into a die 12 in which it is coated with a second material, this second material in the molten state coming from an extruder 13 and feeding the die through, for example, a flexible pipe 14.
• the second material is identical or different from the first material and is introduced into the extruder in the form of granules 15 and / or wires, etc.
• the second strip 3 thus formed by sheathing the first strip is then wound around the mandrel in rotation about its axis (here for example in the direction indicated by the arrow), a roller 16 adjacent to the mandrel can also help the application of the second strip (this roller may or may not be considered to be part of the laying device).
• the bodies of revolution obtained according to the invention can be used in various applications, such as the transport or storage of fluids.

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• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Composite Materials (AREA)
• Laminated Bodies (AREA)
• Moulding By Coating Moulds (AREA)
• Reinforced Plastic Materials (AREA)
• Extrusion Moulding Of Plastics Or The Like (AREA)

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• 2002
  • 2002-07-04 FR FR0208419A patent/FR2841816B1/fr not_active Expired - Fee Related
• 2003
  • 2003-06-25 JP JP2004520714A patent/JP2006508821A/ja not_active Withdrawn
  • 2003-06-25 BR BRPI0312310-3A patent/BR0312310B1/pt not_active IP Right Cessation
  • 2003-06-25 CA CA002491315A patent/CA2491315A1/fr not_active Abandoned
  • 2003-06-25 WO PCT/FR2003/001954 patent/WO2004007179A1/fr active Application Filing
  • 2003-06-25 CN CNB038157381A patent/CN100345674C/zh not_active Expired - Fee Related
  • 2003-06-25 US US10/519,949 patent/US7691219B2/en not_active Expired - Fee Related
  • 2003-06-25 EP EP03763920A patent/EP1519826A1/de not_active Withdrawn
  • 2003-06-25 MX MXPA04012682A patent/MXPA04012682A/es active IP Right Grant
  • 2003-06-25 AU AU2003264672A patent/AU2003264672A1/en not_active Abandoned
  • 2003-06-25 PL PL03373160A patent/PL373160A1/xx unknown

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