Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C19/00—Dental auxiliary appliances
  • A61C19/003—Apparatus for curing resins by radiation
  • A61C19/004—Hand-held apparatus, e.g. guns
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C19/00—Dental auxiliary appliances
  • A61C19/003—Apparatus for curing resins by radiation

Definitions

• the invention relates to a photopolymerization device or lamp for sealing materials, reconstitution, impression, gluing, or bleaching, particularly in the dental field, comprising a light source, and means optical and electronic means for orienting, controlling, modulating, selecting and emitting the light energy produced for different photoinitiators by said source towards an area to be illuminated.
• the composite materials used in dentistry are generally based on a photopolymerizable resin or ionomer glasses that can be loaded with solid elements (inclusions) whose molecular structure is transformed under the effect of light radiation having a length given wave according to the characteristic of said radiation and the absorption capacity of the material used and in particular the sensitivity of photoinitiators.
• this radiation activates the photoinitiators of the material during an exposure time calculated as a function of the energy of this radiation, the composition and the color of the composite.
• Preprogrammed menus for automatically controlling the operation of the light source are stored in the control circuit of the light curing device.
• This management generally consists in controlling the light source according to an energy profile and an illumination time which are determined according to theoretical operating conditions, also called polarization parameters, such as, for example, the type of material to be polymerized or the distance separating the light source from the material to be treated. Since these conditions are set once and for all in the factory, the operator has no choice but to use these preprogrammed menus in an empirical way in the hope of obtaining a correct polymerization.
• the power and / or the duration of illumination are programmed in the apparatus in particular according to a fixed value of the distance between the light source and the material to be treated, it is very difficult for the practitioner to maintain his this distance throughout the treatment to ensure optimal polymerization.
• This also applies to most of the other theoretical operating conditions taken into account in the factory when programming the menus in the device. Indeed, when the light source is used in combination with a waveguide to guide and direct the light towards the site to be treated, the operating conditions relating to the waveguide (optical characteristics) are defined for a waveguide specific and do not take into account the variations of these conditions as in the case of a waveguide with defects (at the origin or following a deterioration) or when replacing this guide of wave.
• the photopolymerization device is used by the practitioner without it being possible to check that the previously defined polymerization parameters are well respected, which leads either to an underpolymerization endangering, for example, the fate of the filling. either a disturbing overexposure for the patient but also degrading for the surface by thermal overexposure.
• EP 1 236 444 discloses the use of a pilot light which allows, with an associated sensor, to measure the distance between the end of the light guide of the photopolymerization device and the material to be cured.
• the pilot light and the associated sensor are used to trigger the activation of the polymerization light when the end of the guide is at a predetermined distance from the material to be treated.
• the polymerization light then illuminates the site for a preprogrammed time. At the end of this period, the polymerization light can be activated again as soon as the predetermined distance is reached again.
• EP 0 933 810 discloses a curing lamp which comprises means for measuring the distance between the light source of polymerization and the material to be treated, the control unit of the lamp adjusting the power or the illumination time of the lamp. source according to this distance.
• this polymerization lamp has the advantage of taking into account the variation of a polymerization parameter to control the light source, it does not guarantee the achievement of optimal polymerization. Indeed, the measurement of the distance between the light source and the material to be treated is not sufficient to guarantee precise control of the polymerization and in particular when using photopolymerizable materials.
• a photopolymerizable material contains photoinitiators whose activation depends in particular on the quantity of photons received by the material at a given wavelength.
• the measurement of the distance between the light source and the photopolymerizable material is not sufficiently representative of the light energy received by the material.
• the measurement of the distance does not make it possible to know, for example, the angle and the shape of the "focal plane" applied to the material.
• the light energy received by the material depends on these parameters.
• the photopolymerization device must be programmed to take into account, when measuring the distance, the length of each waveguide capable of to be used. Moreover, the measurement of the distance does not take into account the transmission variations (attenuation, deviation, etc.) that may occur in the waveguide.
• Document US 2006/0240376 discloses a photopolymerization device which is able to measure the degree of polymerization of a material during the activation of the light source of polymerization.
• the device comprises an infrared sensor which measures the infrared radiation emitted by the material itself during its polymerization.
• the polymerization of the composite materials used in dental surgery to obtain their hardening implements an exothermic reaction. Therefore, the amount of heat released by the material during its polymerization is representative of the degree or rate of polymerization of this material.
• the document US 2006/0240376 uses the principle of the well-known differential scanning calorimetry analysis (called DSC analysis for "Differential Scanning Calorimetry”) which makes it possible to determine the heat produced by a material during its transformation.
• DSC analysis differential scanning calorimetry analysis
• the device of document US 2006/0240376 makes it possible to evaluate the quantity of heat produced by the material and to monitor the degree of polymerization thereof in order to stop the light source or reduce its power.
• the solution proposed in this document is unsatisfactory because it is very difficult to obtain a reliable and accurate measurement, in particular because of the multiple factors (type of polymer, respective percentage of concentration ratios, mixing efficiency, etc.) which can vary the enthalpy measurement by a factor of 1 to 10.
• the solution proposed in this document can not be applied to variable volume composites polymerization analysis methods.
• This solution also has the disadvantage of requiring the use, in addition to the waveguide adapted to transmit at the wavelength of the polymerization light (generally between 350 and 550 nm), an additional waveguide capable of permitting transmission in the wavelength of the infrared radiations to be measured (generally between 3000 and 5000 nm).
• the object of the invention is to remedy the aforementioned drawbacks and to propose a device or lamp for photopolymerization which makes it possible to reliably measure the quantity of light received by the material to be polymerized and to carry out a control of the light source of polymerization according to of this measure.
• a light-curing device comprising a light source of polymerization and optical means for guiding and / or directing the light energy produced by said source towards an area of a photopolymerizable material such as a light-sensitive material. shutter, reconstruction, impression, collage, or still another bleaching material, the device comprising means for measuring the intensity of the light reflected by the material to be polymerized, these means being in connection with means for processing and controlling the light source responsive to the measurement of the intensity to automatically control at least the power and / or duration of illumination of the light source according to the measurement of the intensity of the reflected light.
• the photopolymerization device of the invention can deduce the number of photons received by the material in a given wavelength, independently of the conditions of the invention. application of light (size, shape and angle of applied focal plane) or variations in transmission thereof. Since the number of photons is representative of the optical power, the photopolymerization device can thus carry out a control on the light source by adjusting the control parameters such as the power and / or the duration of illumination of the latter as a function of the value. measured light intensity.
• the measurement of the luminous intensity automatically takes into account the factors which can modify the luminous energy received and which are not always detectable during a measurement of distance. For example, the length, defects or any other aspects of a waveguide influencing the amount of transmitted light are automatically integrated into the measurement of light intensity.
• the photopolymerization device of the invention is, therefore, efficient regardless of the waveguide used.
• the device comprises means for measuring the intensity of the light reflected by the photopolymerizable material in the wavelength of the light emitted by the light source of polymerization.
• the device comprises means for controlling the activation of the light source during a predetermined measurement period and means for determining a duration of illumination of the light source as a function of the intensity of the light source. the light reflected by the material to be polymerized for the duration of measurement, the processing and control means then activating the light source during the duration of illumination thus determined.
• the device further comprises means for reducing the intensity of the polymerization light source during the predetermined measurement time.
• means for reducing the intensity of the polymerization light source during the measurement phase carried out before the polymerization step it is possible to measure the intensity of the light reflected by the material without risk of initiating the polymerization. In other words, in this case, the intensity measurement does not disturb the subsequent polymerization process.
• the device further comprises means for transmitting a measurement beam for illuminating the photopolymerizable material with a light of a length different from that of the light emitted by the light source of polymerization. and means for measuring the intensity of the light reflected by the material to be light cured in the wavelength of the measurement beam.
• the intensity measurement can be performed with a transmitter / receiver system separate from the polymerization light source.
• the measuring beam can be emitted in the visible spectrum and then advantageously be used as a sighting spot and allow the practitioner to point precisely to the site to be treated.
• the polymerization device uses a measuring beam of a length different from that of the light emitted by the light source of polymerization
• the latter comprises means for converting the intensity of the light measured in the wavelength of the beam measuring in an intensity value corresponding to the wavelength of the light emitted by the light source of polymerization.
• the device processing means have exploitable values for automatically controlling at least the duration of illumination and / or the power of the light source as a function of the intensity measured.
• the light source polymerization may be a halogen source, plasma, laser or any other type of source suitable for light curing.
• the light source of polymerization may comprise at least one light emitting diode (LED) in coherent light or not. It may also include several light-emitting diodes emitting light in the same wavelength or at different wavelengths.
• the device comprises means for measuring the intensity of the light reflected by the material to be polymerized in each of the emission wavelengths of the light-emitting diodes of the source.
• the photopolymerization device further comprises means for measuring the intensity of the light reflected by a verification element and means for comparing the measured intensity with a reference intensity value so as to to determine whether the optical power delivered by the device is still in accordance with that specified at the factory.
• This verification makes it possible in particular to detect an optical transmission problem that has appeared in the waveguide or a light source failure.
• the important parameters for the polymerization namely the duration of illumination and / or the power of the light source, can be controlled automatically both before and during exposure.
• This control can be carried out indifferently with any type of light sources, waveguides and photopolymerizable materials that can be used.
• FIG. 1 is an exploded view in perspective of a light-curing device according to an embodiment of the present invention
• FIG. 2 is a partial sectional view along the line AA of FIG. 1
• FIG. 3 is a block diagram of an electronic control circuit of a light-curing device according to an embodiment of the present invention
• FIG. 4 is a graph showing a phase of intensity measurement performed prior to polymerization.
• FIG. 5 is an exploded perspective view of a photopolymerization device according to another embodiment of the present invention
• FIG. 6 is a partial sectional view according to FIG. the landmark
• FIG. 7 is a block diagram of an electronic control circuit of a light curing device according to another embodiment of the present invention.
• the present invention relates to a photopolymerization device for applying to a photopolymerizable material light radiation in at least one given wavelength or in a defined wavelength spectrum.
• photopolymerizable material is meant any type of material whose molecular structure is transformed under the effect of a light radiation of a given wavelength, in particular by the activation of the photoinitiators (for example camphoroquinone) of the material which trigger the polymerization reaction of the material.
• the photopolymerizable materials can be in particular composite materials to be hardened such as sealing materials, reconstruction, impression, gluing or materials to be activated such as a bleaching product.
• the photopolymerization device comprises means for measuring the intensity of the light reflected by the photopolymerizable material in order to control the light source of the device as a function of this measurement.
• the light intensity being representative for a given wavelength of the optical power, it is possible by measuring the intensity
• the light reflected from the material determines the energy or optical power actually received by the material and act on the light-curing light source accordingly.
• the intensity measurement performed by the photopolymerization device of the present invention uses optical properties and in particular reflection.
• the device of the invention uses measuring means that are able to measure the intensity of the light reflected by the material to be polymerized when it is illuminated with a reference light source. This measurement is different from that for evaluating the degree of polymerization as described in document US 2006/0240376.
• the level of radiation e.g., infrared
• the polymerization implements an exothermic reaction whose progress can be monitored by measuring the amount of heat released by the material.
• the measurement made is not based on the optical properties of the material but on the variation of enthalpy which is impossible to measure precisely due in particular to the caloric variation as a function of the volume (Ca word law).
• FIG. 1 illustrates a light-curing device 100 according to a first embodiment of the invention and intended to allow the photopolymerization of impression and reconstitution materials such as composites, in particular in the dental field.
• the light-curing device 100 comprises an anterior part 110 which comprises, in a known manner, a light source 111 equipped with a light-emitting diode or LED 112 coupled to a waveguide 113 making it possible to guide, orient and emit the light energy produced by the source 111 towards a lighting zone corresponding to the area of the composite material to be light cured.
• the waveguide 113 and the light source 111 are coupled within an element 114, the guide 113 being removably mounted at one end of the element 114 and the light source 111 being mounted at the other end. end of the element 114 on a support element 119.
• the waveguide 113 may be constituted by optical fibers.
• the waveguide may also be formed of one or more lenses or a bar known as "ROD" well known by those skilled in the art familiar with the field of waveguides.
• the waveguide 113 is mounted in the element 112 by means of a tip 115 which, as illustrated in FIG. 2, has in its interior part a reflector 116 making it possible to reduce the divergence of the radiation emitted by the LED 112 and having a central opening
• the anterior portion 110 of the photopolymerization device 100 further comprises a light intensity sensor 117 mounted at the light source 111 near the LED 112.
• the light intensity sensor 117 can be constituted by a photosensitive sensor, that is to say a sensor returning a value proportional to the amount of photons it receives.
• the sensor 117 may especially consist of a photodiode or a phototransistor (variation of the current as a function of the number of photons received), or a photoresistor (variation of the resistance as a function of the number of photons received).
• the senor 117 measures the light intensity (ie the number of photons received) in the wavelength or the wavelength spectrum of the light of polymerization emitted by the light source 111. In other words, the sensor 117 delivers a value that is directly representative of the intensity of the polymerization light reflected by the composite material.
• the deflector 116 has an opening 116b to allow the sensor 117 to receive the light reflected by the composite material and returned by the waveguide 113.
• the sensor 117 may also be optionally provided with a prism 118 for directing re fi F rays of light reflected by it through the waveguide material to the photosensitive surface of the sensor 117.
• the light source is not limited to the use of an LED. It may for example consist of a halogen source, plasma, laser, or any other type of source suitable for photopolymerization.
• the light source can comprise several LEDs each emitting a light-curing light, either in the same identical wavelength, which makes it possible in particular to vary the focusing as a function of the optical system or to increase the power of the source, either in a different wavelength (for example by using an LED emitting at 480 nm and another LED emitting at 420 nm), which makes it possible to ensure the polymerization of certain materials of reconstructions using molecules other than than camphoroquinone such as "Lucirin" (LR) from BASF ®.
• LR camphoroquinone
• the photopolymerization device of the invention comprises either a light intensity sensor capable of measuring a value representative of the light intensity in each of the wavelengths emitted, or several sensors, each being able to measure the luminous intensity in a wavelength of one of the LEDs of the source.
• the light-curing device 100 comprises a second part which corresponds to a control unit 120 situated just below the front part 110.
• This control unit 120 comprises a card 121 equipped on one side with a screen 122 and control buttons 123 and, on the other side, an electronic control circuit (not shown in Figure 1).
• the control unit is connected, via connection means 124, to a source of electrical power supply which may in particular be an autonomous power source constituted by rechargeable batteries, an external power source such as the mains or a local power source available for example on the dental block of the practitioner.
• the light source 111 and the light intensity sensor 117 are electrically connected to the electronic control circuit which, on the one hand, receives the light intensity measurement signal delivered by the light intensity sensor 117, and, on the other hand, controls the light source 111 to adapt the duration and / or the illumination power of the latter as a function of the measurement signal received.
• Figure 3 is a block diagram of an electronic control circuit 300 of an embodiment of the photopolymerization device of the invention.
• the circuit 300 comprises a CPU 301 (for example a programmable microcontroller) which is programmed to control all the polymerization parameters.
• This card comprises a non-volatile memory which contains, in the form of selectable menus and possibly modifiable by a download interface 302, the polymerization parameters specific to each type of material. photopolymerizable and for which the optimum light intensity has been defined.
• the practitioner through an LCD 303 and control keys selects one of the proposed menus then triggers the polymerization cycle by a trigger or control button 304.
• the CPU 301 controls a light-curing light source 305 which can be constituted, as previously described, of one or more LEDs, a halogen, plasma, laser or other source.
• the CPU 301 board Based on the measured reflected light intensity, the CPU 301 board sets and controls a DC / DC 307 switching converter (PWM), which minimizes the thermal rises generated in the handpiece.
• a current regulator 308 permanently locks the energy sent into the light source.
• the polymerization parameters are optimized by the CPU 301 which measures the light intensity of the light reflected by the material to be polymerized and adjusts the duration of illumination and / or the power according to this measurement.
• the circuit 300 is connected to an electrical power source 400 which may be either a source from the dental block 401, an external power source 402 such as the mains, or a battery-operated power source 403, such as for example Li-Ion, Ni-Cd, MnAI, etc. batteries, rechargeable by induction, contact or other.
• an electrical power source 400 which may be either a source from the dental block 401, an external power source 402 such as the mains, or a battery-operated power source 403, such as for example Li-Ion, Ni-Cd, MnAI, etc. batteries, rechargeable by induction, contact or other.
• the circuit 300 is connected to a light intensity sensor 309 which can be, as previously described for the sensor 117, a photodiode, a photoresistor, a phototransistor or the like.
• the sensor 309 receives on its photosensitive surface a part of the light-curing light reflected by the material illuminated by the source 305.
• the sensor 309 generates in response a signal representative of the light intensity that it has received and transmits this information to a control loop 310 which can be implemented in the CPU 301 or in a dedicated component.
• the senor 309 is a phototransistor
• the latter generates an electric current I, also called photocurrent, proportional to the number of photons received on its photosensitive base.
• the photocurrent I is then transmitted to the regulation loop 301 while being simultaneously converted into voltage and amplified by a transimpedance amplifier.
• the light intensity information can be transmitted to the control loop in digital form by analog-to-digital conversion (AfD) of the signal delivered by the sensor.
• AfD analog-to-digital conversion
• the regulation loop 310 makes a comparison between the signal representative of the light intensity received by the sensor with a reference light intensity value and generates a regulation signal which allows the CPU 301 to act on the duration of the light. illumination and / or the power of the light-curing light source in response to this control signal.
• the value of the light intensity measured by the sensor can be compared to a reference intensity value, this reference intensity value having been previously defined in the preprogrammed menu according to a power level. lighting of the light source. If the intensity value measured by the sensor is lower than the reference intensity value, it means that the power level delivered by the light source is lower than that expected in the menu. In this case, the regulation loop 310 delivers a control signal to the CPU board 301 which, in response to this signal, will increase the lighting time or the power of the light source.
• the regulation loop 310 delivers a control signal to the CPU board 301 which, in response to this signal, will decrease the illumination time or the power of the light source.
• the electronic control circuit for the photopolymerization device of the invention.
• the electronic control circuit according to the invention further comprises conventional means of controlling a light-curing device, such as least means for acquiring a signal from a light intensity sensor and means for processing and exploiting this signal (for example by comparison with a reference value) in order to allow the control members of the light-curing light source to adapt at least the duration of illumination and / or the power of this source as a function of the light intensity measured by the sensor.
• the photopolymerization device measures the intensity of the light reflected by the material to be polymerized during a phase prior to the actual polymerization.
• the activation phase of the light source for the polymerization is preceded by an intensity measurement phase carried out over a period of time T1, for example 500 ms.
• the processing means of the device like the previously described CPU 301, controls the light-curing light source to illuminate the material to be cured during the predetermined measurement time T1.
• the processing means calculate the illumination duration T2 of the light source as a function of the intensity of the light reflected by the material to be polymerized.
• the treatment means preferably control the light-curing light source so that it illuminates the material to be polymerized with a lower intensity than that used for the polymerization.
• the power of the light source is reduced by a predetermined ratio r (corresponding to a reduction percentage of the power used to polymerize the material) so as not to initiate the polymerization of the material during the preliminary measurement phase. This reduction of intensity makes it possible to measure preliminary without risk of initiating the polymerization and to determine, therefore, an optimal duration of illumination for the polymerization to be carried out.
• the measurement phase is immediately followed by the actual polymerization phase in which the processing means control the light source so that it illuminates the material with a power P Qm ax corresponding to the maximum amount of light absorbed by the material, during the illumination period T2 defined previously during the measurement phase.
• the measurement of the intensity of the light reflected by the material to be polymerized can be carried out during the polymerization phase even when a preliminary measurement phase has already been performed as previously described. In the latter case, the duration of illumination T2 defined during the preliminary measurement phase can be modified during polymerization as a function of the intensity measurement.
• FIG. 5 illustrates another embodiment of a photopolymerization device of the invention.
• the photopolymerization device 200 of FIG. 5 differs from that described above in that it further comprises a source of emission of a measurement beam 220 which emits light in a wavelength different from that of the photopolymerization light source.
• the photopolymerization device 200 comprises a sensor 217 which measures the light intensity in the wavelength of the emission source of the measuring beam 220.
• the source 220 may be constituted by an infrared laser diode 221 which emits, via a prism 222 housed in an opening 116c of the deflector 116, an infrared beam FIR towards the material to be treated through the waveguide 113, the infrared beam Fi RRef i reflected by the material being received by the sensor 217 via a prism 218.
• the intensity of the infrared light reflected by the material when it is illuminated with an infrared measuring beam and not infrared radiation emitted by the material during its polymerization as described in particular in document US 2006/0240376.
• the use of an emission source of a measurement beam emitting light in a wavelength different from that of the light-curing light source makes it possible to avoid the initiation of the polymerization material during this pre-measurement phase.
• the other structural elements of the photopolymerization device 200 are identical to those of the light-curing device 100 shown in FIG. 1 and will not be described again for the sake of simplification. Since the light intensity measured to carry out the control of the light-curing source is in a wavelength different from the light-curing light, the electronic control circuit of the device 200 must also comprise means for converting the measured intensity values. in the wavelength of the emission source of the measuring beam 220 into intensity values corresponding to the wavelength of the light-curing light.
• the electronic control circuit 500 of the device 200 differs from that of FIG. 3 in that it further comprises a processing means 512 of the signal delivered by the sensor 509 and corresponding to the intensity of the light from the measurement beam emission source 511 reflected by the material to convert it into a signal representative of the light intensity in the wavelength of the light-curing light emitted by the light source of 505.
• the processing means 512 converts the signal delivered by the sensor 512 by applying to the measured values a conversion coefficient if the values of measured light intensity vary linearly with respect to the photopolymerization light or using an abacus if this variation is not linear.
• the processing means 512 carrying out this conversion can be implemented in a dedicated component or in the CPU card 501.
• the other elements 501 to 510 and 601 to 603 are identical to the elements 301 to 310 and 401 to 403 already described in relation to FIG. 3.
• the measuring beam can be produced with radiation coming from a large part of the electromagnetic spectrum and especially the visible part of this spectrum.
• the fact of making a measurement beam in the visible part of the spectrum makes it possible to combine both the light intensity measuring function and the aiming function.
• the photopolymerization device can emit, in addition to the polymerization light, visible radiation producing a sighting spot that allows the practitioner to locate the clinical site to be treated. This radiation can be emitted directly from the emission source of the measurement beam or by appropriate wavelength filtering of the light emitted by the polymerization light source.
• the optical intensity sensor is then chosen to allow the measurement of the light intensity in the wavelength of the light used to make the aiming spot.
• the measurement of the light intensity of the photopolymerization device of the present invention may further be advantageously used to verify that, even after many uses, the light-curing device always delivers an optical power according to that specified at the factory.
• the waveguide and the light source may suffer damage and / or aging that may reduce the optical power delivered by the device.
• the waveguide is sterilized by steam in an autoclave. Repetition of the autoclave cycles can lead to the rupture of the waveguide or to the formation of a deposit on the latter, in particular when non-demineralised water is used with the autoclave.
• the intensity of the light source can be affected.
• the photopolymerization device of the invention With the photopolymerization device of the invention, a verification of its proper functioning can be easily performed on site locally, for example in the dental office, by the use of a check block constituting a reference surface.
• the user places this wedge against the light beam emitted by the light-curing device which measures the intensity of the light reflected by the shim and compares it with a reference intensity value. If the measured intensity value differs significantly from the reference value, the device can warn the user by displaying corresponding information on the LCD screen. of the device. The user thus warned of the problem may, for example, change the waveguide and make a new verification measure.

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• Health & Medical Sciences (AREA)
• Oral & Maxillofacial Surgery (AREA)
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• Epidemiology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Veterinary Medicine (AREA)
• Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
• Investigating Or Analysing Materials By Optical Means (AREA)

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• 2006
  • 2006-12-04 FR FR0655290A patent/FR2909276A1/fr active Pending
• 2007
  • 2007-11-27 US US12/517,731 patent/US20100140450A1/en not_active Abandoned
  • 2007-11-27 CN CN2007800445376A patent/CN101563048B/zh active Active
  • 2007-11-27 JP JP2009539785A patent/JP2010511457A/ja active Pending
  • 2007-11-27 EP EP07858740A patent/EP2086461A1/de not_active Withdrawn
  • 2007-11-27 WO PCT/FR2007/052402 patent/WO2008068439A1/fr active Application Filing
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