Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/06—Making microcapsules or microballoons by phase separation
  • B01J13/14—Polymerisation; cross-linking
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/20—After-treatment of capsule walls, e.g. hardening
  • B01J13/22—Coating
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/02—Materials undergoing a change of physical state when used
  • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
  • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
  • D06M23/12—Processes in which the treating agent is incorporated in microcapsules
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2984—Microcapsule with fluid core [includes liposome]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2989—Microcapsule with solid core [includes liposome]

Definitions

• the present invention relates to the field of thermal insulation and relates more particularly to microcapsules comprising at least two organic and / or inorganic compounds.
• thermoregulatory textile materials consist of composite materials in which entrapped air is the main insulating element.
• phase change materials are now also used in development of fibers, fabrics or thermoregulating foams for clothing. Indeed, phase change materials, being liquids that solidify at reasonably low temperatures, or solids that liquefy at higher temperatures, are suitable as thermoregulatory materials for most temperatures to which the human body is exposed.
• phase change materials applied to or embedded in textile substrates are generally microencapsulated by polymers. Microencapsulation also makes it possible to improve the heat transfer by increasing their specific contact surface, thus helping to compensate for the low thermal conductivity, but also to avoid the diffusion of the active principle, while controlling its volume variations, during the various requests. thermal conditions.
• microencapsulation makes it possible to reduce or even annihilate its reactivity with the external medium.
• the microencapsulation techniques vary according to the type of products used and the final application sought, nevertheless, they all start with an oil-in-water or water-in-oil emulsion depending on the solubility of the active ingredient in one or the other of the phases.
• the polymer encapsulating the droplets is introduced as monomers simultaneously with the active ingredient.
• the object of the present invention is to provide aminoplast membrane microcapsules, comprising phase-change-sensitive materials, having novel structures and improved thermal properties, as well as processes for preparing such microcapsules.
• the invention relates to mono or multinuclear microcapsules with aminoplast membrane comprising at least two organic and / or inorganic compounds.
• the microcapsules of the invention are mononucleic, having a conventional structure of core / shell (heart / crown) whose membrane or aminoplast outer wall represents the crown, the latter enveloping the heart which typically comprises at least two organic and / or inorganic compounds.
• the mononucleic microcapsules comprise the mixture of at least two paraffins.
• said paraffins are even alkanes, for example alkanes selected from the group: hexadecane, octadecane and eicosane.
• the microcapsules of the invention are multinucleate and comprise at least one organic compound surrounded by microspheres comprising at least one inorganic compound, said microspheres being coated with the aminoplast resin.
• said organic compound is a paraffin, for example hexadecane or eicosane.
• Said inorganic compound may be a phase-change compound, for example a salt hydrate, or a compound without phase change, for example a phosphate salt.
• the microcapsules of the invention comprising at least two organic and / or inorganic compounds, at least one of which has a phase change, have thermal windows that make it possible to cover wider temperature ranges than those corresponding to microcapsules enclosing a single material. phase change.
• the invention relates to a synthesis method, said mononucleic microcapsules, characterized in that it comprises the following steps: a) introducing into a mixer a base composition A comprising:
• the invention relates to a process for the synthesis of multinucleate microcapsules, characterized in that it comprises:
• the invention relates to the various compositions used in the microencapsulation processes mentioned.
• the invention will now be described in detail.
• the invention relates to mono or multinuclear microcapsules with aminoplast membrane comprising at least two organic and / or inorganic compounds.
• the microcapsules 1 of the invention shown schematically in Figure 1 attached, are mononucleic and have a conventional structure of the core / shell type (heart / crown) whose membrane or aminoplast outer wall 2 represents the crown, the latter enveloping the core 3 which typically comprises at least two organic and / or inorganic compounds.
• the applicants have developed an original mixture of at least two organic phase change materials, said mixture also being formulated with a mineral filler, making it possible to obtain a thermoregulating system with a thermal window and an energy balance. improved.
• the organic phase change materials used are paraffins or n-alkanes, because of their thermal characteristics with enthalpies of phase change of the order of about 200 J / g.
• n-alkanes which may be suitable for textile thermoregulation, none have a sufficiently wide thermal window in the temperature range 19 to 30 ° C.
• the odd n-alkanes appear to be of little interest in view of the existence of a solid / solid low energy transition and a lower solid / liquid phase change enthalpy than for the even n-alkanes, as well as their cost approximately four times higher than that of the even n-alkanes.
• phase transition thermal windows are narrow and tend towards those of the alkane fusion in greater proportion.
• mass fractions between 0.3 and 0.7, the endotherms are widened between 0 and 35 ° C., involving the appearance of new solid / solid transitions within the material during the temperature rise.
• the mass fraction of paraffin introduced into the mononucleic microcapsules is preferably between 25 and 75%.
• This loss is related to the increase in the number of solid / solid transitions less energetic than solid / liquid transitions.
• the 50/50 mixture makes it possible to solicit the material over a larger thermal window observed from 3 to 32 ° C. for an enthalpy of 190 J / g.
• the applicants have demonstrated that the introduction into the C16 / C20 binary mixture of a soluble filler in one or the other of its components makes it possible to increase the energy balance up to values comparable to those of the body. pure, without modifying the thermal window.
• the C16 / C20 binary mixture is supplemented with tetraethyl ortho-silicate.
• the results obtained, represented in the attached FIG. 4, show that the enthalpy increases up to about 4% (by mass) of tetraethyl-ortho-silicate, then it decreases until it reaches its base level at 20% of charge.
• the invention relates to a method for synthesizing mononucleic microcapsules, characterized in that it comprises the following steps: a) introducing into a mixer a base composition A comprising: - a mixture at least two paraffins,
• a surfactant in an aqueous solution b) operating the mixer with a stirring speed of between 9,000 and 14,000 rpm, at a temperature of about 40 ° C. and a pH of about 4 for 10 to 20 minutes, so as to emulsify and homogenize said composition until a stable emulsion is obtained; c) increasing the temperature of the emulsion to about 55 ° C and adjusting the mixer speed to about 600 rpm for about 4 hours to obtain microcapsules.
• the encapsulation protocol is based on the direct emulsion of the paraffin mixture in an aqueous solution containing an aminoplast prepolymer (methoxymethylmelamines).
• the emulsion is made using a rotor / stator for about 15 minutes.
• the synthesis is continued by increasing the temperature of the solution at 55 ° C. for 4 hours at 700 revolutions / min allowing the suspension of the particles.
• the microcapsules obtained are filtered, washed with methanol and then with demineralised water, and oven-dried at 35 ° C. overnight.
• the surfactant used to stabilize the emulsion is Tween® 80.
• the method for synthesizing mononucleic microcapsules will be better understood on reading the description which will be made with reference to the following nonlimiting examples of embodiments.
• Table 1 illustrates the results of nine tests in which the particle size, morphology and the synthesis yield of microcapsules' mononucleic are investigated based on changes in pH, temperature and choice of the prepolymer.
• Adjusting the pH of the solution during emulsion allows for better stabilization of the emulsion through intramolecular interactions.
• the emulsion took place at 40 ° C.
• the lowering of the pH at this temperature conditions the formation of the primary membrane of the microcapsules at the same time as the mechanisms of deformation and rupture of the droplets under strong shear.
• FIGS. 5 and 6 it is observed in the accompanying FIGS. 5 and 6 that the particle size on the SEM and optical plates of the test 2 is thinner than that of the test 1 (FIG. 5: optical plates (X64) and SEM (X 3500 ) microcapsules of the synthesis test 1 and FIG.
• Nonionic surfactants and in particular Tween® 80, are sensitive to the rise in temperature.
• the formation of an emulsion which may be stable at 40 0 C is not necessarily, or at least does not retain its size during the temperature rise. In this case, this rise is accompanied by mechanical agitation of the system using an anchor.
• the formed droplets are then subject to coalescence as the system freezes by the formation of the primary membrane.
• FIG. 7 illustrates the test 3.
• the size distribution visualized on the SEM image shows a large dispersion of the sizes since the diameter varies substantially between 1 and 5 ⁇ m.
• the difference in particle size is not directly related to the ratio, but a low ratio causes a greater surface activity on the part of the resin, its solubility in the aqueous medium is lower, which facilitates all the implementation. emulsion of the system.
• the morphology of the microcapsules is also modified by the ratio F / M. The weaker it is, the more the capsule walls appear smooth, whereas a high ratio causes the formation of a rougher surface, as illustrated in FIGS. 9 (SEM image (X 3500) of the microcapsules of the synthesis test 3) and 10 (SEM plate (X 10000) of the microcapsules of the synthesis test 7) appended.
• the amount of prepolymer introduced changes to a greater or lesser extent the viscosity of the aqueous phase. This change in viscosity is likely to reduce the size distribution of the emulsion and consequently that of the microcapsules, but this effect is limited by the increase in the thickness of the membrane. We are then in the presence of two competitive phenomena. Measurement of the viscosity of the aqueous phases in the tests 3, 4, 5, 6 shows that it increases with the increase in the amount of prepolymer introduced, as shown in Table 2. The measurements are carried out at 20 ° C. 0 C, at 20 rpm, with stirring device No. 1 using the Brookfield viscometer.
• the morphology of the microcapsules is also affected by the level of prepolymer introduced. Thus, an increase leads to obtaining a granular surface and the development of particles similar to berries.
• SEM scanning electron microscope
• SEM images (X 3500, X 7500) and appended FIG. 13: SEM (X 15000), microcapsules of the synthesis (5), suggest a formation mechanism closer to phase coacervation than that of the in situ, bound polymerization. decreasing the solubility of the prepolymer in the aqueous phase by the presence of an acidic pH and increasing the temperature, inducing the bridging formation between the triazine groups.
• a microcapsule appears to be composed of aminoplast precursors that can be formed immediately without liquid-liquid separation of the aqueous phase at the interface of the droplets of the organic phase.
• the membrane of the mononuclear capsules has a thickness of between 120 and 700 nanometers. - 1 -
• the subject of the invention is also a base composition A, implemented in the process for the synthesis of mononucleic microcapsules described above, characterized in that it comprises:
• a soluble filler in said mixture, in an aqueous solution, and in that the mixture ratio of the paraffins / aminoplast prepolymer is between 20 and 80% by weight.
• the surfactant is a mixture (50/50 by volume) of Tween® 20 and Brij®35, at 4% by weight relative to the aqueous phase.
• the aminoplast prepolymer comprises a formalin / melamine molar ratio of greater than 4.
• the invention relates to microcapsules having an original multinuclear structure (shown schematically in Figure 14 attached).
• a microcapsule 10 comprises at least one organic compound 20 surrounded by microspheres 30 comprising at least one inorganic compound 40 and a membrane 50. Said microspheres 30 are coated by the aminoplast outer membrane 60.
• the multinuclear wall 70 encapsulating at least one organic compound 20 is formed of the aminoplast membrane 60 and the microsphere ring 30.
• said organic compound is a paraffin, for example hexadecane or eicosane
• said inorganic compound is a phase-change material, for example a salt hydrate.
• said organic compound is a paraffin and said inorganic compound is a material without phase change, for example a phosphate salt.
• the invention relates to a process for the synthesis of the aforementioned multinucleate microcapsules, characterized in that it comprises:
• the step of microencapsulation of the inorganic compound in a paraffinic medium comprises the following operations: i) introducing into a first mixer a composition B comprising two phases, an aqueous phase containing an inorganic compound and water and a continuous phase containing paraffin and a mixture of surfactants, the mixture of surfactants having a HLB (hydrophilic-lipophilic balance) of between 5 and 7, ii) operating the first mixer at a speed of about 8,500 rpm for 15 at room temperature, so as to emulsify the composition B until a stable emulsion E1 is obtained; iii) introducing into a second mixer a composition C comprising two phases: an aqueous phase containing an aqueous solution of PVA and a continuous phase containing paraffin; iv) operating the second mixer at room temperature at a speed of approximately 13,500 revolutions / min so as to emulsify the composition C until a stable emulsion E2 is obtained; v) mixing the
• the method according to the invention comprises an additional operation after the operation vi) of keeping the salt-containing microspheres in dispersion by mechanical stirring.
• the step of microencapsulation of the salt in a paraffinic medium of the multinucleate microcapsule synthesis process will be better understood at the reading of the description which will be made with reference to the following examples of non-limiting embodiments.
• Emulsion Salt in Paraffin Emulsion El
• the aqueous phase is composed of salt hydrate and water in the proportions 5: 1, and the continuous phase of paraffin either hexadecane or eicosane with the mixture of surfactants (5% by volume) selected so that the volume ratio of the phases is 1 to 4.
• the aqueous phase is dispersed in the organic phase using a homogenizer under strong shear.
• the emulsion formation protocol E1 consists of dispersing 30 ml of a salt solution in 70 ml of hexadecane at 8500 rpm for 15 minutes. The type of emulsion and its granulometry are observed under an optical microscope on a drop taken. Stability is observed over a period of 24 hours at room temperature. The results of the observations are presented in Table 3 (classification: +++, excellent; ++, good; +, satisfactory; - insufficient, E: water; H: oil).
• the size of the particles was mainly influenced by the emulsifier, the concentration of PVA in the solution, but especially by the shearing during the emulsion.
• the particle size of the droplets is related to the physical parameters of the solution by the Weber equation.
• the interfacial energy is likely to vary widely. At low concentrations, it is stable, but when the concentration increases, it decreases logarithmically to reach a limit value at high concentrations. In the PVA / Hexadecane system, the concentrations of between 1 and 10% are sufficiently high to reach an interfacial energy value of the order of 0.6 mN / m.
• the viscoelastic strength of the dispersed phase is one of the forces that prevents fragmentation of the droplets.
• the viscosity of the solution is a direct measure of the viscoelastic force of the fluid. Increasing the viscosity of the dispersed phase requires greater shear forces to prevent coalescence of the particles. Thus, obtaining a fine and stable emulsion is obtained when the ratio of viscosities is close to 1, or for a PVA concentration of less than 10%.
• Table 4 illustrates the ratio of the dispersed phase / continuous phase viscosities. The viscosities of the different solutions were carried out at room temperature using a Brookfield viscometer at 20 rpm at 20 ° C. WO 2006/064099 - 15 -
• This emulsion step is carried out at ambient temperature and at 13,500 rpm, making sure to obtain particles of average particle size comparable to the first solution.
• Obtaining a microgel during the mixing of emulsions E1 and E2 is related to the modification of the PVA network in water.
• the stability of the polymer is ensured by the existence of intra- and intermolecular hydrogen bonds.
• the presence of salt in high concentration will modify the hydration of the PVA chains, until precipitation of these.
• the introduction of large quantities of ions into the medium and the existence of strong intermolecular bonds are responsible for the destruction of the PVA / water network by the rupture of the hydrogen bonds between the hydroxyl groups of the polymer chains.
• microspheres comprising inorganic compounds without phase change, for example phosphate salts
• the introduction of the salt is also likely to cause the formation of hydrogen bonds, in small quantities, between the phosphate and the hydroxyl groups PVA, allowing in a first time to stabilize the network in gel form.
• the coacervation of the polymer in the solution then results directly from the modification of the polymer-polymer, polymer-solvent and polymer-ion interactions.
• Example 7 Cross-linking of the microgel by the MDI.
• microparticles in gel form tends to destabilize the solution during final encapsulation by the aminoplast membrane. Then, to avoid any phenomenon of coalescence and aggregation, the chemical crosslinking of the gel was chosen to obtain solid particles.
• the PVA is easily crosslinkable in an aqueous medium by the introduction of an aldehyde; being in an organic medium, the possibility of establishing polyurethane bonds by the action of MDI (4,4'-diisocyanate-o-diphenylmethane) on PVA was studied.
• the MDI previously dispersed in a little paraffin, is added dropwise using a burette, with vigorous stirring at 50 ° C.
• the salt microspheres are kept in dispersion in paraffin by mechanical stirring.
• the step of forming microcapsules and an aminoplast membrane of the process for synthesizing multinuclear microcapsules comprises the following operations: vii) introducing into a mixer a composition D comprising an aqueous phase containing an aqueous solution of aminoplast prepolymer and a surfactant, for example Tween® 20, and a continuous phase comprising the microspheres of inorganic compound in dispersion; viii) operate the mixer at room temperature at a speed of about 10,500 rpm for about 15 minutes until a stable emulsion E3 is obtained; ix) increase the temperature of the emulsion E3 to about 55 ° C and adjust the mixer speed to about 400 rpm for about 4 hours to obtain microcapsules.
• a composition D comprising an aqueous phase containing an aqueous solution of aminoplast prepolymer and a surfactant, for example Tween® 20, and a continuous phase comprising the microspheres of inorganic compound in dispersion
• the method also comprises steps of filtering, washing and drying the microcapsules obtained in step ix.
• microcapsules show the presence of a bimodal size distribution, the first of a mean diameter of about one micrometer and the second of 5 microns.
• the difference in particle size is probably related to the presence or absence of salt microspheres in the microcapsules. Indeed, when . 1? _
• microcapsules have a diameter of between 1 and 10 microns.
• the particles obtained do not seem perfectly spherical and their walls are granular.
• optical micrograph obtained (FIG. 16 appended showing an optical micrograph (X 64) of the microcapsules) suggests the presence of small particles inside the microcapsules.
• the multinucleic microcapsules comprise at least one organic compound surrounded by microspheres comprising at least one inorganic compound, said microspheres being bonded together by the aminoplast resin.
• the dispersion of the microcapsules in a cyclohexane solution allowed the selection of large particles, which under the effect of mechanical pressure, opened.
• the SEM observations of these particles (appended FIG. 17 illustrating two SEM images (X 5000 and X 6000) of the microcapsules after rupture of the membrane) actually show the production of microcapsules coated with a ring of microspheres.
• microspheres are bonded together by the aminoplast resin 60 thus forming a paraffin encapsulating ring (wall) 70 (references are given with reference to FIG. 14).
• the aminoplast resin 60 thus forming a paraffin encapsulating ring (wall) 70
• the inorganic compound 40 contained within the PVA / MDI membrane microspheres 50 surrounding the organic compound 20 is comprised of phosphate salts ( Figure 14). The SEM observations of these particles (FIG.
• the DSC analyzes of these microcapsules reveal a phase change enthalpy of between 170 and 180 J / g, the corresponding melting and crystallization temperatures of 16 ° C. and 15 ° C. are relative to the presence of hexadecane ( Figure 18).
• the enthalpies are of the order of 150 to 160 J / g. Comparing this energy balance with that of paraffin alone, an encapsulation yield of 67.5% by weight is obtained, so that all the paraffin introduced is found to be microencapsulated.
• thermograms of the microcapsules with those of the hexadecane (appended FIG. 20) also makes it possible to demonstrate the increase in the thermal window of the microencapsulated paraffin fusion by a factor of 1.5. Given the absence of a melting peak relative to the salt hydrate, it can be assumed that the presence of these microspheres in - -
• the membrane significantly modifies the distribution of heat exchanges within the particles.
• the replacement of hexadecane by eicosane does not modify the appearance of the phenomenon, only the phenomena related to the phase change of the paraffins are modified on the thermogram (appended FIG. 21).
• Thermogravimetric analysis of the microcapsules, at 10 ° C./min and under nitrogen (FIG. 22 appended) shows a loss of mass of 73.5% attributable to the presence of paraffin and also to the water contained in the particles, since its degradation begins before that of paraffin.
• the salt / PVA / MDI complex forms a structure capable of storing energy by latent heat.
• composition B comprises two phases: a liquid phase containing an inorganic compound, for example a salt hydrate or phosphate salts and water, in a proportion of 5: 1 and a continuous phase containing paraffin, and a mixture surfactants at 5% by volume; it is characterized in that the ratio by volume aqueous phase - continuous phase is from 1 to 4.
• composition C comprising two phases: an aqueous phase containing an aqueous solution of PVA and a continuous phase containing a paraffin, is characterized by a mass concentration PVA less than 10%.
• Composition D comprising: a dispersion of microcapsules containing salt in paraffin, an aqueous solution containing an aminoplast prepolymer and a surfactant such as Tween® 20, is characterized in that the aminoplast prepolymer is about 30% by weight, the surfactant is about 5% by weight and the pH is about 3.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Dispersion Chemistry (AREA)
• Textile Engineering (AREA)
• Physics & Mathematics (AREA)
• Combustion & Propulsion (AREA)
• Thermal Sciences (AREA)
• Materials Engineering (AREA)
• Manufacturing Of Micro-Capsules (AREA)

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  • 2004-12-14 FR FR0413289A patent/FR2879112B1/fr not_active Expired - Fee Related
• 2005
  • 2005-11-30 US US11/792,710 patent/US20090291309A1/en not_active Abandoned
  • 2005-11-30 EP EP05823085A patent/EP1838429A1/de not_active Withdrawn
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