Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/02—Organic and inorganic ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/43—Compounds containing sulfur bound to nitrogen
  • C08K5/44—Sulfenamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
  • B60C1/0016—Compositions of the tread
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/06—Sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
  • C08K5/40—Thiurams, i.e. compounds containing groups

Definitions

• the field of the present invention is that of rubber compositions based on highly saturated diene elastomer intended for use in a tire, in particular in its tread.
• the level of rigidity of a rubber composition is defined by the degree of vulcanization of the elastomer which depends on both the vulcanization kinetics and the residence time of the rubber composition in the press. cooking. It is known that the rubber compositions continue to bake, even after they have left the baking presses. Continued cooking outside the presses is all the more important as the rubber composition is in the form of a solid object. If the stiffening of the rubber composition is not sufficient at the exit of the press, the viscosity of the rubber composition then allows the formation of bubbles within the rubber composition when the baking continues outside the press .
• the formation of bubbles within the rubber composition represents homogeneity defects in the rubber composition and can lead to a decrease in the endurance of the tire containing the rubber composition. It is therefore desirable that, at the end of cooking in the press, the rubber composition has reached a rigidity sufficient to prevent the formation of bubbles.
• the highly saturated diene elastomers which contain at least 50% by mole of ethylene unit have the drawback of vulcanizing according to slower kinetics than the highly unsaturated diene elastomers which contain more than 50% by mole of diene units.
• Longer residence times in the baking presses are therefore necessary to vulcanize the rubber compositions containing the highly saturated diene elastomers, especially if it is desired to avoid the bubbling phenomena mentioned above.
• the lower reactivity of highly saturated diene elastomers with regard to vulcanization therefore results in a longer press occupation time by rubber composition and therefore longer production cycles, which has the effect of reducing the productivity of tire manufacturing sites.
• the Applicant has found a rubber composition which makes it possible to respond to this concern.
• a first subject of the invention is a rubber composition based at least on a highly saturated diene elastomer, on a carbon black and on a vulcanization system comprising sulfur and a vulcanization accelerator,
• the highly saturated diene elastomer being a copolymer of ethylene and of a 1,3-diene containing ethylene units which represent at least 50 mol% of the monomer units of the copolymer,
• the level of the highly saturated diene elastomer in the rubber composition being at least 50 phr
• the vulcanization accelerator being a mixture of a primary accelerator and a secondary accelerator
• the mass ratio between the quantity of secondary accelerator and the total quantity of accelerators is less than 0.7, the total quantity of accelerators being the sum of the mass quantity of the primary accelerator and the mass quantity of the accelerator secondary in rubber composition,
• Another object of the invention is a tire which comprises a rubber composition in accordance with the invention.
• any range of values designated by the expression “between a and b” represents the range of values greater than “a” and less than “b” (that is, limits a and b excluded) while any range of values designated by the expression “from a to b” means the range of values ranging from “a” to "b” (that is to say including the strict limits a and b).
• the abbreviation “pce” means parts by weight per hundred parts of elastomer (of the total elastomers if several elastomers are present). In the present application, the mass ratios and the mass ratios between various constituents of the rubber composition are calculated from the rates or quantities of the constituents expressed in phr.
• composition based on
• a composition comprising the mixture and / or the in situ reaction product of the various constituents used, some of these basic constituents (for example the elastomer, the filler or the constituents of the vulcanization system or other additive conventionally used in a rubber composition intended for the manufacture of tires) being capable of, or intended to react with each other, at least in part, during the various phases of manufacture of the composition intended for the manufacture of tires.
• the expression "all of the monomer units of the elastomer” or “all of the monomer units of the elastomer” means all of the repeating constituent patterns of the elastomer which result from the insertion of the monomers in the elastomer chain by polymerization. Unless otherwise indicated, the contents of a monomer unit or repeating unit in the highly saturated diene elastomer are given in molar percentage calculated on the basis of all the monomer units of the elastomer.
• the compounds mentioned in the description can be of fossil origin or bio-based. In the latter case, they can be, partially or totally, from biomass or obtained from renewable raw materials from biomass. Are concerned in particular elastomers, plasticizers, fillers ...
• the elastomer useful for the purposes of the invention is a highly saturated, preferably statistical, diene elastomer which comprises ethylene units resulting from the polymerization of ethylene.
• ethylene unit refers to the motif - (CH2-CH2) - resulting from the insertion of ethylene into the elastomer chain.
• the highly saturated diene elastomer is rich in ethylene unit, since the ethylene units represent at least 50 mol% of all the monomer units of the elastomer.
• the highly saturated diene elastomer comprises at least 65 mol% of ethylene unit.
• the ethylene units preferably represent at least 65% by mole of all the monomer units of the highly saturated diene elastomer.
• the highly saturated diene elastomer comprises from 65% to 90 mol% of ethylene unit, molar percentage calculated on the basis of all the monomer units of the highly saturated diene elastomer.
• the highly saturated diene elastomer being a copolymer of ethylene and of a 1,3-diene also comprises 1,3-diene units resulting from the polymerization of a 1,3-diene.
• 1,3-diene unit refers to the units resulting from the insertion of 1,3-diene by a 1,4 addition, a 1,2 addition or a 3,4 addition in the case isoprene.
• the 1,3-diene units are, for example, those of a 1,3-diene having 4 to 12 carbon atoms, such as 1,3-butadiene, isoprene, 1,3-pentadiene, an aryl- 1,3- butadiene.
• the 1,3-diene is 1,3-butadiene, in which case the highly saturated diene elastomer is a copolymer of ethylene and 1,3-butadiene, preferably random.
• the highly saturated diene elastomer useful for the needs of the invention can be obtained according to different synthesis methods known to those skilled in the art, in particular as a function of the targeted microstructure of the highly saturated diene elastomer. Generally, it can be prepared by copolymerization of at least one 1,3-diene, preferably 1,3-butadiene, and ethylene and according to known synthesis methods, in particular in the presence of a catalytic system comprising a metallocene complex.
• the highly saturated diene elastomer can also be prepared by a process using a catalytic system of the preformed type such as those described in documents WO 2017093654 A1, WO 2018020122 A1 and WO 2018020123 A1.
• the highly saturated diene elastomer in the rubber composition as defined in any one of claims 1 to 14 preferably contains units of formula (I) or units of formula (II).
• the presence of a saturated cyclic unit with 6 members, 1,2-cyclohexanediyle, of formula (I) in the copolymer can result from a series of very specific insertions of ethylene and 1,3-butadiene in the polymer chain during its growth.
• the highly saturated diene elastomer comprises units of formula (I) or units of formula (II)
• the molar percentages of the units of formula (I) and of the units of formula (II) in the highly saturated diene elastomer, respectively o and p preferably satisfy the following equation (eq. 1), more preferably the equation (eq. 2), o and p being calculated on the basis of all the monomer units of the highly saturated diene elastomer.
• the highly saturated diene elastomer useful for the needs of the invention can consist of a mixture of highly saturated diene elastomers which differ from one another by their microstructures or by their macrostructures.
• the level of the highly saturated diene elastomer in the rubber composition is at least 50 parts by weight per hundred parts of elastomer of the rubber composition (phr).
• the level of the highly saturated diene elastomer in the rubber composition varies in a range ranging from 80 to 100 phr. More preferably, it varies in a range from 90 to 100 phr.
• the essential characteristic of the vulcanization system useful for the needs of the invention is to include sulfur and a vulcanization accelerator.
• the sulfur level and the rate of the vulcanization accelerator in the vulcanization system are both strictly greater than 0 phr.
• the sulfur content in the rubber composition defined in any one of claims 1 to 15 is greater than 0.3 phr.
• the quantity of the vulcanization accelerator, ie the sum of the quantity of primary accelerator and the quantity of secondary accelerator, in the rubber composition defined in any one of claims 1 to 15 is at least 0.5 pce.
• Sulfur is typically provided in the form of molecular sulfur or a sulfur donor, preferably in molecular form. Sulfur in molecular form is also known as molecular sulfur.
• sulfur donor is understood to mean any compound which releases sulfur atoms, combined or not in the form of a polysulphide chain, capable of being inserted in the polysulphide chains formed during vulcanization and bridging the elastomer chains.
• the sulfur content in the rubber composition is preferably less than 1 phr, preferably between 0.3 and 1 phr.
• the sulfur content in the rubber composition is less than 0.95 phr, preferably between 0.3 phr and 0.95 phr.
• the sulfur content in the rubber composition is less than 0.8 phr, preferably between 0.3 phr and 0.8 phr.
• the vulcanization accelerator is a mixture of a primary accelerator and a secondary accelerator.
• the designation “a primary accelerator” designates a single primary accelerator or a mixture of primary accelerators.
• the designation “a secondary accelerator” denotes a single secondary accelerator or a mixture of secondary accelerators.
• the primary accelerator, whether in the form of a mixture or not, and the secondary accelerator, whether it is in the form of a mixture or not, therefore constitute the only accelerators of the rubber composition.
• the rates of primary accelerator and secondary accelerator in the vulcanization system are both strictly greater than 0 phr.
• accelerators of the sulfenamide types can be used as vulcanization accelerator (primary or secondary) as regards primary accelerators, such as thiurams, dithiocarbamates, dithiophosphates, thioureas and xanthates with regard to secondary accelerators.
• primary accelerators there may be mentioned in particular sulfenamide compounds such as N-cyclohexyl-2-benzothiazyl sulfenamide (“CBS”), N, N-dicyclohexyl-2-benzothiazyl sulfenamide (“DCBS”) , N-ter-butyl-2-benzothiazyl sulfenamide (“TBBS”), and mixtures of these compounds.
• CBS N-cyclohexyl-2-benzothiazyl sulfenamide
• DCBS N-dicyclohexyl-2-benzothiazyl sulfenamide
• TBBS N-ter-butyl-2-benzothiazyl sulfenamide
• the primary accelerator is preferably a sulfenamide, more preferably N-cyclohexyl-2-benzothiazyl sulfenamide.
• secondary accelerators there may be mentioned in particular thiuram disulphides such as tetraethylthiuram disulphide, tetrabutylthiuram disulphide (“TBTD”), tetrabenzylthiuram disulphide (“TBZTD”) and mixtures of these compounds .
• the secondary accelerator is preferably a thiuram disulfide, more preferably tetrabenzylthiuram disulfide.
• the vulcanization accelerator is a mixture of a sulfenamide and a thiuram disulfide.
• the vulcanization accelerator is advantageously a mixture of N-cyclohexyl-2-benzothiazyl sulfenamide and a thiuram disulfide, more advantageously a mixture of N-cyclohexyl-2-benzothiazyl sulfenamide and tetrabenzylthiuram disulfide.
• the mass ratio between the quantity of the secondary accelerator and the total quantity of accelerators is less than 0.7, the total quantity of accelerators being the sum of the mass quantity of the primary accelerator and the quantity mass of the secondary accelerator in the rubber composition.
• the mass rate or mass quantity of the secondary accelerator represents less than 70% by mass of the total quantity of accelerators.
• the mass ratio between the quantity of the secondary accelerator and the total quantity of accelerators is greater than 0.05, more particularly between 0.05 and 0.7.
• the mass ratio between the quantity of the secondary accelerator and the total quantity of accelerators is preferably less than 0.5, even more preferably less than or equal to 0.3.
• These preferential ranges make it possible to further optimize the compromise between the cohesion properties and the curing times in the press by very greatly reducing the duration in the press while maintaining good limit properties, even in the presence of a crack initiator in the rubber composition.
• the mass ratio between the sulfur content and the total amount of accelerators in the rubber composition is less than 1, preferably less than or equal to 0.7, more preferably less than 0.6.
• the use of such ratios makes it possible to obtain compositions with more improved cohesion properties.
• the sulfur content in the rubber composition is less than 1 phr and the mass ratio between the sulfur content and the total amount of accelerators in the rubber composition is less than 1.
• This double condition relating to the sulfur content and the mass ratio between the sulfur content and the total quantity of accelerators makes it possible to obtain compositions with an even stronger cohesion.
• the cohesion properties are all the more improved as the sulfur content and the mass ratio between the sulfur content and the total amount of accelerators are low and are in particular in the preferential ranges mentioned in claims 7 and 8 for the content of sulfur and claim 10 for the mass ratio between the sulfur content and the total quantity of accelerators.
• the vulcanization system can also comprise vulcanization activators such as metal oxides such as zinc oxide or fatty acids such as stearic acid.
• the rubber composition comprises a carbon black as a reinforcing filler.
• a reinforcing filler typically consists of nanoparticles whose average size (by mass) is less than a micrometer, generally less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 nm.
• carbon blacks all carbon blacks are suitable, in particular the blacks conventionally used in tires or their treads (so-called pneumatic grade blacks).
• ASTM grades the blacks N115, N134, N234, N326, N330, N339, N347, N375, N550, N683, N772).
• the carbon black is preferably a carbon black of the 100 or 200 series.
• the level of carbon black can vary to a large extent and is adjusted by a person skilled in the art according to the envisaged application of the rubber composition, in particular in the field of tires.
• the level of carbon black in the rubber composition is preferably between 25 phr and 65 phr.
• the rubber composition may have an insufficient level of reinforcement below 25 phr and may exhibit excessive hysteresis above 65 phr.
• the rubber composition useful for the needs of the invention may also comprise all or part of the usual additives usually used in elastomer compositions intended to be used in a tire, such as for example in a tire tread.
• additives are for example fillers such as silicas, aluminas, processing agents, plasticizers, pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, antioxidants.
• the rubber composition can be manufactured in suitable mixers, using two successive preparation phases according to a general procedure well known to those skilled in the art: a first working phase or thermo-mechanical kneading (sometimes referred to as a "non-phase”). productive ”) at high temperature, up to a maximum temperature between 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C, followed by a second phase of mechanical work (sometimes referred to as" productive phase ”) at a lower temperature, typically less than 110 ° C., for example between 40 ° C. and 100 ° C., the finishing phase during which the sulfur or the sulfur donor and the vulcanization accelerator are incorporated.
• a first working phase or thermo-mechanical kneading (sometimes referred to as a "non-phase”).
• productive at high temperature, up to a maximum temperature between 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C
• a second phase of mechanical work sometimes referred
• the first (non-productive) phase is carried out in a single thermomechanical step during which is introduced, into a suitable mixer such as a usual internal mixer, all the necessary constituents, the possible setting agents. in complementary and other miscellaneous additives, with the exception of sulfur and vulcanization accelerators.
• the total duration of the kneading, in this non-productive phase is preferably between 1 and 15 min.
• the sulfur and the vulcanization accelerator are then incorporated at low temperature, generally in a mixer. external such as a cylinder mixer; the whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
• the rubber composition can be calendered or extruded, preferably to form all or part of a profile of a tire tread.
• the tire another object of the invention, which comprises a rubber composition in accordance with the invention, preferably comprises the rubber composition in its tread.
• its tread the portion of which intended to be in contact with the road surface consists of all or part of a rubber composition according to the invention.
• the tire can be in the raw state (that is to say before the tire curing step) or in the cooked state (that is to say after the tire curing step).
• the tire is preferably a tire for a vehicle intended to carry heavy loads such as, for example, heavy goods vehicles, civil engineering vehicles.
• the microstructure of the elastomers is determined by 1 H NMR analysis, supplemented by 13 C NMR analysis when the resolution of the 1 H NMR spectra does not allow the allocation and quantification of all the species.
• the measurements are carried out using a BRUKER 500 MHz NMR spectrometer at frequencies of 500.43 MHz for the observation of the proton and 125.83 MHz for the observation of the carbon.
• an HRMAS 4mm z-grad probe is used for non-soluble elastomers but having the capacity to swell in a solvent. Spectra are acquired at rotational speeds from 4000Hz to 5000Hz.
• a liquid NMR probe is used to observe the proton and the carbon in decoupled mode from the proton.
• insoluble samples are done in rotors filled with the analyzed material and a deuterated solvent allowing the swelling, in general deuterated chloroform (CDCI3).
• the solvent used must always be deuterated and its chemical nature can be adapted by a person skilled in the art.
• the quantities of material used are adjusted so as to obtain spectra with sufficient sensitivity and resolution.
• the soluble samples are dissolved in a deuterated solvent (about 25 mg of elastomer in lmL), generally deuterated chloroform (CDCI3).
• the solvent or solvent mixture used must always be deuterated and its chemical nature can be adapted by a person skilled in the art.
• a single pulse sequence of 30 ° is used.
• the spectral window is adjusted to observe all of the resonance lines belonging to the molecules analyzed.
• the number of accumulations is adjusted in order to obtain a signal to noise ratio sufficient for the quantification of each pattern.
• the recycling time between each pulse is adapted to obtain a quantitative measurement.
• a 30 ° single pulse sequence is used with a proton decoupling only during acquisition to avoid the “Nuclear Overhauser” (NOE) effects and remain quantitative.
• the spectral window is adjusted to observe all of the resonance lines belonging to the molecules analyzed.
• the number of accumulations is adjusted in order to obtain a signal to noise ratio sufficient for the quantification of each pattern.
• the recycling time between each pulse is adapted to obtain a quantitative measurement.
• the force and the tear deformation are measured on a test specimen stretched at 500 mm / min to cause rupture of the test specimen.
• the tensile test piece consists of a rubber plate of parallelepiped shape, for example of thickness between 1 and 2 mm, length between 130 and 170 mm and width between 10 and 15 mm, the two lateral edges being each covered lengthwise with a cylindrical rubber bead (diameter 5 mm) allowing anchoring in the jaws of the traction machine.
• 3 very fine cuts of length between 15 and 20 mm are made using a razor blade, half-width and aligned lengthwise of the test piece, one at each end and one in the center of the test piece, before the start of the test.
• the force (N / mm) to be exerted to obtain the rupture is determined and the elongation at break is measured.
• the test was conducted in air, at a temperature of 100 ° C. High values reflect good cohesion of the rubber composition although having crack initiators.
• the elongation at break (AR%) and rupture stress (CR) tests are based on standard NF ISO 37 of December 2005 on a H2 type dumbbell test piece and are measured at a tensile speed of 500 mm / min.
• the elongation at break is expressed in% of elongation.
• the breaking stress is expressed in MPa. All these tensile measurements are carried out at 60 ° C. he
• the measurements are carried out at 150 ° C. with an oscillating chamber rheometer, according to standard DIN 53529 - part 3 (June 1983).
• the evolution of the rheometric torque as a function of time describes the evolution of the stiffening of the composition as a result of the vulcanization reaction.
• the measurements are processed according to DIN 53529 - part 2 (March 1983).
• Ti is the induction time, that is to say the time necessary for the start of the vulcanization reaction.
• T95 is the time necessary to reach a conversion of 95%, that is to say 95% of the difference between the minimum and maximum torques.
• the conversion rate constant K (expressed in min 1 ), of order 1, calculated between 30% and 80% conversion, is also measured, which makes it possible to assess the vulcanization kinetics.
• compositions thus obtained are then calendered either in the form of plates (thickness 2 to 3 mm) or of thin sheets of rubber for measuring their physical or mechanical properties, or extruded in the form of a tire tread.
• the elastomer (EBR) is prepared according to the following procedure:
• metallocene [ ⁇ Me SiFlu Nd (p-BH 4 ) Li (THF) ⁇ , the symbol Flu representing the fluorenyl group of formula CI 3 H 8 ] are introduced into a first Steinie bottle in a glove box.
• the catalytic solution is then introduced into the polymerization reactor.
• the temperature in the reactor is then increased to 80 ° C.
• the reaction starts by injecting a gaseous mixture of ethylene and 1,3-butadiene (80/20 mol%) into the reactor.
• the polymerization reaction takes place at a pressure of 8 bars.
• the proportions of metallocene and co-catalyst are respectively 0.00007 mol / L and 0.0004 mol / L.
• the polymerization reaction is stopped by cooling, degassing of the reactor and addition of ethanol.
• An antioxidant is added to the polymer solution.
• the copolymer is recovered by drying in a vacuum oven.
• the rubber compositions C5 to C11 are in accordance with the invention.
• the rubber compositions C12 and C13 are not in accordance with the invention, the ratio between the mass quantity of secondary accelerator and the sum of the mass quantity of primary accelerator and the mass quantity of secondary accelerator not being less than 0.7.
• the compositions C1 to C4 which do not contain a secondary accelerator are not in accordance with the invention.
• compositions C5 to C11 are those which exhibit the best compromise between the cohesion properties and the time for baking in the press.
• compositions C5 to CIO prove to be among the most advantageous both from the point of view of the cohesion properties and of the press cooking times.
• the composition C13, nonconforming, in which the secondary accelerator is the only accelerator in the rubber composition makes it possible to reduce the time for curing in the press, but this result is obtained at the expense of the cohesion properties.
• the non-conforming composition C12, in which the secondary accelerator represents more than 70% by mass of accelerator used also makes it possible to reduce the cooking time in press, but this result is also obtained at the expense of the cohesion properties.
• compositions C1 to C4 which do not conform, they have good cohesion properties, but these results are obtained at the expense of the cooking properties from a productivity point of view, since the cooking times in the press are much higher. .

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• Polymers & Plastics (AREA)
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• Engineering & Computer Science (AREA)
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• Compositions Of Macromolecular Compounds (AREA)
• Tires In General (AREA)

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• 2018
  • 2018-09-11 FR FR1858136A patent/FR3085684B1/fr active Active
• 2019
  • 2019-09-11 US US17/271,833 patent/US20210317287A1/en not_active Abandoned
  • 2019-09-11 CN CN201980059125.2A patent/CN112672890B/zh active Active
  • 2019-09-11 WO PCT/FR2019/052098 patent/WO2020053521A1/fr not_active Ceased
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