Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • 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
  • Y10T152/00—Resilient tires and wheels
  • Y10T152/10—Tires, resilient
  • Y10T152/10495—Pneumatic tire or inner tube
• • 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
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]

Definitions

• the present invention relates to "pneumatic" objects, i.e., by definition, objects that take their usable form when inflated with air or an equivalent inflation gas.
• the radially inner face has an airtight layer (or more generally any inflation gas) which allows the swelling and maintaining the pressure of the tire.
• airtight layer or more generally any inflation gas
• Its sealing properties enable it to guarantee a relatively low rate of pressure loss, making it possible to maintain the swollen bandage in normal operating condition for a sufficient duration, normally of several weeks or several months. It also serves to protect the carcass reinforcement from the diffusion of air from the interior space to the bandage.
• inner liner waterproof inner liner
• butyl rubber-based compositions have significant hysteretic losses, moreover over a wide temperature spectrum, a disadvantage which penalizes the rolling resistance of pneumatic tires.
• the present invention relates to a pneumatic object provided with an elastomer layer impervious to inflation gases, characterized in that said elastomer layer comprises at least, as majority elastomer, a thermoplastic block copolymer polystyrene and polyisobutylene and expanded thermoplastic microspheres.
• thermoplastic copolymer above Compared to a butyl rubber, the thermoplastic copolymer above has the major advantage, because of its thermoplastic nature, to be worked as such in the molten state (liquid) and thus to offer improved processability; such a copolymer makes it possible in particular to prepare very thin layers of tight layer, easily integrate relatively difficult or relatively fragile fillers such as thermoplastic microspheres, significantly reducing the risk of degradation of such charges.
• the invention particularly relates to pneumatic objects of rubber such as pneumatic tires, or inner tubes, in particular tubes for pneumatic tires.
• the invention relates more particularly to pneumatic tires intended to equip tourism-type motor vehicles, SUVs ("Sport Utility Vehicles"), two wheels (in particular motorcycles), planes, such as industrial vehicles such as vans, heavy goods vehicles (that is, metros, buses, road transport vehicles such as trucks, tractors, trailers, off-the-road vehicles such as agricultural or civil engineering vehicles) and other transport or handling vehicles.
• SUVs Sport Utility Vehicles
• two wheels in particular motorcycles
• planes such as industrial vehicles such as vans, heavy goods vehicles (that is, metros, buses, road transport vehicles such as trucks, tractors, trailers, off-the-road vehicles such as agricultural or civil engineering vehicles) and other transport or handling vehicles.
• the invention also relates to the use, for sealing the inflating gases of a pneumatic object, of a thermoplastic copolymer elastomer with polystyrene and polyisobutylene blocks and thermally expandable thermoplastic microspheres.
• any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term “from a to b” means the range from a to b (i.e., including the strict limits a and b).
• the pneumatic object of the invention has the essential feature of being provided with a gastight layer formed of an elastomer composition (or "rubber", both of which are considered in a known manner as synonyms) of the thermoplastic type, said layer or composition comprising at least, as majority elastomer, a thermoplastic copolymer elastomer with polystyrene and polyisobutylene blocks, expanded thermoplastic microspheres and optionally an extension oil and any other additives. All of these components are described in detail below.
• thermoplastic styrene elastomers are thermoplastic elastomers in the form of block copolymers based on styrene.
• thermoplastic polymers and elastomers consist in a known manner of rigid polystyrene blocks connected by flexible elastomer blocks, for example polybutadiene, polyisoprene or poly (ethylene / butylene). They are often triblock elastomers with two rigid segments connected by a flexible segment. The rigid and flexible segments can be arranged linearly, star or connected.
• These TPS elastomers may also be diblock elastomers with a single rigid segment connected to a flexible segment.
• each of these segments or blocks contains at least more than 5, usually more than 10 base units (e.g., styrene units and isoprene units for a styrene / isoprene / styrene block copolymer).
• base units e.g., styrene units and isoprene units for a styrene / isoprene / styrene block copolymer.
• polystyrene and polyisobutylene block copolymer is intended to mean any styrenic thermoplastic copolymer comprising at least one polystyrene block (that is to say one or more polystyrene blocks) and at least one polyisobutylene block. (ie one or more polyisobutylene blocks), to which other saturated or unsaturated blocks (e.g. polyethylene and / or polypropylene) and / or other monomer units (e.g. unsaturated dienes).
• TPS in the present application, is in particular chosen from the group consisting of styrene / isobutylene diblock copolymers (abbreviated as” SIB "), styrene triblock copolymers / isobutylene / styrene (abbreviated "SIBS”) and mixtures of these copolymers SIB and SIBS, by definition fully saturated.
• SIB styrene / isobutylene diblock copolymers
• SIBS styrene triblock copolymers / isobutylene / styrene
• TPS copolymer particularly SIB or SIBS
• SIB or SIBS provides the gastight layer with excellent sealing properties while significantly reducing hysteresis compared to conventional butyl rubber layers.
• the weight content of styrene in the TPS copolymer is between 5% and 50%.
• the thermoplastic nature of the elastomer may decrease significantly while above the maximum recommended, the elasticity of the seal layer may be affected.
• the styrene content is more preferably between 10% and 40%, in particular between 15 and 35%.
• styrene any styrene-based monomer, whether unsubstituted as substituted, should be understood in the present description; among the substituted styrenes may be mentioned, for example, methylstyrenes (for example ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, tert-butylstyrene) and chlorostyrenes (for example monochlorostyrene, dichlorostyrene).
• methylstyrenes for example ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, tert-butylstyrene
• chlorostyrenes for example monochlorostyrene, dichlorostyrene
• the glass transition temperature (Tg, measured according to ASTM D3418) of the TPS copolymer is less than -20 ° C., more preferably less than -40 ° C.
• Tg glass transition temperature
• a value of Tg higher than these minima can reduce the performance of the waterproof layer during use at very low temperatures; for such use, the Tg of the TPS copolymer is more preferably still lower than -50 ° C.
• the number-average molecular weight (denoted Mn) of the TPS copolymer is preferably between 30,000 and 500,000 g / mol, more preferably between 40,000 and 400,000 g / mol.
• Mn number-average molecular weight
• the cohesion between the chains of the elastomer may be affected, particularly because of a possible dilution of the latter by an extension oil.
• a mass that is too high can be detrimental to the flexibility of the gas-tight layer.
• a Mn value within a range of 50,000 to 300,000 g / mol is particularly well suited, especially to a use of the composition in a tire.
• the number-average molecular weight (Mn) of the TPS copolymer is determined in known manner by steric exclusion chromatography (SEC).
• SEC steric exclusion chromatography
• the sample is first solubilized in tetrahydrofuran at a concentration of about 1 g / l; then the solution is filtered on a 0.45 ⁇ m porosity filter before injection.
• the equipment used is a chromatographic chain "WATERS alliance”.
• the elution solvent is tetrahydrofuran, the flow rate 0.7 ml / min, the system temperature 35 ° C and the analysis time 90 min.
• a set of four WATERS columns in series, of trade names "STYRAGEL"("HMW7","HMW6E" and two "HT6E" is used.
• the injected volume of the solution of the polymer sample is 100 ⁇ l.
• the detector is a differential refractometer "WATERS 2410" and its associated software for the exploitation of chromatographic data is the “WATERS MILLENIUM” system.
• the calculated average molar masses relate to a calibration curve made with polystyrene standards.
• the TPS copolymer and the expanded thermoplastic microspheres may alone constitute the gas-tight elastomeric layer or may be associated in the elastomeric composition with other elastomers in a minor amount relative to the TPS copolymer.
• the TPS copolymer constitutes the majority elastomer by weight. Its level is then preferably greater than 70 phr, in particular within a range of 80 to 100 phr (as a reminder, "phr" means parts by weight per hundred parts of total elastomer, that is to say of the total of elastomers present in the composition forming the gas-tight layer).
• Such complementary elastomers, minority by weight could be, for example, diene elastomers such as natural rubber or synthetic polyisoprene, butyl rubber or thermoplastic elastomers other than styrenic, within the limit of the compatibility of their microstructures.
• Such complementary elastomers which are minor in weight, could also be other styrenic thermoplastic elastomers, whether of the unsaturated type as saturated (that is to say in known manner, provided or not with ethylenic unsaturations or double bonds carbon-carbon).
• unsaturated TPS elastomers there may be mentioned, for example, those comprising styrene blocks and diene blocks, in particular those chosen from the group consisting of styrene / butadiene block copolymers (SB) and styrene / isoprene block copolymers (IS).
• SB styrene / butadiene block copolymers
• IS styrene / isoprene block copolymers
• saturated TPS elastomers mention may be made, for example, of those selected from the group consisting of styrene / ethylene / butylene (SEB), styrene / ethylene / propylene (SEP), styrene / ethylene / ethylene / block copolymers.
• propylene (SEEP) styrene / ethylene / butylene / styrene (SEBS), styrene / ethylene / propylene / styrene (SEPS), styrene / ethylene / ethylene / propylene / styrene (SEEPS) and mixtures of these copolymers.
• the gas-tight layer is devoid of such complementary elastomers; in other words, the TPS copolymer, in particular SIB or SIBS, previously described is the only thermoplastic elastomer and more generally the only elastomer present in the elastomeric composition of the gas-tight layer.
• polystyrene and polyisobutylene block copolymers are commercially available, they can be implemented conventionally for TPS elastomers, by extrusion or molding, for example from a raw material available in the form of beads or granules. They are sold for example with regard to the SIB or SIBS by the company
• KANEKA under the name "SIBSTAR” (e.g. "Sibstar 103T”, “Sibstar 102T”, "Sibstar
• TPE elastomers were first developed for biomedical applications then described in various applications specific to TPE elastomers, as varied as medical equipment, parts for automobiles or household appliances, sleeves for electrical wires, sealing parts or elastics (see for example EP 1 431 343, EP 1 561 783, EP 1 566 405, WO 2005/103146).
• thermoplastic microspheres used here are well known, they are spherical, resilient particles composed of a thermoplastic polymer capsule containing a liquid and / or a gas depending on their state of expansion. They can be used in an unexpanded form (for example as a "blowing agent") or in an expanded form. In unexpanded form, their average diameter is generally in a range of 5 to 50 microns.
• the shells of these capsules are for example based on copolymers of acrylonitrile monomers, methyl methacrylate, vinylidene chloride; the liquid acting as swelling agent is typically an alkane (eg isobutane or isopentane).
• thermoplastic microspheres For more details on these thermoplastic microspheres, we can refer to the many technical documents available from their suppliers (see for example Expancel Technical Bulletin No. 40 entitled “Expancel® Microspheres -A Technical Presentation", published by Akzo Nobel the 24/07/2006).
• the level of thermoplastic microspheres foamed in the gas-tight layer is between 0.1 and 30 phr, preferably between 0.5 and 10 phr, particularly in a range of 1 to 8 phr.
• the desired technical effect may be insufficient while beyond the recommended maxima, there is a risk of embrittlement and loss of endurance of the layer, not to mention its increase in cost.
• thermoplastic microspheres are preferentially introduced in the initial state in unexpanded form. They are then foamed, in whole or in part, during the various mixing operations (with the TPS copolymer), of extrusion (of the elastomer composition forming the gas-tight layer) and / or of final cooking or vulcanization (by example of the tire), at the moment in fact when they reach a temperature sufficient for the expansion phase to be triggered.
• TPS copolymer in particular SIB or SIBS
• expanded thermoplastic microspheres previously described are sufficient on their own for the gas-tight function to be performed with respect to the pneumatic objects in which they are used.
• the gas-tight layer may also comprise, as a plasticizer, an extension oil (or plasticizing oil) whose function is to facilitate the implementation, particularly the integration into the pneumatic object by a lowering of the module and an increase in the tackifying power of the gas-tight layer, at the cost, however, of a certain loss of tightness.
• an extension oil or plasticizing oil
• extension oil preferably of a slightly polar nature, capable of extending and plasticizing elastomers, especially thermoplastics, may be used. At room temperature (23 ° C.), these oils, more or less viscous, are liquids (that is to say, as a reminder, substances having the capacity to eventually take on the shape of their container), as opposed to especially to resins that are inherently solid.
• the extender oil is chosen from the group consisting of polyolefinic oils (that is to say derived from the polymerization of olefins, monoolefins or diolefins), paraffinic oils, naphthenic oils (low or high viscosity), aromatic oils, mineral oils, and mixtures of these oils. More preferably, the extender oil is selected from the group consisting of polybutene oils, paraffinic oils and mixtures of these oils.
• Polybutene oils preferably polyisobutylene oils (abbreviated to "PIB"), which have demonstrated the best compromise of properties compared to the other oils tested, in particular paraffinic oils, are particularly used.
• PIB polyisobutylene oils
• polyisobutylene oils are sold in particular by the company UNIVAR under the name "Dynapak PoIy” (eg "Dynapak PoIy 190"), by BASF under the names “Glissopal” (eg “Glissopal 1000") or "Oppanol "(eg” Oppanol B 12 "), by INEOS Oligomer under the name” Indopol H1200 ".
• Paraffinic oils are sold for example by Exxon under the name "Telura 618" or by Repsol under the name "Extensol 51".
• the number-average molecular mass (Mn) of the extender oil is preferably between 200 and 25,000 g / mol, more preferably between 300 and 10,000 g / mol.
• Mn number-average molecular mass
• the molecular weight M n of the extension oil is determined by SEC, the sample being solubilized beforehand in tetrahydrofuran at a concentration of approximately 1 g / l; then the solution is filtered on a 0.45 ⁇ m porosity filter before injection.
• the equipment is the chromatographic chain "WATERS alliance”.
• the elution solvent is tetrahydrofuran, the flow rate is 1 ml / min, the temperature of the system is 35 ° C. and the analysis time is 30 minutes.
• the injected volume of the solution of the polymer sample is 100 ⁇ l.
• the detector is a differential refractometer "WATERS 2410" and its associated software for the exploitation of chromatographic data is the “WATERS MILLENIUM” system.
• the calculated average molar masses relate to a calibration curve made with polystyrene standards.
• an extender oil it is preferred that its level be greater than 5 phr, more preferably between 5 and 100 phr. Below the minimum indicated, the elastomeric layer or composition may have too high rigidity for certain applications while beyond the maximum recommended, there is a risk of insufficient cohesion of the composition and loss of tightness may be harmful depending on the application. For all these reasons, particularly for use of the airtight layer in a tire, it is preferred that the extender oil content be greater than 10 phr, especially between 10 and 90 phr, more preferably still than greater than 20 phr, in particular between 20 and 80 phr.
• the airtight layer or composition described above may furthermore comprise the various additives usually present in the airtight layers known to the man in the air. job.
• reinforcing fillers such as carbon black or silica, non-reinforcing or inert fillers, lamellar fillers that further improve the seal (eg phyllosilicates such as kaolin, talc, mica, graphite, clays or modified clays) may be mentioned.
• organo clays plasticizers other than the above-mentioned extension oils, protective agents such as antioxidants or antiozonants, anti-UV agents, coloring agents that can be advantageously used for coloring the composition, various agents for implementing or other stabilizers, or promoters capable of promoting adhesion to the rest of the structure of the pneumatic object.
• lamellar fillers in the gas-tight layer advantageously makes it possible to further reduce the coefficient of permeability (and therefore of increasing the seal) of the thermoplastic elastomer composition, without excessively increasing its modulus, which makes it possible to preserve the ease of integration of the sealing layer in the pneumatic object.
• Such fillers are generally in the form of plates, platelets, sheets or stacked sheets, with a more or less marked anisometry, whose average length is for example between a few microns and a few hundred microns. They can be used at variable weight rates according to the applications, for example greater than 20 phr, especially greater than 50 phr.
• the gas-tight composition could also comprise, still in a minority weight fraction relative to the TPS copolymer, polymers other than elastomers, such as, for example, thermoplastic polymers compatible with TPS elastomers.
• the layer or tight composition described above is a solid (at 23 ° C) and elastic compound, which is characterized in particular, thanks to its specific formulation, by a very high flexibility and very high deformability.
• pneumatic object It can be used as an airtight layer (or any other inflation gas, for example nitrogen) in any type of pneumatic object.
• pneumatic objects include pneumatic boats, balls or balls used for play or sport.
• an airtight layer in a pneumatic object, finished or semi-finished product, of rubber, especially in a tire for a motor vehicle such as a two-wheeled vehicle, tourism or industrial.
• Such an airtight layer is preferentially disposed on the inner wall of the pneumatic object, but it can also be completely integrated into its internal structure.
• the thickness of the airtight layer is preferably greater than 0.05 mm, more preferably between 0.1 mm and 10 mm, especially between 0.1 and 1.0 mm.
• the preferred thickness may be between 1 and 3 mm.
• the preferred thickness may be between 2 and 10 mm.
• the airtight composition described above has the advantage of having a significantly lower hysteresis, and thus of providing reduced rolling resistance to pneumatic tires, as demonstrated in the following embodiments.
• the density of the sealed layer is less than 1 g / cm 3 , more preferably less than 0.9 g / cm 3 ; it can be in many cases less than 0.8 g / cm 3 .
• the gas-tight elastomeric layer previously described is advantageously usable in pneumatic tires of all types of vehicles, in particular passenger vehicles or industrial vehicles such as heavy goods vehicles.
• the single appended figure shows very schematically (without respecting a specific scale), a radial section of a tire according to the invention for a passenger vehicle.
• This tire 1 has a crown 2 reinforced by a crown reinforcement or belt 6, two sidewalls 3 and two beads 4, each of these beads 4 being reinforced with a rod 5.
• the crown 2 is surmounted by a tread represented in this schematic figure.
• a carcass reinforcement 7 is wound around the two rods 5 in each bead 4, the upturn 8 of this armature 7 being for example disposed towards the outside of the tire 1 which is shown here mounted on its rim 9.
• the carcass reinforcement 7 is in known manner constituted of at least one sheet reinforced by so-called "radial” cables, for example textile or metal, that is to say that these cables are arranged substantially parallel to each other and s' extend from one bead to the other so as to form an angle of between 80 ° and 90 ° with the median circumferential plane (plane perpendicular to the axis of rotation of the tire which is located halfway between the two beads 4 and goes through the middle of the crown frame 6).
• radial cables for example textile or metal
• the inner wall of the tire 1 comprises an airtight layer 10, for example of thickness equal to about 1.1 mm, on the side of the internal cavity 11 of the tire 1.
• This inner layer covers the entire inner wall of the tire, extending from one side to the other, at least to the level of the rim hook when the tire is in the mounted position. It defines the radially inner face of said tire intended to protect the carcass reinforcement from the diffusion of air coming from the space 1 1 inside the bandage. It allows inflation and pressure maintenance of the tire; its sealing properties must enable it to guarantee a relatively low rate of pressure loss, to maintain the swollen bandage, in normal operating condition, for a sufficient duration, normally of several weeks or several months.
• thermoplastic elastomer composition comprising the following components:
• SIBS elastomer a single SIBS elastomer ("Sibstar 102T" with a styrene content of about 15%, a Tg of about -65 ° C and an average molecular weight Mn of about 90,000 g / mol); 2.5 parts of expanded thermoplastic microspheres (Expancel ® 09 Idul 40) per 100 parts by weight of elastomer SIBS (2.5 phr);
• Layer 10 was prepared as follows.
• the mixture of the three constituents (SIBS, thermoplastic microspheres and PIB) was made conventionally, using a twin-screw extruder (LfD equal to about 40), at a temperature typically above the melting temperature of the composition (about 190 ° C).
• the extruder used had a feed (hopper) for the SIBS, another feed (hopper) for the thermoplastic microspheres (powdered, in unexpanded form) and a pressurized liquid injection pump for the polyisobutylene extension oil ; it was provided with a die for extruding the product to the desired dimensions.
• the tire provided with its airtight layer (10) as described above can be made before or after vulcanization (or cooking).
• the airtight layer is simply conventionally applied to the desired location, for formation of the layer 10. Vulcanization is then performed conventionally.
• An advantageous manufacturing variant for those skilled in the tire industry, will for example consist in a first step of laying the airtight layer directly on a manufacturing drum in the form of a flat tire. a layer of suitable thickness, before covering the latter with the rest of the structure of the tire, according to manufacturing techniques well known to those skilled in the art.
• the sealing layer is applied inside the baked tire by any appropriate means, for example by gluing, extrusion, spraying or else extrusion / blowing of a tire. film of appropriate thickness.
• sealing properties were first analyzed on test specimens of butyl rubber-based compositions, on the one hand, and thermoplastic expanded SIBS and microspheres on the other hand (with and without oil).
• extension PIB for the second composition based on SIBS and microspheres).
• a rigid wall permeameter was used, placed in an oven (temperature of 60 ° C. in the present case), provided with a pressure sensor (calibrated in the range of 0 to 6 bar) and connected to a tube equipped with an inflation valve.
• the permeameter can receive standard specimens in the form of a disc (for example 65 mm diameter in this case) and with a uniform thickness of up to 3 mm (0.5 mm in the present case).
• the pressure sensor is connected to a National Instruments data acquisition card (four-channel analog 0-10V acquisition) which is connected to a computer performing a continuous acquisition with a frequency of 0.5 Hz (1 point every two seconds).
• the coefficient of permeability (K) is measured from the linear regression line (average over 1000 points) giving the slope ⁇ of the pressure loss, through the tested test piece, as a function of time, after stabilization of the system, that is to say obtaining a steady state during which the pressure decreases linearly with time.
• the composition comprising only the SIBS copolymer and the expanded thermoplastic microspheres, that is to say without extension oil or other additive, had a very low permeability coefficient, substantially equal to that of the usual composition based on butyl rubber, for the same thickness. This is already a remarkable result for such a composition.
• an extension oil advantageously facilitates the integration of the elastomeric layer in the pneumatic object, by a lowering of the module and an increase in the tackifiant power of the latter.
• pneumatic tires according to the invention of the type for passenger vehicle (size 195/65 Rl 5), were manufactured; their inner wall was covered by an airtight layer (10) with a thickness of 1.1 mm
• pneumatic tires according to the invention were compared to control tires (Michelin "Energy 3" brand) comprising a conventional air-tight layer of the same thickness, based on butyl rubber.
• the rolling resistance of pneumatic tires was measured on a steering wheel according to ISO 87-67 (1992).
• the pneumatic tires of the invention have a very significant and unexpectedly reduced rolling resistance for those skilled in the art, of nearly 4% compared with the control tires.
• the gas-tight layer of the pneumatic object of the invention not only has excellent sealing properties, but also a density and a hysteresis which are both reduced compared to butyl rubber-based layers. .
• the invention thus offers tire designers the opportunity to reduce the fuel consumption of motor vehicles equipped with such tires, while reducing the density of the sealing layers.

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