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    • 专利摘要:
    Multi-composite reinforcement (R1, R2) with improved mechanical properties, comprising at least: - one or more glass-resin composite monofilaments (10) comprising glass filaments (101) embedded in a thermoset resin (102) whose glass transition temperature Tgi is greater than 150 ° C; - Individually covering said single-core, each single-core or collectively several single strand, a layer of a thermoplastic material (12) whose glass transition temperature denoted Tg2 is greater than 20 ° C. Multilayer laminate comprising such a multi-composite reinforcement. Bandages, pneumatic or non-pneumatic, reinforced with such a multi-composite reinforcement or multilayer laminate.
    公开号:FR3015363A1
    申请号:FR1363019
    申请日:2013-12-19
    公开日:2015-06-26
    发明作者:Antonio Delfino
    申请人:Michelin Recherche et Technique SA Switzerland ；Compagnie Generale des Etablissements Michelin SCA；Michelin Recherche et Technique SA France；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The field of the present invention is that of composite reinforcements and multilayer laminates that can be used in particular for the reinforcement of semi-finished products or of finished articles made of rubber such as tires for vehicles, pneumatic or non-pneumatic type. It relates more particularly to single-strand composite reinforcements of the type "CVR" (abbreviated Glass-Resin Composite) with high mechanical and thermal properties, comprising unidirectional continuous multifilament glass fibers embedded in a thermoset resin and particularly usable as reinforcing elements of these bandages. 2. STATE OF THE ART Band designers have long been in search of "reinforcements" (elongated reinforcing elements) of the textile or composite type, with low density, which can advantageously and effectively substitute for conventional metal wires or cables, in particular to reduce in particular the weight of these bandages and also to overcome any corrosion problems. Thus, patent application EP 1,167,080 (or US Pat. No. 7,032,637) has already described a CVR monofilament having high mechanical properties, comprising unidirectional continuous glass fibers impregnated in a vinyl ester-type crosslinked resin. This CVR monofilament has, besides a high compression breaking stress, greater than its extension tensile stress, an elongation at break of the order of 3.0 to 3.5% and an initial modulus in extension of at least 30 GPa; its thermoset resin has a Tg (glass transition temperature) greater than 130 ° C and an initial module in extension of at least 3 GPa.
    [0002] Thanks to the above properties, this application EP 1 167 080 has shown that it was advantageously possible to substitute for steel cables such CVR monobrins, arranged in particular under the tread in parallel sections, as new elements. reinforcement of pneumatic tire belts, thereby significantly reducing the tire structure. Experience has shown, however, that the CVR single strands described in the above patent applications can be further improved, particularly for their use in vehicle tires.
    [0003] In particular, it has been found, in an unexpected manner, that these CVR monobrins of the prior art, when used as reinforcements of belts of certain pneumatic tires, could undergo a certain number of compression breaks, by a visible collapse of their structure, during the manufacture-even of these bandages, in particular during the conformation step and / or the final step of baking in mold of these bandages which is known to be conducted under high pressure and a very high temperature, typically greater than 160 ° C. 3. BRIEF DESCRIPTION OF THE INVENTION While continuing their research, the Applicants have discovered a new composite reinforcement, based on single-strand CVR, whose properties in compression, flexion or transverse shear are significantly improved, particularly at elevated temperatures. , compared to those of single-strand CVR of the prior art. Thus, according to a first object, the present invention relates (with reference to appended FIGS. 1 and 2) to a multi-composite reinforcement (R1, R2) comprising at least: one or more single-strand (s) (10) made of composite glass-glass resin (abbreviated "CVR") comprising glass filaments (101) embedded in a thermoset resin (102) whose glass transition temperature denoted Tgi is greater than 150 ° C; - Individually covering said single-core, each single-core or collectively several single strand, a layer of a thermoplastic material (12) whose glass transition temperature denoted Tg2 is greater than 20 ° C. Moreover, the thermoplastic and therefore hot melt nature of the material covering each single-strand CVR, very advantageously makes it possible to manufacture, as it were by "bonding or thermal assembly", a wide variety of multi-composite reinforcements (multi-stranded) having different shapes and straight sections, this by at least partial melting of the covering material, then cooling of all strands sheathed thermoplastic material once they arranged together, arranged appropriately. The invention also relates to any multilayer laminate comprising at least one multi-composite reinforcement according to the invention, disposed between and in contact with two layers of rubber composition, in particular diene.
    [0004] The invention also relates to the use of a multi-composite or multilayer laminate reinforcement according to the invention, as reinforcing element for semi-finished products or finished articles of rubber such as tires, pneumatic or non-pneumatic. The invention also relates to these semi-finished products, rubber articles and bandages themselves, both in the raw state (that is to say before cooking or vulcanization) and in the cooked state (after cooking) . The bandages of the invention, in particular, may be intended for motor vehicles of the tourism type, 4x4, "SUV" (Sport Utility Vehicles), but also to industrial vehicles chosen from light trucks, "heavy vehicles" - ie , metro, bus, road transport equipment (trucks, tractors, trailers), off-the-road vehicles -, agricultural or civil engineering machinery, airplanes, other commercial vehicles for transport or handling. The multi-composite reinforcement and the multilayer laminate of the invention are particularly useful as reinforcing elements in crown reinforcement (or belts) or in carcass reinforcement of pneumatic tires, as described in particular in documents EP 1 167 080 or US 7,032,637 cited above. They could also be present in the bead area of such bandages. The multi-composite reinforcement of the invention is also advantageously usable, because of its low density and its properties in compression, flexion and transverse shear which are improved, as reinforcing element in tires or non-pneumatic type flexible wheels. that is, structurally supported (without internal pressure). Such tires are well known to those skilled in the art (see, for example, EP 1 242 254 or US Pat. No. 6,769,465, EP 1 359 028 or US Pat. No. 6,994,135, EP 1 242 254 or US Pat. No. 6,769,465), US Pat. 194, WO 00/37269 or US 6,640,859, WO 2007/085414, WO 2008/080535, WO 2009/033620, WO 2009/135561, WO 2012/032000); when they are associated with any rigid mechanical element intended to ensure the connection between the flexible tire and the hub of a wheel, they replace the assembly constituted by the tire, the rim and the disc as known on most current road vehicles.
    [0005] The invention as well as its advantages will be readily understood in the light of the detailed description and the following exemplary embodiments, as well as FIGS. 1 to 9 relating to these examples which schematize (without respecting a specific scale): P10- 3189 - 4 - - cross-section, a CVR (10) single-core used in a multi-composite reinforcement according to the invention (Figure 1); in cross-section, two examples (R-1 and R-2) of multi-composite reinforcements in accordance with the invention (FIG 2a and FIG 2b); in cross-section, another example (R-3) of multi-composite reinforcement according to the invention (FIG 3); - In cross section, another example (R-4) of multi-composite reinforcement according to the invention (Figure 4); - In cross-section, another example (R-5) of multi-composite reinforcement according to the invention (Figure 5); - In cross section, another example (R-6) of multi-composite reinforcement according to the invention (Figure 6); - In cross section, an example (20) of multilayer laminate according to the invention comprising a multi-composite reinforcement according to the invention (R-7) itself embedded in a diene rubber matrix (Figure 7); a device that can be used for manufacturing a CVR monofilament (10) that can be used as the basic constituent element of a multi-composite reinforcement according to the invention (FIG. in radial section, an example of a pneumatic tire according to the invention, incorporating a multi-composite reinforcement and a multilayer laminate according to the invention (FIG 9). 4. DETAILED DESCRIPTION OF THE INVENTION In the present application, unless expressly indicated otherwise, all the percentages (%) indicated are percentages by weight. 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 expression "from a to b" means the range from a to b (i.e., including the strict limits a and b). The invention therefore relates to a reinforcement of the multi-composite type, in other words a composite composite, used in particular for the reinforcement of rubber articles such as tires for vehicles, whose essential characteristics include at least: one or more CVR monofilaments comprising glass filaments embedded in a thermoset resin whose glass transition temperature denoted Tgi is greater than 150 ° C .; P10-3189 - 5 - individually covering said single strand, each single strand or collectively several single-strand, a layer of a thermoplastic material whose glass transition temperature denoted Tg2 is greater than 20 ° C.
    [0006] In other words, the multi-composite reinforcement of the invention comprises a single or several monofilament (s) or CVR yarn (s), each yarn or monofilament in CVR being covered (individually or collectively) by at least a layer of thermoplastic material. It has been found that the presence of this sheath, which is a layer of thermoplastic material, gives the CVR monofilament endurance properties in compression, flexion or transverse shear (perpendicular to the axis of the single-spindle) which are notably improved, in particular in a high temperature (typically higher than 150 ° C), compared to those of the CVR single stranders of the prior art.
    [0007] The structure of the multi-composite reinforcement of the invention is described in detail below. The diameter DR of the multi-composite reinforcement of the invention is preferably between 0.3 and 3.0 mm, more preferably between 0.4 and 2.5 mm, in particular between 0.5 and 2.2 mm.
    [0008] This definition covers both multi-composite reinforcements of substantially cylindrical shape (circular cross-section) and multi-composite reinforcements of different shapes, for example oblong reinforcements (of more or less flattened shape) or of rectangular cross-section (y). included square). In the case of a non-circular straight section, DR is by convention the thickness of the multi-composite reinforcement.
    [0009] The elongation at break noted Ar of the multi-composite reinforcement, measured at 20 ° C., is preferably equal to or greater than 3.0%, more preferably equal to or greater than 3.5%. Its initial ER20 extension module, measured at 20 ° C., is preferably greater than 9 GPa, more preferably greater than 12 GPa.
    [0010] In this multi-composite reinforcement of the invention, the initial modulus in extension (EM20) of the or each CVR monofilament, measured at 20 ° C., is preferably greater than 30 GPa, more preferably greater than 33 GPa.
    [0011] The mechanical properties in extension above (Ar, ER20 and EM20) are measured in a known manner using an "INSTRON" traction machine of the type 4466 (BLUEHILL-2 software supplied with the traction machine), according to ASTM D 638, on multi-composite reinforcements or unreinforced raw CVR monobrins, that is to say unsized, or glued (that is to say ready to use), or extracts of the semi-finished product or rubber article that they reinforce. Before measurement, these multi-composite reinforcements or these single strands in CVR are subjected to a preliminary conditioning (storage for at least 24 hours in a standard atmosphere according to the European standard DIN EN 20139 (temperature of 20 ± 2 ° Humidity of 50 ± 5%.) The tested samples are pulled over an initial length of 400 mm at a nominal speed of 100 m / min, under a standard pretension of 0.5 cN / tex. an average of 10 measurements The elementary CVR monofilament constituting the multi-composite reinforcement of the invention can take any known shape, it can act for example of a cylindrical monofilament of large diameter (preferably greater than 100 μm). ), that is to say of substantially circular cross section, or of an elementary ribbon of substantially rectangular cross section (including square), it being understood that a layer of thermoplastic material covers individual uellement said single-core or each single-stranded.
    [0012] Typically, the glass filaments are present in the form of a single multifilament fiber or of several multifilament fibers (if they are several, they are preferably essentially unidirectional), each of which may comprise several tens, hundreds or even thousands of unit glass filaments. These very fine unitary filaments generally and preferably have a mean diameter of the order of 5 to 30 μm, more preferably 10 to 201 μm. By "resin" is meant here the resin as such and any composition based on this resin and comprising at least one additive (that is to say one or more additives). By "thermoset" or "cross-linked" resin, it is of course understood that the resin is hardened (photocured and / or thermoset), in other words that it is in the form of a network of three-dimensional bonds, in a state proper to so-called thermosetting polymers (as opposed to so-called thermoplastic polymers). The glass transition temperature denoted Tgi of the resin is preferably greater than 160 ° C., more preferably greater than 170 ° C., in particular greater than 180 ° C. According to a particularly preferred embodiment, the real part of the complex module (E'150) of each single-core CVR, measured at 150 ° C. by the DTMA method, is greater than 25 GPa, preferably greater than 30 GPa.
    [0013] According to another particularly preferred embodiment, for an optimized compromise of thermal and mechanical properties of the multi-composite reinforcement of the invention, the ratio E '(ro-25) / E'20 is greater than 0.85, preferably greater than 0.90, E'20 and E '(ro - 25) being the real part of the complex modulus of each monobrin measured by DMTA, respectively at 20 ° C and at a temperature expressed in ° C equal to (Tgi - 25 ). The measurements of E 'are carried out in a known manner by DMTA ("Dynamical Mechanical Thermal Analysis"), with a "DMA + 450" viscoanalyzer from ACOEM (France), using the "Dynatest 6.83 / 2010" software controlling flexural, tensile or torsional tests.
    [0014] According to this device, the three-point bending test does not allow in known manner to enter the initial geometric data for a single-strand circular section, we can only introduce the geometry of a rectangular section (or square). In order to obtain an accurate measurement of the module E 'for a CVR monofilament of diameter DM, the software therefore conventionally introduces a square section of side "a" having the same surface moment of inertia, in order to work with the same stiffness R tested test pieces. The well-known relations which follow must apply (E being the modulus of the material, Is the moment of inertia of surface of the body considered, and * the symbol of multiplication): R = Ecomposite * 'circular section = Ecomposite *' section square with: 'circular section = n * Dm4 / 64 and Square isect on = a4 / 12 It is easy to deduce the value of the side "a" of the equivalent square of the same surface inertia as that of the (circular) section of the single strand in CVR of diameter DM, according to the equation: a = Dm * (r1 / 6) 0.25.
    [0015] In the case where the cross-section of the tested sample is not circular (or rectangular), whatever its particular form, the same method of calculation will apply by determining beforehand the moment of inertia of surface Is on a straight cut of the tested sample. The test piece to be tested, generally of circular section and of DM diameter, has a length of 35 mm. It is arranged horizontally on two supports 24 mm apart. A repeated bending stress is applied perpendicularly to the center of the test piece, halfway between the two supports, in the form of a vertical displacement of amplitude equal to 0.1 mm (deformation therefore asymmetrical, the inside of the specimen being stressed only in compression and not in extension), at a frequency of 10 Hz.
    [0016] The following program is then applied: under this dynamic stress, the test piece is gradually heated from 25 ° C to 260 ° C with a ramp of 2 ° C / min. At the end of the test we obtain the measurements of the elastic modulus E ', the viscous modulus E "and the loss angle (δ) as a function of the temperature (where E' is the real part and E" the imaginary part of the complex module); it will be recalled here simply that the glass transition temperature can also be measured by DTMA, it corresponds to the maximum (peak) of tan (8). According to a preferred embodiment, the elastic deformation under flexural compression of each single strand CVR is greater than 3.0%, more preferably greater than 3.5%. According to another preferred embodiment, the compression stress under flexural compression is greater than 1000 MPa, more preferably greater than 1200 MPa. The above properties in bending compression are measured on the CVR single-strand as described in the above-mentioned application EP 1 167 080, by the so-called loop test method (D. Inclair, J. App Phys., 21, 380, 1950). In the present case, a loop is made which is gradually brought to the breaking point. The nature of the break, easily observable due to the large size of the section, immediately reveals that the CVR single-strand of the invention, biased in flexion until rupture, breaks on the side where the material is in extension, which is identified by simple observation. Since in this case the dimensions of the loop are important, it is possible at any time to read the radius of the circle inscribed in the loop. The radius of the circle inscribed just before the breaking point corresponds to the critical radius of curvature, denoted by Rc. The following formula then makes it possible to determine by calculation the critical elastic deformation denoted by Ec (where r corresponds to the radius of the single-strand, that is to say Dm / 2): Ec = r / (Rc + r) The breaking stress in compression under flexure noted csc is obtained by the calculation by the following formula (where E is the initial module in extension): = Ec * E Since, in the case of a single strand in CVR, the rupture of the loop appears in the part in extension, it is concluded that, in bending, the compressive breaking stress is greater than the extension tensile stress. Bending of a rectangular bar can also be performed by the so-called three-point method (ASTM D 790). This method also makes it possible to verify, visually, that the nature of the rupture is indeed in extension. According to a preferred embodiment, the breaking stress in pure compression is greater than 700 MPa, more preferably greater than 900 MPa, in particular greater than 1100 MPa. To avoid buckling of the CVR monofilament under compression, this quantity is measured according to the method described in the publication "Critical P10-3189 -9- compressive stress for continuous fiber unidirectional composites" by Thompson et al, Journal of Composite Materials, 46 ( 26), 3231-3245. Preferably, in each CVR monofilament, the alignment ratio of the glass filaments is such that more than 85% (% by number) of the filaments have an inclination with respect to the axis of the single strand which is less than 2.0 degrees more preferably less than 1.5 degrees, this inclination (or misalignment) being measured as described in the above publication by Thompson et al.
    [0017] Preferably, the weight ratio of glass fibers in the or each single strand CVR is between 60 and 80%, preferably between 65 and 75%. This weight ratio is calculated by comparing the title of the initial fiberglass to the CVR monofilament titre. The titre (or linear density) is determined on at least three samples, each corresponding to a length of 50 m, by weighing this length; the title is given in tex (weight in grams of 1000 m of product - as a reminder, 0, 111 tex equals 1 denier). Preferably, the density (or density) of the or each single-core CVR is between 1.8 and 2.1. It is measured (at 23 ° C) using a specialized scale of the Mettler Toledo company of the "PG503 DeltaRange" type; the samples, a few cm, are successively weighed in the air and immersed in ethanol; the device software then determines the average density over three measurements.
    [0018] The diameter DM of the or each single strand is preferably between 0.2 and 2.0 mm, more preferably between 0.3 and 1.5 mm, in particular between 0.4 and 1.2 mm. This definition covers both monobrins of substantially cylindrical shape (circular cross section) and monofilaments of different shape, for example oblong monofilaments (more or less oval, flattened shape) or rectangular cross section. In the case of a non-circular section, for example oval or rectangular, and unless otherwise specified, DM is conventionally the so-called clutter diameter, that is to say the diameter of the cylinder of imaginary revolution enveloping the single-strand in other words the diameter of the circle circumscribing its cross-section.
    [0019] The starting resin used is, by definition, a crosslinkable (ie curable) resin that can be crosslinked, cured by any known method, for example by UV (or UV-visible) radiation, preferably emitting in a spectrum of at least from 300 nm to 450 nm.
    [0020] As the crosslinkable resin, a polyester or vinyl ester resin, more preferably a vinyl ester resin, is preferably used. By "polyester" resin is meant in known manner an unsaturated polyester resin. Vinylester resins are well known in the field of composite materials.
    [0021] Without this definition being limiting, the vinylester resin is preferably of the epoxyvinylester type. It is more preferable to use a vinylester resin, in particular of the epoxide type, which is at least partly based (that is to say grafted on a structure of the type) novolac (also called phenoplast) and / or bisphenol, or preferably a vinylester resin containing novolac, bisphenolic, or novolak and bisphenol. A novolac-based epoxyvinylester resin (part in square brackets in formula I below), for example, in a known manner, corresponds to the following formula (I): (I) OH A bisphenol A-based epoxyvinylester resin (part in square brackets) of the formula (II) below) responds for example to the formula (the "A" recalling that the product is manufactured using acetone): A novolak and bisphenol type epoxyvinylester resin showed excellent results. By way of example of such a resin, mention may in particular be made of the vinylester resins "ATLAC 590" and "E-Nova FW 2045" from the company DSM (diluted with approximately 40% styrene) described in EP-A applications. - 1 074 369 and EP-A-1 174 250 above. Epoxyvinylester resins are available from other manufacturers such as for example AOC (USA - "VIPEL" resins). P10-3189 Preferably, in the multi-composite reinforcement of the invention, the initial modulus in extension of the thermoset resin, measured at 20 ° C, is greater than 3.0 GPa, more preferably greater than 3.5 GPa.
    [0022] The constituent CVR monobrins constituting the multi-composite reinforcement of the invention are well known, they can be prepared, and this preferably, according to known methods comprising at least the following steps: - making a rectilinear arrangement of fibers (filaments ) of glass and cause this arrangement in a direction of advancement: - in a vacuum chamber, degassing the arrangement of fibers by the action of the vacuum; - After leaving the vacuum chamber, after degassing, passing through a vacuum impregnation chamber so as to impregnate said fiber arrangement with a resin or thermosetting resin composition, in the liquid state, to obtain an impregnated containing the filaments glass and resin; - Passing said impregnated through a calibration die having a section of predefined surface and shape, to impose a form of single-core (eg a monofilament of round cross section or a ribbon of rectangular cross section); downstream of the die, in a UV irradiation chamber, polymerizing the resin under the action of UV; and then wound for intermediate storage the monobrin thus obtained.
    [0023] All the above steps (arrangement, degassing, impregnation, calibration, polymerization and final winding) are steps well known to those skilled in the art, as well as the materials (multifilament fibers and resin compositions) used; they have, for example, been described in applications EP-A-1 074 369 and EP-A-1 174 250.
    [0024] It will be recalled in particular that before any impregnation of the fibers, a degassing step of the fiber arrangement is preferably carried out by the action of the vacuum, in particular in order to reinforce the effectiveness of the subsequent impregnation and especially to guarantee the absence bubbles inside the final composite monofilament.
    [0025] After passing through the vacuum chamber, the glass filaments enter an impregnation chamber which is totally filled with impregnating resin, thus free of air: it is in this sense that this step can be described as impregnation of "vacuum impregnation". The resin (impregnating resin composition) preferably comprises a sensitive photo-initiator (reagent) with UV radiation above 300 nm, preferably between 300 and 450 nm. This photoinitiator is used at a preferred level of 0.5 to 3%, more preferably 1 to 2.5%. It may also comprise a crosslinking agent, for example at a level of between 5% and 15% (% by weight of impregnating composition).
    [0026] Preferably, this photoinitiator is of the family of phosphine compounds, more preferably a bis (acyl) phosphine oxide such as, for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ("Irgacure 819" from BASF) or a mono (acyl) phosphine oxide (for example "Esacure TPO" from the company Lamberti), such phosphine compounds that can be used in a mixture with other photoinitiators, for example photoinitiators of alpha-hydroxy ketone type such as for example dimethylhydroxyacetophenone (eg "Lamberti KL200") or 1-hydroxycyclohexyl-phenylketone (eg "Lamberti KS300"), benzophenones such as 2,4 , 6-trimethylbenzophenone (eg "Lamberti TZT Esacure") and / or thioxanthone derivatives such as for example isopropylthioxanthone (eg "Lamberti's Esacure ITX"). The so-called calibration die makes it possible, by virtue of a cross-section of determined dimensions, generally and preferably circular or rectangular, to adjust the proportion of resin with respect to the glass fibers while imposing on the impregnated form and thickness targeted for the single-core. The polymerization or UV irradiation chamber then has the function of polymerizing, crosslinking the resin under the action of UV. It comprises one or preferably several UV irradiators, constituted for example each by a UV lamp having a wavelength of 200 to 600 nm. The final CVR monofilament thus formed through the UV irradiation chamber, in which the resin is now in the solid state, is then harvested, for example, on a receiving coil on which it can be wound over a very great length.
    [0027] Between the sizing die and the final receiving medium, it is preferred to maintain the tensions experienced by the glass fibers at a moderate level, preferably between 0.2 and 2.0 cN / tex, more preferably between 0.3 and 1.5 cN / tex; to control this, one can for example measure these voltages directly at the output of the irradiation chamber, using appropriate tensiometers well known to those skilled in the art. Finally, a finished composite block of manufacture is obtained, as schematized in FIG. 1, in the form of a continuous CVR monofilament (10) of diameter DM, of great length relative to its section, whose unit glass filaments ( 101) are homogeneously distributed throughout the volume of cured resin (102). Advantageously, before deposition of the thermoplastic sheath (12), the CVR monofilament (10) may be subjected to an adhesion treatment in order to improve the subsequent adhesion between the thermoset resin (102). ) previously described and the thermoplastic sheath (12). A suitable chemical treatment may for example consist of a prior passage in an aqueous bath based on epoxy resin and / or isocyanate compound, followed by at least one heat treatment to remove the water and polymerize the adhesive layer. Such adhesion treatments are well known to those skilled in the art.
    [0028] Once the CVR monofilament (10) is finished, the latter is sheathed, covered in a known manner with a layer of thermoplastic material (12), for example by passing the single-strand or even, if necessary, several parallel strands arranged in parallel, through an appropriate extrusion head delivering the thermoplastic material in the molten state.
    [0029] The cladding or covering step by the thermoplastic material is carried out in a manner known to those skilled in the art. It consists for example simply to pass the or each CVR monofilament through a die or dies of suitable diameter, in extrusion heads heated to appropriate temperatures, or in a coating bath containing the thermoplastic material put beforehand dissolved in a suitable organic solvent (or solvent mixture). At the outlet of each extrusion head, the sheath or strands thus sheathed are then cooled sufficiently so as to solidify the layer of thermoplastic material, for example with air or another cold gas, or by passing through a bath of water followed by a drying step.
    [0030] By way of example, the covering of a CVR monofilament with a diameter close to 1 mm by a layer of PET of minimum thickness E. equal to about 0.2 mm, to obtain a multi-composite reinforcement having a total diameter of about 1.4 mm, is carried out on an extrusion-cladding line comprising two dies, a first die (counter-die or upstream die) of diameter equal to about 1.05 mm and a second die (or downstream die) of diameter equal to about 1.45 mm, both arranged in an extrusion head heated to about 290 ° C. The polyester, melted at a temperature of 280 ° C. in the extruder, thus covers the CVR monofilament, by means of the cladding head, at a wire running speed typically equal to several tens of m / min, for an extrusion pump flow typically of several tens of cm3 / min. At the outlet of this first cladding, the wire can be immersed in a cooling tank filled with cold water, to solidify and freeze the polyester in its amorphous state, then dried for example in line by an air nozzle, or by passage from the receiving coil to the oven. The layer or sheath covering the or each CVR monofilament (10) consists of a thermoplastic material (12) whose glass transition temperature (Tg2) is greater than 20 ° C., preferably greater than 50 ° C. ° C, more preferably greater than 70 ° C. On the other hand, the melting temperature (denoted Tf) of this thermoplastic material (12) is preferably greater than 150 ° C., more preferably greater than 200 ° C. Preferably, the minimum thickness (denoted E.) of the layer of thermoplastic material covering the or each single strand is between 0.05 and 0.5 mm, more preferably between 0.1 and 0.4 mm, in particular between 0 , 1 and 0.3 mm.
    [0031] Preferably, the initial modulus in extension of this thermoplastic material (12) is between 500 and 2500 MPa, preferably between 500 and 1500 MPa; its elastic elongation is preferably greater than 5%, more preferably greater than 8%, in particular greater than 10%; its elongation at break is preferably greater than 10%, more preferably 15%, in particular greater than 20%. Typically, the thermoplastic material is a polymer or a polymeric composition (composition based on at least one polymer and at least one additive).
    [0032] This thermoplastic polymer is preferably selected from the group consisting of polyamides, polyesters, polyimides and mixtures of such polymers, more particularly in the group consisting of aliphatic polyamides, polyesters, and mixtures of such polymers. Among the aliphatic polyamides, there may be mentioned polyamides 4-6, 6, 6-6, 11 or 12. The thermoplastic polymer is preferably a polyester; among the polyesters, mention may be made, for example, of PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PBN (polybutylene naphthalate), PPT (polypropylene terephthalate), PPN (polypropylene naphthalate).
    [0033] To the polymer or mixture of polymers above, may be optionally added to form a polymeric composition, various additives such as dye, filler, plasticizer, antioxidant or other stabilizer. It is advantageous to add to the thermoplastic material above, compatible components, preferably themselves thermoplastic, capable of promoting adhesion to a diene rubber matrix, for example unsaturated TPS (styrene thermoplastic) elastomers, in particular epoxides, as described for example in the applications WO 2013/117474 and WO 2013/117475 Tgi and Tg2 are measured in a known manner by DSC (Differential Scanning Calorimetry), in the second pass, for example and unless different indications specified in this P10 -3189 -15- according to the ASTM D3418 standard of 1999 (Mettler Toledo DSC "822-2" apparatus, nitrogen atmosphere, samples previously brought from ambient temperature (20 ° C) to 250 ° C (10 ° C / min), then rapidly cooled to 20 ° C, before final recording of the DSC curve from 20 ° C to 250 ° C, with a ramp of 10 ° C / min).
    [0034] FIG. 2 schematizes, in cross section, two examples (R-1 and R-2) of multicomponent reinforcements according to the invention, in which a single CVR monofilament (10) as described above, for example of equal diameter DM; at 1 mm, was covered by its layer, sheath of thermoplastic material, for example PET, minimum thickness denoted 1 () E. (for example equal to about 0.2 mm); in these two examples, the cross-section of the multi-composite reinforcement is either rectangular (here essentially square) or circular (respectively Fig. 2a and Fig. 2b). The diameter (for Fig. 2a) or the thickness (for Fig. 2b) denoted DR of these reinforcements R-1 and R-2 of the invention, equal to Dm + 2 Em, is therefore equal to about 1.4 mm in these two examples. Thanks to the combined presence of its glass filaments, its thermoset matrix and the thermoplastic sheath filling a sort of hooping function of the CVR monofilament, the multi-composite reinforcement of the invention is characterized by improved transverse cohesion. , high dimensional, mechanical and thermal stability. In the case where a plurality of CVR monobrins are used, the thermoplastic layer or sheath can be deposited individually on each single strand as illustrated for example in FIGS. 2, 5 and 6, or collectively deposited on several of the suitably arranged monobrins, for example aligned in a main direction, as illustrated for example in Figures 3, 4 and 7. Figure 3 shows schematically, in cross-section, another example of a multi-composite reinforcement (R-3) in which two single-spoke CVR (10), substantially of the same diameter (for example equal to about 1 mm), were covered together with a sheath of thermoplastic material (12), for example PET, of minimum thickness E. (for example equal to about 0.25 mm). In these examples, the cross section of the multi-composite reinforcement is rectangular, of thickness DR equal to Dm + 2 Em, is for example of the order of 1.5 mm. FIG. 4 schematizes, in cross section, another example of a multi-composite reinforcement (R-4) in which four CVR monobrins (10), of substantially the same diameter (for example equal to about 0.5 mm) were covered with a sheath of thermoplastic material, for example PET, to form a multi-composite reinforcement of substantially square cross-section, of thickness DR. The thermoplastic and therefore thermofusible nature of the material (12) covering each strand (10) made of CVR, makes it very advantageous to manufacture by thermal bonding a large variety of multi-strand multi-strand reinforcements having different shapes and straight sections, this by at least partial melting of the covering material, then cooling of all strands (10) sheathed thermoplastic material (12) once they are arranged together, arranged appropriately. This at least partial melting will be conducted at a temperature preferably between the melting temperature Tf of the thermoplastic material 12 and the glass transition temperature Tg2 of the thermoset resin 102.
    [0035] Thus, FIG. 5 schematizes, in cross-section, another example of a multicomposite reinforcement (R-5) according to the invention in which two elementary multi-composite reinforcements R-2 as shown diagrammatically in FIG. 2 (FIG. ) were brought into contact, bonded, welded together by superficial melting of their thermoplastic sheath (12) and then cooling step to obtain this R-5 reinforcement DR thickness. FIG. 6 shows another example of a multi-composite reinforcement according to the invention in which three elementary multi-composite reinforcements R-2 as schematized in FIG 2 (FIG 2b) have been aligned, brought into contact and then bonded, welded together by superficial melting of their thermoplastic sheath and cooling, to obtain another multi-composite reinforcement (R-6) of cross-section of thickness DR. The invention also relates to a multilayer laminate comprising at least one multi-composite reinforcement according to the invention as described above, disposed between and in contact with two layers of rubber or elastomer composition, in particular diene. In the present application, the term "laminate" or "multilayer laminate" is understood to mean in the known sense of the International Patent Classification: any product comprising at least two layers, of flat or non-planar shape, in contact with each other. one of the other, the latter being able to be or not connected, connected to each other; the term "bound" or "connected" should be interpreted extensively to include all connecting or joining means, in particular by gluing; "Diene" rubber: any elastomer (elastomer alone or mixture of elastomers) which is derived, at least in part (ie, a homopolymer or a copolymer), from monomers dienes, that is to say from monomers carrying two double carbon-carbon bonds, whether the latter are conjugated or not. FIG. 7 represents an example of such a multilayer laminate (20) comprising a multi-composite reinforcement (R-7) consisting of three CVR monobrins (10a, 10b, 10c) (such as P10-3189 -17- schematized). in FIG 1) embedded in their thermoplastic sheath (12), this reinforcement according to the invention R-7 itself being coated with a particularly diene elastomer sheath (14) to form a multilayer laminate according to the invention .
    [0036] This multilayer laminate lightweight and high performance, insensitive to corrosion, can advantageously replace conventional plies reinforced with steel cables. In addition to the presence of a significant amount of thermoplastic material, this laminate of the invention has the further advantage of being slightly hysteretic compared to these conventional fabrics. However, a major goal of tire manufacturers is also to lower the hysteresis of their constituents to reduce the rolling resistance of these tires. Each layer of rubber composition, or hereinafter "rubber layer", constituting the multilayer laminate of the tire of the invention is based on at least one elastomer, preferably of the diene type. This diene elastomer is preferably chosen from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), the various butadiene copolymers, the various copolymers of isoprene, and mixtures of these elastomers, such copolymers being chosen in particular from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and copolymers of isoprene-butadiene-styrene (SBIR).
    [0037] A particularly preferred embodiment consists in using an "isoprene" elastomer, that is to say a homopolymer or a copolymer of isoprene, in other words a diene elastomer chosen from the group consisting of natural rubber (NR ), the synthetic polyisoprenes (IR), the various isoprene copolymers and the mixtures of these elastomers. The isoprene elastomer is preferably natural rubber or synthetic polyisoprene of the cis-1,4 type. Among these synthetic polyisoprenes, polyisoprenes having a content (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%, are preferably used. According to a preferred embodiment, each layer of rubber composition comprises 50 to 100 phr of natural rubber. According to other preferred embodiments, the diene elastomer may consist, in whole or in part, of another diene elastomer such as, for example, an SBR elastomer used in or with another elastomer, for example type BR.
    [0038] The rubber composition may contain one or more diene elastomer (s), the last one (s) may be used in combination with any type of synthetic elastomer P10-3189 -18- other than diene, or even with polymers other than elastomers. The rubber composition may also comprise all or part of the additives normally used in rubber matrices intended for the manufacture of tires, such as, for example, reinforcing fillers such as carbon black or silica, coupling agents, anti-blocking agents, aging, antioxidants, plasticizers or extension oils, whether these are of aromatic or non-aromatic nature, plasticizing resins with a high glass transition temperature, processing agents, tackifying resins, anti-eversion agents, methylene acceptors and donors, reinforcing resins, a crosslinking or vulcanization system.
    [0039] Preferably, the crosslinking system of the rubber composition is a so-called vulcanization system, that is to say based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator. To this basic vulcanization system may be added various known secondary accelerators or vulcanization activators. The sulfur is used at a preferential rate of between 0.5 and 10 phr, the primary vulcanization accelerator, for example a sulfenamide, is used at a preferential rate of between 0.5 and 10 phr. The level of reinforcing filler, for example carbon black or silica, is preferably greater than 50 phr, especially between 50 and 150 phr.
    [0040] Carbon blacks are suitable for all carbon blacks, in particular blacks of the HAF, ISAF, SAF type conventionally used in tires (so-called pneumatic grade blacks). Among the latter, mention will be made more particularly of carbon blacks of (ASTM) grade 300, 600 or 700 (for example N326, N330, N347, N375, N683, N772). Suitable silicas are in particular precipitated or pyrogenic silicas having a BET surface area of less than 450 m 2 / g, preferably from 30 to 400 m 2 / g. Those skilled in the art will know, in the light of the present description, adjust the formulation of the rubber composition in order to achieve the desired levels of properties (including modulus of elasticity), and adapt the formulation to the application specific consideration.
    [0041] Preferably, the rubber composition has, in the crosslinked state, a secant modulus in extension, at 10% elongation, which is between 4 and 25 MPa, more preferably between 4 and 20 MPa; values in particular between 5 and 15 MPa have proved to be particularly suitable for reinforcing tire belts.
    [0042] The modulus measurements are carried out in tension, unless otherwise indicated according to ASTM D 412 of 1998 (specimen "C"): the secant modulus is measured in second elongation (that is to say after an accommodation cycle). "true" (that is to say, brought back to the actual section of the test piece) at 10% elongation, noted here Ms and expressed in MPa (normal temperature and humidity conditions according to standard ASTM D 1349 of 1999). According to a preferred embodiment, in the multilayer laminate of the invention, the thermoplastic layer (12) is provided with an adhesive layer with respect to each layer of rubber composition with which it is in contact with .
    [0043] To adhere the rubber to this thermoplastic material, it is possible to use any suitable adhesive system, for example a simple textile glue of the "RFL" type (resorcinolformaldehyde-latex) comprising at least one diene elastomer such as natural rubber, or any equivalent adhesive known to confer a satisfactory adhesion between rubber and conventional thermoplastic fibers such as polyester or polyamide fibers, such as for example the adhesive compositions described in applications WO 2013/017421, WO 2013/017422, WO 2013/017423. By way of example, the sizing process can essentially comprise the following successive steps: passing through a bath of glue, followed by dewatering (for example by blowing, calibrating) in order to eliminate the excess of glue; then drying for example by passing through a heating oven or tunnel (for example for 30 s at 180 ° C) and finally heat treatment (for example for 30 s at 230 ° C).
    [0044] Before the above sizing, it may be advantageous to activate the surface of the thermoplastic material, for example mechanically and / or physically and / or chemically, to improve its adhesion of adhesive and / or its final adhesion to rubber . Mechanical treatment may for example consist of a preliminary step of matting or scratching of the surface; a physical treatment may for example consist of a radiation treatment such as an electron beam; a chemical treatment may for example consist of a prior passage in an epoxy resin bath and / or isocyanate compound. Since the surface of the thermoplastic material is generally smooth, it may also be advantageous to add a thickener to the glue used, in order to improve the total adhesive uptake of the multi-composite reinforcement during its gluing. Those skilled in the art will readily understand that the connection between the thermoplastic polymer layer of the multi-composite reinforcement of the invention and each layer of rubber with which it is in contact in the multilayer laminate of the invention is ensured definitively during the final cure (crosslinking) of the rubber article, in particular bandage, for which the laminate is intended. It goes without saying that in all the particular examples of the invention previously described and shown schematically in FIGS. 1 to 7, the CVR monobrins, with a diameter DM and with a circular cross-section, could be replaced by monobrins made of CVR of different shape, for example with rectangular cross-section (including square) or other (eg oval), DM then conventionally representing the so-called clutter diameter, that is to say the diameter of the circle circumscribing their cross section. EXAMPLES OF EMBODIMENT OF THE INVENTION The following are examples of the manufacture of single-stranded CVR, multicomponent reinforcements and multilayer laminates according to the invention based on these single strands in CVR, and their use as reinforcing elements of the invention. pneumatic tires. FIG. 8 appended schematizes very simply an example of a device 100 allowing the production of CVR monobrins (10) as schematized in FIG.
    [0045] It shows a coil 110 containing, in the example shown, glass fibers 111 (in the form of multifilaments). The coil is unwound continuously by driving, so as to achieve a rectilinear arrangement 112 of these fibers 111. In general, the reinforcing fibers are delivered in "rovings", that is to say already in groups of fibers wound in parallel on a coil ; for example, fibers sold by Owens Corning under the designation "Advantex" fiber, with a titre of 1200 tex (as a reminder, 1 tex = 1 g / 1000 m fiber), are used. This is for example the traction exerted by the rotary reception 126 which will allow the advancement of the fibers in parallel and the CVR monobrin all along the installation 100.
    [0046] This arrangement 112 then passes through a vacuum chamber 113 (connected to a vacuum pump not shown), disposed between an inlet pipe 113a and an outlet pipe 113b opening onto an impregnation chamber 114, the two pipes preferably to rigid wall having for example a minimum upper section (typically twice as much) to the total fiber section and a much greater length (typically 50 times more) to said minimum section. As already taught by the above-mentioned application EP-A-1 174 250, the use of rigid wall pipes, both for the inlet port in the vacuum chamber and for the outlet orifice of the vacuum chamber. and the transfer from the vacuum chamber to the impregnation chamber, is compatible both with high rates of passage of the fibers through the orifices without breaking the fibers, but also ensures a sufficient seal . It suffices, if necessary experimentally, to search for the largest section of passage, taking into account the total section of the fibers to be treated, again making it possible to provide sufficient sealing, taking into account the speed of advance of the fibers and the length P10-3189 - 21 - tubing. Typically, the vacuum inside the chamber 113 is for example of the order of 0.1 bar, the length of the vacuum chamber is about 1 meter. At the outlet of the vacuum chamber 113 and the outlet pipe 113b, the arrangement 112 of fibers 111 passes through an impregnation chamber 114 comprising a feed tank 115 (connected to a metering pump, not shown) and a storage tank. impregnation 116 sealed completely filled with impregnating composition 117 based on a vinylester-type curable resin (eg, "E-Nova FW 2045" from DSM). By way of example, the composition 117 further comprises (at a weight ratio of 1 to 2%) a photoinitiator suitable for the UV and / or UV-visible radiation by which the composition will subsequently be treated, for example bis- (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ("Irgacure 819" from BASF). It may also comprise (for example about 5% to 15%) of a crosslinking agent such as, for example, tris (2-hydroxyethyl) isocyanurate triacrylate ("SR 368" from Sartomer). Of course, the impregnating composition 117 is in the liquid state. Preferably, the length of the impregnation chamber is several meters, for example between 2 and 10 m, in particular between 3 and 5 m. Thus, spring of the impregnation chamber 114, in a sealed outlet pipe 118 (still under primary vacuum), an impregnated material comprising for example (% by weight) from 65 to 75% of solid fibers 111, the rest ( 25 to 35%) being constituted by the liquid impregnation matrix 117. The impregnated material then passes through calibration means 119 comprising at least one calibration die 120 whose channel (not shown here), for example of a shape circular, rectangular or conical, is adapted to the particular conditions of implementation. By way of example, this channel has a minimum cross section of circular shape whose downstream orifice has a diameter slightly greater than that of the targeted single-core. The die has a length that is typically greater than at least 100 times the minimum dimension of the minimum section. Its function is to ensure a high dimensional accuracy to the finished product, it can also play a role of dosing the fiber ratio with respect to the resin. According to a possible variant embodiment, the die 120 may be directly integrated with the impregnation chamber 114, which avoids, for example, the use of the outlet pipe 118. Preferably, the length of the calibration zone is several centimeters, for example between 5 and 50 cm, in particular between 5 and 20 cm. Thanks to the calibration means (119, 120) is obtained at this stage a "liquid" composite monofilament (121), liquid in the sense that its impregnating resin is at this stage still liquid, 40 whose shape of the cross-section is preferentially essentially circular. P10-3189 - 22 - At the outlet of the calibration means (119, 120), the liquid composite monofilament (121) thus obtained is then polymerized by passing through a UV irradiation chamber (122) comprising a sealed glass tube ( 123) through which the composite monofilament circulates; said tube, whose diameter is typically a few cm (for example 2 to 3 cm), is irradiated with a plurality (here, for example 4 in number) of UV irradiators (124) in line (lamps "UVAprint" of the company Dr. Hnle, wavelength 200 to 600 nm) arranged at a short distance (a few cm) from the glass tube. Preferably, the length of the irradiation chamber is several meters, for example between 2 and 15 m, in particular between 3 and 10 m. In this example, the irradiation tube 123 is traversed by a stream of nitrogen. The irradiation conditions are preferably adjusted in such a way that, at the outlet of the impregnation chamber, the temperature of the CVR monofilament, measured at the surface of the latter (for example using a thermocouple), is greater than the Tg (Tgi) of the crosslinked resin (in other words greater than 150 ° C), and more preferably less than 270 ° C. Once the resin has polymerized (cured), the CVR (125) solid state, this time in the solid state, driven in the direction of arrow F, then arrives on its final receiving coil (126). Finally, a finished composite block of manufacture is obtained, as shown schematically in FIG. 1, in the form of a continuous CVR monofilament (10), of very great length, whose unit glass filaments (101) are homogeneously distributed. throughout the volume of cured resin (102). Its diameter is for example equal to about 1 mm. The process described above can be carried out at high speed, preferably above 50 m / min, for example between 50 and 150 m / min. The CVR monofilament thus obtained was then subjected to a sizing operation by passing through an aqueous bath (approximately 94% water) essentially based on epoxy resin (polyglycol polyglycidyl ether "DENACOL" EX-512 from Nagase ChemteX Corporation , about 1%) and isocyanate compound (blocked caprolactam, "GRILBOND" IL-6 from EMS, about 5%), sizing step followed by drying (30 s at 185 ° C) and heat treatment (30 s at 200 ° C).
    [0047] Thus glued, it was then subjected to a cladding operation by the thermoplastic material (12), in this case a PET ("Artenius Design +" from the company Artenius, density> 1.39, Tg2 equal to about 76 ° C, Tf = about 230 ° C) per pass (10 m / min) through an extrusion line (extrusion head at 290 ° C), as already described in detail above.
    [0048] The multi-composite reinforcement of the invention thus obtained, as schematized for example in FIG. 2b, had the following final properties: DM equal to about 1.0 mm; E. equal to about 0.2 mm; DR equal to about 1.4 mm; Tgi equals about 180 ° C; Tg2 is about 76 ° C; Ar equal to about 3.8%; ER20 equal to about 14 GPa; EM20 equal to about 34 GPa; E'150 equal to about 30 GPa; E9 (Tgl - 25) / E'20 equal to about 0.92; elastic deformation in flexural compression of the single strand equal to about 3.6%; compressive stress under flexural compression of the single strand equal to about 1350 MPa; weight ratio of glass fibers in the single-core pipe equal to about 70%; initial module in extension of the thermoset vinylester resin, at 20 ° C, equal to about 3.6 GPa; initial PET extension module (at 20 ° C) equal to about 1100 MPa; elastic stretching of PET (at 20 ° C) greater than 5%; elongation at break of PET (at 20 ° C) greater than 10%.
    [0049] The multi-composite reinforcement of the invention thus produced is advantageously usable, especially in the form of a multilayer laminate according to the invention, for reinforcing tires, pneumatic or non-pneumatic, of all types of vehicles, in particular passenger vehicles or industrial vehicles such as heavy vehicles, civil engineering, aircraft, other transport or handling vehicles.
    [0050] For example, Figure 9 shows very schematically (without respecting a specific scale), a radial section of a tire, whether or not conforming to the invention in this general representation.
    [0051] This tire 200 has a top 202 reinforced by a crown reinforcement 206, two sidewalls 203 and two beads 204, each of these beads 204 being reinforced with a rod 205. The top 202 is surmounted by a tread represented in this schematic figure. A carcass reinforcement 207 is wound around the two rods 205 in each bead 204, the upturn 208 of this armature 207 being for example disposed towards the outside of the tire 200 which is shown here mounted on its rim 209. Of course, this bandage pneumatic 200 further comprises in a known manner a layer of rubber 201, commonly called gum or sealing layer, which defines the radially inner face of the tire and which is intended to protect the carcass ply of the air diffusion from the tire. interior space to the tire.
    [0052] The carcass reinforcement 207, in the tires of the prior art, generally consists of at least one rubber ply reinforced by "radial" textile or metal reinforcements, that is to say that these reinforcements are arranged substantially parallel to each other and extending from one bead to the other so as to form an angle of between 80 ° and 90 ° to the median circumferential plane (plane perpendicular to the axis of rotation of the P10-3189 A tire which is located halfway between the two beads 204 and passes through the middle of the crown reinforcement 206). The belt 206 is for example constituted, in the tires of the prior art, by at least two layers of rubber called "working plies" or "triangulation plies", superimposed and crossed, reinforced with metal cables arranged substantially parallel to each other. relative to the others and inclined relative to the median circumferential plane, these working plies may or may not be associated with other plies and / or fabrics of rubber. These working plies have the primary function of giving the tire a high rigidity of drift. The belt 206 may furthermore comprise, in this example, a rubber sheet called a "hooping sheet" reinforced by so-called "circumferential" reinforcing threads, that is to say that these reinforcing threads are arranged substantially parallel to each other. other and extend substantially circumferentially around the tire so as to form an angle preferably within a range of 0 to 10 ° with the medial circumferential plane. These circumferential reinforcing threads have the particular function of resisting the centrifugation of the top at high speed. A pneumatic tire 200, when in accordance with the invention, has the preferred feature that at least its belt (206) and / or its carcass reinforcement (207) comprises a multilayer laminate according to the invention, consisting of at least one multi-composite reinforcement according to the invention arranged between and in contact with two layers of diene rubber composition. According to a particular embodiment of the invention, this multi-composite reinforcement of the invention can be used in the form of parallel sections arranged under the tread, as described in the above-mentioned application EP 1 167 080. According to another possible embodiment of the invention, it is the bead zone which can be reinforced with such a multi-composite reinforcement; it is for example the rods (5) which could consist, in whole or in part, of a multi-composite reinforcement according to the invention.
    [0053] In these examples of FIG. 9, the rubber compositions used for the multilayer laminates according to the invention are, for example, conventional compositions for calendering textile reinforcements, typically based on natural rubber, carbon black or silica, vulcanization system and usual additives. Thanks to the invention, compared to rubber compositions reinforced with steel cables, they are advantageously free of metal salt such as cobalt salt. The adhesion between the multi-composite reinforcement of the invention and the rubber layer which coats it can be ensured in a simple and known manner, for example by a conventional RFL-type glue (resorcinol-formaldehyde-latex), or using more recent glues as described for example in the aforementioned applications WO 2013/017421, WO 2013/017422, WO 2013/017423.
    [0054] In conclusion, the advantages of the multilayer laminate and the multi-composite reinforcement of the invention are numerous (low thickness, low density, low cost, insensitivity to corrosion) compared to conventional metal fabrics, and the The results obtained by virtue of the invention suggest a very large number of possible applications, in particular as a reinforcing element for the tire belt, placed between the tread and the carcass reinforcement of such tires. P10-3189
    权利要求:
    Claims (25)
    [0001]
    REVENDICATIONS1. Multi-composite reinforcement (R1, R2) comprising at least: one or more monofilres (10) of glass-resin composite (abbreviated "CVR") comprising glass filaments (101) embedded in a thermoset resin ( 102) whose glass transition temperature denoted Tgi is greater than 150 ° C; - Individually covering said single-core, each single-core or collectively several single strand, a layer of a thermoplastic material (12) whose glass transition temperature denoted Tg2 is greater than 20 ° C.
    [0002]
    2. multi-composite reinforcement according to claim 1, wherein Tgi is greater than 160 ° C, preferably greater than 170 ° C.
    [0003]
    3. Multi-composite reinforcement according to claims 1 or 2, wherein Tg2 is greater than 50 ° C, preferably greater than 70 ° C.
    [0004]
    4. A multi-composite reinforcement according to any one of claims 1 to 3, whose elongation at break (Ar), measured at 20 ° C, is equal to or greater than 3.0%, preferably equal to or greater than 3.5%.
    [0005]
    5. Multi-composite reinforcement according to any one of claims 1 to 4, whose initial modulus in extension (ER20), measured at 20 ° C, is greater than 9 GPa, preferably greater than 12 GPa.
    [0006]
    6. Multi-composite reinforcement according to any one of claims 1 to 5, wherein the initial modulus in extension (Em20) of the or each CVR monofilament, measured at 20 ° C, is greater than 30 GPa, preferably greater at 33 GPa.
    [0007]
    7. Multi-composite reinforcement according to any one of claims 1 to 6, wherein the real part of the complex module (E'150) of the or each CVR monofilament, measured at 150 ° C by the DTMA method, is greater at 25 GPa, preferably greater than 30 GPa.
    [0008]
    8. multi-composite reinforcement according to any one of claims 1 to 7, whose ratio E '(Tgl-25) / E'20 is greater than 0.85, preferably greater than 0.90, E'20 and E '(Tgl -25) being the real part of the complex module of the or each CVR monobrin measured by DTMA, respectively at 20 ° C and at a temperature expressed in ° C equal to (Tgi - 25). 40 P10-3189- 27 -
    [0009]
    9. Multi-composite reinforcement according to any one of claims 1 to 8, wherein the elastic deformation in flexural compression of the or each single-strand CVR is greater than 3.0%, preferably greater than 3.5%.
    [0010]
    10. A multi-composite reinforcement according to any one of claims 1 to 9, wherein the compression stress under flexure of the or each single strand CVR is greater than 1000 MPa, preferably greater than 1200 MPa.
    [0011]
    11. multi-composite reinforcement according to any one of claims 1 to 10, wherein the weight ratio of glass fibers in the or each single-core CVR, is between 60 and 80%, preferably between 65 and 75; %.
    [0012]
    The multi-composite reinforcement of any one of claims 1 to 11, wherein the thermoset resin is a vinylester resin.
    [0013]
    13. Multi-composite reinforcement according to any one of claims 1 to 12, wherein the initial modulus in extension of the thermoset resin, measured at 20 ° C, is greater than 3.0 GPa, preferably greater than 3.5. GPa.
    [0014]
    14. A multi-composite reinforcement according to any one of claims 1 to 13, wherein the thermoplastic material is a polymer or a polymer composition.
    [0015]
    The multi-composite reinforcement of claim 14, wherein the polymer is a polyester.
    [0016]
    16. multi-composite reinforcement according to any one of claims 1 to 15, wherein the initial modulus in extension of the thermoplastic material, measured at 20 ° C, is between 500 and 2500 MPa, preferably between 500 and 1500 MPa .
    [0017]
    17. Multi-composite reinforcement according to any one of claims 1 to 16, wherein the elastic elongation of the thermoplastic material, measured at 20 ° C, is greater than 5%, preferably greater than 8%.
    [0018]
    18. Multi-composite reinforcement according to any one of claims 1 to 17, wherein the elongation at break of the thermoplastic material, measured at 20 ° C, is greater than 10%, preferably greater than 15%.
    [0019]
    19. A multi-composite reinforcement according to any one of claims 1 to 18, wherein the diameter (DM) of the or each CVR monofilament is between 0.2 and 2.0 mm, preferably between 0.3 and 1.5 mm. P10-3189- 28 -
    [0020]
    20. multi-composite reinforcement according to any one of claims 1 to 19, wherein the minimum thickness (E.) of the layer of thermoplastic material covering the or each single-core is between 0.05 and 0.5 mm, preferably between 0.1 and 0.4 mm.
    [0021]
    21. Multilayer laminate comprising at least one multi-composite reinforcement according to any one of claims 1 to 20, disposed between and in contact with two layers of rubber composition.
    [0022]
    22. A finished article or semi-finished rubber product comprising a multi-composite reinforcement according to any one of claims 1 to 20 or a multilayer laminate according to claim 21.
    [0023]
    23. A bandage comprising a multi-composite reinforcement according to any one of claims 1 to 20 or a multilayer laminate according to claim 21.
    [0024]
    The tire of claim 23, wherein the multi-composite reinforcement or multilayer laminate is present in the tire belt or in the carcass reinforcement of the tire.
    [0025]
    A bandage according to claim 23, wherein the multi-composite reinforcement or the multilayer laminate is present in the bead area of the bandage. P10-3189
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    EP3027395B1|2021-09-01|Method for manufacturing a glass-fiber-reinforced monofilament
    WO2012016757A1|2012-02-09|Composite reinforcement
    WO2010105975A1|2010-09-23|Self-adhesive composite reinforcement
    FR3089219A1|2020-06-05|MULTI-COMPOSITE MATERIAL BASED ON GLASS-RESIN COMPOSITE
    同族专利:
    公开号 | 公开日
    JP2017500457A|2017-01-05|
    JP6488309B2|2019-03-20|
    CN105829408B|2018-08-31|
    US20160318342A1|2016-11-03|
    CN105829408A|2016-08-03|
    EP3083775B1|2017-09-06|
    KR20160102182A|2016-08-29|
    FR3015363B1|2016-02-05|
    KR102348477B1|2022-01-07|
    EP3083775A1|2016-10-26|
    WO2015090973A1|2015-06-25|
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    法律状态:
    2015-12-21| PLFP| Fee payment|Year of fee payment: 3 |
    2016-12-22| PLFP| Fee payment|Year of fee payment: 4 |
    2017-12-21| PLFP| Fee payment|Year of fee payment: 5 |
    2019-09-27| ST| Notification of lapse|Effective date: 20190906 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1363019A|FR3015363B1|2013-12-19|2013-12-19|MULTI-COMPOSITE REINFORCEMENT|FR1363019A| FR3015363B1|2013-12-19|2013-12-19|MULTI-COMPOSITE REINFORCEMENT|
    EP14808950.1A| EP3083775B1|2013-12-19|2014-12-03|Reinforment for tyres comprising a multi-composite structure|
    KR1020167015923A| KR102348477B1|2013-12-19|2014-12-03|Multi-composite reinforcement for a tyre|
    JP2016541651A| JP6488309B2|2013-12-19|2014-12-03|Multi-component composite reinforcement for tires|
    PCT/EP2014/076446| WO2015090973A1|2013-12-19|2014-12-03|Multi-composite reinforcement for a tyre|
    CN201480069089.5A| CN105829408B|2013-12-19|2014-12-03|More composite material reinforcement bodies for tire|
    US15/104,438| US20160318342A1|2013-12-19|2014-12-03|Multicomposite reinforcer|
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