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    • 专利摘要:
    Radial tire, in particular for passenger cars or vans, with improved belt structure (10) comprising a multilayer composite laminate (10a, 10b, 10c) of specific construction, with a first layer (10a) of rubber (C1) comprising circumferential textile reinforcements (110) heat-shrinkable, for example nylon or polyester, in the form of multifilament fibers twisted individually on themselves at a twist greater than 100 turns per meter; this first layer (10a) overlaps radially (in the Z direction) two further layers (10b, 10c) of rubber (respectively C2, C3) reinforced reinforcements (120, 130) which are for all or part of the composite reinforcements consist of monofilaments steel sheathed with a thermoplastic material having a glass transition temperature greater than 20 ° C. This laminate makes it possible in particular to lighten the tire belts by reducing the thickness of the rubber layers constituting part of their structure, thus reducing the weight and the rolling resistance of the tires, without the risk of direct contact between the reinforcements (110). , 120, 130).
    公开号:FR3032148A1
    申请号:FR1550813
    申请日:2015-02-03
    公开日:2016-08-05
    发明作者:Aurore Lardjane；Camille Astaix
    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 present invention relates to tires for vehicles, and to their crown reinforcement or belt. It relates more particularly to multilayer composite laminates used in the belt of such tires, particularly for passenger cars or vans. 2. State of the art A radial carcass reinforcement tire for a passenger vehicle or a van has, as is known, a tread, two inextensible beads, two flexible flanks connecting the beads to the tread, and a rigid crown reinforcement. or "belt" (Wh ") disposed circumferentially between the carcass reinforcement and the tread.
    [0002] The tire belt is generally constituted by at least two rubber plies known as "working plies", "triangulation plies" or "working reinforcement", superimposed and crossed, most often reinforced with metal cables arranged substantially parallel to one another. 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 rigidity or high drift ("drift thrust" or "cornering"), necessary in a known manner to obtain good road handling ("handling"). ") on a motor vehicle.
    [0003] The above belt, which is particularly the case for tires likely to run at high speed in a sustained manner, may further comprise an additional rubber ply above the working plies (tread side), called " "hooping web" or "hooping reinforcement", which is generally reinforced by so-called "circumferential" reinforcing yarns, that is to say that these reinforcement yarns are arranged substantially parallel to one another and extend substantially circumferentially around the tire envelope so as to form an angle preferably within a range of -50 to +5 ° with the median circumferential plane. These circumferential reinforcing son have the primary function, it is recalled, to resist the centrifugation of the top at high speed. Such belt structures, ultimately consisting of a multilayer composite laminate comprising at least one hooping web, most often textile, and two generally metal working webs, are well known to those skilled in the art and do not need to be described here in more detail.
    [0004] The general state of the art describing such belt structures is illustrated in particular by the documents US Pat. No. 4,371,025, FR 2,504,067 or US Pat. No. 4,819,705, EP 738,615, EP 795,426 or US Pat. No. 5,858,137. 1,162,086 or US 2002/0011296, EP 1,184,203 or US 2002/0055583.
    [0005] The availability of increasingly resistant and long-lasting steels means that tire manufacturers are moving as far as possible towards use in belts of rope tires with a very simple structure, especially just two wires. even unitary filaments, in part to simplify manufacturing and reduce costs, on the other hand to reduce the thickness of the reinforcement plies and thus the hysteresis of the tires, ultimately reduce the consumption of energy from vehicles equipped with such tires. Efforts to reduce the mass of tires, in particular by reducing the thickness of their belts and the layers of rubber constituting them, are, of course, encountering physical limitations which may give rise to a certain number of difficulties. . In particular, it may occur that the hooping function provided by the hooping reinforcement and that of stiffening provided by the reinforcement are no longer sufficiently differentiated from one another and may be mutually interfering. This is detrimental to the proper functioning of the tire crown, the performance and the overall endurance of the tire. Thus, patent applications WO 2013/117476 and WO 2013/117477 filed by the Applicants have proposed a multilayer composite laminate with a specific structure which makes it possible to appreciably reduce the tire belt, and thus to reduce their resistance to rolling, while overcoming the disadvantages mentioned above. These applications disclose a radial tire, defining three main directions, circumferential, axial and radial, having a crown surmounted by a tread, two sidewalls, two beads, each side connecting each bead at the top, a carcass reinforcement anchored in each flanges and extending in the flanks and in the apex, a crown reinforcement or belt extending circumferentially in the circumferential direction and located radially between the carcass reinforcement and the tread, said belt comprising a laminate multilayer composite comprising at least three superimposed layers of reinforcement, said reinforcements being in each layer unidirectional and embedded in a thickness of rubber, with in particular: - tread side, a first layer of rubber comprising a first row reinforcements, oriented at an alpha angle of -5 to +5 degrees from the directio n circumferential, these reinforcements said first reinforcements being heat shrink textile material; in contact with the first layer and disposed beneath the latter, a second rubber layer comprising a second row of reinforcements, oriented at a given beta angle, positive or negative, between 10 and 30 degrees with respect to the circumferential direction; reinforcement said second reinforcements being metal reinforcements; in contact with the second layer and disposed beneath the latter, a third rubber layer comprising a third row of reinforcements, oriented at a gamma angle opposite to the angle beta, itself between 10 and 30 degrees relative to the circumferential direction, said reinforcements said third reinforcements being metal reinforcements. The first reinforcements consist of multifilament fibers, polyamide or polyester, conventionally twisted together in the form of textile ropes. The second and third reinforcements consist of steel monofilaments, in particular very high strength carbon steel. The above patent applications have demonstrated that it is possible, thanks to the specific construction of their multilayer laminate, in particular to the use of textile circumferential reinforcements whose heat shrinkability is controlled and metal reinforcements in the form of single unit monofilaments of low diameter, significantly reduce the overall thickness of the tire belts, and this without affecting the proper implementation and differentiation of functions on the one hand shrinking provided by the circumferential reinforcements of the first layer, on the other hand stiffening provided by the metal reinforcements of the other two layers. Thus, the weight of the tires and their rolling resistance can be reduced, at a reduced cost thanks to the use of steel monofilaments that do not require any prior assembly operation, this without penalizing the rigidity of drift and therefore the road behavior, neither overall endurance while driving. Nevertheless, it has proved to be the case, according to the particular conditions of implementation of the multilayer laminates described in the above applications, that the reduction of the thicknesses of the (first, second and third) rubber layers could collide here. or there at the P10-3530 - 4 - risk of direct contact, if not too close, in the radial direction (Z), between the reinforcements of these different layers. This can be detrimental to the proper functioning, long-term endurance of the multilayer composite laminate.
    [0006] For example, a direct contact or too close proximity on the one hand textile circumferential threads, which are known to naturally contain a certain amount of water, variable depending on the nature of the heat-shrinkable textile material, and secondly steel monofilaments, could lead to surface corrosion of these, not to mention a risk of degradation of adhesion with the surrounding rubber.
    [0007] A direct contact between the steel monofilaments of the second layer with those of the third layer, for cross-referencing with respect to each other in the reinforcement of work, could mean for him a repeated friction and a premature wear of these monofilaments in working conditions, finally a risk of degradation of the overall endurance of this frame of work after a prolonged rolling of the tires. 3. BRIEF DESCRIPTION OF THE INVENTION Continuing their research, the Applicants have developed an improved multilayer composite laminate, of new architecture, which makes it possible to overcome, at least in part, the aforementioned problems due to risks of direct contact between reinforcements, and which can advantageously replace the laminates described in the two aforementioned applications.
    [0008] Thus, according to a first object, the present invention relates (according to the references given in FIGS. 1 and 2 appended) to a radial tire (1), defining three main directions, circumferential (X), axial (Y) and radial (Z), having a top (2) surmounted by a tread (3), two sidewalls (4), two beads (5), each sidewall (4) connecting each bead (5) to the top (2), a carcass reinforcement (7) anchored in each of the beads (5) and extending in the flanks (4) to the top (2), a crown reinforcement or belt (10) extending into the top (2) in the direction circumferential (X) and located radially between the carcass reinforcement (7) and the tread (3), said belt (10) comprising a multilayer composite laminate (10a, 10b, 10c) comprising at least three superposed layers of reinforcements (110, 120, 130), said reinforcements being in each layer unidirectional and embedded in a rubber thickness (re spectively C1, C2, C3), with: - tread side, a first layer (10a) of rubber (C1) having a first row of reinforcements (110), oriented at an angle alpha of -5 to +5 degrees by relative to the circumferential direction (X), these reinforcements (110) called first P10-3530 - 5 - reinforcements having a bulk diameter denoted D1 between 0.30 mm and 0.60 mm and being heat shrink textile material; - In contact with the first layer (10b) and disposed beneath the latter, a second layer (10b) of rubber (C2) comprising a second row of reinforcements (120), oriented at a given beta angle, positive or negative, between 10 and 30 degrees relative to the circumferential direction (X), these reinforcements (120) said second reinforcements having a diameter or thickness, noted (e) D2, included (e) between 0.20 mm and 0.50 mm; - In contact with the second layer (10b) and disposed under the latter, a third layer (10c) of rubber (C3) having a third row of reinforcements (130), oriented at a gamma angle opposite the angle beta, -even between 10 and 30 degrees relative to the circumferential direction (X), these reinforcements (130) said third reinforcements having a diameter or thickness, noted (e) D3, included (e) between 0.20 mm and 0, 50 mm, characterized in that: - all or part of the first reinforcements (110) of heat-shrinkable textile material are multifilament fibers twisted individually on themselves at a twist T greater than 100 turns per meter; all or part of the second (120) and / or third (130) reinforcements are composite reinforcements comprising steel monofilaments (120a, 130a) which are covered with a sheath (120b, 130b) of a thermoplastic material whose glass transition temperature Tg is greater than 20 ° C.
    [0009] The invention thus offers the possibility, according to the particular applications concerned, to maintain at a low level or even to further reduce the thickness of the tire belts and that of the rubber layers constituting part of their structure, and ultimately the weight and the rolling resistance of the tires, without risk of direct contact between the different reinforcements. The thermoplastic sheath also constitutes an effective barrier against corrosive agents that can penetrate the multilayer laminate in the event of tire stresses. In addition, this sheath having an intermediate stiffness between the rigidity of the steel monofilaments and the rigidity of the rubber matrix coating them, the stresses exerted on the interfaces are reduced, which is likely to further improve the overall endurance of the multilayer laminate. of the tire of the invention. The multilayer composite laminate according to the invention can be used as a belt-reinforcing element of any type of tire, particularly for a P10-3530 - 6 - tourism vehicle including in particular 4x4 vehicles and "SUV" (Sport Utility Vehicles) or for a van vehicle. . The invention as well as its advantages will be easily understood in the light of the detailed description and the following exemplary embodiments, as well as FIGS. 1 to 3 relating to these examples which are diagrammatic (unless otherwise indicated, without respecting a specific scale. ): - in radial section (that is to say in a plane containing the axis of rotation of the tire), an example of tire (1) according to the invention, incorporating in its belt (10) a composite laminate multilayer according to the invention (Fig. 1); in cross-section, an example of multilayer composite laminate (10a, 10b, 10c) usable in the tire (1) according to the invention, incorporating reinforcements (110) made of heat-shrinkable textile material in the form of a multifilament fiber twisted on itself (Fig. 2) and reinforcements (120, 130) (Fig. 2); in cross-section, examples of reinforcements (respectively 120, 130) in the form of composite reinforcements (120a, 120b, 130a, 130b) usable in the multilayer laminate according to the invention, consisting of steel monofilaments (respectively 120a, 130a). ) which are covered with a sheath (120b, 130b respectively) of a thermoplastic material, sheath can take different shapes of cross section, for example with circular, square or rectangular contours (Figure 3, respectively Fig. 3a, 3b). and 3c). 4. DEFINITIONS In the present application, the following terms are used: - "rubber" or "elastomer" (both terms being considered synonymous): any type of elastomer, whether of the diene type or of the non-diene type, for example thermoplastic; "rubber composition" or "rubber composition" means a composition which comprises at least one rubber and a filler; - "layer": a sheet, strip or any other element of relatively small thickness relative to its other dimensions, preferably whose ratio of the thickness on the largest of the other dimensions is less than 0.5, more preferably less than 0.1; - "axial direction": a direction substantially parallel to the axis of rotation of the tire; "circumferential direction" means a direction that is substantially perpendicular both to the axial direction and to a radius of the tire (in other words, tangential to a circle whose center is on the axis of rotation of the tire); "Radial direction": a direction along a radius of the tire, that is to say any direction passing through the axis of rotation of the tire and substantially perpendicular to that direction, that is, that is to say, making with a perpendicular to this direction an angle not diverging by more than 5 degrees; - "monofilament" or indistinctly "monofil", in general, any unit filament, whatever the shape of its cross section, whose diameter (case of a circular cross section) or the thickness (case of a section non-circular right) are greater than 100 μm. This definition covers both substantially cylindrical monofilaments (circular cross section) and monofilaments of different shape, for example oblong monofilaments (flattened shape), or rectangular or square cross section; - "oriented along an axis or a direction" while speaking of any element such as a reinforcement, an element which is oriented substantially parallel to this axis or this direction, that is to say doing with this axis or this direction an angle not deviating by more than 5 degrees (therefore zero or at most equal to 5 degrees); - "oriented perpendicular to an axis or direction": speaking of any element such as a reinforcement, an element that is oriented substantially perpendicular to that axis or direction, that is to say, with a perpendicular at that axis or direction an angle not diverging by more than 5 degrees; - "median circumferential plane" (denoted M): the plane perpendicular to the Y axis of rotation of the tire which is located midway between the two beads and passes through the middle of the crown reinforcement or belt; - "reinforcement" or "reinforcing thread": any long and thin strand that is to say filiform, elongate, of great length relative to its cross section, especially any unitary filament, any multifilament fiber or any assembly of such filaments or fibers such as a plied yarn or cable, this strand or yarn being rectilinear as non-rectilinear, for example twisted, or corrugated, such yarn or yarn being capable of reinforcing a rubber matrix (i.e. increase the tensile properties of the matrix); - "Unidirectional reinforcements": reinforcements substantially parallel to each other, that is to say oriented along the same axis; - "laminate" or "multilayer laminate": within the meaning of the International Patent Classification, any product having at least two layers, of flat or non-planar shape, in contact with each other, which may be or unrelated, connected to each other; the term "bound" or "connected" must be interpreted extensively to include all connecting or joining means, in particular by gluing. On the other hand, unless expressly indicated otherwise, all the percentages (%) indicated are% by mass. P10-3530 - 8 - The expression "x and / or y" means "x" or "y" or both (ie "x and y"). 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., "a" and "b" terminals excluded ) while any range of values referred to as "a to b" means the range of values from "a" to "b" (ie including the strict "a" and "a" limits). "B"). 5. DETAILED DESCRIPTION AND EXAMPLES OF CARRYING OUT THE INVENTION By way of example, FIG. 1 very schematically represents (that is to say, without respecting a specific scale) a radial section of a compliant tire. to the invention, for example for tourism-type vehicle or van, whose belt comprises a multilayer composite laminate according to the invention.
    [0010] This tire (1) according to the invention, defining three perpendicular, circumferential (X), axial (Y) and radial (Z) directions, comprises an apex (2) surmounted by a tread (3), two sidewalls (4), two beads (5), each flank (4) connecting each bead (5) to the top (2), a carcass reinforcement (7) anchored in each of the beads (5) and extending into the flanks ( 4) to the top (2), a crown reinforcement or belt (10) extending in the crown (2) in the circumferential direction (X) and radially between the carcass reinforcement (7) and the web rolling (3). The carcass reinforcement (7) is in a known manner constituted by at least one rubber ply reinforced by so-called "radial" textile cords arranged substantially parallel to each other and extending from one bead to the other so as to form an angle generally between 80 ° and 90 ° with the median circumferential plane M; it is here, for example, wrapped around two rods (6) in each bead (5), 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).
    [0011] According to the present invention, in accordance with the representations of Figures 2 and 3 which will be detailed later, the belt (10) of the tire (1) comprises a multilayer composite laminate comprising three layers (10a, 10b, 10c) superimposed reinforcements, said reinforcements being in each unidirectional layer and embedded in a thickness of rubber (respectively Cl, C2, C3), with: tread side, a first layer (10a) of rubber (Cl) having a first row of reinforcements (110), oriented according to an angle alpha of -5 to +5 degrees with respect to the circumferential direction (X), these reinforcements (110) said first reinforcements having a bulk diameter denoted D1 between 0.30 mm and 0.60 mm and being in heat-shrinkable textile material; P10-3530 -9- - in contact with the first layer (10b) and disposed under the latter, a second layer (10b) of rubber (C2) having a second row of reinforcements (120), oriented at a given angle beta, positive or negative, between 10 and 30 degrees relative to the circumferential direction (X), these reinforcements (120) said second reinforcements having a diameter or thickness, noted (e) D2, included (e) between 0.20 mm and 0.50 mm; - In contact with the second layer (10b) and disposed under the latter, a third layer (10c) of rubber (C3) having a third row of reinforcements (130), oriented at a gamma angle opposite the angle beta, -Even between 10 and 30 degrees relative to the circumferential direction (X), identical to or different from the angle beta, these reinforcements (130) said third reinforcements having a diameter or thickness, noted (e) D3, inclusive ( e) between 0.20 mm and 0.50 mm. According to the invention, the angles p and 'y of opposite directions, both between 100 and 30 °, may be identical or different, that is to say that the second (120) and third (130) reinforcements may be arranged symmetrically or not, on either side of the median circumferential plane (M) previously defined. In this tire shown schematically in Figure 1, it will be understood of course that the tread (3), the multilayer laminate (10) and the carcass reinforcement (7) may or may not be in contact with each other, even if these parts have been voluntarily separated in Figure 1, schematically, for reasons of simplicity and clarity of the drawing. They could be physically separated, at least for a part of them, for example by bonding gums, well known to those skilled in the art, intended to optimize the cohesion of the assembly after baking or crosslinking. In the tire of the invention, according to a first essential characteristic, all or part of the first reinforcements (110) of heat-shrinkable textile material are multifilament fibers twisted individually on themselves at a twist T greater than 100 tr / m (revolutions per second). metre). In other words, for all or part, these first reinforcements (110) are each constituted by a single-stranded multifilament fiber which is twisted individually on itself, commonly called "surtors" as opposed to a twisted pair in which, in a well-known manner, at least two fibers (or strands) are first twisted individually in a given direction (for example in the S direction) and then (at least) two twisted together in the opposite direction (Z direction) to constitute finally this twists assembly of at least two strands. P10-3530 - The torsion (individual) denoted T of this multifilament fiber is preferably between 100 and 450 tr / m, more preferably in a range from 120 to 350 tr / m, in particular in a range from 140 to at 300 rpm.
    [0012] The linear density or titer of the multifilament fibers is preferably between 50 and 250 tex (g / 1000 m of fiber), more preferably in a range from 65 to 200 tex. The overall diameter (average) D1 of these first textile reinforcements (110) is for its part between 0.30 mm and 0.60 mm, preferably between 0.35 and 0.55 mm, in particular included in a range from 0.40 to 0.50 mm; the diameter of the cylinder of imaginary revolution which surrounds such first textile reinforcements (110) in the case where they are not circular in cross section is customarily understood as the overall diameter.
    [0013] Preferably, the thermal contraction (denoted by CT) of the first reinforcers (110) of heat-shrinkable textile material, after 2 min at 185 ° C., is less than 7.5%, more preferably less than 7.0%, in particular less than 6.0%, values which proved preferable for the manufacturing and dimensioning stability of the tire casings, in particular during the phases of cooking and cooling of the latter.
    [0014] This is the relative contraction of these first reinforcements (110) under the conditions described hereinafter of the test. The quantity CT is measured, except for different precisions, according to the ASTM D1204-08 standard, for example on a device of the "TESTRITE" type, under a so-called standard pretension of 0.5 cN / tex (thus reduced to the title or linear density of the sample tested).
    [0015] At constant length, the maximum of the contraction force (denoted FO) is also measured using the above test, this time at a temperature of 180 ° C. and under a 3% elongation. preferably, greater than 10 N (Newton) A high contraction force proved to be particularly favorable to the hooping capacity of the first reinforcements (110) of heat-shrinkable textile material, with respect to the crown reinforcement of the tire when the latter heats up under a high rolling speed The CT and Fc quantities above can be indistinctly measured on the initial textile reinforcements glued before their incorporation into the laminate and then into the tire, or else measured on these reinforcements once extracted of the central zone of the vulcanized tire and preferably "degummed" (that is to say, freed of the rubber which coats them in the layer C1). tile is suitable, in particular and preferably a textile material satisfying the contraction characteristics CT stated above is suitable.
    [0016] Preferably, this heat-shrinkable textile material is selected from the group consisting of P10-3530 polyamides, polyesters and polyketones. Among the polyamides (or nylons), there may be mentioned polyamides 4-6, 6, 6-6, 11 or 12. Among the polyesters, there may be mentioned for example PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PBN (polybutylene naphthalate), PPT (polypropylene terephthalate), PPN (polypropylene naphthalate). More preferably, the heat-shrinkable textile material constituting the first reinforcements (110) is a polyamide (nylon) or a polyester.
    [0017] Preferably, the multifilament fibers individually twisted on themselves represent the majority (by definition majority in number), preferably all of the first (110) reinforcements of the first layer (10a) of rubber (Cl). Thanks to their greater compactness, these surtors have the advantage, compared to textile ropes formed of conventionally twisted multifilament fibers, to better protect against humidity the rest of the multilayer composite laminate, thus limiting the risk of penalizing the adhesion between the various reinforcements of the laminate and their surrounding rubber matrix, not to mention the risks of surface corrosion of the steel monofilaments.
    [0018] In the tire of the invention, according to a second essential characteristic, all or part of the second (120) and / or third (130) reinforcements are composite reinforcements consisting of steel monofilaments (120a, 130a) which are covered with a sheath (120b, 130b) of a thermoplastic material, these monofilaments, for reminder, not being twisted, wired together but used in the unitary state. The glass transition temperature Tg of the thermoplastic is greater than 20 ° C; it is preferably greater than 50 ° C, more preferably greater than 70 ° C. Its melting temperature (denoted Tf) is preferably greater than 150 ° C., more preferably greater than 200 ° C. Tg and Tf are measured in a known manner by differential scanning calorimetry (DSC), in the second pass, for example, and unless otherwise specified in the present application, according to ASTM D3418 of 1999 (Mettler Toledo DSC apparatus "822-2"). Nitrogen atmosphere: samples previously brought from room temperature (23 ° C) to 250 ° C (10 ° C / min), then cooled rapidly to 23 ° C, before final recording of the DSC curve of 23 ° C at 250 ° C, with a ramp of 10 ° C / min). The minimum thickness (denoted Em) of the thermoplastic sheath (120b, 130b) covering the steel monofilaments (120a, 130a) of the second (120) and / or third (130) (more preferably P10-3530 - 12) second and third) composite reinforcements, as schematized in FIGS. 3a, 3b and 3c, is preferably between 5 and 150 pm, more preferably between 10 and 100 pm, in particular between 15 and 50 pm
    [0019] As this thermoplastic sheath has rigidity intermediate the rigidity of the steel monofilaments and the rigidity of the rubber matrix coating them, the stresses exerted on the interfaces are reduced, which is likely to further improve the overall endurance of the multilayer laminate of the tire. of the invention. 1 () Typically, the thermoplastic material is a polymer or a polymeric composition (i.e. a composition based on at least one polymer and at least one additive). This thermoplastic polymer is preferably selected from the group consisting of polyamides, polyesters, polyimides and mixtures of such polymers; more particularly, this polymer is a polyamide or a polyester. Among the (aliphatic) polyamides, mention may be made especially of polyamides 4-6, 6, 6-6, 11 or 12. Among the polyesters, mention may be made more particularly of PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene terephthalate), PBN (polybutylene naphthalate), PPT (polypropylene terephthalate), PPN (polypropylene naphthalate). To the above polymer or polymer blend, various additives such as dye, filler, plasticizer, antioxidant or other stabilizer may optionally be added to form a polymeric composition. 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 type TPS (styrene thermoplastic) elastomers, in particular epoxidized, as described for example in the applications WO 2013/117474 and WO 2013/117475. According to a preferred embodiment, the sheath comprises a single layer of thermoplastic material. As a variant, the sheath could however comprise several distinct layers, at least one or even all of them being thermoplastic material. The different materials and layers described in applications 35 and WO2012 / 104281 can thus be used. The second (120) and third (130) reinforcements according to the invention have a diameter (or by definition a thickness if their cross section is not circular), respectively denoted D2 and 40 D3, which is between 0.20 mm and 0.50 mm. D2 and D3 may be the same or P10-3530 W02010 / 136389, WO2010 / 105975, WO2011 / 012521, WO2011 / 051204, WO2012 / 016757, WO2012 / 038340, WO2012 / 038341, WO2012 / 069346, WO2012 / 104279, WO2012 / 104280 - 13 - different from one layer to another; if they are different, D3 may be greater than D2 or less than D2, depending on the particular embodiments of the invention. Preferably D2 and / or D3 (more preferably D2 and D3) are greater than 0.25 mm and less than 0.40 mm. More preferentially, for optimum endurance of the tire of the invention, especially under severe driving conditions, it is preferred that D 2 and / or D 3 (more preferably D 2 and D 3) be in a range from 0.28 to 0.35. mm. Preferably, the steel is a carbon steel, such as for example those used in the "steel cords" type cables for tires; but it is of course possible to use other steels, for example stainless steels, or other alloys. According to a preferred embodiment, when a carbon steel is used, its carbon content (% by weight of steel) is in a range of 0.5% to 1.2%, more preferably 0.7%. % to 1.0%. The invention applies in particular to steels of the steel cord type with normal resistance (called "NT" for "Normal Tensile") or with high resistance (called "HT" for "High Tensile"), the (second and third ) reinforcing carbon steel then having a tensile strength (Rm) which is preferably greater than 2000 MPa, more preferably greater than 2500 MPa. The invention also applies to steels of the steel cord type with very high strength (called "SHT" for "Super High Tensile"), ultra-high strength (called "UHT" for "Ultra High Tensile" or "MT" for "Mega Tensile"), the (second and third) carbon steel reinforcements then having a tensile strength (Rm) which is preferably greater than 3000 MPa, more preferably greater than 3500 MPa. The total elongation at break (Δt) of these reinforcements, sum of the elastic elongation and the plastic elongation, is preferably greater than 2.0%. For reinforcements (second and third) in steel, tensile strength, tensile strength Rm (in MPa) and elongation at break noted At (total elongation in%) are measured. in tension according to ISO 6892 of 1984.
    [0020] The steel used, whether it is in particular a carbon steel or a stainless steel, may itself be coated, before cladding by the thermoplastic material, with a metal layer improving, for example, the properties implementation of the steel monofilament, or the properties of use of the reinforcement and / or the tire themselves, such as adhesion properties, corrosion resistance or resistance to aging. The steel may for example be covered with a layer of brass (Zn-Cu alloy) or zinc; it is recalled in particular that during the wire manufacturing process, the coating of brass or zinc facilitates the drawing of the wire, as well as the bonding of the wire with the rubber. P10-3530 - 14 - The step of cladding or covering the steel monofilaments with the thermoplastic material is carried out in a manner that is well known to those skilled in the art, for example by passing the monofilament, or even, if appropriate, several monofilaments arranged in parallel. , through one or more dies of suitable diameter, in extrusion heads heated to appropriate temperatures, or in a coating bath containing the thermoplastic material previously placed in solution in a suitable organic solvent (or mixture of solvents) . At the outlet of the extrusion head, the one or more monofilaments 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. Advantageously, before deposition of the thermoplastic material sheath, the steel monofilaments can be subjected to an adhesion treatment in order to improve the subsequent adhesion between the steel and the thermoplastic sheath. Preferably, the thermoplastic material sheath is then provided with an adhesive layer with respect to each layer of rubber composition with which it is in contact. 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 (resorcinol-formaldehyde-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, 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).
    [0021] 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. It will be readily understood by those skilled in the art that the connection between the thermoplastic sheath and each layer of rubber with which it is in contact is definitely ensured during the final baking (crosslinking) of the bandage for which it is intended. the laminate.
    [0022] According to a preferred embodiment of the invention, the steel monofils sheathed by the thermoplastic sheath represent the majority (by definition, majority in number), more preferably all, of the second (120) reinforcements of the second layer (10b). of rubber (C2). According to another preferred embodiment, combined or not with the preceding, the steel monofilaments sheathed by the thermoplastic sheath represent the majority, more preferably all, of the third reinforcements (130) of the third layer (10c) of rubber (C3) . Each layer (C1, C2, C3) of rubber composition (or hereinafter "rubber layer") constituting the multilayer composite laminate, is based on at least one elastomer and a filler. Preferably, the rubber is a diene rubber, that is to say for all elastomeric recall (single elastomer or elastomer mixture) which is derived, at least in part (ie, a homopolymer or a copolymer), monomers dienes that is to say monomers bearing two carbon-carbon double bonds, whether the latter are conjugated or not. This diene elastomer is more preferably selected from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), butadiene copolymers, isoprene copolymers, and mixtures of these elastomers. such copolymers being especially chosen from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene-copolymers. butadiene-styrene (SBIR).
    [0023] 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.
    [0024] Each rubber composition may comprise one or more diene elastomer (s), also all or part of the additives normally used in rubber matrices for the manufacture of tires, such as, for example, reinforcing fillers such as black rubber. carbon or silica, coupling agents, anti-aging agents, antioxidants, plasticizing agents or extension oils, whether these are of aromatic or non-aromatic nature (in particular very low or non-aromatic oils, for example of the naphthenic or paraffinic type, with high or preferably low viscosity, MES or TDAE oils), plasticizing resins with a high glass transition temperature (greater than 30 ° C.), agents facilitating the use (processability ) green compositions, tackifying resins, anti-eversion agents, methylene acceptors and donors such as for example Mple HMT (hexamethylenetetramine) or H3M (hexamethoxymethylmelamine), reinforcing resins (such as resorcinol or bismaleimide), known adhesion promoter systems such as metal salts for example, including salts of cobalt, nickel or lanthanide, a system crosslinking or vulcanization. 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 and / or silica, is preferably greater than 30 phr, especially between 30 and 100 phr.
    [0025] 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).
    [0026] 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 compositions in order to achieve the desired levels of properties (in particular modulus of elasticity), and adapt the formulation to the specific application considered. Preferably, each 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 particularly suitable. 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). In order to adhere the first, second and third reinforcements to their three respective rubber layers (C1, C2, C3) previously described, any suitable adhesive system, for example a textile glue of the "RFL" type (resorcinol-formaldehyde), may be used. latex) or equivalent as regards the first textile reinforcements and steel monofilaments sheathed by their thermoplastic material. The tire of the invention has, for other preferential characteristics, at least one, preferably the two following ones: the density d1 of the first reinforcements (110) in the first rubber layer (C1), measured in the axial direction (Y) is between 90 and 150 threads / dm (decimetre, i.e., 100 mm of rubber layer); the density, respectively denoted d2 and d3, of the second (120) and third (130) reinforcements in respectively the second (C2) and third (C3) rubber layers, measured in the axial direction (Y), is between 100 and 180 threads / dm. More preferably, at least one, preferably the two following characteristics are verified: the density d1 is between 100 and 140 son / dm; densities d2 and d3 are between 110 and 170, more preferably still between 120 and 160 threads / dm.
    [0027] On the other hand and according to another preferred embodiment of the invention, at least one of the following characteristics is verified (more preferably all three): the average thickness Ezi of rubber separating a first reinforcement (110) from the first layer (C1) of the second reinforcement (120) of the second layer (C2) which is closest thereto, measured in the radial direction (Z), is less than 0.40 mm, more preferably between 0.20 and 0.40 mm, in particular between 0.20 and 0.35 mm; the average thickness Ez2 of rubber separating a second reinforcement (120) from the second layer (C2), the third reinforcement (130) of the third layer (C3) which is closest to it, measured in the radial direction (Z ), is less than 0.60 mm, more preferably between 0.35 and 0.60 mm, in particular between 0.35 and 0.55 mm; the total thickness of the multilayer composite laminate, that is to say of its three superimposed layers (C1, C2, C3), measured in the radial direction Z, is between 1.8 and 2.7 mm, in especially between 2.0 and 2.5 mm. All the data indicated previously (Dl, D2, D3, Em, d1, d2, d3, Ezi, Ez2 and total thickness) are average values measured experimentally by an operator on photographs of radial cuts of vulcanized tires, operated in the part central belt, 5 cm on either side of the median plane (M), or over a total width of 10 cm (or between - 5 cm and + 5 cm from the median plane M). FIG. 2 schematically represents (in a specific scale), in cross-section, an example of a multilayer composite laminate (10a, 10b, 10c) used as a belt (10) in the tire (1) according to FIG. invention of Figure 1, the laminate (10) incorporating: - Reinforcements (110) of heat-shrinkable textile material (for example polyester or polyamide) in the form of a multifilament fiber twisted on itself with a twist greater than 100 tr / m; second (120) and / or third (130) composite reinforcements as illustrated in greater detail in FIG. 3, comprising steel monofilaments (120a, 130a) which are covered with a sheath (120b, 130b), a thermoplastic material of Tg greater than 20 ° C, for example polyester or polyamide. By way of example, the sheath (120b, 130b) may be circular, square or rectangular (Fig. 3a, 3b and 3c). It could also be oblong, for example.
    [0028] The steel monofilaments sheathed by the thermoplastic material can be sheathed individually as indicated by way of example in Figures 3a and 3b, this being a preferred embodiment. But, according to another preferred embodiment, it is several steel monofilaments (all or part of the reinforcements 120 and / or 130 of the laminate) which could be collectively sheathed by the same thermoplastic sheath, as indicated by way of example to FIG. 3c where the final reinforcement 130 is constituted by 4 P10-3530 steel monofilaments (130a) which have been collectively sheathed by a single sheath of thermoplastic material (130b). It should be emphasized that the use of the same thermoplastic material, for example polyester or polyamide, to constitute on the one hand the heat-shrinkable textile material and on the other hand the material sheathing the steel monofilaments, can be particularly advantageous since no Compatibility problem arises then between the respective reinforcements, especially in case of parasitic direct contact between them.
    [0029] As illustrated in FIG. 2, Ezi is the average of the thicknesses (Ezi (1), Ezi (2), Ezi (3), Eziw) of rubber separating a first reinforcement (110) from the second reinforcement (120) which is the same closer, these thicknesses being each measured in the radial direction Z, and averaged over a total axial distance of between - 5.0 cm and + 5.0 cm with respect to the center of the belt (ie, for example in total about 100 measurements if there are ten reinforcements (110) per cm in the layer C1). Expressed otherwise, Ezi is the average of the minimum distances Eziw separating "back to back" each first reinforcement (110) of the second reinforcement (120), of course including sheath, which is closest to it in the radial direction Z, this average being calculated on all the first reinforcements (110) present in the central part of the belt, in an axial interval extending between -5 cm and + 5 cm with respect to the median plane M. Similarly, Ez2 is the average of rubber thicknesses (Ez2 (1), Ez2 (2), Ez2 (3), - - - Ez2 (0) separating a second reinforcement (120) from the third reinforcement (130) which is closest thereto, measured in the direction Radial Z, this average being calculated over a total axial distance of between - 5.0 cm and + 5.0 cm from the center of the belt.Expressed differently, these thicknesses represent the minimum distances that separate "back to back" the second reinforcement (120) of the third reinforcement (130) which is the most close in the radial direction Z.
    [0030] Expressed differently, Ez2 is the average of the minimum distances Ez2 () separating "back to back" each second reinforcement (120) of the third reinforcement (130), including sheaths included, which is closest to it in the radial direction Z, this average being calculated on all of the second reinforcements (120) present in the central part of the belt, in an axial gap extending between -5 cm and + 5 cm with respect to the median plane M. For optimized performance in terms of of rolling resistance, drift thrust and rolling endurance, the tire of the invention preferably satisfies at least one of the following inequalities (more preferably all three): P10-3530 - 20 - 0,15 <Ezi / (Ezi + D1 + D2) <0.30 0.20 <Ez2 / (Ez2 + D2 + D3) <0.50 0.20 <(Ezi + Ez2) / (Ezi + Ez2 + D1 + D2 + D3) <0.40.
    [0031] In conclusion, the invention offers the possibility of keeping the thickness of the tire belts at a low level or even further reducing the thickness of the tire belts and that of the rubber layers constituting part of their structure, ultimately the weight and the rolling resistance of the tires. pneumatic tires, without the risk of direct contact between the different reinforcements.
    [0032] The multilayer composite laminate is better protected from moisture by using in its first layer of multifilament textile fibers twisted individually on themselves. The thermoplastic sheath also constitutes an effective barrier against corrosive agents that can penetrate the multilayer laminate in the event of tire stresses. Finally, this sheath having an intermediate rigidity between those of the steel monofilaments and the rubber matrix coating them, the stresses exerted on the interfaces are reduced, which is likely to improve the overall endurance of the multilayer composite laminate of the tire of FIG. 'invention.
    [0033] P10-3530
    权利要求:
    Claims (25)
    [0001]
    REVENDICATIONS1. Radial tire (1), defining three main directions, circumferential (X), axial (Y) and radial (Z), comprising a crown (2) surmounted by a tread (3), two sidewalls (4), two bead (5), each flank (4) connecting each bead (5) to the top (2), a carcass reinforcement (7) anchored in each of the beads (5) and extending in the flanks (4) to vertex (2), a crown reinforcement or belt (10) extending in the crown (2) in the circumferential direction (X) and radially between the carcass reinforcement (7) and the tread (3) said belt (10) comprising a multilayer composite laminate (10a, 10b, 10c) comprising at least three superposed layers of reinforcements (110, 120, 130), said reinforcements being in each layer unidirectional and embedded in a rubber thickness (respectively C1, C2, C3), with: - tread side, a first layer (10a) of rubber (Cl) comprising a first row of reinforcements (110), oriented at an angle alpha of -5 to +5 degrees with respect to the circumferential direction (X), these reinforcements (110) said first reinforcements having a bulk diameter denoted D1 between 0, 30 mm and 0.60 mm and being made of heat-shrinkable textile material; - In contact with the first layer (10b) and disposed beneath the latter, a second layer (10b) of rubber (C2) comprising a second row of reinforcements (120), oriented at a given beta angle, positive or negative, between 10 and 30 degrees relative to the circumferential direction (X), these reinforcements (120) said second reinforcements having a diameter or thickness, noted (e) D2, included (e) between 0.20 mm and 0.50 mm; - In contact with the second layer (10b) and disposed under the latter, a third layer (10c) of rubber (C3) having a third row of reinforcements (130), oriented at a gamma angle opposite the angle beta, -even between 10 and 30 degrees relative to the circumferential direction (X), these reinforcements (130) said third reinforcements having a diameter or thickness, noted (e) D3, included (e) between 0.20 mm and 0, 50 mm, characterized in that: - all or part of the first reinforcements (110) of heat-shrinkable textile material are multifilament fibers twisted individually on themselves at a twist T greater than 100 turns per meter; all or part of the second (120) and / or third (130) reinforcements are composite reinforcements comprising steel monofilaments (120a, 130a) which are covered with a sheath (120b, 130b) of a thermoplastic material whose glass transition temperature Tg is greater than 20 ° C.
    [0002]
    2. A tire according to claim 1, wherein the twist T of the multifilament fibers is between 100 and 450 rpm, preferably in a range of 120 to 350 rpm.
    [0003]
    3. A tire according to claims 1 or 2, wherein the linear density of the multifilament fibers is between 50 and 250 tex, preferably in a range from 65 to 200 tex.
    [0004]
    A tire according to any one of claims 1 to 3, wherein D1 is between 0.35 mm and 0.55 mm, preferably in a range of 0.40 mm to 0.50 mm.
    [0005]
    A tire according to any one of claims 1 to 4, wherein the density of first reinforcements (110) in the first rubber layer (C1) measured in the axial direction (Y) is between 90 and 150. son / dm, preferably between 100 and 140 son / dm.
    [0006]
    6. A tire according to any one of claims 1 to 5, wherein the thermal contraction CT of the first reinforcements (110) of heat-shrinkable textile material after 2 min at 185 ° C is less than 7.5%.
    [0007]
    The tire of claim 6, wherein CT is less than 7.0%, preferably less than 6.0%.
    [0008]
    8. A tire according to any one of claims 1 to 7, wherein the heat-shrinkable textile material constituting the first reinforcements (110) is a polyamide or a polyester.
    [0009]
    Tire according to any one of claims 1 to 8, in which the multifilament fibers twisted individually on themselves represent the majority, preferably all, of the first (110) reinforcements of the first layer (10a) of rubber (C1). .
    [0010]
    10. The tire according to any one of claims 1 to 9, wherein D2 and / or D3 are greater than 0.25 mm and less than 0.40 mm.
    [0011]
    Tire according to claim 10, wherein D2 and / or D3 are within a range of 0.28 to 0.35 mm. P10-3530 35- 23 -
    [0012]
    12. A tire according to any one of claims 1 to 11, wherein the minimum thickness denoted Em of the thermoplastic sheath (120b, 130b) covering the steel monofilaments (120a, 130a) of the second (120) and / or third (130) composite reinforcements is between 5 and 150 μm, preferably between 10 and 100 μm.
    [0013]
    13. A tire according to any one of claims 1 to 12, wherein Tg is greater than 50 ° C, preferably greater than 70 ° C.
    [0014]
    Tire according to any one of claims 1 to 13, wherein the thermoplastic material is a polymer or a polymer composition.
    [0015]
    The tire of claim 14, wherein the polymer is a polyamide or a polyester.
    [0016]
    16. A tire according to any one of claims 1 to 15, wherein the density, respectively d2 and d3, of the second (120) and third (130) reinforcements in the second (C2) and third (C3) rubber layers respectively. , measured in the axial direction (Y), is between 100 and 180 threads / dm.
    [0017]
    17. A tire according to claim 16, wherein the densities d2 and d3 are between 110 and 170, preferably between 120 and 160 son / dm.
    [0018]
    18. A tire according to any one of claims 1 to 17, wherein the constituent steel of the second and third reinforcements (120, 130) is a carbon steel.
    [0019]
    19. A tire according to any one of claims 1 to 18, in which the steel monofilaments sheathed by the thermoplastic sheath represent the majority, preferably all, of the second (120) reinforcements of the second layer (10b) of rubber (C2). .
    [0020]
    20. A tire according to any one of claims 1 to 19, in which the steel monofilaments sheathed by the thermoplastic sheath represent the majority, preferably all, of the third reinforcements (130) of the third layer (10c) of rubber (C3). .
    [0021]
    Tire according to any one of claims 1 to 20, wherein the following characteristic, measured in the central part of the belt of the tire in the vulcanized state, on either side of the median plane (M) on a 10 cm axial width, is checked: P10-3530 30 35 40- 24 - _ the average thickness Ezi rubber separating a first reinforcement (110) of the second reinforcement (120) which is closest to it, measured in the radial direction (Z) is less than 0.40 mm, preferably between 0.20 and 0.40 mm.
    [0022]
    22. A tire according to any one of claims 1 to 21, wherein the following characteristic, measured in the central part of the belt of the tire in the vulcanized state, on either side of the median plane (M) on a total axial width of 10 cm, is verified: - the average thickness Ez2 rubber separating a second reinforcement (120) of the third reinforcement (130) which is closest thereto, measured in the radial direction (Z), is less than 0.60 mm, preferably between 0.35 and 0.60 mm.
    [0023]
    23. A tire according to any one of claims 1 to 22, wherein the following inequality is verified: 0.15 <Ezi / (Ezi + D1 + D2) <0.30
    [0024]
    24. A tire according to any one of claims 1 to 23, wherein the following inequality is verified: 0.20 <Ez2 / (Ez2 + D2 + D3) <0.50
    [0025]
    25. A tire according to any one of claims 1 to 24, wherein the following inequality is verified: 0.20 <(Ezi + Ez2) / (Ezi + Ez2 + D1 + D2 + D3) <0.40 P10 -3530
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    同族专利:
    公开号 | 公开日
    EP3253596A1|2017-12-13|
    FR3032148B1|2017-02-17|
    JP6896634B2|2021-06-30|
    JP2018504317A|2018-02-15|
    KR20170115510A|2017-10-17|
    EP3253596B1|2020-06-03|
    WO2016124418A1|2016-08-11|
    US20180022158A1|2018-01-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP2505386A1|2009-11-26|2012-10-03|Bridgestone Corporation|Pneumatic tire|
    EP2380754A2|2010-04-26|2011-10-26|The Goodyear Tire & Rubber Company|Hybrid cord in a belt ply for a pneumatic tire|
    DE112012005462T5|2011-12-26|2014-09-11|The Yokohama Rubber Co., Ltd|Pneumatic radial tire|
    DE2853006C2|1978-12-07|1993-12-16|Uniroyal Englebert Gmbh|Pneumatic vehicle tires|
    JP4053727B2|2000-11-22|2008-02-27|住友ゴム工業株式会社|Pneumatic radial tire|
    FR2971188B1|2011-02-03|2013-03-08|Michelin Soc Tech|SOLDER COMPOSITE REINFORCEMENT OF A SELF-ADHERING RUBBER POLYMER LAYER|
    FR2986739B1|2012-02-09|2014-03-21|Michelin & Cie|PNEUMATIC WITH ALLEGE BELT STRUCTURE|
    FR2986740B1|2012-02-09|2014-03-21|Michelin & Cie|PNEUMATIC WITH ALLEGE BELT STRUCTURE|
    FR3008998B1|2013-07-29|2016-01-01|Michelin & Cie|LOW THICKNESS AND PNEUMATIC REINFORCED PRODUCT COMPRISING THIS PRODUCT|FR3048638B1|2016-03-11|2018-03-30|Compagnie Generale Des Etablissements Michelin|RADIAL TIRE HAVING IMPROVED BELT STRUCTURE|
    CN112004691A|2018-04-17|2020-11-27|米其林集团总公司|Protective reinforcement comprising different layers for a pneumatic tire for a heavy civil engineering vehicle|
    KR102288493B1|2020-03-19|2021-08-10|넥센타이어 주식회사|Steel cord for tire and method of manufacturing the same|
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    2016-08-05| PLSC| Search report ready|Effective date: 20160805 |
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    2019-10-25| ST| Notification of lapse|Effective date: 20191006 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1550813A|FR3032148B1|2015-02-03|2015-02-03|RADIAL TIRE HAVING IMPROVED BELT STRUCTURE|FR1550813A| FR3032148B1|2015-02-03|2015-02-03|RADIAL TIRE HAVING IMPROVED BELT STRUCTURE|
    KR1020177021234A| KR20170115510A|2015-02-03|2016-01-22|Radial tires with improved belt structure|
    EP16701180.8A| EP3253596B1|2015-02-03|2016-01-22|Radial tyre having an improved belt structure|
    PCT/EP2016/051304| WO2016124418A1|2015-02-03|2016-01-22|Radial tyre having an improved belt structure|
    US15/547,979| US20180022158A1|2015-02-03|2016-01-22|Radial tire having an improved belt structure|
    JP2017541096A| JP6896634B2|2015-02-03|2016-01-22|Radial tire with improved belt structure|
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