• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The reinforcing member has a generally flattened section extending in a main direction and comprising at least one side edge of a polymeric composition comprising a thermoplastic polymer, the side edge extending in a generally parallel direction to the main direction. The method comprises a step of heating at least a portion of the side edge during which energy is transferred to the side edge portion so as to raise the temperature of the side edge portion beyond the temperature. melting the thermoplastic polymer.
    公开号:FR3013622A1
    申请号:FR1361728
    申请日:2013-11-28
    公开日:2015-05-29
    发明作者:David Doisneau；Nicole Dajoux；Clerc Christophe Le；Thomas Guy
    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] The subject of the invention is a method for treating a reinforcing element, a reinforcement element that can be obtained by such a method, a composite element comprising such a reinforcing element and a tire comprising such elements. [002] The invention applies to passenger vehicles, two-wheeled vehicles, industrial vehicles chosen from vans, heavy vehicles such as "heavy truck" - ie, subway, bus, road transport equipment (trucks tractors, trailers), off-the-road vehicles -, agricultural or engineering machinery, aircraft, other transport or handling vehicles. [003] Documents W02010 / 115860 and WO2010 / 115861 are known, a tire for a passenger vehicle comprising a carcass reinforcement anchored in two beads and radially surmounted by a crown reinforcement itself surmounted by a tread which is joined to the beads by two flanks. [004] In such a tire, the crown reinforcement comprises a reinforcement comprising reinforcement elements embedded in an elastomer matrix. Each reinforcing element has a section of generally flattened shape and extends in a main direction. The reinforcing elements are substantially parallel to each other in a direction substantially parallel to the main direction.
    [0002] Each reinforcing element is made of polyethylene terephthalate (PET). [5] During a low load (1 ° of drift) of the tire in turns, it has been observed that the rigidity or drift thrust ("drift thrust" or "cornering") was not altered with respect to conventional reinforcing elements comprising metallic or textile cords. However, during strong stresses (greater than 5 ° of drift), it was observed that the rigidity or thrust drift of the tire of the state of the art was altered, albeit in a small way but that this alteration was significant and was susceptible to make the handling of the tire less efficient. The object of the invention is to improve the stiffness or thrust of a tire using reinforcing elements having a section of generally flattened shape. [7] For this purpose, the subject of the invention is a process for treating a reinforcing element having a section of generally flattened shape and extending in a main direction and comprising at least one lateral edge in a polymeric composition comprising a thermoplastic polymer, the lateral edge extending in a general direction substantially parallel to the main direction. The method according to the invention comprises a step of heating at least a part of the lateral edge during which energy is transferred to the part of the lateral edge so as to raise the temperature of the part of the lateral edge beyond the melting temperature of the thermoplastic polymer. [008] The reinforcing element obtained by the method according to the invention allows the tire to have improved rigidity or drifting thrust relative to the tire of the state of the art as shown by the comparative tests below. [9] Indeed, the inventors at the origin of the invention explain a posteriori the improvement in drift rigidity by decreasing the stiffness gradient between each reinforcing element and the elastomer matrix in which it is embedded. this reduction in rigidity being obtained by modifying the structure of the thermoplastic polymer by heating. Thus, the shearing forces between the reinforcing element and the elastomer matrix are reduced, in particular during heavy stresses in tire drift. [10] The reinforcing element has a section of generally flattened shape, that is to say that the section has two dimensions extending in directions substantially perpendicular to one another and one of which is bigger than the other. In other words, the reinforcing element is wider than it is thick. The section of the reinforcing element is the section along a cutting plane substantially perpendicular to the main direction of the reinforcing element. [11] Examples of sections of generally flattened shape are sections of oblong, elliptical, oval, rectangular, parallelogram or rhombus. Preferably, the section has a generally rectangular shape. [012] The polymeric composition may comprise additives added to the thermoplastic polymer, in particular at the time of shaping of the latter, these additives possibly being, for example, anti-aging agents, plasticizers, fillers such as silica, clay, talc, kaolin or short fibers; fillers may for example be used to make the surface of the reinforcing element more rough and thus contribute to improving its adhesion of adhesive and / or its adhesion to the elastomer matrix. The polymer composition may comprise other polymers than the thermoplastic polymer, for example other thermoplastic polymers or elastomers, as well as other non-polymeric components. [014] The reinforcing element is a three-dimensional element having a length G, a width L and a thickness E each extending in a general direction P10-3194_FR - 3 - substantially perpendicular to the general directions along which extend the two other dimensions and wherein G> L> E. [15] By definition, the thickness of the reinforcing element is the space requirement, that is to say the maximum dimension of the reinforcing element in a direction substantially parallel to the general direction of the thickness of the reinforcement element. the reinforcing element. [16] By definition, the width of the reinforcing element is the space requirement, that is to say the maximum dimension of the reinforcing element in a direction substantially parallel to the general direction of the width of the reinforcement element. reinforcing element. [17] In one embodiment, the energy is transferred by radiation from an energy source. By radiation is meant the heat transfer caused by the propagation of electromagnetic waves. Examples of radiation are UV (ultraviolet), IR (Infrared) or LASER ("Light Amplification by Stimulated Emission of Radiation"). [18] In yet another embodiment, energy is transferred by conduction from an energy source. By conduction is meant the heat transfer due to the thermal agitation transmitted between molecules or elements of a solid. An example of transfer by conduction is a heating blade in contact with which the side edge of the reinforcing element scrolls. [19] In another embodiment, energy is transferred by convection from an energy source. By convection is meant the heat transfer caused by the movement of particles of a fluid or a gas. [20] In a preferred embodiment, the energy is transferred by subjecting at least a portion of the side edge to a plasma stream. A plasma makes it possible to generate, from a gas subjected to an electrical voltage, a heat flux comprising molecules in the gaseous state, ions and electrons. [21] Preferably, the heating step is carried out at atmospheric pressure, especially when this is performed by means of a plasma stream. In addition, perform the heating step at atmospheric pressure allows the establishment of a relatively simple and inexpensive industrial installation in contrast to a process requiring reduced pressure and therefore the establishment of a depressurized chamber. [22] Preferably; the plasma flow is generated by means of a plasma torch. The physical modification, generated by the use of a plasma torch, consists of at least partial amorphization, that is to say a decrease in the degree of crystallinity of the portion of the exposed edge. Thus, this part of the edge being less organized, it has less rigidity. P10-3194_EN - 4 - [023] The plasma torch makes it possible, thanks to the power of its plasma flow, to round off any edges present or delimiting the lateral edge which could serve as a starting point for breaking the interface between the elastomer matrix and the reinforcing element. [024] Preferably, the plasma is of the cold plasma type. Such a plasma, also called non-equilibrium plasma is such that the temperature comes mainly from the movement of electrons. A cold plasma must be distinguished from a hot plasma, also called thermal plasma in which the electrons, but also the ions confer on this plasma certain properties, in particular thermal, different from those of the cold plasma. [25] Advantageously, the plasma stream is generated from a gas comprising at least one oxidizing component. By oxidizing component is meant any component capable of increasing the degree of oxidation of one or more chemical functions present in the polymeric composition. In addition, the chemical modification, generated by the use of the gas comprising at least one oxidizing component, consists of an increase in the polarity of the portion of the exposed edge. Thus, this portion of the exposed edge is more hydrophilic which improves the wettability of the side edge. In addition, the portion of the exposed edge carries polar groups created by the flow of plasma capable of chemically reacting with the elastomer matrix and a possible adhesion adhesive. [26] Advantageously, the oxidizing component is chosen from carbon dioxide (002), carbon monoxide (CO), hydrogen sulphide (H2S), carbon disulfide (CS2), dioxygen (O2), nitrogen (N2), chlorine (Cl2), ammonia (NH3) and a mixture of these components. Preferably, the oxidizing component is chosen from oxygen (O 2), nitrogen (N 2) and a mixture of these components. More preferably, the oxidizing component is air. [27] Preferably, the reinforcing element is scrolled with respect to at least one energy source. Thus, large amounts of reinforcing element can be processed. Those skilled in the art will be able to choose the speed of travel, the intensity of the energy source as well as the distance between the energy source and the lateral edge so as to cause an increase in the temperature of the lateral edge above the temperature of the energy source. melting of the thermoplastic polymer. [28] In particular, in the case of a plasma flow, it will be possible to vary a very large number of parameters such as the running speed V, the distance D between the lateral edge and an outlet orifice of the plasma flow. , the plasma activation time ("PCT" for Plasma Cycle Time), the nature of the gas or even the frequency of pulsation of the plasma torch. [29] Preferably, after the step of heating the portion of the side edge, the reinforcing member is coated with an adhesion adhesive. The adhesive used is, for example, of the RFL (Resorcinol-Formaldehyde-Latex) type or, for example, as described in publications VV02013017421, WO2013017422, WO2013017423. [30] Preferably, the thermoplastic polymer is semi-crystalline. A semicrystalline polymer comprises, on the one hand, crystalline zones, and, on the other hand, amorphous zones. [31] Advantageously, the thermoplastic polymer is chosen from a polyester, a polyamide, a polyketone or a mixture of these materials and preferably is a polyester. Examples of polyesters are terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), polypropylene terephthalate (PPT) or polypropylene naphthalate (PPN). Examples of polyamides are, for example, aliphatic polyamides such as nylon. [32] Preferably, the reinforcing element has a thickness ranging from 0.05 to 1 mm, more preferably from 0.10 to 0.70 mm. For example, thicknesses ranging from 0.20 to 0.60 mm have been found to be most suitable for most uses. [33] Advantageously, the width of the reinforcing element is greater than or equal to 2.5 mm, preferably to 5 mm and more preferably to 10 mm. [34] In a preferred embodiment, the reinforcing element comprises at least one wire element consisting of a film of the polymeric composition. [35] Preferably, the film is stretched multiaxially. [36] Any film of the multiaxially stretched polymeric composition, that is stretched, oriented in more than one direction, is usable. Such multiaxially stretched films are well known and used essentially to date especially in the packaging industry. These films and their methods of obtaining are described in numerous documents, for example GB2134442, DE3621205, US4876137, US4867937, US5409657 US2007 / 0031691 and WO2010 / 115861. [037] Preferably, the film has, regardless of the traction direction considered, a modulus in extension greater than 500 MPa (in particular between 500 and 4000 MPa), more preferably greater than 1000 MPa (in particular between 1000 and 4000 MPa). and even more preferably greater than 2000 MPa. Module values E of between 2000 and 4000 MPa are particularly desirable, particularly for the reinforcement of tires. P10-3194_EN - 6 - [38] According to a preferred embodiment, the film has, whatever the traction direction considered, a maximum tensile stress denoted amax greater than 80 MPa (in particular between 80 and 500 MPa), plus preferably greater than 100 MPa (in particular between 100 and 500 MPa) Amax stress values greater than 150 MPa, in particular between 150 and 500 MPa, are particularly desirable, in particular for reinforcing tires. [39] According to another embodiment preferential, regardless of the direction of traction considered, the plastic deformation threshold noted Yp (also known by the term "Yield point") of the film is located beyond 3% elongation, especially between 3 and 15 Yp values in excess of 4%, in particular between 4 and 12%, are particularly desirable, in particular for reinforcing tires. [40] According to another preferred embodiment, whatever the di traction considered, the film has an elongation at break noted Ar which is greater than 20% (especially between 20 and 200%), more preferably greater than 50%. Ar values between 30 and 200% are particularly desirable, especially for the reinforcement of tires. [41] The mechanical properties stated above are well known to those skilled in the art, deduced from force-elongation curves, measured for example according to ASTM D638-02 for strips of thickness greater than 1 mm, or according to the ASTM D882-09 standard for thin sheets or films whose thickness is at most equal to 1 mm; the values of modulus E and stress amax above, expressed in MPa, are calculated with respect to the initial section of the test specimen. [42] The film used is preferably of the thermally stabilized type, that is to say that it has undergone, after drawing, one or more heat treatments intended in a known manner to limit its thermal contraction (or shrinkage) at a high temperature. temperature ; such heat treatments may consist in particular of annealing, tempering or combinations of such annealing or quenching. [43] Thus, and preferably, the film used has, after 30 min at 150 ° C, a relative contraction of its length which is less than 5%, preferably less than 3% (measured except for different precisions according to ASTM D1204- 08). [44] The melting temperature Tf of the thermoplastic polymer is preferably greater than 100.degree. C., more preferably greater than 150.degree. C., in particular greater than 200.degree. C., especially in the case of reinforcing tires. P10-3194_EN - 7 - [45] Examples of films, in particular multiaxially stretched PET, are the PET films bi-stretched marketed under the names "Mylar" and "Melinex" (DuPont Teijin Films company), or "Hostaphan" (Mistubishi Polyester Film Company). Another object of the invention is a reinforcing element obtainable by a method as described above. [47] The invention also relates to a composite element comprising at least one reinforcing element as defined above embedded in an elastomer matrix. [48] In a preferred embodiment, the composite member has a general band shape. The width L 'and the thickness E' of the composite element are such that L '> E', preferably L '> 10.E'. In one embodiment, the composite member forms a conveyor belt or a belt. [049] Preferably, the composite element comprises several reinforcing elements as defined above embedded in the elastomer matrix and arranged substantially parallel to each other in a direction substantially parallel to the main direction. [050] The elastomer matrix is based on at least one elastomer. [051] Preferably, the elastomer is a diene elastomer. In known manner, the diene elastomers can be classified in two categories: "essentially unsaturated" or "essentially saturated". The term "essentially unsaturated" means a diene elastomer derived at least in part from conjugated diene monomers having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%); Thus, diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated" diene elastomers ( low or very low diene origin, always less than 15%). In the category of "essentially unsaturated" diene elastomers, the term "highly unsaturated" diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%. [052] Although it is applicable to any type of diene elastomer, the present invention is preferably carried out with a diene elastomer of the highly unsaturated type. P10-3194_EN - 8 - [53] This diene elastomer is more preferably selected from the group consisting of polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), different copolymers of butadiene, 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-copolymers of styrene (SIR) and isoprene-butadiene-styrene copolymers (SBIR). [54] A particularly preferred embodiment is to use an "isoprene" elastomer, i.e. a homopolymer or copolymer of isoprene, in other words a diene elastomer selected from the group consisting of rubber natural (NR), synthetic polyisoprenes (IR), different isoprene copolymers and 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. [55] 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. [56] The elastomer matrix may contain one or more diene elastomer (s), which latter (s) can be used in combination with any type of synthetic elastomer other than diene, 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-aging agents. antioxidants, plasticizers or extension oils, whether the latter are of aromatic or non-aromatic nature (in particular very weak 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 Tg greater than 300 ° C, agents facilitating the implementation (processability) of the compositions in the green state, tackifying resins, anti-reversion agents, methylene acceptors and donors such as, for example, HMT (hexamethylenetetramine) or H3M (hexamethoxymethylmelamine), P10-resins. Reinforcing agents (such as resorcinol or bismaleimide), known adhesion promoter systems of the metal salt type, for example, in particular cobalt, nickel or lanthanide salts, a crosslinking or vulcanization system. [57] Preferably, the system for crosslinking the elastomer matrix is a so-called vulcanization system, that is to say based on sulfur (or a sulfur-donor agent) and a primary accelerator vulcanization. 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. [58] Suitable carbon blacks are all carbon blacks, including 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. [059] Those skilled in the art will, 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 specific application envisaged. [60] Preferably, the elastomer matrix has, in the crosslinked state, a secant modulus in extension, at 10% elongation, which is between 4 and 80 MPa, more preferably between 4 and 70 MPa; values in particular between 25 and 60 MPa have proved to be particularly suitable for the reinforcement of tire crown reinforcement. The modulus measurements are carried out in tension, unless otherwise indicated, according to the ASTM D 412 standard of 1998 (specimen "C"): the second elongation (that is to say after an accommodation cycle) is measured secant "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 conditions of temperature and humidity according to ASTM D 1349 of 1999). [61] Advantageously, the reinforcing element is coated with a layer of adhesion adhesive between the reinforcing element and the elastomer matrix. P10-3194_EN -10- [062] The glue used is for example of the type RFL (Resorcinol-FormaldehydeLatex) or for example, as described in publications WO2013017421, WO2013017422, WO2013017423. [063] The invention also relates to a tire comprising a reinforcing element as defined above or a composite element as defined above. [64] In one embodiment, the tire comprises a crown surmounted by a tread, two sidewalls, two beads, each side connecting each bead at the top, a carcass reinforcement anchored in each of the beads and extending into the flanks into the crown, the carcass reinforcement comprising the reinforcing element or the composite element. [65] Preferably, in this embodiment, the main direction is at an angle of 80 to 90 °, preferably 85 ° to 90 ° with the circumferential direction of the tire. [066] In another embodiment, the tire comprises a crown surmounted by a tread, two sidewalls, two beads, each side connecting each bead at the top, a carcass reinforcement anchored in each of the beads and extending in the flanks into the crown, a crown reinforcement radially interposed between the carcass reinforcement and the tread, the crown reinforcement comprises the reinforcing element or the composite element. [67] Preferably, in this embodiment, the main direction is at an angle of 0 ° to 80 °, preferably 5 ° to 50 ° with the circumferential direction of the tire. [68] In one embodiment, the tire is intended for a passenger vehicle including 4x4 vehicles and "SUV" (Sport Utility Vehicles). [69] In another embodiment, the tire is intended for an industrial vehicle comprising vans, heavy vehicles such as "heavy goods vehicles" ie, metro, buses, road transport vehicles (trucks, tractors, trailers), off-road vehicles. -the-road -, agricultural or engineering machinery, aircraft and other transport or handling vehicles. [70] The invention will be better understood on reading the following description, given solely by way of nonlimiting example and with reference to the drawings in which: - Figure 1 is a sectional view of a pneumatic according to the invention; P10-3194_FR - Figure 2 is a sectional view of a composite element according to the invention forming a working ply of the tire of Figure 1; FIG. 3 is a sectional view of a reinforcing element according to a first embodiment of the invention of the composite element of FIG. 2; FIG. 4 is an enlargement of a lateral edge of the reinforcing element of FIG. 3; FIG. 5 is a view similar to that of FIG. 3 of a reinforcing element according to a second embodiment of the invention; - Figure 6 is a view similar to that of Figure 4 of the reinforcing member of Figure 5; FIG. 7 is a diagram of a processing installation of a reinforcing element; FIG. 8 is a diagram of plasma flow generation devices of the installation of FIG. 7; FIG. 9 is a detailed diagram of a device for generating a plasma flow of the installation of FIG. 7; FIG. 10 is a diagram illustrating steps of the treatment method of the reinforcing element according to the invention; FIG. 11 is a graph comprising several force-elongation curves of several composite elements, two of which according to the invention; FIG. 12 is a sectional view of a reinforcement element according to the invention obtained by a plasma treatment method, and FIG. 13 is a view similar to that of FIG. 12 of a reinforcement element of FIG. state of the art. [071] In the following description, in the use of the term "radial", it is appropriate to distinguish several different uses of the word by the person skilled in the art. First, the term refers to a radius of the tire. It is in this sense that a point P1 is said to be "radially interior" at a point P2 (or "radially inside" of the point P2) if it is closer to the axis rotation of the tire as the point P2. Conversely, a point P3 is said to be "radially external to" a point P4 (or "radially outside" of the point P4) if it is farther from the axis of rotation of the tire than the point P4. We will say that we are advancing "radially inwards (or outwards)" as we move towards smaller (or larger) radii. When it comes to radial distances, this sense of the term also applies. On the other hand, a reinforcing element or a reinforcement is said to be "radial" when the reinforcing element or reinforcing elements of the reinforcement make with the circumferential direction an angle greater than or equal to 65 ° and less than or equal to 90 °, preferably from 80 ° to 90 ° and more preferably from 85 ° to 90 °. [073] An "axial" direction is a direction parallel to the axis of rotation of the tire. A point P5 is said to be "axially inner" at a point P6 (or "axially inside" of the point P6) if it is closer to the median plane M of the tire than the point P6. Conversely, a point P7 is said to be "axially outside at" a point P8 (or "axially outside" of the point P8) if it is farther from the median plane M of the tire than the point P8. [74] The "median plane" M of the tire is the plane which is normal to the axis of rotation of the tire and which is equidistant from the annular reinforcing structures of each bead. [75] On the other hand, any range of values designated by the expression "from a to b" means the range of values from terminal "a" to terminal "b", that is to say including the strict limits "a" and "b". Any range of values designated by the expression "between a and b" means the range of values varying between the "a" terminal and the "b" terminal, that is to say excluding the strict "a" and "b" terminals. ". [076] EXAMPLES OF PNEUMATIC AND REINFORCING ELEMENT ACCORDING TO THE INVENTION [077] FIGS. 1 and 2 show a reference X, Y, Z corresponding to the usual directions respectively axial (X), radial (Y) and circumferential (Z) of a tire. [078] There is shown in Figures 1 and 2 a tire according to the invention and designated by the general reference 10. The tire 10 is substantially of revolution about an axis substantially parallel to the axial direction X. The tire 10 is here intended for a passenger vehicle. [079] The tire 10 has an apex 12 comprising a crown reinforcement 14 comprising a working reinforcement 16 comprising a working ply 17 of reinforcing elements and a reinforcement frame 18 comprising a hooping ply 19. The reinforcement top 14 is surmounted by a tread 20. Here, the hooping reinforcement 18, here the hooping web 19, is radially interposed between the working reinforcement 16 and the tread 20. Two flanks 22 extend the top 12 radially inward. The tire 10 further comprises two beads 24 radially internal to the sidewalls 22 and each having a reinforcing ring structure 26, in this case a bead wire, and a radial carcass reinforcement 28. The armature 14 is radially interposed between the carcass reinforcement 28 and the tread 20. Each flank 22 connects each bead 24 to the top 14. [080] The carcass reinforcement 28 preferably comprises a single carcass ply 30. Radial textile reinforcing elements 32. The carcass reinforcement 28 is anchored to each of the beads 24 by a turn around the rod 26 so as to form in each bead 24 a forward strand extending from the beads 24 through the beads. flanks 22 to the top 12, and a return strand, the radially outer end of the return strand being radially outside the bead wire 26. The carcass reinforcement 30 thus extends from the beads 24 through the flanks 22 to the apex 12. In this embodiment, the carcass reinforcement 28 also extends axially through the apex 12. [81] The working ply 16 forms a composite element according to the invention comprising reinforcement elements 34 according to the invention extending in a main direction Z1 forming an angle α ranging from 0 ° to 80 °, preferably ranging from 5 ° to 50 °, more preferably ranging from 15 ° to 40 ° and even more preferably ranging from 20 ° to 30 ° and here equal to 26 ° with the circumferential direction Z of the tire 10. In a variant, the working reinforcement 16 comprises a plurality of working plies, for example two working plies, each comprising reinforcement elements 34 according to the invention. [82] The hooping web 19 comprises shrink reinforcing elements 36 forming an angle at most equal to 10 °, preferably ranging from 5 ° to 10 ° with the circumferential direction Z of the tire 10. In this case, the The hoop reinforcement elements 36 are aramid yarns with each yarn consisting of two yarns of 167 tex which have been twisted together (on a direct capper) at 230 revolutions / meter. Alternatively, other textile materials, such as PET, may be used, but also metal reinforcing elements. [83] Each working ply 16, shrink 19 and carcass 30 respectively comprises an elastomer matrix 21, 23 and 25 in which are embedded the reinforcing elements of the corresponding ply. The rubber compositions of the elastomeric matrices of the working plies 16, the hooping plies 19 and the carcass plies 30 are conventional compositions for calendering reinforcing elements comprising, in a conventional manner, a diene elastomer, for example natural rubber, a reinforcing filler. , for example carbon black and / or silica, a crosslinking system, for example a vulcanization system, preferably comprising sulfur, stearic acid and zinc oxide. and optionally an accelerator and / or a vulcanization retarder and / or various additives. [84] The reinforcing elements 34 of the composite element 16 are arranged side by side. The reinforcing elements 34 extend parallel to each other.
    [0003] The composite element 16 comprises bridges 38 of the elastomer matrix separating two successive reinforcing elements 34. [85] There is shown in Figures 3 and 4 the reinforcing element 34 of the composite element 16 and forming a reinforcing element according to a first embodiment of the invention. [86] In Figure 3, there is shown a reference X1, Y1, Z1 corresponding to the general directions in which respectively extend the width (X1), thickness (Y1) and length (Z1) of an object three-dimensional. [87] The reinforcing element 34 has a length G extending in a main general direction Z1. In the tire 10, the main direction Z1 makes an angle α with the circumferential direction Z of the tire 10. The reinforcing element 34 has a width L extending in a general direction X1. The reinforcing element 34 has a thickness E extending in a general direction Y1. [088] The reinforcing element 34 has, in the plane perpendicular to the main direction Z1, a section of generally flattened shape. The section may have an oblong, elliptical, oval, rectangular, parallelogram or diamond shape. The reinforcing element 34 has a section of generally rectangular shape [89] The reinforcing element 34 comprises at least one wire element 35. By wire element is meant any elongate element of great length relative to its cross section, whatever either the shape of the latter, for example circular, oblong, rectangular or square, or even flat, this wire element can be for example twisted or corrugated. When it is circular in shape, its diameter is preferably less than 5 mm, more preferably in a range from 200 μm to 1.5 mm. [90] The wire element 35 is constituted by a film of polymeric composition comprising at least one thermoplastic polymer. The thermoplastic polymer is semi-crystalline and is selected from a polyester, a polyamide, a polyketone or a mixture of these materials and is preferably a polyester.
    [0004] P10-3194_FR -15- [091] In the present case, the wire element 35 consists of a multiaxially stretched polyethylene terephthalate (PET) film, here bi-stretched ("Mylar A" from the company DuPont Teijin Films) . Other thermoplastic polymers could be used, for example other polyesters or nylon. [092] The reinforcing element 34 has a thickness E ranging from 0.05 to 1 mm, preferably from 0.1 to 0.7 mm and is here equal to 0.5 mm. The reinforcing element 34 has a width L greater than or equal to 2.5 mm, preferably 5 mm and more preferably 10 mm and here equal to 25 mm. [93] The reinforcing element 34 comprises two longitudinal faces 40, 42 and two lateral edges 44, 46 each comprising an outer lateral face 48, 50. Each lateral edge 44, 46 extends in a generally parallel direction to the main direction Zl. [94] Each side edge 44, 46 is in the polymeric composition comprising the thermoplastic polymer, here PET. [095] There is shown in Figure 3 a first median plane M1 of the width L of the reinforcing element 34 and a second median plane M2 of the thickness of the reinforcing element 34. The first and second M1, M2 median planes extend substantially parallel to the main direction Z1 and are substantially perpendicular to each other. The central point C defined as the point of intersection between the first and second median planes M1, M2 in the section plane of FIG. 3 has been represented. [96] FIG. 4 shows the lateral edge 46 of FIG. reinforcing element 34. The lateral edge 46 has a point Pl, referred to as measurement, belonging to the second median plane M2. The measuring point P1 is distant from a point P2, called the end point, belonging to the second median plane M2 and to the outer face 50 delimiting the lateral edge 46 by a distance d in a range 10 pm; 50 μm], preferably [15 μm, 50 μm]. Here d = 15 pm. [97] FIG. 4 also shows the variation of the stiffness U of the polymeric composition as a function of the distance d to the lateral face 50 in a direction substantially parallel to the direction X1. The curve CO (continuous curve) represents the variation of the stiffness U of a reinforcement element of the state of the art and not in accordance with the invention. The curve C1 (curve in broken lines) represents the variation of the stiffness U of the reinforcement element 34. [98] Uc represents the average value of the stiffness of the reinforcing element 34 measured at the central point C. U1 represents the average value of the stiffness of the reinforcing element 34 measured at the measuring point P1. Ur represents the average value of the rigidity of a reinforcing element of the state of the art and therefore not in accordance with the invention at the measuring point P1. What has just been described for the lateral edge 46 applies mutatis mutandis to the lateral edge 44. [099] Each reinforcing element 34 is coated with a layer of an adhesion primer and a layer of adhesive. an adhesion adhesive coating the layer of the adhesion primer. In a variant, the adhesion layer directly assumes the polymeric composition (absence of the adhesion primer layer). The adhesion primer generally comprises an epoxy resin, which is well known to those skilled in the art. The adhesion adhesive comprises an RFL adhesive or a phenol-aldehyde resin based on at least one polyphenol and a polyaldehyde such as those described in the publications WO2013017421, WO2013017422 and WO2013017423. Alternatively, other types of glues may be used, for example thermoplastic glues. Preferably, the adhesion adhesive comprises at least one diene elastomer. Such an elastomer makes it possible to improve the raw tack and / or bake glue with the rubber matrix. Advantageously, the diene elastomer is chosen from natural rubber, a copolymer of styrene and butadiene, a terpolymer of vinylpyridine, styrene and butadiene and a mixture of these diene elastomers. There is shown in Figures 5 and 6 a reinforcing element 34 according to a second embodiment. Unlike the reinforcing element 34 according to the first embodiment, the reinforcing element according to the second embodiment has a section of generally elliptical shape. EXAMPLE OF THE PROCESS ACCORDING TO THE INVENTION FOR OBTAINING THE REINFORCEMENT ELEMENT ACCORDING TO THE INVENTION FIGS. 7 to 9 show a treatment plant for the reinforcement element 34 making it possible to implement a process of treatment, in particular by plasma torch. The installation is designated by the general reference 60. The installation 60 comprises two devices 62a, 62b for generating a plasma stream and a device 64 for coating the reinforcing element 34. [0107] A plasma makes it possible to generate, from a gas subjected to an electrical voltage, a heat flux comprising molecules in the gaseous state, ions and electrons. Advantageously, the plasma is of the cold plasma type. Such a plasma, also called out-of-equilibrium plasma is such that the temperature comes mainly from the movement of electrons. A cold plasma must be distinguished from a hot plasma, also called thermal plasma in which the electrons, but also the ions confer on this plasma certain properties, in particular thermal, different from those of the cold plasma. Each device 62a, 62b comprises a plasma torch 66 illustrated in detail in FIG. 9. Each device 62a, 62b is intended to respectively treat at least a portion of each lateral edge 44, 46. The coating device 64 comprises a first bath 67 containing the adhesion primer and a second bath 68 containing the adhesion adhesive, here an RFL type adhesive. The devices 62a, 62b are arranged on either side of the reinforcing element 34, here in a substantially symmetrical manner with respect to the median plane M1 of the reinforcing element 34. [0110] The installation 60 also comprises two upstream and downstream storage rollers respectively designated by the references 70, 72. The upstream roller 70 carries the reinforcing element 34 untreated while the roller 72 carries the reinforcing element 34 treated by plasma using the devices 62a, 62b and coated with the primer and the adhesive adhesive by means of the coating device 64. The devices 62a, 62b and 64 are arranged in this order between the rollers 70, 72 in the direction of travel of the reinforcing element 34. The devices 62a, 62b are located upstream with respect to the device 64 in the direction of scrolling of the reinforcing element 34. FIG. 8 shows the devices 62a, 62b for generating a plasma flow, here plasma torches 66 sold by Plasmatreat GmbH. Each plasma torch 66 is powered by an alternating current of less than 360 V voltage and frequency between 15 and 25 kHz. With reference to FIG. 9, the plasma torch 66 comprises means 74 for supplying gas to a plasma flow generating chamber 76 as well as means 78 for outputting the plasma generated in the chamber 76 under the FIG. form of a flow of plasma 80, here a plasma jet. The plasma torch 66 also comprises means 82 for generating a rotary electric arc 84 in the chamber 76. The supply means 74 comprise a conduit 86 for entering the gas into the chamber 76. Generation 82 of the electric arc comprises an electrode 88. The output means 78 comprise an outlet 90 of the flow of the plasma flow 80.
    [0005] FIG. 10 is a diagram illustrating the main steps 100 to 300 of the treatment method making it possible to manufacture the reinforcing element 34 according to the invention. During a heating step 100, at least a portion of each lateral edge 44, 46 is subjected to the flow 80 generated by means of two plasma torches 66. In this step 100, the element of FIG. reinforcement 34 continuously. The treatment process is at atmospheric pressure. The use of a plasma at atmospheric pressure makes it possible to set up a relatively simple and inexpensive industrial installation, unlike a process requiring the use of a plasma under reduced pressure associated with the setting up of a chamber. depressurized. Thus, during this step 100, energy is transferred to the portion of each side edge 44, 46 by radiation, convection or conduction from an energy source, here by convection. The portion of each side edge 44, 46 is heated so as to raise the temperature of this portion of the lateral edge beyond the melting temperature Tf of the thermoplastic polymer so as to amorphize the structure of the thermoplastic polymer. The stream 80 is obtained from a gas comprising at least one oxidizing component. By oxidizing component is meant any component capable of increasing the degree of oxidation of the chemical functions present in the polymeric composition and in particular in the thermoplastic polymer. Advantageously, the oxidizing component is selected from carbon dioxide (002), carbon monoxide (CO), hydrogen sulfide (H2S), carbon disulfide (CS2), oxygen (O2), nitrogen (N2), chlorine (Cl2), ammonia (NH3) and a mixture of these components. Preferably, the oxidizing component is chosen from oxygen (O 2), nitrogen (N 2) and a mixture of these components. More preferably, the oxidizing component is air. Here, the flow 80 is obtained from a mixture of air and nitrogen at a rate of 2400 L / h. The orifice 90 is disposed opposite each lateral edge 44, 46 to be treated, here facing each surface 48, 50. The orifice 90 is situated at a constant distance D from each lateral edge 44, 46. For example, this distance is between 1 mm and 20 mm and preferably between 2 mm and 10 mm. The reinforcing element 34 is deflected with respect to at least one energy source, here relative to two energy sources formed by two plasma streams at an average velocity V of between 1 and 100 m.min-1 and preferably between 1 and 50 m.min-1. The average speed V is equal to the ratio of the distance traveled by the flow of plasma 80 with respect to the edge to be exposed over a predetermined time taken to cover this distance, in this case 30s. The movement of the flux with respect to the reinforcing element 34 may be rectilinear or curved or a mixture of both. In this case, the reinforcing element 34 has a uniform continuous rectilinear movement with respect to the energy sources. Then, during a step 200, the reinforcing element 34 is coated with the adhesion primer of the first bath 67. Then, in a step 300, subsequent to the steps 100 and 200, it is coated. the reinforcing element 34 of the adhesion adhesive of the second bath 68. [0124] Other subsequent steps, not shown, may also be implemented. By way of example, it will be possible to carry out a spinning step (for example by blowing, calibrating) in order to eliminate the excess of glue; then a drying step for example by passing through an oven (for example for 30 s at 180 ° C) and finally a heat treatment step (for example for 30 s at 230 ° C). Those skilled in the art will readily understand that the definitive adhesion between the reinforcing element 34 and the elastomer matrix in which it is embedded is definitely ensured during the final firing of the tire of the invention. COMPARATIVE TESTS In a first test, two reinforcing elements 34, 34 'and a reinforcing element T of the state of the art were compared. The reinforcing elements 34, 34 'are in accordance with the invention and obtained by the treatment method described above respectively with running speeds and distances with respect to the outlet orifice of the plasma flow V = 10 m .min-1 and D = 3.5 mm (element 34 shown in Figure 12) and V = 10 m.min-1 and D = 1 mm (element 34 '). The reinforcing element T has not been treated by the method described above and is shown in FIG. 13. In FIG. 12, a deformation of the edges of the longitudinal edge of the reinforcing element is observed. according to the invention with respect to the reinforcing element of the state of the art. This deformation makes it possible to obtain a reinforcement element without ridges, which are by nature projecting, which could facilitate the creation of rupture primers of the interface between the elastomer matrix and the reinforcing element. Firstly, the stiffness of each reinforcement element was measured as described below. Each average stiffness value is equal to the arithmetic mean of 10 measurements each made on a section substantially perpendicular to the main direction at the central point (measurement of Uc) and at the measurement point (measurement of Ur and U1) P10- 3194_EN -20- of each section. The ten sections are made over a length of 10 cm of the reinforcing element, for example every centimeter. The rigidity of the polymeric composition is measured by microhardness measurement. In this case, a nanoindenter is used ("Ultra Nanonlndentation Tester UNHT" model from CSM Instruments). The polymeric composition is solicited in compression in a low deformation range, here less than 10%. Each measurement is based on measuring the penetration depth of a pyramidal indenter (Berkovich type indenter) at a given load and at a given point. Each measurement is in the form of a substantially linear charge / discharge cycle. The mechanical model used for the treatment of charge / discharge cycles is the Oliver and Pharr model, a model commonly used for linear elastomeric materials. This model meets the IS014577-4: 2007 standard reproduced here. The preparation of each test specimen comprises the coating of each reinforcing element in an epoxy resin. Then, the reinforcing element thus coated is cut off along a cutting plane substantially perpendicular to the main direction Z1 and the specimen is polished using papers of different grains (600, 1200) and then felts using different diamented solutions (9). pm, 3 μm, 1 μm and 0.25 μm). The microhardness measurement is then performed by moving the indenter perpendicular to the cutting plane, here along the main direction Z1. The values of the ratios R = (Uc-U1) / Uc and R = (UcUr) / Uc indicating the relative variation of the rigidity of the polymeric composition between the center of the reinforcing element and its composition were also compared. side edge. The results of these measurements are summarized in Table 1 below.
    [0006] Uc Treatment Element (GPa) Ur (GPa) U1 (GPa) Plasma Reinforcing PET Film T No 4.23 3.82 / 10% PET Film 34 Yes 4.13 / 2.81 32% PET Film 34 'Yes 4, 19 / 2,89 31% Table 1 P10-3194_EN - 21 - [0134] The reinforcing element T is such that R 11% and here R = 10%. Indeed, edge effect, the closer we get to the outer face, the stiffness of the reinforcing element T decreases. However, since the relative drop in stiffness R = (Uc-Ur) / Uc is limited to 10%, it does not sufficiently limit the variation in stiffness between the elastomer matrix and the reinforcement element, unlike the invention. Indeed, the reinforcing elements 34, 34 'are such that R> 11%. We have even R k 15%, preferably R 20% and more preferably R k 25%. There is also R 40% for these reinforcing elements 34, 34 '. In a second test, a force-elongation curve well known to those skilled in the art of composite elements 16, 16 'according to the invention and K according to the state of the art was produced. Each composite element 16, 16 'respectively comprises reinforcing elements 34, 34' as described above. The curves of this test are shown in FIG. 11 and represent the variation of the force F as a function of the elongation A. The force-elongation curve of the composite element 16 is shown in broken lines (curve Ca). The force-elongation curve of the composite element 16 'in dashed lines (curve Cb) is represented. The force-elongation curve of the composite element K is shown in solid lines (curve Cc). The values of the breaking force of the composite elements tested are summarized in Table 2 below.
    [0007] Composite element Treatment element Fm (%) reinforcement Plasma K PET film T No 10% 100 16 PET film 34 Yes 32% 117 16 'PET film 34' Yes 31% 118 Table 2 [0136] In a third test, we compared tires 10, 10 'according to the invention respectively comprising the composite elements 16, 16' according to the invention and tires P1, P2 of the state of the art. The dimension of the tires tested is 175/65 R14. The tire P1 comprises a conventional architecture comprising a conventional working frame comprising two crown plies comprising wire reinforcing elements consisting of metal cables of structure 2.30 arranged in a pitch of 1.2 mm and a hooping reinforcement comprising a ply. The reinforcement comprises wire reinforcing elements consisting of polyamide 66 twists (140 tex / 2, 250 μm-1/250 μm -1). The tire P2 has an identical architecture to the tires 10, 10 'but does not include a composite element whose reinforcing elements have been treated by the treatment method described above and therefore does not have any element of reinforcement such as R> 11%. In this third test, the tires 10, 10 ', P1 and P2 were subjected to a drift thrust test Dz described below. The results are given in base 100 with respect to the tire P1. Thus, the higher the value is greater than 100, the better is the drifting thrust Dz of the tire relative to the tire P1 of the state of the art. To measure the drifting thrust Dz, each tire was rolled at a constant speed of 80 km / h on an appropriate automatic machine (ground-plane machine marketed by the MTS company), by varying the load "Z", under a relatively high drift angle of 8 degrees, and the drift thrust was continuously measured and the drift rigidity denoted "D" (corrected for the zero drift thrust) was recorded, by recording using sensors the transverse force on the wheel as a function of this load Z; this gives the rigidity of drift. We then obtain, for a chosen load, here 450 daN, the value reported in Table 3 below. Pneumatic Treatment Tablecloths R Dz Working Plasma P1 Classic No / 100 P2 K No 10% 94 10 16 Yes 32% 100 10 '16' Yes 31% 102 Table 3 [0141] Thus, the tires 10 and 10 'exhibit all the advantages of the tire P1 without the rigidity of drifting at high angles is impaired as is the case for the tire P2. The invention is not limited to the embodiments described above. P10-3194_EN -23- [0143] Indeed, it can also consider a tire according to the invention wherein the crown reinforcement also comprises a protective armature radially interposed between the hooping frame and the working frame. It may also be envisaged a tire according to the invention in which the crown reinforcement does not comprise a hooping reinforcement but a protective reinforcement and a working reinforcement, the protective reinforcement being radially interposed between the web rolling and frame work. We can also consider other wired elements that a film. It may also be provided to use the reinforcing element according to the invention in the carcass reinforcement. It is also possible to combine the characteristics of the different embodiments described or envisaged above provided that they are compatible with each other. P10-3194_FR
    权利要求:
    Claims (9)
    [0001]
    REVENDICATIONS1. A method of treating a reinforcing member (34, 34 ') having a generally flattened section extending in a main direction (Z1) and comprising at least one side edge (44, 46) of a polymeric composition comprising a thermoplastic polymer, the lateral edge extending in a general direction (Z1) substantially parallel to the main direction (Z1), characterized in that the method comprises a step of heating at least a portion of the lateral edge (44, 46) during which energy is transferred to the portion of the side edge (44, 46) so as to raise the temperature of the portion of the side edge (44, 46) beyond the melting point of the polymer thermoplastic.
    [0002]
    2. Method according to the preceding claim, wherein the energy is transferred by radiation, convection or conduction from an energy source.
    [0003]
    The method of any of the preceding claims, wherein the energy is transferred by subjecting at least a portion of the side edge to a plasma stream.
    [0004]
    4. Method according to the preceding claim, wherein the plasma stream is generated by means of a plasma torch.
    [0005]
    5. The method of claim 3 or 4, wherein the plasma is of the cold plasma type.
    [0006]
    6. Process according to any one of claims 3 to 5, wherein the plasma stream is generated from a gas comprising at least one oxidizing component.
    [0007]
    7. Process according to the preceding claim, in which the oxidizing component is chosen from carbon dioxide, carbon monoxide, hydrogen sulphide, carbon disulfide, dioxygen, nitrogen, chlorine and ammonia. and a mixture of these components, preferably selected from dioxygen, nitrogen and a mixture of these components and more preferably is air.
    [0008]
    8. Method according to any one of the preceding claims, wherein the reinforcing element is scrolled with respect to at least one energy source.
    [0009]
    9. A method according to any one of the preceding claims, wherein, after the step of heating the portion of the side edge, the reinforcing summer is coated with an adhesion adhesive. 1-0. A process as claimed in any one of the preceding claims wherein the thermoplastic polymer is semi-crystalline. 11. The process according to any one of the preceding claims, wherein the thermoplastic polymer is selected from polyester, polyamide, polyketone or a mixture of these materials and preferably is a polyester. 12. Method according to any one of the preceding claims, wherein the reinforcing element (34, 34 ') has a thickness (E) ranging from 0.05 to 1 mm, preferably from 0.10 to 0.70. mm. 13. A method according to any one of the preceding claims, wherein the reinforcing element (34, 34 ') has a width (L) greater than or equal to 2.5 mm, preferably greater than 5 mm and more preferably greater than 10 mm. mm. 14. Method according to any one of the preceding claims, wherein the reinforcing element (34, 34 ') comprises at least one wire element (35) consisting of a film of the polymeric composition. 15. Method according to the preceding claim, wherein the film (35) is stretched multiaxially. 16. reinforcement element (34, 34 ') three-dimensional, characterized in that it is obtainable by a method according to any one of the preceding claims. 17. Composite element (16, 16 '), characterized in that it comprises at least one reinforcing element (34, 34') according to the preceding claim embedded in an elastomer matrix (21). 18. Pneumatic tire (10), characterized in that it comprises at least one reinforcing element (34, 34 ') according to claim 16 or a composite element (16, 16') according to claim 17. 19. Manufacturing process of a tire, characterized in that a reinforcing element (34; 34 ') is treated according to a method according to any one of claims 1 to 15 and the reinforcement element (34; 34') is embedded in an elastomer matrix. P10-3194_FR
    类似技术:
    公开号 | 公开日 | 专利标题
    EP2416955B1|2016-12-21|Pneumatic tyre, the belt of which is reinforced by a thermoplastic polymer film
    EP3074199B1|2019-04-10|Method for the treatment of a reinforcing element
    FR2986740A1|2013-08-16|PNEUMATIC WITH ALLEGE BELT STRUCTURE
    FR2986739A1|2013-08-16|PNEUMATIC WITH ALLEGE BELT STRUCTURE
    EP3074243B1|2017-10-25|Reinforcing element having a flattened cross-section
    EP2619019B1|2014-11-12|Tyre comprising a protective reinforcement
    WO2013178539A1|2013-12-05|Reinforcing element having polyester layers
    EP2619020B1|2014-09-03|Tyre comprising a protective reinforcement
    WO2019020886A1|2019-01-31|Tyre with improved belt structure
    EP2619018B1|2014-11-19|Tyre comprising a protective reinforcement
    EP3463839B1|2020-03-25|Straight ply and angle ply comprising metallic monofilaments
    FR2967611A1|2012-05-25|PNEUMATIC HAVING FLANKS REINFORCED BY A THERMOPLASTIC POLYMER FILM
    WO2019020887A1|2019-01-31|Tyre with improved belt structure
    EP3658389A1|2020-06-03|Tyre with improved belt structure
    FR3045670A1|2017-06-23|CARBON STEEL STRIP, ITS USE FOR REINFORCING RUBBER ARTICLES
    FR2996806A1|2014-04-18|Treating e.g. film, used in reinforcement ply of rubber article used for forming pneumatic tyre of e.g. motor vehicle, by exposing a textile reinforcement element to a plasma flow generated from a gas including an oxidizing component
    FR2991344A1|2013-12-06|Treating e.g. film, used in reinforcement ply of rubber article used for forming pneumatic tyre of e.g. motor vehicle, by exposing a textile reinforcement element to a plasma flow generated from a gas including an oxidizing component
    同族专利:
    公开号 | 公开日
    WO2015078946A1|2015-06-04|
    US20170001341A1|2017-01-05|
    EP3074199A1|2016-10-05|
    FR3013622B1|2016-06-24|
    US10543624B2|2020-01-28|
    EP3074199B1|2019-04-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3853657A|1972-02-14|1974-12-10|Monsanto Co|Bonding of poly induced by low-temperature plasmas|
    US4606930A|1984-03-02|1986-08-19|Sumitomo Chemical Company, Limited|Method for treating fibers|
    EP0172057A1|1984-07-05|1986-02-19|Shin-Etsu Chemical Co., Ltd.|An improvement in a fabric-reinforced rubber article|
    WO1987003021A1|1985-11-14|1987-05-21|Deutsches Textilforschungszentrum Nord-West E.V.|Fibre, filament, yarn and/or surface formations containing any of these and/or debris material and process for producing any of these|
    DE3636395A1|1986-10-25|1988-05-05|Deutsches Textilforschzentrum|Process for modifying the surface of fibres, filaments, yarns and/or sheet materials and/or assemblies containing same|
    EP0451425A2|1990-03-30|1991-10-16|The Goodyear Tire & Rubber Company|Process for the surface treatment of polymers for reinforcement-to-rubber adhesion|
    WO1994028568A1|1993-05-28|1994-12-08|The University Of Tennessee|Method and apparatus for glow discharge plasma treatment of polymer materials at atmospheric pressure|
    EP1514894A1|2003-08-21|2005-03-16|Amt Laboratory Co., Ltd.|Biaxially oriented saturated polyester film, method of making the same. Laminate of biaxially oriented saturated polyester film and method of making the same|
    US20130059494A1|2011-09-06|2013-03-07|Honeywell International Inc.|High performance ballistic composites and method of making|
    GB2134442B|1983-01-18|1987-05-28|Diafoil Co Ltd|Polyester film for magnetic recording media|
    JPH0625267B2|1985-12-17|1994-04-06|ダイアホイルヘキスト株式会社|Polyethylene-2,6-naphthalate film for high density magnetic recording media|
    DE3621205A1|1986-06-25|1988-01-07|Hoechst Ag|Process for producing biaxially stretched flat films and device for this process|
    US4867937A|1987-02-17|1989-09-19|Minnesota Mining And Manufacturing Company|Process for producing high modulus film|
    AU618821B2|1988-12-22|1992-01-09|E.I. Du Pont De Nemours And Company|High tenacity, oblong cross-section monofilaments|
    FR2682915B1|1991-10-24|1997-09-19|Rhone Poulenc Films|ORIENTED SEMI-CRYSTALLINE POLYESTER FILMS, THEIR METHOD OF OBTAINING AND THEIR USE AS A MAGNETIC COATING SUPPORT|
    US8178210B2|2003-07-30|2012-05-15|Cryovac, Inc.|Multilayer oriented high-modulus film|
    FR2944227B1|2009-04-09|2013-08-16|Soc Tech Michelin|MULTILAYER LAMINATE FOR PNEUMATIC BANDAGE|
    FR2944230B1|2009-04-09|2011-04-08|Michelin Soc Tech|TIRE WITH RADIAL CARCASS FRAMES|
    FR2967604B1|2010-11-22|2012-12-14|Michelin Soc Tech|SELF-ADHERENT COMPOSITE REINFORCEMENT|
    FR2978771B1|2011-08-04|2013-09-27|Michelin Soc Tech|AQUEOUS ADHESIVE COMPOSITION BASED ON POLYALDEHYDE AND 2,2 ', 4,4'-TETRAHYDROXYDIPHENYL SULFIDE|
    FR2978769B1|2011-08-04|2013-09-27|Michelin Soc Tech|AQUEOUS ADHESIVE COMPOSITION BASED ON POLYALDEHYDE AND POLYPHENOL|
    FR2978770B1|2011-08-04|2013-09-27|Michelin Soc Tech|AQUEOUS ADHESIVE COMPOSITION BASED ON POLYALDEHYDE AND PHLOROGLUCINOL|
    KR20150016981A|2012-06-01|2015-02-13|꽁빠니 제네날 드 에따블리세망 미쉘린|Method for treating a textile reinforcement element with plasma|
    FR3013625B1|2013-11-28|2016-06-24|Michelin & Cie|REINFORCING ELEMENT A SECTION APLATIE|CN106029333B|2014-02-24|2018-06-12|英派尔科技开发有限公司|The interlayer adhesion of increased 3 D-printing article|
    US10404369B2|2016-06-07|2019-09-03|Siklu Communication ltd.|Systems and methods for using drones for determining line-of-sight conditions in wireless networks|
    CA2999175A1|2017-03-28|2018-09-28|Mcrae Imaging|In-store fixture or signage with location based intelligence|
    WO2022003741A1|2020-06-29|2022-01-06|Pirelli Tyre S.P.A.|Manufacturing process of a reinforcing component for a tyre, and related manufacturing process of tyres|
    法律状态:
    2015-11-19| PLFP| Fee payment|Year of fee payment: 3 |
    2016-11-18| PLFP| Fee payment|Year of fee payment: 4 |
    2017-11-21| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1361728A|FR3013622B1|2013-11-28|2013-11-28|PROCESS FOR TREATING AN APLATIE SECTION REINFORCING ELEMENT|FR1361728A| FR3013622B1|2013-11-28|2013-11-28|PROCESS FOR TREATING AN APLATIE SECTION REINFORCING ELEMENT|
    EP14808556.6A| EP3074199B1|2013-11-28|2014-11-27|Method for the treatment of a reinforcing element|
    PCT/EP2014/075747| WO2015078946A1|2013-11-28|2014-11-27|Method for the treatment of a reinforcing element, reinforcing element and tyre comprising a reinforcing element|
    US15/039,499| US10543624B2|2013-11-28|2014-11-27|Process for treating a reinforcing element having a flattened cross-section|
    [返回顶部]