Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L7/00—Compositions of natural rubber
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T152/00—Resilient tires and wheels
  • Y10T152/10—Tires, resilient
  • Y10T152/10495—Pneumatic tire or inner tube
  • Y10T152/10765—Characterized by belt or breaker structure
  • Y10T152/1081—Breaker or belt characterized by the chemical composition or physical properties of elastomer or the like

Definitions

• the invention relates to tires for motor vehicles and reinforcements of the crown reinforcement, also called “belts", of these tires, as well as rubber compositions usable for the manufacture of such tires.
• the noise emitted by a rolling tire originates, inter alia, from the vibrations of its structure consecutive to the contact of the tire with the irregularities of the roadway, also causing a generation of various acoustic waves.
• the whole thing finally comes in the form of noise, both inside and outside the vehicle.
• the amplitude of these various manifestations is dependent on the vibration modes of the tire itself but also on the nature of the coating on which the vehicle moves.
• the frequency range corresponding to the noise generated by the tires typically ranges from about 20 to about 4000 Hz.
• the acoustic waves emitted by the tire are directly propagated by air inside the vehicle, the latter acting as a filter; this is referred to as airborne transmission, which generally dominates in the high frequencies (about 600 Hz and beyond).
• the so-called “road noise” refers rather to the perceived overall level in the vehicle and in a frequency range up to 2000 Hz.
• the noise called “road noise” refers to the annoyance due to the resonance of the inflation cavity of the tire envelope.
• the various interactions between the tire and the road surface, the tire and the air, which will cause discomfort to the residents of the vehicle when the latter is driving on a road, are relevant. floor.
• sources of noise such as the so-called “indentation” noise due to the impact of roughness of the road in the contact area, the noise called “friction” essentially generated in the output of the 'contact area, the noise' says of sculpture 'due to the arrangement of the elements of sculpture and to the resonance in the various furrows.
• the frequency range concerned by these external noises here typically corresponds to a range of about 300 to 3 000 Hz.
• a first object of the invention relates to a radial tire for a motor vehicle, comprising: a top (2) comprising a tread (3) and a crown reinforcement (7);
• the crown reinforcement or belt (7) disposed circumferentially between the tread (3) and the carcass reinforcement (6), comprising textile or metal reinforcements embedded in a rubber composition called "coating gum characterized in that the belt-coating gum comprises at least one diene elastomer and, as a high-density filler, more than 50 phr of so-called high-density particles whose density is greater than 4 g / cm 3 .
• the tires of the invention are particularly intended to equip tourism-type motor vehicles, including 4x4 vehicles (four-wheel drive) and SUV vehicles ("Sport Utility Vehicles"), two-wheel vehicles (including motorcycles) as industrial vehicles chosen in particular from vans and "heavy goods vehicles” (ie, metro, buses, road transport vehicles such as trucks, tractors, trailers, off-the-road vehicles such as agricultural or civil engineering vehicles).
• 4x4 vehicles four-wheel drive
• SUV vehicles Sport Utility Vehicles
• two-wheel vehicles including motorcycles
• industrial vehicles chosen in particular from vans and "heavy goods vehicles” (ie, metro, buses, road transport vehicles such as trucks, tractors, trailers, off-the-road vehicles such as agricultural or civil engineering vehicles).
• the invention relates to the above tires both in the green (i.e., before firing) and the fired (i.e., after crosslinking or vulcanization) state.
• any range of values designated by the expression “between a and b” represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term “from a to b” means the range from a to b (i.e., including the strict limits a and b).
• the tire of the invention therefore has the essential characteristic of being provided with a belt or crown reinforcement whose reinforcements, textile and / or metal, are embedded in a specific elastomeric composition or gum coating (called coating gum of belt) which comprises at least one diene elastomer and, as high density filler, more than 50 phr of so-called high density particles whose density is greater than 4 g / cm 3 , optionally a reinforcing filler and other optional additives , components which will be described in detail below.
• coating gum of belt which comprises at least one diene elastomer and, as high density filler, more than 50 phr of so-called high density particles whose density is greater than 4 g / cm 3 , optionally a reinforcing filler and other optional additives , components which will be described in detail below.
• the diene elastomers can be classified in known manner into two categories: those known as “essentially unsaturated” and those known as “essentially saturated”.
• essentially saturated diene elastomers having a rate of diene origin units which is low or very low, always less than 15% (% in moles)
• essentially unsaturated diene elastomer is understood to mean a diene elastomer derived at least in part from conjugated diene monomers having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%). ).
• 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%.
• Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), isoprene-copolymers of butadiene-styrene (SBIR) and mixtures of such copolymers.
• SBR butadiene-styrene copolymers
• BIR isoprene-butadiene copolymers
• SIR isoprene-styrene copolymers
• SBIR isoprene-copolymers of butadiene-styrene
• the elastomers can be for example block, statistical, sequenced, microsequenced, and be prepared in dispersion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization.
• the diene elastomer is chosen from the group consisting of natural rubber and synthetic polyisoprenes.
• Polybutadienes and, in particular, those having a content of 1,2-units of between 4% and 80% and those having a cis-1,4 content of greater than 80%, the polyisoprenes and the copolymers are preferably suitable. of butadiene-styrene and in particular those having a styrene content of between 5% and 50% by weight and more particularly between 20% and 40%, a 1,2-butadiene content of the butadiene part between 4%> and 65%>, a content of trans-1,4 bonds of between 20%> and 80%>, copolymers of butadiene-isoprene and in particular those having an isoprene content of between 5% and 90% by weight and a glass transition temperature ("Tg" - measured according to ASTM D3418-82) of -80 ° C to -40 ° C, isoprene-styrene copolymers and especially those having a styrene content of between 5%> and 50% > by
• butadiene-styrene-isoprene copolymers those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40% are especially suitable, an isoprene content of between 15% and 50% by weight.
• the belt-coating gum comprises, as diene elastomer, 50 to 100 phr of natural rubber or of a synthetic polyisoprene, the latter being able to be combined or no to a second diene elastomer.
• This second diene elastomer is preferably chosen from the group consisting of polybutadienes, butadiene copolymers and mixtures of these elastomers, in particular from the SBR copolymers (SBR solution or emulsion) with more preferably a Tg greater than -40 ° C.
• the belt coating gum comprises, as diene elastomer, from 50 to 80 phr of natural rubber or synthetic polyisoprene with 20 to 50 phr of an SBR copolymer having more preferably, a Tg greater than -40 ° C (in particular in a range of -30 ° C to + 30 ° C) or a polybutadiene (BR) more preferably having a cis-1,4 bond ratio greater than 90 %>, more preferably still greater than 95%.
• diene elastomers previously described could be associated, in a minor amount, with synthetic elastomers other than dienes, or even polymers other than elastomers, for example thermoplastic polymers. 4. I .B. High density charge
• Such high density fillers are well known to those skilled in the tire industry, they have been used essentially until now in tire treads, as a replacement or complement to less dense conventional fillers such as silica or carbon black. in an attempt to improve some of their properties of use or compromise of properties such as, for example, rolling resistance, wear resistance or adhesion (see in particular US Pat. No. 6,734,245 and US Pat. No. 6,838,495).
• the high density charge used may be in the form of isometric or anisometric particles. It is preferably of micrometric size, that is to say that it is in the form of "microparticles” whose size is by definition greater than one micrometer. Preferably, these microparticles have a median diameter (or a median size if the particles are not substantially spherical), denoted hereinafter "D", which is between 1 and 500 ⁇ ; more preferably, the median diameter D of the particles is between 2 and 400 ⁇ , in particular between 2 and 200 ⁇ .
• D median diameter
• the high density charge is preferably in the form of a powder. According to another preferred embodiment (whether in powder form or not), it is in the form of solid particles, but particles or hollow beads with high density could also be used.
• the high density charge rate is more preferably between 50 and 500 phr. Below the minimum indicated, the technical effect is insufficient, while beyond the maximum recommended, we risk exposing our to problems of increase of the module, weakening of the composition, as well as difficulties of dispersion of the charge and processability, not to mention a significant penalty for hysteresis. For all these reasons, this rate is more particularly included in a range of 70 to 450 phr, especially in a range of 100 to 450 phr.
• the high density charge is preferably metallic (that is to say based on metal or a metal derivative); it is preferably constituted by metals such as alkaline-earth metals, transition metals or rare earths, or else by derivatives of such metals such as, for example, sulphates, carbonates, sulphides, oxides and / or hydroxides, particularly by oxides such metals.
• alkaline earth metals mention will be made in particular of barium and strontium.
• transition metals iron, copper, tin, zinc, molybdenum, silver, niobium, tungsten, rhenium, tantalum, hafiiium, bismuth and manganese will be mentioned in particular.
• rare earths mention will in particular be made of lanthanum, neodymium, cerium or samarium.
• the metal of the high-density filler is chosen from the group consisting of iron, copper, tin, nickel and the like. Zinc, Tungsten, Bismuth, Cerium, Neodymium and mixtures of these metals.
• metals and / or metal derivatives, particularly metal oxides are preferably chosen from those whose density is greater than 5 g / cm 3 .
• particularly preferred metal oxides mention may be made especially of those selected from the group consisting of Fe 2 O 3 (density 5.1 g / cm 3 ), ZnO (5.7 g / cm 3 ), CuO ( 6.3 / cm 3 ), Sn0 2 (7.0 g / cm 3 ), WO 3 (7.2 g / cm 3 ), CeO 2 (7.3 g / cm 3 ), Nd 2 O 3 (7 , 2 g / cm 3 ), Bi 2 O 3 (8.9 g / cm 3 ) and mixtures of such oxides.
• the introduction of the high density filler into the elastomeric composition can be carried out according to various known methods, for example by solution mixing, by mass mixing in an internal mixer, or by extrusion mixing.
• the belt coating rubber may also comprise any type of reinforcing filler known for its ability to reinforce a rubber composition that can be used for the manufacture of tires, for example an organic filler such as carbon black, a reinforcing inorganic filler such as only silica with which is associated in a known manner a coupling agent, or a mixture of these two types of filler.
• an organic filler such as carbon black
• a reinforcing inorganic filler such as only silica with which is associated in a known manner a coupling agent, or a mixture of these two types of filler.
• Such a reinforcing filler preferably consists of nanoparticles whose average size (in mass) is less than one micrometer, generally less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 nm.
• the density of this reinforcing filler is generally less than 3 g / cm 3 , in particular less than 2.5 g / cm 3 .
• the content of total reinforcing filler is greater than 20 phr, in particular between 20 and 100 phr. Above 100 phr, there is a risk of increasing the hysteresis and therefore the rolling resistance of the tires. For this reason, the total reinforcing filler content is more preferably within a range of 30 to 90 phr.
• carbon blacks are suitable all carbon blacks conventionally used in tires or their treads (so-called pneumatic grade black).
• the reinforcing carbon blacks of the 100, 200, 300 series, or 500, 600 or 700 series blacks (ASTM grades), for example blacks NI 15, N134, N234, N326, will be mentioned more particularly.
• the carbon blacks could for example already be incorporated into the diene elastomer, in particular isoprene in the form of a masterbatch (see for example applications WO 97/36724 or WO 99/16600).
• organic fillers other than carbon blacks mention may be made of functionalized polyvinyl organic fillers as described in applications WO-A-2006/069792 and WO-A-2006/069793, WO-A-2008/003434. and WO-A-2008/003435.
• Reinforcing inorganic filler means any inorganic or mineral filler, irrespective of its color and origin (natural or synthetic), also called “white” filler, “clear” filler or sometimes “non-black filler””As opposed to carbon black, capable of reinforcing on its own, with no other means than an intermediate coupling agent, a rubber composition for the manufacture of tires, in other words able to replace, in its function of reinforcement, a conventional carbon black of pneumatic grade; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.
• Suitable reinforcing inorganic fillers are mineral fillers of the siliceous type, in particular silica (SiO 2 ).
• the silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g, especially between 60 and 300 m 2 / g.
• highly dispersible precipitated silicas called "HDS"
• an at least bifunctional coupling agent is used in a well-known manner to ensure a sufficient chemical and / or physical connection between the inorganic filler (surface of its particles) and the diene elastomer.
• organosilanes or at least bifunctional polyorganosiloxanes are used.
• polysulfide silanes called “symmetrical” or “asymmetrical” silanes according to their particular structure, are used, as described for example in the applications WO03 / 002648 (or US 2005/016651) and WO03 / 002649 (or US 2005/016650).
• polysulphide silanes having the following general formula (I) are not suitable for the following definition:
• the symbols A which are identical or different, represent a di-substituted hydrocarbon radical (preferably a C 1 -C 18 alkylene group or a C 6 -C 12 arylene group, more particularly a C 1 -C 10 alkylene, especially a C 1 -C 4 alkylene radical; , in particular propylene);
• the radicals R 1 which may be substituted or unsubstituted, which are identical to or different from one another, represent a Ci-C18 alkyl, C 5 -C 8 cycloalkyl or C 6 -C 18 aryl group (preferably C 1 -C 8 alkyl groups); C 6 , cyclohexyl or phenyl, especially C 1 -C 4 alkyl groups, more particularly methyl and / or ethyl).
• silane polysulfides are more particularly the bis (mono, trisulfide or tetrasulfide) of bis (alkoxyl (Ci-C 4) alkyl (Ci-C 4) silyl alkyl (Ci-C 4 )), such as polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl).
• bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT of formula [(C 2 H 5 O) 3 Si (CH 2 ) 3 S 2 ] 2 or bis (triethoxysilylpropyl) disulphide is especially used.
• TESPD abbreviated TESPD, of formula [(C 2 H 5 O) 3 Si (CH 2 ) 3 S] 2 .
• polysulfides in particular disulfides, trisulphides or tetrasulfides
• bis-monoethoxydimethylsilylpropyl tetrasulfide as described in the aforementioned patent application WO 02/083782 (or US Pat. No. 7,217,751).
• silanes carrying at least one thiol function (-SH) (called mercaptosilanes) and / or of at least one blocked thiol function, as described for example in patents or patent applications US 6,849,754, WO 99/09036, WO 2006/023815, WO 2007/098080.
• the content of coupling agent is preferably between 2 and 15 phr, more preferably between 3 and 12 phr.
• the belt coating gum may also comprise all or part of the usual additives normally used in tire rubber compositions, such as, for example, protective agents such as chemical antioxidants, anti-oxidants, plasticizers or plasticizers.
• extension oils whether the latter are of aromatic or non-aromatic nature, especially very weak or non-aromatic oils, for example of the naphthenic or paraffmic type, with high or preferably low viscosity, MES or TDAE oils, high Tg hydrocarbon plasticizing resins, agents facilitating processing (processability) of the compositions in the green state, tackifying resins, reinforcing resins (such as resorcinol or bismaleimide), methylene acceptors or donors such as hexamethylenetetramine or hexamethoxymethylmelamine, a crosslinking system based on either sulfur or donor s of sulfur and / or peroxide and / or bismaleimides, vulcanization accelerators, vulcanization activators, known
• hydrocarbon plasticizing resins with a high Tg preferably greater than 20 ° C., more preferably greater than 30 ° C. (measured according to ASTM D3418-1999), are advantageously usable because they can make it possible to further improve the technical effect of "sound barrier" provided by the belt coating gum previously described.
• the macrostructure (Mw, Mn and Ip) of the hydrocarbon resin is determined by steric exclusion chromatography ("SEC"): solvent tetrahydrofuran; temperature 35 ° C; concentration 1 g / 1; flow rate 1 ml / min; filtered solution on 0.45 ⁇ porosity filter before injection; Moore calibration with polystyrene standards; set of 3 "WATERS” columns in series (“STYRAGEL” HR4E, HR1 and HR0.5); differential refractometer detection (“WATERS 2410”) and its associated operating software (“WATERS EMPOWER”).
• SEC steric exclusion chromatography
• hydrocarbon plasticizing resins By way of examples of above-mentioned hydrocarbon plasticizing resins, mention may be made in particular of homopolymer or copolymer resins of cyclopentadiene or dicyclopentadiene, resins of terpene homopolymers or copolymers (eg alphapinene, betapinene, dipentene or polylimonene), resins of homopolymers or copolymers of C5 or C9 cut, for example C5 / styrene cut copolymer or C5 cut / C9 cut copolymer.
• homopolymer or copolymer resins of cyclopentadiene or dicyclopentadiene resins of terpene homopolymers or copolymers (eg alphapinene, betapinene, dipentene or polylimonene), resins of homopolymers or copolymers of C5 or C9 cut, for example C5 / styrene cut
• compositions through an improvement of the dispersion of the load in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to processability in the green state; these agents are for example hydroxysilanes or hydrolysable silanes such as alkyl-alkoxysilanes, polyols, polyethers, amines, hydroxylated or hydrolysable polyorganosiloxanes. 4. I .E. Production of compositions
• the rubber compositions forming the belt coating rubber are manufactured in suitable mixers, for example using two successive preparation phases according to a general procedure well known to those skilled in the art: a first thermomechanical working or mixing phase (sometimes referred to as a "non-productive" phase) at a high temperature, up to a maximum temperature of between 130 ° C and 200 ° C, preferably between 145 ° C and 185 ° C, followed by a second mechanical working phase (sometimes referred to as a "productive" phase) at a lower temperature, typically less than 120 ° C, for example between 60 ° C and 100 ° C, finishing phase during which the crosslinking or vulcanization system is incorporated.
• a first thermomechanical working or mixing phase sometimes referred to as a "non-productive" phase
• a second mechanical working phase sometimes referred to as a "productive” phase
• a process which can be used for the manufacture of such rubber compositions comprises, for example, and preferably the following steps: - incorporating in a mixer, to the diene elastomer or to the mixture of diene elastomers, the high density filler and the possible other filler reinforcing, thermomechanically kneading the whole, in one or more times, until a maximum temperature of between 130 ° C and 200 ° C;
• accelerator primary or secondary
• any compound capable of acting as an accelerator of vulcanization of diene elastomers in the presence of sulfur in particular thiazole-type accelerators and their derivatives, accelerators of thiuram type, zinc dithiocarbamates.
• These accelerators are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated “CBS”), N, N-dicyclohexyl-2-benzothiazyl sulfenamide (“DCBS”), N-tert-butyl-2-benzothiazylsulfenamide (“TBBS”), N-tert-butyl-2-benzothiazylsulfenimide (“TBSI”), zinc dibenzyldithiocarbamate (“ZBEC”) and mixtures thereof. these compounds.
• MBTS 2-mercaptobenzothiazyl disulfide
• CBS N-cyclohexyl-2-benzothiazyl sulfenamide
• DCBS N-dicyclohexyl-2-benzothiazyl sulfenamide
• the vulcanization (or cooking) is conducted in a known manner at a temperature generally between 130 ° C and 200 ° C, for a sufficient time which may vary for example between 5 and 90 min depending in particular on the cooking temperature, the system of vulcanization adopted and the kinetics of vulcanization of the composition under consideration.
• the belt coating gum has, in the vulcanized state (ie, after curing), a density or density which is greater than 1.4 g / cm 3 , in particular between 1, 5 and 3. 0 g / cm 3 .
• Its secant modulus in extension (noted E10) is preferably less than 30 MPa, more preferably between 3 and 30 MPa, in particular in a range of 4 to 20 MPa.
• This secant modulus in extension (E10) is the tensile modulus measured in second elongation (ie, after an accommodation cycle) at 10% elongation (according to ASTM D412-1998, specimen "C"), this module being the module secant "true” that is to say, brought back to the actual section of the specimen (normal temperature and humidity conditions according to ASTM D 1349-1999).
• the rubber composition described above is therefore used, in the radial tire of the invention, as a coating gum of the crown reinforcement or belt disposed between the tread and the carcass reinforcement.
• this belt-coating rubber can constitute all or part of the rubber matrices coating the textile and / or metal reinforcements present in the belt itself of the tire, for example as a coating or calendering rubber for frettage top plies, top protection plies or working top plies, all constituting said belt.

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• 2010
  • 2010-06-17 FR FR1054829A patent/FR2961516B1/fr not_active Expired - Fee Related
• 2011
  • 2011-05-24 JP JP2013514616A patent/JP2013531714A/ja active Pending
  • 2011-05-24 US US13/701,979 patent/US20130133805A1/en not_active Abandoned
  • 2011-05-24 EP EP11721052.6A patent/EP2582746A1/fr not_active Withdrawn
  • 2011-05-24 WO PCT/EP2011/058443 patent/WO2011157514A1/fr not_active Ceased

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