Classifications

• • 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
  • C08K3/04—Carbon
• • 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
• • 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
  • B60C1/0041—Compositions of the carcass layers
• • 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
  • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
  • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
  • B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
  • B60C9/22—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • 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
  • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
  • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
  • B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
  • B60C2009/2012—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel with particular configuration of the belt cords in the respective belt layers
  • B60C2009/2016—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel with particular configuration of the belt cords in the respective belt layers comprising cords at an angle of 10 to 30 degrees to the circumferential direction
• • 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
  • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
  • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
  • B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
  • B60C2009/2012—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel with particular configuration of the belt cords in the respective belt layers
  • B60C2009/2019—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel with particular configuration of the belt cords in the respective belt layers comprising cords at an angle of 30 to 60 degrees to the circumferential direction
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/006—Additives being defined by their surface area
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

• Rubber composition comprising a reinforcing filler with a low specific surface area
• the present invention relates to a rubber composition comprising predominantly an isoprene elastomer and a tire comprising this composition.
• Document FR 2 981 298 discloses a tire comprising a layer of rubber material disposed between the ends of the two working crown plies, based on a predominantly isoprene elastomeric matrix and a reinforcing filler consisting of either surface carbon black specific BET greater than 60 m 2 / g, or carbon black BET surface area greater than 60 m 2 / g, or a white filler silica and / or alumina, this layer having a modulus of elasticity under voltage at 10% elongation less than 8 MPa and a maximum value of tan (delta) less than 0.10.
• the tires thus produced effectively improve performance, particularly in terms of endurance and rolling resistance.
• the invention relates to a rubber composition based on: an elastomeric matrix comprising at least 90 phr of at least one isoprene elastomer;
• a reinforcing filler comprising predominantly at least one carbon black, called black NC, in the context of the present invention, having a BET specific surface area at most equal to 30 m 2 / g and a dye oil absorption index; compressed samples (COAN) of not less than 60 ml / 100 g;
• composition not comprising, or comprising, at most 10 phr of carbon black having a BET specific surface area greater than 30 m 2 / g and COAN greater than 40 ml / 100 g, and not comprising, or comprising at most 10 phr of silica.
• part by weight per hundred parts by weight of elastomer (or phr) is meant for the purposes of the present invention, the part, in mass per hundred parts by mass of elastomer or rubber, the two terms being synonymous.
• 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 interval represented by the expression "between a and b" is also designated and preferentially.
• a majority compound in the sense of the present invention, it is understood that this compound is predominant among the compounds of the same type in the composition, that is to say that it is the one which represents the largest amount by mass among the compounds of the same type.
• a majority polymer is the polymer representing the largest mass relative to the total mass of the polymers in the composition.
• a so-called majority charge is that representing the largest mass among the charges of the composition.
• the majority polymer accounts for more than half of the mass of the polymers.
• the term “majority” means more than 50%, preferably more than 60%, 70%, 80%, 90%, and more preferably the "majority" compound represents 100%.
• composition based on is meant a composition comprising the mixture and / or the reaction product in situ of the various constituents used, some of these constituents being able to react and / or being intended to react with each other, less partially, during the various phases of manufacture of the composition; the composition can thus be in the fully or partially crosslinked state or in the non-crosslinked state.
• the circumferential direction of the tire is the direction corresponding to the periphery of the tire and defined by the rolling direction of the tire.
• the transverse or axial direction of the tire is parallel to the axis of rotation of the tire.
• the radial direction is a direction intersecting the axis of rotation of the tire and perpendicular to it.
• the axis of rotation of the tire is the axis around which it rotates under normal use.
• a radial or meridian plane is a plane that entrusts the axis of rotation of the tire.
• the circumferential median plane is a plane perpendicular to the axis of rotation of the tire and which divides the tire into two halves.
• the compounds comprising carbon mentioned in the description may be of fossil origin or biobased. In the latter case, they can be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. These include polymers, plasticizers, fillers, etc. Elastomers
• the rubber composition according to the invention is based on at least 90 phr of at least one isoprene elastomer.
• the composition according to the invention may contain a single isoprene elastomer or a mixture of one or more isoprenic elastomers with one or more other elastomers.
• composition according to the invention may also comprise any type of non-isoprene diene elastomer, or other than diene, such as, for example, olefinic or thermoplastic elastomers.
• iene elastomer or indistinctly rubber, whether natural or synthetic, must be understood in known manner an elastomer consisting at least in part (ie, a homopolymer or a copolymer) of monomeric diene units (monomers carrying two carbon-carbon double bonds, conjugated or not).
• diene elastomers can be classified into two categories: “essentially unsaturated” or “essentially saturated”.
• the term “essentially unsaturated” is generally understood to mean 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%);
• 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%).
• iene elastomer that may be used in the compositions according to the invention is particularly understood to mean:
• the other monomer may be ethylene, an olefin or a diene, conjugated or otherwise.
• Suitable conjugated dienes are conjugated dienes having from 4 to 12 carbon atoms, in particular 1,3-dienes, such as in particular 1,3-butadiene and isoprene.
• unconjugated dienes are suitable non-conjugated dienes having 6 to 12 carbon atoms, such as 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene.
• Suitable olefins are vinylaromatic compounds having 8 to 20 carbon atoms and aliphatic ⁇ -monoolefins having 3 to 12 carbon atoms.
• vinylaromatic compounds are suitable for example styrene, ortho-, meta-, para-methylstyrene, the commercial mixture "vinyl-toluene", para-tert-butylstyrene.
• aliphatic ⁇ -monoolefins are particularly suitable aliphatic acetic oc-mono-olefins having from 3 to 18 carbon atoms.
• the diene elastomer is:
• the diene elastomer may be modified, that is to say coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization.
• the diene elastomer may be coupled and / or starred, for example by means of a silicon or tin atom which bonds the elastomeric chains together.
• the diene elastomer may be simultaneously or alternatively functionalized and comprise at least one functional group.
• functional group is meant a group comprising at least one heteroatom selected from Si, N, S, O, P.
• Particularly as functional groups include those comprising at least one function such as: an alkoxysilane, silanol, a primary amine , secondary or tertiary, cyclic or not, a thiol, an epoxide.
• isoprene elastomer a homopolymer or copolymer of isoprene, in other words a diene elastomer selected from the group consisting of natural rubber (NR) which can be plasticized or peptized, synthetic polyisoprenes (IR ), the various isoprene copolymers, in particular the copolymers of isoprene-styrene (SIR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene (SBIR), and mixtures of these elastomers.
• NR natural rubber
• IR synthetic polyisoprenes
• composition according to the invention is preferably based on at least one isoprene elastomer chosen from the group consisting of natural rubber, synthetic polyisoprenes and their mixtures, advantageously in the group consisting of natural rubber, polyisoprenes comprising a mass ratio of cis 1,4 bonds of at least 90%, more preferably at least 98% relative to the mass of isoprene elastomer and mixtures thereof.
• composition according to the invention will advantageously comprise a substantially unsaturated diene elastomer, in particular of the (a ') or ( b ') described above.
• the diene elastomer other than isoprene of the composition according to the invention may be chosen preferentially from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated as "BR"), butadiene copolymers and mixtures of these elastomers.
• BR polybutadienes
• Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), butadiene-acrylonitrile copolymers (NBR), butadiene-styrene-acrylonitrile copolymers (NSBR) or a mixture of two or more of these compounds.
• the rubber composition according to the invention is based on at least 100 phr of at least one isoprene elastomer.
• the composition according to the invention does not contain thermoplastic elastomer or contains less than 10 phr, preferably less than 5 phr.
• the composition according to the invention does not comprise, or comprises less than 2 phr, preferably less than 1 phr, preferably less than 0.5 phr of polybutadienes. Indeed, beyond these levels, the presence of polybutadiene ("BR" abbreviated) is likely to reduce the cohesive properties of the composition according to the invention.
• BR polybutadiene
• composition according to the invention comprises a reinforcing filler comprising predominantly at least one carbon black, called "NC black” in the context of the present invention, said NC black having a BET specific surface area at most equal to 30 m 2 / g, and a compressed sample oil absorption index (COAN) of at least 60 ml / 100 g.
• NC black a reinforcing filler comprising predominantly at least one carbon black, called "NC black” in the context of the present invention, said NC black having a BET specific surface area at most equal to 30 m 2 / g, and a compressed sample oil absorption index (COAN) of at least 60 ml / 100 g.
• COAN compressed sample oil absorption index
• COAN or Compressed Oil Absorption Number, of carbon blacks, is measured according to ASTM D3493-16.
• the BET specific surface area of the carbon blacks is measured according to the D6556-10 standard (multipoint method (at least 5 points) - gas: nitrogen - relative pressure range R / R0: 0.1 to 0.3).
• said NC black has a BET specific surface area of less than or equal to 25 m 2 / g, preferably a BET specific surface area in a range from 15 to 25 m 2 / g.
• said NC black has a COAN oil absorption index of at least 65 ml / 100 g, preferably at least 70 ml / 100 g.
• said NC black has a COAN at most equal to 90 ml / 100 g, and preferably in a range of 70 ml / 100 g to 80 ml / 100 g.
• black carbon black NC is the "S204" marketed by the company Orion Engineered Carbon. These carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a carrier for some of the rubber additives used. These carbon blacks could for example already be incorporated into the isoprene elastomer in the form of a masterbatch, produced by the dry or liquid route (see, for example, WO 97/36724 or WO 99/16600).
• the reinforcing filler may also comprise any type of reinforcing filler known for its ability to reinforce a rubber composition that can be used for manufacturing tires, for example an organic filler such as carbon black other than black CN, a reinforcing inorganic filler. such as silica, or a blend of these two types of filler.
• an organic filler such as carbon black other than black CN
• a reinforcing inorganic filler such as silica
• silica a blend of these two types of filler.
• carbon blacks other than a black NC are suitable all carbon blacks, including the black type HAF, ISAF, SAF conventionally used in tires (so-called pneumatic grade black).
• carbon blacks reinforcing series 100, 200 or 300 such as blacks NI15, N134, N234, N326, N330, N339, N347, N375, or else according to the targeted applications, the blacks of higher series (for example N660, N683, N772).
• the carbon blacks could for example already be incorporated into an isoprene elastomer in the form of a masterbatch (see for example 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, WO-A-2006/069793, WO-A-2008/003434 and WO-A-2008/003435.
• any inorganic or mineral filler (whatever its color and its natural or synthetic origin), also called “white” filler, “clear” filler or “non-black filler” as opposed to carbon black, capable of reinforcing on its own, with no other means than an intermediate coupling agent, a composition of rubber intended for the manufacture of tires, in other words able to replace, in its reinforcing function, 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.
• -OH hydroxyl groups
• reinforcing inorganic filler is present indifferent whether in the form of powder, microbeads, granules, beads or any other suitable densified form.
• reinforcing inorganic filler also refers to mixtures of various reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described below.
• Suitable reinforcing inorganic fillers are, in particular, mineral fillers of the siliceous type, in particular silica (SiO 2 ), or of the aluminous type, in particular alumina (Al 2 O 3 ).
• 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 CT AB specific surface area both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
• HDS highly dispersible precipitated silicas
• the Ultrasil 7000 and Ultrasil 7005 silicas from Degussa the Zeosil 1165MP, 1135MP and 1115MP silicas from Rhodia
• the Hi-Sil EZ150G silica from the PPG company
• the Zeopol 8715, 8745 and 8755 silicas of the Huber Company the high surface area silicas as described in the application WO 03/16837.
• the BET specific surface area of the silica is determined in a known manner by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society” Vol. 60, page 309, February 1938, specifically according to the French standard NF ISO 9277 of December 1996 (multipoint volumetric method (5 points) - gas: nitrogen - degassing: time at 160 ° C - relative pressure range p / po: 0.05 at 0.17).
• the CTAB specific surface area of the silica is determined according to the French standard NF T 45-007 of November 1987 (method B).
• the reinforcing inorganic filler used in particular if it is silica, preferably has a BET surface area of between 45 and 400 m 2 / g, more preferably between 60 and 300 m 2 / g.
• a bifunctional coupling agent intended to ensure a sufficient chemical and / or physical connection between the inorganic filler (surface of its particles) and the elastomer, in particular organosilanes, or bifunctional polyorganosiloxanes.
• polysulfide silanes known as "symmetrical” or “asymmetrical” silanes, may be used, depending on their particular structure, as described, for example, in claims WO00 / 002648 (or US 2005/016651) and WO00 / 002649 (or US 2005/016650). .
• polysulphurized silanes By way of examples of polysulphurized silanes, mention may be made more particularly of bis (alkoxyl (C 1 -C 4) alkyl (C 1 -C 4) silyl-alkyl (C 1 -C 4) polysulfides (especially disulfides, trisulphides or tetrasulfides), as for example polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl).
• the coupling agent is present at a level corresponding to a range from 5 to 15% by weight relative to the mass of silica.
• the level of coupling agent is in a range from 5 to 11% by weight relative to the mass of silica.
• the level of NC black in the rubber composition is advantageously in a range of values ranging from 20 to 80 phr, this range of values making it possible to obtain a tire whose endurance and rolling resistance properties are improved.
• the black NC level is in a range from 35 to 70 phr, preferably from 40 to 65 phr, and preferably from 45 to 60 phr.
• the reinforcing filler comprises predominantly, that is to say at least 50% by weight, black NC.
• the reinforcing filler comprises 60%, 70%, 80%, 90% by mass of NC black.
• the reinforcing filler consists of NC black.
• composition according to the invention does not comprise silica, or comprises at most 10 phr, advantageously at most 5 phr.
• Said composition does not comprise carbon black whose BET surface area is greater than 30 m 2 / g and the COAN is greater than 40 ml / 100 g, or comprises at most 10 phr, advantageously at most 5 phr.
• the composition according to the invention does not comprise carbon black whose BET specific surface area is less than 15 m 2 / g or comprises at most 10 phr, advantageously at most 5 phr.
• Crosslinking system
• the crosslinking system may be any type of system known to those skilled in the art of rubber tire compositions. It may especially be based on sulfur, and / or peroxide and / or bismaleimides.
• the crosslinking system is based on sulfur, it is called a vulcanization system.
• Sulfur can be provided in any form, especially in the form of molecular sulfur, or a sulfur-donor agent.
• At least one vulcanization accelerator is also preferably present, and, optionally, also preferred, various known vulcanization activators such as zinc oxide, stearic acid or equivalent compound such as stearic acid salts and salts may be used. transition metals, guanidine derivatives (in particular diphenylguanidine), or known vulcanization retarders.
• Sulfur is used at a preferential rate of between 2 and 6 phr, in particular between 3 and 5 phr.
• the vulcanization accelerator is used at a preferred level within a range from 0.3 to 1.2 phr, preferably from 0.5 to 1 phr.
• Any compound capable of acting as an accelerator for vulcanizing diene elastomers in the presence of sulfur especially thiazole accelerators and their derivatives, accelerators of sulfenamide, thiuram, dithiocarbamate, dithiophosphate, thiourea and xanthate type, may be used as accelerator.
• Examples of such accelerators include the following compounds: 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), N-cyclohexyl-2-benzothiazyl sulfenamide (“CBS”), N, N-dicyclohexyl- 2-benzothiazyl sulfenamide (“DCBS”), N-tert-butyl-2-benzothiazyl sulfenamide (“TBBS”), N-tert-butyl-2-benzothiazyl sulfenimide (“TBSI”), tetrabenzylthiuram disulfide (“TBZTD”) Zinc dibenzyldithiocarbamate (“ZBEC”) and mixtures thereof.
• MBTS 2-mercaptobenzothiazyl disulfide
• CBS N-cyclohexyl-2-benzothiazyl sulfenamide
• DCBS N-dicyclohexyl- 2-benzothiazy
• the rubber composition in accordance with the invention may also comprise all or part of the usual additives normally used in elastomer compositions, for example pigments, protective agents such as anti-ozone waxes, chemical ozonants, antioxidants, plasticizers, anti-fatigue agents, reinforcing resins, secondary vulcanization accelerators, vulcanization activators, etc.
• additives normally used in elastomer compositions for example pigments, protective agents such as anti-ozone waxes, chemical ozonants, antioxidants, plasticizers, anti-fatigue agents, reinforcing resins, secondary vulcanization accelerators, vulcanization activators, etc.
• composition according to the invention may in particular comprise an alkaline earth metal, alkaline or lanthanide salt.
• the salt of an alkaline earth metal, alkali metal or lanthanide may advantageously be an acetylacetonate of an alkaline earth metal, alkali or lanthanide.
• the alka-earth metal, alkan or lanthanide of the salt is selected from the group consisting of iumium, sodium, potassium, calcium, magnesium, lanthanum, cerium, praseodymium, neodymium, samarium , erbium and mixtures thereof. More preferably, the salt of an alkaline earth metal, alkan or lanthanide is a salt of magnesium or neodymium. In other words, the salt of an alkaline earth metal, alkan or lanthanide is advantageously a magnesium or neodymium acetylacetonate, preferably a magnesium acetylacetonate.
• the content of the alkaline earth metal salt, alcaün or lanthanide may be for example in a range from 0.1 to 5 phr, preferably from 0.5 to 4 phr and more preferably from 0.5 to 2 phr.
• composition according to the invention may further comprise a cobalt salt.
• the cobalt salt may be selected from the group consisting of abietates, acetylacetonates, tallates, naphthenates, resinates and mixtures thereof.
• the level of cobalt salt may advantageously be in a range from 0.5 to 3 phr, preferably from 0.5 to 2 phr, preferably from 0.5 to 1.2 phr.
• the composition according to the invention may further comprise an antioxidant selected from the group consisting of substituted p-phenylene diamines, substituted diphenylamines, substituted triphenylamines, quinoline derivatives, and mixtures thereof.
• the antioxidant is selected from the group consisting of substituted p-phenylene diamines and mixtures thereof.
• the level of antioxidant may advantageously be in a range from 1 to 5 phr, preferably from 1 to 3 phr.
• the composition may comprise a vulcanization retarder or be free from it.
• the composition according to the invention may contain less than 1 phr, preferably less than 0.6 phr, preferably less than 0.3 phr, of vulcanization retarder.
• a vulcanization retarder mention may be made of N-cyclohexylthiophthalimide (CTP), marketed for example under the name "Vulkalent G" by the company Lanxess.
• the composition according to the invention does not comprise resorcinol and / or resorcinol derivative and / or hexamethylene triamine and / or melamine derivative, or comprises less than 0.5 phr, preferably less than 0. , 4 pce. More preferably, the composition according to the invention does not comprise a reinforcing resin, or comprises less than 0.5 phr, preferably less than 0.4 phr. Finished or semi-finished rubber articles
• the present invention also relates to a finished or semi-finished rubber article, and a tire comprising a composition according to the invention.
• a finished or semi-finished rubber article and a tire comprising a composition according to the invention.
• concerned articles and tires both in the state cm (that is, before cooking) and in the cooked state (that is, after crosslinking or vulcanization).
• the radially inner zone and in contact with the inflation gas this zone being generally constituted by the inflation-gas-tight layer, sometimes called inner waterproof layer or inner liner.
• the inner area of the tire that is to say the area between the outer and inner zones.
• This zone includes layers or plies which are here called internal layers of the tire. These are, for example, carcass plies, tread underlays, lap belt plies or any other layer that is not in contact with the ambient air or the inflation gas of the tire.
• composition defined in the present description is particularly well suited to the inner layers of the tires.
• the finished or semi-finished rubber article according to the invention or the inner layer of the tire according to the invention may comprise at least one textile or metal reinforcing element. It may be any textile or metal reinforcement known to those skilled in the art.
• reinforcing element or metal or textile reinforcing element is meant that said reinforcing element may be all or part of metal or textile.
• said reinforcing element may be textile in nature, that is to say made of an organic material, in particular a polymeric material, or an inorganic material, such as for example glass, quartz, basalt or carbon.
• the polymeric materials may be of the thermoplastic type, such as, for example, aliphatic polyamides, in particular polyamides 6-6, and polyesters, in particular polyethylene terephthalate.
• the polymeric materials may be of the non-thermoplastic type, such as, for example, aromatic polyamides, especially aramid, and cellulose, both natural and artificial, especially rayon.
• Said reinforcing element may be of a metallic nature, that is to say comprise a metal selected from the group consisting of iron, copper, zinc, tin, aluminum, cobalt, nickel and the like. alloys comprising at least one of these metals.
• the alloys can be, for example, binary or ternary alloys, such as steel, bronze and brass.
• said reinforcing member comprises a metal surface.
• the metal surface of the reinforcing element constitutes at least a portion, and advantageously the entire surface of said reinforcing element and is intended to come into contact with the composition according to the invention.
• the composition according to the invention coats at least a portion of the reinforcing element, advantageously all of said reinforcing element.
• the reinforcing element is advantageously partly or wholly metallic, the metal part comprising at least the metal surface. Preferably all of the reinforcing element is metal.
• the metal surface of the reinforcing element is made of a material different from the rest of the reinforcing element.
• the reinforcing element is made of a material which is at least partly, advantageously completely, covered by a metal layer which constitutes the metal surface.
• the material at least partly, advantageously completely, covered by the metal surface is of a metallic or non-metallic nature, preferably metal.
• the reinforcing element is made of the same material, in which case the reinforcing element is made of a metal which is identical to the metal of the metal surface.
• the metal surface comprises a metal selected from the group consisting of iron, copper, zinc, tin, aluminum, cobalt, nickel and alloys comprising at least one of these metals.
• the alloys can be, for example, binary or ternary alloys, such as steel, bronze and brass.
• the metal of the metal surface is iron, copper, tin, zinc or an alloy comprising at least one of these metals. More preferably, the metal of the metal surface is steel, brass (Cu-Zn alloy), zinc or bronze (Cu-Sn alloy), even more preferably brass or zinc, and very favorite way brass.
• the expression "the metal of the metal surface is the metal hereinafter designated” is tantamount to saying that the metal surface is of metal hereinafter referred to.
• the phrase “the metal of the metal surface is brass” written above means that the metal surface is brass.
• the metal surface is steel
• the steel is preferably a carbon steel or a stainless steel.
• its carbon content is preferably between 0.01% and 1.2% or between 0.05% and 1.2%, or between 0.2% and 1.2%, especially between 0.4% and 1.1%.
• the steel is stainless, it preferably comprises at least 11% chromium and at least 50% iron.
• the reinforcing element can be in any form.
• the reinforcing element is in the form of a wire or a cable.
• the invention also relates to a tire comprising a rubber composition according to the invention.
• the present invention relates particularly to tires intended to equip motor vehicles of the tourism type, SUV ("Sport Utility Vehicles"), or two wheels (in particular motorcycles), or planes, or industrial vehicles chosen from light trucks, "Poids- heavy goods vehicles' - that is to say, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering machinery - and the like, and so on preferred tires for equipping vehicles of the "heavy truck” type.
• SUV Sport Utility Vehicles
• two wheels in particular motorcycles
• planes or industrial vehicles chosen from light trucks, "Poids- heavy goods vehicles' - that is to say, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering machinery - and the like, and so on preferred tires for equipping vehicles of the "heavy truck” type.
• the radial carcass reinforcement tire mainly comprises, as well known to those skilled in the art, a tread, two beads each reinforced with a rod, two flanks connecting the beads to the tread, an armature carcass extending from one bead to the other wrapped around the two rods in each bead and comprising a reversal disposed, for example, towards the outside of the tire, and a sealing layer ("inner liner" in English). ) extending between the two beads and located axially inside the carcass reinforcement.
• a rigid crown reinforcement is disposed circumferentially between the carcass reinforcement and the tread.
• the tire advantageously comprises a so-called internal reinforcing layer situated between the sealing layer and the carcass reinforcement and extending from one bead to the other.
• the invention relates to a tire in which the rubber composition according to the invention is present in at least one inner layer of said tire.
• said inner layer of said tire is selected from the group consisting of carcass plies, crown plies, bead-fillers, toe feet, decoupling layers, edging gums, tamping gums, the sub-ply. tread layer, the inner reinforcing layer and the combinations of these inner layers and preferably chosen from the group consisting of carcass plies, crown plies, toe feet, decoupling layers, edge gums, the inner reinforcing layer and the combinations of these inner layers.
• the term "edge rubber” means a layer positioned in the tire directly in contact with the end of a reinforcing ply, the end of a reinforcing element or another rubber of border.
• composition according to the invention is particularly well suited for the rubber layers C described in the applications FR 2981297 and FR 2981298, or the layers of crown layer calenders described in the application FR 2981299.
• the tire according to the invention may for example be a tire as defined in application FR 2981297 or FR 2981298 in which composition C comprises or consists of a composition according to the present invention.
• the tire according to the invention may also be a tire as defined in application FR 2981299 in which the calender layer of at least one working crown layer comprises or consists of a composition according to the present invention.
• the invention relates to a radial carcass reinforcement tire comprising a crown reinforcement formed of at least two plies of superimposed work and formed of parallel reinforcing elements within each ply and crossed from one ply to the next, forming with the circumferential direction angles between 10 ° and 45 °, a layer C of rubber mix being disposed between minus the ends of said at least two working plies, characterized in that the layer C of rubbery mixture is a rubber composition according to the invention.
• the invention in another preferred arrangement, relates to a radial carcass reinforcement tire comprising a crown reinforcement formed of at least two superimposed working plies, each formed of parallel reinforcing elements inserted between two layers of calendering rubber mix crossed from one ply to the other by making with the circumferential direction angles of between 10 ° and 45 °, characterized in that at least one calendering layer of at least one working ply is a composition according to invention.
• said crown reinforcement advantageously also comprises at least one layer of circumferential metallic reinforcing elements.
• the at least one layer of circumferential metal reinforcing elements is a layer comprising mutually parallel metallic reinforcement elements which make angles with the circumferential direction in the range + 2.5 ° to -2.5 °, ie substantially around 0 °.
• the at least one layer of circumferential metal reinforcing elements is advantageously radially arranged between two working plies.
• the presence of the at least one layer of circumferential metal reinforcing elements advantageously makes it possible to use in the rubber composition according to the invention a black content NC in the range from 45 to 60 phr, the reinforcing filler preferably being constituted of said black NC.
• thermomechanical mixing a first phase of work or thermomechanical mixing (so-called "nonproductive" phase), which can be conducted in a single thermomechanical step during which is introduced into a suitable mixer such as a conventional internal mixer (for example of the type 'Banbury'), all the necessary constituents, in particular the elastomeric matrix, the fillers, any other various additives, with the exception of the crosslinking system.
• a suitable mixer such as a conventional internal mixer (for example of the type 'Banbury')
• Incorporation of the filler with the elastomer can be carried out one or more times by thermomechanically kneading.
• the charge is already incorporated wholly or partly into the elastomer in the form of a masterbatch, as described for example in the applications WO 97/36724 or WO 99 / 16600, it is the masterbatch which is directly kneaded and if necessary is incorporated the other elastomers or fillers present in the composition which are not in the form of masterbatch, as well as any other various additives other than the crosslinking system.
• the non-productive phase is carried out at high temperature, up to a maximum temperature of between 110 ° C. and 190 ° C., preferably between 130 ° C. and 180 ° C., for a period generally of between 1 and 15 minutes.
• a second phase of mechanical work (so-called "productive" phase), which is performed in an external mixer such as a roll mill, after cooling the mixture obtained during the first non-productive phase to a lower temperature typically below 110 ° C, for example between 40 ° C and 100 ° C.
• the crosslinking system is then incorporated, and the whole is then mixed for a few minutes, for example between 2 and 15 minutes.
• the final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for a characterization in the laboratory, or else extruded in the form of a semifinished (or profiled) of rubber usable by example as an inner layer in a tire.
• the composition can be either in the green state (before crosslinking or vulcanization), or in the fired state (after crosslinking or vulcanization), can be a semi-finished product that can be used in a tire.
• the crosslinking of the composition may be carried out in a manner known to those skilled in the art, for example at a temperature of between 130 ° C. and 200 ° C., under pressure.
• the dynamic property tan ( ⁇ ) max was measured on a viscoanalyzer (Metravib VA4000) according to ASTM D 5992-96.
• the response of a sample of vulcanized composition (cylindrical specimen of 4 mm thickness and 400 mm 2 section), subjected to a sinusoidal stress in alternating simple shear, at the frequency of 10 Hz and at a temperature of 100 is recorded. ° C.
• a strain amplitude sweep of 0.1 to 100% (forward cycle) followed by 100% at 0.1% (return cycle) was performed.
• the result exploited is the loss factor (tan (ô)).
• the maximum value of tan d observed (tan ( ⁇ ) max) was given between the values at 0.1% and at 100% deformation (Payne effect).
• Rolling resistance is the resistance that occurs when the tire is rolling. It is represented by the hysteretic losses related to the deformation of the tire during a revolution.
• the frequency values related to the revolution of the tire correspond to values of tan ( ⁇ ) measured between 30 and 100 ° C.
• the value of tan ( ⁇ ) at 100 ° C thus corresponds to an indicator of the rolling resistance of a heavy goods vehicle tire when taxiing.
• the mixture thus obtained is recovered, cooled and the vulcanization system is then incorporated on a mixer (homo-finisher) at 30 ° C., mixing the whole (productive phase) for a suitable time (for example between 5 and 12 hours). min).
• compositions thus obtained are then calendered in the form of plates (thickness of 2 to 3 mm) or thin sheets of rubber and are then subjected to a baking step at 140 ° C. for 50 minutes before the measurement of their physical or mechanical properties. .
• the mixtures T1 and T2 respectively correspond to the low hysteretic loss mixtures 1 and 3 of document FR 2 981 298, T1 comprising a reinforcing filler carbon black and T2 a reinforcing filler silica.
• the mixtures whose compositions are indicated below are prepared.
• the carbon black content of the mixture II is adjusted to obtain the same MA 10 module as the mixture Tl.
• N-cyclohexylthiophthalimide sold under the name "Vulkalent G” by the company Lanxess The amounts of the constituents are expressed in phr (parts by weight per hundred parts of elastomers).
• the composition according to the invention has lower tan ( ⁇ ) max hysteretic losses than the control mixture Tl.
• the composition according to the invention also has lower hysteretic losses than the low loss mixture.
• T2 based on silica will provide a tire with a lower rolling resistance.
• the compliant composition II is compared with a mixture T3 of the prior art having a similar rigidity and a low hysteretic loss.
• the mixture T3 corresponds to the mixture 4 of the document FR 2 981 298.
• the mixtures whose compositions are indicated below are prepared.
• the tensile modulus of elasticity at 10% elongation (MA 10 ) and the tan ( ⁇ ) max values are measured for each, these values being expressed in base 100 using T3 as a reference.
• Percentages of elongation at break are determined after preparation of the specimens and after the specimens have been subjected to heat treatment for 10 days at 110 ° C. under nitrogen. The evolution of the percentage of elongation at break makes it possible to estimate the resistance of the composition to thermal aging. The results are expressed on a 100 basis for each test piece, the value of 100 corresponding to the elongation at break of the specimen prior to the heat treatment.
• the mixture according to the invention has a decreased hysteresis for a stiffness similar to the composition T3, and has a better resistance to thermal aging with an elongation at break which is less diminished after aging.

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• 2018
  • 2018-04-09 FR FR1853079A patent/FR3079838B1/fr active Active
• 2019
  • 2019-04-01 US US17/046,338 patent/US20210115218A1/en not_active Abandoned
  • 2019-04-01 EP EP19719564.7A patent/EP3774388A1/de active Pending
  • 2019-04-01 WO PCT/FR2019/050751 patent/WO2019197746A1/fr unknown
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