Classifications

• • 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
• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/40—Polyamides containing oxygen in the form of ether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

• the present invention relates to tires comprising a composition based on a mixture of thermoplastic elastomer and thermoplastic polymer.
• the inner area of the tire that is to say the area between the outer and inner zones.
• This zone includes layers or webs which are here called internal layers of tires.
• This type of layer may be for example a tread underlayer, a tire crown layer, a carcass ply, a layer of the lower zone of the tire (preferably the bead), or any other layer which does not is not in contact with the ambient air or the inflation gas of the tire.
• An essential property of these inner layers is to be sufficiently deformable on the one hand, to absorb deformations during rolling and crossing obstacles and, on the other hand, to present a high module to give the structural rigidity that will give the required drift stiffness to the tire for guidance.
• One known way to obtain such properties is the use of reinforced plies, for example with wire reinforcements such as wire ropes.
• these reinforced plies of metal cables have a number of disadvantages. First, these cables are relatively expensive, and involve reduced manufacturing speeds. This disadvantage is of course reflected in the cost of - - tires themselves. Other known drawbacks of these metal cables are their relatively high sensitivity to corrosion, their weight and their bulk (external diameter).
• a layer consisting of a polymeric composition comprising a specific polymeric matrix and a reinforcing filler reconciled excellent stiffness and elongation properties. breaking without the use of wire reinforcement.
• the present invention relates to a tire comprising at least one layer consisting of a polymer composition based on at least: a polymer matrix comprising 65 to 95% of one or more thermoplastic polymers; whose glass transition temperature (Tg) is in a range from 120 to 250 ° C and 5 to 35% of one or more thermoplastic elastomers;
• one or more reinforcing fillers at a total content ranging from 1 to 60 parts by weight per 100 parts by weight of polymeric matrix (pcm);
• the invention relates to a tire as defined above, wherein the polymeric matrix comprises 70 to 90% thermoplastic polymer and 10 to 30% thermoplastic elastomer; more preferably, the polymeric matrix comprises 75 to 85% of thermoplastic polymer and 15 to 25% of thermoplastic elastomer.
• the invention also relates to a tire as defined above wherein said composition is adjacent to an elastomeric layer, forming with the latter a laminate. - -
• the invention relates to a tire as defined above, wherein said composition constitutes a tread underlayer, a layer of the tire crown, a carcass ply, a layer of the low zone of the tire. (preferably the bead), or any other layer that is not in contact with the ambient air or the inflation gas of the tire.
• the tires of the invention may be intended for motor vehicles of the tourism type, 4x4, "SUV” (Sport Utility Vehicles), but also to two-wheeled vehicles such as motorcycles or bicycles, or industrial vehicles chosen from vans, "heavy goods vehicles” ie metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural vehicles or Civil engineering, aircraft, other transport or handling vehicles.
• SUV Sport Utility Vehicles
• two-wheeled vehicles such as motorcycles or bicycles, or industrial vehicles chosen from vans, "heavy goods vehicles” ie metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural vehicles or Civil engineering, aircraft, other transport or handling vehicles.
• the invention relates to the above tire in the green state (before crosslinking of the rubber) as in the cooked state (after crosslinking, vulcanization of the rubber).
• the term "rubber” or “elastomer” (both terms being considered synonymous), any type of elastomer (diene or non-diene);
• "diene rubber” means any elastomer (elastomer alone or mixture of elastomers) which is derived, at least in part (either a homopolymer or a copolymer), from monomers dienes, that is to say from monomers carrying two double carbon-carbon bonds, whether or not they are conjugated;
• "layer” means a strip or any other three-dimensional element of relatively small thickness with respect to its other dimensions, the ratio of the thickness of which to the largest of the other dimensions is less than 0.5, preferably less than 0, 1;
• laminate or “multilayer laminate”, as defined in the International Patent Classification, means any product having at least two layers, of flat or non-planar shape, in contact with each other, which may or may not be in contact with each other related, interconnected, the term “bound” or “connected” must be interpreted extensively to include all means of
• pcm means in the sense of the present patent application, part by weight per hundred parts of polymeric matrix, any type of confused polymers, including thermoplastic elastomers and thermoplastic polymers combined.
• 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 (that is to say, limits a and b excluded) while any interval
• the term "from a to b” refers to the range of values from a to b (i.e. including the strict limits a and b).
• Tg glass transition temperature
• a majority reinforcing filler is the reinforcing filler representing the largest mass relative to the total weight of the reinforcing fillers in the composition.
• a “minor” compound is a compound that does not represent the largest mass fraction among compounds of the same type.
• the tire of the invention therefore has the essential feature of comprising at least one layer consisting of a polymer composition based on at least one polymer matrix comprising 65 to 95% of one or more thermoplastic polymers whose temperature glass transition (Tg) is in a range from 120 to 250 ° C and 5 to 35% of one or more thermoplastic elastomers; one or more reinforcing fillers at a total level within a range of from 1 to 60 parts by weight per 100 parts by weight of polymeric matrix (pcm); said one or more thermoplastic elastomers being compatible with said one or more thermoplastic polymers.
• Tg temperature glass transition
• pcm polymeric matrix
• thermoplastic elastomers are compatible with said one or more thermoplastic polymers when the elongation at break of the mixture of these polymers is greater than or equal to the elongation at break of the thermoplastic polymers alone.
• thermoplastic polymers thermoplastic elastomers and reinforcing fillers required for the invention will be described in detail below, as well as the preferred embodiments of the invention.
• the polymer matrix of the composition of the tire layer according to the invention comprises 65 to 95% of one or more thermoplastic polymers whose glass transition temperature (Tg) is in a range from 120 to 250 ° vs. - -
• the thermoplastic polymer or polymers have a Tg ranging from 140 to 230 ° C, preferably from 150 ° C to 220 ° C, more preferably from 160 ° C to 210 ° C.
• thermoplastic polymer or polymers are preferably chosen from the group consisting of polyamides, polycarbonates, and mixtures thereof.
• the thermoplastic polymer or polymers are one or more amorphous polyamides and more preferably the thermoplastic polymer or polymers are one or more amorphous polyamides, homopolymers or copolymers consisting of cycloaliphatic and / or aromatic monomers.
• a thermoplastic polymer suitable for the invention mention may be made of the amorphous polyamide "Rilsan clear G 170" from Arkema, which has a Tg of 168 ° C.
• thermoplastic polymer that is to say the thermoplastic polymer or polymers
• the thermoplastic polymer represents from 65 to 95%, preferably from 70 to 90% by weight, more preferably from 75 to 75% by weight. at 85% by weight of all the polymers present in the composition.
• the polymer matrix of the composition of the tire layer according to the invention comprises 5 to 35% of one or more thermoplastic elastomers (TPE).
• TPE thermoplastic elastomers
• thermoplastic elastomers have an intermediate structure between thermoplastic polymers and elastomers. They are block copolymers, made up of rigid, thermoplastic blocks, connected by flexible blocks, elastomers.
• said thermoplastic elastomer may preferably be a specific TPE, block copolymer comprising at least one elastomer block of polyether type and at least one thermoplastic block of non-styrenic type (TPNS).
• TPNS thermoplastic block of non-styrenic type
• a polyether block when reference is made to a polyether block, it is therefore a predominantly elastomeric block (that is, that is to say more than 50% by weight, preferably more than 80% by weight) composed of a polymer resulting from the polymerization of monomer-type - - ether, and, when it is referred to a non-styrenic block, it is a block composed predominantly (that is to say more than 50% by weight, preferably more than 80 % by weight) of a polymer resulting from the polymerization of monomer other than the styrenic compounds (ie styrene and substituted and / or functionalized styrenes).
• styrenic compounds ie styrene and substituted and / or functionalized styrenes
• thermoplastic elastomer may be another specific TPE, block copolymer comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block (H) SBR and at least one styrenic copolymer-type thermoplastic block (PS). ).
• a block (H) SBR when reference is made to a block (H) SBR, it is therefore a predominantly elastomeric block (that is to say more than 50% by weight, preferably more than 80% by weight) composed of a random copolymer of butadiene and styrene, this copolymer may or may not be hydrogenated, and, when it is referred to a styrenic block, it is a predominantly composed block (that is to say more than 50% by weight, preferably more than 80% by weight) of a styrenic polymer such as polystyrene.
• the thermoplastic elastomer is chosen from the group consisting of block copolymers comprising at least one elastomer block of polyether type and at least one thermoplastic block of non-styrenic type, block copolymers comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic type thermoplastic block (TPE (H) SBR-PS), and mixtures of these thermoplastic elastomers.
• block copolymers comprising at least one elastomer block of polyether type and at least one thermoplastic block of non-styrenic type
• block copolymers comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic type thermoplastic block (TPE (H) SBR-PS)
• TPE (H) SBR-PS styrenic type thermoplastic block
• thermoplastic elastomer is chosen from the group consisting of block copolymers comprising at least one elastomer block of polyether type and at least one polyamide thermoplastic block (PEBA), the block copolymers comprising at least one elastomeric block of the type polyether and at least one polyester thermoplastic block (COPE), the block copolymers comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic type thermoplastic block (TPE (H) SBR-PS), and mixtures of these thermoplastic elastomers.
• PEBA polyamide thermoplastic block
• COPE polyester thermoplastic block
• TPE (H) SBR-PS styrenic type thermoplastic block
• thermoplastic elastomer is chosen from the group consisting of block copolymers comprising at least one elastomer block of polyether type and at least one polyamide thermoplastic block (PEBA), and the mixtures of these thermoplastic elastomers.
• TPEs and in particular the preferential TPEs, are described in more detail in the following. - -
• the number-average molecular weight (denoted Mn) of the TPE is preferably between 30,000 and 500,000 g / mol, more preferably between 40,000 and 400,000 g / mol.
• Mn number-average molecular weight
• the number-average molecular weight (Mn) of the TPE elastomer is determined in a known manner by steric exclusion chromatography (SEC).
• SEC steric exclusion chromatography
• the sample is solubilized beforehand in tetrahydrofuran at a concentration of approximately 1 g / l; then the solution is filtered on 0.45 ⁇ porosity filter before injection.
• the apparatus used is a "WATERS alliance" chromatographic chain.
• the elution solvent is tetrahydrofuran, the flow rate 0.7 ml / min, the system temperature 35 ° C and the analysis time 90 min.
• a set of four WATERS columns in series, of trade names "STYRAGEL” ("HMW7", “HMW6E” and two “HT6E”) is used.
• the injected volume of the solution of the polymer sample is 100 ⁇ .
• the detector is a "WATERS 2410" differential refractometer and its associated software for the exploitation of chromatographic data is the “WATERS MILLENIUM” system.
• the calculated average molar masses relate to a calibration curve made with polystyrene standards. The conditions are adaptable by those skilled in the art.
• the TPEs have two glass transition temperature peaks (Tg, measured according to ASTM D3418), the lowest temperature being relative to the elastomeric portion (for example polyether) of the block TPE, and the temperature the highest being relative to the thermoplastic part (for example polyamide) of the TPE.
• Tg glass transition temperature peaks
• the soft blocks of the TPEs are defined by a Tg lower than the ambient temperature (25 ° C), while the rigid blocks have a Tg greater than 80 ° C.
• the Tg when reference is made to the glass transition temperature of the TPE, it is the Tg relative to the elastomeric block.
• the TPE presents - preferentially a glass transition temperature ("Tg") which is preferably less than or equal to 25 ° C, more preferably less than or equal to 10 ° C.
• Tg glass transition temperature
• a value of Tg higher than these minima can reduce the performance of the tread when used at very low temperatures; for such use, the Tg of the TPE is more preferably still less than or equal to -10 ° C.
• the Tg of the TPE is greater than -100 ° C.
• the TPE may be copolymers with a small number of blocks (less than 5, typically 2 or 3), in which case these blocks preferably have high masses, greater than 15000 g / mol.
• These TPEs can be, for example, diblock copolymers, comprising a thermoplastic block and an elastomer block. They are often also triblock elastomers with two rigid segments connected by a flexible segment. The rigid and flexible segments can be arranged linearly, star or connected. Typically, each of these segments or blocks often contains at least more than 5, usually more than 10 base units (e.g. ether units and amide units for a polyamide / polyether / polyamide block copolymer).
• the TPE may also comprise a large number of blocks (more than 30, typically from 50 to 500) smaller, in which case these blocks preferably have low masses, for example from 500 to 5000 g / mol, these TPEs will be called multiblock TPEs later, and are a sequence of elastomeric blocks - thermoplastic blocks.
• the TPE is in a linear form.
• TPE is a diblock copolymer: thermoplastic block / elastomeric block.
• the TPE can also be a triblock copolymer: thermoplastic block / elastomer block / thermoplastic block, that is to say a central elastomer block and two terminal thermoplastic blocks, at each of the two ends of the elastomeric block.
• the multiblock TPE may be a linear sequence of elastomeric blocks-thermoplastic blocks.
• the TPE useful for the purposes of the invention is in a star shape at least three branches.
• the TPE may then consist of a stellate elastomer block with at least three branches and a thermoplastic block, located at the end of each of the branches of the elastomeric block.
• the number of branches of the central elastomer can vary, for example from 3 to 12, and preferably from 3 to 6. - -
• the TPE is in a branched form or dendrimer.
• the TPE can then consist of a connected elastomeric block or dendrimer and a thermoplastic block, located at the end of the branches of the dendrimer elastomer block.
• elastomeric blocks of TPE for the purposes of the invention may be any elastomer known to those skilled in the art.
• the fraction of elastomeric block in the TPE is in a range from 30 to 95%, preferably from 40 to 92%, more preferably from 50 to 90%.
• These elastomer blocks preferably have a Tg (glass transition temperature) measured by DSC according to the ASTM D3418 standard of 1999, less than 25 ° C, preferably less than 10 ° C, more preferably less than 0 ° C and very preferably below -10 ° C. Also preferably, the T g of the elastomeric blocks is greater than -100 ° C. In particular, blocks having a Tg of between 20 ° C. and -70 ° C. and more particularly between 0 ° C. and -50 ° C. are suitable.
• the elastomeric blocks of the TPE have in total a number-average molecular weight ("Mn") ranging from 25,000 g / mol to 350,000 g / mol, preferably from 35,000 g / mol to 250,000 g / mol. g / mol so as to give the TPE good elastomeric properties and sufficient mechanical strength and compatible with the use in tread tire.
• Mn number-average molecular weight
• the elastomer block is of random copolymer type of butadiene and styrene ((H) SBR).
• the (H) SBR block comprises a styrene content, a 1,2-butadiene content of the butadiene part, and a -1,4-linkage content of the butadiene part, the latter consisting of a content of trans-1,4 bonds and a content of cis-1,4 bonds when the butadiene part is not hydrogenated.
• the determination of the hydrogenation rate is carried out by NMR analysis.
• the spectra are acquired on a BRUKER 500 MHz Avance spectrometer equipped with a 1H-X 5 mm Cryoprobe.
• the quantitative 1H NMR experiment uses a 30 ° single pulse sequence and a 5 second repetition time between each acquisition. 64 accumulations are made.
• the samples (approximately 25 mg) are solubilized in the CS 2 approximately 1 ml, ⁇ of deuterated cyclohexane are added to make the lock during the acquisition.
• the chemical shifts are calibrated against the impurity protonated CS 2? Ppm to 7.18 ppm 1H referenced on TMS (? Ppm in 1H OPPM).
• the 1H NMR spectrum makes it possible to quantify the microstructure by integrating the signal mass characteristic of the different patterns:
• Styrene from (H) SBR and polystyrene blocks It is quantifiable in the aromatics zone between 6.0ppm and 7.3ppm for 5 protons (by removing the signal integral of the CS2 impurity at 7.18ppm).
• PB 1-4 from (H) SBR. It is quantifiable in the ethylenic zone between 5.1 ppm and 6.1 ppm for 2 protons and by removing 1 proton from the PB 1-2 motif.
• the hydrogenated PB 1-2 from the hydrogenation and having only aliphatic protons.
• the CH3 during hydrogenated PB 1-2 have been identified and are quantifiable in the aliphatic zone between 0.4 and 0.8 ppm for 3 protons.
• the double bond content of the butadiene part of the (H) SBR block can decrease to a content of 0 mol% for a totally SBR block (H). hydrogen.
• the elastomer block (H) SBR is hydrogenated in such a way that a proportion ranging from 25 to 100 mol% of the double bonds in the butadiene portion are hydrogenated. More preferably from 50 to 100 mol% and very preferably from 80 to 100 mol% of the double bonds in the butadiene portion are hydrogenated.
• the styrenic part of the blocks (H) SBR may be composed of monomers chosen from styrene monomers, and in particular selected from the group consisting of unsubstituted styrene, substituted styrenes and mixtures thereof.
• substituted styrenes those selected from the group consisting of methylstyrenes (preferentially ⁇ -methylstyrene, m-methylstyrene and p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha 4-dimethylstyrene and diphenylethylene), para-tert-butylstyrene, chlorostyrenes (preferentially ⁇ -chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene and 2-chlorostyrene).
• methylstyrenes preferentially ⁇ -methylstyrene, m-methylstyrene and p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha 4-
• bromostyrenes preferably ⁇ -bromostyrene, m-bromostyrene, p-bromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene and 2,4,6-tribromostyrene
• fluoro styrenes preferentially ⁇ -fluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,4-difluorostyrene, 2,6-difluorostyrene and 2,4,6-trifluorostyrene
• para-hydroxy-styrene and mixtures thereof.
• the elastomer blocks may be of polyether type, in particular a polyether may be composed of monomers chosen from cyclic alcohols or ethers, preferably aliphatic aliphatic alcohols or ethers, such as, for example ethanol or tetrahydrofuran.
• a polyether may be composed of monomers chosen from cyclic alcohols or ethers, preferably aliphatic aliphatic alcohols or ethers, such as, for example ethanol or tetrahydrofuran.
• the polyethers those selected from the group consisting of polytetramethylene glycol (PTMG), polyethylene glycols (PEG), polypropylene ether glycol (PPG), polyhexamethylene ether glycol, polytrimethylenether glycol (PO 3 G), poly ( 3- alkyltetrahydrofuran), and mixtures thereof.
• the polyether is selected from the group consisting of polytetramethylene glycol (PTMG), polyethylene glycols (PEG) and mixture
• the elastomeric block may also consist of several elastomeric blocks as defined above. 1.2.3. Nature of thermoplastic blocks
• the glass transition temperature characteristic (Tg) of the thermoplastic rigid block will be used.
• This characteristic - - is well known to those skilled in the art. It allows in particular to choose the temperature of industrial implementation (transformation).
• the implementation temperature is chosen to be substantially greater than the Tg.
• Tf melting temperature
• the TPE elastomers comprise one or more thermoplastic block (s) preferably having a Tg (or Tf, where appropriate) greater than or equal to 80 ° C.
• this thermoplastic block has a Tg (or Tf, if applicable) in a range of 80 ° C to 250 ° C.
• the Tg (or Tf, if appropriate) of this thermoplastic block is preferably from 80 ° C to 200 ° C, more preferably from 80 ° C to 180 ° C.
• thermoplastic block fraction in the TPE is in a range from 5 to 70%, preferably 8 to 60%, more preferably 10 to 50%.
• the thermoplastic blocks of the TPE have in total a number-average molecular weight ("Mn") ranging from 5,000 g / mol to 150,000 g / mol, so as to give the TPE good elastomeric properties and sufficient mechanical strength and compatible with the use in tire tread.
• Mn number-average molecular weight
• thermoplastic blocks of the TPE are constituted (s) from polymerized styrenic monomers (PS).
• PS polymerized styrenic monomers
• Preferred polystyrenes (PS) are obtained from styrenic monomers selected from the group consisting of unsubstituted styrene, substituted styrenes, and mixtures thereof.
• substituted styrenes those selected from the group consisting of methylstyrenes (preferentially ⁇ -methylstyrene, m-methylstyrene and p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha 4-dimethylstyrene and diphenylethylene), para-tert-butylstyrene, chlorostyrenes (preferentially o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichloro styrene and 2,4,6-trichlorostyrene), bromostyrenes (preferentially o- bromostyrene, m-bromostyrene, p-bromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene and 2,4,
• the PS blocks are blocks obtained from unsubstituted polystyrene.
• the polystyrene block as defined above may be copolymerized with at least one other monomer so as to form a thermoplastic block having a Tg (or Tf, where appropriate) as defined above.
• this other monomer capable of copolymerizing with the polymerized monomer may be chosen from diene monomers, more particularly conjugated diene monomers having 4 to 14 carbon atoms, and vinylaromatic-type monomers having from 8 to 20 carbon atoms.
• diene monomers more particularly conjugated diene monomers having 4 to 14 carbon atoms
• vinylaromatic-type monomers having from 8 to 20 carbon atoms.
• TPEs with an optionally hydrogenated butadiene-styrene butadiene-styrene copolymer block and a styrene-type thermoplastic block (TPE (H) SBR-PS), are also sometimes denoted SOE, and they are most preferred for the needs of the invention.
• thermoplastic blocks of the TPE are constituted (s) from polymerized non-styrenic monomers (TPNS).
• TPNS polymerized non-styrenic monomers
• Non-styrenic thermoplastic blocks (TPNS) are non-styrenic blocks, that is to say preferably thermoplastics resulting from the polymerization of any suitable monomer and not comprising styrenic monomers or less than 5%.
• the TPNS blocks are blocks selected from polyamide blocks, polyesters, and mixtures thereof.
• the TPNS blocks are blocks of polyamide and / or polyester type.
• the TPNS blocks are chosen from the group consisting of polyamides of PA6, PA1 1 or PA12 type, or polyesters of PET or PBT type and mixtures of these.
• TPE-E TPE-E or TPC
• thermoplastic copolyester or COPE (ether-ester block copolymer), and they are also preferred for the purposes of the invention.
• TPEs with particular polyether blocks and TPNS in which the non-styrenic thermoplastic blocks are polyamides are usually denoted TPE-A or TPA (thermoplastic copolyamide) or PEBA (amide block copolyether), and they are particularly preferred for the needs of the invention.
• TPE-A or TPA thermoplastic copolyamide
• PEBA amide block copolyether
• thermoplastic block may also consist of several thermoplastic blocks as defined above.
• PEBA elastomers of the "PEBAX” type sold by the company Arkema, for example under the name "PEBAX 4033", “PEBAX”. 6333 "or COPE elastomers of" Pelprene P "type, marketed by Toyobo, for example under the name” Pelprene P40B ".
• the TPE elastomer (that is to say the TPE elastomer or elastomers) represents from 5 to 35%, preferably from 10 to 30% by weight, more preferably from 15 to 25% by weight of all the polymers present in the composition.
• composition of the layer of the tire according to the invention comprises one or more reinforcing fillers at a total content ranging from 1 to 60 parts by weight per 100 parts by weight of polymeric matrix (pcm) .
• filler usually used for the manufacture of tires, for example an organic filler such as carbon black, a filler - Inorganic such as silica, or a blend of these two types of filler, including a black carbon and silica blend.
• organic filler such as carbon black
• silica a filler - Inorganic such as silica
• a blend of these two types of filler including a black carbon and silica blend.
• carbon blacks are suitable all carbon blacks conventionally used in tires (so-called pneumatic grade black).
• pneumatic grade black For example, mention will be made more particularly of reinforcing carbon blacks of the series 100, 200 or 300 (ASTM grades), such as for example the blacks NI 15, N134, N234, N326, N330, N339, N347, N375, or else according to targeted applications, blacks of higher series (for example N660, N683, N772), or even N990.
• any inorganic or mineral filler (whatever its color and origin (natural or synthetic), also called “white” charge, charge “clear” 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 rubber composition for manufacturing tire, in other words able to replace, in its reinforcing function, a conventional carbon black pneumatic grade, such a charge is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) at its area.
• -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 different reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described below.
• reinforcing inorganic fillers are especially suitable mineral fillers of the siliceous type, in particular of silica (SiO 2 ), or of the aluminous type, in particular of 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 CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
• HDS highly dispersible precipitated silicas
• an at least bifunctional coupling agent intended to ensure a sufficient connection, of a chemical and / or physical nature, between the inorganic filler (surface of its particles) and the elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.
• the reinforcing filler is carbon black and / or silica.
• the majority reinforcing filler is carbon black.
• the majority reinforcing filler is silica.
• the level of reinforcing filler is preferably in a range from 2 to 50 pcm, more preferably from 3 to 30 pcm, more preferably from 5 to 20 pcm.
• composition of the tire layer according to the invention may comprise additives added to the composition, these additives being able to be well known to those skilled in the art, by examples of other elastomers, anti-aging agents, plasticizers, non-reinforcing fillers, reinforcing resins (such as resorcinol or bismaleimide), or a crosslinking system.
• the crosslinking system may in particular be a so-called vulcanization system, that is to say based on sulfur (or a sulfur donor agent) and a vulcanization accelerator .
• sulfur or a sulfur donor agent
• a vulcanization accelerator To this basic vulcanization system may be added various known secondary accelerators or vulcanization activators such as stearic acid, zinc oxide, guanidine derivatives, retarders or anti-eversion agents.
• the composition does not comprise a crosslinking system. - -
• the composition of the tire layer according to the invention makes it possible to obtain particular properties and in particular a high Young's modulus, even at the high temperatures encountered in a tire during its use.
• High Young's modulus means a modulus greater than 1000 MPa, preferably greater than 1300 MPa and more preferably greater than 1500 MPa.
• the composition of the layer described above has a Young's modulus at 110 ° C. which is greater than 1000 MPa, preferably greater than 1300 MPa and more preferably greater than 1500 MPa. It is known that high modulus compositions generally have a low elongation at break, that is to say most of the time less than 70%. With the compositions described for the tire of the invention, it is possible to obtain a much higher breaking elongation, which is to allow the tire to have good resistance to deformation. It is known that the elongation rupture tends to increase with temperature, it is therefore useful that from room temperature, this elongation at break is sufficiently high and especially greater than 100%. In this case, this elongation at break will remain greater than 100% at 110 ° C for example.
• the composition of the layer described above has an elongation at break at 25.degree. C. greater than 100%, preferably greater than 130% and more preferably greater than 150.degree. %).
• the present invention relates to a tire comprising at least one layer consisting of a polymeric composition defined above. This layer is preferably used as the inner layer of the tire. - -
• this inner layer is a tread underlayer, a tire crown layer, a carcass ply, a low tire zone layer (preferably the bead), or any other layer that is not in contact with the ambient air or the inflation gas of the tire.
• the thickness of this layer is preferably between 0.5 and 40 mm, more preferably between 1 and 10 mm. For example, layer thicknesses of 1 to 5 mm have proved to be quite suitable for use in tire crowns.
• this layer is adjacent to an elastomeric layer, well known to those skilled in the art and usually used in the tire, forming with the latter a laminate.
• the polymer layer is provided with an adhesive layer with respect to each layer of rubber composition with which it is in contact.
• the invention also applies to cases where no adhesive layer is used, the polymer layer itself and / or each layer of rubber composition may have a self-adhesive property due to its or their formulation clean.
• any suitable adhesive system may be used, for example a simple textile glue of the "RFL” type (resorcino-1-formaldehyde latex).
• the polymeric layer of the tire of the invention may be prepared by the usual means known to those skilled in the art, such as extrusion, by mixing all the ingredients of the composition, at a temperature above Highest Tg between the Tg of the thermoplastic block of the thermoplastic elastomer or the Tg of the thermoplastic polymer.
• a flat die, placed at the exit of the extruder makes it possible to obtain sheets of the desired thickness, for example about 2 mm thick. For thinner thicknesses, the resulting sheet may be deposited on a calender that allows the sheet to be stretched to refine it, for example to about 1 mm thick.
• the layer obtained above can be assembled, especially flat, that is to say before the conformation of the tire, with the other layers, according to the techniques known to the man of the 'art.
• the tire is then baked, according to techniques also known to those skilled in the art.
• compositions Tl, T2 and Cl were carried out on an extruder "Kraus Maffei", mixing all the ingredients (polyamide “RILSAN CLEAR G 170” from the company ARKEMA, where appropriate ether block copolyamide (PEBA) " PEBAX 7033 "from the company ARKEMA, and where appropriate the carbon black N234 series from CABOT) at a temperature ranging from 250 to 270 ° C.
• PEBA ether block copolyamide
• PEBAX 7033 from the company ARKEMA
• CABOT carbon black N234 series from CABOT
• the sheets of 1 mm obtained above are then cut by means of a ZUND cutting table to obtain specimens of 2.5 mm * 200 mm * 1 mm, for measurements of Young's modulus, breaking test pieces for breaking elongation measurements, and 20mm * 10mm * 1mm "bar" test pieces for the DMA module measurement test.
• the Young's modulus measurements, and the breaking elongation measurements are made at room temperature or at 110 ° C as the case as defined above in the present application.
• the Young's modulus at 110 ° C. is calculated from the Young's modulus measured at 25 ° C., by applying the variation curve of the module as a function of temperature, as obtained by DMA.
• the bar specimen is applied to which a sinusoidal deformation is applied without static deformation, and - - varies the temperature from 25 to 250 ° C.
• the module is then read according to the temperature.
• the ability to deform is also evaluated for a sheet of 2 mm thick, by manual folding of this sheet, at room temperature, to form an angle of 180 °.
• a note (-) is assigned to a sheet that breaks during this manipulation, while a note (+) is assigned to a sheet that does not break during this manipulation.
• compositions produced are presented in Table 1 below.
• thermoplastic polymer improves the deformability of the layer but reduces the Young's modulus value of T2 with respect to Tl.
• the addition of the reinforcing filler in the composition C1 according to the invention makes it possible to find a level of modulus which is very satisfactory and even better than the thermoplastic polymer alone (Tl), while retaining good aptitude for deformation.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Tires In General (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=55451387

Family Applications (1)

Country Status (4)

Family Cites Families (7)

• 2015
  • 2015-12-21 FR FR1562935A patent/FR3045638B1/fr not_active Expired - Fee Related
• 2016
  • 2016-12-08 EP EP16819997.4A patent/EP3394165A1/de not_active Withdrawn
  • 2016-12-08 WO PCT/FR2016/053281 patent/WO2017109326A1/fr active Application Filing
  • 2016-12-08 CN CN201680075429.4A patent/CN108473722A/zh not_active Withdrawn

Also Published As

Similar Documents

Legal Events