rubber composition

Abstract

The present invention relates to a rubber composition based on at least one unfunctionalized first diene elastomer E1 having a glass transition temperature TgE1, one functionalized second diene elastomer E2 having a glass transition temperature TgE2, a reinforcing filler capable of interacting with the functionalized diene elastomer E2, and a crosslinking system, - the glass transition temperature TgE1 is -50 ° C or higher, TIFF2023527883000031.tif6150--concerns the rubber composition, wherein the content of the non-functionalized diene elastomer E1 is 50 phr or more. The present invention also relates to a tread and / or a pneumatic or non-pneumatic tire comprising at least one composition as defined above.

Description

[Technical Field]

[0001] The field of the invention is that of rubber compositions reinforced with reinforcing fillers, in particular those used in the manufacture of pneumatic or non-pneumatic vehicle tires, and more particularly those used for the manufacture of treads. [Background technology]

[0002] Treads for pneumatic or non-pneumatic tires are required in a known manner to satisfy many, often conflicting, technical requirements, including low rolling resistance, high wear resistance, and high adherence on wet ground. This tradeoff in properties, particularly in terms of rolling resistance and wear resistance, has been improved in recent years, particularly for energy-saving "green tires" intended for passenger cars, by using new low-hysteresis rubber compositions as treads. These rubber compositions are primarily reinforced with specific inorganic fillers (described as reinforcing fillers), particularly highly dispersible silica (HDS), and are comparable in reinforcing power to conventional tire-grade carbon black. However, the presence of a high silica content in such rubber compositions is not optimal for the wet grip performance of tires, which is lower than that of compositions with insufficient filling. It is known that the grip of a pneumatic tire on wet ground can be achieved by increasing the contact area of ​​the tread with the running ground, in particular by using a deformable material in the tread (in this case, a deformable rubber composition). One way to make a rubber composition more deformable is to add a large amount of plasticizer to the rubber composition. However, a highly deformable rubber composition has the disadvantage of a wide range of hysteresis potential. However, improving rolling resistance requires reducing hysteresis loss. Therefore, the rubber composition of the tread must meet two contradictory requirements: maximum hysteresis potential to meet the grip requirement, and as low hysteresis as possible to meet the rolling resistance requirement. Summary of the Invention

[0003] One object of the present invention is therefore to propose a new rubber composition, in particular a rubber composition for treads, which in particular overcomes the above-mentioned drawbacks and maintains or even improves its wet grip performance, while at the same time also exhibiting in particular improved hysteresis properties. The applicant has surprisingly achieved this object by discovering that the above-mentioned drawbacks can be overcome by a specific combination of diene elastomers containing rubber compounds with a clear difference in glass transition temperature, specifically, a rubber composition comprising at least one non-functionalized diene elastomer E1 having a glass transition temperature TgE1 of -50°C or higher, said elastomer E1 being present in a content of 50 phr or higher; and at least one functionalized second diene elastomer E2 having a glass transition temperature TgE2 satisfying TIFF0007734698000001.tif6170, the composition provides excellent rolling resistance while maintaining good grip on wet ground.

[0004] A first subject of the present invention is therefore a rubber composition based on at least one unfunctionalized first diene elastomer E1 having a glass transition temperature TgE1, at least one functionalized second diene elastomer E2 having a glass transition temperature TgE2, a reinforcing filler capable of interacting with the functionalized diene elastomer E2, and a crosslinking system, - the glass transition temperature TgE1 is -50 ° C or higher, TIFF0007734698000002.tif6150--concerns the rubber composition, wherein the content of the non-functionalized diene elastomer E1 is 50 phr or more. Advantageously, the glass transition temperature TgE2 is It can satisfy TIFF0007734698000003.tif6170. Advantageously, the glass transition temperature TgE2 is TIFF0007734698000004.tif11170 may be satisfied. Advantageously, the glass transition temperature TgE1 may be in the range of -50°C to 0°C, more preferentially in the range of -40°C to 0°C, more preferentially in the range of -30°C to 0°C. Advantageously, the glass transition temperature TgE2 may be in the range of -110°C to -23°C, preferably in the range of -100°C to -28°C and more preferentially in the range of -95°C to -30°C. Advantageously, the content of non-functionalized diene elastomer E1 may be in the range from 50 phr to 70 phr, preferably in the range from 55 phr to 70 phr and more preferentially in the range from 55 phr to 65 phr.

[0005] Advantageously, the content of reinforcing filler may be in the range of 20 to 100 phr, preferably in the range of 30 to 90 phr and even more preferentially in the range of 40 to 90 phr. Advantageously, the reinforcing filler may mainly comprise at least one inorganic reinforcing filler, and even more preferentially may mainly comprise at least one silica. Preferentially, the inorganic reinforcing filler, preferably silica, represents more than 50% by mass, preferably more than 55% by mass, of the total mass of reinforcing fillers in the rubber composition. Even more preferentially, the reinforcing filler may mainly comprise at least one silica, and may also contain a small amount of at least one carbon black. Preferentially, the rubber composition may further comprise an agent for coupling the reinforcing filler with the diene elastomer. Preferentially, this coupling agent may be an organosilane polysulfide. Advantageously, the non-functionalized diene elastomer E1 may be selected from the group consisting of synthetic polyisoprene, polybutadiene, butadiene / styrene copolymers, butadiene / isoprene copolymers, isoprene / styrene copolymers, and butadiene / styrene / isoprene copolymers. Preferentially, the non-functionalized diene elastomer E1 is selected from polybutadiene and styrene / butadiene copolymers. Even more preferentially, the non-functionalized diene elastomer E1 is a styrene / butadiene copolymer. Advantageously, the functionalized diene elastomer E2 may be selected from the group consisting of natural rubber, synthetic polyisoprene, polybutadiene, butadiene / styrene copolymers, butadiene / isoprene copolymers, isobutene / isoprene copolymers, isoprene / styrene copolymers, and butadiene / styrene / isoprene copolymers. Preferentially, the functionalized diene elastomer E2 is selected from polybutadiene and ethylene / butadiene copolymers. Even more preferentially, the functionalized diene elastomer E2 is a styrene / butadiene copolymer.

[0006] Advantageously, the functionalized diene elastomer E2 may contain at least one chemical functional group capable of interacting with the reinforcing filler, the chemical functional group containing at least one heteroatom selected from the group consisting of nitrogen, sulfur, oxygen, phosphorus, tin and silicon. Advantageously, the reinforcing filler mainly comprises a reinforcing inorganic filler, preferentially silica, and the functionalized diene elastomer E2 may comprise at least one chemical functional group capable of interacting with the reinforcing inorganic filler, the chemical functional group comprising at least one heteroatom selected from the group consisting of nitrogen, sulfur, oxygen and phosphorus. Advantageously, the chemical functional group capable of interacting with the reinforcing filler may be a polar functional group comprising at least one oxygen atom. Advantageously, the polar functional groups may be selected from the group consisting of silanols, alkoxysilanes which may carry amine groups, epoxides, ethers, esters, carboxylic acids and hydroxyls.

[0007] Advantageously, the functionalized diene elastomer E2 may comprise polar functional groups which are silanols. Preferentially, the silanols may be present at the chain ends or in the middle of the main chain of the functionalized diene elastomer, and more preferably, the silanols are present at the chain ends of the main chain of the functionalized diene elastomer. Advantageously, the functionalized diene elastomer E2 may comprise a polar functional group which is an alkoxysilane which may have an amine group. Preferentially, the alkoxysilane which may have an amine group may be present at the chain end or in the middle of the main chain of the functionalized diene elastomer E2, and more preferentially, the alkoxysilane group which may have an amine group may be present in the middle of the main chain of the functionalized diene elastomer E2. Preferentially, the amine group may be a tertiary amine. Advantageously, the content of functionalized diene elastomer E2 in the composition of the invention is less than or equal to 40 phr, more preferentially in the range from 30 phr to 50 phr, preferably in the range from 30 phr to 45 phr, more preferentially in the range from 35 phr to 45 phr. Advantageously, the content of unfunctionalized diene elastomer E1 in the composition of the invention is in the range of 50 phr to 70 phr, and the content of functionalized diene elastomer E2 in the composition of the invention is in the range of 30 phr to 50 phr. Advantageously, the content of unfunctionalized diene elastomer E1 in the composition of the invention is in the range of 55 phr to 70 phr, and the content of functionalized diene elastomer E2 in the composition of the invention is in the range of 30 phr to 45 phr. Advantageously, the rubber composition defined above further comprises at least one plasticizer.

[0008] Advantageously, the rubber composition defined above and its preferred embodiments can be obtained according to a manufacturing process comprising the following steps: - introducing the non-functionalized diene elastomer E1 having the above-mentioned glass transition temperature TgE1, and, if necessary, other ingredients such as plasticizers, into an internal mixer and subjecting them to thermomechanical operation up to a maximum temperature of 200°C, to obtain a first masterbatch; - introducing the functionalized diene elastomer E2 having the above-mentioned glass transition temperature TgE2, the reinforcing filler, and, if necessary, the coupling agent and other ingredients, such as plasticizers, into an internal mixer and subjecting them to thermomechanical operation up to a maximum temperature of 200°C to obtain a second masterbatch; - introducing the first and second masterbatches obtained in the above steps into an internal mixer and subjecting them to thermomechanical manipulation up to a maximum temperature of 180°C to obtain a mixture; - recovering the mixture from the above step and cooling the mixture to a temperature of 110°C or less; - incorporating a crosslinking system into the cooled mixture and kneading it to a maximum temperature of less than 110°C, preferentially less than 80°C, and recovering the rubber composition.

[0009] Another subject of the invention relates to a tread comprising at least one composition as defined above. Another subject of the invention relates to a tire comprising at least one composition as defined above, or a tire comprising at least one tread as defined above. A first subject of the present invention is a rubber composition based on at least one unfunctionalized first diene elastomer E1 having a glass transition temperature TgE1, one functionalized second diene elastomer E2 having a glass transition temperature TgE2, a reinforcing filler capable of interacting with the functionalized diene elastomer E2, and a crosslinking system, - the glass transition temperature TgE1 is -50 ° C or higher, TIFF0007734698000005.tif6150--concerns the rubber composition, wherein the content of the non-functionalized diene elastomer E1 is 50 phr or more. DETAILED DESCRIPTION OF THE INVENTION

[0010] The expression "rubber composition based on" is to be understood as meaning a composition comprising a mixture and / or a product of in situ reactions of the various components used, some of which can and / or are intended to react with one another, at least in part, during the various stages of the preparation of said composition; the composition can therefore be fully or partially crosslinked or not crosslinked. For the purposes of the present invention, the expression "parts by weight per 100 parts by weight of elastomer" (or phr) should be understood to mean parts by weight per 100 parts by weight of elastomer of the composition. In this specification, unless expressly indicated otherwise, all percentages (%) refer to percentages (%) by weight. Furthermore, any interval of values ​​indicated by the expression "between a and b" refers to a range of values ​​greater than a to less than b (i.e., excluding the endpoints a and b), whereas any interval of values ​​indicated by the expression "a to b" refers to a range from the value a to the value b (i.e., including the exact endpoints a and b).

[0011] When referring to a "major" compound, for the purposes of the present invention, this is understood to mean that this compound is predominant among the compounds of the same type in the rubber composition, i.e., represents the largest mass among the compounds of the same type. Thus, for example, the major elastomer is the elastomer that represents the largest mass relative to the total mass of elastomers in the composition. Similarly, a "major" filler is the filler that represents the largest mass among the fillers of the composition. For example, in a system containing only one elastomer, this elastomer is predominant within the meaning of the present invention, and in a system containing two elastomers, the major elastomer represents more than half of the mass of the elastomer. In contrast, a "minor, minor" compound is one that does not represent the largest mass among the compounds of the same type. Preferably, the term "major" means that it is present in an amount of more than 50%, preferably more than 60%, 70%, 80%, or 90%; more preferentially, a "major" compound is understood to represent 100%. The carbon-containing compounds referred to herein may be of fossil origin or bio-based. In the latter case, the carbon-containing compounds may be partially or completely derived from biomass or may be obtained from renewable starting materials derived from biomass. In particular, polymers, plasticizers, fillers, etc. are concerned.

[0012] "Diene" elastomers (or, without distinction, rubbers) are to be understood as meaning elastomeric compounds, whether natural or synthetic, which are composed, as is known, at least in part (i.e., homopolymers or copolymers), of diene monomer units (monomers having two conjugated or non-conjugated carbon-carbon double bonds). "Elastomeric matrix" is understood to mean all the elastomers that form the rubber composition of the invention. Diene elastomers can be divided into two categories: "essentially unsaturated" or "essentially saturated". The term "essentially unsaturated" is generally understood to mean diene elastomers derived at least in part from conjugated diene monomers with a content of diene-derived (conjugated diene) units of more than 15% (mol %). Diene elastomers such as butyl rubber or copolymers of dienes with α-olefins of the EPDM type are therefore not included in the above definition and can be described in particular as "essentially saturated" diene elastomers (low or very low content (always less than 15 mol %) of diene-derived units). The diene elastomers that can be used in the compositions of the invention are intended to mean more specifically: any homopolymer of a conjugated or non-conjugated diene monomer having from 4 to 18 carbon atoms, - any copolymer of a conjugated or non-conjugated diene having from 4 to 18 carbon atoms with at least one other monomer.

[0013] The other monomer may be an olefin or a conjugated or non-conjugated diene. Suitable conjugated dienes include those containing from 4 to 12 carbon atoms, particularly 1,3-dienes, particularly, for example, 1,3-butadiene and isoprene. Suitable non-conjugated dienes include those containing 6 to 12 carbon atoms, such as 1,4-hexadiene, ethylidene norbornene, or dicyclopentadiene. Suitable olefins include vinyl aromatic compounds containing from 8 to 20 carbon atoms and aliphatic α-monoolefins containing from 3 to 12 carbon atoms. Suitable vinyl aromatic compounds include, for example, styrene, ortho-, meta-, or para-methylstyrene, commercial mixtures of "vinyltoluene," or para-(tert-butyl)styrene. More specifically, the diene elastomer is any homopolymer of a conjugated diene monomer, in particular any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms; any copolymer obtained by copolymerization of one or more conjugated dienes with another conjugated diene having from 8 to 20 carbon atoms or with one or more vinyl aromatic compounds; copolymers of isobutene and isoprene (butyl rubber) and halogenated copolymers of this type of copolymer, in particular chlorinated or brominated copolymers.

[0014] The rubber composition of the present invention comprises at least one unfunctionalized first diene elastomer E1 having a glass transition temperature TgE1 of -50°C or higher, and and at least one functionalized second diene elastomer E2 having a glass transition temperature TgE2 satisfying TIFF0007734698000006.tif6170, the unfunctionalized diene elastomer E1 being present in a content of 50 phr or more. Surprisingly, this combination makes it possible to obtain a rubber composition having outstanding wet grip properties while at the same time having excellent hysteresis properties (and therefore reduced rolling resistance). The glass transition temperatures TgE1 and TgE2 are measured in accordance with standard ASTM D3418:2008. For the purposes of the present invention, "functionalized diene elastomer" is understood to mean a diene elastomer (whether natural or synthetic) having chemical functional groups capable of interacting with reinforcing fillers. The chemical functional groups capable of interacting with reinforcing fillers may in particular be heteroatoms or groups containing at least one heteroatom selected from nitrogen, sulfur, oxygen, phosphorus, tin and silicon. For the purposes of the present invention, "non-functionalized diene elastomer" is understood to mean a diene elastomer (whether natural or synthetic) that does not have chemical functional groups capable of interacting with reinforcing fillers. Preferentially, non-functionalized diene elastomers may consist essentially of carbon and hydrogen atoms. Non-functionalized diene elastomers may be free of heteroatoms or may contain heteroatoms in amounts resulting from impurities and the synthesis method of the diene elastomer.

[0015] Diene Elastomer E1 The diene elastomer E1 is not functionalized and has a glass transition temperature TgE1 of greater than or equal to −50° C. More preferentially, the glass transition temperature TgE1 is in the range of −50° C. to 0° C., more preferentially in the range of −40° C. to 0° C., more preferentially in the range of −30° C. to 0° C. The non-functionalized diene elastomer E1 may be any of the above-mentioned diene elastomers, provided that its glass transition temperature TgE1 is greater than or equal to -50°C. Preferentially, the non-functionalized diene elastomer E1 is selected from the group consisting of synthetic polyisoprene, polybutadiene, butadiene / styrene copolymers, butadiene / isoprene copolymers, isoprene / styrene copolymers, and butadiene / styrene / isoprene copolymers. Preferentially, the non-functionalized diene elastomer E1 is selected from polybutadiene and styrene / butadiene copolymers. Advantageously, the non-functionalized diene elastomer E1 is a styrene / butadiene copolymer.

[0016] Suitable non-functionalized diene elastomers E1 are in particular butadiene / styrene copolymers having a Tg in the range from −50° C. to 0° C., a styrene content in the range from 1% to 30% by weight relative to the weight of the copolymer, a vinyl-1,2 butadiene content in the range from 14% to 93% by weight relative to the weight of the copolymer, a cis-1,4 butadiene content in the range from 2% to 22% by weight relative to the weight of the copolymer, and a trans-1,4 butadiene content in the range from 3% to 33% by weight relative to the weight of the copolymer. Suitable non-functionalized diene elastomers E1 are in particular polybutadienes having a Tg in the range from −50° C. to 0° C., a vinyl-1,2 butadiene content in the range from 52% to 95% by weight, relative to the weight of the copolymer, a cis-1,4 butadiene content in the range from 0% to 38% by weight, relative to the weight of the copolymer, and a trans-1,4 butadiene content in the range from 0% to 48% by weight, relative to the weight of the copolymer. Preferentially, the content of non-functionalized diene elastomer E1 in the composition of the invention is in the range from 50 phr to 70 phr, preferably in the range from 55 phr to 70 phr, more preferentially in the range from 55 phr to 65 phr. Such non-functionalized diene elastomers are commercially available from sources such as Nippon Zeon, JSR, Bayer, and the like.

[0017] Diene Elastomer E2 As mentioned above, the rubber composition comprises at least one diene elastomer E2, which elastomer is functionalized and It has a glass transition temperature TgE2 that satisfies TIFF0007734698000007.tif6170. Preferentially, the glass transition temperature TgE2 of the functionalized diene elastomer E2 is Fill in TIFF0007734698000008.tif6170. Advantageously, the glass transition temperature TgE2 of the functionalized diene elastomer E2 is: Fill in TIFF0007734698000009.tif11170. Even more advantageously, the glass transition temperature TgE2 of the functionalized diene elastomer E2 is in the range of from -110°C to -23°C, preferably in the range of from -100°C to -28°C and more preferentially in the range of from -95°C to -30°C. The functionalized diene elastomer E2 may be any of the diene elastomers described above, as long as it is functionalized and its glass transition temperature satisfies the mathematical relationship described above.

[0018] Preferentially, the functionalized diene elastomer E2 may be chosen from the group consisting of natural rubber, synthetic polyisoprene, polybutadiene, butadiene / styrene copolymers, butadiene / isoprene copolymers, isobutene / isoprene copolymers, isoprene / styrene copolymers and butadiene / styrene / isoprene copolymers. Preferentially, the functionalized diene elastomer E2 is chosen from polybutadiene and styrene / butadiene copolymers. Even more preferentially, the functionalized diene elastomer E2 is a styrene / butadiene copolymer. Suitable functionalized diene elastomers E2 are in particular butadiene / styrene copolymers having a Tg in the range from −100° C. to −28° C., a styrene content in the range from 1% to 30% by weight relative to the weight of the copolymer, a vinyl-1,2 butadiene content in the range from 0% to 74% by weight relative to the weight of the copolymer, a cis-1,4 butadiene content in the range from 10% to 40% by weight relative to the weight of the copolymer, and a trans-1,4 butadiene content in the range from 15% to 59% by weight relative to the weight of the copolymer. Suitable functionalized diene elastomers E2 are in particular polybutadienes having a Tg in the range from −110° C. to −23° C., a vinyl-1,2 butadiene content in the range from 0% to 82% by weight, relative to the weight of the copolymer, a cis-1,4 butadiene content in the range from 0% to 100% by weight, relative to the weight of the copolymer, and a trans-1,4 butadiene content in the range from 0% to 100% by weight, relative to the weight of the copolymer.

[0019] The functionalization of diene elastomers E2 is known: The functionalization of diene elastomers E2 can be carried out by grafting chemical functional groups onto the monomers of the diene elastomer during or after its synthesis. The functionalized diene elastomer E2 comprises at least one chemical functional group capable of interacting with the reinforcing filler, said chemical functional group comprising at least one heteroatom selected from the group consisting of nitrogen, sulfur, oxygen, phosphorus, tin, and silicon. Among these functional groups, mention may be made, for example, of cyclic or acyclic primary, secondary, or tertiary amines, isocyanates, imines, cyanos, thiols, carboxylates, epoxides, or primary, secondary, or tertiary phosphines. The interaction between the functionalized diene elastomer E2 and the reinforcing filler can be established, for example, by covalent, hydrogen, ionic, and / or electrostatic bonds between the functional groups of the diene elastomer and the chemical functional groups present on the surface of the reinforcing filler. Preferentially, when the reinforcing filler mainly comprises a reinforcing inorganic filler, preferentially silica, the functionalized diene elastomer E2 may comprise at least one chemical functional group capable of interacting with the reinforcing filler, said chemical functional group comprising at least one heteroatom selected from the group consisting of nitrogen, sulfur, oxygen and phosphorus.

[0020] Preferentially, the chemical functional groups of the diene elastomer E2 capable of interacting with the reinforcing fillers are polar functional groups containing at least one oxygen atom. Preferentially, the polar functional groups may be selected from the group consisting of silanols, alkoxysilanes, alkoxysilanes with amine groups, epoxides, ethers, esters, carboxylic acids, and hydroxyls. Such functionalized elastomers are known per se and are described in particular in the following documents: FR 2740778, US 6013718, WO 2008 / 141702, FR 2765882, WO 01 / 92402, WO 2004 / 09686, EP 1127909, US 6503973, WO 2009 / 000750 and WO 2009 / 000752. The functionalized diene elastomer is a diene elastomer that contains polar functional groups, which are preferably silanols. Preferentially, the silanols are present at the chain ends or in the middle of the backbone of the functionalized diene elastomer. Preferentially, the functionalized diene elastomer may be a diene elastomer (in particular SBR) in which a silanol functional group is present at the chain end. The functionalized diene elastomer has, at one end of its main chain, a silanol functional group or a group of the formula -(SiR1R2-O-) m H, wherein m represents an integer of 3 to 8, preferably 3; R1 and R2 may be the same or different and represent alkyl groups of 1 to 10 carbon atoms, preferably alkyl groups containing 1 to 4 carbon atoms.

[0021] This type of elastomer can be obtained according to the process described in document EP 0 778 311, more particularly by functionalizing a living elastomer with a functionalizing agent of cyclic polysiloxane type, after a step of anionic polymerization, such as those corresponding to formula (V): [ka] In the formula, m represents an integer of 3 to 8, preferably 3, and R1 and R2 may be the same or different and represent an alkyl group containing 1 to 10 carbon atoms, preferably an alkyl group containing 1 to 4 carbon atoms. Among these compounds, hexamethylcyclotrisiloxane can be mentioned.

[0022] The functionalized diene elastomer E2 can be a diene elastomer (especially SBR) containing a polar functional group, which is an alkoxysilane optionally carrying another functional group, in particular an amine functional group. Preferentially, the alkoxysilane optionally carrying another functional group, preferably an amine group, is located at the chain end or in the middle of the main chain of the functionalized diene elastomer, and more preferentially, the alkoxysilane group optionally carrying an amine group is located in the middle of the main chain of the functionalized diene elastomer. Thus, the functionalized diene elastomer E2 may contain within its structure at least one alkoxysilane group and at least one other functional group, the silicon atom of which is attached to the elastomer chain and which may be partially or completely hydrolyzed to a silanol.

[0023] According to some variants, the alkoxysilane groups are predominantly present at one end of the main chain of the elastomer. According to another variant, the alkoxysilane group is primarily present in the main elastomer chain, and the diene elastomer is said to be attached or functionalized mid-chain, as opposed to at the "chain end" position, although the position of the group is not strictly in the middle of the elastomer chain. The silicon atom of this functional group connects two branches of the main chain of the diene elastomer. The alkoxysilane groups include C1-C10 alkoxy groups which may be partially or completely hydrolyzed to hydroxyl, or further C1-C8, preferably C1-C4 alkoxy groups, more preferentially methoxy and ethoxy. The silicon atom of the alkoxysilane group preferably carries the other functional group directly or via a spacer group defined as an atom or group of atoms. Preferentially, the spacer group is a saturated or unsaturated, cyclic or acyclic, linear or branched, divalent C1-C18 aliphatic hydrocarbon-based group or a divalent C6-C18 aromatic hydrocarbon-based group. The other functional group is preferably a functional group containing at least one heteroatom selected from N, S, O or P. Examples include, among these functional groups, cyclic or acyclic primary, secondary or tertiary amines, isocyanates, imines, cyanos, thiols, carboxylates, epoxides, or primary, secondary or tertiary phosphines.

[0024] Examples of secondary or tertiary amine functional groups include amines substituted with C1-C10 alkyl groups, preferably C1-C4 alkyl groups, more preferably methyl or ethyl groups, or cyclic amines forming a heterocycle containing a nitrogen atom and at least one carbon atom (preferably 2 to 6 carbon atoms). Examples include methylamino, dimethylamino, ethylamino, diethylamino, propylamino, dipropylamino, butylamino, dibutylamino, pentylamino, dipentylamino, hexylamino, dihexylamino, or hexamethyleneamino groups, preferably diethylamino and dimethylamino groups. Examples of imine functional groups include ketimines. Examples include (1,3-dimethylbutylidene)amino, (ethylidene)amino, (1-methylpropylidene)amino, (4-N,N-dimethylaminobenzylidene)amino, (cyclohexylidene)amino, dihydroimidazole, and imidazole groups. Carboxylate functional groups include acrylate or methacrylate. Such functional groups are preferably methacrylate. Epoxide functional groups include epoxy or glycidyloxy groups. Secondary or tertiary phosphine functional groups include phosphines substituted with C1-C10 alkyl groups, preferably C1-C4 alkyl groups, more preferentially methyl or ethyl groups, or diphenylphosphine. For example, methylphosphino-, dimethylphosphino-, ethylphosphino-, diethylphosphino-, ethylmethylphosphino-, and diphenylphosphino- groups are suitable. The other functional group is preferably a tertiary amine, more preferentially a diethylamino- or dimethylamino-group.

[0025] The alkoxysilane group has the formula: ( * -) a Si(OR') b R c X It can be expressed as During the ceremony, * - represents a bond to the elastomer chain, the R group represents a substituted or unsubstituted C1-C10, or even C1-C8 alkyl group, preferably a C1-C4 alkyl group, more preferentially methyl and ethyl; in the alkoxyl group of formula -OR', which may be partially or completely hydrolyzed to hydroxyl, R' represents a substituted or unsubstituted C1-C10, or even C1-C8 alkyl group, preferably a C1-C4 alkyl group, more preferentially methyl and ethyl, X represents a group containing another functional group; a is 1 or 2, b is 1 or 2, and c is 0 or 1, provided that a+b+c=3.

[0026] This type of elastomer is primarily obtained by functionalizing a living elastomer obtained from anionic polymerization with a compound containing an alkoxysilane group, in particular an alkoxysilane group selected from trialkoxysilane and dialkoxyalkylsilane compounds, which alkoxysilane group is substituted with a group containing another functional group bonded to the silicon atom directly or via a spacer group, the functional group and the spacer group being as defined above. It should be noted that those skilled in the art will recognize that when an elastomer is modified by reacting a functionalizing agent with the living elastomer obtained from the anionic polymerization process, a mixture of modified elastomers is obtained, the composition of which depends on the conditions of the modification reaction, in particular the ratio of the reactive sites of the functionalizing agent to the number of living elastomer chains. This mixture may include chain end functionalized, bonded, star-branched, and / or non-functionalized elastomers.

[0027] Preferentially, the content of functionalized diene elastomer E2 in the composition of the invention is less than or equal to 40 phr, more preferentially in the range from 30 phr to 50 phr, preferably in the range from 30 phr to 45 phr, more preferentially in the range from 35 phr to 45 phr. These non-functional diene elastomers are commercially available from sources such as Nippon Zeon, JSR, Bayer, etc., or can be synthesized according to known processes.

[0028] Reinforcing filler The rubber composition of the present invention may contain one or more reinforcing fillers capable of interacting with the diene elastomer E2. Any type of "reinforcing" filler known for its ability to reinforce rubber compositions, particularly those that can be used in the manufacture of pneumatic tires, can be used, for example, organic fillers such as carbon black, inorganic fillers such as silica, or a mixture of the two types of fillers. The expression "reinforcing filler capable of interacting with the functionalized diene elastomer" is understood to mean any reinforcing filler (in particular inorganic fillers such as silica), for example, capable of forming physical or chemical bonds with the functionalized diene elastomer in the rubber composition. This interaction can be established, for example, by covalent, hydrogen, ionic and / or electrostatic bonds between said functionalized elastomer and the functional groups present on the surface of the reinforcing filler. All carbon blacks are suitable, in particular those conventionally used in pneumatic or non-pneumatic tires or their treads. More specifically, among the latter, mention may be made of 200 series reinforcing carbon blacks, such as N234 black. These carbon blacks can be used in the form commercially available or in any other form, for example, as a support for some rubber additives used. Carbon blacks may, for example, already be contained in diene elastomers (see, for example, applications WO97 / 36724-A2 and WO99 / 16600-A1).

[0029] Examples of organic fillers other than carbon black include the functionalized polyvinyl organic fillers described in applications WO2006 / 069792-A1, WO2006 / 069793-A1, WO2008 / 003434-A1 and WO2008 / 003435-A1. Preferentially, the reinforcing filler capable of interacting with the diene elastomer E2 comprises predominantly at least one reinforcing inorganic filler, and even more preferentially comprises predominantly at least one silica. The term "reinforcing inorganic filler" is to be understood in this specification to mean any inorganic or mineral filler, whatever its color or origin (natural or synthetic), which, in contrast to carbon black, is also called a "white", "clear" or "non-black" filler, and which is capable of reinforcing rubber compositions intended for the manufacture of pneumatic or non-pneumatic tires by itself, without any other means than intermediate coupling agents. As is known, some reinforcing inorganic fillers can be characterized in particular by the presence of hydroxyl (-OH) groups present on their surface. Mineral fillers of the siliceous type, preferentially silica (SiO2), or mineral fillers of the aluminous type, in particular alumina (Al2O3), are particularly suitable as reinforcing inorganic fillers.

[0030] The silica used may be any reinforcing silica known to those skilled in the art, in particular a silica having a BET specific surface area and a CTAB specific surface area of ​​450 m 2 / g or less, preferably 30 to 400m 2 / g range, especially 60-300m 2The silica may be any precipitated or fumed silica having a solubility in the range of 0.15 to 0.15 g / g. Any type of precipitated silica may be used, in particular highly disperse precipitated silica (called "HDS" for "highly disperse" or "highly disperse silica"). These precipitated silicas are well known to those skilled in the art, and may or may not be highly disperse. Examples include the silicas described in applications WO 03 / 016215-A1 and WO 03 / 016387-A1. Among commercially available HDS silicas, Ultrasil® 5000GR and Ultrasil® 7000GR silicas manufactured by Evonik, or Zeosil® 1085GR, Zeosil® 1115MP, Zeosil® 1165MP, Zeosil® Premium 200MP and Zeosil® HRS1200MP silicas manufactured by Solvay may in particular be used. As non-HDS silicas, the following commercially available silicas can be used: Ultrasil® VN2GR and Ultrasil® VN3GR silicas from Evonik, Zeosil® 175GR silica from Solvay, or Hi-Sil EZ120G(-D), Hi-Sil EZ160G(-D), Hi-Sil EZ200G(-D), Hi-Sil 243LD, Hi-Sil 210 and Hi-Sil HDP320G silicas from PPG.

[0031] The physical state in which the reinforcing inorganic filler is provided is immaterial, whether in the form of powder, micropearls, granules or beads, or in any other suitable compacted form. Of course, reinforcing inorganic filler is also understood to mean mixtures of different reinforcing inorganic fillers, in particular the silicas mentioned above. According to a preferred embodiment of the present invention, the reinforcing filler is predominantly an inorganic reinforcing filler (preferably silica), i.e., comprises more than 50% by mass (>50%) of an inorganic reinforcing filler such as silica, relative to the total mass of the reinforcing filler. Optionally, according to this embodiment, the reinforcing filler may also comprise carbon black. According to this option, carbon black is used in a content of not more than 20 phr, more preferentially not more than 10 phr, in the rubber composition (for example, the carbon black content may be in the range of 0.5 to 20 phr, in particular in the range of 1 to 10 phr). Within the indicated range, the colorability (black pigment) and UV stability of carbon black are beneficial, without adversely affecting the typical performance qualities provided by reinforcing inorganic fillers.

[0032] Those skilled in the art will understand that as an alternative to the reinforcing inorganic fillers described above, reinforcing fillers of other nature may be used, which are either covered with an inorganic layer, e.g., silica, or contain functional sites, particularly hydroxyl sites, on the surface of the reinforcing filler, which necessitate the use of a coupling agent to establish a bond between the reinforcing filler and the diene elastomer. A person skilled in the art will know how to adjust the total content of reinforcing fillers depending on the application in question, in particular depending on the type of pneumatic tire in question, for example for passenger cars or for utility vehicles such as vans or large vehicles. Preferably, the content of reinforcing filler in the rubber composition is in the range of 20 to 100 phr, more preferentially in the range of 30 to 90 phr, even more preferentially in the range of 40 to 90 phr, the optimum depending, as is known, on the particular intended use.

[0033] In this specification, the BET specific surface area is determined by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society" (vol. 60, page 309, February 1938), more specifically according to the method derived from standard NF ISO 5794-1, Appendix E (June 2010) [multipoint (5-point) volumetric method - gas: nitrogen - degassed under vacuum: 160 °C for 1 hour - relative pressure p / p / o range: 0.05 to 0.17]. For inorganic fillers such as silica, for example, the value of the CTAB specific surface area is determined according to standard NF ISO 5794-1, Appendix G (June 2010). This method is based on the adsorption of CTAB (N-hexadecyl-N,N,N-trimethylammonium bromide) on the "external" surface of the reinforcing filler. For carbon black, the STSA specific surface area is determined in accordance with standard ASTM D6556-2016.

[0034] Coupling agent for inorganic reinforcing filler As mentioned above, the reinforcing filler itself can interact with the functionalized diene elastomer E2. However, when the reinforcing filler is an inorganic filler such as, for example, silica, it may be advantageous to increase the reinforcing power of this filler by using a coupling agent that makes it possible to bond the reinforcing inorganic filler to the diene elastomer. In a well-known manner, any at least difunctional coupling agent (or bonding agent) can be used that is intended to provide a sufficient bond of chemical and / or physical nature between the inorganic filler (the surface of its particles) and the diene elastomer. In particular, at least difunctional organosilanes or polyorganosiloxanes are used. The term "difunctional" is understood to mean a compound having a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the diene elastomer. For example, such a difunctional compound can have a first functional group containing a silicon atom and capable of interacting with the hydroxyl group of the inorganic filler, and a second functional group containing a sulfur atom and capable of interacting with the diene elastomer.

[0035] Preferentially, the organosilane is selected from the group consisting of (symmetrical or asymmetrical) organosilane polysulfides, such as bis(3-triethoxysilylpropyl)tetrasulfide (abbreviated as TESPT) sold by Evonik under the trade name Si69, or bis(3-triethoxysilylpropyl)disulfide (abbreviated as TESPD) sold by Evonik under the trade name Si75, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, such as S-(3-(triethoxysilyl)propyl)octanethioate sold by Momentive under the trade name NXT Silane. More preferentially, the organosilane is an organosilane polysulfide. Of course, mixtures of the above mentioned coupling agents may also be used. The content of coupling agent in the rubber composition of the present invention is advantageously 20 phr or less, and it is generally understood that it is desirable to use as little coupling agent as possible. Typically, the content of coupling agent represents 0.5% to 15% by mass relative to the amount of reinforcing inorganic filler. The content of coupling agent is preferentially in the range of 0.5 to 20 phr. This content can be easily adjusted by those skilled in the art based on the content of reinforcing inorganic filler used in the composition of the present invention.

[0036] coating agent The rubber composition may also contain an agent for coating the reinforcing inorganic filler, if used, to improve the processability of the rubber composition in the uncured state. These coating agents are well known (see, for example, patent applications WO 2006 / 125533-A1, WO 2007 / 017060-A1, and WO 2007 / 003408-A1). Examples of suitable coating agents include hydrolyzable silanes such as hydroxysilanes (see, for example, WO 2009 / 062733-A2), alkylalkoxysilanes, polyols (e.g., diols or triols), polyethers (e.g., polyethylene glycols), primary, secondary, or tertiary amines, hydroxylated polyorganosiloxanes, or hydrolyzable polyorganosiloxanes (e.g., α,ω-dihydroxypolyorganosilanes (see, for example, EP 0 784 072-A1)).

[0037] Crosslinked system The rubber composition of the present invention comprises at least one crosslinking system, which may be of any type known to those skilled in the art in the field of rubber compositions for pneumatic or non-pneumatic tires, and in particular may be a crosslinking system based on sulfur and / or peroxide and / or bismaleimide. Preferentially, the crosslinking system is based on sulfur and is called a vulcanization system. The sulfur can be provided in any form, in particular in the form of molecular sulfur or sulfur donors. Also, at least one vulcanization accelerator is preferentially present, and preferentially various known vulcanization activators may be used, such as zinc oxide, stearic acid or equivalent compounds (e.g., stearates), and salts of transition metals, guanidine derivatives (especially diphenylguanidine), or other known vulcanization retarders. Sulphur is used in a preferred content ranging from 0.5 to 12 phr, more preferably from 0.7 to 10 phr. Vulcanisation accelerators are used in a preferred content ranging from 0.5 to 10 phr, more preferably from 0.5 to 5.0 phr. As the accelerator, any compound capable of functioning as a vulcanization accelerator for diene elastomers in the presence of sulfur may be used, in particular thiazole-type accelerators and their derivatives, or sulfenamide-type, thiuram-type, dithiocarbamate-type, dithiophosphate-type, thiourea-type, and xanthate-type accelerators.

[0038] plasticizer The rubber composition of the present invention may contain at least one plasticizer. As known to those skilled in the art of rubber compositions for pneumatic or non-pneumatic tires, the plasticizer is preferably selected from hydrocarbon resins having a high glass transition temperature (Tg), low Tg hydrocarbon resins, plasticizing oils, and mixtures thereof. Preferably, the plasticizer is selected from high Tg hydrocarbon resins, plasticizing oils, and mixtures thereof. As is known, plasticizers in rubber compositions can alter the viscosity of the rubber composition and adjust the glass transition temperature of the rubber composition for its optimum use. High Tg hydrocarbon resins, by definition, are solid at ambient temperature and pressure (20°C, 1 atm), whereas plasticizing oils are liquid at ambient temperature and pressure, and low Tg hydrocarbon resins are viscous at ambient temperature and pressure.

[0039] Hydrocarbon resins, also known as hydrocarbon plasticizers, are polymers well known to those skilled in the art that are essentially based on carbon and hydrogen but can contain other types of atoms, such as oxygen, and can be used, among other things, as plasticizers. Hydrocarbon resins are inherently at least partially miscible (i.e., compatible) with the intended rubber composition at the amounts used; hydrocarbon plasticizer resins that act as true diluents are described, for example, in the book "Hydrocarbon Resins" by R. Mildenberg, M. Zander, and G. Collin (New York, VCH, 1997, ISBN 3-527-28617-9), where Chapter 5 is devoted to their applications, particularly in the field of pneumatic tire rubber (5.5 "Rubber Tires and Mechanical Goods"). As is known, these hydrocarbon resins can also be called thermoplastic resins, in the sense that they soften when heated and can therefore be molded. The softening point of the hydrocarbon resin is measured according to standard ISO 4625 (the "Ring and Bail" method). Tg is measured according to standard ASTM D3418 (2008). The macrostructure (Mw, Mn and PI) of the hydrocarbon resin is determined by size exclusion chromatography (SEC) (solvent: tetrahydrofuran; temperature: 35°C; concentration: 1 g / L; flow rate: 1 mL / min; solution filtered through a filter with 0.45 μm pores before injection; Moore calibration with polystyrene standards; set of three Waters columns in series (Styragel HR4E, HR1 and HR0.5); detection by a differential refractometer (Waters 2410) and its associated operating software (Waters Empower)). The hydrocarbon resin may be aliphatic or aromatic, or of the aliphatic / aromatic type, i.e., based on aliphatic and / or aromatic monomers. Hydrocarbon resins can be natural or synthetic, and may or may not be petroleum-based (if petroleum-based, they are also known as petroleum resins).As is known, a high Tg hydrocarbon resin is a thermoplastic hydrocarbon resin, the Tg of which is above 20°C.

[0040] Preferably, the plasticizer may comprise a hydrocarbon resin, which is solid at ambient temperature and pressure and is referred to as a high Tg resin. Preferably, the high Tg hydrocarbon plasticizing resin exhibits at least one of the following properties: - Tg above 30 °C; - number average molecular weight (Mn) between 300 and 2000 g / mol, more preferentially between 400 and 1500 g / mol; a polydispersity index (PI) of less than 3, more preferentially less than 2 (note: PI=Mw / Mn, Mw=weight average molecular weight). More preferentially, the high Tg hydrocarbon plasticized resin exhibits all of the above preferential properties. Plasticizers may include hydrocarbon resins that are viscous at 20°C, referred to as "low Tg" resins (ie, by definition, have a Tg in the range of -40°C to 20°C). Preferably, the low Tg hydrocarbon plasticizing resin exhibits at least one of the following properties: a Tg between -40°C and 0°C, more preferentially between -30°C and 0°C, and even more preferentially between -20°C and 0°C; - a number average molecular weight (Mn) of less than 800 g / mol, preferably less than 600 g / mol, and more preferentially less than 400 g / mol; a softening point in the range from 0°C to 50°C, preferentially in the range from 0°C to 40°C, more preferentially in the range from 10°C to 40°C, preferably in the range from 10°C to 30°C; a polydispersity index (PI) of less than 3, more preferentially less than 2 (note: PI=Mw / Mn, Mw=weight average molecular weight). More preferentially, the low Tg hydrocarbon resin exhibits all of the above preferential properties.

[0041] The plasticizer may also include extender oils (or plasticizing oils) called "low Tg" plasticizers (i.e., by definition, have a Tg below -20°C, preferably below -40°C), which are liquid at 20°C. Any extender oil known for its plasticizing properties with respect to elastomers can be used, whether of aromatic or non-aromatic nature. At ambient temperature (20°C), these oils have some viscosity but are liquid (i.e., a substance that has the ability to ultimately take the shape of its container), which is particularly different from high Tg hydrocarbon resins, which are essentially solid at ambient temperature. Particularly suitable are plasticizing oils selected from the group consisting of naphthenic oils (low or high viscosity, in particular hydrogenated or not), paraffinic oils, MES (medium extract solvates), TDAE (treated distillate aromatic extract) oils, RAE (residual aromatic extract) oils, TRAE (treated residual aromatic extract) oils and SRAE (safe residual aromatic extract) oils, mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers, sulfonate plasticizers, and mixtures of these compounds. High Tg hydrocarbon resins, low Tg hydrocarbon resins, and the preferred plasticizing oils mentioned above are well known to those skilled in the art and are commercially available.

[0042] Other additives The rubber composition of the present invention may also contain all or part of the usual additives and processing aids known to those skilled in the art and commonly used in rubber compositions for pneumatic or non-pneumatic tires, in particular for treads, such as fillers (reinforcing or non-reinforcing / other than those mentioned above), pigments, protective agents (such as anti-ozonant waxes, chemical anti-ozonants or antioxidants), anti-fatigue agents or reinforcing resins (such as those described in application WO 02 / 10269).

[0043] Obtaining the rubber composition of the present invention The rubber composition can be obtained by any conventional process for producing rubber compositions, for example by dry mixing the various ingredients. According to one embodiment, the rubber compositions of the present invention are prepared in a suitable mixer using two successive preparation steps well known to those skilled in the art. The first thermomechanically processing or kneading stage ("non-productive" stage) can be carried out in a single thermomechanical step, during which the following components are introduced in the following order into a suitable mixer, such as a standard internal mixer (for example, of the "Banbury" type): a functionalized diene elastomer E2 having a glass transition temperature TgE2, a reinforcing filler, and an optional coupling agent for the reinforcing filler. After thermomechanical kneading, these components are maintained at a temperature in the range of 140°C to 200°C for 1 to 2 minutes, while an unfunctionalized diene elastomer E1 having a glass transition temperature TgE1 and all the necessary components, except the crosslinking system, are introduced into the internal mixer. These components are then thermomechanically kneaded for 2 to 10 minutes up to a maximum temperature (called the "dropping temperature") in the range of 110°C to 200°C, preferably in the range of 130°C to 185°C. The second mechanical processing stage ("productive" stage) is carried out in an external mixer, such as an open mill, after cooling the mixture obtained during the first non-productive stage to a lower temperature, typically below 120°C (for example in the range of 40°C to 100°C). The crosslinking system is then incorporated by mixing for 5 to 15 minutes, in order to obtain the rubber composition of the invention.

[0044] According to another preferred embodiment of the invention, the rubber composition of the invention is prepared in the form of two masterbatches which are then mixed so as to obtain the rubber composition of the invention. More specifically, according to this embodiment, a first masterbatch is prepared by mixing the unfunctionalized diene elastomer E1 with other optional components (e.g., plasticizers, antiozonants, etc.) excluding the vulcanization system in a suitable mixer, such as a standard internal mixer (e.g., "Banbury" type). Thermomechanical processing is carried out for 2 to 10 minutes up to a maximum temperature (called the "dropping temperature") in the range of 110°C to 200°C, preferably 130°C to 185°C. In this way, a first masterbatch containing at least the unfunctionalized diene elastomer E1 is recovered.

[0045] A second masterbatch is then prepared by mixing the functionalized diene elastomer E2, the reinforcing filler, and any other optional components (except for the vulcanization system) (e.g., coupling agents for the reinforcing filler and / or plasticizer, antiozonants, etc.) in a suitable mixer, such as a standard internal mixer (e.g., "Banbury" type). Thermomechanical processing is carried out for 2 to 10 minutes up to a maximum temperature (called the "dropping temperature") in the range of 140°C to 200°C, preferably in the range of 140°C to 185°C. In this way, a second masterbatch is recovered, which contains at least the functionalized diene elastomer E2 and the reinforcing filler capable of interacting with the functionalized diene elastomer E2. The two masterbatches from the previous steps are introduced into a standard internal mixer (for example, of the "Banbury" type). Thermomechanical processing is carried out for 2 to 10 minutes up to a maximum temperature (called the "dropping temperature") in the range of 110°C to 180°C, preferably in the range of 130°C to 180°C. Next, the mixture from the previous step is cooled to a temperature of 110° C. or less on an external mixer such as an open mill, and then mixed for 5 to 15 minutes to incorporate the crosslinking system, and the rubber composition is recovered.

[0046] Regardless of the method for preparing the rubber composition, the final composition thus obtained is then calendered, for example in the form of sheets or slabs, in particular for laboratory characterization, or extruded in the form of rubber semi-finished products (or profiled elements) that can be used, for example, as treads in pneumatic or non-pneumatic tires, in particular for passenger cars. The composition may be in either an uncured state (before crosslinking or vulcanization) or in a cured state (after crosslinking or vulcanization), and may be a semi-finished product that can be used in pneumatic or non-pneumatic tires. Crosslinking of the rubber composition can be carried out by methods known to those skilled in the art, for example, at a temperature in the range of 130°C to 200°C under pressure.

[0047] Other Subject Matter of the Invention Another subject of the invention relates to a tread comprising at least one composition as defined above. The rubber composition of the invention can constitute the entire tread or a part of the tread. Another subject of the invention relates to a pneumatic or non-pneumatic tire comprising at least one composition as defined above or a tread as defined above. A "pneumatic tire" is understood to mean a tire intended to form a cavity by cooperating with a support element, for example a rim, which cavity can be pressurized to a pressure higher than atmospheric pressure. A "non-pneumatic tire", on the other hand, cannot be pressurized. A non-pneumatic tire is therefore a torus made of at least one polymer material, which is intended to function as a tire without the application of tire inflation pressure. A non-pneumatic tire may be solid or hollow. A hollow non-pneumatic tire may contain air at atmospheric pressure, i.e., it does not have the hardness of inflation provided by inflation gas at a pressure higher than atmospheric pressure.

[0048] The pneumatic tire of the present invention is intended to be mounted on any type of vehicle, such as a passenger car, motorcycle, heavy vehicle, agricultural vehicle, construction plant vehicle or aircraft, or more generally on rotating equipment. The non-pneumatic tire is particularly intended to be mounted on a passenger car or motorcycle. Preferably, the pneumatic tire of the present invention is intended to be mounted on a passenger car. Preferentially, the pneumatic or non-pneumatic tire comprises at least one tread comprising at least one rubber composition as described above.

[0049] Measurement method Determination of the glass transition temperature of elastomers The glass transition temperature (Tg) of the elastomers was determined before use using a differential scanning calorimeter according to standard ASTM D3418:2008. Dynamic friction coefficient μ max Decision The measurements of the dynamic friction coefficient were carried out according to the same method as described in "Modeling of Dry and Wet Friction of Silica-Filled Elastomers on Self-Affine Road Surfaces" by L. Busse, A. Le Gal and M. Kuppel, Elastomer Friction, 2010, 51, p. 8. Test specimens were prepared by molding square rubber supports (50 mm x 50 mm) with a thickness of 6 mm. After closing the mold, the mold was placed in a press with heated platens at a temperature of 150 °C and a pressure of 16 bar for the time required for crosslinking of the material (typically several tens of minutes). The surfaces used to carry out these measurements were cores taken from real road surfaces made of bituminous concrete of the BBTM type (standard NF P98-137). To prevent the phenomenon of dewetting and the appearance of secondary grip forces between the ground and the material, the ground + specimen system was immersed in a 5% aqueous solution of a surfactant (Sinnozon - CAS number: 25155-30-0). The temperature of the aqueous solution was controlled using a thermostatic bath. The specimen was subjected to a sliding movement moving parallel to the ground. The sliding velocity SV was set to 1.2 m / s. The applied normal stress σ n was 400 kPa (i.e., 4 bar). Hereafter, these conditions are referred to as "wet ground conditions". The tangential stress σ that opposes the movement of the specimen on the ground t was continuously measured. n Tangential stress σ t The coefficient of dynamic friction μ is obtained by the ratio of the above. The value of the coefficient of dynamic friction is measured by sweeping the temperature of the aqueous solution from 3°C to 44°C, and the tangential stress σ t is obtained at steady state after stabilization of the value of

[0050] In the example, the maximum value of the dynamic friction coefficient (μ max (denoted by ). Unless otherwise clearly indicated, results are expressed on a scale of 100. To calculate and compare the maximum dynamic friction coefficients of various test samples, an arbitrary value of 100 was assigned to the comparative composition. The scale of 100 value of a test sample was calculated by the following formula: (μ of test sample) max Value / μ of comparative composition max The coefficient of friction was calculated according to the following formula: (value) × 100. In this way, a result below 100 would indicate a decrease in the maximum dynamic friction coefficient and therefore a decrease in wet grip performance. Conversely, a result above 100 would indicate an increase in the maximum dynamic friction coefficient and therefore an improvement in wet grip performance.

[0051] Measurement of dynamic properties after curing The dynamic properties tan(δ)max were measured with a viscometer (Metravib VA4000) according to the standard ASTM D5992-96. Samples of the vulcanized compositions (2 mm thick and 78.5 mm cross section) were 2 The response of two cylindrical specimens (one for each specimen) to a simple alternating sinusoidal shear stress was recorded at a frequency of 10 Hz and a temperature of 40°C. A peak-to-peak strain amplitude sweep was performed from 1% to 100% (forward cycle) followed by 100% to 1% (return cycle). The result used was the loss factor, tan(δ). For the return cycle, tan(δ) 40℃におけるmax The maximum observed tan(δ) value (tan(δ)max) is shown. The results are expressed as a performance reference of 100, i.e., the tan(δ) of the various test rubber compositions. 40℃におけるmax For purposes of calculating and comparing, a value of 100 was arbitrarily assigned to the comparative composition. The reference value of 100 was calculated by the operation: (tan(δ) of the comparative composition) 40℃におけるmax Value of / tan(δ) of sample 40℃におけるmax The hysteresis curve was calculated according to the following formula: (value of hysteresis curve) * 100. In this way, a lower value represents a decrease in hysteresis properties, while a higher value represents an improvement in hysteresis properties. [Example]

[0052] 1. Ingredients: The ingredients used in the examples are as follows: Elastomer (1A): non-functionalized styrene / butadiene copolymer having a Tg of −28° C., measured according to standard ASTM D3418:2008 (styrene content of 41% by weight, relative to the total weight of the copolymer; vinyl-1,2 butadiene content of 14% by weight, relative to the total weight of the copolymer; trans-1,4 butadiene content of 27% by weight, relative to the total weight of the copolymer). Elastomer (1B): styrene / butadiene copolymer having silanol functional groups at the ends of the elastomer chains and having a Tg of −24° C. measured in accordance with standard ASTM D3418:2008 (styrene content of 25% by weight relative to the total weight of the copolymer, vinyl-1,2 butadiene content of 43% by weight relative to the total weight of the copolymer, trans-1,4 butadiene content of 16% by weight relative to the total weight of the copolymer). Elastomer (1C): styrene / butadiene copolymer having a Tg of -65°C measured according to standard ASTM D3418:2008 (styrene content of 16% by weight relative to the total weight of the copolymer, vinyl-1,2 butadiene content of 20% by weight relative to the total weight of the copolymer, trans-1,4 butadiene content of 39% by weight relative to the total weight of the copolymer).

[0053] Elastomer (1D): styrene / butadiene copolymer with aminoalkoxysilane functional groups in the middle of the chain and a Tg of -65°C measured according to standard ASTM D3418:2008 (styrene content of 16% by weight relative to the total weight of the copolymer, vinyl-1,2 butadiene content of 20% by weight relative to the total weight of the copolymer, trans-1,4 butadiene content of 39% by weight relative to the total weight of the copolymer). Elastomer (1F): styrene / butadiene copolymer having aminoalkoxysilane functional groups in the middle of the chain and having a Tg of −48° C. measured according to standard ASTM D3418:2008 (styrene content of 27% by weight relative to the total weight of the copolymer, vinyl-1,2 butadiene content of 17.5% by weight relative to the total weight of the copolymer, trans-1,4 butadiene content of 33.5% by weight relative to the total weight of the copolymer). Elastomer (1G): non-functionalized styrene / butadiene copolymer having a Tg of -48°C measured according to standard ASTM D3418:2008 (styrene content of 27% by weight relative to the total weight of the copolymer, vinyl-1,2 butadiene content of 17.5% by weight relative to the total weight of the copolymer, 1,4-butadiene content of 33.5% by weight relative to the total weight of the copolymer).

[0054] Carbon black (2): ASTM grade N234 carbon black sold by Cabot Corporation Silica (3): Zeosil 1165MP silica sold by Solvay Silane (4): Bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT) silane sold by Evonik under the reference number Si69. DPG(5): Diphenylguanidine, Perkacit DPG from Flexsys Plasticizer (6): DCPD resin with a softening point of 100°C and a glass transition temperature of 51°C, sold by ExxonMobil under the reference PR-383. Ozone Resistant Wax (7): Varazon 4959 Ozone Resistant Wax by Sasol Wax Antioxidant (8): N-(1,3-dimethylbutyl)-N-phenyl-para-phenylenediamine sold by Flexis under the reference Santoflex 6-PPD. ZnO(9): Zinc oxide (industrial grade) sold by Umicore Stearic acid (10): Pristerene 4031 stearin sold by Uniquema

[0055] 2. Test 1: Effect of the location of reinforcing fillers in the rubber composition The examples presented in Table 1 are intended to compare various rubber properties of rubber composition CI1 of the present invention with a series of comparative rubber compositions CC1 and CC2. Table 1 presents the formulations of these rubber compositions, the proportions being given in phr (ie parts by weight per 100 parts by weight of elastomer of the composition). [Table 1]

[0056] Comparative rubber composition CC1 was obtained from two masterbatches, Masterbatch 1 and Masterbatch 2, which were obtained by dry mixing according to the following process. In one or more steps, all of the components from Table 2 are reacted with 414 cm 3 The mixture was introduced into a Polylab internal mixer and filled to 70% by volume. The initial temperature of the vessel was 90°C. Thermomechanical operation was carried out for 6 minutes until a maximum dropping temperature of 165°C was reached. The mixture thus obtained (designated Masterbatch 1) was recovered. In one or more steps, all of the components from Table 3 are mixed with another 414 cm 3 The mixture was introduced into a Polylab internal mixer and filled to 70% by volume. The initial temperature of the vessel was 90°C. Thermomechanical operation was carried out for 6 minutes until a maximum dropping temperature of 165°C was reached. The mixture thus obtained (designated Masterbatch 2) was recovered.

[0057] Next, the previously obtained Masterbatch 1 and Masterbatch 2 were added to 414 cm 3 The mixture was introduced into a Polylab internal mixer and filled to 70% by volume. Thermomechanical operation was carried out for 6 minutes until a maximum dropping temperature of 150°C was reached. The mixture obtained in the previous step was then introduced into an external mixer, such as an open mill, so as to cool it to a temperature of 40°C. A crosslinking system (1.8 phr of sulfur and 2.2 phr of CBS (N-cyclohexyl-2-benzothiazole sulfenamide, sold by Flexis under the reference Santocure CBS) was then mixed in and mixed for 20 minutes. The rubber compositions thus obtained were then calendered into slabs in order to measure their physical or mechanical properties. Unless otherwise specified, the rubber properties of the rubber compositions were measured after curing at 170°C for 2 minutes.

[0058] [Table 2]

[0059] [Table 3]

[0060] Comparative rubber composition CC2 and inventive rubber composition CI1 were prepared according to the process described for rubber composition CC1 with masterbatches 1 and 2 from Tables 4 and 5 for comparative composition CC2 and masterbatches 1 and 2 from Tables 6 and 7 for inventive rubber composition CI1, respectively.

[0061] [Table 4]

[0062] [Table 5]

[0063] [Table 6]

[0064] [Table 7]

[0065] The rubber properties of rubber compositions CC1, CC2 and CI1, measured after curing, are presented in Table 8. [Table 8]

[0066] Despite containing the same amount of reinforcing filler (58.80 phr), the rubber composition CI1 of the present invention differs from the comparative rubber compositions CC1 and CC2 in that the reinforcing filler, particularly silica, interacts with the elastomer having the lowest glass transition temperature (i.e., with the elastomer having the glass transition temperature TgE2). In the rubber composition CC1, which does not contain a functionalized elastomer, the reinforcing filler is uniformly distributed between the two elastomers with different glass transition temperatures. In the rubber composition CC2, the reinforcing filler interacts with the functionalized elastomer having the highest glass transition temperature (i.e., with the elastomer having the glass transition temperature TgE1). Compared to comparative rubber composition CC1, in which the reinforcing filler is uniformly distributed in the elastomer matrix, rubber composition CC2 exhibits comparable hysteresis properties (tan(δ) 40℃におけるmax ), the coefficient μ max Thus, when the reinforcing filler interacts with the elastomer having the highest glass transition temperature (in this case, TgE1 of rubber composition CC2), a decrease in wet grip performance is observed for hysteresis properties comparable to those of comparative rubber composition CC1. Surprisingly, when the reinforcing filler interacts with the elastomer with the lowest Tg (in this case a functionalized elastomer with a glass transition temperature TgE2, see the rubber composition CI1 of the present invention), significantly improved hysteresis properties and coefficient μ compared to the comparative rubber composition CC1. maxAn increase in hysteresis and therefore improved wet grip performance is observed. This result is surprising because the improvement in hysteresis properties is not achieved at the expense of wet grip performance.

[0067] 3. Test 2: Effect of difference in glass transition temperature of elastomers forming rubber composition The examples presented in Table 9 are intended to compare various rubber properties of the rubber composition CI1 of the present invention with two comparative rubber compositions CC3 and CC4. Table 9 presents the formulations of the test rubber compositions, with proportions given in phr (ie parts by weight per 100 parts by weight of elastomer in the composition). [Table 9]

[0068] Comparative rubber compositions CC3 and CC4 were prepared according to the process of Test 1, using the masterbatches in Table 6 (Masterbatch 1-CI1) and Table 10 (Masterbatch 2-CC3) for comparative composition CC3, and the masterbatches in Table 11 (Masterbatch 1-CC4) and Table 7 (Masterbatch 2-CC1) for comparative composition CC4, respectively.

[0069] [Table 10]

[0070] [Table 11]

[0071] The rubber properties of these compositions, measured after cure, are shown in Tables 12 and 13. [Table 12] The inventive rubber composition CI1 differs from the comparative rubber composition CC3 in that it is a lower glass transition temperature elastomer (ie, an elastomer having a glass transition temperature TgE2). When the formulation of comparative composition CC3 was changed so that the difference in glass transition temperatures of the elastomers was 23°C or more to obtain rubber composition CI1 of the present invention, it was found that the hysteresis properties of rubber composition CI1 of the present invention were significantly improved compared to comparative composition CC3. Surprisingly, the improvement in the hysteresis properties of the rubber composition CI1 of the present invention is due to the coefficient μ max This has not been achieved at the expense of wet grip performance.

[0072] [Table 13] The inventive rubber composition CI1 differs from the comparative rubber composition CC4 in that it is a higher glass transition temperature elastomer (ie, an elastomer having a glass transition temperature TgE1). When the compounding of the comparative composition CC4 is changed so that the difference in the glass transition temperature of the elastomer becomes 23°C or more to obtain the rubber composition CI1 of the present invention, the coefficient μ of the rubber composition CI1 of the present invention is higher than that of the comparative composition CC4. max It was found that the wet grip performance was significantly improved. Therefore, the rubber composition of the present invention has better wet grip performance than the comparative composition CC4. Surprisingly, the improvement in wet grip performance was not achieved at the expense of the hysteresis property, which was equivalent to that of the comparative rubber composition CC4.

[0073] 4. Test 3: Comparison with Prior Art The example presented in Table 14 is intended to compare various rubber properties of the rubber composition CI1 according to the invention with the comparative rubber composition CC5, which represents Example 4 of document EP 3 372 638 A1. The formulation of rubber composition CC5 is given in Table 14, with proportions given in phr. [Table 14]

[0074] Rubber composition CC5 was prepared according to the process of Test 1 with the masterbatches from Tables 15 and 16, respectively. [Table 15]

[0075] [Table 16]

[0076] The rubber properties of the rubber compositions measured after curing are shown in Table 17. [Table 17]

[0077] Compared to the rubber composition CC5, which represents the prior art, the rubber composition CI1 of the present invention has a significantly improved coefficient μ max This result shows that the wet grip of the rubber composition CI1 of the present invention is significantly better than that of the rubber composition CC5. Surprisingly, the coefficient μ max The significant improvement in δ is not achieved at the expense of hysteresis properties, since the two rubber compositions have the same δ 40℃におけるmax Because it has value. All of the above tests show that the rubber composition CI1 of the present invention has significantly improved hysteresis properties and therefore reduced rolling resistance compared to the comparative rubber compositions, while maintaining very good wet grip performance.

Claims

1. 1. A rubber composition based on at least one unfunctionalized first diene elastomer E1 having a glass transition temperature TgE1, one functionalized second diene elastomer E2 having a glass transition temperature TgE2, a reinforcing filler capable of interacting with the functionalized diene elastomer E2, and a crosslinking system, the second diene elastomer E2 is an aminoalkoxysilane-functionalized styrene-butadiene copolymer, the reinforcing filler mainly comprises at least one silica, - the glass transition temperature TgE1 is -50°C or higher, the glass transition temperature TgE2 satisfies the mathematical relationship TgE2≦TgE1−23° C., the glass transition temperature TgE2 satisfies the mathematical relationship TgE2 ≥ TgE1 - 65°C, the rubber composition, wherein the content of non-functionalized diene elastomer E1 is between 50 phr and 70 phr.

2. The rubber composition according to claim 1, wherein the glass transition temperature TgE2 satisfies the mathematical relationship TgE2≦TgE1−28°C.

3. The rubber composition according to claim 1 or 2, wherein the glass transition temperature TgE2 satisfies the mathematical relationship TgE2≧TgE1−50°C.

4. The rubber composition according to any one of claims 1 to 3, wherein the glass transition temperature TgE2 is within the range of -110°C to -23°C.

5. The rubber composition according to any one of claims 1 to 4, wherein the glass transition temperature TgE1 is within the range of -50°C to 0°C.

6. The rubber composition according to any one of claims 1 to 5, wherein the content of the diene elastomer E1 is in the range of 55 phr to 70 phr.

7. 7. The rubber composition according to claim 1, wherein the non-functionalized diene elastomer E1 is selected from the group consisting of synthetic polyisoprene, polybutadiene, butadiene / styrene copolymer, butadiene / isoprene copolymer, isoprene / styrene copolymer, and butadiene / styrene / isoprene copolymer.

8. 8. The rubber composition according to claim 1, wherein the non-functionalized diene elastomer E1 is selected from polybutadiene and styrene / butadiene copolymers.

9. The rubber composition according to any one of claims 1 to 8, wherein the content of the reinforcing filler is within a range of 20 to 100 phr.

10. The rubber composition according to any one of claims 1 to 9, wherein the content of the functionalized diene elastomer E2 is in the range of 30 phr to 50 phr.

11. A tread comprising at least one composition according to any one of claims 1 to 10.

12. A pneumatic or non-pneumatic tire comprising at least one composition according to any one of claims 1 to 10 or a tread according to claim 11.

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