CA3213296A1 - Rubber composition - Google Patents

Abstract

The invention relates to a rubber composition based on at least one diene elastomer, on at least one reinforcing filler comprising, predominantly by weight, a reinforcing inorganic filler, on at least one agent for coupling the reinforcing inorganic filler to the diene elastomer, on at least one processing agent and on a crosslinking system. According to the invention, the content of agent for coupling the reinforcing inorganic filler to the diene elastomer is within a range extending from 12% to 18% by weight relative to the weight of the reinforcing inorganic filler, and the processing agent essentially consists of a mixture of at least one carboxylic acid comprising 4 to 28 carbon atoms and of at least one aliphatic polyol comprising 2 to 22 carbon atoms. The invention also relates to a tread or a tyre comprising such a rubber composition.

Description

RUBBER COMPOSITION
The present invention relates to a rubber composition, in particular intended for manufacturing a tread, in particular a tread for a tire, in particular of tourism vehicle.
The tread is the part of the tire intended to come into contact with the ground via a rolling surface. This tread is responsible for a large part dc the rolling resistance and road behavior of the tire. These contributions are good heard very variable depending on the design of the tire, but a order of magnitude of the order of 50% can be reached.
The tire tread must therefore obey a large number technical requirements among which include rolling resistance, grip on the ground wet, a good road behavior (associated with good rigidity of the cooked compositions), at the same time to good raw properties such as viscosity of rubber compositions in the raw state (associated with ease of industrial implementation of the compositions, also called processability).
However, it is well known to those skilled in the art that improving performance for tires is often obtained at the expense of its other performances.
For example, a way to give the tire high grip on the ground wet is to use, for the tread, a rubber composition which has good hysteretic potential.
However, at the same time, this tread must have a contribution to the rolling resistance as low as possible to limit energy losses linked to rolling;
that is to say, it must be as least hysterical as possible.
The improvement in rolling resistance was made possible thanks to news employment rubber compositions reinforced with inorganic fillers, in particular of specific silicas highly dispersible type, capable of competing from the reinforcing point of view with carbon black conventional pneumatic grade. These specific silicas of the highly type dispersible have typically a BET specific surface area within a range of 100 at 250 m2/g.
However, the use of reinforcing inorganic fillers although having a positive effect on hysteretic properties of a rubber composition is not without inconvenience. Indeed, due to the fact of their reciprocal affinity between them, the particles of charges reinforcing inorganic agglomerate between them in the rubber composition resulting in a part of limiting their dispersion and on the other hand to increase the consistency in the cm state of the rubber compositions therefore to make their industrial implementation (processability) more difficult than in the presence of carbon black.

2 It is known to use inorganic charge coupling agents elastomer reinforced diene in order to promote the dispersion of the reinforcing inorganic filler within the composition of rubber. These agents for coupling the inorganic filler to the elastomer diene are expensive compounds which increase the cost price of the composition of rubber to which they are incorporated. Furthermore, in order not to risk influencing others interactions of the constituents of the rubber composition, those skilled in the art know that it is desirable to use the right amount necessary coupling agent, or in a known manner a quantity at most equal to 8% by mass per relative to the mass of the reinforcing inorganic filler. Despite the use of coupling agents of the inorganic filler reinforcing the diene elastomer, it sometimes remains necessary to improve the processability of rubber compositions.
In order to improve the raw processability of rubber compositions reinforced by loads inorganic, it is known to use processing agents or plasticizers. The betting agents also called processing aids are very chemical in nature varied and make it possible to improve as their name indicates the processability of rubber compositions. This are, for example, mineral oils, resins of petroleum origin, acid derivatives fats such as acid esters fatty, metallic salt soaps, etc.
However, the use of processing agents can lead to softening of the composition of rubber, therefore reduced rigidity being synonymous with less good road behavior of the pneumatic.
Thus, improvement of the adhesion properties, in particular on ground wet, without penalizing the rolling resistance and rigidity while maintaining good processability of the composition of Rubber remains a constant problem for tire designers.
The aim of the present invention is to address this problem.
Continuing his research, the applicant has developed a composition of special rubber, base of at least one diene elastomer, of at least one reinforcing filler including predominantly a reinforcing inorganic filler, of at least one conditioning agent load coupling inorganic reinforcing agent with diene elastomer, at least one setting agent implemented and at least a crosslinking system; this composition having a high rate charge coupling agent inorganic reinforcing agent with diene elastomer in combination with an agent of implementation specific; this rubber composition having good processability and properties improved hysteretics while maintaining very good rigidity and very good grip on the ground wet. Thus, the rubber compositions of the invention have a compromise of performance ¨ wet grip/ hysteretic properties/ rigidity/
improved processability compared to the compositions of the prior art.

3 The subject of the invention is therefore a rubber composition based on at least a diene elastomer, of at least one reinforcing filler comprising mainly by weight a inorganic filler reinforcing, of at least one inorganic charge coupling agent reinforcing with elastomer diene, at least one implementation agent and at least one system of crosslinking, characterized in that the rate of coupling agent of the reinforcing inorganic filler at the diene elastomer is included in a range ranging from 12% to 18% by weight relative to the weight of the inorganic filler reinforcing and in that the implementation agent consists essentially of a mixture of at least a carboxylic acid containing 4 to 28 carbon atoms and at least one aliphatic polyol containing from 2 to 22 carbon atoms.
The invention also relates to a tread comprising all or part of a composition defined above.
Another object of the present invention relates to a tire comprising a such composition of rubber or such a tread.
Methods Mooney viscosity We use an oscillating consistometer as described in the French standard ISO 289-1 (2015). The measure of the Mooney index is done according to the following principle: the composition of rubber in its raw state (ie, before cooking) is molded in a cylindrical enclosure heated to 100 C. After a minute of preheating, the rotor rotates within the test tube at 2 revolutions/minute and the useful torque to maintain this movement after 4 minutes of rotation. The Mooney index (ML 1 +4) is expressed in Mooney unit (UM, with 1UM = 0.83 Nm (Newton.meter)).
Mooney index results are expressed in terms of base performance 100, that is to say that the value 100 is arbitrarily assigned to the witness, in order to compare consecutively the Mooney index of the different sample compositions subjected to testing (i.e. their processability). The value in base 100 of the sample composition subjected to test is calculated according to the operation: (value the index Mooney of the control / Mooney index value of the sample) * 100. A result greater than 100 indicates improved performance, i.e. the composition of the sample considered presents a reduction in its viscosity, corroborating better processability through compared to the control composition.
Glass transition temperature Glass transition temperatures (Tg) of elastomers and resins plasticizers are determined using a differential calorimeter (called Terential scanning calorimeter ), according to ASTM standard D3418-99.
Microstructural analysis of elastomers WO 2023/27549

4 The microstructure of elastomers is characterized by the technique of near infrared spectroscopy (N1R).
Near infrared (NIR) spectroscopy is used to determine quantitatively the mass rate dc styrene in the elastomer as well as its microstructurc (relative distribution 1,2 butadiene units, 1,4-trans and 1,4 cis). The principle of the method is based on Beer’s law-Lambert generalized to a multi-component system. The method being indirect, it uses a multivariate calibration [Vilmin, F.; Dussap, C.; Costc, N. Applicd Spcctroscopy 2006, 60, 619-29] carried out at using standard elastomers of composition determined by 13C NMR. Styrene content and microstructure are then calculated at from the NIR spectrum of an elastomer film approximately 730 Jim thick.
Spectrum acquisition is carried out in transmission mode between 4000 and 6200 cm-1 with a resolution of 2 cm-1, using a Bruker Tensor 37 Fourier transform near-infrared spectrometer equipped with a detector InGaAs cooled by Peltier effect.
Dynamic properties:
The dynamic properties G* and tan(8) are measured on a viscoanalyzer (Metravib VA4000), according to ASTM D5992-96. We record the response of a sample of vulcanized composition (cylindrical specimen 4 mm thick and 10 mm in diameter), subjected to a request sinusoidal in alternating simple shear, at a frequency of 10 Hz, when a temperature scan from -80 C to +100 C with a ramp of +1.5 C/min, under maximum stress of (),7 MPa. The value of the tangent of the loss angle (tan delta or tan()) is then raised to 00. The value of the module dynamic G* is recorded at 60 C. The results used are therefore the values of tan(8) at 0 C and the complex dynamic shear modulus G* at 60 C obtained on the scanning in temperature at 0.7 MPa.
The results of tan(8) at 0 C are expressed in terms of base performance 100, that is to say that the value 100 is arbitrarily assigned to the witness, in order to compare consecutively the tan(8) at 0 C
(i.e. wet grip) of the different compositions samples submitted for testing. There value in base 100 of the sample composition tested is calculated depending on the operation: (value of tan(8) at 0 C of the sample / tan(8) value at 0 C of the control) * 100. A
result greater than 100 indicates improved performance, i.e. the composition of the sample considered presents better grip on wet surfaces compared to the control composition.
The results of G* at 60 C are expressed in terms of performance in base 100, that is to say that the value 100 is arbitrarily assigned to the witness, in order to consecutively compare the G*at 60 C (i.e.
rigidity and, consequently, handling) of the different sample compositions submitted to essay. The value in base 100 of the sample composition tested is calculated according to the operation:
(G* value at 60 C of the control / G* value at 60 C of the sample) * 100. By therefore, a result greater than 100 indicates improved performance, i.e.
improvement of rigidity, corroborating an improvement in road holding performance.
The dynamic property tan(8)max at 23 C is measured on a viscoanalyzer (Metravib VA4000), according to ASTM D5992-96. We record the response of a sample of vulcanized composition (cylindrical specimen 4 mm thick and 10 mm in diameter) subjected to a request sinusoidal in alternating simple shear, at the frequency dc 10 Hz, in the normal conditions of temperature 23 C according to standard ASTM D 1349-09. We carry out a scan in amplitude of deformation from 0.1% to 100% (forward cycle), then from 100% to 0.1% (return cycle).
The result used is the maximum of the tangent of the loss angle tan(6) at 23 C on the cycle return, noted tan(6)max at 23 C.
The results of tan(6)max at 23 C are expressed in terms of performance in base 100, that is to say that the value 100 is arbitrarily assigned to the witness, in order to compare consecutively the tan(b)max at 23 C (i.e. the hysteresis properties) of the different compositions samples submitted for testing.
The value in base 100 for the sample is calculated according to the operation:
(value of tan(8)max at 23 C of control / tan(8)max value at 23 C of the sample) * 100. A result greater than 100 indicates a improved performance, i.e. sample composition considered presents improved hysteretic properties corroborating better resistance to bearing in relation to the control rubber composition.
Definition By the expression composition based on, we must understand a composition comprising the mixture and/or the in situ reaction product of the different constituents used, some of these constituents may react and/or being intended to react with each other, at least partially, when of the different phases of manufacturing of the composition; the composition can thus be in the state totally or partially crosslinked or in the non-crosslinked state.
By the expression part by weight per hundred parts by weight of elastomer (or pce), it is necessary to understand in the present description, the part, by mass per hundred parts by mass elastomer.
Herein, unless expressly stated otherwise, all percentages (%) indicated are percentages (%) by mass.
On the other hand, any interval of values designated by the expression between a and b represents the domain dc values ranging from more than a to less than b (i.e. terminals a and b excluded) while any interval of values designated by the expression from a to b means the domain of values going from a to b (that is i.e. including the strict limits a and b).
When we refer to a majority compound, we mean in the this description, that this compound is the majority among compounds of the same type in the composition, that is to say it is that which represents the greatest quantity by mass among the compounds of the same type. Thus, by example, a majority elastomer is the elastomer representing the most large mass compared to the total mass of elastomers in the composition. In the same way, a so-called majority charge is that representing the greatest mass among the charges in the composition. HAS
as an example, in a system comprising a single elastomer, this is the majority within the meaning of the this description; And in a system comprising two elastomers, the majority elastomer represents more than half of the mass of the elastomers. Preferably by majority, we mean present at more than 50%, preferably more than 60%, 70%, 80%, 90%, and more preferably the compound majority represents 100%.
The compounds mentioned in the description may be of fossil origin or biosourced. In this last case, they can be, partially or totally, derived from the biomass or obtained from renewable raw materials from biomass. Obviously, the compounds mentioned may also come from the recycling of materials already used, that is to say that they can be, partially or totally, from a recycling process, or even obtained from materials raw materials themselves resulting from a recycling process. Are concerned notably polymers, plasticizers, fillers, etc.
In the present description, the term “pneumatic” is understood to mean tire ) a bandage pneumatic or non-pneumatic tire.
Description of the invention An object of the present invention is a rubber composition based of at least one elastomer diene, of at least one reinforcing filler comprising mainly weight a load reinforcing inorganic, of at least one charge coupling agent reinforcing inorganic the diene elastomer, at least one processing agent and at least one crosslinking system, characterized in that the level of coupling agent of the inorganic charge reinforcing with elastomer diene is included in a range ranging from 12% to 18% by weight relative to to the weight of the load reinforcing inorganic and in that the implementation agent consists essentially a mixture at least one carboxylic acid containing 4 to 28 carbon atoms and of at least one polyol aliphatic containing 2 to 22 carbon atoms.
Diene elastomer As indicated above, the rubber composition of the invention comprises at least one diene elastomer.
By diene elastomer (or indiscriminately rubber), whether it is natural or synthetic, must be understood in a known manner an elastomer constituted at least in part (ie, an homopolymer or a copolymer) of diene monomer units (monomers carrying two double carbon bonds-carbon, conjugated or not).

These diene elastomers can be classified into two categories:
essentially unsaturated or essentially saturated. We generally mean essentially unsaturated , an elastomer diene derived at least in part from conjugated diene monomers, having a rate of patterns or units of diene origin (conjugated dienes) which is greater than 15% (/0 in moles);
this is how diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins EPDM type do not fall into the previous definition and can be notably described as elastomers essentially saturated dienics (low rate of units of diene origin or very weak, always less than 15 mol%).
In the present application, diene elastomers are by definition not thermoplastics and are preferably random homopolymers or copolymers.
The term diene elastomer capable of being used is particularly understood to mean in compositions conforming to the invention:
- any homopolymer of a diene monomer, conjugated or not, having from 4 to 18 carbon atoms;
- any copolymer of a diene, conjugated or not, having 4 to 18 atoms of carbon and at least another monomer.
The other monomer may be an olefin or a diene, conjugated or not.
As conjugated dienes suitable are conjugated dienes having from 4 to 12 carbon atoms, in particularly 1,3-dienes, such as in particular 1,3-butadiene and isoprene.
As olefins, vinylaromatic compounds having from 8 to 20 are suitable.
carbon atoms and aliphatic alpha-monoolefins having 3 to 12 carbon atoms.
Suitable vinyl aromatic compounds include, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial vinyl-toluene mixture, the para-tert-butylstyrene.
As aliphatic alpha-monoolefins, alpha-monolefins are suitable in particular aliphatic monoolefins acyclics having 3 to 12 carbon atoms.
More particularly, the diene elastomer is:
- any homopolymer of a conjugated diene monomer, in particular any homopolymer obtained by polymerization of a conjugated diene monomer having 4 to 12 carbon atoms;
- any copolymer obtained by copolymerization of one or more dienes conjugated together or with one or more vinyl aromatic compounds having 8 to 20 atoms of carbon;
- a copolymer of isobutene and isoprene (butyl rubber), as well as halogenated versions, in particular chlorinated or brominated, of this type of copolymer.
- any copolymer obtained by copolymerization of one or more dienes, conjugated or not, with an alpha-monoolefin.

Preferably, the diene elastomer is chosen from the group consisting of by natural rubber (NR), isoprene synthetic elastomers, synthetic elastomers butadiene and mixtures of these elastomers.
By isoprene synthetic elastomer, we mean in a known manner a homopolymer or a isoprene copolymer, in other words a diene elastomer chosen from the group made up of synthetic polyisoprenes (IR), the different isoprene copolymers and mixtures of these elastomers.
Among the isoprene copolymers, we will cite in particular the copolymers isobutene-isoprene (butyl rubber - IIR) or isoprene-styrene (SIR). This elastomer isoprene is preferably an synthetic cis-1,4 polyisoprene; more preferably still one synthetic polyisoprene having a rate (molar %) of cis-1,4 bonds greater than 90%, more preferably still higher than 98%.
By butadiene elastomer is meant in a known manner a homopolymer or a copolymer of butadiene, in particular a diene elastomer chosen from the group made up of polybutadienes (BR), the different butadiene copolymers and mixtures of these elastomers. Among the copolymers butadiene, mention will be made in particular of butadiene-styrene copolymers (SBR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene (SBIR).
Preferably, the diene elastomer is a synthetic elastomer butadiene, more still preferably is a copolymer of styrene and butadiene.
Preferably, the synthetic butadiene elastomer, preferably the copolymer of styrene and butadiene, has a glass transition temperature measured according to the standard ASTM D3418-99 lower or equal to -50 C, preferably within a range from -110 C to -50 C, more preferably still included in a range from -90 C to -50 C.
The diene elastomer can be modified, that is to say either coupled and/or starry, either functionalized or coupled and/or star-shaped and simultaneously functionalized.
Preferably, the diene elastomer, preferably the polymer butadiene, more preferably the copolymer of styrene and butadiene, can be functionalized and can include at least functional group. By functional group, we mean a group comprising at least one heteroatom chosen from Si, N, S, 0, P. Particularly suitable as of functional groups those comprising at least one polar function comprising at least one atom of oxygen and being chosen the group consisting of silanol, alkoxysilanes, carriers or not of an amine group, epoxide, ethers, esters, carboxylic acids and hydroxyl.
As functionalized elastomers, those prepared by using a primer functional, in particular those carrying an amine function. Such elastomers functional and their Obtaining processes are known to those skilled in the art.

As functionalized elastomers, those obtained by copolymerization of least one diene monomer and one monomer carrying a function.
As functionalized elastomers, those obtained by post-edit reaction polymerization with a functionalization agent introducing at least one function within the structure of the elastomer. Such functionalized elastomers and their methods of obtaining are known to those skilled in the art. Such functionalization can thus be classically carried out by various reactions, for example by radical grafting on the elastomer diene, by reaction 1,3-dipolar on the diene elastomer, by reaction of the diene elastomer (pseudo)alive obtained at the outcome of a polymerization, coordinate or anionic, with a functionalization.
Preferably, the diene elastomer is a copolymer of butadiene and styrene, said copolymer comprising at least one alkoxysilane group carrying or not another function.
This modified diene elastomer comprises within its structure at least one alkoxysilane group and at least one other function, the silicon atom of the alkoxysilane group being linked to the channel(s) elastomers, the alkoxysilane group optionally being partially or totally hydrolyzed into silanol. In the present description, the concept of alkoxysilane group located within the structure of the elastomer is understood as a group whose silicon atom is located in the polymer skeleton and directly connected to it. This positioning within the structure includes the ends of polymer chains. Thus, the terminal grouping is included in this notion.
The alkoxysilane group is not a pendant group.
According to certain variants, the alkoxysilane group is mainly located in one end of the chain main part of the elastomer.
According to other variants, the alkoxysilane group is mainly located in the elastomer chain main, we will then say that the diene elastomer is coupled or even functionalized in the middle of chain, as opposed to the position at the end of the chain and although the grouping is not located precisely in the middle of the elastomer chain. The silicon atom of this function connects the two branches of the main chain of the diene elastomer.
It should be noted that it is known to those skilled in the art that when a elastomer is modified by reaction of a functionalization agent on the living elastomer from a polymerization stage anionic, we obtain a mixture of modified species of this elastomer whose composition depends the conditions of the modification reaction and in particular the proportion of agent responsive sites of function ()filialization in relation to the number of elastomer chains alive. This mixture includes species functionalized at the end of the chain, coupled, star-shaped and/or not functionalized.
Advantageously, the first diene elastomer comprises as a species majority elastomer diene functionalized in the middle of the chain by an alkoxysilane group linked to two branches of the diene elastomer via the silicon atom, the radical alkoxy possibly being partially or completely hydrolyzed to hydroxyl. More particularly again, the diene elastomer functionalized in the middle of the chain by an alkoxysilane group represents 70%
in weight of the first diene elastomer.
The alkoxysilane group comprises a Cl -C10 alkoxyl radical, optionally partially or totally hydrolyzed to hydroxyl, or even to C1-C8, preferably to C1-C4, and is more preferably methoxy and ethoxy.
The other function is preferably carried by the silicon of the group alkoxysilane, directly or by via a spacer group defined as an atom or a group of atoms.
Preferably the spacer group is a divalent hydrocarbon radical, linear or branched, aliphatic in Cl-C18, saturated or not, cyclic or not, or a radical aromatic divalent hydrocarbon in C6-C18.
The other function is preferably a function comprising at least one heteroatom chosen from N, S, 0, P. We can, by way of example, cite among these functions, the amines primary, secondary or tertiaries, cyclic or not, isocyanates, imines, cyanos, thiols, carboxylates, epoxides, primary, secondary or tertiary phosphines.
Thus, as a secondary or tertiary amine function, we can cite the amines substituted with Cl-C10 alkyl radicals, preferably Cl-C4 alkyl, plus preferably a methyl radical or ethyl, or cyclic amines forming a heterocycle containing a nitrogen atom and at least a carbon atom, preferably 2 to 6 carbon atoms. For example, suitable methylamino-, dimethylamino-, ethylamino-, diethylamino-, propylamino-, dipropylamino-, butylamino-, dibutylamino-, pentylamino-, dipentylamino-, hexylamino-, dihexylamino-, hexamethyleneamino-, preferably diethylamino- groups and dimethylamino As an imine function, we can cite ketimines. For example, suitable groups (1,3-dimethylbutylidene)amino-, (ethylidene)amino-, (1 -methylpropylidene)amino-, (4-N,N-dimethylaminobenzylidene)amino-, (cyclohexylidene)amino-, dihydroimidazole and imidazole.
Thus, as a carboxylate function, we can cite acrylates or methacrylates. Such a function is preferably a methacrylate.
As an epoxy function, we can cite epoxy groups or glycidyloxy.
As a secondary or tertiary phosphine function, we can cite the phosphines substituted by alkyl radicals in Cl -Cl 0, preferably alkyl in Cl-C4, more preferably a methyl radical or ethyl, or diphenylphosphine. For example, suitable methylphosphino- groups, dimethylphosphino-, ethylphosphino-, diethylphosphino, ethylmethylphosphino-and diphenylphosphino-.
The other function is preferably an amine, preferably an amine tertiary, more preferably a diethylamino- or dimethylamino- group. Thus, preferably, the diene elastomer is a copolymer of butadiene and styrene, said copolymer comprising at least a group alkoxysilane carrying or not an amine function, preferably carrying of an amine function secondary or tertiary.
The alkoxysilane group can be represented by formula (I) (*¨)aSi (OR')bRcX (I) in which :
- *¨ represents the connection to an elastomer chain;
- the radical R represents an alkyl radical, substituted or unsubstituted, in Cl -C10, or even Cl -C8, preferably a Cl -C4 alkyl radical, more preferably methyl and ethyl;
- in the alkoxyl radical(s) of formula ¨OR', optionally partially or totally hydrolyzed to hydroxyl, R' represents an alkyl radical, substituted or not substituted, being in Cl -C10, or even Cl -C8, preferably an alkyl radical in Cl -C4, more preferably methyl and ethyl;
- X represents a grouping including the other function; preferably one amine, more preferably also a secondary or tertiary amine;
- a is 1 or 2, b is 1 or 2, etc is 0 or 1, provided that a + b + c = 3.
Those skilled in the art will understand that the value of a depends on the positioning of the group alkoxysilane within the elastomer structure. When a is 1, the group is located at the end of chain. When a is 2, it is located in the middle of the chain.
We can cite, as a function comprising a nitrogen atom, the functions amines. Suitable particularly primary amines, protected or not by a group protective, secondary, protected or not by a protective group, or tertiary.
Thus, as a secondary or tertiary amine function, we can cite the amines substituted with Cl-C10 alkyl radicals, preferably Cl-C4 alkyl, plus preferably a methyl radical or ethyl, or cyclic amines forming a heterocycle containing a nitrogen atom and at least a carbon atom, preferably 2 to 6 carbon atoms. For example, suitable methylamino-, dimethylamino-, ethylamino-, diethylamino-, propylamino-, dipropylamino-, butylamino-, dibutylamino-, pentylamino-, dipentylamino-, hexylamino-, dihexylamino-, hexamethyleneamino-, preferably diethylamino- groups and dimethylamino-. Also suitable when the amine is cyclic the groups morpholine, piperazine, 2,6-dimethylmorpholine, 2,6-dimethylpiperazine, 1 - ethylpip erazine, 2-methylpiperazine, 1-b enzy lpip erazine, piperidine, 3,3 -dimethylpiperidine, 2, 6- dimethy lpiperidine, 1 -methyl1-4-(methylamino)piperidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine, 2,5-dimethylpyrrolidine, az etidine, hexamethyleneimine, heptamethyleneimine, 5 -b enzy loxyindo le, 3 -az aspiro [5,5] undecane, 3 -aza-bicycle[3.2.2]nonane, carbazole, bistrimethylsilylamine, pyrrolidine and hexamethyleneamine, preferably pyrrolidine groups and hexamethyleneamine.
Preferably, the amine function is a tertiary amine function, of preferably diethylamine or dimethylamine.
Advantageously, the functionalized butadiene elastomer usable in the frame of the composition, preferably the copolymer of styrene and butadiene has at least two, preferably at least three, preferably at least four, more preferably all of the following characteristics:
- the amine function is a tertiary amine, more particularly a diethylamino group or dimethylamino-, - the amine function is carried by the alkoxysilane group by through a group spacer defined as an aliphatic hydrocarbon radical in Cl -C10, plus preferably again the linear hydrocarbon radical in C2 or C3, - the alkoxysilane group is a methoxysilane or an ethoxysilane, possibly partially or totally hydrolyzed into silanol, - said elastomer is mainly functionalized in the middle of the chain by a group alkoxysilane linked to the two branches of the first diene elastomer by through the silicon atom, - said elastomer has a glass transition temperature less than or equal to -50 C.
Particularly preferably, the functionalized butadiene elastomer usable in the context of the composition, preferably the copolymer of styrene and butadiene has at least two, preferably at least three, preferably at least four, more preferably all of the following characteristics:
- the function comprising a nitrogen atom is a tertiary amine, more particularly one diethylamino- or dimethylamino- group, - the function comprising a nitrogen atom is carried by the group alkoxysilane by via a linear aliphatic hydrocarbon radical at C3, - the alkoxysilane group is methoxysilane or ethoxysilane, possibly partially or totally hydrolyzed into silanol, - said elastomer is mainly functionalized in the middle of the chain by a group alkoxysilane linked to the two branches of the first diene elastomer by through the silicon atom, - said elastomer has a glass transition temperature comprised in a field ranging from -110 C to -50 C.
Functionalized diene elastomer, in particular butadiene elastomer functionalized, more particularly the functionalized styrene butadiene copolymer, usable within the framework of the present composition can be mainly obtained by functionalization a living elastomer from of an anionic polymerization by a compound comprising a group alkoxysilane, in particular chosen from substituted trialkoxysilane and dialkoxyalcylsilane compounds by a group comprising another function linked directly or via a spacer group at the atom of silicon, the function and the spacer group being as defined more high. It should be clarified that it is known to those skilled in the art that when an elastomer is modified by reaction of an agent functionalization on the living elastomer resulting from a polymerization step anionic, we obtain a mixture of modified species of this elastomer whose composition depends on the reaction conditions modification and in particular the proportion of reactive sites of the functionalization by compared to the number of living elastomeric chains. This mixture includes functionalized species at the end of the chain, coupled, star-shaped and/or non-functionalized. According to variant particularly preferred, the modified diene elastomer comprises as majority species the diene elastomer functionalized in the middle of the chain by a group alkoxysilane whose atom silicon is the connection point of the two branches of the elastomer diene. More particularly again, the diene elastomer functionalized in the middle of the chain by a group alkoxysilane represents 70% by weight of the modified diene elastomer.
Preferably, the rubber composition of the invention may contain a single elastomer diene or a mixture of several diene elastomers.
Preferably, the level of the diene elastomer, preferably of butadiene elastomer, more preferably copolymer of styrene and butadiene, in the rubber composition is included in a range ranging from 50 to 100 phr, preferably ranging from 55 to 100 pce.
Preferably the rubber composition may comprise at least one first elastomer butadiene El and a second diene elastomer E2 which can be chosen from the group made up of natural rubber, synthetic polyisoprenes and elastomers butadiene of chemical nature different from the butadiene elastomer El. Preferably, the elastomer butadiene El is a copolymer of styrene and butadiene, more preferably still a copolymer of styrene and functionalized butadiene as described above and a second elastomer diene E2 which can be chosen in the group consisting of natural rubber, polyisoprenes of synthesis and elastomers butadiene elastomer of a chemical nature different from the butadiene elastomer El.
Preferably, the rate of the second diene elastomer E2 is included in a range from 0 to 50 pce, preferably 0 at 45 p.c.
The rubber composition according to the invention can also contain minority way everything type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example thermoplastic polymers.
Reinforcing filler The rubber composition of the invention comprises at least one filler reinforcing including predominantly by weight a reinforcing inorganic filler. A load reinforcing is known to its abilities to reinforce a rubber composition usable for tire manufacturing.
The rubber composition of the invention may comprise one or more reinforcing fillers.
We can use any type of so-called reinforcing load, known for scs capacity to strengthen a rubber composition usable in particular for the manufacture of tires, for example a organic filler such as carbon black, an inorganic filler reinforcing such as silica or even a mixture of these two types of charges.
All carbon blacks are suitable as carbon blacks, in particular carbon blacks.
black conventionally used in tires or their treads rolling. Among the latter, we will particularly mention the reinforcing carbon blacks of the series 100, 200, 300, or the blacks of 500, 600 or 700 series (ASTM D-1765-2017 grades), such as black N115, N134, N234, N326, N330, N339, N347, N375, N550, N683, N772). These carbon blacks can be used as is isolated, as commercially available, or in any other form, by example as support for some of the rubber additives used. Carbon blacks could for example already be incorporated into the diene elastomer, in particular isoprene in the form of a masterbatch (see example requests W097/36724-A2 or W099/16600-A1).
By reinforcing inorganic filler, must be understood here any filler inorganic or mineral, whatever its color and origin (natural or synthetic), also called charge white, light charge or even non-black charge as opposed to carbon black, capable to strengthen on its own, with no other means than a coupling agent intermediate, a composition of rubber intended for the manufacture of tires. As is known, certain charges reinforcing inorganic substances can be characterized in particular by the presence of hydroxyl groups (-OH) on their surface.
As reinforcing inorganic fillers are suitable in particular fillers minerals of the type siliceous, preferably silica (SiO2) or of the aluminous type, in particularly alumina (A1203). There silica used can be any reinforcing silica known to those skilled in the art.
profession, in particular any silica precipitated or pyrogenic having a BET specific surface as well as a CTAB specific surface both less than 450 m2/g, preferably included in a domain ranging from 30 to 400 m2/g, in particular from 60 to 300 m2/g.
Any type of precipitated silica can be used, in particular silicas highly dispersible precipitates (called HDS for highly dispersible or highly dispersible silica).
These precipitated silicas, highly dispersible or not, are well known to those skilled in the art. We can cite, for example, the silicas described in applications W003/016215-Al and W003/016387-Al. From HDS silicas commercial, we can in particular use Ultrasil 5000GR silicas, Ultrasil 7000GR
the Evonik company, the silicas Zeosil (A) 1085GR, Zeosil 1115 MP, Zeosife 1165MP, Zeosil0 Premium 200MP, Zeosil0 HRS 1200 MP from the Solvay Company. As silica no HDS, the following commercial silicas can be used: silicas Ultrasil VN2GR, Ultrasil VN3GR from the company Evonik, Zeosile 175GR silica from the Solvay company, silicas Hi-Sil EZ120G(-D) , Hi-Sil EZ160G(-D) , Hi-Sil EZ200G(-D) , Hi-Sil 243LD, Hi-Sil 210, Hi-Sil HDP 320G from PPG.
As other examples of reinforcing inorganic fillers capable of to be used in rubber compositions of the invention can also be cited as mineral fillers of the type aluminous, in particular alumina (A1203), aluminum oxides, aluminum hydroxides, aluminosilicates, titanium oxides, carbides or nitrides of silicon, all of the reinforcing type as described for example in applications W099/28376-A2, W000/73372-A1, Al, W02004/003067-A1, W02004/056915-A2, US6610261-B1 and US6747087-B2. We can to quote in particular Baikalox A125 or CR125 aluminas (Baikowski company), (Condea), Aluminoxid C (Evonik) or AKP-G015 (Sumitomo Chemicals).
Preferably, the reinforcing inorganic filler in the composition of rubber of the invention is a silica, preferably a precipitated silica.
The physical state in which the reinforcing inorganic filler appears is indifferent, whether under form of powder, microbeads, granules, or even beads or any other densified form appropriate. Of course, we also mean by inorganic filler reinforcing mixtures of different reinforcing inorganic fillers, in particular silica as described above.
Those skilled in the art will understand that as a replacement for the inorganic filler reinforcing described below above, a reinforcing filler of another nature could be used, from when this load reinforcing material of another nature would be covered with an inorganic layer such as silica, or would contain functional sites on its surface, in particular hydroxyl, requiring the use of a coupling agent to establish the connection between this reinforcing filler and diene elastomer. As for example, we can cite carbon blacks partially or entirely covered with silica, or carbon blacks modified by silica, such as, without limitation, Ecoblacke type fillers of the CRX2000 series or CRX4000 series from the Cabot company Corporation.
A person skilled in the art will know how to adapt the total reinforcing load rate according to the use concerned, in particular depending on the type of tire concerned, for example pneumatic for motorcycle, for vehicle for tourism or for utility vehicles such as vans or weights heavy. Preferably, this rate total reinforcing load is included in a range from 10 to 200 pce, more preferably dc 30 to 180 pcc, ct cncorc more preferably from 50 to 160 pcc; the optimum being in a known manner different depending on the particular applications targeted.
Preferably, the rate of the reinforcing inorganic filler is included in the area ranging from at 120 phr, preferably from 30 to 120 phr, preferably from 50 to 90 phr.
The reinforcing filler is mainly an inorganic reinforcing filler (preferably from silica), that is to say that the reinforcing filler comprises more than 50% (>50%) in weight of a load inorganic reinforcing material such as silica relative to the total weight of the reinforcing load, preferably more than 55% by weight, more preferably more than 60% by weight.
Preferably, the reinforcing inorganic reinforcing filler, in particular silica, more preferably silica precipitated, represents 60% to 100% by weight of the total weight of the charge reinforcing, more preferably represents from 60% to 98% by weight of the total weight of the reinforcing load.
The reinforcing filler may further comprise carbon black. According to this option, the black of carbon is used at a rate less than or equal to 20 pce, more preferably less than or equal to 10 pce (for example the level of carbon black can be included in a domain ranging from 0.5 to 8 pce, notably ranging from 0.5 to 4 pce). In the indicated intervals, we benefit coloring properties (black pigmentation agent) and anti-UV of carbon blacks, without penalizing moreover the typical performances provided by the reinforcing inorganic filler.
Even more preferably, the reinforcing filler essentially consists in a mixture of black carbon and a reinforcing inorganic filler, in particular a silica, in especially a silica precipitated, the reinforcing inorganic filler being the majority by weight, by relative to the weight of black carbon.
In this presentation, the BET specific surface area is determined by gas adsorption to. the help of the Brunauer-Emmett-Teller method described in The Journal of the American Chemical Society (Vol. 60, page 309, February 1938), and more precisely according to a method adapted from the NF ISO standard 5794-1, appendix F. of June 2010 [multipoint volumetric method (5 points) -gas: nitrogen ¨ degassing under vacuum: one hour at 160 C - relative pressure range p/in: 0.05 to 0.17].
For inorganic fillers such as silica for example, the values of CTAB specific surface were determined according to standard NF ISO 5794-1, appendix G of June 2010. The process is based on the adsorption of CTAB (N-hexadecyl-N,N,N-trimethylammonium bromide) on the external surface of the reinforcing load.
Coupling agent for the reinforcing inorganic filler to the diene elastomer As indicated above, the rubber composition of the invention comprises at least one agent coupling of the reinforcing inorganic filler to the diene elastomer, the rate dc this agent dc coupling of the inorganic filler to the diene elastomer being included in a domain ranging from 12% to 18%
in weight relative to the weight of the reinforcing inorganic filler.
To couple the inorganic reinforcing filler to the diene elastomer, we use it well known at least bifunctional coupling agent (or binding agent) intended to ensure a sufficient connection, of chemical and/or physical nature, between the charge inorganic (surface of its aggregates) and the diene elastomer. By bifunctional, we mean a compound having a first functional group capable of interacting with the inorganic charge and a second functional group capable of interacting with the diene elastomer. For example, such a compound bifunctional can comprise a first functional group comprising a silicon atom, said first group functional being able to interact with the hydroxyl groups of a charge inorganic and a second functional group comprising a sulfur atom, said second group functional being able to interact with the diene elastomer.
Surprisingly, and contrary to customs of using a quantity by a maximum of 8% in weight of the coupling agent of the reinforcing inorganic filler to diene elastomer compared to the weight of the inorganic reinforcing filler, the applicant noticed that in increasing significantly the amount of the inorganic charge coupling agent reinforcing with elastomer diene in the presence of a specific processing agent in a rubber composition, could reach an unexpected property compromise and obtain a rubber composition exhibiting both good processability and hysteretic properties improved while maintaining very good rigidity and very good grip on wet surfaces.
Preferably, the level of inorganic charge coupling agent reinforcing with elastomer diene is included in a range ranging from 13% to 17% by weight relative to to the weight of the load reinforcing inorganic. Even more preferentially, the rate of this agent load coupling inorganic being included in a range ranging from 13% to 16% by weight, more preferably still from 13.5% to 15.5% by weight relative to the weight of the inorganic filler reinforcing.
Preferably, the agent for coupling the reinforcing inorganic filler to the diene elastomer is chosen from polysulphide silanes, polyorganosiloxanes, mercaptosilanes, mercaptosilanes blocked, mercaptosilane dimers, blocked mercaptosilane dimers, the oligomers of mercaptosilane, blocked mercaptosilane oligomers and mixtures thereof.

Even more preferably, the inorganic charge coupling agent reinforcing with elastomer diene is a polysulfide silane.
More particularly, it is possible to use polysulfide silanes, called symmetrical or asymmetrical according to their particular structure, as described for example in lcs applications W003/002648 (or US 2005/016651) and W003/002649 (or US 2005/016650).
Preferably, are suitable in particular, without the definition below after being limiting, silanes polysulphides corresponding to the following general formula (11):
Z - A - Sx - A - Z (II) , in which:
- x is an integer from 2 to 8 (preferably from 2 to 5);
- the symbols A, identical or different, represent a radical divalent hydrocarbon (from preferably a C1-C18 alkylene group or a C6-arylene group C12, more particularly a Cl -C10 alkylene, in particular a C1-C4 alkylene, in especially the propylene);
- the Z symbols, identical or different, correspond to one of the three formulas below: [Chcm 1]
Ra Rb in which:
- W radicals, substituted or unsubstituted, identical or different between them, represent a C1-C18 alkyl group, a C5-C18 cycloalkyl group or an aryl group in C6-C18 (preferably Cl -C6 alkyl groups, cyclohexyl or phenyl, notably C1-C4 alkyl groups, more particularly methyl and/or ethyl).
- the radicals le, substituted or unsubstituted, identical or different between them, represent a C1-C18 alkoxyl group or a C5-C18 cycloalkoxyl group (from preferably one group chosen from C1-C8 alkoxyls and C5-C8 cycloalkoxyls, more preferably also a group chosen from Cl-C4 alkoxyls, in especially the methoxyl and ethoxyl), or a hydroxyl group, or such as 2 Rh radicals represent a dialkoxyl group at C3-C18 In the case of a mixture of polysulfurized alkoxysilanes corresponding to the formula (II) above, in particular of the usual commercially available mixtures, the average value of the x is a number fractional preferably between 2 and 5, more preferably close to 4. But the rubber composition can also advantageously be understood as example with disulfurized alkoxysilanes (x = 2).
As examples of polysulfurized silanes, mention will be made more particularly polysulphides (in particular disulfurcs, trisulfurcs or tetrasulfurcs) dc bis-(alkoxyl(C1 -C4)-alkyl(C1 -C4)silyl-alkyl(C 1-C4)), such as for example bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl).
Among these compounds, bis(3-) tetrasulfide is used in particular.
trietboxysilylpropyl), abbreviated TESPT, of formula [(C2H50)3Si(CH2)3S212 or bisulfide (triethoxysilylpropyl), for short TESPD, of formula [(C2H50)3Si(CH2)3S]2. We will also cite as examples preferential polysulphides (in particular disulphides, trisulphides or tetrasulphides) of bis-(monoalkoxyl(C1-C4)-dialkyl (CI-C4)silylpropyl), more particularly bis-tetrasulfide monoethoxydimethylsilylpropyl as described in the aforementioned patent application W002/083782 (or US7217751).
Preferably, the agent for coupling the reinforcing inorganic filler to diene elastomer corresponds to formula (II) with x is an integer from 2 to 8 (preferably from 2 to

5), the symbols A, identical or different, represent a Cl -C10 alkylene group, preferably into a Cl-C4 alkylene, more preferably propylene, the symbols Z, identical or different answer the formula Si(Rb)3 with Rb, identical or different from each other, representing a group alkoxyl in Cl - C4, in particularly methoxyl and ethoxyl.
Even more preferably, the reinforcing filler coupling agent inorganic elastomer diene is chosen from the group consisting of tetrasulfide of bis(triethoxysilylpropyl), bis(trimethoxysilylpropyl) tetrasulfide, bis-(triethoxysilylpropyl) and the disulfide of bis-(trimethoxysilylpropyl), more preferably is chosen in the group made up of the bis(triethoxysilylpropyl) tetrasulfide and bis(triethoxysilylpropyl) tetrasulfide bis(trimethoxysilylpropyl).
As an example of coupling agents other than a polysulfurized alkoxysilane, we will cite in particular Bifunctional POS (polyorganosiloxanes) or even polysulfides of hydroxysilane (Rb = OH in formula I above) as described for example in applications for patent W002/30939-Al (or US6774255-B1), W002/31041-A1 (or US2004/051210-A1), and W02007/061550-A1, or more silanes or POS carrying azo-dicarbonyl functional groups, such as described for example in patent applications W02006/125532-Al, W02006/125533-Al, W02006/125534-Al.
As examples of other sulfurized silanes, we will cite for example the silanes carrying at least one thiol function (-SH) (known as mercaptosilanes) and/or at least one function thiol blocked, such as by example NXT-Silane marketed by the company Momentive, the dimers or oligomers of these silanes, as described for example in patents or patent applications US6849754, W099/09036, W02006/023815, W02007/098080, W02007/98120, EP1994038, EP2079793, W02010/072685 and W02008/055986.
Implementation agent The rubber composition of the invention comprises at least one setting agent in specific implementation, said implementing agent essentially consists of a mixture of at least a carboxylic acid comprising from 4 to 28 carbon atoms and at least one aliphatic polyol comprising from 2 to 22 carbon atoms.
Surprisingly, the applicant realized that the use of an agent of implementation specific in the presence of a level of inorganic charge coupling agent reinforcing to diene elastomer higher than that usually used (rate usually used is less than or equal to 8/0 by weight compared to the weight of the load reinforcing inorganic) in a rubber composition, makes it possible to achieve a compromise of properties unexpected and get a rubber composition having both good processability and hysteretic properties improved while maintaining very good rigidity and very good grip on wet ground.
By implementation agent is meant any compound capable of improving the Moncy index, therefore capable of improving the processability of a rubber composition including a charge reinforcing. These compounds are also called processing aids in English.
By essentially consists of within the meaning of the present description, we hears the fact that the agent implementation may contain, in addition to carboxylic acid comprising from 4 to 28 atoms of carbon and aliphatic polyol containing 2 to 22 carbon atoms, other ingredients in proportions that do not affect the characteristics and function of the agent of implementation, namely its ability to improve the processability of a rubber composition reinforced by at least one reinforcing load. Other ingredients that may be present in the implementing agent can be, for example, ethylene glycol, polyethylene glycol or dioxin.
Preferably other ingredients which may possibly be present in the setting agent implementation represents less than 10% by weight of the total weight of the processing agent work, more preferably represents less than 6% by weight of the total weight of the agent of implementation.
The processing agent used in the compositions of the invention is so a mixture of two ingredients: a polyol as defined above and a carboxylic acid as as defined above, these two ingredients representing more than 50% by weight of all the ingredients of the implementation agent work, more preferably more than 84% by weight of all of the setting agent ingredients used, more preferably even more than 90% by weight of the whole agent ingredients of implementation. The carboxylic acid usable in the conditioning agent work can be a mixture carboxylic acids as defined in the present description.

Preferably, the aliphatic polyol of the implementation agent contains 2 to 15 atoms of carbon, preferably from 2 to 10 carbon atoms.
Preferably, the aliphatic polyol of the implementation agent is chosen from the group by 1,2-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-sec-butyl-2-methyl-1,3-propanediol, trimethylolpropane, Perythritol, xylitol, sorbitol, dulcitol, mannitol, inositol and mixtures thereof.
Even more preferably, the aliphatic polyol of the setting agent work is chosen from the group consisting of 1,2-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-sec-butyl-2-methyl-1,3-propanediol, trimethylolpropane and their mixtures.
Even more preferably, the aliphatic polyol of the setting agent work is the trimethylolpropane.
Preferably, the carboxylic acid of the implementing agent comprises from 6 to 22 atoms of carbon, preferably 8 to 20 carbon atoms, even more preferably comprises from 14 to 20 carbon atoms.
Preferably, the carboxylic acid of the implementing agent is chosen from the group by caprylic acid, lauric acid, palmitic acid, acid stearic, oleic acid, acid linoleic, linolenic acid and mixtures thereof.
Preferably, the carboxylic acid of the implementing agent is a mixture of several acids carboxylic acids having 16 to 18 carbon atoms.
Preferably, the implementation agent consists essentially of an aliphatic polyol chosen from the group consisting of 1,2-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-sec-butyl-2-methyl-1,3-propanediol, trimethylolpropane and a carboxylic acid comprising 14 to 20 carbon atoms, more preferably comprising from 16 to 18 carbon atoms.
Preferably, the implementation agent consists essentially of trimethylolpropane and into a carboxylic acid comprising 16 to 18 carbon atoms.
Preferably, in the implementation agent, the weight ratio between said aliphatic polyol and said carboxylic acid is included in a range ranging from dc 1: 20 to 10: 1, dc preference is included in a range from 1:10 to 5:1.
Preferably, in the rubber composition, the setting agent rate implemented as described below above is included in a range ranging from 1 to 10 pce, preferably ranging from 1 to 5 pce.

Preferably, in the rubber composition, the level of setting agent implemented as described above is included in a range ranging from 0.2% to 3% by weight relative to to the total weight of constituents of the rubber composition, more preferably going from 0.5% to 2% by total weight constituents of the rubber composition.
The implementation agents which can be used in the context of the invention are known and marketed. HAS
As an example, we can cite the implementation agent marketed under the reference Afflux 37.
Plasticizers The rubber composition of the invention may further comprise at least a plasticizer. This plasticizer is preferably chosen from high-quality hydrocarbon resins transition temperature vitreous (Tg), low Tg hydrocarbon resins, oils plasticizers, and their mixtures. Of preferably, the plasticizer is chosen from hydrocarbon resins of high Tg, plasticizing oils, and their mixtures. Even more preferably, the plasticizer is a high quality hydrocarbon resin Tg.
The total level of plasticizer in the composition is greater than or equal to 10 pce, more preferably greater than or equal to 20 pcc, preferably 20 to 70 pcc, in particular 30 at 60 pcc.
By definition, a high Tg hydrocarbon resin is by definition a solid at temperature ct ambient pressure (20 C, 1 atm), while a plasticizing oil is liquid at room temperature and that a low Tg hydrocarbon resin is viscous at room temperature.
In known manner, high Tg hydrocarbon resins are resins hydrocarbons, thermoplastics, whose Tg is greater than 20 C.
Hydrocarbon resins, also called plasticizing resins hydrocarbons, are polymers well known to those skilled in the art, essentially based on carbon and hydrogen but can contain other types of atoms, for example oxygen, which can be used in particular as agents plasticizers or tackifying agents in polymeric matrices. They are by nature at least partially miscible (ie, compatible) at the rates used with the polymer compositions for which they are intended, so as to act as real agents diluents. They have been described for example in the work entitled Hydrocarbon Resins by R.
Mildenberg, M. Zander and G.
Collin (New York, VCH, 1997, ISBN 3-527-28617-9) whose chapter 5 is dedicated to their applications, particularly in pneumatic rubber (5.5. Rubber Tires and Mechanical Goods).
In known manner, these hydrocarbon resins can also be described as resins thermoplastic in the sense that they soften on heating and can thus be molded.
Hydrocarbon resins can be aliphatic, or aromatic or even aliphatic type/
aromatic, that is to say based on aliphatic and/or aromatic monomers.
They can be natural or synthetic, petroleum-based or not (if this is the case, also known as resins oil). As aromatic monomers suitable for example are styrene, alpha-methylstyrene, indene, ortho-, meta-, para-methylstyrene, vinyl-toluene, the para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene, any vinylaromatic monomer from a C9 cut (or more generally of a section C8 to C10). Preferably, the vinylaromatic monomer is styrene or a monomer aromatic vinyl from a C9 cut (or more generally from a C8 cut to C10). Preferably, the vinylaromatic monomer is the minority monomer, expressed as a fraction molar, in the copolymer considered.
According to a particularly preferential embodiment, the resin hydrocarbon plasticizer is chosen from the group consisting of homopolymer resins or cyclopentadiene copolymers (abbreviated CPD) or dicyclopentadiene (abbreviated DCPD), resins of homopolymers or copolymers terpene, terpene phenol homopolymer or copolymer resins, homopolymer resins or C5 cutting copolymers, cutting homopolymer or copolymer resins C9, resins of homopolymers and copolymers of alpha-methyl-styrene and mixtures of these resins.
The above preferred high Tg hydrocarbon resins are well known to man trade and commercially available, for example sold with regard to THE :
- polylimonene resins: by the company DRT under the name "Dercolyte L120"
(Mn=625 g/mol; Mw=1010 g/mol; Ip=1.6; Tg=72 C) or by the company ARIZONA under there name "Sylvagum TR7125C" (Mn=630 g/mol; Mw=950 g/mol; Ip=1.5; Tg=70 VS) ;
- C5/vinylaromatic cut copolymer resins, in particular C5/cut styrene or cut C5/C9 cut: by Neville Chemical Company under the names "Super Nevtac 78", "Super Nevtac 85" or "Super Nevtac 99", by Goodyear Chemicals under denomination "Wingtack Extra", by Kolon under the names "Hikorez T1095" and "Hikorez T1100", by Exxon under the names “Escorez 2101” and “Escorez 1273”;
- limonene/styrene copolymer resins: by DRT under the name "Dercolyte TS 105"
the company DRT, by ARIZONA Chemical Company under the names “ZT115LT” and “ZT5100”;
- hydrocarbon resins, possibly hydrogenated, composed mostly from monomers chosen from the group consisting of cyclopentadiene, dicyclopentadiene, methylcyclopentadiene and mixtures of these monomers are available commercially from suppliers such as Exxon Mobil, particularly under the references Escorez E5600, Escorez E5415, Escorez E5320, Oppera PR-383.

According to a particular embodiment of the invention, when it is included in the composition, the rate of hydrocarbon plasticizing resin Tg greater than 20 C is included in a field ranging from at 70 pce, preferably ranging from 20 to 70 pce, even more preferably from 30 to 60 pce.
The plasticizer may also contain an extcnsion oil (or oil plasticizer) liquid at 20 C, said to low Tg, that is to say which by definition has a Tg lower than -20 C, preferably lower at -40'C.
Any extension oil, whether aromatic or non-aromatic in nature known for its properties plasticizers with respect to elastomers, can be used. At room temperature (20 C), these oils, more or less viscous, are liquids (that is to say, as a reminder, substances having the capacity to eventually take the shape of their container), by difference in particular with the hydrocarbon resins high Tg which are by nature solid at room temperature.
The plasticizing oils chosen from the group are particularly suitable made up of oils naphthenics (low or high viscosity, in particular hydrogenated or not), paraffinic oils, MES (Medium Extracted Solvates) oils, TDAE (Treated Distillate) oils Aromatic Extracts), RAE oils (Residual Aromatic Extract oils), TRAE oils (Treated Residual Aromatic Extract) and SRAE oils (Safety Residual Aromatic Extract oils), mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers, sulfonate plasticizers and mixtures of these compounds.
Other additives The rubber compositions in accordance with the invention may comprise also all or part usual additives and processing agents, known to those skilled in the art and usually used in rubber compositions for tires, in particular treads, like for example fillers (reinforcing or non-reinforcing / other than those aforementioned), pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants, agents anti-fatigue, reinforcing resins (as described for example in application WO 02/10269).
Reticulation system The crosslinking system can be any type of system known to man of art in the field rubber compositions for tires. It can in particular be based sulfur, and/or peroxide and/or bismaleimides.
Preferably, the crosslinking system is based on sulfur, we then speaks of a system of vulcanization. Sulfur can be provided in any form, particularly in sulfur forin molecular, or a sulfur donor agent. At least one accelerator vulcanization is also preferentially present, and, optionally, preferentially also, we can use various known vulcanization activators such as zinc oxide, acid stearic, guanidic derivatives (in particular diphenylguanidine), or even retarders of known vulcanization.
Sulfur is used at a preferential rate of between 0.2 and 12 pce, in particularly between 1 and 10 pce.
The vulcanization accelerator is used at a preferential rate including between 0.2 and 10 pce, more preferably between 0.2 and 5.0 pce.
Any compound capable of acting as an accelerator can be used as an accelerator.
accelerator vulcanization of diene elastomers in the presence of sulfur, in particular accelerators of the type thiazoles as well as their derivatives, sulfenamide type accelerators, thiurams, dithiocarbamates, dithiophosphates, thioureas and xanthates. As examples of such accelerators, we can cite in particular the following compounds: 2-mercaptobenzothiazyl disulfide (in abbreviated MBTS), N-cyclohexy1-2-benzothiazyl sulfenamide ( CBS ), N,N-dicyclohexy1-2-benzothiazyl sulfenamide (DCBS), N-ter-buty1-2-benzothiazyl sulfenamide (TBBS), N-ter-buty1-2-benzothiazyl sulfenimide (TBSI), tetrabenzylthiuram disulfide (TBZTD), dibenzyldithiocarbamate zinc (ZBEC) and mixtures of these compounds.
Preparation of rubber compositions The rubber composition according to the invention is manufactured in suitable mixers, in using two successive preparation phases well known to those skilled in the art job :
- a first phase of work or thermomechanical mixing (so-called non-productive phase), which can be carried out in a single thermomechanical step during which we introduce, in a suitable mixer such as a usual internal mixer (for example kind Banbury), all the necessary constituents, in particular the elastomer(s) dienics, the or reinforcing fillers including the reinforcing inorganic filler, the reinforcing agent coupling of the reinforcing inorganic filler with diene elastomer, the implementation agent specific, the possible other various additives, with the exception of the crosslinking system.
The incorporation of the reinforcing filler with elastomer can be carried out in one or several times by kneading thermomechanically. In the case where the load is already incorporated in full or partly to the elastomer in the form of a masterbatch as it is described for example in applications WO 97/36724 or WO 99/16600, it is the masterbatch which is directly kneaded and if necessary the others are incorporated elastomers or fillers present in the composition which are not in the form of masterbatch, as well as possible other various additives other than the crosslinking system.
- a second phase of mechanical work (so-called productive phase ), which is carried out in a external mixer such as a roller mixer, after cooling the mixture obtained from during the first non-productive phase until a lower temperature, typically less than 120 C, for example between 40 C and 100 C. We then incorporate the system of crosslinking, and everything is then mixed for a few minutes, by example between 5 and 15 min.
The non-productive phase can be carried out at high temperature, up to a maximum temperature between 110 C and 200 C, preferably between 130 C and 185 C, for a duration generally between 2 and 10 minutes.
The final composition thus obtained is then calendered for example under the shape of a leaf or of a plate, in particular for characterization in the laboratory, or even extruded in the form of a semi-finished (or profiled) rubber. Preferably, the composition of rubber according to the invention is calendered to form a tire tread.
The composition can be either in the raw state (before crosslinking or vulcanization), or in the cooked state (after crosslinking or vulcanization), can be a semi-finished product which can be used in a tire.
The crosslinking of the composition can be carried out in a known manner in the skilled person, by example at a temperature between 130 C and 200 C, under pressure.
Tread and tire Another object of the present invention relates to a tread of pneumatic tire including a rubber composition as defined in the description above including in its fashions favorite dc achievement.
In known manner, the tread of a tire, whether it is intended to equip a vehicle with tourism or any other type of vehicle, has a rolling surface intended to be in contact with the ground when the tire rolls. The tread is provided of a sculpture including in particular sculpture elements or elementary blocks delimited by various main grooves, longitudinal or circumferential, transverse or even oblique, the elementary blocks that can be in addition to having various incisions or finer strips. The grooves constitute channels intended to evacuate water when driving on wet ground and the walls of these grooves define the edges attack and flight of the sculpture elements, depending on the direction of turn.
A tread can be made up of one and the same composition of rubber: or it can also, and advantageously, include several portions (or diapers), for example two, superimposed in the radial direction. In other words, the portions (or layers) are parallel, at least substantially, between them, as well as in the tangential plane (or longitudinal), plane defined as being orthogonal to the radial direction.
Thus, the rubber composition according to the invention can be present in the entirety of the tread according to the invention.

According to another preferred embodiment, the tread comprises at least minus one serving radially inner and a radially outer portion, the composition of rubber conforming to the invention being advantageously present in a portion radially inner band rolling of the tire according to the invention. In this case, the portion radially outer the tread is preferably constituted by a composition of rubber different from that in accordance with the present invention. The tread can also understand two compositions different from each other but both conforming to this invention, one being present in a radially outer portion of the tread, the other in a portion radially interior.
A tire having a geometry of revolution relative to an axis of rotation, its geometry is usually described in a meridian plane containing the axis of rotation of the pneumatic. For a plan given meridian, the radial, axial and circumferential directions designate respectively the directions perpendicular to the axis of rotation of the tire, parallel to the axis of rotation of the tire and perpendicular to the meridian plane. By convention, the expressions radially interior, respectively radially outer mean closer, respectively further from the axis of rotation of the tire. By axially interior, respectively axially exterior, we hear closer, respectively further away from the equatorial plane of the tire, the equatorial plane of tire being the plane passing through the middle of the rolling surface of the pneumatic and perpendicular to the axis of rotation of the tire.
The radially inner portion of the tread does not enter, by definition, not in contact with the ground when the tire is new or when the portion radially exterior of the band bearing is not sufficiently worn. On the other hand, the portion radially inner band bearing is intended to be in contact with the ground after wear of the portion radially outer the tread. Those skilled in the art therefore understand well that the part more radially external of the radially inner portion of the tread according to the invention is advantageously located above the tire tread wear indicator.
Another object of the present invention relates to a tire comprising a composition of rubber as defined in the description above including in its favorite modes of realization or comprising a tread as defined in the description above included in his favorite modes.
The tire of the invention is preferably intended to equip type motor vehicles tourism and SUV (Sport Utility Vchicics).
In the present application, pneumatic means (in English tire) a pneumatic tire or a non-pneumatic tire.

By pneumatic tire we mean a tire intended to form a cavity by cooperating with a support element, for example a rim, this cavity being able to be pressurized to one pressure greater than atmospheric pressure.
In contrast, a non-pneumatic tire means a tire which is not not fit to be pressurized.
Thus, a pneumatic tire usually has two beads intended to to get in touch with a rim, a top composed of at least one top frame and a strip of bearing, two sidewalls, the tire being reinforced by a carcass reinforcement anchored in the two beads. THE
pneumatic tires according to the invention are intended to equip in particular vehicles of all types such as passenger vehicles, two-wheeled vehicles, vehicles heavy goods vehicles, vehicles agricultural vehicles, civil engineering vehicles or aircraft or, more generally, on any rolling device.
A non-pneumatic tire is a toric body consisting of at least one polymeric material, intended to ensure the function of a tire but without being subjected to a inflation pressure. A
Non-pneumatic tire can be solid or hollow. A non-pneumatic tire hollow can hold air, but at atmospheric pressure, that is to say it has no pneumatic rigidity provided by an inflation gas at a pressure greater than atmospheric pressure.
Thus, a non-pneumatic tire usually has a base, designed for example for mounting on a rigid rim, a crown reinforcement, ensuring the connection with a tread and a deformable structure, such as rays, ribs or cells, this structure being arranged between the base and the top. Of such non-pneumatic tires do not necessarily include a sidewall. Of the non-bandages tires are described for example in documents WO 03/018332 and FR2898077. THE
non-pneumatic tires are intended to equip vehicles with tourism or both wheels.
Preferably, the tire of the invention comprising at least one tread of the invention or at least one rubber composition according to the invention is a pneumatic tire, more preferably a pneumatic tire intended to equip vehicles tourism.
The invention relates to tires both in the raw state (that is to say, before cooking) than in the cooked state (it is i.e., after vulcanization).
Preferred embodiments In view of the above, the preferred embodiments of the invention are described below:
1. Rubber composition based on at least one diene elastomer, at least minus one charge reinforcing material comprising mainly by weight an inorganic filler reinforcing, of at least one agent for coupling the reinforcing inorganic filler to the elastomer diene, of at least one agent of implementation and at least one crosslinking system, characterized in that that the agent rate of coupling of the reinforcing inorganic filler to the diene elastomer is included in a domain ranging from 12% to 18% by weight relative to the weight of the inorganic filler reinforcing and in that the implementation agent essentially consists of a mixture of at least one carboxylic acid comprising from 4 to 28 carbon atoms and at least one aliphatic polyol comprising from 2 to 22 carbon atoms.
2. Rubber composition according to embodiment 1, in which the rate coupling agent reinforcing inorganic filler with diene elastomer is included in a area ranging from 13% to 17% by weight relative to the weight of the reinforcing inorganic filler, preferably in a range ranging from 13% to 16% by weight, more preferably still 13.5%
at 15.5% by weight per relative to the weight of the reinforcing inorganic filler.
3. Rubber composition according to any of the embodiments previous, in which the agent coupling of the reinforcing inorganic filler to the diene elastomer is chosen from silanes polysulphides, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, the dimers of mercaptosilane, dimers of blocked mercaptosilane, oligomers of mercaptosilane, oligomers of blocked mercaptosilane and their mixtures.
4. Rubber composition according to any one of the embodiments previous, in which the agent coupling of the reinforcing inorganic filler to the diene elastomer is a polysulfide silane.
5. Rubber composition according to any one of the embodiments previous, in which the agent coupling of the reinforcing inorganic filler to the diene elastomer is a polysulfide silane following formula (II):
Z - A - Sx - A - Z (II) , in which:
- x is an integer from 2 to 8 (preferably from 2 to 5);
- the symbols A, identical or different, represent a radical divalent hydrocarbon (from preferably a C1 -C18 alkylene group or a C6-arylene group C12, more particularly a Cl-C10 alkylene, in particular a Cl-C4 alkylene, especially the propylene);
- the Z symbols, identical or different, correspond to one of the three formulas below: [Chem 2]

______________ If ____ R ___________ If __ R ____________ If ___ Rb R.L.
in which:
- Ra radicals, substituted or unsubstituted, identical or different between them, represent a C1-C18 alkyl group, C5-C18 cycloalkyl group or C5-C18 aryl group C6-C18 (d.c.
preferably C1-C6 alkyl groups, cyclohexyl or phenyl, especially groups C1-C4 alkyl, more particularly methyl and/or ethyl).
- Rb radicals, substituted or unsubstituted, identical or different between them, represent a C1-C18 alkoxyl group or a C5-C18 cycloalkoxyl group (preferably a group chosen from Cl -C8 alkoxyls and C5-C8 cycloalkoxyls, more preferably another group chosen from C1-C4 alkoxyls, in particular methoxyl and ethoxyl), or a hydroxyl group, or such that 2 Rb radicals represent a group C3-C dialkoxyl 1 8

6. Rubber composition according to embodiment 5, in which the agent load coupling reinforcing inorganic diene elastomer corresponds to formula (II) with x is an integer from 2 to 8 (from preferably from 2 to 5), the symbols A, identical or different, represent an alkylene group in Cl-C10, preferably into a Cl-C4 alkylene, more preferably the propylene, the symbols Z, identical or different correspond to the formula Si(Rb)3 with Rb, identical or different from each other, representing a Cl-C4 alkoxyl group, in particular methoxyl and ethoxyl.

7. Rubber composition according to any one of the embodiments previous, in which the agent coupling of the inorganic reinforcing filler to the diene elastomer is chosen from the group consisting of bis(trietboxysilylpropyl) tetrasulfide, tetrasulfide bis(trimetboxysilylpropyl), bis-(triethoxysilylpropyl) disulfide and bis-(triethoxysilylpropyl) disulfide (trimethoxysilylpropyl), more preferably is chosen from the group consisting of tetrasulfide of bis(triethoxysilylpropyl) and bis(trimethoxysilylpropyl) tetrasulfide.

8. Rubber composition according to any one of the embodiments previous, in which the aliphatic polyol of the processing agent has from 2 to 15 atoms of carbon, preferably 2 to 10 carbon atoms.

9. Rubber composition according to any one of the embodiments previous, in which the aliphatic polyol of the processing agent is chosen from the group constituted by 1,2-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-see-butyl-2-methyl-1,3-propanediol, trimethylolpropane, erythritol, xylitol, sorbitol, dulcitol, mannitol, inositol and their mixtures.

10. Rubber composition according to any one of the embodiments previous, in which the aliphatic polyol of the processing agent is chosen from the group constituted by 1,2-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-sec-butyl-2-methyl-1,3-propanediol, trimethylolpropanc and mixtures thereof.

11. Rubber composition according to any one of the embodiments previous, in which the aliphatic polyol of the processing agent is trimethylolpropane.

12. Rubber composition according to any one of the embodiments previous, in which the carboxylic acid of the implementing agent comprises from 6 to 22 atoms of carbon, preferably from 8 to 20 carbon atoms, more preferably from 14 to 20 atoms of carbon.

13. Rubber composition according to any one of the embodiments previous, in which the carboxylic acid of the processing agent is chosen from the group made up of acid caprylic acid, auric acid, palmitic acid, stearic acid, acid oleic, linoleic acid, linolenic acid and mixtures thereof.

14. Rubber composition according to any one of the embodiments previous, in which the weight ratio in the processing agent between said aliphatic polyol and said carboxylic acid is included in a range from 1:20 to 10:1, preferably is included in a field ranging from 1:10 to 5:1.

15. Rubber composition according to any one of the embodiments previous, in which the rate implementation agent is included in a range ranging from 1 to 10 pce, from preference ranging from 1 to 5 pee.

16. Rubber composition according to any one of the embodiments previous, in which the rate of implementation agent is included in a range ranging from 0.2% to 3% in weight compared to total weight of the constituents of the rubber composition, plus preferably ranging from 0.5% to 2% by weight.

17. Rubber composition according to any one of the embodiments previous, in which the diene elastomer is chosen from the group consisting of rubber natural, elastomers synthetic isoprene elastomers, synthetic butadiene elastomers and mixtures of these elastomers.

18. Rubber composition according to any one of the embodiments previous, in which the diene elastomer is an elastomer functionalized by at least one polar function including minus one oxygen atom.

19. Rubber composition according to embodiment 17, in which diene elastomer is a synthetic butadiene elastomer.

20. Rubber composition according to embodiment 19, in which diene elastomer is a DC styrene and DC butadiene copolymer.

21. Rubber composition according to embodiment 20, in which diene elastomer is a copolymer of styrene and butadiene comprising at least one polar function including at least an oxygen atom and being chosen the group consisting of silanol, the alkoxysilanes, carriers or not of an amine group, epoxide, ethers, esters, acids carboxylic and hydroxyl.

22. Rubber composition according to embodiment 21, in which diene elastomer is a copolymer based on butadiene and styrene, said copolymer comprising at least minus one group alkoxysilane carrying or not an amine function.

23. Rubber composition according to any one of embodiments 19 to 22, in which the butadiene elastomer has a measured glass transition temperature according to ASTM standard D3418-99 less than or equal to -50 C, preferably within a range ranging from -110 C to -50 C, more preferably still included in a range going dc -90 C
at -50 C.

24. Rubber composition according to any one of embodiments 19 to 23, in which the rate of the butadiene elastomer is included in a range ranging from 50 to 100 pce, preferably going from 55 to 100 pce.

25. Rubber composition according to any one of the embodiments previous, in which the rubber composition further comprises a second diene elastomer, said second elastomer diene being either natural rubber or a synthetic elastomer isoprene or an elastomer butadiene and the level of the second diene elastomer ranging from 0 to 50 phr, of preferably from 0 to 45 pce.

26. Rubber composition according to any one of the embodiments previous, in which the reinforcing inorganic filler is a silica, preferably a silica rushed.

27. Rubber composition according to any one of the embodiments previous, in which the rate of the reinforcing inorganic filler is included in the range ranging from 10 to 120 pce, from preferably from 30 to 120 phr, more preferably from 50 to 90 phr.

28. Rubber composition according to any one of the embodiments previous, in which the reinforcing filler additionally includes carbon black.

29. Rubber composition according to embodiment 28, in which the rate of carbon black is included in a range ranging from 0.5 to 8 phr, preferably from 0.5 to 4 phr.

30. Rubber composition according to any one of the embodiments previous, in which the rate of the total reinforcing load is included in a range ranging from 10 to 200 pce, preferably 30 at 180 pce, and even more preferably from 50 to 160 pce.

31. Rubber composition according to any one of the embodiments previous, in which lc crosslinking system is a sulfur vulcanization system.

32. Rubber composition according to any one of the embodiments previous ones including besides a plasticizer.

33. Rubber composition according to embodiment 32, in which the rate of plasticizer is higher or equal to IO pce, preferably is included in a range from 20 to 70 pce, preferably going from 30 to 60 pce.

34. Tire tread comprising a rubber composition defined according to one any of the realizations 1 to 33.

35. Tire comprising a rubber composition defined according to one any of embodiments 1 to 33 or comprising a tread according to the embodiment 34.
EXAMPLES
The examples presented below are intended to compare the different properties of the rubber composition according to the invention (composition Cl) in a series of compositions of sample rubber Ti to T6 and an art rubber composition anterior (TO composition).
Formulation of rubber compositions The levels of the different constituents of the rubber compositions presented in table 1 are expressed in pce, unless otherwise stated. All compositions (TO to Cl) present a system of identical crosslinking. Since the quantity of coupling agent of the inorganic filler reinforcing with the diene elastomer varies in the compositions and that this coupling agent chosen for the examples release sulfur during the crosslinking reaction, the rate of molecular sulfur is adapted accordingly for compositions TI, T2, T5, T6 and CI so that the crosslinking takes place with a sulfur level identical to the TO, T3 and T4 rubber compositions.

[Table 2]

Cl Elastomer 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 (1) Charge (2) 70.00 70.00 70.00 70.00 70.00 70.00 70.00 70.00 Load (3) 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Agent of 5.60 7.00 10.50 5.60 5.60 7.00 10.50 10.50 coupling (4) Stake agent (-) (-) 4.00 (-) 4.00 (-) 4.00 implemented (5) (-) Stake agent (-) (-) (-) (-) 6.00 (-) 6.00 (-) ) in work (6) Plasticizer (7) 39.00 39.00 39.00 39.00 39.00 39.00 39.00 39.00 Anti-oxidant 2.75 2.75 2.75 2.75 2.75 2.75 2.75 2.75 (8) DPG (9) 1.60 1.60 1.60 1.60 1.60 1.60 1.60 1.60 Antioxidant 4.60 4.60 4.60 4.60 4.60 4.60 4.60 4.60 (10) Wax (11) 1.85 1.85 1.85 1.85 1.85 1.85 1.85 1.85 Acid 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 stearic (12) Zinc oxide 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 (13) Accelerator of 1.73 1.73 1.73 1.73 1.73 1.73 1.73 1.73 vulcanization 1(14) Accelerator 0.72 0.72 0.72 0.72 0.72 0.72 0.72 0.72 of vulcanization 2(15) Sulfur (16) 1.00 0.86 0.53 1.00 1.00 0.86 0.53 0.53 Rate(**) 8% 10% 15% 8% 8% 10% 15%
15%
1.Diene elastomer: copolymer of styrene and butadiene solution amino-functionalized mid-chain alkoxysilane having a Tg = -65 C, comprising 16% by weight of styrene versus by weight of the elastomer, 46% by weight of 1,4-trans butadiene relative to the part weight butadiene, 24% by weight of 1,4-cis butadiene relative to the weight of the butadienic part and 30%
by weight of 1,2 vinyl butadiene relative to the weight of the part butadienic. This elastomer functionalized is obtained by anionic polymerization according to the process described in the description below above.
2.Reinforcing inorganic filler: precipitated silica marketed by Solvay under the name Zcosil 1165 MP specific surface BET = 160 m2/g and CTAB = 155 m2ig the surfaces being measured with the methods described in the description.
3.Carbon black: Grade N234 carbon black marketed by Cabot Corporation 4.Agent for coupling the reinforcing inorganic filler to the elastomer diene: Bis[3-(triethoxysilyl)propyl] Tetrasulfide silane (TESPT) marketed by Evonik under reference Si69;
5. Implementation agent: mixture of 25% by weight of trimethylolpropane, 70%
by weight of acids carboxylic acids having 16 to 18 carbon atoms and 5% by weight of other of ingredients, product marketed by Rheinchemie under the reference Aflux 37.
6. Implementation agent: Zinc stearate marketed by PMC Biogenix under reference Lubrazinc W with stearate purity greater than 97% by weight, 3% by weight remaining being acid octadecanoic 7.Plasticizer: DCPD resin marketed by Exxon Mobil under the reference Oppera PR-383 having a Tg = 51 C.
8.Anti-oxidant: TMQ, 1,2-dihydro-2,2,4-trimethylquinoline polymer marketed by Nocil Limited under the name Pilnox TDQ.
9.DPG: diphenylguanidine marketed by Flexys under the reference Perkacit.

36 10.Anti-oxidant: N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine marketed by Flexys under the reference Santoflex 6-PPD.
11.Wax: Redezon 500 wax marketed by Repsol Quimica 12.Stearic acid: stearic acid marketed by the company Uniqcma under the Pristcrcnc reference 4931.
13.0 zinc oxide: industrial grade zinc oxide marketed by the Umicorc company.
14.Vulcanization accelerator 1: N-cyclohexy1-2-benzothiazyl-sulfenamide marketed by Flexys under the reference Santocure CBS
15.Vulcanization accelerator 2: 2-2'-Dithiobis(benzothiazole) marketed by Nocil Limited under the trade name PILCURE MBTS
16. Sulfur: molecular sulfur marketed by SF Sulfur Corporation (**) Rate: rate of the inorganic charge coupling agent reinforcing with diene elastomer.
This rate is expressed as a percentage by weight of the coupling agent of the reinforcing inorganic filler to the diene elastomer compared to the weight of the inorganic filler reinforcing.
The TO rubber composition is representative of a composition of prior art rubber in which the level of coupling agent of the inorganic charge at diene elastomer is 8% in weight relative to the weight of the reinforcing inorganic filler.
Control rubber compositions T1 and T2 differ from composition TO
in that the rate of coupling agent of the reinforcing inorganic filler to the elastomer diene is respectively 10% and 15% by weight relative to the weight of the reinforcing inorganic filler.
Control rubber compositions T3 and T4 differ from composition TO
in that they further comprise a processing agent of a different chemical nature.
The control rubber composition T5 differs from the composition T3 in that the agent rate coupling of the reinforcing inorganic filler to the diene elastomer is 10% by weight compared to the weight of the reinforcing inorganic filler.
The control rubber composition T6 differs from the T4 composition in that the agent rate coupling of the reinforcing inorganic filler to the diene elastomer is 15% by weight compared to the weight of the reinforcing inorganic filler.
The rubber composition according to the invention Cl differs from the composition T6 by chemical nature of the implementing agent.
Preparation of rubber compositions:

37 For the following tests, we proceed to the preparation of the compositions of rubber in the way following: introduced into an internal mixer, filled to 70% by volume and whose initial temperature of tank is approximately 50 C, the diene elastomer, the reinforcing fillers, the coupling agent of the reinforcing inorganic filler with the diene elastomer, then, after one to two minutes of mixing, the various other ingredients including the processing agent with the exception of the system of vulcanization. We then carry out thermomechanical work @hase non-productive) in one step (duration total mixing equal to approximately 5 min), until reaching a temperature maximum fall about 165 C.
The mixture thus obtained is recovered, cooled, then added the vulcanization system (sulfur and accelerators) on an external mixer (homo-finisher) at 70 C, in mixing everything (phase productive) for approximately 5 to 6 min.
The compositions thus obtained are then calendered either in the form of plates (thickness from 2 to 3 mm) or thin sheets of rubber for measuring their properties physical or mechanical after cooking, or in the form of profiles that can be used directly, after cutting and/or assembly in the desired dimensions, for example as semi-finished products for tires, in particular as tire treads.
The crosslinking of the rubber compositions is carried out at 150 C for 40 min under pressure.
Properties of rubber compositions:
The properties of the compositions are presented in Table 2 below.
[Table 2]
TO Ti T2 T3 T4 T5 T6 Cl Mooney Index (performance 100 109 117 118 118 118 124 131 in base 100) G* at 60 C
(performance 100 97 98 98 104 103 103 97 in base 100) tan(8) at 0 C
(performance 100 101 102 112 115 112 102 107 in base 100)

38 tan(8)max at (performance in base 100) When increasing the level of inorganic charge coupling agent reinforcing with elastomer diene (comparison of the TO composition to the Ti and T2 compositions), we observed, at iso-rigidity (descriptor G* at 60 C), a significant increase in the Monney index reflecting a decrease of the viscosity of the Ti and T2 compositions therefore an improvement in their processability in relation to control composition TO. The values of tan(8)max at 23 C of the Ti and T2 are also increased compared to that of the control composition TO, representing a improvement of hysteretic properties at 23 C, therefore a reduction in resistance to turnover compared to that of the TO composition. The wet adhesion property of the compositions Ti and T2 (descriptor tan(8) at 0 C) is not significantly modified.
When adding a processing agent to the TO rubber composition to get respectively the rubber composition T3 and the rubber composition T4, we see, at iso-stiffness, as expected, a significant improvement in the processability of compositions 13 and 14 compared to that of the TO composition. We also note a significant improvement in wet grip (tan (8) at 0 C significantly increased) but to the detriment of properties hysteretic at 23 C, therefore to the detriment of rolling resistance. There rolling resistance of the composition TO is better than those of compositions 13 and 14. Both implementation agents, although they have different chemical natures, they make it possible to obtain the same properties dc rubber jack for compositions 13 and 14 when these rubber compositions include 8% by weight of coupling agent of the reinforcing inorganic filler to the elastomer diene.
Increasing the rate of inorganic charge coupling agent reinforcing with elastomer diene in composition 13 to obtain composition 15 does not improve none of the properties of rubber material measured. The processability, wet grip of the composition 15, iso-rigidity, are equivalent to those of composition 13. Just like the composition T3, composition 15 nc does not present the desired hysteretic properties. In fact, the rolling resistance dc la composition 15 is less good than that of composition TO.
The increase in the level of coupling agent with the inorganic filler reinforcing with elastomer diene in composition 14 to obtain composition 16 allows gain in processability (comparison composition 16 compared to 14). On the other hand, the properties wet grip and the hysteretic properties of composition 16, at iso-rigidity, are less than or equivalent to those of composition 14. As for composition 14, the properties hysterics of the

39 composition T6 are significantly lower than those of the composition TO, translating a unsatisfactory rolling resistance.
Completely unexpectedly, when replacing the implementation agent (6) by the placing agent implemented (5) in the composition T6 to obtain the composition Cl according to the invention we observe a significant improvement in processability which is not carried out at detriment of properties hysteretic at 23 C (comparison Cl composition according to the invention with composition T6 control). In Indeed, the Cl composition according to the invention has properties hysteretic at 23 C equivalent to the composition TO witness. In addition compared to the control composition TO, the Cl composition according to the invention presents, at iso-rigidity, a significant improvement in wet grip (value of tan (O) at 0 C increased significantly for the Cl composition by relation to the composition witness TO).
These examples show that a specific implementation agent associated with a high rate of agent coupling of the reinforcing inorganic filler to the diene elastomer in the composition conforming to the invention makes it possible to improve, in a surprising manner, the compromise of performance processability-wet grip-rolling resistance at iso-rigidity.

Claims (15)

40 1. Rubber composition based on at least one diene elastomer, at least minus one charge reinforcing material comprising mainly by weight an inorganic filler reinforcing, minus one agent for coupling the reinforcing inorganic filler to the elastomer diene, from at least one processing agent and at least one crosslinking system, characterized in that that the rate of coupling agent of the reinforcing inorganic filler at diene elastomer is included in a range ranging from 12% to 18% by weight relative to the weight of the load reinforcing inorganic and in that the implementation agent consists essentially in one mixture of at least one carboxylic acid containing 4 to 28 atoms carbon and least one aliphatic polyol comprising 2 to 22 carbon atoms. 2. Rubber composition according to claim 1, in which the coupling agent rate of the reinforcing inorganic filler to the diene elastomer is included in a domain going from 13% to 17% by weight relative to the weight of the inorganic filler reinforcing, preferably in a range ranging from 13% to 16% by weight, more preferably still from 13.5% to 15.5% by weight relative to the weight of the inorganic filler reinforcing. 3. Rubber composition according to any one of the claims precedents, in in which the agent for coupling the reinforcing inorganic filler to the diene elastomer is chosen from polysulphide silanes, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, mercaptosilane dimers, dimers of blocked mercaptosilane, mercaptosilane oligomers, blocked mercaptosilane oligomers and their mixtures. 4. Rubber composition according to any one of the claims previous, in in which the agent for coupling the reinforcing inorganic filler to diene elastomer is a polysulfide silane. 5. Rubber composition according to any one of claims previous, in in which the aliphatic polyol of the implementing agent comprises from 2 to 15 carbon atoms, preferably from 2 to 10 carbon atoms. 6. Rubber composition according to any one of the claims previous, in in which the aliphatic polyol of the implementing agent is chosen from the group formed by 1,2-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-sec-butyl-2-methyl-1,3-propanediol, trimethylolpropane, erythritol, xylitol, sorbitol, dulcitol, mannitol, inositol and mixtures thereof. 7. Rubber composition according to any one of claims previous, in in which the aliphatic polyol of the implementing agent is chosen from the group formed by 1,2-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-sec-butyl-2-methyl-1,3-propanediol, trimethylolpropane and their mixtures. 8. Rubber composition according to any one of claims previous, in which the carboxylic acid of the agent used comprises dc 6 to 22 atomcs dc carbon, preferably 8 to 20 carbon atoms, preferably 14 to 20 carbon atoms. 9. Rubber composition according to any one of claims previous, in in which the diene elastomer is chosen from the group consisting of natural rubber, isoprene synthetic elastomers, synthetic elastomers butadiene and mixtures of these elastomers. 10. Rubber composition according to any one of claims previous, in which the diene elastomer is an elastomer functionalized by at least a function polar comprising at least one oxygen atom. 11. Rubber composition according to any one of the claims, in which the diene elastomer is a synthetic butadiene elastomer; more preferably one synthetic butadiene elastomer having a transition temperature vitreous measured according to the ASTM D3418-99 standard less than or equal to -50 C, preferably having a temperature of glass transition included in a range from -110 C to -50 C, more preferably still included in a range from -90 C to -50 C. 12. Rubber composition according to any one of claims previous, in in which the reinforcing inorganic filler is a silica, preferably a precipitated silica. 13. Rubber composition according to any one of claims previous ones including in addition a plasticizer. 14. Pneumatic tread comprising a rubber composition defined according to any one of claims 1 to 13. 15. Tire comprising a rubber composition defined according to one any of claim 1 to 13 or comprising a tread according to claim 14.