WO2002072689A1 - Composition de caoutchouc pour bande de roulement de pneumatique et pneumatique - Google Patents
Composition de caoutchouc pour bande de roulement de pneumatique et pneumatiqueInfo
- Publication number
- WO2002072689A1 WO2002072689A1 PCT/EP2002/002560 EP0202560W WO02072689A1 WO 2002072689 A1 WO2002072689 A1 WO 2002072689A1 EP 0202560 W EP0202560 W EP 0202560W WO 02072689 A1 WO02072689 A1 WO 02072689A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rubber composition
- phr
- composition according
- diene
- diene elastomer
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
Definitions
- Rubber composition for tire and tire tread Rubber composition for tire and tire tread:
- the present invention relates to a crosslinkable or crosslinked rubber composition which can be used to form a tire casing tread, such a tread having in particular improved wear resistance, and a tire casing incorporating this tread rolling.
- the invention applies in particular to passenger car type tires.
- tread compositions of amorphous or semi-crystalline polymers having a high glass transition (Tg) or melting temperature and a reduced molecular mass use which has the effect of improve the grip on dry or wet ground of the corresponding tires but also to penalize their resistance to wear.
- the patent document US-A-5,901,766 discloses, in its exemplary embodiments, the use in a tread composition intended to exhibit improved abrasion: of a polybutadiene with a high cis linkage rate which exhibits a glass transition temperature (Tg) of -103 ° C, in an amount equal to or greater than 50 phr (phr: parts by weight per hundred parts of elastomers), - of a copolymer of styrene and butadiene prepared in emulsion and presenting a
- Tg of -55 ° C. in an amount less than or equal to 50 phr, of a plasticizing resin belonging to the group consisting of hydrocarbon resins (including in particular resins of the polydicyclopentadiene type), phenol / acetylene resins (non-hydrocarbon), resins derived from rosin and mixtures of such resins.
- a plasticizing resin belonging to the group consisting of hydrocarbon resins (including in particular resins of the polydicyclopentadiene type), phenol / acetylene resins (non-hydrocarbon), resins derived from rosin and mixtures of such resins.
- resins of the coumarone / indene type and optionally of the phenol / acetylene type according to a total amount of resin equal to 15 phr, of an aromatic plasticizer oil, in an amount greater than or equal to 28.75 pce, and - a reinforcing filler consisting of 70 pce
- a disadvantage of the rubber composition described in this latter document lies in the relatively high amount of aromatic plasticizer oil which is used, due to the polluting nature of the latter vis-à-vis the environment. Indeed, this oil tends to exude from the tread by compression during prolonged rolling, due to its volatility.
- a drawback common to all of the known tread compositions lies in the relative disparity in the performance levels achieved by the corresponding tires, in particular in rolling resistance and grip, in plus improved wear resistance.
- the object of the present invention is to remedy this state of affairs, and it is achieved in that the applicant has unexpectedly discovered that the association, with one or more diene elastomers comprising (pce: parts by weight per hundred parts of elastomer (s)): - in an amount ranging from 30 to 100 phr, one or more diene elastomers each having a glass transition temperature of between -65 ° C and -10 ° C, and
- the bearings comprise a plasticizing oil as a plastic
- this improvement in wear resistance implies a reduction in compression compaction to which the tread according to the invention is subjected during rolling and, consequently, a reduction in the rolling loss of the plasticizing oil, such as aromatic oil.
- this initial quantity of oil in the composition according to the invention varies from 0 to 15 phr and, even more preferably, said composition is completely devoid of plasticizing oil.
- Said composition then comprises said diene elastomer (s) having a Tg of between -65 ° C and -10 ° C in an amount ranging from 30 to 50 phr, and said diene elastomer (s) having a Tg of between -110 ° C and - 80 ° C in an amount ranging from 70 to 50 pce.
- the plasticizing hydrocarbon resin it is then present in said composition in an amount ranging from 25 to 35 phr.
- this plasticizing hydrocarbon resin according to the invention makes it possible to confer improved endurance on a tire casing incorporating it in its tread, because this resin makes it possible to minimize the migration of plasticizing oils, such as aromatic, paraffinic or naphthenic oils, into the adjacent mixtures of the envelope and, consequently, to minimize the alteration of the properties of said mixtures, such as their rigidity and their resistance to cracking, which improves the resistance of the envelope to the separation of the triangulation crown plies which it comprises in its crown reinforcement (this resistance to the separation of the plies is sometimes called resistance to "cleavage" by man of the job).
- plasticizing oils such as aromatic, paraffinic or naphthenic oils
- diene elastomer is understood in known manner an elastomer derived at least in part (homopolymer or copolymer) from diene monomers (monomers carrying two carbon-carbon double bonds, conjugated or not).
- the or each diene elastomer of the composition according to the invention is said to be
- highly unsaturated that is to say that it is derived from conjugated diene monomers having a molar level of units derived from conjugated dienes which is greater than 50%.
- said diene elastomer (s) whose Tg is between -65 ° C and -10 ° C belong to the group consisting of styrene and butadiene copolymers prepared in solution, copolymers of styrene and butadiene prepared, in emulsion, polyisoprenes natural, synthetic polyisoprenes with a cis-1,4 chain rate greater than 95% and by a mixture of these elastomers, and
- Said diene elastomer (s) of Tg between -110 ° C and -80 ° C preferably have a glass transition temperature ranging from -105 ° C to -90 ° C, and they include butadiene units at a rate equal to or greater than 70%. Even more preferably, said or each minority elastomer consists of a polybutadiene having a rate of cis-1,4 chains greater than 90%.
- said composition comprises, as diene elastomer (s) whose Tg is between -65 ° C and -10 ° C, at least one styrene copolymer and of butadiene prepared in solution which has a Tg of between -50 ° C and -15 ° C, or a copolymer of styrene and of butadiene prepared in emulsion having a Tg of between -65 ° C and -30 ° C.
- diene elastomer whose Tg is between -65 ° C and -10 ° C
- a copolymer of styrene and of butadiene prepared in emulsion having a Tg of between -65 ° C and -30 ° C.
- said composition comprises a cutting of said one or more diene elastomers of Tg between -65 ° C and -10 ° C with said one or more diene elastomers of Tg between -110 ° C and -80 ° C.
- said composition comprises cutting at least one of said polybutadienes having a rate of cis-1,4 chains greater than 90% with at least one of said copolymers styrene and butadiene prepared in solution.
- said composition comprises cutting at least one of said polybutadienes having a rate of cis-1,4 linkages greater than 90% with at least one of said copolymers styrene and butadiene prepared as an emulsion.
- said composition comprises cutting at least one of said polybutadienes having a rate of cis-1,4 chains greater than 90% with at least one of said polyisoprenes natural or synthetic.
- copolymer of styrene and butadiene prepared as an emulsion it is advantageous to use copolymers having a varying amount of emulsifier. substantially from 1 phr to 3.5 phr, for example the E-SBR copolymers comprising respectively 1J phr and 1.2 phr of emulsifier. which are both described in the French patent application n ° 00 01339 (see paragraph I. examples of embodiments contained in the description of this request).
- the plasticizing resin which is specifically selected to be used in the composition according to the invention is a resin which is exclusively hydrocarbon-based, that is to say which contains only carbon and hydrogen atoms.
- This resin can be of aliphatic and / or aromatic type and it is such that it is miscible in said diene elastomer (s).
- Its glass transition temperature is between 10 and 150 ° C and its number average molecular weight is between 400 and 2000 g / mol.
- aliphatic resins suitable, for example, resins based on pentene, butene, isoprene, piperylene and comprising reduced amounts of cyclopentadiene or dicyclopentadiene;
- polycyclopentadiene or polydicyclopentadiene type resins that is to say comprising mainly cyclopentadiene or dicyclopentadiene units, cannot be used in a composition according to the present invention (these dicyclopentadiene based resins are defined in the article by MJ Zohuriaan-Mehr and H. Omidian JMS REV MACROMOL. CHEM. PHYS. C40 (l), 23-49 (2000)).
- the plasticizing resin of the composition according to the invention has a glass transition temperature ranging from 30 ° C to 100 ° C, a number average molecular weight of between 400 and 1000 g / mol, and a lower polymolecularity index. to 2.
- an aliphatic resin which has a glass transition temperature ranging from 50 ° C. to 90 ° C. and whose mass fractions of aliphatic and aromatic units are respectively higher is used as plasticizing resin. 95% and less than 3%.
- an aromatic resin which has a glass transition temperature ranging from 30 to 60 ° C. and whose mass fractions of aliphatic and aromatic units vary by 30% respectively is used as plasticizing resin. at 50% and from 70% to 50%.
- an aliphatic / aromatic type resin which has a glass transition temperature of 60 ° C. and whose mass fractions of aliphatic and aromatic units are respectively of 80% and 20%.
- composition according to the invention also comprises a reinforcing filler, which can be present in said composition in an amount varying from 50 to 150 phr.
- said composition comprises carbon black as a reinforcing filler.
- said composition comprises a reinforcing white filler as a reinforcing filler.
- the term "reinforcing white filler" means a filler
- the reinforcing white filler is, in whole or at least mainly, silica (Si ⁇ 2).
- the silica used can be any reinforcing silica known to a person skilled in the art, in particular any precipitated silica having a BET surface as well as a CTAB specific surface both of which are less than 450 m 2 / g, even if the highly dispersible precipitated silicas are preferred. .
- said silica having specific BET or CTAB surfaces which both range from 80 m 2 / g to 260 m 2 / g.
- the BET specific surface is determined in a known manner, according to the Brunauer-Emmet-Teller method described in "The Journal of the American Chemical Society” Vol. 60, page 309, February 1938 and corresponding to standard AFNOR-NFT-45007 (November 1987); the CTAB specific surface is the external surface determined according to the same standard AFNOR-NFT-45007 of November 1987.
- highly dispersible silica is understood to mean any silica having a very high ability to disaggregate and to disperse in an elastomeric matrix, observable in a known manner by electron or optical microscopy, on fine sections.
- Such preferential highly dispersible silicas mention may be made of Perkasil KS 430 silica from Akzo, BV 3380 silica from Degussa, Zeosil 1165 MP and 1115 MP silica from Rhodia, Hi- silica Sil 2000 from the company PPG, the Zeopol 8741 or 8745 silicas from the Huber company, treated precipitated silicas such as for example the silicas "doped" with aluminum described in application EP-A-0 735 088.
- the physical state under which the reinforcing white charge is present is immaterial, whether in the form of powder, microbeads, granules, or even beads.
- the term reinforcing white filler is also understood to mean mixtures of different reinforcing white fillers, in particular highly dispersible silicas as described above.
- aluminas (of formula A1 2 0 3 ), such as aluminas with high dispersibility which are described in the European patent document EP-A-810 258, or also
- a reinforcing white filler as a reinforcing filler in the composition according to the invention makes it possible to improve overall the adhesion and rolling resistance performances, in comparison with the use of carbon black for said filler, this for the same improvement in wear resistance compared to that of known compositions comprising a plasticizer oil as a plasticizer.
- a cutting (mixture) of a reinforcing white filler and carbon black is used, as reinforcing filler.
- all the carbon blacks conventionally used in the treads of tire covers in particular blacks of the HAF, ISAF, SAF type, are suitable. Mention may be made, without limitation, of the blacks NI 15, N134, N234, N339, N347, N375.
- Carbon blacks which are partially or entirely covered with silica are also suitable for constituting the reinforcing filler.
- carbon blacks modified with silica such as, without limitation, reinforcing fillers which are marketed by the company CABOT under the name "CRX 2000", and which are described in the international patent document OA-96 / 37547.
- the or at least one of the diene elastomers which can be used in the composition according to the invention may comprise one or more functional groups specifically active for coupling to said reinforcing filler.
- this document teaches the use of a functionalizing agent for a living polymer obtained anionically, with a view to obtaining an active function for coupling to silica.
- This functionalizing agent consists of a cyclic polysiloxane, such as a polymethylcyclo -tri, -tetra or -deca siloxane, said agent being, preferably, hexamethylcyclotrisiloxane.
- the functionalized polymers thus obtained can be separated from the reaction medium leading to their formation by steam extraction of the solvent, without their macrostructure and, consequently, their physical properties changing.
- the rubber composition according to the invention also conventionally comprises a reinforcing white filler / elastomer matrix bonding agent (also called coupling agent), which has the function of ensuring a sufficient bonding (or coupling), of a nature chemical and / or physical, between said white charge and the matrix, while facilitating the dispersion of this white charge within said matrix.
- a reinforcing white filler / elastomer matrix bonding agent also called coupling agent
- Such a bonding agent has for example as simplified general formula "YTX", in which: - Y represents a functional group (function "Y") which is capable of binding physically and / or chemically to the charge white, such a bond being able to be established, for example, between a silicon atom of the coupling agent and the hydroxyl (OH) groups on the surface of the filler (for example the surface silanols when it is silica );
- - X represents a functional group (“function X”) which is capable of physically and / or chemically bonding to the elastomer, for example via a sulfur atom;
- - T represents a hydrocarbon group making it possible to link Y and X.
- Such liaison agents have been described in a very large number of documents and are well known to those skilled in the art. It is possible in fact to use any binding agent known for or capable of ensuring effectively, in the diene rubber compositions which can be used for the manufacture of tires, the bond between silica and diene elastomer, such as for example organosilanes, in particular polysulphurized alkoxysilanes or mercaptosilanes, or polyorganosiloxanes carrying the abovementioned X and Y functions.
- organosilanes in particular polysulphurized alkoxysilanes or mercaptosilanes
- polyorganosiloxanes carrying the abovementioned X and Y functions.
- the coupling agent - preferably used in the rubber compositions in accordance with the invention is a polysulphurized alkoxysilane, carrying in a known manner two functions denoted here "Y” and “X”, graftable on the one hand on the white filler at by means of the "Y” function (alkoxysilyl function) and on the other hand on the elastomer by means of the function
- polysulphurized alkoxysilanes called “symmetrical” or “asymmetrical” according to their particular structure, are used, as described for example in patents US-A-3,842,111, US-A-3,873,489, US-A-3 978 103, US-A-3 997 581, US-A-4 002 594, US- A-4 072 701, US-A-4 129 585, or in more recent patents US-A-5 580 919, US -A-5 583 245, US-A-5 650 457, US-A-5 663 358, US-A-5 663 395, US-A-5 663 396, TJS-A-5 674 932, US-A -5,675,014, US-A-5,684,171, US-A-5,684,172, US-A-5,696,197, US-A-5,708,053, US- A-5,892,085, EP-A-1 043 357 which detail such known compounds.
- - A is a divalent hydrocarbon radical
- radicals R 1 substituted or unsubstituted, identical or different from each other, represent a C 1 -C 6 alkyl group , C 5 -C 18 cycloalkyl group or C ⁇ -C ⁇ $ aryl group;
- radicals R ⁇ substituted or unsubstituted, identical or different from each other, represent a C ⁇ -C 18 alkoxyl or C 5 -C 18 cycloalkoxyl group.
- n is preferably an integer from 3 to 5.
- the average value of "n" is a fractional number, preferably between 3 and 5, more preferably close to 4.
- the radical A substituted or unsubstituted, is preferably a divalent hydrocarbon radical, saturated or unsaturated, containing from 1 to 18 carbon atoms.
- Particularly suitable are C ⁇ -C ⁇ 8 alkylene groups or C 6 -C 12 arylene groups, more particularly C ⁇ -C ⁇ 0 alkylene, in particular C 2 -C, especially propylene.
- the radicals R * are preferably C 1 -C 6 alkyl, cyclohexyl or phenyl groups, in particular C 1 -C 4 alkyl groups, more particularly methyl and / or ethyl.
- the R radicals are preferably alkoxyl groups or C ⁇ -C 8 cycloalkoxy, C 5 -C 8, more particularly methoxy and / or ethoxy.
- Such so-called "symmetrical" polysulphurized alkoxysilanes, as well as some of their methods of production, are for example described in recent patents US-A-5,684,171 and US-A-5,684,172 giving a detailed list of these known compounds, for n varying from 2 to 8.
- the polysulphurized alkoxysilane used in the invention is a polysulphide, in particular a tetrasulphide, of bis (alkoxyl (C ⁇ -C4) silylpropyl), more preferably of bis (trialkoxyl (C ⁇ -C4) silylpropyl), in particular of bis (3-triethoxysilylpropyl) or bis (3-trimethoxysilylpropyl).
- TESPT bis (triethoxysilylpropyl) tetrasulfide
- Si69 or X50S when it is supported at 50% by weight on carbon black
- Silquest A1289 in both cases commercial mixture of polysulphides with an average value for n which is close to 4
- the content of polysulphurized alkoxysilane can be within a range of 1% to 15% relative to the weight of reinforcing white filler.
- the polysulphurized alkoxysilane could be grafted beforehand (via the "X” function) on the diene elastomer of the composition of the invention, the elastomer thus functionalized or “precoupled” then comprising the free "Y” function for the reinforcing white filler.
- the polysulphurized alkoxysilane could also be grafted beforehand (via the "Y” function) onto the reinforcing white filler, the filler thus "precoupled” can then be linked to the diene elastomer via the free "X" function.
- the coupling agent either grafted onto the reinforcing white filler, or in the free state (Le., Not grafted).
- compositions in accordance with the invention contain, in addition to the abovementioned diene elastomer (s), said plasticizing resin, optionally said plasticizing oil, said reinforcing filler and said reinforcing white filler / elastomer binding agent, all or part of the other constituents and additives usually used in rubber mixtures, such as pigments, antioxidants, anti-ozonizing waxes, a crosslinking system for example based on sulfur and / or peroxide and / or bismaleimides, one or more agents for covering any filler reinforcing white, such as alkylalkoxysilanes, polyols, amines, aids, etc.
- compositions according to the invention can be prepared according to known methods of thermomechanical working of the constituents in one or more stages. They can for example be obtained by thermomechanical work in one step in an internal mixer which lasts from 3 to 7 minutes, with a speed of rotation of the pallets of 50 rpm, or in two stages in an internal mixer which last 3 to 5 minutes and 2 to 4 minutes respectively, followed by a finishing step carried out at around 80 ° C, during which the sulfur and the vulcanization accelerators are incorporated in the case of a composition to be crosslinked with sulfur .
- a tire casing tread according to the invention consists of said rubber composition according to the invention, and a tire casing according to the invention comprises this tread.
- Size exclusion chromatography or SEC makes it possible to physically separate the macromolecules according to their size in the swollen state on columns filled with porous stationary phase.
- the macromolecules are separated by their hydrodynamic volume, the largest being eluted first.
- the SEC makes it possible to understand the distribution of the molecular weights of the resins. From commercial standard products of low molecular weight polystyrene (between 104 and 90,000 g / mol), the average masses in number Mn and in weight Mw are determined and the polydispersity index Ip calculated.
- Each resin sample is dissolved in tetrahydrofuran at a concentration of approximately 1 g / l.
- the apparatus used is a "WATERS, Alliance 2690 model” chromatograph.
- the elution solvent is tetrahydrofuran (mobile phase), the flow rate of 1 ml / min., The system temperature of 35 ° C and the analysis time of 40 min.
- For the stationary phase a set of three columns in series is used, with respective trade names "WATERS type STYRAGEL HR4E” (mixed bed column), "WATERS type STYRAGEL HR1" (porosity 100 Angstrom) and "WATERS STYRAGEL HR0.5 »(Porosity 50 Angstrom).
- the volume injected with the solution of each resin sample is 100 ⁇ l.
- the detector is a “WATERS model 2410” N differential refractometer and the software for operating the chromatographic data is the “WATERS MILLENIUM” system (version 3-2).
- Tg of the elastomers and of the plasticizers were measured using a differential scaror calorimeter.
- the performances of the tire casings whose treads are based on these rubber compositions have been measured by means of relative performance indices, with respect to a reference index 100 characterizing a “control” envelope (a performance index greater than this base 100 reflecting a performance greater than that of the corresponding “control” envelope).
- the rolling resistance of each of the envelopes tested was measured by rolling on a steering wheel, at an ambient temperature of 25 ° C, under a load of 392 daN and at a speed of 80 km / h, the internal pressure of the envelope being 2.1 bars.
- each casing has been determined by means of a relative wear index which is a function of the remaining rubber height, after driving on a hazy road circuit (or, in the case of the example 4, on a severe circuit for wear which is very hazy and whose coating is characterized by micro-roughness), at an average speed of 77 km / h and until the wear reaches the indicators d 'wear arranged in the grooves of the treads.
- this relative wear index was obtained by comparing the height of the remaining rubber of a tread according to the invention with the height of the remaining rubber of a "control" tread, which by definition has a wear index of 100.
- the grip of each tire casing tested was assessed by measuring the braking distances in "two-wheel locked” braking mode and in "ABS" braking mode, and this on both dry and wet ground . More precisely, the braking distance in “two-wheel locked” mode was measured by passing from a speed of 40 km / h to a speed of 0 km / h, both on dry and on wet ground, while the braking distance in "ABS” mode was measured, on dry ground, passing from a speed of 70 km / h to 20 km / h and, on wet ground, passing from a speed of 40 km / h to 10 km / h.
- This resistance was measured by a rolling test on a steering wheel, the surface of which is provided with obstacles (bars and "polar" which come to stress the edges of the seat belt.
- the envelope consisting of two working top plies NSTl and NST2), at an ambient temperature of 20 ° C., under a load of 490 daN or 569 daN (respectively in Examples 3 and 5 below) and at a speed of 75 km / h, the internal pressure of the casing being regulated at 2.5 bar.
- This test is stopped when a deformation of the crown reinforcement of the envelope is detected.
- Each envelope was previously “steamed” (not assembled) for 4 weeks at 65 ° C.
- a “control” rubber composition T1 and a rubber composition according to invention II were prepared, each being intended to constitute a tread for a tire of the “touring” type.
- Table 1 contains: the formulation of each of these compositions T1 and II; the properties of each composition T1 and II in the unvulcanized and vulcanized state; the performance of tires, the respective treads of which consist of these compositions T1 and II.
- S-SBR A copolymer of styrene and butadiene prepared in solution having: a rate of 1.2 chains of 58%, a rate of styrenic chains of 25%, a rate of trans chains of 23%, a Mooney ML viscosity (l + 4) at 100 ° C of 54, an amount of extension oil equal to 37.5 phr, and a glass transition temperature Tg of -30 ° C.
- BR A polybutadiene having: a very high rate of cis-1,4 linkages, of approximately 93%, and a glass transition temperature Tg of -103 ° C.
- plasticizing resin RI resin sold by the company Cray Valley under the name "W100", having: an aliphatic chain rate of 49%, an aromatic chain rate of 51%, average molecular weights in number Mn and by weight Mw of 750 g / mol and 1300 g / mol, respectively, and - a glass transition temperature Tg of 55 ° C.
- composition II under a dynamic modulus of high modulus (0J MPa) is provided for substantially equal to the corresponding Tg of the “control” composition Tl.
- Tire performance results show that the incorporation of a plasticizing resin with a Tg equal to 55 ° C. and a Mn equal to 750 g / mol in the tread composition II comprising silica as reinforcing filler makes it possible to improve the wear resistance of a tire whose tread consists of said composition II, thanks to the aforementioned miscibility of the resin according to the invention, this without penalizing the adhesion on dry or wet soils such tires, the behavior of a vehicle fitted with these tires and the rolling resistance of the latter.
- composition II comprises plasticizing oil in an amount which is significantly reduced compared to that which characterizes the composition Tl.
- S-SBR B copolymer of styrene and butadiene prepared in solution having a rate of styrenic sequences of 29%, a rate of trans-1,4 sequences of 78%, a Mooney viscosity ML (l + 4) at 100 ° C of 58, an amount of extension oil equal to 37.5 phr, and a glass transition temperature Tg of -50 ° C.
- S-SBR C copolymer of styrene and butadiene prepared in solution having, a rate of 1,2 chains of 24%, a rate of styrenic chains of 40%, a Mooney viscosity ML (l + 4) at 100 ° C of 54, an amount of extension oil equal to 37.5 phr, and a glass transition temperature Tg of -30 ° C.
- S-SBR D copolymer of styrene and butadiene prepared in solution having a rate of styrenic sequences of 27.5%, a rate of trans-1,4 sequences of 78%, a Mooney viscosity ML (l + 4) at 100 ° C of 54, and a glass transition temperature Tg of -50 ° C.
- plasticizing resin R2 resin marketed by the company HERCULES under the name "R2495", having: an aliphatic linkage rate of 97%, an aromatic linkage rate of 0%, average molecular weights in number Mn and in weight Mw of 820 g / mol and 1050 g / mol respectively, and a glass transition temperature Tg of 88 ° C. It will be noted that the Tg of composition 12 according to the invention under a dynamic stress of high modulus (0.7 MPa) is expected to be relatively close to the corresponding Tg of the “control” composition T2.
- Tire performance results show that the incorporation of a plasticizing resin of Tg equal to 88 ° C. and of Mn equal to 820 g / mol in the tread composition 12 comprising, as reinforcing filler, a cutting of 50% silica and 50% carbon black makes it possible to improve the resistance to wear and the grip on dry ground of a tire of the “high-end” type whose tread consists of said composition 12, thanks to the aforementioned miscibility of the resin according to the invention, practically without penalizing the grip on wet ground of such tires, the behavior on wet ground of a vehicle equipped with these tires and the rolling resistance of the latter.
- composition 12 comprises plasticizing oil in an amount which is significantly reduced compared to that which characterizes the composition T2.
- S-SBR E copolymer of styrene and butadiene prepared in solution having a rate of styrene sequences of 25%, a rate of sequences 1.2 of 58%, a Mooney viscosity ML (l + 4) at 100 ° C of 54, an amount of extension oil equal to 0 phr, and a glass transition temperature Tg of -30 ° C.
- composition 13 under a dynamic modulus of high modulus (0.7 MPa) is expected to be equal to the corresponding Tg of the “control” composition T3.
- the difference (3 ° C) between the Tg of compositions 13 and T3 which were measured under a dynamic stress of reduced modulus, equal to 0.2 MPa, is relatively close to the zero deviation between the Tg of said compositions 13 and T3 which were measured under said high modulus constraint.
- This absence of offset between the Tg when going from a high modulus stress to a reduced modulus constraint reflects the fact that the resin R2 is well miscible in the elastomer matrix constituted by the BR A and the S-SBR E.
- the performance results of the tires show that the incorporation, in an amount of 30 phr, of a plasticizing resin of Tg equal to 88 ° C and of Mn equal to 820 g / mol in the tread composition 13 which comprises silica by way of reinforcing filler and which is advantageously completely devoid of plasticizing oil, makes it possible to improve the wear resistance of a tire whose tread consists of said composition 13, thanks to the aforementioned miscibility of the resin according to the invention, this without penalizing the grip on dry or wet ground of such tires, the behavior on wet ground of a vehicle equipped with these tires and without penalizing in a appreciable manner the rolling resistance of these last.
- plasticizing resin R3 polydicyclopentadiene type resin marketed by the company NISSEKI under the name "EPI 00", having: an aliphatic chain rate of 86%, an average molecular weight Mn of 800 g / mol, and a glass transition temperature Tg of 75 ° C.
- Tg of the composition NC4 not in accordance with the invention under a dynamic stress of high modulus (0J MPa) is provided for substantially equal to the corresponding Tg of the “control” composition T4.
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Abstract
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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JP2002571588A JP2004518807A (ja) | 2001-03-12 | 2002-03-08 | タイヤトレッド及びタイヤ用ゴム組成物 |
CA002409428A CA2409428A1 (fr) | 2001-03-12 | 2002-03-08 | Composition de caoutchouc pour bande de roulement de pneumatique et pneumatique |
BR0204474-9A BR0204474A (pt) | 2001-03-12 | 2002-03-08 | Composição de borracha reticulável ou reticulada, banda de rodagem de capa de pneumático, e, capa de pneumático |
EP02703627A EP1379588A1 (fr) | 2001-03-12 | 2002-03-08 | Composition de caoutchouc pour bande de roulement de pneumatique et pneumatique |
US10/655,782 US20040122157A1 (en) | 2001-03-12 | 2003-09-05 | Rubber composition for tire tread and tire |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR01/03354 | 2001-03-12 | ||
FR0103354A FR2821848A1 (fr) | 2001-03-12 | 2001-03-12 | Composition de caoutchouc pour bande de roulement de pneumatique et enveloppe de pneumatique l'incorporant |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/655,782 Continuation US20040122157A1 (en) | 2001-03-12 | 2003-09-05 | Rubber composition for tire tread and tire |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002072689A1 true WO2002072689A1 (fr) | 2002-09-19 |
Family
ID=8861022
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/002560 WO2002072689A1 (fr) | 2001-03-12 | 2002-03-08 | Composition de caoutchouc pour bande de roulement de pneumatique et pneumatique |
Country Status (9)
Country | Link |
---|---|
US (1) | US20040122157A1 (fr) |
EP (1) | EP1379588A1 (fr) |
JP (1) | JP2004518807A (fr) |
CN (1) | CN1458953A (fr) |
BR (1) | BR0204474A (fr) |
CA (1) | CA2409428A1 (fr) |
FR (1) | FR2821848A1 (fr) |
MX (1) | MXPA02011980A (fr) |
WO (1) | WO2002072689A1 (fr) |
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EP2142387A1 (fr) * | 2007-03-29 | 2010-01-13 | Société de Technologie MICHELIN | Bande de roulement de pneu avec de la résine |
WO2011075121A1 (fr) | 2009-12-16 | 2011-06-23 | Michelin Recherche Et Technique S.A. | Haute teneur en silice pour pneus de véhicules lourds |
WO2011101056A1 (fr) | 2010-02-17 | 2011-08-25 | Continental Reifen Deutschland Gmbh | Mélange de caoutchouc vulcanisable au soufre |
US8178605B2 (en) | 2006-12-27 | 2012-05-15 | Michelin Recherche Et Technique S.A. | Tread for tire |
EP2452972A1 (fr) | 2010-11-10 | 2012-05-16 | Continental Reifen Deutschland GmbH | Pneu de véhicule utilitaire |
WO2012084847A1 (fr) * | 2010-12-23 | 2012-06-28 | Compagnie Generale Des Etablissements Michelin | Pneumatique dont la bande de roulement comporte une resine poly(alkylene-ester) |
WO2020128250A1 (fr) * | 2018-12-21 | 2020-06-25 | Compagnie Generale Des Etablissements Michelin | Composition de caoutchouc |
EP3467020B1 (fr) | 2016-06-01 | 2020-10-28 | Bridgestone Corporation | Composition de caoutchouc, et pneumatique |
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FR2821849A1 (fr) * | 2001-03-12 | 2002-09-13 | Michelin Soc Tech | Composition de caoutchouc pour bande de roulement de pneumatique et enveloppe de pneumatique l'incorporant |
AU2003250130A1 (en) * | 2002-07-29 | 2004-02-23 | Michelin Recherche Et Technique S.A. | Rubber composition for the thread cap of a pneumatic tyre |
FR2866028B1 (fr) * | 2004-02-11 | 2006-03-24 | Michelin Soc Tech | Systeme plastifiant pour composition de caoutchouc |
JP5006532B2 (ja) * | 2004-09-08 | 2012-08-22 | 東洋ゴム工業株式会社 | 冬用空気入りタイヤ用ゴム組成物及び冬用空気入りタイヤ |
JP4476151B2 (ja) * | 2005-04-01 | 2010-06-09 | 住友ゴム工業株式会社 | ランフラットタイヤ |
JP5006531B2 (ja) * | 2005-09-06 | 2012-08-22 | 東洋ゴム工業株式会社 | 冬用空気入りタイヤ用ゴム組成物及び冬用空気入りタイヤ |
FR2916201B1 (fr) * | 2007-05-15 | 2009-07-17 | Michelin Soc Tech | Systeme plastifiant et composition de caoutchouc pour pneumatique incorporant ledit systeme |
US9062189B2 (en) * | 2008-01-18 | 2015-06-23 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions comprising hydrocarbon polymer additives |
JP5656366B2 (ja) * | 2008-04-30 | 2015-01-21 | 株式会社ブリヂストン | 変性重合体を含有するゴム組成物を使用したタイヤ |
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JP4883172B2 (ja) * | 2009-12-10 | 2012-02-22 | 横浜ゴム株式会社 | タイヤ用ゴム組成物 |
US20120252929A1 (en) * | 2009-12-23 | 2012-10-04 | CGEM and MRT, S.A. | Rubber composition for aircraft tire treads |
US8653195B2 (en) | 2010-10-13 | 2014-02-18 | Exxonmobil Chemical Patents Inc. | Hydrocarbon polymer modifiers for elastomeric compositions |
FR2968006B1 (fr) | 2010-11-26 | 2012-12-21 | Michelin Soc Tech | Bande de roulement de pneumatique |
US9361715B2 (en) * | 2011-06-02 | 2016-06-07 | Microsoft Technology Licensing, Llc | Global composition system |
US10179479B2 (en) | 2015-05-19 | 2019-01-15 | Bridgestone Americas Tire Operations, Llc | Plant oil-containing rubber compositions, tread thereof and race tires containing the tread |
FR3039558B1 (fr) * | 2015-07-31 | 2017-07-21 | Michelin & Cie | Composition de caoutchouc comprenant une resine hydrocarbonee de faible temperature de transition vitreuse |
FR3039557B1 (fr) * | 2015-07-31 | 2017-07-21 | Michelin & Cie | Composition de caoutchouc comprenant une resine hydrocarbonee de faible temperature de transition vitreuse |
US20180229553A1 (en) * | 2017-02-13 | 2018-08-16 | Cooper Tire & Rubber Company | Tire tread compound |
MX2019009453A (es) | 2017-02-13 | 2019-11-05 | Cooper Tire & Rubber Co | Compuesto de rodadura de neumaticos de guayule. |
EP3597696B1 (fr) * | 2017-04-14 | 2023-05-17 | Sumitomo Rubber Industries, Ltd. | Composition de caoutchouc pour pneumatique, et pneumatique |
JP7407512B2 (ja) * | 2017-04-14 | 2024-01-04 | 住友ゴム工業株式会社 | 空気入りタイヤ |
WO2019122600A1 (fr) * | 2017-12-19 | 2019-06-27 | Compagnie Generale Des Etablissements Michelin | Bande de roulement de pneumatique dont le système de réticulation est à base de peroxyde organique |
WO2019213186A1 (fr) * | 2018-05-04 | 2019-11-07 | Bridgestone Americas Tire Operations, Llc | Composition de caoutchouc pour bande de roulement de pneumatique |
WO2019213226A1 (fr) * | 2018-05-04 | 2019-11-07 | Bridgestone Americas Tire Operations, Llc | Composition de caoutchouc pour bande de roulement de pneumatique |
JP2021523260A (ja) * | 2018-05-04 | 2021-09-02 | ブリヂストン アメリカズ タイヤ オペレーションズ、 エルエルシー | タイヤトレッドゴム組成物 |
US20210246319A1 (en) | 2018-05-07 | 2021-08-12 | Basf Polyurethanes Gmbh | Epoxy resin-based cathodic electrodeposition (ced) of metal components as an adhesion promoter for pu systems |
US20220235208A1 (en) * | 2019-05-29 | 2022-07-28 | Bridgestone Americas Tire Operations, Llc | Tire Tread Rubber Composition And Related Methods |
FR3099166B1 (fr) * | 2019-07-26 | 2022-02-11 | Michelin & Cie | Pneu incorporant une composition de caoutchouc comprenant une résine hydrocarbure spécifique |
EP3789629A1 (fr) | 2019-09-03 | 2021-03-10 | BASF Polyurethanes GmbH | Palier amortisseur pour un véhicule |
US11731461B2 (en) | 2020-06-30 | 2023-08-22 | The Goodyear Tire & Rubber Company | Tire having a multilayer tread cap |
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US2449929A (en) * | 1944-02-26 | 1948-09-21 | Pennsylvania Ind Chemical Corp | Elastomer plasticizing composition composed of coumarone resin and an aromatic hydrocarbon oil |
EP0477682A1 (fr) * | 1990-09-24 | 1992-04-01 | The Goodyear Tire & Rubber Company | Pneumatique comportant une bande de roulement |
EP0899297A2 (fr) * | 1997-08-26 | 1999-03-03 | The Goodyear Tire & Rubber Company | Pneumatique dont la composition de la bande de roulement contient des quantités élevées d'un polymère ayant une température de transition vitreuse (Tg) basse et une résine |
EP1069160A1 (fr) * | 1999-07-13 | 2001-01-17 | Bridgestone Corporation | Composition de caoutchouc et bandage pneumatique utilisant la même composition |
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US5229459A (en) * | 1991-10-17 | 1993-07-20 | The Goodyear Tire & Rubber Company | Rubber stock containing high trans polybutadiene |
-
2001
- 2001-03-12 FR FR0103354A patent/FR2821848A1/fr active Pending
-
2002
- 2002-03-08 EP EP02703627A patent/EP1379588A1/fr not_active Withdrawn
- 2002-03-08 JP JP2002571588A patent/JP2004518807A/ja active Pending
- 2002-03-08 CA CA002409428A patent/CA2409428A1/fr not_active Abandoned
- 2002-03-08 BR BR0204474-9A patent/BR0204474A/pt not_active IP Right Cessation
- 2002-03-08 CN CN02800617A patent/CN1458953A/zh active Pending
- 2002-03-08 WO PCT/EP2002/002560 patent/WO2002072689A1/fr not_active Application Discontinuation
- 2002-12-03 MX MXPA02011980A patent/MXPA02011980A/es unknown
-
2003
- 2003-09-05 US US10/655,782 patent/US20040122157A1/en not_active Abandoned
Patent Citations (4)
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US2449929A (en) * | 1944-02-26 | 1948-09-21 | Pennsylvania Ind Chemical Corp | Elastomer plasticizing composition composed of coumarone resin and an aromatic hydrocarbon oil |
EP0477682A1 (fr) * | 1990-09-24 | 1992-04-01 | The Goodyear Tire & Rubber Company | Pneumatique comportant une bande de roulement |
EP0899297A2 (fr) * | 1997-08-26 | 1999-03-03 | The Goodyear Tire & Rubber Company | Pneumatique dont la composition de la bande de roulement contient des quantités élevées d'un polymère ayant une température de transition vitreuse (Tg) basse et une résine |
EP1069160A1 (fr) * | 1999-07-13 | 2001-01-17 | Bridgestone Corporation | Composition de caoutchouc et bandage pneumatique utilisant la même composition |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8178605B2 (en) | 2006-12-27 | 2012-05-15 | Michelin Recherche Et Technique S.A. | Tread for tire |
EP2142387A4 (fr) * | 2007-03-29 | 2011-02-16 | Michelin Soc Tech | Bande de roulement de pneu avec de la résine |
EP2142387A1 (fr) * | 2007-03-29 | 2010-01-13 | Société de Technologie MICHELIN | Bande de roulement de pneu avec de la résine |
US8815995B2 (en) | 2007-03-29 | 2014-08-26 | Compagnie Generale Des Etablissements Michelin | Tire tread with resin |
EP2512824A1 (fr) * | 2009-12-16 | 2012-10-24 | MICHELIN Recherche et Technique S.A. | Haute teneur en silice pour pneus de véhicules lourds |
WO2011075121A1 (fr) | 2009-12-16 | 2011-06-23 | Michelin Recherche Et Technique S.A. | Haute teneur en silice pour pneus de véhicules lourds |
EP2512824A4 (fr) * | 2009-12-16 | 2013-07-31 | Michelin Rech Tech | Haute teneur en silice pour pneus de véhicules lourds |
WO2011101056A1 (fr) | 2010-02-17 | 2011-08-25 | Continental Reifen Deutschland Gmbh | Mélange de caoutchouc vulcanisable au soufre |
WO2012062534A1 (fr) | 2010-11-10 | 2012-05-18 | Continental Reifen Deutschland Gmbh | Pneumatique de véhicule utilitaire |
EP2452972A1 (fr) | 2010-11-10 | 2012-05-16 | Continental Reifen Deutschland GmbH | Pneu de véhicule utilitaire |
FR2969630A1 (fr) * | 2010-12-23 | 2012-06-29 | Michelin Soc Tech | Pneumatique dont la bande de roulement comporte une resine poly (alkylene-ester) |
WO2012084847A1 (fr) * | 2010-12-23 | 2012-06-28 | Compagnie Generale Des Etablissements Michelin | Pneumatique dont la bande de roulement comporte une resine poly(alkylene-ester) |
EP3467020B1 (fr) | 2016-06-01 | 2020-10-28 | Bridgestone Corporation | Composition de caoutchouc, et pneumatique |
WO2020128250A1 (fr) * | 2018-12-21 | 2020-06-25 | Compagnie Generale Des Etablissements Michelin | Composition de caoutchouc |
FR3090658A1 (fr) * | 2018-12-21 | 2020-06-26 | Compagnie Generale Des Etablissements Michelin | Composition de caoutchouc |
Also Published As
Publication number | Publication date |
---|---|
CA2409428A1 (fr) | 2002-09-19 |
US20040122157A1 (en) | 2004-06-24 |
CN1458953A (zh) | 2003-11-26 |
MXPA02011980A (es) | 2003-05-27 |
EP1379588A1 (fr) | 2004-01-14 |
BR0204474A (pt) | 2003-05-13 |
FR2821848A1 (fr) | 2002-09-13 |
JP2004518807A (ja) | 2004-06-24 |
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