Patent Application
20130267640
The field of the invention is that of rubber compositions for the tread of tyres, more specifically rubber compositions for the tread of snow tyres or winter tyres that are capable of running on snow-covered ground. As is known, these snow tyres, identified by an inscription M+S or M.S. or else M&S, marked on their sidewalls, are characterized by a tread design and a structure that are intended above all to ensure, in mud and fresh snow or slush, a better behaviour than that of a road type tyre designed for running on non-snowy ground.
Snowy ground, referred to as white ground, has the feature of having a low friction coefficient, which leads to the development of snow tyres that comprise treads based on diene rubber compositions that have a low glass transition temperature, Tg. However, the grip performance, on wet ground, of these tyres comprising such treads is generally inferior to that of road tyres, the treads of which are generally based on rubber compositions of different formulations, in particular that have a higher Tg.
From the aforegoing, it is a constant objective of tyre manufacturers to further improve the grip performance of winter tyres on wet ground without however deteriorating the grip performance on snow.
By continuing their research, the Applicants have unexpectedly discovered that the combined use of certain functional diene elastomers, a reinforcing inorganic filler and a specific plasticizing system makes it possible to improve further the grip performance of snow tyres on wet ground without degrading the grip on snow.
Thus, one subject of the invention is a snow tyre, the tread of which comprises a rubber composition, said rubber composition comprising at least:
The tyres of the invention are particularly intended to be fitted onto motor vehicles of the passenger type, including 4×4 (four-wheel drive) vehicles and SUV vehicles (Sport Utility Vehicles), and also industrial vehicles chosen in particular from vans and heavy-duty vehicles (i.e., buses and heavy road transport vehicles such as lorries).
The invention and its advantages will be readily understood in the light of the description and the exemplary embodiments that follow.
In the present description, unless expressly indicated otherwise, all the percentages (%) shown are % by weight. The abbreviation “phr” stands for parts by weight per hundred parts of elastomer (of the total of the elastomers if several elastomers are present). All the values of the glass transition temperature “Tg” are measured in a known manner by DSC (Differential Scanning calorimetry) according to the standard ASTM D3418 (1999).
Moreover, any range of values denoted by the expression “between a and b” represents the field of values ranging from more than a to less than b (that is to say limits a and b excluded) whereas any range of values denoted by the expression “from a to b” means the field of values ranging from a up to b (that is to say including the strict limits a and b).
A “diene” elastomer (or “rubber”, the two terms being considered to be synonymous) should be understood, in a known manner, to mean an (one or more is understood) elastomer resulting at least in part (i.e., a homopolymer or a copolymer) from diene monomers (monomers bearing two carbon-carbon double bonds which may or may not be conjugated).
These diene elastomers can be classified into two categories: “essentially unsaturated” or “essentially saturated”. Generally, the expression “essentially unsaturated” is understood to mean a diene elastomer resulting at least in part from conjugated diene monomers having a content of units of diene origin (conjugated dienes) which is greater than 15% (mol %); thus it is that diene elastomers such as butyl rubbers or diene/α-olefin copolymers of the EPDM type do not fall under the preceding definition and may especially be described as “essentially saturated” diene elastomers (low or very low content of units of diene origin, always less than 15%). In the category of “essentially unsaturated” diene elastomers, the expression “highly unsaturated” diene elastomer is understood to mean in particular a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
Although it applies to any type of diene elastomer, a person skilled in the art of tyres will understand that the invention is preferably employed with essentially unsaturated diene elastomers.
Given these definitions, the expression diene elastomer capable of being used in the compositions in accordance with the invention is understood in particular to mean:
The following are suitable in particular as conjugated dienes: 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C1-C5 alkyl)-1,3-butadienes, such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene or 2-methyl-3-isopropyl-1,3-butadiene, an aryl-1,3-butadiene, 1,3-pentadiene or 2,4-hexadiene. The following, for example, are suitable as vinylaromatic compounds: styrene, ortho-, meta- or para-methylstyrene, the “vinyltoluene” commercial mixture, para-(tert-butyl)styrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene or vinylnaphthalene.
The copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units.
More preferably, use is made of a first diene elastomer selected from the group consisting of polybutadienes (BRs) (especially those having a content of cis-1,4-bonds of greater than 90%), synthetic polyisoprenes (IRs), natural rubber (NR), butadiene copolymers, and blends of these elastomers; such copolymers are selected more preferably from the group consisting of butadiene-styrene copolymers (SBRs) and blends of such copolymers.
The following are suitable: polybutadienes, in particular those having a content (molar %) of 1,2-units of between 4% and 80% or those having a content (molar %) of cis-1,4-units of greater than 80%, polyisoprenes, butadiene-styrene copolymers and in particular those having a Tg (glass transition temperature Tg, measured according to standard ASTM D3418) of between 0° C. and −80° C., a styrene content of between 5% and 60% by weight and more particularly between 10% and 50%, a content (molar %) of 1,2-bonds of the butadiene part of between 4% and 75% and a content (molar %) of trans-1,4-bonds of between 10% and 80%.
According to one particular embodiment of the invention, the first diene elastomer has a glass transition temperature in a range extending from −80° C. to −35° C., preferably extending from −70° C. to −40° C.
The first diene elastomer may have any microstructure which depends on the polymerization conditions used, in particular on the presence or absence of a modifying and/or randomizing agent and on the amounts of modifying and/or randomizing agent employed. This elastomer may, for example, be a block, statistical, sequential or microsequential elastomer and may be prepared in dispersion or in solution.
An essential feature of the rubber composition of the tread of the snow tyre in accordance with the invention is to comprise a first diene elastomer bearing at least one (i.e., one or more) SiOR function, R being hydrogen or a hydrocarbon radical, especially an alkyl, preferably having 1 to 12 carbon atoms, in particular methyl or ethyl.
The expression “hydrocarbon radical” means a monovalent group essentially consisting of carbon and hydrogen atoms, it being possible for such a group to comprise at least one heteroatom, knowing that the assembly formed by the carbon and hydrogen atoms represents the major number fraction in the hydrocarbon radical.
According to one particular embodiment of the invention, the hydrocarbon radical is a branched, linear or else cyclic alkyl having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, more preferably still having 1 to 4 carbon atoms, in particular a methyl or an ethyl.
According to another particular embodiment of the invention, the radical R is an alkoxyalkyl, more particularly having 2 to 8 carbon atoms.
In the present application, the expression “SiOR function” is used to denote at least one SiOR function, i.e., one or more SiOR functions.
Generally, a function borne by an elastomer may be located on the elastomer chain according to one of three possible configurations: along the elastomer chain as a pendent group, at one end of the elastomer chain or else within the actual elastomer chain (i.e., not at the ends). The latter case occurs especially in the case where the elastomer is functionalized by the use of a coupling or star-branching agent which provides the function in question.
In particular, the SiOR function borne by the first diene elastomer may be located along the elastomer chain as a pendent group, at one end of the elastomer chain or else within the actual elastomer chain. In the case where there are several SiOR functions borne by the elastomer, they may occupy one or another of the above configurations.
The first diene elastomer may be a linear or star-branched, or even branched polymer. If it is a linear polymer, it may or may not be coupled. This elastomer may have a monomodal, bimodal or polymodal molecular distribution.
According to another preferred embodiment of the invention, the first diene elastomer is predominantly in a linear form, that is to say that if it comprises star-branched or branched chains, these represent a minority weight fraction in this elastomer.
According to another particular embodiment of the invention, the first diene elastomer is prepared by anionic polymerization.
According to one particularly preferred embodiment, the first diene elastomer bears at least one (i.e., one or more) function, referred to as a “silanol” function, of formula SiOH(R is hydrogen).
Diene elastomers corresponding to such a definition are well known, they have for example been described in documents EP 0 778 311 B1, WO 2008/141702, WO 2006/050486, EP 0 877 047 B1 or EP 1 400 559 B1. The silanol function SiOH is preferably located at the chain end of the diene elastomer, in particular in the form of a dimethylsilanol group —SiMe2SiOH.
According to one particular embodiment of the invention, the silanol function may be bonded to a polysiloxane which constitutes one of the blocks of a block copolymer that also comprises a polydiene block, as described for example in patent EP 0 778 311 B1.
According to another particular embodiment of the invention, the silanol function may be bonded to a polyether constituting one of the blocks of a block copolymer that also comprises a polydiene block, as described for example in application WO 2009/000750.
According to another particularly preferred embodiment, the first diene elastomer bears at least one (i.e., one or more) function of formula SiOR in which R is a hydrocarbon radical.
Diene elastomers corresponding to such a definition are also well known, they have for example been described in documents JP 63-215701, JP 62-227908, U.S. Pat. No. 5,409,969 or WO 2006/050486.
According to one particular embodiment, the SiOR function (with R being a hydrocarbon radical), in particular alkoxysilane function, may be bonded to a polyether which constitutes one of the blocks of a block copolymer that also comprises a polydiene block, as described for example in application WO 2009/000750.
According to another particularly preferred embodiment, the first diene elastomer, bearing at least one (i.e., one or more) function of formula SiOR in which R is hydrogen or a hydrocarbon radical, also bears at least one other (i.e., one or more) function that is different from the SiOR function. This other function is preferably selected from the group consisting of epoxy, tin or amine functions, it being possible for the amine to be a primary, secondary or tertiary amine. Amine functions are particularly preferred.
Elastomers bearing both an SiOR function and an epoxy function have for example been described in patents EP 0 890 607 B1 and EP 0 692 492 B1. Elastomers bearing both an SiOR function and a tin function have for example been described in patent EP 1 000 970 B1.
According to a more preferred embodiment, this other function borne by the first diene elastomer is an amine function, more preferably a tertiary amine.
The amine function may be located on the same end (or the same ends) of the elastomer chain as the SiOR function. Elastomers having an SiOR function and an amine function on the same chain end have been described for example in the patents or patent applications EP 1 457 501 B1, WO 2006/076629, EP 0 341 496 B1 or WO 2009/133068 or else in WO 2004/111094.
As a functionalizing agent that gives rise to the synthesis of an elastomer bearing an alkoxysilane function and an amine function, mention may be made, by way of example, of N,N-dialkylaminopropyltrialkoxysilanes, cyclic azadialkoxysilanes such as N-alkyl-aza-dialkoxysilacycloalkanes, 2-pyridylethyltrialkoxysilanes, 3-carbazolethyltrialkoxysilanes, 3-alkylideneaminopropyltrialkoxysilanes, N-trialkoxysilylpropylmorpholines, especially 3-(N,N-dimethylaminopropyl)trimethoxysilane, 3-(1,3-dimethylbutylidene)aminopropyltriethoxysilane, N-n-butyl-aza-2,2-dimethoxysilacyclopentane, 2-(4-pyridylethyl)triethoxysilane and 2-(trimethoxysilyl)pyridine.
According to another embodiment, the amine function may be present on a chain end that does not bear the SiOR function. Such a configuration may be produced for example by the use of an initiator bearing an amine function, in particular by the use of an initiator that is a lithium amide, such as lithium pyrrolidide or lithium hexamethyleneimide, or an organolithium compound bearing an amine function such as dimethylaminopropyllithium and 3-pyrrolidinopropyllithium. Such initiators have been described for example in patents EP 0 590 490 B1 and EP 0 626 278 B1. Such elastomers bearing an SiOR function and an amine function at their different chain ends have for example been described in patents EP 0 778 311 B1 and U.S. Pat. No. 5,508,333.
According to another particularly preferred embodiment, which can be applied to each of the embodiments described previously, the first diene elastomer comprises, besides the diene units, vinylaromatic units, in particular styrene units. Preferably, the diene units are butadiene units, preferably combined with styrene units. Advantageously it is a copolymer of styrene and butadiene, SBR, preferably a solution SBR(SSBR).
According to a most particularly preferred embodiment of the invention, the SBR, as first diene elastomer, has a glass transition temperature in a range extending from −80° C. to −35° C., preferably from −70° C. to −40° C.
Thus, according to one advantageous embodiment of the invention, the first diene elastomer is an SBR, preferably an SSBR, bearing at least one silanol function, preferably positioned at the chain end.
According to an even more preferred embodiment of the invention, the first diene elastomer is an SBR, preferably an SSBR, bearing a single silanol function, preferably positioned at the chain end.
According to another advantageous embodiment of the invention, the first diene elastomer is an SBR, preferably an SSBR, bearing at least one SiOR function (with R being a hydrocarbon radical), in particular alkoxysilane function, and at least one amine function, preferably a tertiary amine function, which are preferably both positioned in the chain, and more preferably still within the elastomer chain.
According to an even more preferred embodiment of the invention, the first diene elastomer is an SBR, preferably an SSBR, bearing a single alkoxysilane function and a single amine function, preferably a tertiary amine function, which are preferably both positioned in the chain, and more preferably still within the elastomer chain.
It is understood that the first diene elastomer bearing an SiOR function may be formed by a mixture of elastomers that differ from one another by the chemical nature of the SiOR function, by its position on the elastomer chain, by the presence of an additional function other than SiOR, by their microstructure or else by their macrostructure.
The content of the first diene elastomer is in a range extending from 20 to 100 phr, preferably from 40 to 100 phr, more preferably still from 50 to 100 phr.
When the composition of the tread of the tyre in accordance with the invention comprises an optional, second diene elastomer, this elastomer is different from the first diene elastomer in so far as it does not bear an SiOR function. Nevertheless, this second elastomer may have a microstructure or a macrostructure that may be identical to or different from those of the first diene elastomer. It is used in a proportion ranging from 0 to 80 phr, preferably from 0 to 60 phr, more preferably still from 0 to 50 phr.
According to one preferred embodiment of the invention, this second diene elastomer is selected from the group consisting of polybutadienes, natural rubber, synthetic polyisoprenes, butadiene copolymers, isoprene copolymers and blends of these elastomers.
According to one particular embodiment of the invention, this second diene elastomer is a polybutadiene. The polybutadiene is preferably a cis-1,4-polybutadiene, i.e., a polybutadiene having a content of cis-1,4-bonds of greater than 90% (molar %), preferably greater than or equal to 96% (molar %).
According to another particular embodiment of the invention, this second diene elastomer is a butadiene copolymer, in particular an SBR, preferably a solution SBR.
According to another particular embodiment of the invention, this second elastomer may bear at least one function (other than an SiOR function of course), in particular a tin function. This second elastomer is advantageously a diene elastomer coupled or star-branched to tin.
It is understood that the second diene elastomer may be formed by a mixture of elastomers that differ from one another by their microstructure, by their macrostructure or by the presence of a function, by the nature or the position of the latter on the elastomer chain.
As functions other than the aforementioned tin, mention may be made, by way of example, of amino functional groups such as benzophenone for example, carboxylic groups (as described for example in WO 01/92402 or U.S. Pat. No. 6,815,473, WO 2004/096865 or US 2006/0089445), polyether groups (as described for example in EP 1 127 909 or U.S. Pat. No. 6,503,973) or epoxy groups.
As another essential feature, the rubber composition of the tread of the snow tyre in accordance with the invention comprises a reinforcing inorganic filler in a specific amount, in a proportion ranging from 100 to 160 phr.
The expression “reinforcing inorganic filler” should be understood here to mean any inorganic or mineral filler, whatever its colour and its origin (natural or synthetic), also referred to as “white filler”, “clear filler” or even “non-black filler”, in contrast to carbon black, capable of reinforcing by itself alone, without means other than an intermediate coupling agent, a rubber composition intended for the manufacture of pneumatic tyres, in other words capable of replacing, in its reinforcing role, a conventional tyre-grade carbon black; such a filler is generally characterized, in a known manner, by the presence of hydroxyl (—OH) groups at its surface.
Mineral fillers of the siliceous type, preferably silica (SiO2), are suitable in particular as reinforcing inorganic fillers. The silica used may be any reinforcing silica known to a person skilled in the art, in particular any precipitated or pyrogenic silica having a BET surface area and a CTAB specific surface area that are both less than 450 m2/g, preferably from 30 to 400 m2/g, in particular between 60 and 300 m2/g. Mention will be made, as highly dispersible precipitated silicas (“HDSs”), for example, of the Ultrasil 7000 and Ultrasil 7005 silicas from Degussa, the Zeosil 1165 MP, 1135 MP and 1115 MP silicas from Rhodia, the Hi-Sil EZ150G silica from PPG, the Zeopol 8715, 8745 and 8755 silicas from Huber or the silicas with a high specific surface area as described in application WO 03/16387.
Mention will also be made, as reinforcing inorganic filler, of mineral fillers of the aluminous type, in particular alumina (Al2O3) or aluminium (oxide)hydroxides, or else reinforcing titanium oxides.
A person skilled in the art will understand that a reinforcing filler of another nature, in particular organic nature, such as carbon black, might be used as filler equivalent to the reinforcing inorganic filler described in the present section, provided that this reinforcing filler is covered with an inorganic layer, such as silica, or else comprises, at its surface, functional sites, in particular hydroxyls, requiring the use of a coupling agent in order to form the connection between the filler and the elastomer. By way of example, mention may be made, for example, of carbon blacks for tyres, such as described, for example, in patent documents WO 96/37547 and WO 99/28380.
Advantageously, the content of reinforcing inorganic filler is in a range extending from 100 to 150 phr, more advantageously from 105 to 140 phr.
According to one preferred embodiment of the invention, the reinforcing inorganic filler comprises from 50% to 100% by weight of silica.
According to another advantageous embodiment, the rubber composition of the tread of the snow tyre in accordance with the invention may comprise carbon black. The carbon black, when it is present, is preferably used at a content of less than 20 phr, more preferably of less than 10 phr (for example between 0.5 and 20 phr, in particular between 2 and 10 phr). In the ranges indicated, the colouring properties (black pigmenting agent) and UV-stabilizing properties of the carbon blacks are benefited from, without, moreover, adversely affecting the typical performances provided by the reinforcing inorganic filler.
In order to couple the reinforcing inorganic filler to the diene elastomer, use is made, in a known manner, of a coupling agent (or bonding agent) intended to provide a satisfactory connection, of chemical and/or physical nature, between the inorganic filler (surface of its particles) and the diene elastomer. This coupling agent is at least bifunctional. Use is made in particular of at least bifunctional organosilanes or polyorganosiloxanes.
Use is made in particular of silane polysulphides, referred to as “symmetrical” or “asymmetrical” depending on their particular structure, as described, for example, in applications WO 03/002648 (or US 2005/016651) and WO 03/002649 (or US 2005/016650).
Particularly suitable, without the definition below being limiting, are silane polysulphides corresponding to the following general formula (I):
Z-A-Sx-A-Z, (I)
in which:
in which:
In the case of a mixture of alkoxysilane polysulphides corresponding to the above formula (I), in particular the standard commercially available mixtures, the mean value of the “x” index is a fractional number preferably between 2 and 5, more preferably close to 4. However, the invention may also advantageously be carried out, for example, with alkoxysilane disulphides (x=2).
Mention will more particularly be made, as examples of silane polysulphides, of bis((C1-C4)alkoxyl(C1-C4)alkylsilyl(C1-C4)alkyl) polysulphides (in particular disulphides, trisulphides or tetrasulphides), such as, for example, bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl) polysulphides. Use is in particular made, among these compounds, of bis(3-triethoxysilylpropyl) tetrasulphide, abbreviated to TESPT, of formula [(C2H5O)3Si(CH2)3S2]2, or bis(triethoxysilylpropyl) disulphide, abbreviated to TESPD, of formula [(C2H5O)3Si(CH2)3S]2. Mention will also be made, as preferred examples, of bis(mono(C1-C4)alkoxyldi(C1-C4)alkylsilylpropyl) polysulphides (in particular disulphides, trisulphides or tetrasulphides), more particularly bis(monoethoxydimethylsilylpropyl) tetrasulphide, such as described in the aforementioned patent application WO 02/083782 (or U.S. Pat. No. 7,217,751).
Mention will in particular be made, as examples of coupling agents other than an alkoxysilane polysulphide, of bifunctional POSs (polyorganosiloxanes) or else of hydroxysilane polysulphides (R2═OH in the above formula I), such as described, for example, in patent applications WO 02/30939 (or U.S. Pat. No. 6,774,255), WO 02/31041 (or US 2004/051210) and WO 2007/061550, or else of silanes or POSs bearing azodicarbonyl functional groups, such as described, for example, in patent applications WO 2006/125532, WO 2006/125533 and WO 2006/125534.
Mention will be made, as examples of other silane sulphides, for example, of the silanes bearing at least one thiol (—SH) function (referred to as mercaptosilanes) and/or at least one masked thiol function, such as described, for example, in patents or patent applications U.S. Pat. No. 6,849,754, WO 99/09036, WO 2006/023815, WO 2007/098080, WO 2008/055986 and WO 2010/072685.
Of course, use might also be made of mixtures of the coupling agents described above, as described in particular in the abovementioned application WO 2006/125534.
The content of coupling agent is preferably between 2 and 20 phr, more preferably between 3 and 15 phr.
Another essential feature of the rubber composition of the tread of the snow tyre in accordance with the invention is to comprise a specific plasticizing system, comprising, on the one hand, in a content A of between 10 and 60 phr, a hydrocarbon resin having a Tg above 20° C., and on the other hand, in a content B of between 10 and 60 phr, a liquid plasticizing agent, it being understood that the total content A+B is greater than 50 phr.
According to one preferred embodiment of the invention, the content A of hydrocarbon resin is between 10 and 50 phr and the content B of liquid plasticizer is between 10 and 50 phr.
According to another preferred embodiment of the invention, the total content A+B of hydrocarbon resin and liquid plasticizer is between 50 and 100 phr, more preferably is in a range extending from 55 to 90 phr, in particular from 60 to 85 phr.
According to another particular embodiment of the invention, the ratio of A to B is between 1:5 and 5:1 (i.e., between 0.2 and 5.0), preferably between 1:4 and 4:1 (i.e., between 0.25 and 4.0).
According to another particular embodiment of the invention, the weight ratio of (A+B) to the mass of reinforcing inorganic filler, in particular silica, is between 50% and 80%, preferably in a range extending from 55% to 75%.
In a manner known to a person skilled in the art, the designation “resin” is reserved in the present application, by definition, for a compound which is solid at ambient temperature (23° C.), in contrast to a liquid plasticizing compound, such as an oil.
Hydrocarbon resins are polymers well known to those skilled in the art, essentially based on carbon and hydrogen but which may comprise other types of atoms, which can be used in particular as plasticizing agents or tackifiers in polymeric matrices. They are by nature miscible (i.e., compatible) in the contents used with the polymer compositions for which they are intended, so as to act as true 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), Chapter 5 of which is devoted to their applications, especially in rubber tyres (5.5. “Rubber Tires and Mechanical Goods”). They may be aliphatic, cycloaliphatic, aromatic, hydrogenated aromatic, of the aliphatic/aromatic type, i.e., based on aliphatic and/or aromatic monomers. They may be natural or synthetic resins, whether or not based on petroleum (if such is the case, they are also known as petroleum resins). Their Tg is preferably above 0° C., in particular above 20° C. (usually between 30° C. and 95° C.).
As is known, these hydrocarbon resins may also be termed thermoplastic resins in the sense that they soften when heated and may thus be moulded. They may also be defined by a softening point or temperature. The softening point of a hydrocarbon resin is generally about 50 to 60° C. higher than its Tg value. The softening point is measured according to standard ISO 4625 (ring-and-ball method). The macrostructure (Mw, Mn and Ip) is determined by size exclusion chromatography (SEC) as indicated below.
To recapitulate, SEC analysis, for example, consists in separating the macromolecules in solution according to their size through columns filled with a porous gel; the molecules are separated according to their hydrodynamic volume, the bulkiest being eluted first. The sample to be analysed is simply dissolved beforehand in an appropriate solvent, tetrahydrofuran at a concentration of 1 g/litre. The solution is then filtered through a filter with a porosity of 0.45 μm, before injection into the apparatus. The apparatus used is, for example, a “Waters Alliance” chromatographic line according to the following conditions:
A Moore calibration is carried out with a series of commercial polystyrene standards having a low Ip (less than 1.2), with known molar masses, covering the range of masses to be analysed. The weight-average molar mass (Mw), the number-average molar mass (Mn) and the polydispersity index (Ip=Mw/Mn) are deduced from the data recorded (curve of distribution by mass of the molar masses).
All the values for molar masses shown in the present application are thus relative to calibration curves produced with polystyrene standards.
According to one preferred embodiment of the invention, the hydrocarbon resin exhibits at least any one, more preferably all, of the following characteristics:
As examples of such hydrocarbon resins, mention may be made of those selected from the group consisting of cyclopentadiene (abbreviated to CPD) homopolymer or copolymer resins, dicyclopentadiene (abbreviated to DCPD) homopolymer or copolymer resins, terpene homopolymer or copolymer resins, C5-cut homopolymer or copolymer resins, C9-cut homopolymer or copolymer resins, α-methylstyrene homopolymer or copolymer resins and blends of these resins. Among the above copolymer resins, mention may more particularly be made of those selected from the group consisting of (D)CPD/vinylaromatic copolymer resins, (D)CPD/terpene copolymer resins, terpene/phenol copolymer resins, (D)CPD/C5-cut copolymer resins, (D)CPD/C9-cut copolymer resins, terpene/vinylaromatic copolymer resins, terpene/phenol copolymer resins, C5-cut/vinylaromatic copolymer resins and blends of these resins.
The term “terpene” includes here, as is known, α-pinene, β-pinene and limonene monomers. It is preferable to use a limonene monomer, a compound which, as is known, is in the form of three possible isomers: L-limonene (laevorotatory enantiomer), D-limonene (dextrorotatory enantiomer), or else dipentene, the racemic mixture of the dextrorotatory and laevorotatory enantiomers. Suitable vinylaromatic monomers are for example: styrene, α-methylstyrene, ortho-methylstyrene, meta-methylstyrene and para-methylstyrene, vinyltoluene, para-(tert-butyl)styrene, methoxystyrenes, chlorostyrenes, hydroxystyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene and any vinylaromatic monomer derived from a C9-cut (or more generally a C8- to C10-cut).
More particularly, mention may be made of resins selected from the group consisting of (D)CPD homopolymer resins, (D)CPD/styrene copolymer resins, polylimonene resins, limonene/styrene copolymer resins, limonene/D(CPD) copolymer resins, C5-cut/styrene copolymer resins, C5-cut/C9-cut copolymer resins and blends of these resins.
All the above resins are well known to those skilled in the art and are commercially available, for example sold by DRT under the name “Dercolyte” as regards polylimonene resins, sold by Neville Chemical Company under the name “Super Nevtac”, by Kolon under the name “Hikorez” or by Exxon Mobil under the name “Escorez” as regards C5-cut/styrene resins or C5-cut/C9-cut resins, or else by Struktol under the name “40 MS” or “40 NS” (blends of aromatic and/or aliphatic resins).
The rubber composition of the tread of the tyre of the invention has another essential feature of comprising between 10 and 60 phr of a liquid plasticizing agent (which is liquid at 23° C.), the role of which is to soften the matrix by diluting the elastomer and the reinforcing filler; its Tg is preferably below −20° C., more preferably below −40° C.
Any extending oil, whether of aromatic or non-aromatic nature, any liquid plasticizing agent known for its plasticizing properties with regard to diene elastomers, can be used. At ambient temperature (23° C.), these plasticizers or these oils, which are more or less viscous, are liquids (that is to say, as a reminder, substances that have the ability to eventually take on the shape of their container), as opposed, in particular, to plasticizing hydrocarbon resins which are by nature solid at ambient temperature.
Liquid plasticizing agents selected from the group consisting of liquid diene polymers, polyolefin oils, naphthenic oils, paraffinic oils, DAE oils, MES (Medium Extracted Solvate) oils, TDAE (Treated Distillate Aromatic Extract) oils, RAE (Residual Aromatic Extract) oils, TRAE (Treated Residual Aromatic Extract) oils and SRAE (Safety Residual Aromatic Extract) oils, mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers, sulphonate plasticizers and mixtures of these compounds are particularly suitable. According to a more preferred embodiment, the liquid plasticizing agent is selected from the group consisting of MES oils, TDAE oils, naphthenic oils, vegetable oils and mixtures of these oils.
According to one particular embodiment of the invention, the liquid plasticizer is a petroleum oil, preferably a non-aromatic petroleum oil.
A liquid plasticizer is described as non-aromatic when it has a content of polycyclic aromatic compounds, determined with the extract in DMSO according to the IP 346 method, of less than 3% by weight, relative to the total weight of the plasticizer.
Therefore, use may be made of a liquid plasticizing agent selected from the group consisting of MES oils, TDAE oils, naphthenic oils (of low or high viscosity, in particular which are hydrogenated or non-hydrogenated), paraffinic oils and mixtures of these oils.
Also suitable as petroleum oils are RAE oils, TRAE oils and SRAE oils or mixtures of these oils, which contain low contents of polycyclic compounds.
According to another particular embodiment of the invention, the liquid plasticizer is a terpene derivative. By way of example, the product Dimarone from Yasuhara may be mentioned.
Also suitable are the liquid polymers resulting from the polymerization of olefins or dienes, such as polybutenes, polydienes, in particular polybutadienes, polyisoprenes (also known under the name LIRs) or copolymers of butadiene and isoprene, or else copolymers of butadiene or isoprene and styrene or blends of these liquid polymers. The number-average molar mass of such liquid polymers is preferably in a range extending from 500 g/mol to 50000 g/mol, more preferably from 1000 g/mol to 10000 g/mol. Mention may be made, by way of example, of the RICON products from SARTOMER.
According to another particular embodiment of the invention, the liquid plasticizer is a vegetable oil. By way of example, mention may be made of an oil selected from the group consisting of linseed, safflower, soybean, corn, cottonseed, turnip seed, castor, tung, pine, sunflower, palm, olive, coconut, groundnut and grapeseed oils, and mixtures of these oils. The vegetable oil is preferably rich in oleic acid, that is to say that the fatty acid (or all of the fatty acids if several are present) from which it derives, comprises oleic acid in a weight fraction at least equal to 60%, more preferably still in a weight fraction at least equal to 70%. As vegetable oil, use is advantageously made of a sunflower oil which is such that all of the fatty acids from which it derives comprise oleic acid in a weight fraction greater than or equal to 60%, preferably 70% and, according to one particularly advantageous embodiment of the invention, in a weight fraction greater than or equal to 80%.
According to another particular embodiment of the invention, the liquid plasticizer is a triester selected from the group consisting of carboxylic acid triesters, phosphoric acid trimesters, sulphonic acid triesters and mixtures of these triesters.
Particularly suitable are the liquid plasticizers selected from the group consisting of ester plasticizers, phosphate plasticizers, sulphonate plasticizers and mixtures of these compounds.
Mention may be made, as phosphate plasticizers for example, of those that contain between 12 and 30 carbon atoms, for example trioctyl phosphate.
As examples of carboxylic acid ester plasticizers, mention may especially be made of the compounds selected from the group consisting of trimellitates, pyromellitates, phthalates, 1,2-cyclohexane dicarboxylates, adipates, azelates, sebacates, glycerol triesters and mixtures of these compounds. Among the above triesters, mention may especially be made of glycerol triesters, preferably consisting predominantly (of more than 50%, more preferably of more than 80% by weight) of an unsaturated C18 fatty acid, i.e., selected from the group consisting of oleic acid, linoleic acid, linolenic acid and mixtures of these acids. The glycerol triester is preferred. More preferably, whether it is of synthetic origin or natural origin (the case for example for sunflower or rapeseed vegetable oils), the fatty acid used consists of more than 50% by weight, more preferably still more than 80% by weight, of oleic acid. Such triesters (trioleates) having a high content of oleic acid are well known; they have been described for example in application WO 02/088238 as plasticizing agents in tyre treads.
According to another particular embodiment of the invention, the liquid plasticizer is an ether. Therefore, mention may be made of polyethylene glycols or polypropylene glycols.
The rubber compositions of the treads of the tyres in accordance with the invention may also comprise all or some of the standard additives customarily used in elastomer compositions intended for the manufacture of treads for tyres, especially winter tyres, fillers other than those mentioned above, for example non-reinforcing fillers such as chalk, or else platy fillers such as kaolin and talc, pigments, protective agents such as antiozone waxes, chemical antiozonants, antioxidants, reinforcing resins (such as resorcinol or bismaleimide), methylene acceptors (for example phenolic novolac resin) or methylene donors (for example HMT or H3M) as described for example in application WO 02/10269, a crosslinking system based either on sulphur, or on sulphur donors and/or on peroxide and/or on bismaleimides, vulcanization accelerators or vulcanization retarders, and vulcanization activators.
These compositions may also contain coupling activators when a coupling agent is used, agents for covering the inorganic filler or more generally processing aids capable, in a known way, by virtue of an improvement in the dispersion of the filler in the rubber matrix and of a lowering of the viscosity of the compositions, of improving their ability to be processed in the uncured state, these agents are, for example, hydrolysable silanes, such as alkylalkoxysilanes, polyols, polyethers, amines, or hydroxylated or hydrolysable polyorganosiloxanes.
The compositions used in the treads of the tyres of the invention may be manufactured in appropriate mixers using two successive preparation phases well known to a person skilled in the art: a first phase of thermomechanical working or kneading (referred to as a “non-productive” phase) at high temperature, up to a maximum temperature of between 110° C. and 190° C., preferably between 130° C. and 180° C., followed by a second phase of mechanical working (referred to as a “productive” phase) up to a lower temperature, typically below 110° C., for example between 40° C. and 100° C., during which finishing phase the crosslinking system is incorporated.
The process for preparing such compositions comprises, for example, the following stages:
By way of example, the non-productive phase is carried out in a single thermomechanical stage during which, in a first step, all the base constituents (the diene elastomer(s), the plasticizing system, the reinforcing inorganic filler and the coupling agent) are introduced into an appropriate mixer, such as a standard internal mixer, followed, in a second step, for example after kneading for one to two minutes, by the other additives, optional additional filler-covering agents or processing aids, with the exception of the crosslinking system. The total kneading time, in this non-productive phase, is preferably between 1 and 15 min.
After cooling the mixture thus obtained, the crosslinking system is then incorporated in an external mixer, such as an open mill, maintained at a low temperature (for example, between 40° C. and 100° C.). The combined mixture is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
The crosslinking system itself is preferably based on sulphur and on a primary vulcanization accelerator, in particular an accelerator of the sulphenamide type. Added to this vulcanization system are various known secondary accelerators or vulcanization activators, such as zinc oxide, stearic acid, guanidine derivatives (in particular diphenylguanidine), etc., incorporated during the first non-productive phase and/or during the productive phase. The sulphur content is preferably between 0.5 and 3.0 phr and the primary accelerator content is preferably between 0.5 and 5.0 phr.
Use may be made, as (primary or secondary) accelerator, of any compound capable of acting as accelerator of the vulcanization of diene elastomers in the presence of sulphur, in particular accelerators of the thiazole type and also their derivatives, accelerators of the thiuram and zinc dithiocarbamate types. These accelerators are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulphide (abbreviated to “MBTS”), N-cyclohexyl-2-benzothiazyl sulphenamide (abbreviated to “CBS”), N,N-dicyclohexyl-2-benzothiazyl sulphenamide (abbreviated to “DCBS”), N-tert-butyl-2-benzothiazyl sulphenamide (abbreviated to “TBBS”), N-tert-butyl-2-benzothiazyl sulphenimide (abbreviated to “TBSI”), zinc dibenzyldithiocarbamate (abbreviated to “ZBEC”) and mixtures of these compounds. Preferably, a primary accelerator of the sulphenamide type is used.
The final composition thus obtained may then be calendered, for example in the form of a sheet or a slab, in particular for laboratory characterization, or else is extruded, for example to form a rubber profiled element used for manufacturing a snow tyre tread.
According to one particular embodiment, the Shore A hardness of the rubber composition according to the invention is in a range extending from 50 to 70, in particular from 55 to 65. The Shore A hardness of the compositions after curing is assessed in accordance with the standard ASTM D 2240-86.
The invention relates to the tyres described above, both in the uncured state (i.e., before curing) and in the cured state (i.e., after crosslinking or vulcanization).
The invention also applies to the cases where the rubber compositions described above form only one part of treads of composite or hybrid type, especially those consisting of two radially superposed layers of different formulations (referred to as “cap-base” construction), that are both patterned and intended to come into contact with the road when the tyre is rolling, during the service life of the latter. The base part of the formulation described above could then constitute the radially outer layer of the tread intended to come into contact with the ground from the moment when a new tyre starts rolling, or on the other hand its radially inner layer intended to come into contact with the ground at a later stage.
The tests below are carried out in the following manner: the elastomers, the silica, the coupling agent, the plasticizers, and also the various other ingredients, with the exception of the vulcanization system, are successively introduced into an internal mixer (final fill ratio: around 70% by volume), the initial vessel temperature of which is around 60° C. Thermomechanical working (non-productive phase) is then carried out in one stage, which lasts in total approximately 5 min, until a maximum “dropping” temperature of 165° C. is reached.
The mixture thus obtained is recovered and cooled and then sulphur and an accelerator of sulphenamide type are incorporated in a mixer (homofinisher) at 23° C., everything being mixed (productive phase) for an appropriate time (for example, between 5 and 12 min).
Compositions T1, C1 and C2 thus obtained are described (in phr) in Table 1.
Composition T1 is a conventional composition that can be used to form a tread for a winter tyre, based on polybutadiene and on an SBR copolymer.
In this control composition, the two elastomers used are devoid of SiOR function, the content of reinforcing inorganic filler is less than 100 phr, and the content A+B of plasticizing system is less than 50 phr, consisting of plasticizing resin (polylimonene, 20 phr) and sunflower vegetable oil (15 phr) and MES oil (5 phr) as liquid plasticizing agent.
Compositions C1 and C2, in accordance with the invention, are characterized by the presence of at least 20 phr of a diene elastomer bearing a silanol function, of at least 100 phr of a reinforcing inorganic filler, of more than 50 phr of a plasticizing system consisting of plasticizing resin (polylimonene) and liquid plasticizing agent (sunflower vegetable oil) at contents respectively between 10 and 60 phr. The elastomer SBR3 of composition C1 bears a dimethylsilanol function at one chain end and was prepared according to the process described in patent EP 0 778 311 B1. The elastomer SBR4 of composition C2 contains a mixture of 85% of an SBR(SBR4A) bearing a dimethylsilanol function at one chain end and 15% of an SBR (SBR4B) star-branched to tin and of the same microstructure as SBR4A.
These three compositions were extruded in the form of a tread, in order to be tested as indicated in the following paragraph.
Compositions T1, C1 and C2 are then used as treads for radial carcass passenger vehicle winter tyres, denoted respectively PT1 (control tyres) and P1 and P2 (tyres in accordance with the invention), with dimensions of 225/45 R17, which are conventionally manufactured and are in all respects identical apart from the constituent rubber compositions of their treads.
The tyres are subjected to braking tests on wet ground and on snowy ground as described below.
To test the braking on wet ground, the tyres are fitted to a motor vehicle of Audi make and A4 model, equipped with an ABS braking system and the distance needed to go from 80 km/h to 10 km/h is measured during sudden braking on sprayed ground (bituminous concrete). A value above that of the control, arbitrarily set at 100, indicates an improved result, that is to say a shorter braking distance.
To test the braking on snowy ground, the tyres are fitted to a motor vehicle of Volkswagen make and Golf model, equipped with an ABS braking system, and the distance needed to go from 50 km/h to 5 km/h is measured during emergency braking on snow. A value above that of the control, arbitrarily set at 100, indicates an improved result, that is to say a shorter braking distance.
The results of the running tests are reported in Table 2, in relative units, the base 100 being used for the control tyre PT1.
It is observed that the snow tyres in accordance with the invention P1 and P2 have respective values of the grip performance on wet ground of 112 and 107, surprisingly much higher than those of the control snow tyre PT1. It is also noted that these results are obtained without being at the expense of the performance on snowy ground, which is even improved in the case of the snow tyre P2 (106).
In conclusion, the snow tyres in accordance with the invention have a greatly improved grip on wet ground, without degrading, or even while improving, the grip on snowy ground.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1059805 | Nov 2010 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2011/070892 | 11/24/2011 | WO | 00 | 6/26/2013 |
