Patent Application
20190322136
The present invention relates to “inflatable” articles, that is to say, by definition, to articles which assume their usable form when they are inflated with air or with an equivalent inflation gas.
More particularly, the present invention relates to a tyre comprising a tread comprising a) an elastomeric matrix which comprises predominantly by weight one or more thermoplastic elastomers, and b) a crosslinking system based on sulfur or a sulfur donor and one or more vulcanization accelerators.
The invention also relates to a process for preparing the tyre according to the invention.
In a conventional tyre, the tread generally comprises predominantly by weight one or more diene elastomers.
A constant aim of tyre manufacturers is to improve the wet grip of tyres. At the same time, another aim is to reduce the rolling resistance of tyres. However, these two aims are difficult to reconcile in that the improvement in grip implies increasing the hysteresis losses whereas the improvement in the rolling resistance implies lowering the hysteresis losses. There is therefore a compromise in performance to be optimized.
Consequently, the applicant companies previously developed (WO 2012/152686) tyres equipped with a tread comprising a thermoplastic elastomer. These tyres have a very good compromise in grip and rolling resistance performance.
Furthermore, the treads made of thermoplastic elastomers have an easier processing due to a low viscosity at temperature.
However, on the finished tyre, it may be that the low stiffness at high temperature that is desired for the processing is then a problem for the performance of the tyre, in particular during use at high temperature. Specifically, during tyre use cycles such as braking cycles, this may result, in extreme cases, in a softening of the tread which would have the consequence of reducing the endurance of the tread.
In patent application WO 2014/041167, the Applicants presented a tyre comprising a tread predominantly comprising by weight a thermoplastic elastomer and carbon black.
In general, the temperature resistance performance of treads can be further improved.
Consequently, there is a need to improve the temperature resistance of thermoplastic elastomer treads without degrading the processing possibilities of these elastomer treads.
Nevertheless, a person skilled in the art knows that thermoplastic elastomers are generally not chemically crosslinked. The thermoplastic blocks (“hard” blocks) of thermoplastic elastomers usually act as a physical “crosslinker”. They provide sufficient cohesion to the tread.
In particular, in patent application WO 2014/041167 mentioned above, there is nothing to encourage a person skilled in the art to use a crosslinking system in the tread compositions, in particular in view of the comment in paragraph [0088] of this document.
However the applicant has now surprisingly discovered that a crosslinking of the tread by means of a crosslinking system based on sulfur or a sulfur donor made it possible to respond to the constraints formulated above, in particular to improve the temperature resistance of thermoplastic elastomer treads while retaining the processing possibilities associated with these treads.
Thus, one subject of the invention is a tyre comprising a tread, a crown with a crown reinforcement, two sidewalls, two beads, a carcass reinforcement anchored to the two beads and extending from one sidewall to the other, the tread comprising a) an elastomeric matrix which comprises predominantly by weight one or more thermoplastic elastomers, one or more of these thermoplastic elastomers comprising at least one unsaturated elastomer block and at least one thermoplastic block, and b) a crosslinking system based on sulfur or a sulfur donor and one or more vulcanization accelerators.
The tyre according to the invention has a good compromise in properties, in particular between, on the one hand, an easier processing during its preparation and, on the other hand, an improved stiffness at high temperature.
Another subject of the invention is a process for preparing a tyre comprising a tread as defined above, comprising the following steps:
The invention and its advantages will be easily understood from reading the description and exemplary embodiments which follow and from studying the figures which represent:
In the present invention, unless expressly indicated otherwise, all the percentages (%) given are % by weight.
Furthermore, any range of values denoted by the expression “between a and b” represents the range of values extending from more than a to less than b (that is to say, limits a and b excluded), while any range of values denoted by the expression “from a to b” means the range of values extending from a up to b (that is to say, including the strict limits a and b).
In the present application, the term “parts per hundred parts of elastomer” or “phr” means the part by weight of a constituent per 100 parts by weight of the elastomer(s) of the elastomeric matrix, i.e. of the total weight of the elastomer(s), whether they are thermoplastic or non-thermoplastic, present in the elastomeric matrix. Thus, a constituent at 60 phr will mean, for example, 60 g of this constituent per 100 g of elastomer of the elastomeric matrix.
As described above, the tyre according to the invention comprises in particular a tread which comprises an elastomeric matrix comprising predominantly by weight one or more thermoplastic elastomers.
The term “predominantly by weight one or more thermoplastic elastomers” means that the elastomeric matrix comprises at least 50% by weight, preferably at least 65% by weight, more preferentially at least 70% by weight, and in particular at least 75% by weight of thermoplastic elastomers relative to all of the elastomers present in the elastomeric matrix of the tread.
A thermoplastic elastomer (TPE) is understood, in a known manner, to mean a polymer having a structure intermediate between a thermoplastic polymer and an elastomer.
A thermoplastic elastomer consists of one or more rigid “thermoplastic” segments connected to one or more flexible “elastomer” segments.
Thus, the thermoplastic elastomer(s) of the tread that can be used according to the invention comprise at least one elastomer block and at least one thermoplastic block.
Typically, each of these segments or blocks contains at least more than 5, generally more than 10 base units.
In the present application, when reference is made to the glass transition temperature of a thermoplastic elastomer, it is the glass transition temperature relating to the elastomer block (unless otherwise indicated). Indeed, in a known manner, thermoplastic elastomers have two glass transition temperature peaks (Tg, measured according to ASTM D3418), the lowest temperature being related to the elastomer part of the thermoplastic elastomer and the highest temperature being related to the thermoplastic part of the thermoplastic elastomer. Thus, the flexible blocks of the thermoplastic elastomers are generally defined by a Tg below or equal to ambient temperature (25° C.), whilst the rigid blocks have a Tg above or equal to 80° C. In order to be of both elastomeric and thermoplastic nature, the thermoplastic elastomer must be provided with blocks that are sufficiently incompatible (that is to say different due to their respective weight, their respective polarity or their respective Tg) in order to retain their characteristic elastomer block or thermoplastic block properties.
Thus, the thermoplastic elastomer(s) that can be used according to the invention (therefore the elastomer block(s) of the thermoplastic elastomers) preferentially have a glass transition temperature which is below or equal to 25° C., more preferentially below or equal to 10° C. A Tg value above these minima may reduce the performances of the tread during use at very low temperature; for such a use, the glass transition temperature of the thermoplastic elastomers is more preferentially still less than or equal to −10° C.
Also preferentially, the glass transition temperature of the thermoplastic elastomers that can be used according to the invention is greater than −100° C.
The number-average molecular weight (denoted by Mn) of the thermoplastic elastomers is preferentially between 30 000 and 500 000 g/mol, more preferentially between 40 000 and 450 000 g/mol. Below the minima indicated, there is a risk of the cohesion between the elastomer chains of the thermoplastic elastomers being affected, in particular due to their possible dilution (in the presence of an extender oil); furthermore, there is a risk of an increase in the working temperature affecting the mechanical properties, in particular the properties at break, with the consequence of a reduced “hot” performance. Furthermore, an excessively high Mn weight can be detrimental to the implementation. Thus, it has been found that a value between 50 000 and 300 000 g/mol was particularly well suited to use of the thermoplastic elastomers in a tyre tread.
The number-average molecular weight (Mn) of the thermoplastic elastomers is determined in a known manner, by size exclusion chromatography (SEC). The sample is first dissolved in a suitable solvent at a concentration of about 2 g/l and then the solution is filtered on a filter with a porosity of 0.45 μm before injection. The apparatus used is a Waters Alliance chromatographic line. The injected volume of the solution of the polymer sample is 100 μl. The detector is a Waters 2410 differential refractometer and its associated software, for making use of the chromatographic data, is the Empower system. The conditions can be adjusted by those skilled in the art. For example, in the case of TPEs of COPE type, the elution solvent is hexafluoroisopropanol with sodium trifluoroactetate salt at a concentration of 0.02M, the flow rate is 0.5 ml/min, the temperature of the system is 35° C. and the analysis time is 90 min. Use is made of a set of three PHENOMENEX columns in series, with “PHENOGEL” trade names (pore size: 105, 104, 103 A). For example, in the case of styrene thermoplastic elastomers, the sample is first dissolved in tetrahydrofuran at a concentration of approximately 1 g/l and then the solution is filtered on a filter with a porosity of 0.45 μm before injection. The apparatus used is a Waters Alliance chromatographic line. The elution solvent is tetrahydrofuran, the flow rate is 0.7 ml/min, the temperature of the system is 35° C. and the analysis time is 90 min. A set of four WATERS “STYRAGEL” columns (an HMW7 column, an HMW6E column and two HT6E columns) are used in series. The injected volume of the solution of the polymer sample is 100 μL. The detector is a Waters 2410 differential refractometer and its associated software, for making use of the chromatographic data, is the Waters Millennium system. The calculated average molar weights are relative to a calibration curve produced with polystyrene standards.
The polydispersity index (PI=Mw/Mn, with Mw the weight-average molecular weight) of the thermoplastic elastomer(s) is preferably less than 3; more preferentially less than 2 and more preferentially still less than 1.5.
The thermoplastic elastomers that can be used according to the invention may be copolymers with a small number of blocks (less than 5, typically 2 or 3), in which case these blocks preferably have high weights of greater than 15 000 g/mol.
The thermoplastic elastomers may also be copolymers with a large number of smaller blocks (more than 30, typically from 50 to 500), in which case these blocks preferably have relatively low weights, for example from 500 to 5000 g/mol; these thermoplastic elastomers will subsequently be referred to as multiblock thermoplastic elastomers.
According to a first variant, the thermoplastic elastomers that can be used according to the invention are in a linear form.
In a first particular embodiment of this first variant, the thermoplastic elastomers are diblock copolymers: thermoplastic block/elastomer block.
In a second particular embodiment of this first variant, the thermoplastic elastomers are triblock copolymers: thermoplastic block/elastomer block/thermoplastic block, that is to say a central elastomer block and a terminal thermoplastic block at each of the two ends of the elastomer block.
In a third particular embodiment of this first variant, the thermoplastic elastomers are formed of a linear series of elastomer blocks and thermoplastic blocks (multiblock thermoplastic elastomers).
According to a second variant, the thermoplastic elastomers that can be used according to the invention are in a star-branched form comprising at least three branches.
For example, the thermoplastic elastomers can then be composed of a star-branched elastomer block comprising at least three branches and of a thermoplastic block located at the end of each of the branches of the elastomer block. The number of branches of the central elastomer can vary, for example, from 3 to 12 and preferably from 3 to 6.
According to a third variant, the thermoplastic elastomers that can be used according to the invention are in a branched or dendrimer form. The thermoplastic elastomers can then be composed of a branched or dendrimer elastomer block and of a thermoplastic block located at the end of the branches of the dendrimer elastomer block.
As explained above, one or more thermoplastic elastomers that can be used according to the invention comprise at least one unsaturated elastomer block and at least one thermoplastic block.
The term “unsaturated elastomeric block” means that this block is at least partly derived from conjugated diene monomers, with a content of moieties or units of diene origin (conjugated dienes) which is greater than 15 mol %.
It may then also be referred to as an “essentially unsaturated” elastomeric block.
The term “highly unsaturated” elastomeric block also means an elastomeric block with a content of units of diene origin (conjugated dienes) which is greater than 50 mol %.
The unsaturated elastomeric blocks that may be used according to the invention may be chosen from:
a) any homopolymer obtained by polymerization of a conjugated diene monomer containing from 4 to 12 carbon atoms;
b) any copolymer obtained by copolymerization of one or more dienes conjugated with each other or with one or more vinyl aromatic compounds containing from 8 to 20 carbon atoms;
c) a ternary copolymer obtained by copolymerization of ethylene, of an α-olefin containing from 3 to 6 carbon atoms with a non-conjugated diene monomer containing from 6 to 12 carbon atoms, for instance elastomers obtained from ethylene, from propylene with a non-conjugated diene monomer of the abovementioned type especially such as 1,4-hexadiene, ethylidenenorbornene or dicyclopentadiene;
d) a copolymer of isobutene and of isoprene (diene butyl rubber), and also the halogenated, in particular chlorinated or brominated, versions of this type of copolymer.
Particularly suitable as conjugated dienes are isoprene, 1,3-butadiene, piperylene, 1-methylbutadiene, 2-methylbutadiene, 2,3-dimethyl-1,3-butadiene, 2,4-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2,5-dimethyl-1,3-pentadiene, 2-methyl-1,4-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 2-methyl-1,5-hexadiene, 3-methyl-1,3-hexadiene, 4-methyl-1,3-hexadiene, 5-methyl-1,3-hexadiene, 2,5-dimethyl-1,3-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-neopentyl-1,3-butadiene, 1,3-cyclopentadiene, methylcyclopentadiene, 2-methyl-1,6-heptadiene, 1,3-cyclohexadiene, 1-vinyl-1,3-cyclohexadiene, and a mixture of these conjugated dienes, and preferably these conjugated dienes are selected from isoprene, butadiene and a mixture containing isoprene and/or butadiene.
According to one variant, the monomers polymerized in order to form an unsaturated elastomer block may be copolymerized, randomly, with at least one other monomer so as to form an unsaturated elastomer block. According to this variant, the molar fraction of polymerized monomer, other than a diene monomer, relative to the total number of units of the unsaturated elastomer block, has to be such that this block retains its unsaturated elastomer properties. Advantageously, the molar fraction of this other comonomer can range from 0 to 50%, more preferentially from 0 to 45% and more preferentially still from 0 to 40%.
By way of illustration, this other monomer capable of copolymerizing with the first monomer can be chosen from ethylenic monomers such as ethylene, propylene, butylene, monomers of vinylaromatic type having from 8 to 20 carbon atoms as defined above, or else it may be a monomer such as vinyl acetate.
Styrene monomers, namely methylstyrenes, para-(tert-butyl)styrene, chlorostyrenes, bromostyrenes, fluorostyrenes or else para-hydroxystyrene, are suitable in particular as vinylaromatic compounds. Preferably, the comonomer of vinylaromatic type is styrene.
Thus, according to one preferred embodiment, the at least one elastomer block may be a random copolymer of styrene-butadiene (SBR) type, it being possible for this copolymer to be partially hydrogenated. This SBR block preferably has a Tg (glass transition temperature) measured by DSC according to standard ASTM D3418, 1999, of less than 25° C., preferentially less than 10° C., more preferentially less than 0° C. and very preferentially less than −10° C. Also preferentially, the Tg of the SBR block is greater than −100° C. SBR blocks having a Tg of between 20° C. and −70° C., and more particularly between 0° C. and −50° C., are especially suitable. In a well known way, the SBR block comprises a styrene content, a content of 1,2-bonds of the butadiene part and a content of 1,4-bonds of the butadiene part, the latter being composed of a content of trans-1,4-bonds and a content of cis-1,4-bonds when the butadiene part is not hydrogenated. Preferentially, use is especially made of an SBR block having a styrene content for example within a range extending from 10% to 60% by weight, preferably from 20% to 50% by weight, and for the butadiene part, a content of 1,2-bonds within a range extending from 4% to 75% (mol %) and a content of 1,4-bonds within a range extending from 20% to 96% (mol %).
The degree of hydrogenation is determined by NMR analysis. The spectra are acquired on a Bruker Avance 500 MHz spectrometer equipped with a 1H-X 5 mm Cryoprobe. The quantitative 1HNMR experiment uses a simple 30° pulse sequence and a repetition time of 5 seconds between each acquisition. 64 accumulations are carried out. The samples (approximately 25 mg) are dissolved in approximately 1 ml of CS2, 100 μl of deuterated cyclohexane are added for locking during acquisition. The chemical shifts are calibrated relative to the protonated impurity of the CS2 1H δ ppm at 7.18 ppm, with reference to TMS (1H δ ppm at 0 ppm). The 1H NMR spectrum makes it possible to quantify the microstructure by integration of the signal peaks characteristic of the various units:
The microstructure may be quantified in terms of mol % as follows: mol % of a unit=1H integral of a unit/Σ(1H integrals of each unit). For example, for a styrene unit: mol % of styrene=(1H integral of styrene)/(1H integral of styrene+1H integral of PB1-2+1H integral of PB1-4+1H integral of hydrogenated PB1-2+1H integral of hydrogenated PB1-4).
Preferably, in the thermoplastic elastomers of use for the requirements of the invention, the SBR elastomer block is hydrogenated such that a proportion ranging from 10 mol % to 80 mol % of the double bonds in the butadiene portion are hydrogenated.
Preferably for the invention, the elastomer blocks of the thermoplastic elastomers have, in total, a number-average molecular weight (Mn) ranging from 25 000 g/mol to 350 000 g/mol, preferably from 35 000 g/mol to 250 000 g/mol, so as to confer, on the thermoplastic elastomers, good elastomeric properties and a mechanical strength which is sufficient and compatible with the use as tyre tread.
Particularly preferably in the invention, the unsaturated elastomer block(s) are selected from the group consisting of polyisoprenes, polybutadienes, butadiene-isoprene copolymers, styrene-butadiene copolymers, and mixtures of these elastomers, these elastomers being unhydrogenated or partially hydrogenated.
Preferably, all of the unsaturated elastomer blocks of the thermoplastic elastomers comprising at least one unsaturated elastomer block and at least one thermoplastic block represent at least 50% by weight of all of the saturated or unsaturated elastomer blocks of all of the thermoplastic elastomers of the elastomeric matrix.
As explained above, the thermoplastic elastomers that can be used according to the invention also comprise at least one thermoplastic block.
A thermoplastic block is understood to mean a block consisting of polymerized monomers and having a glass transition temperature, or a melting point in the case of semicrystalline polymers, above or equal to 80° C., preferably varying from 80° C. to 250° C., more preferentially varying from 80° C. to 200° C., and in particular varying from 80° C. to 180° C.
Indeed, in the case of a semicrystalline polymer, a melting point may be observed which is above the glass transition temperature. In this case, the melting point and not the glass transition temperature is taken into account for the definition above.
The thermoplastic block(s) may be formed from polymerized monomers of various types.
In particular, the thermoplastic block(s) may be selected from the group consisting of polyolefins (polyethylene, polypropylene), polyurethanes, polyamides, polyesters, polyacetals, polyethers (polyethylene oxide, polyphenylene ether), polyphenylene sulphides, polyfluorinated compounds (FEP, PFA, ETFE), polystyrenes, polycarbonates, polysulfones, polymethyl methacrylate, polyetherimide, thermoplastic copolymers, such as the acrylonitrile-butadiene-styrene (ABS) copolymer, and mixtures of these polymers.
The thermoplastic block(s) may also be obtained from monomers selected from:
According to one variant of the invention, the above monomers may be copolymerized with at least one other monomer as long as this other monomer does not modify the thermoplastic nature of the block, that is to say that the block has a glass transition temperature, or a melting point in the case of semi-crystalline polymers, above or equal to 80° C.
By way of illustration, this other monomer capable of copolymerizing with the polymerized monomer can be chosen from diene monomers, more particularly conjugated diene monomers having from 4 to 14 carbon atoms, and monomers of vinylaromatic type having from 8 to 20 carbon atoms, such as defined in the part relating to the elastomer block.
As explained above, the thermoplastic block(s) may be selected from polystyrenes and polymers comprising at least one polystyrene block.
Regarding the polystyrenes, these are obtained from styrene monomers.
Styrene monomer should be understood as meaning, in the present description, any monomer comprising styrene, unsubstituted or substituted; mention may be made, among substituted styrenes, for example, of methylstyrenes (for example, o-methylstyrene, m-methylstyrene or p-methylstyrene, α-methylstyrene, α,2-dimethylstyrene, α,4-dimethylstyrene or diphenylethylene), para-(tert-butyl)styrene, chlorostyrenes (for example, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene or 2,4,6-trichlorostyrene), bromostyrenes (for example, o-bromostyrene, m-bromostyrene, p-bromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene or 2,4,6-tribromostyrenes), fluorostyrenes (for example, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,4-difluorostyrene, 2,6-difluorostyrene or 2,4,6-trifluorostyrenes) or else para-hydroxystyrene.
According to a preferential embodiment of the invention, the content by weight of styrene in the thermoplastic elastomers that can be used according to the invention is between 5% and 50%. Below the minimum indicated, there is a risk of the thermoplastic nature of the elastomer being substantially reduced while, above the recommended maximum, the elasticity of the tread can be affected. For these reasons, the styrene content is more preferentially between 10% and 40%.
The proportion of thermoplastic blocks in the thermoplastic elastomers that can be used according to the invention is determined, on the one hand, by the thermoplasticity properties that the thermoplastic elastomers must have.
The thermoplastic block(s) are preferentially present in sufficient proportions to preserve the thermoplastic nature of the thermoplastic elastomers that can be used according to the invention. The minimum content of thermoplastic blocks in the thermoplastic elastomers may vary as a function of the conditions of use of the thermoplastic elastomers.
On the other hand, the ability of the thermoplastic elastomers to deform during the preparation of the tyre can also contribute to determining the proportion of the thermoplastic blocks in the thermoplastic elastomers that can be used according to the invention.
Preferably, the thermoplastic blocks of the thermoplastic elastomers have, in total, a number-average molecular weight (Mn) ranging from 5000 g/mol to 150 000 g/mol, so as to confer, on the thermoplastic elastomers, good elastomeric properties and a mechanical strength which is sufficient and compatible with the use as tyre tread. Particularly preferably in the invention, the thermoplastic block(s) are selected from the group consisting of polystyrenes, polyesters, polyamides, polyurethanes, and mixtures of these polymers.
Very particularly preferably in the invention, the thermoplastic block(s) are selected from the group consisting of polystyrenes, polyesters, polyamides, and mixtures of these polymers.
Preferably in the invention, the thermoplastic elastomer(s) are selected from the group consisting of styrene/butadiene/styrene (SBS), styrene/isoprene/styrene (SIS), styrene/butadiene/isoprene/styrene (SBIS), styrene/optionally partially hydrogenated butadiene-styrene copolymer/styrene (SOE), styrene/partially hydrogenated butadiene/styrene (SBBS) block copolymers, and mixtures of these copolymers.
Mention may be made, as examples of thermoplastic elastomers that are commercially available and that can be used according to the invention, of the elastomers of SIS type sold by Kuraray under the name Hybrar 5125 or sold by Kraton under the name D1161, or else the elastomers of linear SBS type sold by Polimeri Europa under the name Europrene SOLT 166 or of star-branched SBS type sold by Kraton under the name D1184. Mention may also be made of the elastomers sold by Dexco Polymers under the name Vector (for example Vector 4114 or Vector 8508).
Preferably, the thermoplastic elastomer(s) comprising at least one unsaturated elastomeric block and at least one thermoplastic block represent more than 50% by weight, more preferentially more than 65% by weight, even more preferentially at least 70% by weight, and in particular at least 75% by weight, relative to the weight of all of the thermoplastic elastomers of the elastomeric matrix.
Particularly preferably, the thermoplastic elastomer(s) comprising at least one unsaturated elastomeric block and at least one thermoplastic block are the only thermoplastic elastomers of the elastomeric matrix.
It is also possible for the thermoplastic elastomers presented above, whether or not they comprise at least one unsaturated elastomer block, to be in a mixture with other non-thermoplastic elastomers.
Thus, the thermoplastic elastomer content of the elastomeric matrix of the tread generally ranges from 65 to 100 phr, preferably from 70 to 100 phr, more preferentially from 75 to 100 phr, and even more preferentially from 95 to 100 phr.
Particularly preferably, the thermoplastic elastomer(s) that can be used according to the invention are the only elastomers of the elastomeric matrix of the tread.
Very particularly preferably, the thermoplastic elastomer(s) comprising at least one unsaturated elastomer block and at least one thermoplastic block are the only elastomers of the elastomeric matrix of the tread.
The thermoplastic elastomer(s) described above are sufficient by themselves for the tread that can be used according to the invention to be usable.
However, in the case where the thermoplastic elastomers are mixed with non-thermoplastic elastomers, the elastomeric matrix of the tread according to the invention may then comprise one or more diene rubbers as non-thermoplastic elastomer.
A “diene” elastomer or rubber should be understood, in a known manner, as meaning one or more elastomers resulting at least in part (i.e. a homopolymer or a copolymer) from diene monomers (monomers bearing two conjugated or non-conjugated carbon-carbon double bonds).
These diene elastomers can be classified into two categories: “essentially unsaturated” or “essentially saturated”.
“Essentially unsaturated” is generally intended 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 %). In the category of “essentially unsaturated” diene elastomers, a “highly unsaturated” diene elastomer is intended in particular to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
Thus it is that diene elastomers such as some butyl rubbers or copolymers of dienes and of α-olefins of EPDM type can be described as “essentially saturated” diene elastomers (low or very low content of units of diene origin, always less than 15%).
Given these definitions, diene elastomer, regardless of the above category, capable of being used in the tread that can be used according to the invention, is understood more particularly to mean:
The following are especially suitable 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, aryl-1,3-butadienes, 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 of the diene elastomers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units. The diene elastomers can have any microstructure, which depends on the polymerization conditions used, especially on the presence or absence of a modifying and/or randomizing agent and on the amounts of modifying and/or randomizing agent employed. The elastomers can, for example, be prepared in dispersion or in solution; they can be coupled and/or star-branched or else functionalized with a coupling and/or star-branching or functionalization agent. For coupling with carbon black, mention may be made, for example, of functional groups comprising a C—Sn bond or amino functional groups, such as benzophenone, for example; for coupling to a reinforcing inorganic filler such as silica, mention may be made, for example, of silanol functional groups or polysiloxane functional groups having a silanol end (such as described, for example, in FR 2 740 778 or U.S. Pat. No. 6,013,718), alkoxysilane groups (such as described, for example, in FR 2 765 882 or U.S. Pat. No. 5,977,238), carboxyl groups (such as described, for example, in WO 01/92402 or U.S. Pat. No. 6,815,473, WO 2004/096865 or US 2006/0089445) or else polyether groups (such as described, for example, in EP 1 127 909 or U.S. Pat. No. 6,503,973). Mention may also be made, as other examples of functionalized elastomers, of elastomers (such as SBR, BR, NR or IR) of the epoxidized type.
As explained previously, the tread that may used in the tyre according to the invention comprises a crosslinking system based on sufur or a sulfur donor and on one or more vulcanization accelerators.
The term “based on” should be understood as meaning that the crosslinking system includes a mixture and/or the product of reaction of the various constituents used in the crosslinking system, in particular sulfur or the sulfur donor, some of these base constituents being capable of reacting, or intended to react, with each other or with the other constituents of the tread, at least partly, during the various phases of manufacture of the tread, in particular during its crosslinking.
Among the sulfur-donating agents, examples that may be mentioned include dipentamethylenethiuram tetrasulfide (DPTT), polymeric sulfur or caprolactam disulfide (CLD).
Preferably, the content of sulfur or of sulfur donor of the tread ranges from 0.1 to 8 phr, preferably ranges from 0.2 to 6 phr and more preferentially ranges from 0.5 to 5 phr (parts by weight per hundred parts by weight of elastomer).
The crosslinking system also comprises one or more vulcanization accelerators.
The vulcanization accelerator(s) are preferably chosen from accelerators of the thiazole type and derivatives thereof, accelerators of thiuram type, accelerators of dithiocarbamate type, accelerators of dithiophosphate type and mixtures of these compounds.
Particularly preferably, the vulcanization accelerator(s) are chosen from N-cyclohexyl-2-benzothiazyl sulfenamide (CBS), N,N-dicyclohexyl-2-benzothiazyl sulfenamide (DCBS), N-tert-butyl-2-benzothiazyl sulfenamide (TBBS), N-tert-butyl-2-benzothiazyl sulfenimide (TBSI), tetrabenzyl thiuram disulfide (TBzTD), zinc dibenzyldithiocarbamate (ZBEC), zinc dibutyl dithiophosphate (ZBPD) and mixtures of these compounds.
Most particularly preferably, the vulcanization accelerator is N-cyclohexyl-2-benzothiazyl sulfenamide (CBS).
The content of vulcanization accelerators of the tread generally ranges from 0.2 to 10 phr, preferably ranges from 0.7 to 7 phr (parts by weight per hundred parts by weight of elastomer).
In a most particularly preferred mode of the invention, the weight ratio between the content of sulfur or of sulfur donor and the content of vulcanization accelerators of the tread is less than or equal to 1.
The tread that may be used in the tyre according to the invention may also comprise one or more additives chosen from zinc oxide, stearic acid, guanidine derivatives, in particular 1,3-diphenylguanidine and mixtures of these compounds.
The tread that can be used according to the invention may also comprise a reinforcing filler.
In particular, use may be made of any type of filler commonly used for the manufacture of tyres, for example an organic filler, such as carbon black, an inorganic filler, such as silica, or else a blend of these two types of filler, especially a blend of carbon black and silica.
All the carbon blacks conventionally used in tyres (“tyre-grade” blacks) are suitable as carbon blacks. Mention will more particularly be made, for example, of the reinforcing carbon blacks of the 100, 200 or 300 series (ASTI grades), such as, for example, the N115, N134, N234, N326, N330, N339, N347 or N375 blacks, or else, depending on the applications targeted, the blacks of higher series (for example N660, N683 or N772), indeed even N990.
“Reinforcing inorganic filler” should be understood, in the present patent application, by definition, as meaning any inorganic or mineral filler (whatever its colour and its origin, natural or synthetic), also known as “white filler”, “clear filler” or indeed 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 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 way, by the presence of hydroxyl (—OH) groups at its surface.
The physical state in which the reinforcing inorganic filler is provided is not important, whether it is in the form of a powder, of micropearls, of granules, of beads or any other appropriate densified form. Of course, the term “reinforcing inorganic filler” is also understood to mean mixtures of different reinforcing inorganic fillers, in particular of highly dispersible siliceous and/or aluminous fillers as described below.
Mineral fillers of the siliceous type, in particular silica (SiO2), or of the aluminous type, in particular alumina (Al2O3), are especially suitable as reinforcing inorganic fillers. The silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET specific surface area and a CTAB specific surface area which are both less than 450 m2/g, preferably from 30 to 400 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 1165MP, 1135MP and 1115MP 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 as described in application WO 03/16837.
In order to couple the reinforcing inorganic filler to the elastomer, it is possible, for example, to use, in a known way, an at least bifunctional 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 elastomer, in particular bifunctional organosilanes or polyorganosiloxanes.
The content by volume of optional reinforcing filler in the tread (carbon black and/or reinforcing inorganic filler, such as silica) is within a range extending from 0 to 30%, which corresponds approximately to a content of 0 to 100 phr for a plasticizer-free tread. Preferentially, the tread that can be used according to the invention comprises less than 30 phr of reinforcing filler and more preferentially less than 10 phr.
According to a preferential variant of the invention, the tread does not contain reinforcing filler.
In the same way, the tread that can be used according to the invention may contain one or more inert micrometric fillers, such as the platy fillers known to a person skilled in the art.
Preferably, the tread that can be used according to the invention does not contain a micrometric filler.
The thermoplastic elastomer(s) described above are sufficient by themselves for the tread according to the invention to be usable.
Nonetheless, according to one preferential embodiment of the invention, the tread may also comprise at least one plasticizing agent, such as an oil (or a plasticizing oil or extender oil), or a plasticizing resin, the role of which is to facilitate the processing of the tread, in particular its incorporation in the tyre, by lowering the modulus and increasing the tackifying power.
Use may be made of any oil, preferably having a weakly polar nature, capable of extending or plasticizing elastomers, especially thermoplastic elastomers. At ambient temperature (23° C.), these oils, which are more or less viscous, are liquids (that is to say, as a reminder, substances which have the ability to eventually assume the shape of their container), in contrast especially to resins or rubbers, which are by nature solids. Use may also be made of any type of plasticizing resin known to those skilled in the art.
For example, the extender oil is selected from the group consisting of paraffinic oils, such as a low viscosity paraffinic oil (LVPO).
Thus, in one particular embodiment of the present invention, the at least one plasticizing agent is a paraffinic oil.
A person skilled in the art will know, in the light of the description and implementational examples which follow, how to adjust the amount of plasticizer as a function of the thermoplastic elastomers used (as indicated above) and of the specific conditions of use of the tyre provided with the tread.
When it is used, it is preferred that the content of extender oil be within a range varying from 0 to 80 phr, preferentially from 0 to 50 phr, more preferentially from 5 to 50 phr, depending on the glass transition temperature and the modulus which are targeted for the tread.
The tread described above can furthermore comprise the various additives normally present in the treads known to those skilled in the art. The choice will be made, for example, of one or more additives chosen from protection agents, such as antioxidants or antiozonants, UV stabilizers, various processing aids or other stabilizers, or else promoters capable of promoting the adhesion to the remainder of the structure of the pneumatic article.
Preferentially, the tread does not contain all these additives at the same time and, more preferentially still, the tread does not contain any of these agents.
In addition to the elastomers described above, the composition of the tread could also comprise, always according to a minor fraction by weight with respect to the thermoplastic elastomers, polymers other than elastomers, such as, for example, thermoplastic polymers. When they are present in the tread, it is preferable for the total content of non-elastomeric thermoplastic polymers to be less than 40 phr, preferentially between 5 and 30 phr and more preferentially between 10 and 25 phr.
These thermoplastic polymers can in particular be poly(para-phenylene ether) polymers (denoted by the abbreviation “PPE”). These PPE thermoplastic polymers are well known to a person skilled in the art; they are resins which are solid at ambient temperature (20° C.) and are compatible with styrene polymers, which are in particular used to increase the glass transition temperature of thermoplastic elastomers, the thermoplastic block of which is a styrene block (see, for example, “Thermal, Mechanical and Morphological Analyses of Poly(2,6-dimethyl-1,4-phenylene oxide)/Styrene-Butadiene-Styrene Blends”, Tucker, Barlow and Paul, Macromolecules, 1988, 21, 1678-1685).
This tread may be mounted on a tyre in a conventional way, said tyre comprising, in addition to the tread, a crown, two sidewalls and two beads, a carcass reinforcement anchored to the two beads, and a crown reinforcement.
Optionally, the tyre according to the invention may also comprise an underlayer or an adhesion layer between the patterned portion of the tread and the crown reinforcement.
In general, the tyre according to the invention is intended to equip motor vehicles of private passenger type, SUVs (sport utility vehicles), two-wheeled vehicles (especially motorbikes), aeroplanes, and also industrial vehicles such as vans, heavy-goods vehicles and other transportation or material-handling vehicles.
Heavy-duty vehicles may especially comprise underground trains, buses and heavy road transport vehicles such as lorries, tractors, trailers and off-road vehicles, such as agricultural or civil engineering vehicles.
The tread that can be used according to the invention has the distinctive feature of being crosslinked.
Thus, it enables improved high-temperature stiffness to be imparted to the tread.
Consequently, the present invention also relates to a process for preparing a tyre as defined above, comprising the following steps:
Thus, the tread of the tyre according to the invention is firstly prepared in the conventional way, by incorporation of the various components in a twin-screw extruder, so as to melt the matrix and incorporate all the ingredients, followed by use of a die which makes it possible to produce the profiled element.
The various components of the tread are in particular the thermoplastic elastomers seen above which are available for example in the form of beads or pellets.
The tread is then placed on the tyre.
The tyre is then cured. The tread is then generally patterned in the mould for curing the tyre.
The invention and its advantages will be more thoroughly understood in the light of the figures and exemplary embodiments that follow.
The appended
This tyre 1 comprises a reinforced crown 2 comprising a tread 3 (in order to simplify, having a very simple structure), the radially outer part (3a) of which is intended to come into contact with the road, two inextensible beads 4 in which a carcass reinforcement 6 is anchored. The crown 2, joined to said beads 4 by two sidewalls 5, is, in a manner known per se, reinforced by a crown reinforcement or “belt” 7 which is at least partly metallic and which is radially outer with respect to the carcass reinforcement 6.
More specifically, a tyre belt is generally composed of at least two superimposed belt plies, sometimes referred to as “working” plies or “crossed” plies, the reinforcing elements or “reinforcers” of which are positioned virtually parallel to one another inside a ply, but crossed from one ply to the other, that is to say inclined, symmetrically or asymmetrically, with respect to the median circumferential plane, by an angle which is generally between 10° and 45°, according to the type of tyre under consideration. Each of these two crossed plies is composed of a rubber matrix or “calendering rubber” which coats the reinforcers. In the belt, the crossed plies can be supplemented by various other auxiliary rubber plies or layers, with widths which can vary as the case may be, comprising or not comprising reinforcers; mention will be made, by way of example, of simple rubber cushions, “protection” plies having the role of protecting the remainder of the belt from external attacks or perforations, or else “hooping” plies comprising reinforcers oriented substantially along the circumferential direction (“zero-degree” plies), whether radially outer or inner with respect to the crossed plies.
For the reinforcing of the above belts, in particular of their crossed plies, protection plies or hooping plies, use is generally made of reinforcers in the form of steel cords or textile cords composed of thin threads assembled together by braiding or twisting.
The carcass reinforcement 6 is here anchored in each bead 4 by winding around two bead wires (4a, 4b), the turn-up (6a, 6b) of this reinforcement 6 being, for example, positioned towards the outside of the tyre 1, which is here depicted mounted on its rim 8. The carcass reinforcement 6 is composed of at least one ply reinforced by radial textile cords, that is to say that these cords are positioned virtually parallel to one another and extend from one bead to the other so as to form an angle of between 80° and 90° with the median circumferential plane (plane perpendicular to the axis of rotation of the tyre which is located halfway between the two beads 4 and passes through the middle of the crown reinforcement 7). Of course, this tyre 1 additionally comprises, in a known manner, a layer 9 of inner rubber or elastomer (commonly known as “inner liner”) which defines the radially inner face of the tyre and which is intended to protect the carcass ply from the diffusion of air originating from the space interior to the tyre.
Measurement Method
Measurement of G′(T) (Elastic Shear Modulus)
The method of measurement of G′(T) uses an RPA 2000LV rheology device (oscillating disc rheometer) equipped with the standard 200 in·lbs (22.6 Nm) viscosity sensor. The RPA device makes it possible to stress in torsion a sample of material enclosed in a chamber having biconical walls.
In order to carry out the measurement, a sample of material having a diameter of approximately 30 mm and a weight of approximately 5 g is deposited in the chamber of the RPA (a total volume of 8 cm3 is regarded as optimal; the amount is sufficient when a small amount of sample escapes from each side of the chamber and is visible at the end of the test). Preferably, the material is cut out beforehand from a sheet of this material. In the case where this sheet of material is insufficiently thick, it is possible to stack the sections of this sheet of material.
In a first stage, the optimum crosslinking time T95 at 170° C. for the sample is determined using an RPA 200LV rheometer according to the standard DIN 53529—part 3 (June 1983). The change in the rheometric torque, Δtorque, as a function of time describes the change in the stiffness of the composition following the vulcanization reaction. The measurements are treated according to the standard DIN 53529—part 2 (March 1983): Tα (for example T95) is the time required to reach a conversion of α %, i.e. α % (for example 95%) of the difference between the minimum and maximum torques.
Secondly, a shaping operation is carried out, by applying to the sample enclosed in the chamber a temperature of 170° C. for the time T95, defined in the first step with a peak-to-peak strain of 2.8% at 1.7 Hz.
At the end of this operation, the sample is completely moulded in the closed chamber of the RPA. The sample is subsequently cooled to 40° C. directly in the chamber of the RPA. It is then possible to begin the measurement of the value of G′ at 5% peak-to-peak strain and 10 Hz within a temperature range varying from 40 to 200° C. (ramp: 3° C./min).
A curve of variation in G′ as a function of the temperature is obtained such as that from
The forming step and G′ measurement step are carried out without intervention, by programming the RPA device.
Finally, the ratio G′(200° C.)/G′(40° C.) is calculated.
The higher this ratio, the better the conservation of the mechanical properties with respect to temperature.
A comparative tread composition A0 and compositions of treads that can be used in a tyre according to the invention A1 to A5 were prepared by extrusion on the basis of Table 1 below. The values are indicated in phr.
(1)SIS thermoplastic elastomer, Hybrar 5125, from Kuraray (styrene-isoprene styrene block copolymer)
(2)CBS: N-cyclohexyl-2-benzothiazolesulfenamide
The G′(T) moduli at 40° C. and 200° C. of the treads A0 to A5 were measured. The results are presented in Table 2 below.
It is found that all the formulations containing sulfur show an improvement in the heat resistance.
A comparative tread composition B0 and tread compositions that may be used in a tyre according to the invention B1 to B5 were prepared by extrusion on the basis of Table 3 below. The values are indicated in phr.
(1)SIS Thermoplastic elastomer Kraton D1161 from the company Kaneka
(2)CBS: N-cyclohexyl-2-benzothiazolesulfenamide
The G′(T) moduli at 40° C. and 200° C. of the treads B0 to B5 were measured.
The results are presented in Table 4 below.
Thus, these curves highlight a much lower high-temperature flow for the treads that have undergone a crosslinking than for the comparative tread which has not undergone crosslinking.
A comparative tread composition B0 and tread compositions that may be used in a tyre according to the invention C1 to C5 were prepared by extrusion on the basis of Table 5 below. The values are indicated in phr.
(1)SBS thermoplastic elastomer Europrene Solt 166 from the company Polimeri Europa
(2)CBS: N-cyclohexyl-2-benzothiazolesulfenamide
The G′(T) moduli at 40° C. and 200° C. of the treads C0 to C5 were measured. The results are presented in Table 6 below.
Thus, these results for three types of thermoplastic elastomer highlight a much lower high-temperature flow for the treads comprising sulfur and a vulcanization accelerator relative to a comparative tread not comprising any.
Thus, it is found that the treads comprising sulfur and a vulcanization accelerator show an improvement in the heat resistance relative to treads not comprising any.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1661142 | Nov 2016 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/079292 | 11/15/2017 | WO | 00 |
