Abstract:
A tire for vehicle a wheel includes a carcass structure including at least one carcass ply shaped in a substantially toroidal configuration, the opposite lateral edges of which are associated with respective right-hand and left-hand bead wires enclosed in respective beads; a belt structure applied in a circumferentially external position relative to the carcass structure; a tread band circumferentially superimposed on the belt structure, the tread band including a radially outer surface with a tread pattern including a plurality of longitudinal and transverse grooves which define a corresponding plurality of blocks and/or ribs; a plurality of studs partially projecting from the radially outer surface of the tread band; and a pair of side walls applied laterally on opposite sides relative to the carcass structure. The tread band includes a crosslinked elastomeric composition including at least one diene elastomeric polymer and at least one layered nanosized inorganic material as reinforcing filler.

Description:
FIELD OF THE INVENTION 
       [0001]    The present invention relates to a studded tire for a vehicle wheel. 
         [0002]    As studded tire is generally intended a tire particularly suitable for driving on icy or snowy surfaces. It is characterized by a tread band containing a plurality of anti-slip elements (hereinafter referred to as “studs”) partially projecting from the radially outer surface of the tread band. The tread band is provided with a tread pattern suitable for use on snow-covered and/or icy ground, and showing a plurality of longitudinal and transverse grooves which define a corresponding plurality of blocks and/or ribs into which the studs are inserted. A studded tire normally has about 200/400 studs. 
       PRIOR ART 
       [0003]    Commonly, a studs is substantially a rigid metallic body, preferably made of steel, comprising a cylindrical or double-conical rod having, at the end contacting the ground, a tip made of a very hard material such as a tungsten carbide-based alloy, and at the other end an enlarged base to hold the stud in the tread band. 
         [0004]    The studs can be fixed in the tread band after the tire has been cured by providing predetermined portions of the tread band with cavities for the positioning of the studs. The optional presence of an adhesive inside each cavity helps to retain the stud in position during use. 
         [0005]    In more recent techniques, methods have been developed by which a studded tire is produced by fixing the studs to the tread band during curing. Generally, the studs are inserted in seats provided in the vulcanization mold—before loading the latter with the green tire—so as to incorporate and fix said studs in the tread band during molding and vulcanization of the tire. 
         [0006]    The adhesion of the stud to the tread band represents one of the critical aspect of this technology. When subjected to intense driving or bracing torques or to the action of high transverse forces, such as those which occur with sports type driving conditions, in particular during competitions, the studs are forced out of tread band, thus being lost along the road and adversely affecting in this way the performance of the tire. 
         [0007]    Rubber compositions which are suitable for the tread bands usually do not show sufficient adhesion to the metal materials forming the core of the stud. In this connection, as reported, e.g., by EP 1 055 509, the stud can be treated with a chemical agent or provided with a coating layer which acts as an interface, creating a bond between the metal and the rubber composition. On the other side, adhesion promoting additives can be employed as ingredients of the rubber composition, for example, organo-metallic complexes based on boron and/or cobalt, a resorcin/hexa-methoxy-methyl-melamine (HMMM) system, or a combination thereof. 
         [0008]    The tread band for studded tires desirably shows high modulus, especially at low deformations (10%, 50%, 100% modulus) combined with good tear resistance, which is related to high values of stress at break. 
         [0009]    In order to increase the modulus of the tread band rubber composition, it is known in the art to add the rubber composition with polyaramide microfibers (for example, Kevlar® pulp). However such a reinforcing filler is able to improve the moduli, but lessening the poor break properties, thus impairing the retention of the studs in the tread. 
         [0010]    In addition, the presence of said filler negatively affects the workability of the rubber compositions because it confers an adversely high viscosity. 
         [0011]    Therefore the need for a studded tire having a tread band with high modulus, being capable of retaining the studs in position even under heavy stresses, and being easily processed is still felt. 
       SUMMARY OF THE INVENTION 
       [0012]    The Applicant found that a studded tire with a tread band comprising layered nanosized inorganic material as reinforcing filler is endowed with the modulus and tear resistance features sought for this kind of tire. 
         [0013]    The present invention relates to a tire for vehicle wheel, comprising: 
         [0014]    a carcass structure including at least one carcass ply shaped in a substantially toroidal configuration, the opposite lateral edges of which are associated with respective right-hand and left-hand bead wires, each bead wire being enclosed in a respective bead; 
         [0015]    a belt structure applied in a circumferentially external position relative to said carcass structure; 
         [0016]    a tread band circumferentially superimposed on said belt structure, comprising a radially outer surface with a tread pattern including a plurality of longitudinal and transverse grooves which define a corresponding plurality of blocks and/or ribs; 
         [0017]    a plurality of studs partially projecting from said radially outer surface of the tread band; and 
         [0018]    a pair of side walls applied laterally on opposite sides relative to said carcass structure; 
         [0000]    wherein said tread band comprises a crosslinked elastomeric composition including:
 
(a) at least one diene elastomeric polymer;
 
(b) at least one layered nanosized inorganic material as reinforcing filler.
 
         [0019]    Preferably the layered nanosized inorganic material (b) has an individual layer thickness of from 0.01 nm to 30 nm, more preferably from 0.1 nm to 15 nm. 
         [0020]    According to one preferred embodiment, said layered inorganic material (b) is intercalated in the elastomeric material. 
         [0021]    According to one preferred embodiment, said layered inorganic material (b) is present in the elastomeric composition in an amount of from 1 phr to 120 phr, preferably from 5 phr to 80 phr. 
         [0022]    For the purposes of the present description and the claims, the term “phr” means the parts by weight of a given component of the elastomeric composition per 100 parts by weight of the polymer components. 
         [0023]    According to one preferred embodiment, the layered inorganic material (b) which may be used in the present invention may be selected, for example, from phyllosilicates such as: smectites, for example, montmorillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite; vermiculite; halloisite; sericite; or mixtures thereof. 
         [0024]    Montmorillonite is particularly preferred. 
         [0025]    Example of layered inorganic material (b) which may be used according to the present invention and is available commercially is the product known by the name of Dellite® 67G from Laviosa Chimica Mineraria S.p.A. 
         [0026]    In order to render the layered inorganic material (b) more compatible with the diene elastomeric polymer (a) said layered inorganic material (b) may be surface-treated with at least one compatibilizer. 
         [0027]    According to one preferred embodiment, said compatibilizer may be selected, for example, from the quaternary ammonium or phosphonium salts having general formula (I): 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein: 
         [0028]    Y represents N or P; 
         [0029]    R 1 , R 2 , R 3  and R 4 , which may be the same or different, represent a linear or branched C 1 -C 20  alkyl or hydroxyalkyl group; a linear or branched C 1 -C 20  alkenyl or hydroxyalkenyl group; a —R 5 —SH or —R 5 —NH group wherein R 5  represents a linear or branched C 1 -C 20  alkylene group; a C 6 -C 18  aryl group; a C 7 -C 20  arylalkyl or alkylaryl group; a C 5 -C 18  cycloalkyl group, said cycloalkyl group optionally containing hetero atom such as oxygen, nitrogen or sulfur; 
         [0030]    X n−  represents an anion such as chlorine ion, sulfate ion or phosphate ion; and 
         [0031]    n represents 1, 2 or 3. 
         [0032]    The surface treatment of the layered inorganic material (b) with the at least one compatibilizer can be carried out according to known methods such as, for example, by an ion exchange reaction between the layered inorganic material and the compatibilizer: further details are described, for example, in U.S. Pat. No. 4,136,103, U.S. Pat. No. 5,747,560 or U.S. Pat. No. 5,952,093. 
         [0033]    According to one preferred embodiment, the diene elastomeric polymer (a) which may be used in the present invention may be selected from those commonly used in sulfur-crosslinkable elastomeric compositions, that are particularly suitable for producing tires, that is to say from elastomeric polymers or copolymers with an unsaturated chain having a glass transition temperature (T g ) generally below 20° C., preferably below 10° C. These polymers or copolymers may be of natural origin or may be obtained by solution polymerization, emulsion polymerization or gas-phase polymerization of one or more conjugated diolefins, optionally blended with at least one comonomer selected from monovinylarenes and/or polar comonomers in an amount of not more than 60% by weight. 
         [0034]    The conjugated diolefins generally contain from 4 to 12, preferably from 4 to 8 carbon atoms, and may be selected, for example, from the group comprising 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene, or mixtures thereof. Particularly preferred are 1,3-butadiene and isoprene. 
         [0035]    Monovinylarenes which may optionally be used as comonomers generally contain from 8 to 20, preferably from 8 to 12 carbon atoms, and may be selected, for example, from: styrene; 1-vinylnaphthalene; 2-vinylnaphthalene; various alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl derivatives of styrene, for example, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-p-tolylstyrene, 4-(4-phenylbutyl)styrene, or mixtures thereof. Styrene is particularly preferred. 
         [0036]    Polar comonomers which may optionally be used may be selected, for example, from vinylpyridine, vinylquinoline, acrylic acid and alkylacrylic acid esters, nitrites, or mixtures thereof, such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylonitrile, or mixtures thereof. 
         [0037]    Preferably, the diene elastomeric polymer (a) which may be used in the present invention may be selected from cis-1,4-polyisoprene (natural or synthetic, preferably natural rubber), 3,4-polyisoprene, polybutadiene (in particular polybutadiene with a high 1,4-cis content), optionally halogenated isoprene/isobutene copolymers, 1,3-butadiene/acrylonitrile copolymers, styrene/1,3-butadiene copolymers, styrene/isoprene/1,3-butadiene copolymers, styrene/1,3-butadiene/acrylonitrile copolymers, or mixtures thereof. 
         [0038]    According to one preferred embodiment, said elastomeric composition comprises at least 10% by weight, preferably from 20% by weight to 90% by weight, with respect to the total weight of the at least one diene elastomeric polymer (a), of natural rubber. 
         [0039]    A diene elastomeric polymer (a) functionalized by reaction with suitable terminating agents or coupling agents may also be used. In particular, the diene elastomeric polymers obtained by anionic polymerization in the presence of an organometallic initiator (in particular an organolithium initiator) may be functionalized by reacting the residual organometallic groups derived from the initiator with suitable terminating agents or coupling agents such as, for example, imines, carbodiimides, alkyltin halides, substituted benzophenones, alkoxysilanes or aryloxysilanes (see, e.g., European patent EP 451 604, or U.S. Pat. No. 4,742,124 and U.S. Pat. No. 4,550,142). 
         [0040]    Advantageously, the elastomeric composition of the tread band of the invention further comprises at least one carbon black (c) as additional reinforcing filler. The optional presence of carbon black helps to provide the studded tire according to the invention with improved ultimate properties, e.g. tear, break, wear and fatigue resistance. Said at least one carbon black is preferably selected from those having a surface area of not less than 20 m 2  μg (determined by CTAB absorption as described in ISO standard 6810). 
         [0041]    According to one preferred embodiment, said at least one carbon black reinforcing filler (c) is present in the elastomeric composition in an amount of from 0.1 phr to 120 phr, preferably from 20 phr to 90 phr. 
         [0042]    Optionally, at least another one additional reinforcing filler may be added to the elastomeric composition of the tread band of the invention, in an amount generally of from 0.1 phr to 120 phr, preferably from 20 phr to 90 phr. Said another one additional rein-forcing filler may be selected from those commonly used in the tire field, for example, silica, alumina, aluminosilicates, calcium carbonate, kaolin, or mixtures thereof. 
         [0043]    The silica which may be used in the present invention may generally be a pyrogenic silica or, preferably, a precipitated silica, with a BET surface area (measured according to ISO standard 5794/1) of from 50 m 2 /g to 500 m 2 /g, preferably from 70 m 2 /g to 200 m 2 /g. 
         [0044]    The elastomeric composition may advantageously further incorporate a silane (d). Besides to the capacity of the silane of interacting with the silica optionally present in the tread band of the invention as another additional reinforcing filler, and of linking said silica to the diene elastomeric polymer during the vulcanization, said silane provides the tread band of the studded tire of the invention with advantages also in the absence of silica by acting as an anti-reversion agent during the use of the tire. 
         [0045]    The silane (d) advantageously used in the present invention may be selected from those having at least one hydrolizable silane group which may be identified, for example, by the following general formula (II): 
         [0000]      (R) 3 Si—C y H 2y -Z  (II) 
         [0000]    wherein the groups R, which may be the same or different, are selected from alkyl, alkoxy or aryloxy groups or from halogen atoms, with the proviso that at least one of the groups R is an alkoxy or aryloxy group; n is an integer from 1 to 6; Z is a group selected from: nitroso, mercapto, amino, epoxide, vinyl, imide, chloro, —(S) m C y H 2y —Si—(R) 3  wherein m and y are integers from 1 to 6 and the groups R are defined as above. 
         [0046]    Among the silanes, particularly preferred are bis(3-triethoxysilyl-propyl)tetrasulfide and bis(3-triethoxysilylpropyl)-disulfide. Said silanes may be used as such or as a suitable mixture with an inert filler (for example carbon black) so as to facilitate their incorporation into the elastomeric composition. 
         [0047]    According to one preferred embodiment, said silane (d) is present in the elastomeric composition in an amount of from 0.01 phr to 10 phr, preferably from 0.5 phr to 5 phr. 
         [0048]    The elastomeric composition according to the present invention may be vulcanized according to known techniques, in particular with sulfur-based vulcanizing systems commonly used for diene elastomeric polymers. 
         [0049]    The vulcanizing agent most advantageously used is sulfur, or molecules containing sulfur (sulfur donors), with accelerators and activators known to those skilled in the art. 
         [0050]    Activators that are particularly effective are zinc compounds, and in particular ZnO, ZnCO 3 , zinc salts of saturated or unsaturated fatty acids containing from 8 to 18 carbon atoms, such as, for example, zinc stearate, which are preferably formed in situ in the elastomeric composition from ZnO and fatty acid, and also BiO, PbO, Pb 3 O 4 , PbO 2 , or mixtures thereof. 
         [0051]    Accelerators that are commonly used may be selected from: dithiocarbamates, guanidine, thiourea, thiazoles, sulphenamides, thiurams, amines, xanthogenates, or mixtures thereof. 
         [0052]    Optionally, the elastomeric composition according to the present invention comprises other additives. For example, the following may be added to said composition: antioxidants, anti-ageing agents, adhesives, anti-ozone agents, modifying resins, or mixtures thereof. 
         [0053]    For example, for the purpose of further improving the processability, a plasticizer generally selected from mineral oils, vegetable oils, synthetic oils, or mixtures thereof, such as, for example, aromatic oil, naphthenic oil, phthalates, soybean oil, or mixtures thereof, can be added to the elastomeric composition according to the present invention. The amount of plasticizer generally ranges from 1 phr to 100 phr, preferably from 5 phr to 50 phr. 
         [0054]    For example, the elastomeric composition according to the present invention is prepared by mixing together the diene elastomeric polymer (a) with the layered nanosized inorganic material (b), with the additional reinforcing filler(s) and with the other additives optionally present, according to techniques known in the art. The mixing may be carried out, for example, using an open mixer of open-mill type, or an internal mixer of the type with tangential rotors (Banbury) or with interlocking rotors (Intermix), or using continuous mixers of Ko-Kneader type (Buss), or using co-rotating or counter-rotating twin-screw extruders or single-screw extruders. 
         [0055]    According to one preferred embodiment, said elastomeric composition further comprises at least one adhesion promoting additive (e). 
         [0056]    A preferred adhesion promoting additive can be an organometallic complex based on boron and/or cobalt, the latter being linked together through oxygen. Particularly preferred complexes are cobalt carboxylates such as cobalt abietate, cobalt resonate, cobalt stearate, cobalt naphthenate, cobalt neodecanoate, cobalt boroacylate, cobalt naphthenates being the more preferred. Said complexes are commercially known with the trade name of Manobond® and are generally used in combination with a high amount of sulfur. 
         [0057]    A further adhesion promoting additive can be a resorcin/hexa-methoxy-methyl-melamine (HMMM) system which is generally used in combination with a medium/low amount of sulfur. Resorcin and HMMM react together and give rise to a layer interposed between the rubber blend and the metallic stud, said layer promoting the adhesion with the rubber and protecting the metal from aging, sulfur attack, moisture. 
         [0058]    Moreover, it is also possible to use together an organometallic complex based on boron and/or cobalt and a resorcin/HMMM system, generally in combination with a high amount of sulfur. 
         [0059]    Silica can also be used since it is known that, in general, it promotes the adhesion of rubber to metals. 
         [0060]    The studs of the studded tire according to the invention can be chemically treated with a rubber-to-metal bonding agent prior to their insertion into radially outer surface of the tread band. More specifically, after cleaning, for example by sandblasting and/or phosphating, the studs are treated with a rubber-to-metal bonding agent, preferably by means of immersion. Examples of rubber-to-metal bonding agents for the present invention are products marketed by the company Henkel under the trade name Chemosil®. 
         [0061]    Furthermore, according to another embodiment of the present invention, the studs are generally made of an internal steel core coated with one or more layers of a another metal or metal alloy apt to improve the adhesion to rubber and to protect the steel core from corrosion. 
         [0062]    The preferred coating material is brass, although other coating materials, such as alloys containing Cu, Zn, Ni, Co or Mn, can be used. In the preferred case a brass coating is used, adhesion is particularly favored by the formation during vulcanization of bisulfide bridges (—S—S—) between the elastomeric matrix of the tread band and the copper, which is a component of brass. Methods which can be employed for coating a stud with a brass layer are, for instance, plating or diffusion. The first comprises electrolytic plating of copper and zinc, while the second comprises electroplating of one or more layers of copper on the stud followed by the electro-plating of a layer of zinc and by a thermal treatment that diffuses the zinc in the copper layers, thus forming a brass layer. Studs are, preferably, brass-coated with a metal composition consisting of from 30% to 40% by weight in zinc and from 70% to 60% by weight in copper, to form a layer of brass which is from 1 μm to 2 μm, preferably equal to 1.5 μm, in thickness. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0063]    The invention will be further illustrated hereinafter with reference to the following examples and figures, wherein  FIG. 1  shows a cross right section through a studded tire according to the present invention. 
       
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
       [0064]    Tire  1  comprises a toroidally shaped carcass  2  comprising at least one rubberized fabric ply  4  (hereinafter referred to as “carcass ply”). The carcass ply  4  generally consists of a plurality of reinforcing cords arranged parallel to each other and at least partially coated with a layer of elastomeric material. These reinforcing cords are usually made of textile fibers, for example rayon, nylon or polyethylene terephthalate, or of steel wires stranded together, coated with a metal alloy (for example copper/zinc, zinc/manganese, zinc/molybdenum/cobalt alloys and the like). 
         [0065]    The carcass ply  4  is usually of radial type, i.e. it incorporates reinforcing cords arranged in a substantially perpendicular direction relative to a circumferential direction. 
         [0066]    In one embodiment, the carcass ply  4  has its ends  6  each fixed to a metallic, annular core, known and referred to hereinbelow as reinforcing bead core  8 . Said bead core  8  is provided on its radially external surface with a rubber filling element  12 . As is known, the zone of the tire comprising bead core  8  and filling element  12  forms the bead assembly  3  which is intended for fixing tire  1  to a corresponding mounting rim. 
         [0067]    The association between carcass ply  4  and bead assemblies  3  is achieved here by folding back the opposite ends  6  of the carcass ply  4  around the bead assemblies  3  so as to form the so-called carcass back-folds shown in  FIG. 1 . 
         [0068]    Alternatively, the conventional bead assemblies  3  may be replaced with a pair of annular inserts formed from elongate components arranged in concentric coils (not represented in  FIG. 1 ) (see, for example, EP-A-0 928 680 and EP-A-0 928 702 in the name of the Applicant). In this case, the carcass ply  4  is not back-folded around said annular inserts, the coupling being provided by a second carcass ply (not represented in  FIG. 1 ) applied externally over the first. 
         [0069]    A belt structure  26  which is arranged in a radial external position with respect to the crown of carcass  2 , and substantially extends from one side to the other of the tire, i.e. as wide as tread band  34 . According to the present embodiment, belt structure  26  comprises at least two rubberized fabric strips  28  and  30  which are radially superimposed and provided with textile or metallic reinforcing cords which are parallel to one another in each layer, mutually intersecting with those of the adjacent layer and with respect to the equatorial plane of the tire. Belt structure  26  also comprises a radially outermost strip  32  provided with textile or metallic reinforcing cords, oriented at 0°, i.e. in a circumferential direction with respect to the tire. 
         [0070]    Sidewalls  10  are applied externally onto the carcass ply  4 , these sidewalls extending, in an axially external position, from the bead assemblies  3  to the end of the belt structure  26 . 
         [0071]    A tread band  34 , whose lateral edges are connected to sidewalls  10 , is applied circumferentially in a position radially external to the belt structure  26 . The tread band  34  comprises a radially outer surface intended for the rolling contact of the tire on the ground is arranged in known manner. The outer surface is provided with grooves  22  which are formed in the thickness of the tread band  34  and define a plurality of blocks and/or ribs  18 . The combination of these structural elements, in various configurations, produces different tread patterns suitable for performing on snowy and/icy grounds. 
         [0072]    The thickness of the tread band in studded tires for four-wheeled vehicles is normally of from 14 mm to 25 mm, more preferably of from 15 mm to 20 mm. In any case, the thickness of the tread band may also be not uniform but, for example, greater near its outer edges and/or at the central zone thereof. 
         [0073]    Tread band  34  has, inserted in it a plurality of studs, some of which are shown with reference sign  300  in  FIG. 1 , wherein only the part projecting from the external surface of tread band  34  can be seen. The whole body of only one stud is shown. 
         [0074]    It can be noted that, for reasons of curvature of the external surface of the tread band, the studs, which are perpendicular to said surface, are not arranged parallel to one another but along axes y converging radially towards the inside of the tire. 
         [0075]    Examples of studs  300  are illustrated, e.g., EP-A-1 055 509 in the Applicant&#39;s name. 
         [0076]    A strip made of elastomeric material, commonly known as a “mini-sidewall” (not represented in  FIG. 1 ), may optionally be present in the connecting zone between the sidewalls  10  and the tread band  34 , this mini-sidewall generally being obtained by co-extrusion with the tread band  34  and allowing an improvement in the mechanical interaction between the tread band  34  and the sidewalls  10 . Alternatively, the end portion of the sidewall  10  directly covers the lateral edge of the tread band  34 . 
         [0077]    A layer of elastomeric material (not represented in  FIG. 1 ) which serves as an attachment sheet to provide connection between the tread band  34  and the belt structure  26 , may be placed between the tread band  34  and the belt structure  26 . 
         [0078]    A rubber layer (not shown in  FIG. 1 ) generally known as a “liner”, which affords the necessary impermeability to the inflation air of the tire, is provided in a radially internal position relative to the carcass ply  4 . 
         [0079]    The process for producing the studded tire according to the present invention may be carried out according to techniques and using apparatus that are known in the art, as described, for example, in EP-B-0 199 064, U.S. Pat. No. 4,872,822, U.S. Pat. No. 4,768,937, said process including at least one stage of manufacturing the green tire and at least one stage of vulcanizing this tire. 
         [0080]    More particularly, the process for producing the tire comprises the stages of preparing, beforehand and separately from each other, a series of semi-finished products corresponding to the various structural elements of the tire (carcass plies, belt structure, bead wires, fillers, sidewalls and tread band) which are then combined together using a suitable manufacturing machine. Next, the subsequent vulcanization stage welds the abovementioned semi-finished products together to give a monolithic block, i.e. the finished tire. 
         [0081]    The stage of preparing the abovementioned semi-finished products will be preceded by a stage of preparing and molding the various blends, of which said semi-finished products are made, according to conventional techniques. 
         [0082]    The green tire thus obtained is then passed to the subsequent stages of molding and vulcanization. To this end, a vulcanization mold is used which is designed to receive the tire being processed inside a molding cavity having walls which are counter-molded to define the outer surface of the tire when the vulcanization is complete. 
         [0083]    Alternative processes for producing a tire or parts of a tire without using semi-finished products are disclosed, for example, in the abovementioned EP-A-0 928 680 and EP-A-0 928 702. 
         [0084]    The green tire can be molded by introducing a pressurized fluid into the space defined by the inner surface of the tire, so as to press the outer surface of the green tire against the walls of the molding cavity. In one of the molding methods widely practiced, a vulcanization chamber made of elastomeric material, filled with steam and/or another fluid under pressure, is inflated inside the tire closed inside the molding cavity. In this way, the green tire is pushed against the inner walls of the molding cavity, thus obtaining the desired molding. Alternatively, the molding can be carried out without an inflatable vulcanization chamber, by providing inside the tire a toroidal metal support shaped according to the configuration of the inner surface of the tire to be obtained as described, for example, in EP-B-0 242 840. The difference in coefficient of thermal expansion between the toroidal metal support and the crude elastomeric material is exploited to achieve an adequate molding pressure. 
         [0085]    At this point, the stage of vulcanizing the crude elastomeric material present in the tire is carried out. To this end, the outer wall of the vulcanization mold is placed in contact with a heating fluid (generally steam) such that the outer wall reaches a maximum temperature generally of from 100° C. to 230° C. Simultaneously, the inner surface of the tire is heated to the vulcanization temperature using the same pressurized fluid used to press the tire against the walls of the molding cavity, heated to a maximum temperature of from 100° C. to 250° C. The time required to obtain a satisfactory degree of vulcanization throughout the mass of the elastomeric material can vary in general from 3 min to 90 min and depends mainly on the dimensions of the tire. When the vulcanization is complete, the tire is removed from the vulcanization mold. 
         [0086]    The studs can be inserted in the tread band at two different stages of the manufacturing of a studded tire. 
         [0087]    In one embodiment, the studs can be fixed in the tread band after the tire has been cured. More precisely this method consists in providing predetermined portions of the tread band with cavities for the positioning of the studs. The studs are placed, usually manually, in these cavities so as the end designed to contact the ground projects from the tread band to a predetermined distance. The optional presence of an adhesive inside each cavity and the shape of each stud, in which the diameter of the base is greater than the rod, help to retain the stud in position during use. 
         [0088]    Another method provide fixing the studs to the tread band during curing. For example, document EP 1 055 509 in the Applicant&#39;s name shows a method for manufacturing a studded tire comprising the following steps: making a green tire, inserting and securing the studs in specific seats of a curing mold, inserting the green tire in said mold, closing the mold, and vulcanizing to obtained the studded tire. 
       Examples 1-4 
     Preparation of the Elastomeric Compositions 
       [0089]    The elastomeric compositions given in Table 1 were prepared as follows (the amounts of the various ingredients are given in phr). 
         [0090]    All the ingredients, except sulfur, accelerator and retardant, were mixed together in an internal mixer (model Pomini PL 1.6) for about 5 min (1 st  Step). As soon as the temperature reached 145±5° C., the elastomeric composition was discharged. The sulfur, the accelerator and the retardant were then added and mixing was carried out in an open roll mixer (2 nd  Step). 
         [0000]    
       
         
               
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
             
             
               
                   
                   
               
               
                   
                 EXAMPLE 
               
             
          
           
               
                   
                 1 (*) 
                 2 (*) 
                 3 
                 4 
               
               
                   
                   
               
             
          
           
               
                 1 st  Step 
               
             
          
           
               
                 NR STR 20 
                 66.5 
                 66.5 
                 70 
                 70 
               
               
                 Buna CB-24 
                 30 
                 30 
                 30 
                 30 
               
               
                 Kevlar ® Pulp Latex 
                 4.35 
                 4.35 
                 — 
                 — 
               
               
                 Carbon black N234 
                 40 
                 40 
                 40 
                 40 
               
               
                 Silica Ultrasil ® VN3 
                 20 
                 20 
                 — 
                 — 
               
               
                 Silane Degussa X50S 
                 3.2 
                 3.2 
                 3.2 
                 3.2 
               
               
                 Resorcine 
                 2.5 
                 — 
                 2.5 
                 — 
               
               
                 Aromatic oil 
                 6 
                 6 
                 6 
                 6 
               
               
                 Cobalt Naphthenate 
                 1 
                 — 
                 1 
                 — 
               
               
                 Dellite ® 67G 
                 — 
                 — 
                 20 
                 20 
               
             
          
           
               
                 2 nd  Step 
               
             
          
           
               
                 TBBS 
                 1 
                 1 
                 1 
                 1 
               
               
                 Insoluble Sulfur 
                 4.5 
                 4.5 
                 4.5 
                 4.5 
               
               
                 6PPD 
                 2 
                 2 
                 2 
                 2 
               
               
                 Hexamethoxymethyl melamine 
                 4 
                 — 
                 4 
                 — 
               
               
                   
               
               
                 (*) comparative. 
               
               
                 NR: natural rubber; 
               
               
                 Buna CB-24: butadiene rubber: 
               
               
                 Kevlar ® Pulp Latex: highly fibrillated aramid dispersed in natural rubber (manufactured by DuPont); 
               
               
                 Silica Ultrasil ® VN3: amorphous precipitated silica by Degussa 
               
               
                 Silane Degussa X50S: bis(3-triethoxysilylpropyl)tetrasulfide dispersed at 50 wt % in carbon black N330 
               
               
                 Aromatic oil: Agip Esar-90 
               
               
                 6PPD: N-(1,3-dhnethylbutyl)-N′-phenyl-p-phenylenediamine (Vulkanox ® 4020 by Bayer) 
               
               
                 Dellite ® 67G: organo-modified montmorillonite belonging to the smectite family (Laviosa Chimica Mineraria S.p.A.). 
               
             
          
         
       
     
         [0091]    The following Table 2 set forth physical and dynamic properties of the mixtures above. 
         [0092]    The Mooney viscosity ML(1+4)? at 100° C. was measured, according to ISO standard 289/1, on the non-crosslinked materials obtained as described above. 
         [0093]    The static mechanical properties according to ISO standard 37 were measured at different elongation (10%, 50% 100% and 300%) both in the direction of calendering and in the direction perpendicular thereto on samples of said elastomeric compositions crosslinked at 170° C. for 10 minutes. 
         [0094]    Stress and elongation at break tests were carried out according to ISO 37-2 on dumbbell specimens. 
         [0095]    The hardness in IRHD degrees at 23° C. were measured on samples of said elastomeric compositions crosslinked at 150° C. for 30 minutes, according to ISO standard 48. The Shore A was measured at 23° C. according to ASTM Standard D2240. 
         [0096]    The dynamic mechanical properties were measured using an Instron dynamic device in the traction-compression mode according to the following methods. A test piece of the crosslinked material having a cylindrical form (length 25 mm; diameter=14 mm) compression-preloaded up to 10% longitudinal deformation with respect to the initial length and kept at the prefixed temperature (23° C.) for the whole duration of the test, was submitted to a dynamic sinusoidal strain with an amplitude ±3.33% with respect to the length under pre-load, with a frequency of 100 Hz. The dynamic mechanical properties are expressed in terms of dynamic elastic modulus (E′) and tandelta (loss factor) values. As is known, the tandelta value is calculated as a ratio between the viscous modulus (E″) and the elastic modulus (E′), both of them being determined with the above dynamic measurements. 
         [0000]    
       
         
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 2 
               
             
             
               
                   
                   
               
               
                   
                 EXAMPLE 
               
             
          
           
               
                   
                 1 (*) 
                 2 (*) 
                 3 
                 4 
               
               
                   
                   
               
             
          
           
               
                 Viscosity ML (1 + 4) 
                 64.3 
                 77.4 
                 48.2 
                 56.4 
               
             
          
           
               
                 DUMBELL STRESS VS. STRAIN 
               
             
          
           
               
                 10% Modulus (MPa) 
                 1.78 
                 0.82 
                 1.83 
                 1.70 
               
               
                 50% Modulus (MPa) 
                 4.06 
                 1.63 
                 4.18 
                 3.92 
               
               
                 100% Modulus (MPa) 
                 6.28 
                 3.13 
                 7.17 
                 6.95 
               
               
                 300% Modulus (MPa) 
                 17.84 
                 13.83 
                 20.25 
                 17.04 
               
               
                 Stress at break (MPa) 
                 19.97 
                 18.77 
                 22.50 
                 19.95 
               
               
                 Elongation at break (%) 
                 352 
                 453.4 
                 345 
                 420.2 
               
             
          
           
               
                 DYNAMIC MECHANICAL PROPERTIES 
               
             
          
           
               
                 E′ (23° C.) (MPa) 
                 22.81 
                 6.62 
                 28.45 
                 14.55 
               
               
                 Tan delta (23° C.) 
                 0.218 
                 0.170 
                 0.221 
                 0.1269 
               
             
          
           
               
                 HARDNESS 
               
             
          
           
               
                 IRHD at 23° C. 
                 90.2 
                 70.5 
                 91.3 
                 80.4 
               
               
                 Shore A at 23° C. 
                 85.0 
                 68.0 
                 84.7 
                 82 
               
               
                   
               
               
                 (*) comparative. 
               
             
          
         
       
     
         [0097]    The results given in Table 2 show that the composition comprising the layered nanosized inorganic material according to the present invention (Examples 3 and 4) provides reinforcement to the elastomeric composition at least comparable to that provided by Kevlar® and silica (Examples 1 and 2), while decreasing the viscosity value, thus improving the workability of the material. 
       Example 5 
     Stud Retention Test 
       [0098]    Vehicle A and B (Subaru Impreza WRC passenger cars) were equipped with tires (Pirelli P-Zero J1) having a tread band comprising the elastomeric composition of Example 1 and 3, respectively. Each tire bore 384 studs provided in three circumferential rows (external, central and internal with respect to the vehicle side, the external being composed by three circumferential sub-rows). 
         [0099]    The vehicles run along an ice-paved circuit of 10 km. 
         [0100]    At the end of the test the number of studs missing from the front tires was counted. The results are set forth in Table 3. 
         [0101]    As from Table 3 below, the vehicle equipped with the tire according to the invention showed no lost studs. In addition, said vehicle run the circuit in a time almost 10 seconds shorter than that equipped with the reference tires. 
         [0000]    
       
         
               
               
             
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
                 TABLE 3 
               
             
             
               
                   
                   
               
               
                   
                 Lost Studs 
               
             
          
           
               
                   
                 Going time 
                 Back time 
                 Right-side tire 
                 Left-side tire 
               
             
          
           
               
                   
                 (minutes) 
                 (minutes) 
                 External row 
                 Central row 
                 Internal row 
                 Total 
                 Internal row 
                 Central row 
                 External row 
                 Total 
               
               
                   
                   
               
             
          
           
               
                 A 
               
             
          
           
               
                   
                 03:55.29 
                 03:54.10 
                 0 
                 3 
                 1 
                 4 
                 4 
                 6 
                 0 
                 10 
               
               
                   
                 03:51.85 
                 03:53.23 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
             
          
           
               
                   
                 07:47.14 
                 07:47.33 
                 Lost studs total 14 
               
             
          
           
               
                 B 
               
             
          
           
               
                   
                 03:48.23 
                 03:48.73 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                   
                 03:45.48 
                 03:47.27 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
             
          
           
               
                   
                 07:33.71 
                 07:36.00 
                 Lost studs total 0