WO2013039499A1

WO2013039499A1 - Low rigidity tire tread

Info

Publication number: WO2013039499A1
Application number: PCT/US2011/051651
Authority: WO
Inventors: Raymond STUBBLEFIELD; Xavier Saintigny
Original assignee: Michelin Recherche Et Technique S.A.; Societe De Technologie Michelin
Priority date: 2011-09-14
Filing date: 2011-09-14
Publication date: 2013-03-21
Also published as: CA2848657A1; BR112014005815A2; US20140371346A1

Abstract

Treads and tires having such treads having improved characteristics that break the compromise between wet/dry traction and wear. Such treads may comprise a rubber composition based upon a cross-linkable elastomer composition having a highly unsaturated diene elastomer and between 100 phr and 160 phr of an inorganic reinforcing filler. Embodiments may further include an effective amount of a plasticizing system that includes a plasticizing resin having a glass transition temperature (Tg) of at least 25 °C and a plasticizing liquid. The effective amount of the plasticizer system may be between 60 phr and 130 phr for particular embodiments and is effective in the amount for providing the rubber composition with a shear modulus G* measured at 60 C° of between 0.4 MPa and 1 MPa, Particular embodiments may further include the rubber composition forming the tire tread, to have a glass transition temperature of between -30 °C and 0 °C.

Description

LOW RIGIDITY TIRE TREAD

BACKGROUND OF THE INVENTION

Field of the .Invention

[0001] This invention relates generally to passenger and light truck tires and more particularly, to treads and materials from which they are made.

^'Descriptio of the. Related A l

[0001 ] It is known in the industry that tire designers must often compromise on certain characteristics of the tires they are designing. Changing a tire design to improve one Characteristic of the lire will often result in a compromise; .<?., an offsetting decline in another tire characteristic. One such comprise exists between tire wear and wet braking. Tire, wear may be improved by increasing, the amount of poiybutadiene blended into the tread's rubber composition. However, increasing the poiybutadiene content in. the tread's rubber composition typically results in a loss of the wet braking performance that is known to be improved, for example, by decreasing the poiybutadiene content of the tire tread.

[0002] Tire designers and those conducting, research in the tire industry search for materials and tire structures that can break some of the known compromises_* it would be desirable to provide new tire designs that break the compromise between, wear and wet braking.

SUMMARY Off THE INVENTION

[0003] Particular embodiments of the presen invention include treads and tires having such treads that have improved characteristics breaking the compromise between wet/dry traction and wear. Such embodiments include a tread for a tire comprising a rubber ^•composition based upon a cross-linkable elastomer composition having a highly unsaturated dlene elastomer and between 100 phr and 160 phr of an inorganic reinforcing filler. Embodiments may further include an effective amount -of a piasticizing system that includes a plastieizing resin having a glass transition temperature (Tg) of at least 25 °C and a piasticizing liquid.

^"i [00041 The effective amount of the plastieizer ^'system may be between 60 phr and 130 phi- for particular embodiments and is effective in the amount for providing the rubber composition with a shear modul us G* measured at 60 °C of between 0.4 MPa and 1 MPa,

[0005] Particular embodiments may fxulher include the rubber composition forming the tire tread to have a glass transition temperature- of between - 30 °C and 0 °C.

[0006] The foregoing and other objects, features and advantages of the invention ^■Will be apparent from the following more detailed descriptions of particular embodiments of the invention.

DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS

[0007] Particular embodiments of the present invention include treads and tires having, such treads that have improved traction, i.e., improved performance in wet braking, damp braking and dry braking. This improved traction has been achieved by forming unique tire treads from a rubber composition havin a high loading of an inorganic reinforcing filler coupled with an effective amount of a p!-asticizmg system, added to- adjust the shear modulus CP measured at 60 °C to be between 0.4 MPa. and 1. MPa while surprisingly -still maintaining good wear characteristics for the tire,. Such tires are particularly useful as all-weather tires and/or summer tires for passenger cars and/or light trucks.

[0008] As used herein, "phr" is "parts per hundred parts of rubber by weight' - and is ^•a common measurement in the art wherein components -of a rubber composition are measured relative to the total weight of rubber in the composition, i.e., parts by weight of the component per 100 parts by weight of the total rubber(s) in the composition.

[0009] As used herein, elastomer and rubber are. synonymous terms.

0010] As used herein, "based upon" is a term recognizing that embodiments of the present invention are made of vulcanized or cured rubber compositions that were, at the time of their assembly, uncured. The cured rubber composition is theret- ore "based upon" the uncured rubber composition. In other words, the cross-Jinked rubber composition is based upon or comprises the constituents of the cross-linkable rubber composition.

[001 1] As I known generally, a tire tread is the road-contacting portion of a vehicle tire that extends circumfere-ntiaily about the tire, ft is designed to provide the handling characteristics- required by the vehicle; e.g., traction, dry braking, wet braking, cornering and so forth - all being preferably provided with a minimum amount of noise being generated and at a low rolling resistance.

[Q01 ] Treads of th e type that are disclosed herein include tread elements that are the sirucntrai features of the tread that contact the ground. Such structural features may be of any type or shape, examples of which include tread blocks and tread ribs. Tread blocks have a perimeter defined by one or more grooves thai create an isolated structure in the tread while a rib runs substantially in the longitudinal (c-ireiimferential) direction and is not interrupted b any grooves that run in the substantially lateral direction or any other grooves that are oblique thereto.

[001:3] The radially outermost faces of these tread elements make up the contact surface of the tire tread - the actual surface area of the tire tread that is adapted for making contact with the road as the tire rotates. The total contact surface of the tire tread is therefore the total surface area of all the radially Outermost faces of the tread elements that are adapted for making contact with the road.

[0014] Particular embodiments of the present invention include a diene elastomer blended into the rubber composition from which treads are .manufactured. The diene elastomers or rubbers that are useful for such rubber compositions as disclosed herein are understood to be those elastomers resulting at least in part, Le., a homopojymer or a copolymer, from diene monomers, i.e., monomers having two double carbon-carbo bonds, whether conjugated or not.

[0015] These diene elastomers may be classified as either "essentially unsaturated" diene. elastomers or "essentially saturated" diene elastomers. As used herein, essentially unsaturated diene- elastomers are diene elastomers resulting at least in part from conjugated diene monomers, the essentially unsaturated diene elastomers having a content of such members or units of diene origin (conjugated dieft.es) that is at least 15 mol, , Within the category -of essentially unsaturated diene elastomers are highly unsaturated diene elastomers, which are diene elastomers having a content of units of diene origin (conjugated diene) that is greater than 50 mol, %. [0016] Those diene elastomers that do not fall intp the definition of being essentially unsaturated are, therefore, the essentially saturated diene elastomers. Such elastomers include, for example, butyl rubbers and copolymers of dienes and of alpha-oieims of the EFDM type. These diene elastomers have low or very low content of units of diene origin (conjugated dien.es), such content being less than 15 mol. %.

[0017] The elastomers usefu! in the present ..invention may have any microstructure, such microstructure being a function of the polymerization conditions used, in particular of the presence or absence of a modifying and/or randomizing agent and. the quantities of modifying and/or randomizing agent used. The elastomers may, for example, be block, random, sequential or micro-sequential elastomers, and may be prepared in dispersion or in solution; they may be coupled and/or starred or alternatively fanetionalized with a coupling and/or starring or fimotionalizing agent,

[0018] Functionaiized rubbers, i.e., those appended with active moieties, are well known in the industry. The backbone or the branch ends, of the elastomers may be tunetionalized by attaching these active moieties to the ends of the chains or to the backbone of the polymer Examples of functionaiized elastomers Include sihmo! or poJysiloxane end- functionaiized elastomers,, examples of which may be found in. US Patent No. 6,013,718, issued Januar 11 , 2000, which is hereby fully incorporated by reference. Other examples of functionaiized. elastomers include those having alkoxysilane groups as described in US 5,977,238, carboxylie groups as described in US 6,815,473 or polyether groups as described in US 6,503.973, all these cited patents being incorporated herein by reference,

[0019] Examples of suitable diene elastomers include polybutadienes, particularly those having a content, of 1.2- units of between 4 mol. ^'% and 80 mol, % or those ^"having a cis- 1,4 content of more than 80 mol. %. Also included, are poiyisoprenes and butadiene/isoprene copolymers, particularly those having an isoprene content of between 5 vvt. % and 90 wt. % and a glass transition temperature (Tg, measured in accordance with AST^'M D3418) of -40° C to -80° C.

}^'0020J Particular embodiments of the present invention include treads and tires having such treads manufactured from such rubber composition that includes at least 50 phr of SB.Il, the remainder of the rubber, component being a second diene rubber, SBRL is a copolymer of styrene and butadiene and is one of the most commonly used rubbers. It is typically manufactured by one of two processes - an emulsion process produci ng E-SBR and a solution process producing S-SBR. Particular embodiments of the present invention contemplate utilizing S-SBR, E-SBR or combinations thereof and may also, .in some embodiments, utilize such materials- having a- low Tg, i.e., a Tg that is less than -SO °C,

[0021] The. microstraeture of SBR is typically described in terms of the amount -of bound styrene and the- form of the butadiene portion of the polymer. A typical SBR thai is often suitable for use in tires is around 25 wt % bound styrene. Materials having a very high content of bound styrene, e.g., around SO wt, ¾, are identified as high styrene resins and are not suitable as an elastomer for manufacturing treads, Particular embodiments of the present invention may ^' .utilize an SBR having -a bound styrene content of between 3 wt. % and 40 wt. % or alternatively between 3 wt. % and 30 wt,^■%, between 3 wt, % and 25 wt % or between 15 wt. % and 30 wt, % bound styrene,

[0022] Because of the double bond present in the butadiene portion of the SBR, the butadiene portion is made u of three forms: d,v~L4, trana~\_f 4 and vinyl* 1,2. SBR materials suitable for use as the low Tg SBR may be described as having a vinyl- .1 ,2- ond content of between 4 mol. % and 30 moL % or alternatively, between 4 mol. % and 25 mol. % or between 4 mol, % and 20 mol. %. Low Tg SBR materials- include those having a glass transition, temperature of between -100 °C and -50 °C or alternatively, between -100 °C -and -55 *C_S betwee -100 °C and -60 °C or between -90 °C and -50 °C. Th glass transition temperature of -such materials may also range between greater than -8.0 °C and. -55 °C, between -75 °C and -60 °C or between -75 °C and -65 °C. Glass transition temperatures for the low Tg SBR and other elastomers are determined by differential scanning ealorimetry (DSC) according to ASTM El 356.

[0023] It is noted that while low Tg SBR may be suitable for particular embodiments of the present invention, the invention is not so limited and embodiments of the pie-sent invention include the full range of suitable SBR materials. Particular embodiments of the present invention may include the SBR material in amounts of at least 50 phr or alternatively, at least 60 phr, at least 70 phr, at least 80 phr, at least 90 phr or 100 phr of the SBR, Of course other embodiments may include SBR blended into the rubber composition at amounts

(00241 Folybutadienes that have glass transition temperatures in the same ranges as the low Tg SBR materials described above may also be utilized similarly to the low Tg SBR. The glass transition temperatures of poiyhutadiene may be adjusted by varying the vinyl content of the polymer using methods thai are well known, in the art. Particular embodiments of the rubber compositions disclosed herein may include greater than 90 phr or alternatively, greater than 95 phr or 100 phr of a low Tg SBR, a low Tg polybutadiene, i.e., a polybutadiene having the same glass transition temperature range as defined above for a low Tg SBR, or combma ti n ί here f .

[0025] In summary, suitable diene elastomers for particular embodiments of the present invention Include one or more highly unsaturated diene elastomers such as polybutadienes (BR), poiyisoprenes (IR), natural rubber ( R), butadiene copolymers, isoprene copolymers and mixtures of these elastomers. Such copolymers include hutadiene/styrene copolymers (SBR), isoprene/butadiene copolymers (BIR), .isoprene/styrene copolymers (SIR) and isoprene/butadiene/styrene copolymers (SBIR). Suitable elastomers may also include any of these -elastomers being mnctionalized elastomers as mentioned above.

[0026] As such, the diene elastomer included in particular embodiments of the present invention may be one diene elastomer or a mixture of several diene elastomers. The diene elastomer may further be selected from the highly unsaturated diene elastomers, the essentially unsaturated diene elastomers, the essentially saturated diene elastomers or combinations thereof. There are embodiments that include only highly unsaturated diene elastomers as the elastomer component while other embodiment include at least a majority, or alternatively at least 80 phr or at least 90 phr of the elastomer component, being a highly unsaturated diene elastomer.

[0027] In addition to the rubber, the rubber composition disclosed herein may further include reinforcing filler. Reinforcing fillers are added to rubber compositions to, inter alia, improve their tensile strength and wear resistance. Particular embodiments of the present invention include treads that are made of a rubber composition that includes high loadings of inorganic reinforcing fillers such as silica, with which a coupling agent is typically associated, [0028] Carbon black, although a useful reinforcing filler in many tire applications, is explicitly excluded from the useful rubber compositions disclosed herein except, for some embodiments, very small quantities tha may be included to provide coloring (black) to the tire composition and/or UV protection. Such benefits may be obtained by adding at least 0,5 phr but no more than. 20 phr of carbon black or alternatively, less than 10 phr, less than 5 phr or between 0.5 phr and 10 phr of carbon black.

[0029] Inorganic reinforcing fillers include any inorganic or mineral fillers, whatever its color or origin (natural or synthetic), that -are capable -without any other means, other than an intermediate coupling agent, or reinforcing a rubber composition intended fo the manufacture of tires. Such morganie reinforcing fillers can replace conventional tire-grade carbon blacks, in whole or in part, in a rubber composition intended for the manufacture- -of tires. Typically such fillers ma be characteri ed as having the presence of hydroxy! (~OH) groups on its surface.

[0030] Inorganic reinforcing fillers may take many useful forms including, for .example, as powder, microbeads, granules, balls and/or ally other suitable form as well as mixtures thereof. Examples of suitable inorganic reinforcing fillers include mineral fillers of the siliceous type, such as silica (Si{¾), of She aluminous type, such as alumina (AK¾) or combination s t hereof.

[0031] Useful silica reinforcing fillers known in the art include fume-d, precipitated and/or highly dispersible silica (known as ^WHD" silica). Examples o highly dispersible silicas include Ultrasil 7000 and Ultrasi! 7005 from Degussa, the silicas Zeos.il Π65 Ρ, 1135MP and 1115MP from Rhodia, the silica Hi-Sil EZ150G from PPG and the silicas Zeopol 8715, 8745 and 8755 from Huber. In particular embodiments, the silica may have a BET surface area, for example, of between 60 m7g and 250 m²/g or alternatively between 80 m²/g and 230 ns'Vg.

[0032] Examples of .useful reinforcing aluminas are the aluminas Baikalox A125 or CRl-25 from Baikowski, APA-I OORDX from Condea, Ahmunoxid C from. Degussa or A P- G0I5 from Sumitomo Chemicals.

[0033] For coupling the inorganic reinforcing filler to the diene elastomer, a coupling agent thai is at least bifunctional provides a sufficient chemical and/or physical connection between the inorganic reinforcement filler and the diene elastomer. Examples of such coupling agents include bifunciional organosi lanes or polyorganostloxanes. Such coupling agents and their use are well known in the art. The: coupling agent may optionally be grafted beforehand onto the diene elastomer or onto the inorganic reinforcing filler as is known. Otherwise U may be mixed into .the rubber composition in its free or non-grafted slate. One useful coupling agent is X 50-S, a 50-50 blend b weight of Si69 (the active ingredient) and N330 carbon black, available. from Evo ik Degussa.

[0034] in the rubber compositions according to the invention,- the coupling agent may be included, at any suitable amount for the given application, examples of which are. between 2 phr and 15 plir or alternatively, between 2 phr and 12 phr. it is generally desirable to minimize its use. In particular embodiments,, the amount of coupling agent may represent between 0.5 and 1.5 wt. % relative to the total weight of the silica filler. In. the case for example of tire treads for passenger - vehicles, the coupling .agent ma be less than 12 wt. % or even less than 8 wt. % relative to the total weigh of the silica filler.

[0035] In particular embodiments, the amount of inorganic reinforcing filler is included in the rubber compositions disclosed herein at a fairly high loading for such tread applications because it. is the high loading, coupled with the use of the plasticizing system to adjust the rigidity of the rubber composition,, that provides the desired characteristics of the- treads and tires of the present invention. Indeed, the amount of inorganic filler added to the rubber compositions may include between 100 phr and 160 phr of the inorganic filler or alternatively^'-, between 1 10 phr and 150 phr or between 1 15 phr and 150 phr of the inorganic filler,

[0036] As noted above, particular embodiments of the present invention further include a plasticizing system that includes both a high Tg resin and a plasticizing liquid. The plasticizing system may provide both an impro vement to the pioeessability of the rubber mix and/or a means for adjusting the rubber composition's glass transition temperature and/or its rigidity. In particular embodiments of the present invention, an effective amount of the plasticizing system is added to the rubber composition to adjust the shear modulus O* measured -at 60 °C to between 0.4 MPa and 1 MPa. Such amounts of the plasticizing system may be between 60 phr and I 30 phr or alternatively between 70 ph and 120 phr, between 70 phr and 1 10 phr, between 80 phr and 120 phr or between 90 phr and 1 .10 phr.

[0037] Suitable plasticizing liquids may include any liquid known for its plasticizing properties with dieaie elastomers. At room temperature (23 °C), these liquid piasticizers or these oils of varying viscosity are liquid as opposed to the resins that are solid. Examples include those derived from petroleum stocks, those having a vegetable base and combinations thereof. Examples of oiis that are petroleum based include aromatic oils, paraffimc oils, naphthenic oil^'s, ES oils, TDAE oils and so forth as known in the industry.. Also, known are liquid diene polymers, the poiyoiefin oils., ether piasticizers, ester piasticizers, phosphate piasticizers, sulfonate piasticizers and combinations of liquid piasticizers.

[0038] Examples of suitable vegetable oils include -sunflower oil, soybean oil, saffiower oil, corn oil, linseed oil and cotton seed oil. These- oils and other such vegetable -oils- may be used singularly or in combination. In some embodiments, sunflower oil having a high oleic acid content (at least 70 weight percent or alternatively, at least 80 weight percent) is useful an example being AGRI-PURE 80, available from Cargill with offices in Minneapolis, MN, in particular embodiments of the present invention, the selection of a suitable plasticizing liquid, is limited to a vegetable oil having a high oleic acid content.

[0039] The amount of plasticizing liquid useful in any particular, embodiment of the present invention depends upon the particular circumstances and the desired result. In general, for .example, the plasticizing liquid may be present in the rubber composition in an amount of between 5 phr and ^'70 phr or alternatively, between 10 phr and 60 phr, between 10 phr and 50 phr, between 5 phr and 40 phr or between 10 phr and 40 phr of the plasticizing liquid.

[0040] A plasticizing- hydrocarbon resin is a hydrocarbon compound thai is solid at ambient temperature (e.g., 23 °C) as opposed to a liquid, plasticizing -compound, such as a plasticizing oil. Additionally a plasticizing hydrocarbon resin is compatible, /„«?., miseibie,. with the rubber composition with which the resin is mixed at a concentration that allows the resin to act as a true plasticizing -agent, e.g., at a concentration that: is typically at least 5 phr (parts per hundred parts rubber by weight), [0041] Plasticizing hydrocarbon resins are polymers that can be aliphatic, aromatic or combinations of these types, meaning that the polymeric base of the resin may he formed from aliphatic and/or aromatic monomers. These resins can be natural or synthetic materials and can be petroleum based, in which case -the resins may be called petroleum plasticizing_. resins, or based on plant materials, In particular embodiments, although not limiting the invention, these resins may contain essentially only hydrogen and carbon atoms,

[0042] The plasticizing hydrocarbon resins^' useful in particular embodiment of the present invention include those that are homopotymers or copolymers of cyelopentadiene (CPD) or dicyc!operrtadiene (DCPD), hornopoiymers or copolymers of terpene, ^'homopol mers or copolymers of Cs cut and mixtures thereof.

[0043] Such copolymer plasticizing hydrocarbon resins as discussed generally above may include,, for example, resins made up of copolymers of (D)CPD/ vinyl-aromatic, of ^'(D)CPD/ terpene, of (D)CPD/ C$ cut, of terpene/ vinyl-aromatic, of Cs cut/ vinyl-aromatic and of combinat ions thereof.

[0044] Terpene monomers useiul for the terpene homopolysner and copolymer resins include alpha-pinene, beta-pinene and iirno^'nene. Particular embodiments include polymers of the iimonene monomers that Include three isomers: the L-limonene (Iaevorotator enantiomer), the D-iimonene (dextrorotatory enantiomer), or even the dipentene, a racemic mixture of the dextrorotatory and iaevorotatory enantiomers.

[0045] Examples of vinyl aromatic monomers include styrene, alpha- methyl styrene, o tho-, meta-, para-methylstyrene, vinyl-toluene, para-iertiobulylstyrene, methoxystyrenes, chloro-siyrenes, vinyl-ntesitylene, divinylhenzene, vinyinaphthalene, any vinyl -aromatic monomer coming from the <¾ cut for, more generally, from a Cg to Cio cut). Particular embodiments^' that include a vinyl-aromatic copolymer include the vinyl-aromatic in the minority monomer, expressed in molar fraction, in the. copolymer.

[0046] Particular embodiments of the present invention include as the plasticizing hydrocarbon resin the (D)CPD homopolymer resins, the (D)CPD/ styrene copolymer resins, the polylimonene resins, the Iimonene/ styrene copolymer resins, the Iimonene/ D(CPD) copolymer resins, Cs cut/ styrene copolymer resins, C$ cut/ <¾ cut copolymer resins, and mixtures thereof, [0047] Commercially available plasticizing resins that include ferpene resins suitable for use in the present invention include a polyaiphapmene resin, marketed under the name Resin R2495 by Hercules- Inc. of Wilmington, DEL Resin 112495 has a molecular weight of about 932, a softening point of about 135°C and a glass transition temperature of about 9i °C- Another commercially available product that may be used in the present invention includes DERCOLYTE LI 20 sold by the company DR of France. DERCOLYTE LI 20 polyterpetje- limonene resin has a number average molecular weight of about 625, a weight average molecular weight of about 1010, an ip of about 1.6, a softening point of about 1 i.9°C and has a glass transition temperature of about 72° C. Still another commercially available terpene resin that may be used in the present invention includes SYLVARES TR 7125 and/or SYLVARES TR. 5147 polylimonene resin sold by the Arizona Chemical Company of Jacksonville, PL. SYLVARES 7125 polyl monene resin has a molecular weight of about 1090, has softening point of about 125°- C, and has a glass transition temperature of about 73°C while the SYLVARES TR 5147 has a molecular weight of about 945, a softening point of about 120 °C. and has a glass transition, temperature of about 71° C.

[0048] Other suitable piasticizing hydrocarbo resins that are commercially available include C-s cut/ vinyl-aromatic styren copolymer, notably C$ cut / styrene or Cj cut / (¾ cut irom Neville Chemical Company under the names SUPER NEVTAC 78, SUPER. NEVTAC 85 and SUPER NEVTAC 99; from Goodyear Chemicals under the name WINGTACK EXTRA; from Kolon under names HIKOREZ ΊΊ 095 and HIKOREZ ΤΪ .Ι00; and from Exxon under names ESCOREZ 2101 and ECR 373.

[0049] Yet other suitable piasticizing hydrocarbon resins that are Mmonene/styre-tte copolymer resins that are commercially available include DERCOLYTE TS 105 from DR of France; and from Arizona Chemical Company under the name ZTTISLT and ZT5100.

[0050] it may be noted that the glass transition temperatures of piasticizing resins may be measured by Differential Scanning Caiorimeiry (DCS) in accordance: with ASTM D3418 (1999). In particular embodiments, useful, resins- may be have a glass transition temperature that is at least 25 °C or alternatively, at least 40 °C or at least 60 °C or between 25 °C and 95 °C, between 40 °C and 85 °C or between 60 °C and 80 °C,

I I [0051] The amount of pkstieizmg hydrocarbon resin useful in any particular embodiment of the present invention depends upon the particular circumstances and the desired result, i.e., a G* measured at 60 °C of between 0.4 MPa and 1 MPa. In general, for example, the total amount of plasticizing resin a ed to complement the plasticizing liquid in the rubber composition may be between 5 phr and 125 phr or alternatively,, between 30 phr and 120 phr or between 35 phr and 100 phr. In particular embodiments, the plasticizing resin may be present in an amount of between 40 phr and 80 phr, between 40 phr and 90 phr or between 35 phr and 90 phr of the plasticizing resin.

[0052] The ratio of the plasticizing resin to the plasticizing oil may be at any suitable amount to achieve the desired shear modulus but in particular embodiment may range, for example, between 1 :5 and 5: 1 or alternatively between 1 :4 and 4:1.

[0053] As noted previously, the present invention obtains the surprising improvement in traction while, maintaining good wear characteristics of tire treads by adjusting the amount of the plasticizing system in the rubber composition having a high loading, of inorganic filler to maintain a shear modulus G* measured at 60 °C of between 0,4 MPa and 1 MPA, Such measurements are made in accordance with ASTM D59 2-96, Other embodiments may include the shear modulus G* measured at 60 °C of between O.SMPa and 1.0 MPa. between 0,6 MPa and 0.9 MPa, between 0.5 MPa and 0.8 MPa or between 0.4 MPa and 0.8 MPa.

[0054] The rubber compositions disclosed herein may be cured with any suitable curing system including a peroxide curing system or a sulfur curing system. Particular embodiments are cured with a sulfu curing system that, includes free sulfur and may further include, fo example, one or more of accelerators, stearic acid and zinc oxide. Suitable free sulfur includes, for example, pulverized sulfur, rubber maker's sulfur, commercial sulfur, and insoluble sulfur. The amount of free sulfur included in the rubber composition is not limited and may range, for example, between 0.5 phr and 10 phr or alternatively between 0.5 phr and 5 phr or between 0.5 phr and 3 phr. Particular embodiments may include no free sulfur added in the curing system but instead include sulfur donors,

[0055] Accelerators are used to control, the time and/or temperature required for vulcanization and to improve the properties of the cured rubber composition. Particular embodiments of the present invention include one or more .accelerators. One example of a suitable primary accelerator useful in the present invention is a sulfonamide. Examples of suitable sulfenamide accelerators include n-eyclohexyl -2-beiizothiazole sulfenamide (CBS), N~tert-butyl-2 benzothiazole Sulfenamide (T.BBS), N-Oxydieihyl-2-benzihiazolsiiifenainid (MBS) and N^?-dicyclohexy{-2-benzothiazolesu!fenaniide (DCBS). Combinations of accelerators are often useful to improve the properties of the -cured rubber composition and the particular embodiments include the addition of secondary accelerators,

[0056] Particular embodiments may include as a secondary accelerant the use of a ^•moderately fast accelerator such as, for example, dipbenylguanidine (DP(¾ triphenyl guanidine (IPG), iorthotolyl guanidine (DOTG), o-tolylbigaunide- (OTBG) or hexamethylene tetramme (HMTA). Such accelerators may be added in an amount of up to 4 phr, between 0,5 and 3 phr, between 0,5 and 2.5 phr or between 1 and 2 phr. Particular -embodiments .may exclude the use of fast accelerators and/or ultra-fast accelerators such as, lor example, the fast accelerators; disulfides and benzothiazo!es; and the ultra-accelerators: thiurams, xanihaies. dithioearbamates and dithiophosphates.

[0057] Other additives can be added to the rubber compositions- disclosed herein as known in the art. Such additives may include, for example, some or ail of the following: antklegradants, antioxidants,, tatty acids, waxes, stearic acid and zinc oxide, Examples of antidegradants and. antioxidants include 6PPD, 77PD, IPPD and TMQ and may be added to rubber compositions in an amount, for example, of from 0,5 phr and 5 phr. Zinc oxide may be added in an amount, for example, of between 1 phr and 6 phr or alternatively, of between 1 ,5 phr and 4 phr. Waxes may be added in an amount, for example, of between 1 phr and 5 phr.

[0058] The rubber compositions that are embodiments of the present invention may be produced in suitable mixers,. In a manner known to those having ordinary skill in the art, typically using two successive preparation phases, a first phase of thermo-meehanical working at high temperature, followed by a second phase of mechadcal working at lower temperature,

[0059] The first phase of thermo-meehanical working (sometimes referred to as "non-productive" phase) is intended to mix thoroughly, by kneading-,, the various ingredients of he composition, with the exception of the vulcanization system. It is carried out in a suitable kneading device, such as an internal mixer or an. extruder, until, under the action of the mechanical working and the high shearing imposed, on the mixture, a maximum temperature generally between. 120 °C and 190 °C, more narrowly between 130 °C and Γ/0 °C, is reached.

[0060] After cooling of the mixture, a second phase of mechanical working is implemented at a lower temperature. Sometimes referred to as "productive" phase, this finishing phase consists of incorporating by mixing, the vulcanization (or cross-linking) system (sulfur or other vulcanizing. agent and accelerators)), in a suitable device, for example an open mill, it is performed for an appropriate time (typically between 1 and 30 minutes, for example between 2 and 10 minutes) and at a sufficiently low temperature lower than the vulcanization temperature of the mixture, so as to protect against, premature vulcanization.

[0061 ] The rubber composition can be formed into useful articles, including treads for use on vehicle tires. The treads may be formed as tread bands and then later made a part of a tire or they be formed directly onto a tire carcass by, for example, extrusion and then cured in a mold, As such, tread bands may be cured before being disposed on a tire carcass or they may be cured after being disposed on the tire carcass. Typically a tire tread is cured in a known, manner in a mold that molds the tread elements, into the tread, including, e.g., the sipes molded into the tread blocks,

[0062] It is recognized that treads may be formed from only one rubber composition or in two or more layers of differing rubber compositions, e.g., a cap and base construction.. In a ca and base construction, the cap portion of the tread is made of one rubber composition that is designed for contact with the road. The cap is supported on the base portion of the tread, the base portion made of a different rubber composition. In. particular .embodiments of the presen invention the entire tread may be made from the rubber compositions as disclosed herein while in other embodiments only the cap portions of the tread may be made from sucli rubber compositions,

[0063] It is recognized that the contact surface of a tread block, i.e., that portion of the tread block that contacts the oad, may be formed totally from the rubber composition having the low Tg as disclosed herein, ma be formed totally from another rubber composition or may be formed as combinations thereof. For -example,, a tread block may be formed as a composit of layered rubber compositions such that half of the block laterally is a layer of t he low Tg rubber composition and the other half of the block laterally is a layer of an alternative rubber composition. Such -construction would provide a tread block having 80 percent of its contact surface formed of the low Tg rubber composition.

[0064] As such, hi particular embodiments of the present invention, at least 80 percent of_. the total contact surface of- all the tread blocks on a tread may be formed from the rubber composition having the- low Tg as disclosed herein. Alternatively, at least 90 percent, at least 95 percent or 100 percent of the total contact surface of all the tread blocks on a tread may be formed from such rubber composition,

[0065] While the tire treads disclosed herein are suitable for many types of vehicles, particular embodiments include tire treads for use on. vehicles such as passenger cars and/or light trucks. Such tire treads are also useful tor all weather tires and/or summer tires. As such, the- properties of the cured rubber compositions from which the treads disclosed herein may be manufactured may have a glass transition temperature of between -30 °C and 0 °C and/or alternatively, between -25 °C and 0 °C, between -20 °C and 0 °C, between. -20 °C and -10 C, between -20 °C and -5 ^QC, between -15 °C and -5 °C and/or between -25 °C and -15

°e.

[0066] The- invention is further illustrated by the following examples, which are to be regarded only as illustrations and not del imitative of the invention in any way.. The properties of the compositions disclosed in the examples were evaluated as described below and these utilized methods are suitable for measurement of the claimed properties of the present invention.

[0067] Wet braking for a tire mounted, on an automobile fitted with an ABS braking system was determined by measuring the distance necessary to go from 50 Fv!PH to 0 MPH upon sudden braking on wetted ground (asphalt concrete). A value greater than that of the control, which is arbitrarily set to 100, indicates an improved result, that, is to say a shorter wet braking distance.

[0068] Dry braking of a tire mounted on an automobile fitted with an ABS braking system was measured by determining the distance necessary to go from 60 mph to a complete stop upon sudden braking on a dry asphalt surface. A value- greater than that of the control, which is arbitrarily set to 100, indicates an Improved result, i.e., a shorter braking distance and improved dry grip,

[0069] Wear resistance of a tire mounted on art automobile was measured by subjecting the tire to actual on-road travel and measuring lis wear rate (grams of tread lost per 1000 miles) at between 10,000 and 12,000 miles traveled. A value greater than that of the control, arbitrarily set to 1 00, indicates an improved result, that is to say less wear rate.

[0070] Dynamic properties (Tg and G*) for the rubber compositions were measured on a Metravib Model VA400 Visco Analyzer Test System, in accordance with ASTM D-5992- 96. The response of a sample of vulcanized material (double shear geometry with each of the two 10 mm diameter cylindrical samples being. 2 mm thick) was recorded as it was being subjected .to an alternating^' single sinusoidal shearing stress of a- constant 0.7 Pa rid at a frequency of 10 Hz over a temperature sweep from -60 °C to 100 °C with the temperature increasing_, at a rate of 1.5. °C/nim. The shear modulus G* at 60 °C was captured and the temperature at which the max tan delt occurred was recorded as the glass transition temperature, Tg.

Example 1

[0071] Rubber compositions were prepared using the components -shown in Table I, The amoun of each component making up the rubber compositions shown in Table 1. are provided in parts per hundred parts of rubber by weight (phr).

Table 1 - Rubber Formulations

1.6 Tire Tests

Wet Braking IQO m 136 14 1 129 135 138

Dry Braking 100 J 07 106 H I 96 1 10 106

Wear 100 1 11 100 1 19 96 100 76

[0072] The terpene resin was SYLVARES TR-5347, a poiylhttonene resin available fi¾m Arizona Chemical, Savannah, GA. The plastlcizmg oil was AGRI-PURE 80. The silica was 2E0SIL 1 0. a highly dispersible silica available from Rhodia having a BET of 160 ra²/g. The silane coupling agent was X 50-S available from Evontk Degussa. The curative package included sulfur, accelerators, zinc oxide and stearic acid.

[0073] The rubber formulations were prepared by mixing the components given in Table t , except for the sulfur and the accelerators, in a Banbury mixer operating between 25 and 65 RPM until a temperature ₀f between 130° C and 170° G was reached. The accelerators and sulfur were added in the second phase on a null Vulcanisation was effected at 150° C for 40 minutes. The formulations were then tested to measure their physical properties, the results of which are shown in ^'Table 1.

[0074] Tires were built with treads formulated from the rubber compositions-. The tires were then tested as described above, The grip performances all improved remarkably with surprising little reduction in. tread wear or, in some cases, improved wear rates. In Table 1, a lower number indicates improved wear rate over the witness. The witness tire was a Michelin brand all-season tire that is currently on the- market.

[0075] The terms "comprising," "including," and "having," as used in the claims and specification hei'eiu, shall be considered as indicating an open group that may include other elements not specified. The term "consisting essentially of," as used in the claims and specification herein, shall be considered as indicating a partially open group that may include other elements not specified, so long as tiros© other elements do not materially alter the basic and novel characteristics of the claimed invention. The terms "a," "an," and the singular forms of words shall be taken to include the plural form, of the same words, such that the terms mean that one or more of something- is provided. The terms "at. least one" and "one or more* are used, interchangeably. The term "one" or "single" shall be used to indicate that one and only one of something is intended. Similarly, other specific integer values, such as "two," are used when a specific number of things- Is intended. The terms "preferably," "preferred/^* "pi¾fe*/ "optionaily," "may-," and similar terms are used, to indicate thai an item, condition or step being referred to is an optional (not required) feature of the invention. Ranges that are described^' as being "between a and b" are inclusive of the values for "a" and "b."

[0076] It should be understood from the foregoing description, that various modifications and changes may be made, to the embodiments of the present inventio without departing from its true spirit. The foregoing description is provided for the purpose of illustration only and should not be construed in a limiting sense. Only -the language of the following claim should limit the scope of this invention.

Claims

CLAIMS What is claimed is:

1. A tread for a tire, the tread comprising a rubber composition that is based upon a cross- linkable elastomer composition, the cross-linkable elastomer composition comprising, per 100 parts by weight of rubber (phr):

a highly unsaturated diene elastomer;

between 100 phr and 160 phr of an inorganic reinforcing filler;

an effective amount -of -a. piastiei^'zing system that includes a . plasticizing resin having a glass transition temperature (Tg) of at least 25 °C and a plastieizing liquid, wherein the effective amount of the plasticizing -system provides the rubber -composition with a shear m dulus G* measured at 60 °C of between 0,4 MPa and 1 MPa, the effective amount of the. plasticizing system being between 60 phr and^' 330 phr, and wherein the rubber composition ^'has a glass transition temperature of between - 30 °C and 0 °C.

2. The tread of claim 1 , wherein, the highly unsaturated diene elastomer is at least 50 phr of a styrene-butadiene rubber (SBR) and no more than 50 phr of. a second diene rubber,

3. The tread of claim 1, wherein the highly unsaturated, diene elastomer is selected from a p.olybutadiene, a polyi.soprene_s natural, rubber, a butadiene copolymer, an isoprene copolymer or mixtures thereof,

4. The tread of claim 1₅ wherein the highly unsaturated diene elasiomer is -at leas 90 phr of an SBR or polybutadiene having a. glass transition temperature of between -100 °C and less than -50° C.

5. The tread of claim L wherein the inorganic- filler is a silica,

6. The tread of claim 1, wherein the cross-linkable elastomer composition comprises between 1 15 phr and 150 phr of the inorganic reinforcing filler.

7. The tread of claim 1, wherein the effective amount of the plasticizing system is between 70 phr and ί 10 phr,

8. The tread of claim 1, wherein the rubber composition has a glass transition temperature of between - 20 °€ and -5 °C,

9. The tread of claim 1 , wherein the shear modulus G* measured at 60. °C is between 0,5 MPa and 0.8 MPa.

10. The tread of claim 1, wherein the shear modulus G* measured at 60 °C is: between 0,6 MPa and 0.9 MPa

11. The tread of claim 1 , wherein, the plasticking resin has a glass transition temperature of between 40° C and 85° C.

12. The tread of claim 1 1 , wherein the plasticizing resin is a poiyiinionen resin,

13. The tread of claim 1, wherein the plasticizing liquid is a selected from sunflower oil., soybean oil, saffiower oil, corn oil, linseed oil, cotton seed oil or combinations thereof.

14. The tread of claim 13, wherein the plasticizing liquid has an oleic content of at least 80 wt. %.

15. The tread of claim 1 , wherein the highly unsaturated diene elastomer ^'is functional ized with an active moiety.

16. The tread of claim 1 5, wherein the highly unsaturated diene elastomer includes end chains having a si!anol functional group attached as the active moiety.

17. The -tread of claim 1., wherein the rubber composition comprises between 10 phr and 50 phr of t he plasticizing li quid.