Patent Application
20170361658
This invention relates generally to tires for vehicles and more particularly, to tread sculptures and tread materials.
It is known in the industry that tire designers must often compromise on certain characteristics of tires they are designing. Changing a tire design to improve one characteristic of the tire will often result in a compromise; i.e., an offsetting decline in another tire characteristic. One such compromise exists between snow traction and dry braking. Snow traction may be improved by decreasing the glass transition temperature of the tread mix and/or by increasing the number of sipes in the tread. These moves, however, typically result in a decrease in dry braking performance that is known to be improved by increasing the glass transition temperature of the tread mix and/or by decreasing the number of sipes in the tread.
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 dry braking and snow traction.
A tire tread formed from a rubber composition having a functionalized SBR and a BR that is reinforced with between 95 phr and 125 phr of a silica filler and includes a plasticizing system to adjust the glass transition temperature to be between −30° C. and −15° C. and the dynamic modulus G* at 60° C. to be between 0.9 MPa and 1.15 MPa. The tread includes central tread blocks having an average central tread block length of between 6.5 mm and 10 mm and shoulder tread blocks having an average shoulder tread block length of between 10 mm and 20 mm. Furthermore the tread is limited to being between 6.5 mm and 7.7 mm thick.
Particular embodiments of the present invention include tires and tire treads that have improved snow traction properties while surprisingly maintaining good dry traction properties. Such tires are particularly useful as all-weather tires and/or winter tires for passenger cars and/or light trucks.
The compromise between dry traction and snow traction was broken through a unique combination of materials and sculpture design. The treads that are disclosed herein are made of a rubber composition that includes a functionalized styrene-butadiene rubber (SBR) and further are of a thin design. By using the functionalized SBR that is known to provide improved wear, the inventors of these treads were able to adjust the sculpture and rubber properties that in combination provide the tread characteristics of improved snow traction without significant loss of dry traction, thereby breaking that compromise.
As used herein, the “longitudinal” direction is in the tire circumferential direction and is perpendicular to the tire axis of rotation.
As used herein, the “lateral” direction is along the tire width and is substantially parallel to the axis of rotation. However, unless otherwise indicated, a “lateral groove or sipe” is any groove or sipe generally oriented at an angle less than 45 degrees with the purely lateral direction while a “longitudinal groove or sipe” is any groove generally oriented at an angle greater than or equal to 45 degrees with the purely lateral direction.
As used herein, the “tread thickness” is the tread depth bonded by a top, ground-engaging side and a bottom side of the tread
As used herein, a “groove” has a width opening to the tread face of 0.6 mm or more while a “sipe” is a small slit molded or otherwise formed in a tread block or rib and has a width opening to the tread face of less than 0.6 mm. Grooves are troughs formed within the tread for, inter alia, the channeling of water and other substances encountered by the tire while sipes typically provide surface edges for traction and may often reduce tread element stiffness.
As used herein, a “tread element” is any type or shape of a structural feature found in the tread that contacts the ground. Examples of tread elements include tread blocks and tread ribs.
As used herein, a “tread block” is a tread element that has a perimeter defined by one or more grooves and/or sipes, creating an isolated structure in the tread.
As used herein, a “rib” is a tread element that runs substantially in the longitudinal direction of the tire and is not interrupted by any grooves that run in the substantially lateral direction or any other grooves oblique thereto.
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.
As used herein, rubber and elastomer are synonymous terms.
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 therefore “based upon” the uncured rubber composition. In other words, the cross-linked rubber composition is based upon or comprises the constituents of the cross-linkable rubber composition.
As is known generally, a tire tread is the road-contacting portion of a vehicle tire that extends circumferentially about the tire. It 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.
Reference will now be made in detail to embodiments of the invention, one or more examples of which are illustrated in the drawings. Each example is provided by way of explanation of the invention. For example, features illustrated or described as part of one embodiment can be used with another embodiment to yield still a third embodiment. It is intended that the present invention include these and other modifications and variations.
The tread 10 includes a shoulder portion 31 and a central portion 32 that are separated from each other by a shoulder longitudinal or circumferential groove 33. The central portion 32 may include one or more central longitudinal or circumferential grooves 34. The central portion 32 is therefore positioned between the two shoulder portions 31 and bordered by the two shoulder longitudinal grooves 33.
Also included in the tread 10 are a plurality of central tread blocks 35 that are formed by lateral central sipes 37 extending between two of the central longitudinal grooves 34 or between a central longitudinal groove 34 and a shoulder longitudinal groove 33. A plurality of shoulder tread blocks 36 are formed in the shoulder portion 31 of the tread 10 by lateral shoulder sipes 38 extending from the shoulder longitudinal groove 33 towards the sidewall 25 side of the tread 10.
The tread 10 is supported by the crown section 21 that is positioned radially-inward of the tread 10, the crown 21 having a belt package (not shown) to stiffen the casing and to provide improved wear and handling response. The belt package, as is well known, may include one or more layers of cords, typically steel cords, embedded in a thin layer of rubber and typically arranged circumferentially around the tire.
The pair of bead sections 23 are arranged to face each other in the tire width or axial direction. The bead section 23 includes the bead (not shown), as well known, which is an inextensible bead core that anchors the plies and locks the tire onto a wheel assembly. The carcass ply (not shown) extends between the bead sections 23, extending from one bead through one sidewall section 25, through the crown section 21, typically below the belt package and through the other sidewall section 25 to the other bead.
Typically, the carcass ply may be constructed from a plurality of mutually parallel textile or metal cords embedded in an elastomeric matrix, such as a thin layer of a rubber composition. As known to one having ordinary skill in the art, the carcass ply is typically formed using a calendaring process wherein the cords are laid parallel to each other and encased in the elastomeric matrix. The carcass ply is then arranged in a manner such that the cords are typically oriented in a radial direction along the sidewalls 25 of the tire 20. More specifically, along the sidewalls 25 of the tire 20, the cords of the carcass ply are substantially perpendicular to the axis of rotation of tire.
The tread 10 includes the shoulder longitudinal grooves 33 that border the shoulder portions 31 and the central portion 32. The central portion 32 includes the central longitudinal grooves 34 and the plurality of central tread blocks 35.
In particular embodiments of the treads disclosed herein, the tread thickness is between 6.5 mm and 7.7 mm. Since it is typical that treads will taper towards the lateral ends in the shoulder area, the tread is thickness is measured in the central portion of the tread. Alternatively the tread thickness may be between 6.5 mm and 7.3 mm or between 6.5 mm and 7 mm thick. As noted previously, it is the thinness of the tread coupled with the functionalized SBR of the tread and tread elements that provide the break in the compromise between dry traction and snow traction.
It should be noted that for particular embodiments of the treads disclosed herein, the central tread blocks are always formed by the lateral central sipes, there being no lateral grooves in the central portion of the treads. As was noted in the definitions, a sipe is a small slit molded or otherwise formed in a tread block or rib and has an opening to the tread face of less than 0.6 mm. Grooves are defined as having openings on the tread face of 0.6 mm or more. Optionally particular embodiments may include a limited number of lateral grooves in the central portion, such as no more than 10% of the total number of lateral grooves and sipes or alternatively, no more than 5%, no more than 3% or no more than 1%.
Likewise it should be noted that for particular embodiments of the treads disclosed herein, the shoulder tread blocks are always formed by the lateral shoulder sipes, there being no lateral grooves in the shoulder portions of the treads. Optionally particular embodiments may include a limited number of lateral grooves in the shoulder portion, such as no more than 35% of the total number of lateral grooves and sipes or alternatively, no more than 30%, no more than 25%, no more than 20%, no more than 10%, no more than 5%, no more than 3% or no more than 1%.
The use of lateral sipes rather than lateral grooves in the shoulder and central portions of the tread improve the performance of the tread by providing the necessary structure and if too many of the sipes are replaced with lateral grooves, then the desired performance of the tire will be lost.
In those embodiments that include a limited number of lateral grooves in the central portion and/or in the shoulder portion, the tread block lengths are measured by treating the limited number of lateral grooves as though they were sipes for purposes of the measurement of the tread block length. Furthermore, in particular embodiments of the treads disclosed herein, such limited numbers of lateral grooves are distributed essentially evenly around the circumference of the tire.
For the central portion of the treads disclosed herein there is an average central tread block length. The average central tread block length is the calculated average of all the central tread block lengths dCB in the central portion divided by the number of central tread blocks. To obtain the average central tread block length, the central tread block length dCB of every central tread block is measured and added together and then this sum is divided by the number of central tread blocks to provide the average central tread block length.
Particular embodiments of the treads disclosed herein may be characterized as having an average central tread block length of between 6.5 mm and 10 mm or alternatively between 6.8 mm and 9 mm or between 7 mm and 8 mm.
For the shoulder portions of the treads disclosed herein there is an average shoulder tread block length. The average shoulder tread block length is the calculated average of all the shoulder tread block lengths dSB in the shoulder portion divided by the number of shoulder tread blocks in the shoulder portion. To obtain the average shoulder tread block length, the shoulder tread block length dSB of every shoulder tread block is measured and added together and then this sum is divided by the number of shoulder tread blocks to provide the average shoulder tread block length in the shoulder portion.
Particular embodiments of the treads disclosed herein may be characterized as having an average shoulder tread block length of between 10 mm and 20 mm or alternatively between 11 mm and 19 mm, between 12 mm and 18 mm or between 14 mm and 17 mm.
It may be noted that optionally a portion of the lateral sipes may have chamfered openings onto the tread face. As may be seen in
The longitudinal grooves 33 and 34 extend from their opening on the face of the tread 10 to a groove bottom 43. The distance between the groove bottom 43 and the tread face is the depth of the groove. Since the purpose of the grooves includes channeling of water from the roadway when it is raining, the tire tread is provided with a wear bar 42 that appears intermittently around the groove so that when the tread wears to the wear bar, the user knows that the tire needs to be removed from service. Wear bar depth is often set by government regulation and marks the minimum tread depth for tire operation on the roads. The wear bar depth is the distance from the tread face to the top face of the wear bar.
Likewise the distance between a sipe bottom and the tread face is the depth of the sipe. Particular embodiments of the treads disclosed herein provide that the lateral central sipes and/or the lateral shoulder sipes that form the tread blocks in the central and shoulder portions may be characterized as extending across their entire length (from one lateral edge of the tread block to the other lateral edge of the tread bock) to a depth of at least 90% of the depth of the wear bar or at least 100% of the depth of the wear bar. For example a lateral sipe that extends to 100% of the depth of the wear bar would extend so that the bottom of the sipe was level with the top of the wear bar. In other embodiments, the lateral central sipes and/or the lateral shoulder sipes that form the tread blocks in the central and shoulder portions may be characterized as extending across their entire length to a depth of at least 90% of the groove depth bordering the tread block of the sipe or at least 100% of such depth. For example a lateral sipe that extends to 100% of the depth of the groove depth would extend so that the bottom of the sipe was level with the bottom of the groove.
While particular embodiments of such treads provide that all such sipes have these depths extending across their entire length, it is recognized that alternatively, in particular embodiments, at least 80% of the total of the sipes may be characterized as extending to such depths across their entire lengths or alternatively, at least 90% or at least 95%. Such alternatives may apply, in particular different embodiments, just to the shoulder lateral sipes or just to the central lateral sipes or to both the lateral shoulder and central sipes.
The treads as described above all are formed at least in part from a rubber composition that includes both a functionalized SBR and a polybutadiene rubber (BR) or alternatively for particular embodiments just a functionalized SBR. Those skilled in the art will recognize that while the treads disclosed herein may be formed entirely of the rubber compositions described below, there are tread designs that would use such rubber compositions to form only a portion of the treads.
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 cap and base construction, the cap portion of the tread is made of one rubber composition that is designed for contract with the road. The cap is supported on the base portion of the tread, the base portion made of different rubber composition. In particular embodiments of the present invention the entire tread may be made from the rubber compositions disclosed herein while in other embodiments only the cap portions of the tread may be made from such rubber compositions.
In other embodiments it is recognized that the contact surface of the tread elements, i.e., that portion of the tread element that contacts the road, may be formed totally and/or only partially from the rubber compositions disclosed herein. In particular embodiments the tread block, for example, may be formed as a composite of laterally layered rubber compositions such that at least one lateral layer of a tread block is of the rubber compositions disclosed herein and another lateral layer of a tread block is of an alternative rubber composition. In particular embodiments of tread constructions, at least 80% of the total contact surface area of the tread is formed solely from the rubber compositions disclosed herein. The total contact surface area of the tread is the total surface area of all the radially outermost faces of the tread elements that are adapted for making contact with the road.
BR is a common rubber component useful in many rubber articles, including tires, and is a homopolymer of conjugated 1,3-butadiene. SBR is a copolymer of styrene and 1, 3-butadiene and is one of the most commonly used synthetic rubbers. The microstructure 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 that 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 80 wt. %, 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 10 wt. % and 35 wt. %, between 15 wt. % and 28 wt. % or between 30 wt. % and 40 wt. % bound styrene.
Because of the double bond present in the butadiene portion of the SBR, the butadiene portion is made up of three forms: cis-1,4, trans-1,4 and vinyl-1,2. Optionally the functionalized SBR materials suitable for use in the rubber compositions disclosed herein are those having a high trans-1,4 content of at least 30 wt. % or alternatively between 30 wt. % and 70 wt. %, between 35 wt. % and 55 wt. % or between 35 wt. % and 45 wt. %.
Methods for determining the microstructure of the butadiene portion of the SBR materials are well known to those having ordinary skill in the art and include, for example, NMR methods and infrared spectroscopy methods. In one suitable NMR spectroscopy method, a carbon-13 NMR analyses may be performed using, for example, a Bruker AM250 spectrometer. The nominal frequency of carbon-13 is 62.9 MHz and the spectra are recorded without the “nuclear Overhauser effect” (NOE) to ensure quantitative results. The spectral width is 240 ppm. The angle pulse used is a 90° pulse, the duration of which is 5 vs. Low-power decoupling with a wide proton band are used to eliminate scalar 1H-carbon-13 coupling during carbon-13 acquisition. The sequence repetition time is 4 seconds. The number of transients accumulated to increase the signal/noise ratio is 8192. The spectra are calibrated against the CDCl3 band at 77 ppm.
Functionalized rubbers, i.e., those appended with active moieties, are well known in the industry. The elastomers may be functionalized by attaching these active moieties to the polymer backbone, along the branches of the polymer or at the branch ends of the polymer. Examples of functionalized elastomers include silanol or polysiloxane functionalized elastomers, examples of which may be found in U.S. Pat. No. 6,013,718, which is hereby fully incorporated by reference. Other examples of functionalized elastomers include those having alkoxysilane groups as described in U.S. Pat. No. 5,977,238, carboxylic groups as described in U.S. Pat. No. 6,815,473, polyether groups as described in U.S. Pat. No. 6,503,973 or amino groups as described in U.S. Pat. No. 6,800,582 and are all incorporated herein by reference. The functional groups are attached to the elastomers to provide interaction between the elastomer and the reinforcement filler.
In particular embodiments of the treads disclosed herein, the SBR is a functionalized elastomer having functional moieties attached to at least a portion of the total number of branch ends or along the branches of the butadiene portion of the polymer. Such functional moieties may include, for example, amino groups, silanol groups, alkoxysilane groups, carboxylic groups or polyether groups. In particular embodiments, the functional moieties may be selected from amino groups, silanol groups or alkoxysilane groups. In particular embodiments, the functionalized SBR may include a mixture of two or more different such functionalized SBR's or limited to one of the functionalized SBR's.
The rubber compositions disclosed herein may include between 50 phr and 85 phr of the functionalized SBR or alternatively between 60 phr and 85 phr, between 70 phr and 85 phr or between 70 phr and 80 phr. Likewise the rubber compositions may include between 15 phr and 50 phr of the polybutadiene rubber or alternatively between 15 phr and 40 phr, between 15 phr and 30 phr or between 20 phr and 30 phr. As noted above, particular embodiments may include only the functionalized SBR. Particular embodiments include only the functionalized SBR and the BR in the rubber compositions.
In addition to the diene elastomer, particular embodiments of the rubber composition useful for the treads disclosed herein further include a plasticizing system. The plasticizing system may provide both an improvement to the processability of the rubber mix and a means for adjusting the rubber composition's dynamic modulus and glass transition temperature. Suitable plasticizing systems include both a plasticizing liquid and a plasticizing resin to achieve the desired braking and wear characteristics of the tread.
Suitable plasticizing liquids may include any liquid known for its plasticizing properties with diene elastomers. At room temperature (23° C.), these liquid plasticizers 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 oils that are petroleum based include aromatic oils, paraffinic oils, naphthenic oils, MES oils, TDAE oils and so forth as known in the industry. Also known are liquid diene polymers, the polyolefin oils, ether plasticizers, ester plasticizers, phosphate plasticizers, sulfonate plasticizers and combinations of liquid plasticizers.
Examples of suitable vegetable oils include sunflower oil, soybean oil, safflower 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, Minn. In particular embodiments of useful rubber compositions disclosed herein, the selection of suitable plasticizing oils is limited to a vegetable oil having a high oleic acid content.
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 50 phr or alternatively, between 10 phr and 50 phr, between 10 phr and 45 phr or between 15 phr and 45 phr. Since both a plasticizing liquid and a plasticizing hydrocarbon resin are included in the plasticizing system, the amounts of both types of plasticizers are adjusted as described below to obtain the desired physical characteristics of the tread.
A plasticizing hydrocarbon resin is a hydrocarbon compound that is solid at ambient temperature (e.g., 23° C.) as opposed to liquid plasticizing compounds, such as plasticizing oils. Additionally a plasticizing hydrocarbon resin is compatible, i.e., miscible, 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.
Plasticizing hydrocarbon resins are polymers/oligomers that can be aliphatic, aromatic or combinations of these types, meaning that the polymeric base of the resin may be 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.
The plasticizing hydrocarbon resins useful in particular embodiment of the present invention include those that are homopolymers or copolymers of cyclopentadiene (CPD) or dicyclopentadiene (DCPD), homopolymers or copolymers of terpene, homopolymers or copolymers of C5 cut and mixtures thereof.
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/C5 cut, of terpene/vinyl-aromatic, of C5 cut/vinyl-aromatic and of combinations thereof.
Terpene monomers useful for the terpene homopolymer and copolymer resins include alpha-pinene, beta-pinene and limonene. Particular embodiments include polymers of the limonene monomers that include three isomers: the L-limonene (laevorotatory enantiomer), the D-limonene (dextrorotatory enantiomer), or even the dipentene, a racemic mixture of the dextrorotatory and laevorotatory enantiomers.
Examples of vinyl aromatic monomers include styrene, alpha-methylstyrene, ortho-, meta-, para-methylstyrene, vinyl-toluene, para-tertiobutylstyrene, methoxystyrenes, chloro-styrenes, vinyl-mesitylene, divinylbenzene, vinylnaphthalene, any vinyl-aromatic monomer coming from the C9 cut (or, more generally, from a C8 to C10 cut). Particular embodiments that include a vinyl-aromatic copolymer include the vinyl-aromatic in the minority monomer, expressed in molar fraction, in the copolymer.
Particular embodiments include as the plasticizing hydrocarbon resin the (D)CPD homopolymer resins, the (D)CPD/styrene copolymer resins, the polylimonene resins, the limonene/styrene copolymer resins, the limonene/D(CPD) copolymer resins, C5 cut/styrene copolymer resins, C5 cut/C9 cut copolymer resins, and mixtures thereof.
Commercially available plasticizing resins that include terpene resins suitable for use in the present invention include a polyalphapinene resin marketed under the name Resin R2495 by Hercules Inc. of Wilmington, Del. Resin R2495 has a molecular weight of about 932, a softening point of about 135° C. and a glass transition temperature of about 91° C. Another commercially available product that may be used in the present invention includes DERCOLYTE L120 sold by the company DRT of France. DERCOLYTE L120 polyterpene-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 119° 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, Fla. SYLVARES 7125 polylimonene resin has a molecular weight of about 1090, has a 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.
Other suitable plasticizing hydrocarbon resins that are commercially available include C5 cut/vinyl-aromatic styrene copolymer, notably C5 cut/styrene or C5 cut/C9 cut from 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 T1095 and HIKOREZ T1100; and from Exxon under names ESCOREZ 2101 and ECR 373.
Yet other suitable plasticizing hydrocarbon resins that are limonene/styrene copolymer resins that are commercially available include DERCOLYTE TS 105 from DRT of France; and from Arizona Chemical Company under the name ZT115LT and ZT5100.
It may be noted that the glass transition temperatures of plasticizing resins may be measured by Differential Scanning calorimetry (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.
The amount of plasticizing hydrocarbon resin useful in any particular embodiment of the present invention depends upon the particular circumstances and the desired result and may be present in an amount of between 15 phr and 60 phr or alternatively, between 20 phr and 50 phr or between 20 phr and 45 phr. As noted above, since both a plasticizing liquid and a plasticizing hydrocarbon resin are included in the plasticizing system, the amount of both types of plasticizers are adjusted as described below to obtain the desired physical characteristics of the tread to improve both the wear and braking properties.
The amount of the plasticizing system is adjusted to provide the rubber composition with a glass transition temperature of between −30° C. and −15° C. or alternatively between −25° C. and −15° C. and a dynamic modulus G* at 60° C. of between 0.9 MPa and 1.15 MPa or alternatively between 0.95 MPa and 1.15 MPa or between 0.95 MPa and 1.07 MPa, both measured in accordance with ASTM D5992-96. As such, the ratio of the amount of liquid plasticizer to the amount of plasticizing resin may be adjusted to achieve the desired physical properties of the rubber composition such that, when the functionalized SBR is used as the majority elastomer in the rubber compositions as disclosed herein, the surprising break in the dry traction-snow traction compromise is achieved. Such ratios may range, for example, from between 0.2 and 2.2 or alternatively between 0.2 and 2.
The rubber compositions disclosed herein further include a reinforcing filler of silica. Useful silica reinforcing fillers known in the art include fumed, precipitated and/or highly dispersible silica (known as “HD” silica). Examples of highly dispersible silicas include Ultrasil 7000 and Ultrasil 7005 from Degussa, the silicas Zeosil 1165MP, 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 m2/g and 250 m2/g or alternatively between 80 m2/g and 230 m2/g. The silica filler may be added to the rubber composition in a quantity of between 60 phr and 125 phr or alternatively between 70 phr and 120 phr, between 80 phr and 110 phr or between 85 phr and 110 phr.
In particular embodiments of the present invention, other reinforcing fillers are excluded so that, for example, no or very little (<10 phr or <5 phr) carbon black is used.
For coupling the silica filler to the diene elastomer, a coupling agent that 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 bifunctional organosilanes or polyorganosiloxanes. 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 it may be mixed into the rubber composition in its free or non-grafted state. One useful coupling agent is X 50-S, a 50-50 blend by weight of Si69 (the active ingredient) and N330 carbon black, available from Evonik Degussa.
In the rubber compositions disclosed herein, the content of coupling agent may range, for example, between 2 phr and 15 phr or alternatively between 6 phr and 12 phr.
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 sulfur curing system that includes free sulfur and may further include, for 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. In particular embodiments of the rubber compositions disclosed herein, the amount of free sulfur included in the rubber composition may range, for example, between 0.5 phr and 6 phr. Particular embodiments may include no free sulfur added in the curing system but instead include sulfur donors.
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 sulfenamide. Examples of suitable sulfenamide accelerators include n-cyclohexyl-2-benzothiazole sulfenamide (CBS), N-tert-butyl-2-benzothiazole Sulfenamide (TBBS), N-Oxydiethyl-2-benzthiazolsulfenamid (MBS) and N′-dicyclohexyl-2-benzothiazolesulfenamide (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.
Particular embodiments may include as a secondary accelerant the use of a moderately fast accelerator such as, for example, diphenylguanidine (DPG), triphenyl guanidine (TPG), diorthotolyl guanidine (DOTG), o-tolylbigaunide (OTBG) or hexamethylene tetramine (HMTA). Such accelerators may be added in an amount, for example, of up to 4 phr, between 0.5 and 4 phr, between 0.5 and 3 phr or between 1 and 2 phr. Particular embodiments may exclude the use of fast accelerators and/or ultra-fast accelerators such as, for example, the fast accelerators: disulfides and benzothiazoles; and the ultra-accelerators: thiurams, xanthates, dithiocarbamates and dithiophosphates.
Other additives can be added to the rubber compositions disclosed herein as known in the art. Such additives may include, for example, some or all of the following: antidegradants, antioxidants, fatty 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.
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-mechanical working at high temperature, followed by a second phase of mechanical working at lower temperature.
The first phase of thermo-mechanical working (sometimes referred to as “non-productive” phase) is intended to mix thoroughly, by kneading, the various ingredients of the 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. is reached.
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 accelerator(s)), in a suitable device, for example an open mill. It is performed for an appropriate time (typically for example between 1 and 30 minutes) and at a sufficiently low temperature lower than the vulcanization temperature of the mixture, so as to protect against premature vulcanization.
The rubber composition can be formed into treads for tires that are useful for passenger cars and/or light trucks. 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 grooves, ribs and/or blocks molded into the tread.
The invention is further illustrated by the following examples, which are to be regarded only as illustrations and not delimitative of the invention in any way. Following is a description of the testing procedures used in the examples that follow.
Modulus of elongation (MPa) was measured at 10% (MA10) at a temperature of 23° C. based on ASTM Standard D412 on dumb bell test pieces. The measurements were taken in the second elongation; i.e., after an accommodation cycle. These measurements are secant moduli in MPa, based on the original cross section of the test piece.
Snow grip (%) on snow-covered ground was evaluated by measuring the forces on a single driven test tire in snow according to the ASTM F1805 test method. The vehicle travels at a constant 5 mph speed and the forces are measured on the single test tire at the target slip. A value greater than that of the Standard Reference Test Tire (SRTT), which is arbitrarily set to 100, indicates an improved result, i.e., improved grip on snow.
Dry grip performance (%) 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.
The maximum tan delta dynamic properties for the rubber compositions were measured at 23° C. on a Metravib Model VA400 ViscoAnalyzer Test System in accordance with ASTM D5992-96. 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 at a frequency of 10 Hz under a controlled temperature of 23° C. Scanning was effected at an amplitude of deformation of 0.05 to 50% (outward cycle) and then of 50% to 0.05% (return cycle). The maximum value of the tangent of the loss angle tan delta (max tan 6) was determined during the return cycle.
Dynamic properties (Tg and G*) for the rubber compositions were measured on a Metravib Model VA400 ViscoAnalyzer Test System in accordance with ASTM D5992-96. 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 MPa and 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./min. The shear modulus G* at 60° C. was captured and the temperature at which the max tan delta occurred was recorded as the glass transition temperature, Tg.
Rubber compositions were prepared using the components shown in Table 1. The amount of each component making up the rubber compositions shown in Table 1 are provided in parts per hundred parts of rubber by weight (phr). The fSBR was functionalized with an amine group and the resin was a C5C9 resin; the silane coupling agent was Si69, the plasticizing oil was AGRI-PURE 80; the carbon black was N234 and the silica was Zeosil 1165.
The rubber formulations were prepared by mixing the components given in Table 1, except for the sulfur and the accelerators, in a Banbury mixer operating between 25 and 65 RPM until a temperature of between 130° C. and 170° C. was reached. The accelerators and sulfur were added in the second phase on a mill and then vulcanization was effected. The formulations were then tested to measure their physical properties, which are also reported in Table 1.
Tires were built using the rubber compositions W1 and F6. One comparative tire C1 having a tread formed of W1 had a tread thickness of 8.2 mm and had an average shoulder tread block length and an average central tread block length of 9 mm. The inventive tire T1 formed of F6 had a tread thickness of 7 mm and had an average shoulder tread block length of 16 mm and an average central tread block length of 8.2 mm. There were no lateral grooves and the sipes were full depth, i.e., to the depth of the wear bars. A second comparative tire T2 was built that was structurally inventive but made from witness material. The tires were mounted and tested in accordance with the procedures provided above. The results are provided in Table 2.
As can be seen, the tire T1 built having both the structural and materials in accordance with the disclosure herein had significantly improved snow and dry traction over the comparative tires.
The terms “comprising,” “including,” and “having,” as used in the claims and specification herein, 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 those 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,” “prefer,” “optionally,” “may,” and similar terms are used to indicate that 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.”
It should be understood from the foregoing description that various modifications and changes may be made to the embodiments of the present invention 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 claims should limit the scope of this invention.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US15/68150 | 12/30/2015 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62098941 | Dec 2014 | US |
