WO2012158505A2 - Pneumatique et articles élastomères offrant une fonctionnalité d'émission d'arômes - Google Patents

Pneumatique et articles élastomères offrant une fonctionnalité d'émission d'arômes Download PDF

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Publication number
WO2012158505A2
WO2012158505A2 PCT/US2012/037484 US2012037484W WO2012158505A2 WO 2012158505 A2 WO2012158505 A2 WO 2012158505A2 US 2012037484 W US2012037484 W US 2012037484W WO 2012158505 A2 WO2012158505 A2 WO 2012158505A2
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WIPO (PCT)
Prior art keywords
tire
belt
tread
pneumatic tire
fragrant
Prior art date
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Ceased
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PCT/US2012/037484
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English (en)
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WO2012158505A4 (fr
WO2012158505A3 (fr
Inventor
James D. ULMER
John L. Turner
Neel K. Mani
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Bridgestone Americas Tire Operations LLC
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Bridgestone Americas Tire Operations LLC
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Publication of WO2012158505A2 publication Critical patent/WO2012158505A2/fr
Publication of WO2012158505A3 publication Critical patent/WO2012158505A3/fr
Publication of WO2012158505A4 publication Critical patent/WO2012158505A4/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/0041—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers
    • B60C11/005—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers with cap and base layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0025—Compositions of the sidewalls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/007—Fragrance additive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients

Definitions

  • One or more embodiments of the present disclosure relate to pneumatic tires comprised of rubber and exhibiting an odor that is not normally associated with articles made from rubber.
  • a pneumatic tire having an indicator of tire wear condition.
  • the pneumatic tire has a circumferential tread and a pair of sidewalls. At least one of the tread and sidewalls comprises a barrier layer and an indicator layer, where the barrier layer is located above or outward from the indicator layer.
  • the indicator layer comprises a tire rubber composition having between 0.1 and 100 phr of at least one fragrant chemical.
  • a pneumatic tire having an indicator of elevated tire temperature.
  • the pneumatic tire has a circumferential tread portion, a pair of sidewall portions, a pair of steel belt plies layered one on top of the other, a rubber belt edge insert between the edges of the layered steel belt plies and a rubber wedge between the inner steel belt ply edge and the body ply.
  • At least one of these tire portions comprises a tire rubber composition having from 0.1 to 20 phr of a thermally-activated fragrant chemical.
  • a pneumatic tire comprising a circumferential tread portion, a pair of sidewall portions, a pair of bead region portions, at least one cap, carcass ply, or belt ply, and an inner liner portion, where at least one of the tread and sidewalls may comprise a barrier layer and an indicator layer, where the barrier layer is located above or outward from the indicator layer.
  • At least one of these tire portions comprises a tire rubber composition having from 0.1 to 100 phr of polymeric or resinous microcapsules containing at least one fragrant chemical. Encapsulating fragrant chemicals whose boiling points are lower than mixing and tire curing temperatures can nonetheless be used in a tire since the chemicals are contained within a capsule during mixing and curing.
  • the fragrant chemicals can be released at a slower rate from the tire than without encapsulation, since their release rate is limited by their diffusion rate not only through the tire rubber, but also through the capsule. Retention of the fragrance by the microcapsule wall until the wall is mechanically ruptured can serve as an indicator of abrasion of the tread indicator layer or abrasion of a sidewall indicator layer due to sidewall scuffing.
  • a capsule is a core of one or more fragrant chemicals with or without a diluent surrounded or enveloped by a wall of yet another substance. Microcapsules can range in size from about 0.01 ⁇ to 200 ⁇ . In tire applications, a preferred size is less than about 10 ⁇ .
  • the present disclosure also discloses a pneumatic tire comprising a circumferential tread and an interior portion located below the circumferential tread.
  • the interior portion comprises a pair of sidewall portions, a pair of bead region portions, at least one cap, carcass ply, or belt ply, and an inner liner portion.
  • At least one interior portion component comprises a tire rubber composition having from 0.1 to 60 phr of at least one fragrant chemical.
  • Figure 1 illustrates a cross-sectional view of one embodiment of a pneumatic tire provided according to this disclosure.
  • Axial or “axially” refer to a direction that is parallel to the axis of rotation of a tire
  • Core refers to polymeric or metallic material in a strand or cable, used to form the belts, plies and/or beads of a tire;
  • “Circumferential” and “circumferentially” refer to lines or directions extending along the perimeter of the surface of the tread parallel to the equatorial plane perpendicular to the axial direction of the tire;
  • Equatorial plane refers to the plane that is perpendicular to the tire's axis of rotation and passes through the center of the tire's tread;
  • Layer refers to a portion of a pneumatic tire that comprises a distinct elastomeric formulation, as compared to surrounding layers, or a portion that has been formed or processed into the tire separately from other layers, or both;
  • “Monomer” refers to any compound with a polymerizable moiety which is added to a reactor in order to produce a polymer
  • Phr refers to parts by weight of an ingredient per 100 parts by weight of rubber
  • Polymer refers to a macromolecular compound prepared by polymerizing monomers of the same or a different type, and generally denotes homopolymers, copolymers, interpolymers, and the like; the term “interpolymer” refers to polymers prepared by the polymerization of at least two types of monomers;
  • Ring or “radially” refer to a direction perpendicular to the axis of rotation of the tire
  • Standardwall refers to that portion of the tire between the tread and the bead;
  • “Tire component” refers to a portion of a tire that has been formed and incorporated into the green tire assembly in a separate process step than any other tire component; examples of separate tire components include the sidewalls, bead portion, cap ply, belt ply, carcass ply and inner liner portions, tire tread, sub-tread and a combination of the tire tread and sub-tread; and,
  • Tread refers to the tire component that comes into contact with the road under normal load.
  • inward and outwardly refer to a general direction towards the equatorial plane of the tire
  • outward and outwardly refer to a general direction away from the equatorial plane of the tire and towards the sidewall of the tire.
  • relative directional terms such as “inner” and “outer” are used in connection with an element, the “inner” element is spaced closer to the equatorial plane of the tire than the “outer” element.
  • FIG. 1 depicts a cross-sectional view of an exemplary pneumatic tire 100 according to the present disclosure.
  • Tire 100 includes a circumferential tread 110, a pair of sidewalls 120 which terminate in a pair of axially spaced bead regions that are indicated generally at 130. Further, tire 100 includes carcass ply 160, which extends circumferentially a bout the tire and axially from one bead region to the other, through sidewalls 120 and beneath the tread of the tire.
  • Carcass ply 160 generally comprises parallel-aligned cords (not shown) that may be biased or aligned with the equatorial plane.
  • Bead regions 130 generally include an annular ring (e.g., a bundle of steel cables) 140, about which carcass ply 160 is generally turned-up. The area between carcass ply 160 that is turned-up is generally filled with bead filler 150.
  • tire 100 further includes belt 170, comprising a first layer 171 and second layer 172, that extends circumferentially about the tire between tread 110 and carcass ply 160.
  • Belt 170 may optionally be a belt ply comprising parallel-aligned cords (not shown) that are biased with the equatorial plane.
  • Belt edge inserts 192 are placed between the carcass ply 160 and belt 170, while belt wedge inserts 194 are placed between individual belt layers 171, 172 comprising belt 170.
  • Tire 100 also includes inner liner 180, that is generally a layer lining the inside portion of a tire that has a high resistance to air permeability to ensure air retention when the tire is inflated.
  • Tire 100 may also include sub-tread layer 190, provided between tread 110 and belt 170.
  • Tire 100 may also include cap ply 200, provided between su b-tread layer 190 and belt 170, where the cords of the cap ply 200 may be aligned with the equatorial plane.
  • one or more of the carcass, cap, and belt plies are coated with a ru bber composition, know generally as a "skim stock" ru bber.
  • the carcass ply cord material may be coated with a relatively thick ru bber layer, and is therefore also sometimes referred to as "carcass ply rubber.”
  • a number of tire components are comprised of a tire rubber composition, including but not limited to tread rubber compositions, sidewall rubber compositions, inner liner rubber compositions, bead filler compositions, skim rubber compositions, and the like.
  • Tire rubber compositions are comprised of at least one elastomer, including but not limited to natural or synthetic rubber, or blends thereof.
  • elastomer and “rubber” are used interchangeably herein. Generally any conventionally-used elastomer for rubber compounding is suitable for use herein.
  • Non-limiting examples include the following, individually as well as in combination, according the desired final viscoelastic properties of the rubber compound: Natural Rubber (Hevea and Guayule), Polyisoprene Rubber, Styrene Butadiene Rubber, Polybutadiene Rubber, Butyl Rubbers, Halobutyl Rubbers, Ethylene Propylene Rubbers, Crosslinked Polyethylene, Neoprenes, Nitrile Rubbers, Chlorinated Polyethylene Rubbers, Silicone Rubbers, Specialty Heat & Oil Resistant Rubbers, Other Specialty Rubbers, and Thermoplastic Rubbers, as such terms are employed in The Vanderbilt Rubber Handbook, Thirteenth Edition, (1990).
  • the elastomers may contain a variety of functional groups, including but not limited to, tin, silicon, and amine-containing functional groups.
  • a tire rubber composition typically also contains any or all of the following additional ingredients: fillers, processing oils/aids, antidegradants, zinc oxide, stearic acid, sulfur, accelerators, coupling agents, and adhesion promoters, and the like.
  • such additional ingredients may be present in the following exemplary amounts: (1) fillers: from 0 to 150 phr, and preferably from 20 to 80 phr; (2) processing oils/aids: from 0 to 75 phr, and preferably from 0 to 50 phr; (3) antidegradants: from 0 to 10 phr, and preferably from 0 to 5 phr; (4) stearic acid: from 0 to 5 phr, and preferably from 0 to 3 phr; (5) zinc oxide: from 0 to 10 phr, and preferably from 0 to 5 phr; (6) sulfur: from 0 to 10 phr, and preferably from 0 to 4 phr; (7) accelerators: from 0 to 10 phr, and preferably from 0 to 5 phr; (8) coupling agent: from 0 to 30 phr, and preferably from 0.5 to 15 phr; and (9) adhesion promoters:
  • tire rubber compositions When forming tire rubber compositions, generally all ingredients may be mixed with standard equipment such as, e.g., Banbury mixers or other internal mixers. Typically, mixing occurs in two or more stages, during which ingredients may be added. In the case of mixing a tire tread rubber composition, typically the mixing process is comprised of a masterbatch initial mixing stage, followed by additional non-productive mixing stage(s), and ending with a final, productive (curative containing) mixing stage.
  • standard equipment such as, e.g., Banbury mixers or other internal mixers.
  • mixing occurs in two or more stages, during which ingredients may be added.
  • the mixing process is comprised of a masterbatch initial mixing stage, followed by additional non-productive mixing stage(s), and ending with a final, productive (curative containing) mixing stage.
  • mixing typically is begun at temperatures of about 90°C to about 130°C and increases until a so-called drop temperature, typically about 165°C, is reached.
  • ingredients such as elastomers, fillers, oils and processing aids, antioxidants and antiozonants, zinc oxide and stearic acid, are added during the initial masterbatch.
  • the initial masterbatch may be followed by a "re-mill", in which additional fillers and additives are added, or a non-productive re-mill mixing stage in which no ingredients are added.
  • the re-mill stage often is performed at temperatures similar to, although often slightly lower than, those employed in the masterbatch stage, i.e., ramping from about 90°C to a drop temperature of about 150°C.
  • masterbatch means the composition that is present during the initial masterbatch stage or the composition as it exists during any subsequent re-mill stage, or both.
  • a final mixing stage is then employed, during which curatives (e.g., sulfur or peroxide-based curing systems), including accelerators, and additional processing aids and antioxidants/antiozonants may be added.
  • curatives e.g., sulfur or peroxide-based curing systems
  • additional processing aids and antioxidants/antiozonants may be added.
  • the fragrant chemical may be added to the mixture at this stage, resulting in the aroma-emitting tire component according to the present disclosure.
  • suitable curatives see Kirk-Othmer, Encyclopedia of Chem. Tech., 3d ed., (Wiley Interscience, New York, 1982), vol. 20, pp. 365-468.
  • this mixing step often is done at lower temperatures, e.g., starting at about 60°C to about 65°C and not going higher than a bout 105°C to a bout 110°C.
  • This final mixing stage may also be followed by a non-productive mixing stage in which no ingredients are added.
  • One skilled in the art may select the most appropriate type of mixing to achieve a vulcaniza ble rubber compound according to the present disclosure.
  • the term "final batch" means the composition that is present during the final mixing stage, or any subsequent non-productive stage. It should be noted that fragrant chemicals may be introduced during a productive and non-productive mixing stages.
  • An alternate to forming tire rubber compositions using internal mixers is the forming of ru bber compositions using solution master batching (see for example U.S. Pu blished Patent Application No. 20070155890).
  • solution master batching the polymer of the rubber composition is dissolved or suspended in a solvent in a vat or vessel to which other typical compounding ingredients are added, and where the mixing of ingredients is typically accomplished with an agitator or pump or other dispersive device.
  • the solution or suspension of polymer may be the polymer cement created during polymerization itself.
  • the mixing temperature is generally a bout 22°C. After adequate dispersion of the ingredients, the solvent is removed from the mixture and the solid ru bber composition is collected.
  • the composition may contain all of the ingredients suita ble for subsequent vulcanization of a finished ru bber product, or the composition may require additional ingredients added subsequently in an internal mixer to provide a final vulcanizable rubber composition.
  • Solution master batching allows for the com bining of rubber ingredients at lower temperatures and with less shear stress than does internal mixing, where the lower shear of solution master batching, compared to internal mixing, would enhance the surviva bility of capsules containing fragrant chemicals, and vaporization of fragrant chemicals added neat would be minimized, due to the lower mixing temperature.
  • the means for building tires are usually semi-automated and well documented in the literature. Multiple types of different tire rubber compositions (e.g., sidewall ru bbers, innerliner rubbers, bead filler rubbers, carcass ply rubbers, skim stock rubbers and tread rubbers) are assembled along with rubber-coated metal beads and metal plies to form a conventional vehicle tire.
  • tire rubber compositions e.g., sidewall ru bbers, innerliner rubbers, bead filler rubbers, carcass ply rubbers, skim stock rubbers and tread rubbers
  • the selection of specific metal alloys and elastomeric compounds, and the configuration and dimensions of the various metallic and elastomeric components is also well understood by those skilled in the art of tire building.
  • a "green" tire is assembled, followed by curing in a press mold at a temperature about 5°C to about 15°C higher than the highest temperatures employed during the mixing stages, most commonly about 170°C, concurrently crosslinking the elastomeric components and molding the elastomeric components into a final tire.
  • Frragrant chemical as used herein may be any fragrant chemical or perfume, or mixtures thereof, that emits an odor that is not normally associated with tire rubber compositions, or products made therefrom, suitable for use herein, including but not limited to fragrant chemical encapsulated by various materials using various techniques including microcapsule walls comprised of polymeric materials, or a fragrant chemical that melts or vaporizes at a selected elevated temperature, as described herein.
  • non-limiting examples include fine fragrances, fabric perfumes, and deodorant perfumes and others comprising a wide range of ethers, esters, aldehydes, alcohols, lactones, linear terpenes, cyclic terpenes, amines, aromatics, ketones, thiols, acetals, organic acids, phenols and unsaturated cyclic and acyclic hydrocarbons.
  • Non-limiting examples further include natural or synthetic fragrant oils, including argumen, allium, cedar, eucalyptus, andrpogon, cymbopogon, lavandula, Mentha species, connifier family Pinacea, sage, juniper berry, dill, clove and other oils.
  • the fragrant oils are musks, rose oil, honeysuckle oil, pine oil, jasmine or oak moss, and combinations thereof. Fragrant chemicals suitable for use herein may generally be found in K.
  • Organoleptic descriptions of these materials may include (see SAFC Specialties catalog "SAFC Flavors and Fragrances Domestic Edition” approximately 2005) strong, pungent, sour, repulsive, penetrating, garlic, fishy, pungent, sulfurous, disagreeable, rancid, sweat-like, sickening, acrid, metallic, unpleasant, ammonia, cabbage-like, cadaverous, fecal, intense, powerful, sharp and so on.
  • one or more fragrant chemicals, the core are encapsulated within another material, the shell or wall, different from the fragrant chemicals, in order to form a microcapsule.
  • a microcapsule there are multiple techniques for creating microcapsules including but not limited to coacervation, polymer-polymer phase separation, interfacial polymerization, dispersion polymerization, in situ polymerization, solvent phase separation, desolvation, precipitation, solvent evaporation, spray drying, spray chilling, matrix encapsulaton and various types of fluid bed, extrusion and hybrid systems.
  • the microcapsule shell or wall may be a polymeric material, a sugar, a starch, fumed silica, proteins such as gelatin, or mixtures of polysaccharides and proteins such as gum arabic, among others.
  • a microcapsule wall that will allow a large fraction of the microcapsules to survive rubber mixing and the temperatures of mixing and curing is desirable.
  • the polymer comprising the microcapsule wall may be created during the encapsulation process itself, or an existing polymer may be added to the encapsulation mixture. Generally any suitable type and mode of manufacture of such polymeric microcapsule may be utilized herein.
  • polymeric shells or walls encapsulating an active agent are produced through heterogeneous polymerization reactions, such as emulsion, dispersion, precipitation, interfacial and suspension polymerizations, where polymerization may occur before or during the encapsulation process.
  • the reaction mechanism is generally not limited, and includes addition polymerization, condensation polymerization and step polymerization.
  • Polymers may be branched or crosslinked. Polymers formed through condensation or step polymerization may be branched or crosslinked by including a fraction of monomer that has more than two functional groups. Crosslinked, rigid polymers are sometimes referred to as resinous, and the prepolymers from which they may be formed are sometimes referred to as resins.
  • thermosetting plastics may proceed starting from prepolymers, which are thermosetting materials whose polymerization is incomplete.
  • the polymer of the microcapsule wall contains sulfur so that elastomer chains in the tire rubber compound can cross-link with polymer chains of the microcapsule polymeric wall.
  • Polymer attachments to fillers are known in the industry to enhance rubber performance.
  • a fraction of the diol monomers would have the general structure HO-R'-OH or a fraction of the diacid monomers would have the general structure H0 2 C-R'-C0 2 H, where R' has the general structure (CH 2 )x-S y -(CH2) z , and where x and z can range from 1 to about 5 and y can range from 1 to about 6.
  • R' can be of the general structure SH
  • x and y can range from 1 to about 5.
  • the fraction of diol and diacid monomers that are replaced by sulfur containing monomer would range from about 0.01 to 1.0 and in another embodiment form about 0.01 to 0.50.
  • Another example of a microcapsule wall that has the advantage of co-curing with the elastomer of the tire rubber component to which the microcapsules are added are aromatic and aliphatic polysulfides, where x of -S x - in the polysulfide polymer chain backbone can range from 1 to about 6.
  • Monomer and reaction conditions may be varied to produce polymeric microcapsules having suitable properties for use herein, such as suitable glass transition temperature, hardness, solubility and polarity.
  • the microcapsule is a thermoplastic or thermoset material.
  • Non- limiting examples of suita ble polymers and polymer families include urea- formaldehyde polymers (urea and formaldehyde monomers), melamine- formaldehyde polymers (urea, melamine and formaldehyde monomers), phenol formaldehyde polymers (phenol and formaldehyde monomers), acrylic polymers (acrylic and methacrylic monomers), polyesters (diacid and diol monomers), polyamides (diamines, diols and amino acid monomers), polyimides (dianhydrides and diamine monomers), polysiloxanes (chlorosilane monomer), and poly (vinyl acetate) (vinyl acetate monomer).
  • urea- formaldehyde polymers urea and formaldehyde monomers
  • melamine- formaldehyde polymers urea, melamine and formaldehyde monomers
  • phenol formaldehyde polymers phenol and formaldehyde
  • Additional polymers and polymer families are cellulose acetate, and aromatic and aliphatic polysulfides, where x of -S x - in the polysulfide polymer chain backbone can range from 1 to a bout 6.
  • Microcapsule walls may include naturally occurring polymers such as alginate and cellulose.
  • the polymeric microcapsule is designed to allow a relatively slow effective release rate of the encapsulated fragrant chemical, depending on the desired duration of fragrant chemical release from the elastomeric article containing the microcapsules (e.g., pneumatic tire).
  • the polymeric material is selected to allow effectively no release of the encapsulated fragrant material, and release fragrant chemical only when the microcapsule is shattered or broken.
  • the polymeric material is selected to provide a release rate resulting in a release of fragrant chemical from the elastomeric article in a relatively short time frame, such as a few months. The release rate is determined by such parameters as the diffusivity and solu bility of the fragrant chemical in the polymeric material, the thickness and porosity of the polymeric material, the concentration of the fragrant chemical, and the polarity of the fragrant chemical and polymeric material.
  • the polymeric microcapsules have a characteristic dimension between 0.1 and 1,000 microns. I n other em bodiments, the polymeric microcapsules have a characteristic length between 0.1 and 100 microns; in yet other embodiments, between 0.1 and 10 microns.
  • a polyurethane microcapsule encapsulating a fragrant cyclic or acyclic hydrocarbon is produced by mixing the hydrocarbon and an isocyanate monomer together with an emulsifier and mechanically dispersing the mixture into fine droplets (with finer droplets resulting in smaller microcapsules).
  • An oligomeric amine in aqueous solution is added to the dispersion, forming microcapsules that encapsulate an amount of the fragrant hydrocarbon.
  • the fragrant chemical is a solid at temperatures below the temperature where it is used to signal potential over heating of a tire component.
  • the fragrant chemical's melting point is in the neighborhood of 70°C to 130°C. While this temperature range includes discharge temperatures of the final mixing stage (the fragrance would be added during or subsequent the final batch stage), and temperatures associated with tire curing, if the fragrant chemical is not soluble in the rubber component, it will re-crystallize upon cooling, when the tire is removed from the curing mold. Since the curing mold is under pressure, release of the fragrance through melting and liquid migration to the tire surface is mitigated.
  • the rubber batch temperature is above 90°C for typically less than one minute, during which migration and release of the melted fragrance is not expected.
  • a pneumatic tire having an indicator of tire wear condition, comprising circumferential tread and a pair of sidewalls. At least one of the tread and sidewalls comprises a barrier layer and an indicator layer, and the barrier layer is located above or outwardly from the indicator layer.
  • the indicator layer comprises a tire rubber composition having between 0.1 and 100 phr of at least one of the fragrant chemicals described above.
  • the relationship of the barrier layer and indicator layer is as follows: the barrier layer is located above (i.e., more proximate the tread of the tire) or outward (i.e., further the equatorial plane of the tire and more proximate the sidewall) relative to the indicator layer, and aids in preventing fragrant chemical from escaping the indicator layer or in preventing microcapsules in the indicator layer from breaking and releasing fragrant chemical, until such time as the barrier layer is worn away or breached, thereby exposing the indicator layer to the atmosphere and road surface. It should be understood that the use of multiple barrier layers and/or multiple indicator layers is contemplated herein.
  • the indicator layer is designed to carry a sufficient level of fragrant chemicals so that exposure of a portion of the indicator layer to the atmosphere will result in an odor that is strong enough to alert a person that the barrier layer has been worn away or breached. This is determined both by the thickness of the barrier layer and the propensity of the indicator layer composition material to retain fragrant chemicals.
  • the composition of the indicator layer is substantially similar to the composition of the barrier layer, with a material exception that the indicator layer includes an amount of polymeric or resinous microcapsules encapsulating an amount of fragrant chemical, described above.
  • the composition of the indicator layer is substantially different than the composition of the barrier layer, such that elastomeric content of the indicator layer is selected to retain an amount of fragrant chemical described above, and the elastomeric content of the barrier layer is selected such that the fragrant chemical has little or no diffusivity through the material.
  • the indicator layer comprises a rubber composition suitable for the tire tread or tire sidewall, or both, in which all or a portion of the process oil plus other processing aids, are replaced or supplemented with at least one fragrant oil.
  • a tread rubber or sidewall rubber composition containing between 0.1 and 60 phr fragrant oil; in others, between 0.1 and 30 phr fragrant oil.
  • no fragrant oils are added to the tread or sidewall, but instead are added to other tire components.
  • the indicator layer comprises a tire tread rubber composition or tire sidewall rubber composition, or both, in which at least one fragrant chemical (e.g., polymeric or resinous microcapsules containing at least one fragrant chemical) is added above formula in an amount of 0.1 to 20 phr.
  • the indicator layer comprises a tire tread rubber composition or tire sidewall rubber composition, or both, in which all or a portion of the filler is replaced with polymeric or resinous microcapsules containing at least one fragrant chemical.
  • Non-limiting examples include a tread rubber or sidewall rubber composition containing between 0.1 and 100 phr polymeric or resinous microcapsules; in others, between 0.1 and 60 phr polymeric or resinous microcapsules.
  • the barrier and indicator layers are different tire components.
  • the barrier layer is the tire tread component and the indicator layer is the sub-tread component.
  • the tire tread contains no fragrant chemicals and the sub-tread contains between 0.1 and 100 phr of polymeric or resinous microcapsules encapsulating at least one fragrant chemical; in another embodiment, the sub-tread contains between 0.1 and 60 phr of polymeric or resinous microcapsules encapsulating at least one fragrant chemical.
  • the barrier layer and the indicator layer form a multi-layered tire tread or multilayered tire sidewalls.
  • Methods for forming a multilayered tire component are known in the art, and include but are not limited to co-extrusion and application of successive layers of a tire on a building drum. See for example F. J. Kovac in "Science and Technology of Rubber", F. R. Eirich, Ed., Academic Press, New York, 1978, pg. 602. Methods for co-extruding a tire component are described in, for example, US Patent Nos. 6,994,817; 4,539,169; 4,556,376; 5,292,472 and 4,657,718, the disclosures of which are incorporated herein.
  • the tire tread is multilayered and comprises an indicator layer and a barrier layer above or outward from the indicator layer, where the indicator layer comprises between 0.1 and 100 phr polymeric or resinous microcapsules encapsulating at least one fragrant chemical, as described above.
  • the microcapsules are selected from the polymer families consisting essentially of urea-formaldehyde polymers, melamine-formaldehyde polymers, phenol formaldehyde polymers, acrylic polymers, polyesters, polyamides, polyimides , polysiloxanes, and poly (vinyl acetate) microcapsules, and combinations thereof.
  • the tire tread is multilayered and has a total thickness of between 0.3 and 1.2 inches, where the upper portion is a barrier layer between 0.15 and 0.95 inches thick, and the lower portion is an indicator layer between 0.02 and 0.3 inches thick.
  • the indicator layer comprises multiple constituent layers, where each constituent layers has a higher loading of fragrant chemicals than the constituent layer above or outward from it.
  • Elevated tire temperature may be an indicator of a deficient running condition, such as low tire pressure or high deformation at the belt edges.
  • low tire pressure may cause the temperature of the tire tread or sidewalls or belt edges, or all three, to exceed about 60 to 80°C.
  • an elevated temperature in any of the tread, sidewall, or belt edges of a tire may be indicated by incorporating a thermally-activated fragrant chemical, described above, in one or more of those regions, or in tire components adjacent one or more of those regions.
  • the thermally-activated fragrant chemical is selected so that its effective release rate of fragrant chemical is sufficiently elevated at a threshold temperature (indicative of a deficient running condition), so that a person may detect an odor caused by the released fragrant chemical.
  • At least one of the tread, sidewall, or belt edge regions of a tire comprise a tire rubber composition having from 0.1 to 20 phr of at least one thermally-activated fragrant chemical having a melting point between 80°C and 100°C; in other embodiments, between 100° C and 130 °C.
  • the belt edge insert, or the belt wedge or both contain between 0.1 to 20 phr of at least one thermally activated fragrant chemical having a melting point between 80°C and 100°C; in other embodiments, between 100°C and 130 °C.
  • the fragrant chemical or chemicals comprise the core of a microcapsule whose shell is a polymer with a glass transition temperature (Tg) greater than about 80°C and less than about 150°C.
  • Tg glass transition temperature
  • the effective diffusion rate of the core fragrant chemical through the microcapsule wall is sufficiently elevated at a threshold temperature (indicative of a deficient running condition) greater than Tg, so that a person may detect an odor caused by the released fragrant chemical.
  • the present disclosure contemplates a tire that may release fragrant chemicals over time and without the need of tire wear or at abnormal operating conditions. This is accomplished generally by providing one or more tire components that have an amount of fragrant chemicals and that are designed to release the fragrant chemical at a desired effective release rate over time, as described above.
  • a pneumatic tire where at least one of the circumferential tread portion, sidewall portions, bead region portions, cap, carcass, belt plies, belt edge insert or belt wedge and inner liner portions comprise a tire rubber composition having from 0.1 to 100 phr of polymeric or resinous microcapsules containing at least one fragrant chemical, described above; in another embodiment from 0.1 to 60 phr of such microcapsules.
  • the tread portion comprises a tread rubber composition having from 0.1 to 100 phr of microcapsules containing at least one fragrant chemical, where the polymer of the microcapsule wall is an aromatic or aliphatic polysulfide containing between 1 and 6 moles of sulfur per monomer unit.
  • the tread rubber composition has from 0.1 to 60 phr of microcapsules, where the polymer of the microcapsule wall is an aromatic or aliphatic polysulfide containing between 1 and 6 moles of sulfur per monomer unit.
  • the tread portion comprises a tread rubber composition having from 0.1 to 100 phr of microcapsules containing at least one fragrant chemical, where the polymer of the microcapsule wall is formed through condensation polymerization of diol monomers or diacid monomers, and where from about 1% to 100% or in another enbodiment 1% to 50% of the diol or diacid monomers have the general structure HO-R'-OH or H0 2 C-R'-C0 2 H, respectively, and
  • the tread rubber composition has from 0.1 to 60 phr of microcapsules, where the polymer of the microcapsule wall is formed through condensation polymerization of diol monomers or diacid monomers, and where from about 1% to 100% and in another embodiment from 1% to 50% of the diol or diacid monomers have the general structure HO-R'-OH or H0 2 C-R'-C0 2 H, respectively, and where R' is t and where x and y can range from 1 to about 5.
  • the tread portion comprises a tread rubber composition having from 0.1 to 100 phr of polymeric microcapsules containing at least one fragrant chemical; in another, from 0.1 to 60 phr of polymeric microcapsules containing at least one fragrant chemical.
  • the microcapsules are selected from the group consisting essentially of urea-formaldehyde, melamine-formaldehyde, phenol formaldehyde, acrylic, polyester, polyamide, polyimide, polysiloxane, poly (vinyl acetate), cellulose acetate and aromatic aliphatic polysulfides, where x of -S x - in the polysulfide polymer chain backbone can range from 1 to about 6, microcapsules, and combinations thereof.
  • a pneumatic tire comprising a circumferential tread and an interior portion located below the tread that comprises a pair of sidewall portions, a pair of bead region portions, at least one cap, carcass, or belt ply, belt edge inserts, belt wedge, and an inner liner portion and where at least one interior portion component comprises a tire rubber composition having from 0.1 to 60 phr of at least one fragrant chemical, described above.
  • the fragrant chemical is a fragrant oil.
  • the fragrant oil is selected from the group consisting essentially of argumen, allium, cedar, eucalyptus, andrpogon, cymbopogon, lavandula, Mentha species, connifier family Pinacea, sage oils, and combinations thereof.
  • cap, carcass, and belt plies comprise polymeric fiber that retains an amount of at least one fragrant chemical.
  • cap, carcass, and belt plies may be made of interwoven or aligned polymeric cord or additionally steel cord in the case of belt plies.
  • suitable cord material are nylons, polyesters, aramids, cotton, polynorbornene and rayons.
  • At least one of the cap, carcass, and belt plies is selected from the group consisting essentially of nylon, polyester, aramid, cotton, polynorbornene and rayon fibers and retains from 0.1% to 10% by weight of at least one fragrant chemical; in others, the at least one ply retains from 0.1% to 5% by weight of at least one fragrant chemical.
  • the manner of incorporating the fragrant chemical in the ply fiber is not material to the present disclosure; a non- limiting example is to immerse the fiber in a solution of the fragrant chemical, or in the chemical itself.
  • a prophetic example of a formulation according to the present disclosure are as follows. Various ingredients were added during the master batch stage for both the tread and for an indicator layer, as shown in Table 1.
  • naphthenic oil 10.0 10.0 ZnO 3.0 3.0
  • Antioxidant 1.0 1.0
  • the master batch may be mixed according to the following procedure.
  • the mixer is preheated to 90°C to 100°C and charged with the solution SBR.
  • the carbon black, ZnO, the antioxidant (such as 6PPD), stearic acid and wax are added.
  • the naphthenic oil is added about a half-minute after completing the addition of carbon black.
  • the master batch is added to a mixer pre-heated to 70°C to 75°C.
  • the final batch ingredients are added immediately after adding the master batch to the mixer.
  • 4-methlyvaleric acid is available from SAFC Flavors and Fragrances Catalog Number W34630-6, FEMA No. 3463, Aldrich Chemical Co. Inc., 6000 N. Teutonia Ave., Milwaukee, Wl, 53209. The final batch is discharged when the temperature of the mixture reaches 95°C.
  • the tread formula is then extruded to a thickness of 8 mm, while the indicator layer is extruded to a thickness of 1.0 mm to provide an indicator layer component.
  • the indicator layer component is added to the tire body immediately before adding the tread. Once the indicator layer is added, the tread may be added.
  • the numerical parameters set forth in the specification, including the attached claims are approximations that may vary depending on the desired properties sought to be obtained according to the exemplary embodiments. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)

Abstract

L'invention concerne un pneumatique comportant un indicateur d'état d'usure du pneu. Le pneumatique comporte une bande de roulement circonférentielle et une paire de flancs, dont au moins un comprend une couche barrière et une couche indicateur, la couche barrière étant située au-dessus ou vers l'extérieur de la couche indicateur, qui comprend une composition de caoutchouc pour pneu comportant au moins un produit chimique parfumé. L'invention concerne aussi un pneumatique comportant un indicateur de température élevée du pneu. Au moins une des parties de pneu comprend une composition de caoutchouc pour pneu comportant un produit chimique parfumé activé thermiquement. En outre, l'invention concerne un pneumatique comprenant une composition de caoutchouc pour pneumatique comportant des microcapsules polymères ou résineuses contenant au moins un produit chimique parfumé.
PCT/US2012/037484 2011-05-16 2012-05-11 Pneumatique et articles élastomères offrant une fonctionnalité d'émission d'arômes Ceased WO2012158505A2 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020028478A1 (fr) * 2018-08-02 2020-02-06 Gates Corporation Produit en caoutchouc avec couches d'indication d'usure
DE102019124177A1 (de) * 2019-09-10 2021-03-11 Bayerische Motoren Werke Aktiengesellschaft Passive Beduftungseinheit zur Anordnung in oder an einem Fahrzeug

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3424732C1 (de) * 1984-07-05 1985-11-21 Hüls AG, 4370 Marl In der Waerme vulkanisierbare Laufstreifen fuer die Herstellung der Laufflaechen von Kraftfahrzeug-Luftreifen
KR100462203B1 (ko) * 2002-10-01 2004-12-17 한국타이어 주식회사 마모한계시점을 표시하는 공기입 타이어
US20080271347A1 (en) * 2003-04-17 2008-11-06 Ronald John Rosenberger Fragrance releasing scented shoes and shoe soles
KR100727403B1 (ko) * 2005-08-18 2007-06-12 금호타이어 주식회사 타이어 트레드용 향기 고무조성물

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020028478A1 (fr) * 2018-08-02 2020-02-06 Gates Corporation Produit en caoutchouc avec couches d'indication d'usure
CN112703117A (zh) * 2018-08-02 2021-04-23 盖茨公司 具有磨损指示层的橡胶产品
US10994521B2 (en) 2018-08-02 2021-05-04 Gates Corporation Rubber product with wear indicating layers
AU2019314391B2 (en) * 2018-08-02 2022-12-15 Gates Corporation Rubber product with wear indicating layers
DE102019124177A1 (de) * 2019-09-10 2021-03-11 Bayerische Motoren Werke Aktiengesellschaft Passive Beduftungseinheit zur Anordnung in oder an einem Fahrzeug

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