Patent Description:
Aspects of the invention relate to assembling a rubber part and a thermoplastic part into a composite structure and, more particularly, producing a non-pneumatic tire comprising the assembled parts.

Pneumatic tires have been the solution of choice for vehicular mobility for over a century and are still dominant on the tire market today. Pneumatic tires are efficient at carrying loads because all of their structure is involved in carrying the load. Pneumatic tires are also desirable because they have low contact pressure, resulting in lower wear on roads due to the distribution of the load of the vehicle. Pneumatic tires also have low stiffness, which ensures a comfortable ride in a vehicle. The primary drawback to a pneumatic tire is that it requires compressed fluid (e.g., air or an inert gas). A conventional pneumatic tire is rendered useless after a complete loss of inflation pressure.

A tire designed to operate without inflation pressure may eliminate many of the problems and compromises associated with a pneumatic tire. Neither pressure maintenance nor pressure monitoring is required. Structurally supported tires such as solid tires or other elastomeric structures to date have not provided the levels of performance required from a conventional pneumatic tire. A structurally supported tire solution that delivers pneumatic tire-like performance would be a desirous improvement.

Non-pneumatic tires are typically defined by their load carrying efficiency. So-called "bottom loaders" are essentially rigid structures that carry a majority of the load in the portion of the structure below the hub. "Top loaders" are designed so that all of the structure is involved in carrying the load. Top loaders thus have a higher load carrying efficiency than bottom loaders, allowing a design that has less mass.

A shearband may be provided to transfer the load from contact with the ground through tension in the connecting structure (including, e.g., spokes or a connecting web) to the hub, creating a top loading structure. When such a shearband deforms, its preferred form of deformation is shear over bending. The shear mode of deformation may occur because of inextensible membranes located on the radially inner and the radially outer portions of the shearband. Non-pneumatic tires may have a shearband made from a shear layer sandwiched between at least two layers of inextensible belts or membranes.

An issue of importance in non-pneumatic tires is the connection between the shearband and the connecting structure. The connecting structure is the part of a non-pneumatic tire that connects the shearband to the wheel hub or to a ring structure that contacts the hub. The role of the connecting structure may be compared with the cushioning function of the air chamber of a pneumatic tire.

The connecting structure may be made of a different material than the shearband. In particular, the connecting structure may be made of a thermoplastic material, whereas the radially inner surface of the shearband may be provided by a rubber compound.

Patent document <CIT> discloses a process for producing non-pneumatic tires, particularly a process for co-vulcanization of a rubber material to a thermoplastic surface, such as a shear band to a connecting structure of a non-pneumatic tire, such as a spoke.

The invention relates to a method in accordance with claims <NUM> or <NUM> respectively.

A preferred aspect of the invention pertains to a method of assembling a rubber part and a thermoplastic part into a composite structure. The method comprises providing a rubber part having a surface and providing the thermoplastic part having a surface comprising a plasma polymerized coating comprising a carbon-carbon double bond. The method further comprises applying a rubber adhesive on the coating and bringing the rubber part surface and the thermoplastic part surface with the rubber adhesive into contact so as to form a composite structure. In addition, the method comprises heat-treating the composite structure to bond the rubber part to the thermoplastic part.

According to a preferred embodiment, the composite structure is assembled in a mold or placed into a mold after assembly and wherein the heat-treatment of the composite structure comprises baking the composite structure in the mold. The rubber, the thermoplastic material or both may be cured (vulcanized) or further cured in this baking step.

According to a preferred embodiment, heat-treating the composite structure comprises heating the composite structure to a temperature in a range from <NUM> to <NUM>, preferably <NUM>° to <NUM>, but below a softening temperature of the thermoplastic part.

According to a preferred embodiment, the method comprises drying the rubber adhesive on the coating before bringing the rubber part and the thermoplastic part with the rubber adhesive into contact so as to form the composite structure.

According to a preferred embodiment, the method comprises plasma coating the thermoplastic part by acetylene atmospheric plasma polymerization so as to provide the thermoplastic part with the surface comprising the plasma polymerized coating comprising a carbon-carbon double bond. The application of the plasma coating may be carried out as described in <CIT>.

According to a preferred embodiment, the applying of the rubber adhesive on the plasma polymerized coating is carried out directly after the plasma coating of the thermoplastic part, e.g. not more than <NUM> minutes, preferably not more than <NUM> minutes, after the coating of the thermoplastic part.

According to a preferred embodiment, the rubber adhesive comprises at least one of a rubber cement and a rubber lattice, e.g. natural rubber latex.

According to a preferred embodiment, the applying the rubber adhesive is carried out by spray coating.

According to a preferred embodiment, the rubber adhesive is water-based.

According to a preferred embodiment, the rubber adhesive comprises at least one of reinforcing fillers (e.g. carbon black), one or more antioxidants, silica (e.g. precipitated amorphous silica). The rubber adhesive may comprise ZnO and/or sulfur. Also, the rubber adhesive may comprise one or more accelerators such as sulfenamides, thiurams, dithiocarbamates, mercaptobenzothiazoles and xanthates.

A further preferred aspect of the present invention relates to a method for producing a non-pneumatic tire. The method comprises providing a shearband comprising curable rubber; the shearband having a radially inner surface formed by the curable rubber and providing a connecting structure for connecting the shearband to a wheel hub, the connecting structure comprising an adhesion interphase part made of thermoplastic material with a plasma polymerized coating comprising a carbon-carbon double bond. The method further comprises applying a rubber adhesive on the coating and bringing the radially inner surface and the adhesion interphase part with the rubber adhesive into contact so as to form a composite structure. In addition, the method comprises heat-treating the composite structure to bond the shearband to the connecting structure, the bond being mediated by at least part of the rubber adhesive and the plasma polymerized coating.

According to a preferred embodiment, the composite structure is assembled in a mold or placed into a mold after assembly and wherein the heat-treatment of the composite structure comprises baking the composite structure in the mold. The curable rubber, the thermoplastic material or both may be cured (vulcanized) or further cured in this baking step.

According to a preferred embodiment, the heat-treating the composite structure comprises heating the composite structure to a temperature in a range from <NUM> to <NUM>, preferably <NUM>° to <NUM>, but below a softening temperature of the thermoplastic part.

According to a preferred embodiment, the method comprises drying the rubber adhesive on the coating before bringing the radially inner surface and the adhesion interphase part with the rubber adhesive into contact so as to form the composite structure.

According to a preferred embodiment, the method comprises plasma coating the connecting structure by acetylene atmospheric plasma polymerization so as to provide the connecting structure with the adhesion interphase part.

According to a preferred embodiment, the applying of the rubber adhesive on the plasma polymerized coating is carried out directly after the plasma coating of the connecting structure, e.g. not more than <NUM> minutes, preferably not more than <NUM> minutes, after the coating of the thermoplastic part.

As used herein, the term "rubber" is intended to include both natural rubber compositions and synthetic rubber compositions. Unless otherwise specified, "rubber" designates a cured rubber (typically obtained from unsaturated rubber by sulfur or non-sulfur vulcanization). The rubber does not need be completely cured, i.e., its molecular chains may contain residual cure sites (e.g., allylic positions) available for crosslinking with other molecular chains. The expression "rubber composition" "compounded rubber" and "rubber compound" may be used interchangeably to refer to rubber (elastomer) which has been blended or mixed with various ingredients and materials, e.g., reinforcing fillers, such as carbon black, precipitated amorphous silica, or the like, and then cured. Specific examples of rubbers include neoprene (polychloroprene), polybutadiene (e.g., cis-<NUM>,<NUM>-polybutadiene), polyisoprene (e.g., cis-<NUM>,<NUM>-polyisoprene), butyl rubber, halobutyl rubber (such as, e.g., chlorobutyl rubber or bromobutyl rubber), styrene/isoprene/butadiene rubber, copolymers of <NUM>,<NUM>-butadiene or isoprene with monomers such as, e.g., styrene, acrylonitrile and methyl methacrylate. Other types of rubber include carboxylated rubber, silicon-coupled rubber, or tin-coupled star-branched polymers. "Curable rubber" designates rubber that has been at most partially cured and that can be cured (vulcanized) further. Curable rubber may include green rubber.

A "thermoplastic" is a plastic polymer that becomes pliable or moldable at an elevated temperature and solidifies upon cooling. Thermoplastics can be shaped by the action of heat and shear forces. The process is purely physical and does not involve either chemical transformation or crosslinking. The thermoplastics can include semi-crystalline (polypropylene, polyethylene, etc.) and/or amorphous thermoplastics (polystyrene, ABS, PC, etc.).

The expressions "axial" and "axially" are used herein to refer to lines or directions that are parallel to the axis of rotation of the tire.

The expressions "radial" and "radially" are used to mean the direction of a line intersecting the tire's axis of rotation at right angle.

In the present document, the verb "to comprise" and the expression "to be comprised of" are used as open transitional phrases meaning "to include" or "to consist at least of". Unless otherwise implied by context, the use of singular word form is intended to encompass the plural, except when the cardinal number "one" is used: "one" herein means "exactly one". Ordinal numbers ("first", "second", etc.) are used herein to differentiate between different instances of a generic object; no particular order, importance or hierarchy is intended to be implied by the use of these expressions. Furthermore, when plural instances of an object are referred to by ordinal numbers, this does not necessarily mean that no other instances of that object are present (unless this follows clearly from context). When reference is made to "an embodiment", "one embodiment", "embodiments", etc., this means that these embodiments may be combined with one another. Furthermore, the features of those embodiments can be used in the combination explicitly presented but also that the features can be combined across embodiments without departing from the invention, unless it follows from context that features cannot be combined.

The reader's attention is drawn to the fact that the drawings are not to scale. Furthermore, for the sake of clarity, proportions between height, length and/or width may not have been represented correctly.

A non-pneumatic tire is shown in <FIG>. The non-pneumatic tire <NUM> may be of the top-loader type and include an outer annular band <NUM>, an inner annular band <NUM>, and a connecting structure <NUM> extending from the outer annular band <NUM> to the inner annular band <NUM>. The inner annular band <NUM> has a first diameter, and the outer annular band <NUM> has a second diameter greater than the first diameter. The inner and outer annular bands <NUM>, <NUM> are substantially coaxial with each other and centered on the tire axis. In the illustrated embodiment, the connecting structure <NUM> comprises a plurality of spokes <NUM> but other configurations may be possible.

The inner annular band <NUM> may be mounted on a hub or rim (not shown). The outer annular band <NUM> may include a circumferential tread <NUM> providing a surface for contacting the ground and a shearband <NUM>. The tread <NUM> may include tread features such as, e.g., grooves, ribs, blocks, lugs, sipes, studs, etc. The tread <NUM> may be configured to improve the performance of the tire in various conditions.

The shearband <NUM> is configured to receive the load exerted on the inner ring as tension in connecting structure <NUM> and to transfer this load to the ground, via the tread <NUM>. When such a shearband <NUM> deforms under load, its preferred form of deformation is shear over bending. The shear mode of deformation may occur because of inextensible membranes located on the radially inner and the radially outer portions of the shearband but other possibilities may exist. The inner structure of the shearband <NUM> is not illustrated in the drawings. The shearband <NUM> could, for instance, include a sandwich structure with first and second reinforced annular rubber layers separated by an annular shear layer. The first and second reinforced rubber layers may be configured as essentially inextensible layers, e.g., may be formed of parallel inextensible reinforcement cords embedded in a rubber coating. The reinforcement cords could comprise, e.g., steel, aramid, or other fibers.

The shearband <NUM> and the connecting structure <NUM> may be configured so that the resulting stiffness is related to the spring rate of the tire <NUM>. The connecting structure <NUM> may be configured to buckle or deform in the tire footprint (i.e., the part of the tire that is in contact with the ground). This implies that the rest of the connecting structure not in the footprint area (i.e., mainly the momentary upper part of the connecting structure) carries the load. The load distribution may be such that approximately <NUM>-<NUM>% of the load is carried by the shearband and the momentary upper part of the connecting structure, so that the momentary lower part of the connecting structure carries only a small part of the load, and preferably less than approximately <NUM>%.

The connecting structure <NUM> is preferably formed of thermoplastic material, even more preferably formed of a thermoplastic elastomer. The thermoplastic material may be selected based upon one or more of the following material properties: Young's modulus, glass transition temperature, yield strain at break, elongation at break, heat deflection temperature, etc. A thermoplastic material having a tensile (Young's) modulus in the range from <NUM> MPa to <NUM> MPa, and more preferably in the range of <NUM> MPa to <NUM> MPa, measured in accordance with the ISO <NUM>-<NUM>/-<NUM> standard test method, is preferred. Thermoplastic material having a glass transition temperature less than -<NUM>, and more preferably less than -<NUM>, are preferred. The yield strain at break of the thermoplastic material preferably amounts to at least <NUM>%, and more preferably to at least <NUM>%. The thermoplastic material preferably has an elongation at break greater than or equal to the yield strain, and more preferably, greater than or equal to <NUM>%. The heat deflection temperature is preferably higher than <NUM>, and more preferably more than <NUM>, under a load of <NUM> MPa. The thermoplastic material preferably comprises a thermoplastic copolyester elastomer, e.g., DSM Products ARNITEL PM581, PL461, EM460, EM550, EM630, PL650, PL420, DUPONT Hytrel, a polyamide (e.g. nylon <NUM>, nylon <NUM>,<NUM>, nylon <NUM>,<NUM>, nylon <NUM>), a thermoplastic polyamide elastomer (e.g. Arkema PEBAX <NUM>, PEBAX <NUM>, PEBAX <NUM>). In case of PEBAX <NUM>, the curing temperature is preferably lowered in the range from <NUM> to <NUM>.

Examples of methods for assembling a rubber part and a thermoplastic part into a composite structure, in particular for producing non-pneumatic tire <NUM> with said parts assembled are discussed below.

The connecting structure <NUM> and the shearband <NUM> are preferably initially provided as separate parts. The connecting structure <NUM> may be prefabricated by any suitable process, e.g., extrusion, injection molding, thermoforming, heat welding, 3D printing, etc. The connecting structure <NUM> and the shearband <NUM> may each be provided as a single part or as a plurality of parts to be assembled. The connecting structure <NUM> comprises a radially outer surface, which is to serve as an interface.

The shearband <NUM> has a radially inner surface formed by curable rubber, which is to serve as a contact surface <NUM> with the connecting structure <NUM>.

One or more cleaning steps of the contact surfaces may be carried out, if necessary. Additionally, or alternatively, preparation may include roughening and/or application of a pretreatment agent. Different surface preparation techniques may be combined when needed.

For example, the surface of the connecting structure <NUM> may be sanded (e.g. by manual sanding, by sandblasting, by dry ice roughening) so as to obtain a roughness equivalent in the range between P120 and P600, preferably in the range from P240 to P400. The roughened surface may be cleaned (e.g. by solvent cleaning, e.g. acetone in a first step followed by isopropanol, or by dry ice cleaning in a second step).

An atmospheric plasma polymerized coating may then be deposited on the, possibly roughened and cleaned, surface using e.g. acetylene as the polymerizable precursor, which may be polymerized using an argon plasma. The coating is chemically bonded to the thermoplastic surface. The thickness of the coating is preferably between <NUM> and <NUM>.

According to an embodiment, a rubber adhesive <NUM> is then applied (e.g. by brushing or spray coating) on the radially outer surface of the connecting structure <NUM>. The rubber adhesive <NUM> comprises rubber. The rubber adhesive <NUM> preferably comprises at least one of a rubber cement and a rubber lattice, e.g. natural rubber latex. The rubber adhesive <NUM> is preferably adapted to both the thermoplastic material with the plasma polymerized coating comprising the carbon-carbon double bond and the curable rubber of the shearband <NUM>. The rubber adhesive <NUM> may comprise at least one of reinforcing fillers (e.g. carbon black), one or more antioxidants, silica (e.g. precipitated amorphous silica). The rubber adhesive may comprise ZnO and/or sulfur. Also, the rubber adhesive may comprise one or more accelerators such as sulfenamides, thiurams, dithiocarbamates, mercaptobenzothiazoles and xanthates. Advantageously, the rubber adhesive <NUM> has the same (or substantially the same) composition as the curable rubber of the shearband <NUM>. The rubber adhesive <NUM> is preferably water-based. The thickness of the rubber adhesive on the connecting structure is preferably between <NUM> and <NUM>, preferably between <NUM> and <NUM>.

The rubber cement preferably comprises rubber dissolved in organic solvent such as toluene or cyclohexane or a mix of n-alkanes. For example, the rubber cement may be prepared as follows: adding <NUM> phr of natural rubber (cis <NUM>-polyisoprene), <NUM> phr of carbon black (N326), <NUM> phr of antioxidants, <NUM> phr of zinc oxide, <NUM> phr of sulfur and <NUM> phr of sulfenamide accelerator. Toluene is then added so that toluene amounts to <NUM>% by weight of the rubber cement. <NUM>% by weight corresponds to the above-mentioned components.

The natural rubber latex may comprise <NUM> phr of natural rubber latex (e.g. <NUM>% solid - cis <NUM>-polyisoprene, low (or high) ammonia stabilized), <NUM> phr of carbon black (N326), <NUM> phr of antioxidants / anti-weathering agents (e.g. mix of anti-oxidants, anti-ozonants and waxes), <NUM> phr of zinc oxide dispersion, <NUM> phr of insoluble sulfur dispersion and <NUM> phr of sulfenamide accelerator. One or more pH stabilizers may be used. SBR based rubber instead of natural rubber is also contemplated.

In a next step, the rubber adhesive is preferably dried e.g. in an oven (for example in a drying tunnel at a temperature in the range from <NUM> to <NUM>, preferably from <NUM> to <NUM>) or at ambient conditions.

In a preferred embodiment, the rubber adhesive is applied directly after the plasma coating of the connecting structure, e.g. not more than <NUM> minutes, preferably not more than <NUM> minutes, after the coating of the thermoplastic part.

After application of the adhesive, the shearband (i.e. the radially inner surface) and the connecting structure (i.e. the adhesion interphase part with the rubber adhesive) are assembled into a composite structure. The green rubber to become the tread <NUM> may be arranged adjacent the radially outer surface of the shearband. The assembly of the individual parts may be carried out in a mold, or the assembled composite structure may be placed into a mold after assembly.

After assembly, the composite structure may be heated so as to durably bond the different parts, in particular the shearband and the connecting structure. The rubber parts may be cured during the same heat treatment step.

It will be understood that the rubber adhesive allows for durably bonding the connecting structure to the shearband. Also, the rubber adhesive has the added benefit of increasing the shelf life of the connecting structure in case the assembling with the shearband is not carried out directly after the coating by acetylene atmospheric plasma polymerization.

It will be understood that the adhesive mediates chemical bonding (including covalent and/or ionic bonding) between the shearband and the connecting structure only upon being subjected to the heat treatment. Nevertheless, the adhesive may be configured to increase the tack of the surface on which it is applied (in wet or dried state). This may be seen as helpful for the assembly and manipulation of the composite structure while it is still uncured. For instance, increased tack may be helpful to position the shearband and the connecting structure relative to each other and to keep these parts in that position until the curing has been effected.

The vulcanization of the rubber parts and the bonding of the shearband to the connecting structure is preferably carried out at a temperature below the softening temperature of the thermoplastic material. The curing temperature may, e.g., be comprised in the range from <NUM> to <NUM> (preferably <NUM>° to <NUM>) with the provison that the softening temperature of the employed thermoplastic material is not exceeded. The carbon-carbon double bond of the coating may participate to the vulcanization process in order to durably bond the connecting structure to the shearband.

It should be noted that the present description focused on assembling the outer annular band <NUM> with the connecting structure <NUM>. Of course, the same is also contemplated for the assembling of the inner annular band <NUM> with the connecting structure <NUM>. As illustrated in <FIG>, a rubber adhesive <NUM> may be provided to the connecting structure <NUM> (e.g. to its radially outer surface), in the same way as for the rubber adhesive <NUM>, for assembling the same to the inner annular band <NUM>. It is worthwhile noting that <FIG> shows an exploded view of the different elements of the non-pneumatic tire.

In some embodiments, at least one of the outer annular band <NUM> and inner annular band <NUM> is assembled according to the disclosure of the present invention. It is also worthwhile noting that the present invention was described with non-pneumatic tire but the principles are also applicable, in general, for assembling a rubber part and a thermoplastic part into a composite structure.

A composite structure is formed by providing a <NUM> thick rubber layer (composition as disclosed in paragraph [<NUM>] without toluene) and two <NUM>"x6" plasma coated thermoplastic plates (ARNITEL EM630) with rubber cement (as disclosed in paragraph [<NUM>]). <NUM> wide mylars films are provided on the side opposite to the rubber layer, bonded to the thermoplastic plates so as to provide a grip for the testing equipment to carry out peeling procedures. The composite structure is then cured in a press at <NUM> for <NUM> minutes.

The cured composite structure is then die-cut into <NUM>"-wide and <NUM>" -long stripes (<NUM>" = <NUM>). A stripe is then placed in the testing equipment (ZwickRoell traction equipment) so as to peel the composite structure. The peeling is carried out according to ASTM D1876 T-Peel test, perpendicularly to the mylar surfaces. Instead of the <NUM>/min recommended in the standard, a rate of <NUM>/min is used, in order to avoid plastic deformation of the thermoplastic plates.

Claim 1:
A method of assembling a rubber part and a thermoplastic part into a composite structure, the method comprising:
providing a rubber part having a surface;
providing a thermoplastic part having a surface comprising a plasma polymerized coating comprising a carbon-carbon double bond;
applying a rubber adhesive (<NUM>, <NUM>) on the coating;
bringing the rubber part surface and the thermoplastic part surface with the rubber adhesive into contact so as to form a composite structure; and
heat-treating the composite structure to bond the rubber part to the thermoplastic part.