Plastic coated thermoplastic articles formed from high purity recovered thermoplastic elastomer material

Abstract

A plastic coated thermoplastic article includes a base component comprising a rigid thermoplastic material and a plastic coated component comprising a recycled thermoplastic elastomer material. The recycled thermoplastic elastomer material includes greater than or equal to about 97% by weight of a leading thermoplastic elastomer material, and less than or equal to about 3% by weight of a leading rigid thermoplastic material, based on the weight of the recycled thermoplastic elastomer material. The recycled thermoplastic elastomer material is obtained by a leading separation process, wherein the leading thermoplastic elastomer material is separated from at least a portion of the leading rigid thermoplastic material.

Description

[0001] Priority Claim

[0002] This application claims priority to U.S. Provisional Patent Application Serial No. 63 / 397,138, filed on August 11, 2022 (Attorney Docket No. 1202207-US-F), which is hereby incorporated by reference in its entirety. Technical Field

[0003] The present disclosure relates to thermoplastic articles, and more particularly to overmolded thermoplastic articles formed from high-purity recycled thermoplastic elastomer materials obtainable from a prior separation process. Background Art

[0004] Multi-component thermoplastic articles having two or more components formed from dissimilar plastic materials can be used to achieve multiple functions in various applications, including protective cases for personal electronic products such as smart phones, tablets, laptops, etc. Industries, including the consumer electronics industry, desire that thermoplastic articles contain increasing amounts of post-consumer and / or post-industrial recycled materials. However, it may be difficult to obtain high-purity materials from post-consumer recycling and post-industrial recycling of multi-component thermoplastic articles.

[0005] Accordingly, there is a need for multi-component thermoplastic articles formed from high-purity recycled thermoplastic elastomer materials. Summary of the Invention

[0006] Embodiments of the present disclosure relate to overmolded thermoplastic articles formed from high-purity recycled thermoplastic elastomer materials.

[0007] According to some embodiments, there is provided an article comprising a substrate component and an overmolded component, the substrate component comprising a rigid thermoplastic material and the overmolded component comprising a recycled thermoplastic elastomer material. The recycled thermoplastic elastomer material comprises greater than or equal to about 97 wt% of the aforementioned thermoplastic elastomer material and less than or equal to about 3 wt% of the aforementioned rigid thermoplastic material, based on the weight of the recycled thermoplastic elastomer material. The recycled thermoplastic elastomer material can be obtained by the aforementioned separation process, wherein at least a portion of the aforementioned thermoplastic elastomer material is separated from the aforementioned rigid thermoplastic material.

[0008] Other features and advantages of the embodiments described herein will be set forth in the detailed description below, and will be readily apparent to those skilled in the art from such description, or recognized by practicing the embodiments described herein, including the following specific embodiments, claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1 is a schematic view of an exemplary article according to one or more embodiments shown and described herein;

[0010] Figure 2 is a schematic view of an exemplary configuration of a magnetic pulley separator according to one or more embodiments shown and described herein;

[0011] Figure 3 is a schematic view of another exemplary article according to one or more embodiments shown and described herein;

[0012] Figure 4 is a schematic view of another exemplary article according to one or more embodiments shown and described herein;

[0013] Figure 5 is a schematic view of another exemplary article according to one or more embodiments shown and described herein; and

[0014] Figure 6 is a schematic view of another exemplary configuration of a magnetic pulley separator according to one or more embodiments shown and described herein. DETAILED DESCRIPTION

[0015] The embodiments of the articles and processes related thereto are described in detail below.

[0016] The articles disclosed herein include a base component and an overmold component. The base component includes a rigid thermoplastic material, and the overmold component includes a recycled thermoplastic elastomer material. The recycled thermoplastic elastomer material includes greater than or equal to about 97 wt% of the aforementioned thermoplastic elastomer material and less than or equal to about 3 wt% of the aforementioned rigid thermoplastic material, based on the weight of the recycled thermoplastic elastomer material. The recycled thermoplastic elastomer material can be obtained by the aforementioned separation process, in which at least a portion of the aforementioned thermoplastic elastomer material is separated from the aforementioned rigid thermoplastic material.

[0017] The present disclosure should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that the present disclosure will be thorough and complete, and will fully convey the subject matter to those skilled in the art.

[0018] Definition

[0019] Unless otherwise clearly defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The terms used in this disclosure are merely for the purpose of describing particular embodiments and are not intended to be limiting.

[0020] Unless otherwise expressly stated, no method disclosed herein is intended to be construed as requiring its steps to be performed in a particular order, or any device described herein to be construed as requiring its components to have a particular order or orientation.

[0021] Unless otherwise expressly stated, it is intended that any composition or mixture disclosed herein may contain the disclosed components, consist essentially of the disclosed components, or consist of the disclosed components.

[0022] As used herein, unless the context clearly indicates otherwise, the singular form of a term shall include the plural form of that term.

[0023] As used herein, a numerical value is not strictly limited to the exact value recited. Instead, unless otherwise expressly stated, each numerical value is intended to represent both the recited exact value and the values covered by "about" (i.e., a functionally equivalent range around that value), such that any possible value may be considered an embodiment disclosed herein.

[0024] As used herein, the term "300% tensile modulus" refers to the stress value of a material measured at 300% strain in accordance with ASTM D412.

[0025] As used herein, the term "antecedent" refers to the time at which a fabricated article, or a prepared material, or a process that occurs is earlier than another article or material or process described herein.

[0026] As used herein, the term "dielectric constant" refers to the dielectric constant of a material measured by the cavity method at frequencies between 35 and 42 GHz, where the dielectric constant measured at 40 GHz is representative of that frequency range.

[0027] As used herein, the term "substantially free of" means, when used to describe the amount and / or absence of a particular component, that the component is not intentionally added. However, in some embodiments, the amount of the component present may be less than 0.1 wt%, or 0.05 wt%, or 0.03 wt%, or 0.01 wt%, or 0.005 wt%, or 0.001 wt%.

[0028] As used herein, the term "flexural modulus" refers to the ratio of stress to strain in a flexural deformation measured in accordance with ASTM D790 at 23 °C and a strain rate of 0.2 mm / min.

[0029] As used herein, the term "formed from (including related terms such as 'formed of')" with respect to an article (or an article component) and a thermoplastic material means that the article (or the article component) is extruded, molded, shaped, pressed, or otherwise made, in whole or in part, of the thermoplastic material under sufficient heating (to effect such shaping). Thus, in some embodiments, the term "formed from (including related terms such as 'formed of')" means that the article (or the article component) may contain the material, consist essentially of the material, or consist of the material; and, in other embodiments, the article (or the article component) consists of the material because the article (or the article component) is made, for example, by an extrusion process or a molding process.

[0030] As used herein, the term "high purity" means, in each embodiment, that the amount of a particular substance or material in a composition or mixture is greater than or equal to 80 wt%, or 85 wt%, or 90 wt%, or 92 wt%, or 95 wt%, or 97 wt%, or 98 wt%, or 99 wt%, or 99.5 wt%, or 99.9 wt%.

[0031] As used herein, the term "neat" means that a substance or material is pure or substantially pure such that the substance or material exists as a single distinct substance or material without any other distinct substance or material present at a level greater than trace amounts (as determined using methods and equipment conventional for such substances or materials).

[0032] As used herein, the term "recovered" means that the material is from a recycled source.

[0033] As used herein, the term "Shore A hardness" means the hardness of a material measured according to ASTM D2240.

[0034] As used herein, the term "specific gravity" means the ratio of the density of a material to the density of water and is measured according to ASTM D792.

[0035] As used herein, the term "tensile elongation" means the tensile elongation at break, which is the ratio of the increase in length after break to the initial length, measured according to ASTM D412, Die C.

[0036] As used herein, the term "tensile strength" means the tensile strength at break, which is the maximum stress that a material can withstand in tension before break, measured according to ASTM D412, Die C.

[0037] As used herein, the term "virgin" refers to a material that is from a non-recycled source.

[0038] As used herein, the term "subsequent" refers to an article that is formed, or a material that is prepared, or a process that occurs at a later time relative to another article or material or process described herein.

[0039] Practicality

[0040] As described above, multi-component thermoplastic articles having two or more components formed of dissimilar plastic materials, such as overmolded thermoplastic articles, can be used to achieve multiple functions in a variety of applications, including protective housings for personal electronic devices (such as smartphones, tablets, laptop computers, etc.). For example, an elastomeric component can be bonded to a rigid resin component to provide balanced performance, including overall stiffness, impact resistance, and shock absorption, while also providing a desired aesthetic (appearance or look) and / or tactile (feel or sensation).

[0041] Industries, including the consumer electronics industry, desire that thermoplastic articles contain increasing amounts of post-consumer and / or post-industrial recycled materials. However, it may be difficult to obtain high-purity materials, particularly high-purity thermoplastic elastomers, from post-consumer recycled multi-component thermoplastic articles and post-industrial recycled multi-component thermoplastic articles.

[0042] In a conventional recycling process, multi-component articles can be granulated, separated, and reprocessed (e.g., melted and extruded) for further use. Conventional methods of separating materials of plastic regrind include float-sink (based on density), centrifugation (based on density), electrostatic separation, optical sorting using near-infrared spectroscopy, and magnetic separation. Multi-component articles having a thermoplastic elastomer overmolded layer on a rigid thermoplastic substrate layer are typically designed to have a strong interfacial adhesion between the thermoplastic elastomer overmolded layer and the rigid thermoplastic substrate layer in order to withstand normal wear and tear and even mechanical abuse of the article during use. The strong interfacial adhesion can generally survive an industrial grinding process that involves mechanical shearing, tearing, and cutting of the article for recycling purposes, resulting in a large portion of the hybrid particles in the regrind of such articles having both a thermoplastic elastomer portion and a rigid thermoplastic portion. The hybrid particles are generally regarded as undesirable contaminants in the thermoplastic elastomer-rich portion or the rigid thermoplastic-rich portion obtainable by conventional separation processes. The separated and recycled thermoplastic elastomer-rich fraction can still have a high level of the rigid thermoplastic material because of the presence of the hybrid particles after the conventional separation process, which has a negative impact on the properties of the recycled thermoplastic elastomer material.

[0043] Thus, currently, multi-component articles, such as overmolded thermoplastic articles, are effectively non-recyclable to provide highly pure recycled materials, and the recycled materials are typically only suitable for further use in forming new articles after being mixed with a relatively large amount of virgin resin (e.g., in a mixture of virgin resin and recycled resin, there is more virgin resin than recycled resin).

[0044] The articles disclosed herein solve the above problems.

[0045] Referring now Figure 1 , article 100 disclosed herein includes a substrate component 102 and an overmolded component 104. Substrate component 102 includes a rigid thermoplastic material, while overmolded component 104 includes a recycled thermoplastic elastomer material. The recycled thermoplastic elastomer material includes greater than or equal to about 97 weight percent of the aforementioned thermoplastic elastomer material and less than or equal to about 3 weight percent of the aforementioned rigid thermoplastic material, based on the weight of the recycled thermoplastic elastomer material. The recycled thermoplastic elastomer material can be provided by a prior separation process.

[0046] Separation process

[0047] In some embodiments, the recycled thermoplastic elastomer material may be provided by a prior separation process, where the prior thermoplastic elastomer material may be separated from at least a portion of the prior rigid thermoplastic material to provide the recycled thermoplastic elastomer material.

[0048] For example, the recycled thermoplastic elastomer material may include regrind of a prior article and / or prior waste material provided by a prior process for manufacturing and / or recycling the prior article, where the prior article and / or prior waste material may include a prior thermoplastic elastomer material coated onto the prior rigid thermoplastic material, and where the regrind of the prior article and / or prior waste material may be subjected to the prior separation process, where the prior thermoplastic elastomer material may be separated from at least a portion of the prior rigid thermoplastic material to provide the recycled thermoplastic elastomer material.

[0049] In some embodiments, the prior separation process may include the step of providing or obtaining a prior article. In some embodiments, the prior article may include a prior substrate assembly and a prior coated assembly, the prior substrate assembly including a prior rigid thermoplastic material, the prior coated assembly including a prior thermoplastic elastomer material, and the structure of the prior article may be the same as or similar to the structure of the article shown in Figure 1 the article shown.

[0050] In some embodiments, the prior separation process may further include the step of reducing the prior article. In some embodiments, the reducing step may include crushing, shredding, grinding, pelletizing, or a combination thereof to produce regrind. In some embodiments, such as in a post-consumer recycling process, the reducing step may include reducing the prior article itself to produce the regrind of the prior article. In other embodiments, such as in an industrial post-application, the reducing step may include reducing prior waste material from a prior process for manufacturing the prior article to produce the regrind of the prior waste material. In such embodiments, the prior waste material may include a prior thermoplastic elastomer material coated onto the prior rigid thermoplastic material.

[0051] To facilitate the separation process, the prior rigid thermoplastic material may include a separation additive as further described elsewhere herein. The separation additive in the prior rigid thermoplastic material may be the separation additive described elsewhere herein for the rigid thermoplastic material of the substrate assembly shown in Figure 1 the substrate assembly shown.

[0052] In some embodiments, the foregoing separation process may further comprise the following steps: separating the regrind of the foregoing article such that at least a portion of the foregoing thermoplastic elastomeric material is separated from the foregoing rigid thermoplastic material to provide the recycled thermoplastic elastomeric material.

[0053] For example, referring now to Figure 2 , in embodiments where a magnetic separation additive is included in the foregoing rigid thermoplastic material, a magnetic roll separator 200 may be used. The magnetic roll separator 200 includes a belt conveyor 202 and a magnetic roll 204. The separator 200 includes a diverter 206 and two collection bins 208, 210. In other embodiments, additional diverter collection bins may be included, allowing separation into more than two fractions. Collection bin 208 collects the regrind without the magnetic separation additive (e.g., the recycled thermoplastic elastomeric material), while collection bin 210 collects the regrind with the magnetic separation additive (e.g., the recycled rigid thermoplastic material). The diverter 206 may be adjusted to achieve a high purity of the recycled thermoplastic elastomeric material.

[0054] As a further example, referring now to Figure 6 , an additional magnetic pulley separator 600 includes a belt conveyor 602 and a magnetic roll 604. The separator 600 includes two diverters 606, 608 and three collection bins 610, 612, 614. In other embodiments, additional diverter collection bins may be included, allowing separation into more than three fractions. The configuration of the diverters 606, 608 may be adjusted depending on other operating conditions. Collection bin 610 primarily collects the regrind particles of the component material without the magnetic separation additive, collection bin 612 primarily collects the regrind particles of the component material with the magnetic separation additive, and collection bin 614 primarily collects the "hybrid" regrind particles.

[0055] When a density separation additive is added to the foregoing rigid thermoplastic material, a statistical flotation cell with a specific medium may be used to facilitate the separation process. The specific medium has an intermediate density between the thermoplastic elastomeric material without the density separation additive and the rigid thermoplastic material with the density separation additive. The lower density regrind (e.g., the thermoplastic elastomeric material without the density separation additive) floats, while the higher density regrind (e.g., the rigid thermoplastic material with the density separation additive) sinks.

[0056] Product

[0057] Returning to Figure 1 , the article 100 disclosed herein includes a substrate assembly 102 and a overmolded assembly 104.

[0058] In some embodiments, at least a portion of the overmolded component 104 may be secured to at least a portion of the base component 102 by interfacial adhesion.

[0059] In some embodiments, the overmolded component 104 may be molded onto at least one side of the base component 102. For example, a typical overmolding process may include pressing a melt of the overmolded component 104 onto at least one side of a previously formed base component 102 in a molding cavity and then cooling to form the article 100. By a typical overmolding process, the base component 102 and the overmolded component 104 may be adhered to each other without an adhesive.

[0060] In some embodiments, the bond between the base component 102 and the overmolded component 104 is relatively strong such that a regrind mixture obtained by physically reducing (e.g., grinding) the article 100 and having an average particle size between about 1 mm and about 10 mm may include at least 10 wt% hybrid particles (i.e., particles having at least a portion composed of the base component 102 and at least another portion composed of the overmolded component 104), based on the total weight of the regrind.

[0061] In some embodiments, the article 100 disclosed herein may further include one or more additional components that include one or more additional thermoplastic materials, as described hereinafter.

[0062] In some embodiments, the article 100 disclosed herein may further include a photoluminescent marker.

[0063] In some embodiments, a precursor article may include a base component and an overmolded component, the base component including a precursor rigid thermoplastic material and the overmolded component including a precursor thermoplastic elastomeric material, or the precursor article may be the same as or different from the article as described herein.

[0064] Substrate component and rigid thermoplastic material

[0065] As disclosed herein, the base component 102 includes a rigid thermoplastic material.

[0066] In some embodiments, the base component 102 may be formed of the rigid thermoplastic material.

[0067] In some embodiments, the base component may include a rigid thermoplastic material, a parting additive, and optionally other additives.

[0068] In some embodiments, the rigid thermoplastic material may comprise a thermoplastic resin, a parting additive, and optionally other additives.

[0069] In some embodiments, the foregoing rigid thermoplastic material may be the same as or different from the rigid thermoplastic materials described herein.

[0070] In some embodiments, the flexural modulus of the substrate assembly and / or the rigid thermoplastic material may be greater than or equal to about 1000 MPa, or greater than or equal to about 1200 MPa; and less than or equal to about 3000 MPa, or less than or equal to about 2500 MPa; for example, about 1000 MPa to about 3000 MPa, about 1000 MPa to about 2500 MPa, about 1500 MPa to about 3000 MPa, or about 1500 MPa to about 2500 MPa, or any and all subranges formed by any of these endpoints.

[0071] In some embodiments, the density of the substrate assembly and / or the rigid thermoplastic material may be: greater than or equal to about 1.0 g / cm 3 , or greater than or equal to about 1.1 g / cm 3 ; and less than or equal to about 1.3 g / cm 3 , or less than or equal to about 1.2 g / cm 3 ; for example, about 1.0 g / cm 3 to about 1.3 g / cm 3 , about 1.0 g / cm 3 to about 1.2 g / cm 3 , about 1.1 g / cm 3 to about 1.3 g / cm 3 , or about 1.1 g / cm 3 to about 1.2 g / cm 3 , or any and all subranges formed by any of these endpoints.

[0072] Thermoplastic resin

[0073] In some embodiments, the rigid thermoplastic material may comprise a thermoplastic resin.

[0074] Suitable thermoplastic resins may include conventional or commercially available thermoplastic resins. The thermoplastic resin may be used alone or in combination with one or more other thermoplastic resins.

[0075] In some embodiments, the thermoplastic resin may be selected from: polycarbonate, thermoplastic polyester, polyamide, aliphatic polyketone, acrylonitrile - butadiene - styrene, polypropylene, and combinations thereof.

[0076] In some embodiments, the thermoplastic resin may be selected from: virgin thermoplastic resin, recycled thermoplastic resin, or a combination thereof.

[0077] Suitable commercial embodiments of the thermoplastic resin are available from Covestro under the brand MARKROLON, such as polycarbonate grade 2407.

[0078] In some embodiments, the amount of the thermoplastic resin present in the rigid thermoplastic material may be from about 50 wt% to about 99.95 wt%, based on the weight of the rigid thermoplastic material, or any and all subranges formed between these endpoints. For example, in some embodiments, the amount of the thermoplastic resin present in the rigid thermoplastic material may be from about 60 wt% to about 99.95 wt%, or from about 70 wt% to about 99.95 wt%, or from about 80 wt% to about 99.95 wt%, or from about 90 wt% to about 99.95 wt%, or from about 95 wt% to about 99.95 wt%, based on the weight of the rigid thermoplastic material, or any and all subranges formed between any of these endpoints.

[0079] Separation additive

[0080] In some embodiments, the rigid thermoplastic material may contain a separation additive to facilitate subsequent separation processes as described elsewhere herein.

[0081] In some embodiments, the amount of the separation additive present in the rigid thermoplastic material may be from about 0.05 wt% to about 10 wt%, based on the weight of the rigid thermoplastic material, or any and all subranges formed between these endpoints.

[0082] For example, in some embodiments, based on the weight of the rigid thermoplastic material, the amount of the separation additive in the rigid thermoplastic material can be: greater than or equal to about 0.05 wt%, greater than or equal to about 0.1 wt%, greater than or equal to about 0.2 wt%, greater than or equal to about 0.5 wt%, greater than or equal to about 1 wt%, greater than or equal to about 3 wt%, greater than or equal to about 5 wt%, greater than or equal to about 5.5 wt%, greater than or equal to about 6 wt%, greater than or equal to about 6.5 wt%, or greater than or equal to about 7 wt%; and less than or equal to about 10 wt%, less than or equal to about 9 wt%, less than or equal to about 8.5 wt%, less than or equal to about 8 wt%, less than or equal to about 6 wt%, less than or equal to about 4 wt%, less than or equal to about 2 wt%, less than or equal to about 1 wt%, or less than or equal to 0.5 wt%; for example, about 0.05 wt% to about 10 wt%, about 0.05 wt% to about 9.5 wt%, about 0.05 wt% to about 9 wt%, about 0.05 wt% to about 8.5 wt%, about 0.05 wt% to about 8 wt%, about 0.05 wt% to about 6 wt%, about 0.05 wt% to about 4 wt%, about 0.05 wt% to about 2 wt%, about 0.05 wt% to about 1 wt%, about 0.05 wt% to about 0.5 wt%, about 0.1 wt% to about 10 wt%, about 0.1 wt% to about 9.5 wt%, about 0.1 wt% to about 9 wt%, about 0.1 wt% to about 8.5 wt%, about 0.1 wt% to about 8 wt%, about 0.1 wt% to about 6 wt%, about 0.1 wt% to about 4 wt%, about 0.1 wt% to about 2 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt% to about 0.5 wt%, about 0.2 wt% to about 10 wt%, about 0.2 wt% to about 9.5 wt%, about 0.2 wt% to about 9 wt%, about 0.2 wt% to about 8.5 wt%, about 0.2 wt% to about 8 wt%, about 0.2 wt% to about 6 wt%, about 0.2 wt% to about 4 wt%, about 0.2 wt% to about 2 wt%, about 0.2 wt% to about 1 wt%, about 0.5 wt% to about 10 wt%, about 0.5 wt% to about 9.5 wt%, about 0.5 wt% to about 9 wt%, about 0.5 wt% to about 8.5 wt%, about 0.5 wt% to about 8 wt%, about 0.5 wt% to about 6 wt%, about 0.5 wt% to about 4 wt%, about 0.5 wt% to about 2 wt%, about 0.5 wt% to about 1 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 9.5 wt%, about 1 wt% to about 9 wt%, about 1 wt% to about 8.5 wt%, about 1 wt% to about 8 wt%, about 1 wt% to about 6 wt%, about 1 wt% to about 4 wt%, about 1 wt% to about 2 wt%, about 3 wt% to about 10 wt%, about 3 wt% to about 9.5 wt%, from about 3 wt% to about 9 wt%, from about 3 wt% to about 8.5 wt%, from about 3 wt% to about 8 wt%, from about 3 wt% to about 6 wt%, from about 3 wt% to about 4 wt%, from about 5 wt% to about 10 wt%, from about 5 wt% to about 9.5 wt%, from about 5 wt% to about 9 wt%, from about 5 wt% to about 8.5 wt%, from about 5 wt% to about 8 wt%, from about 5 wt% to about 6 wt%, from about 5.5 wt% to about 10 wt%, from about 5.5 wt% to about 9.5 wt%, from about 5.5 wt% to about 9 wt%, from about 5.5 wt% to about 8.5 wt%, from about 5.5 wt% to about 8 wt%, from about 5.5 wt% to about 6 wt%, from about 6 wt% to about 10 wt%, from about 6 wt% to about 9.5 wt%, from about 6 wt% to about 9 wt%, from about 6 wt% to about 8.5 wt%, from about 6 wt% to about 8 wt%, from about 6.5 wt% to about 10 wt%, from about 6.5 wt% to about 9.5 wt%, from about 6.5 wt% to about 9 wt%, from about 6.5 wt% to about 8.5 wt%, from about 6.5 wt% to about 8 wt%, from about 7 wt% to about 10 wt%, from about 7 wt% to about 9.5 wt%, from about 7 wt% to about 9 wt%, from about 7 wt% to about 8.5 wt%, or from about 7 wt% to about 8 wt%, or any and all sub-ranges formed between any of these endpoints.

[0083] Suitable separation additives can include conventional or commercially available separation additives. The separation additives can be used alone or in combination with one or more other separation additives.

[0084] Magnetic separation additive

[0085] In some embodiments, the separation additive in the rigid thermoplastic material can be a magnetic separation additive. In some embodiments, the magnetic separation additive can be a metal or a metal oxide. For example, in some embodiments, the magnetic separation additive can be selected from: iron, ferromagnetic steel alloys, ferromagnetic stainless steel alloys, synthetic iron oxide having the chemical formula Fe3O4, magnetite, ferrites, strontium ferrites, neodymium mixed oxides, alnico magnetic steel alloys, samarium-cobalt alloys, neodymium alloys, and combinations thereof.

[0086] Unexpectedly, it has been found that in the substrate assembly or the overmolded assembly, even when only a relatively small amount of the magnetic separation additive is included, a significant portion of the rigid thermoplastic material used to form the substrate assembly can be separated from a significant portion of the thermoplastic elastomer material used to form the overmolded assembly, and an unexpectedly high rate of purity can be achieved for one or both of these thermoplastic materials.

[0087] In some embodiments, the amount of the magnetic separation additive in the rigid thermoplastic material can be from about 0.05 wt% to about 1.0 wt%, based on the weight of the rigid thermoplastic material, or any and all sub-ranges formed between these endpoints.

[0088] For example, in some embodiments, based on the weight of the rigid thermoplastic material, the amount of the magnetic separation additive in the rigid thermoplastic material can be: greater than or equal to about 0.05 wt%, greater than or equal to about 0.1 wt%, or greater than or equal to about 0.2 wt%; and less than or equal to about 1 wt% or less than or equal to about 0.5 wt%. Further, in some embodiments, the amount of the magnetic separation additive in the rigid thermoplastic material can be: based on the weight of the rigid thermoplastic material, from about 0.05 wt% to about 1 wt%, from about 0.05 wt% to about 0.5 wt%, from about 0.1 wt% to about 1 wt%, from about 0.1 wt% to about 0.5 wt%, from about 0.2 wt% to about 1 wt%, or from about 0.2 wt% to about 0.5 wt%, or any and all sub-ranges formed by any of these endpoints.

[0089] In some embodiments, the average particle size D50 of the magnetic separation additive can be: from about 0.5 μm to about 200 μm, from about 0.5 μm to about 150 μm, from about 0.5 μm to about 100 μm, from about 0.5 μm to about 50 μm, from about 0.5 μm to about 25 μm, from about 0.5 μm to about 10 μm, from about 1 μm to about 200 μm, from about 1 μm to about 150 μm, from about 1 μm to about 100 μm, from about 1 μm to about 50 μm, from about 1 μm to about 25 μm, from about 1 μm to about 10 μm, from about 5 μm to about 200 μm, from about 5 μm to about 150 μm, from about 5 μm to about 100 μm, from about 5 μm to about 50 μm, from about 5 μm to about 25 μm, from about 5 μm to about 10 μm, from about 10 μm to about 200 μm, from about 10 μm to about 150 μm, from about 10 μm to about 100 μm, from about 10 μm to about 50 μm, from about 10 μm to about 25 μm, from about 25 μm to about 200 μm, from about 25 μm to about 150 μm, from about 25 μm to about 100 μm, from about 25 μm to about 50 μm, from about 50 μm to about 200 μm, from about 50 μm to about 150 μm, from about 50 μm to about 100 μm, from about 100 μm to about 200 μm, from about 100 μm to about 150 μm, or from about 150 μm to about 200 μm, or any and all sub-ranges formed by these endpoints, and the average particle size D50 is measured according to ASTM B822-20.

[0090] Suitable commercial embodiments of the magnetic separation additive are available from Eriez Manufacturing under the brand POLYMAG, such as ferromagnetic stainless steel powder grades; from Quality Magnetite, LLC under the brand MICROMAG, such as magnetite grade 5; and from LANXESS under the brand BAYFERROX, such as synthetic iron oxide powder grade 318M.

[0091] In some embodiments, the magnetic separation additive is not intentionally added to the overmolded component 104 or the recycled thermoplastic elastomer material, and / or the magnetic separation additive is not present in the overmolded component 104 or the recycled thermoplastic elastomer material. Thus, in some embodiments, the overmolded component 104 and / or the recycled thermoplastic elastomer material may contain less than about 0.03 wt% of the magnetic separation additive, based on the weight of the overmolded component; and / or the recycled thermoplastic elastomer material, or the overmolded component 104 and / or the recycled thermoplastic elastomer material is substantially free of the magnetic separation additive.

[0092] Density separation additive

[0093] In some embodiments, the separation additive in the rigid thermoplastic material may be a density separation additive.

[0094] In some embodiments, the density separation additive may be an inorganic powder. For example, in some embodiments, the density separation additive may be selected from: tungsten, tungsten oxide, barium sulfate, copper, ferromagnetic stainless steel, cerium oxide, and combinations thereof.

[0095] In some embodiments, the amount of the density separation additive present in the rigid thermoplastic material may be from about 5 wt% to about 10 wt%, based on the weight of the rigid thermoplastic material, or any and all subranges formed between these endpoints.

[0096] For example, in some embodiments, the amount of the density separation additive in the rigid thermoplastic material may be: based on the weight of the rigid thermoplastic material, greater than or equal to about 5 wt%, greater than or equal to about 5.5 wt%, greater than or equal to about 6 wt%, greater than or equal to about 6.5 wt%, or greater than or equal to about 7 wt%; and less than or equal to about 10 wt%, less than or equal to about 9.5 wt%, less than or equal to about 9 wt%, less than or equal to about 8.5 wt%, or less than or equal to about 8 wt%. Further, in some embodiments, the amount of the density separation additive in the rigid thermoplastic material may be: based on the weight of the rigid thermoplastic material, about 5 wt% to about 10 wt%, about 5 wt% to about 9.5 wt%, about 5 wt% to about 9 wt%, about 5 wt% to about 8.5 wt%, about 5 wt% to about 8 wt%, about 5.5 wt% to about 10 wt%, about 5.5 wt% to about 9.5 wt%, about 5.5 wt% to about 9 wt%, about 5.5 wt% to about 8.5 wt%, about 5.5 wt% to about 8 wt%, about 6 wt% to about 10 wt%, about 6 wt% to about 9.5 wt%, about 6 wt% to about 9 wt%, about 6 wt% to about 8.5 wt%, about 6 wt% to about 8 wt%, about 6.5 wt% to about 10 wt%, about 6.5 wt% to about 9.5 wt%, about 6.5 wt% to about 9 wt%, about 6.5 wt% to about 8.5 wt%, about 6.5 wt% to about 8 wt%, about 7 wt% to about 10 wt%, about 7 wt% to about 9.5 wt%, about 7 wt% to about 9 wt%, about 7 wt% to about 8.5 wt%, or about 7 wt% to about 8 wt%, or any and all subranges formed by any of these endpoints.

[0097] Suitable commercial embodiments of the density separation additive are: copper powder available from Makin Metal Powders, and tungsten powder available from Buffalo Tungsten, such as high density SR or ST grades.

[0098] Overmolded component and recycled thermoplastic elastomer material

[0099] As disclosed herein, the overmolded component 104 comprises a recycled thermoplastic elastomer material.

[0100] In some embodiments, the overmolded component 102 may be formed from the recycled thermoplastic elastomer material.

[0101] In some embodiments, the recycled thermoplastic elastomer material may be provided by a pre-separation process as described elsewhere herein.

[0102] In some embodiments, the recycled thermoplastic elastomer material may comprise, based on the weight of the recycled thermoplastic elastomer material, greater than or equal to about 97 wt% of a precursor thermoplastic elastomer material and less than or equal to about 3 wt% of a precursor rigid thermoplastic material. Further, in some embodiments, the recycled thermoplastic elastomer material may comprise greater than or equal to about 99 wt% of the precursor thermoplastic elastomer material and less than or equal to about 1 wt% of the precursor rigid thermoplastic material, based on the weight of the recycled thermoplastic elastomer material.

[0103] For example, in some embodiments, the amount of the precursor thermoplastic elastomer material in the recycled thermoplastic elastomer material may be, based on the weight of the recycled thermoplastic elastomer material, greater than or equal to about 97 wt%, greater than or equal to about 97.5 wt%, greater than or equal to about 98 wt%, greater than or equal to about 98.5 wt%, or greater than or equal to about 99 wt%; and less than or equal to about 100 wt% or less than or equal to about 99.5 wt%. Further, in some embodiments, the amount of the precursor thermoplastic elastomer material in the recycled thermoplastic elastomer material may be, based on the weight of the recycled thermoplastic elastomer material, from about 97 wt% to about 100 wt%, from about 97 wt% to about 99.5 wt%, from about 97.5 wt% to about 100 wt%, from about 97.5 wt% to about 99.5 wt%, from about 98 wt% to about 100 wt%, from about 98 wt% to about 99.5 wt%, from about 98.5 wt% to about 100 wt%, from about 98.5 wt% to about 99.5 wt%, from about 99 wt% to about 100 wt%, or from about 99 wt% to about 99.5 wt%, or any and all subranges formed by any of these endpoints.

[0104] In some embodiments, the recycled thermoplastic elastomer material may be substantially free of virgin thermoplastic elastomer material.

[0105] In some embodiments, the amount of the precursor rigid thermoplastic material in the recycled thermoplastic elastomer material may be, based on the weight of the recycled thermoplastic elastomer material, less than or equal to about 3 wt%, less than or equal to about 2.5 wt%, less than or equal to about 2 wt%, less than or equal to about 1.5 wt%, or less than or equal to about 1 wt%; and greater than or equal to about 0 wt% or greater than or equal to about 0.5 wt%.

[0106] For example, in some embodiments, the amount of the antecedent rigid thermoplastic material in the recycled thermoplastic elastomer material may be: based on the weight of the recycled thermoplastic elastomer material, from about 0 wt% to about 3 wt%, from about 0 wt% to about 2.5 wt%, from about 0 wt% to about 2 wt%, from about 0 wt% to about 1.5 wt%, from about 0 wt% to about 1 wt%, from about 0.5 wt% to about 3 wt%, from about 0.5 wt% to about 2.5 wt%, from about 0.5 wt% to about 2 wt%, from about 0.5 wt% to about 1.5 wt%, from about 0.5 wt% to about 1 wt%, or any and all subranges formed by any of these endpoints.

[0107] In some embodiments, the overmolded component 104 may be formed of greater than or equal to about 50 wt%, or greater than or equal to about 75 wt% of the recycled thermoplastic elastomer material, based on the weight of the overmolded component 104.

[0108] For example, in some embodiments, the amount of the recycled thermoplastic elastomer material in the overmolded component 104 may be: based on the weight of the overmolded component 104, greater than or equal to about 50 wt%, greater than or equal to about 55 wt%, greater than or equal to about 60 wt%, greater than or equal to about 65 wt%, greater than or equal to about 70 wt%, or greater than or equal to about 75 wt%; and less than or equal to about 90 wt%, or less than or equal to about 85 wt%; for example, from about 50 wt% to about 90 wt%, from about 50 wt% to about 85 wt%, from about 55 wt% to about 90 wt%, from about 55 wt% to about 85 wt%, from about 60 wt% to about 90 wt%, from about 60 wt% to about 85 wt%, from about 65 wt% to about 90 wt%, from about 65 wt% to about 85 wt%, from about 70 wt% to about 90 wt%, from about 70 wt% to about 85 wt%, from about 75 wt% to about 90 wt%, or from about 75 wt% to about 85 wt%, or any and all subranges formed by any of these endpoints.

[0109] In some embodiments, the amount of the virgin thermoplastic elastomer material in the overmolded component can be: based on the weight of the overmolded component, greater than or equal to about 10 wt%, or greater than or equal to about 15 wt%; and less than or equal to about 50 wt%, less than or equal to about 45 wt%, less than or equal to about 40 wt%, less than or equal to about 35 wt%, less than or equal to about 30 wt%, or less than or equal to about 25 wt%; for example, about 10 wt% to about 50 wt%, about 10 wt% to about 45 wt%, about 10 wt% to about 40 wt%, about 10 wt% to about 35 wt%, about 10 wt% to about 30 wt%, about 10 wt% to about 25 wt%, about 15 wt% to about 50 wt%, about 15 wt% to about 45 wt%, about 15 wt% to about 40 wt%, about 15 wt% to about 35 wt%, about 15 wt% to about 30 wt%, or about 15 wt% to about 25 wt%, or any and all subranges formed by any of these endpoints.

[0110] In some embodiments, the overmolded component can include a recycled thermoplastic elastomer, an optional polymeric chain extender, and optional other additives.

[0111] In some embodiments, the recycled thermoplastic elastomer material can include a thermoplastic elastomer, an optional polymeric chain extender, and optional other additives.

[0112] In some embodiments, the virgin thermoplastic elastomer material can include a thermoplastic elastomer, an optional polymeric chain extender, and optional other additives.

[0113] Suitable commercial embodiments of the thermoplastic elastomer material are available from Avient Corporation under the brand VERSAFLEX, such as the thermoplastic polyurethane grade CE 3120-65.

[0114] In some embodiments, the Shore A hardness of the overmolded component and / or the thermoplastic elastomer material can be greater than or equal to about 50, or greater than or equal to about 60; and less than or equal to about 80, or less than or equal to about 70; for example, about 50 to about 80, about 50 to about 70, about 60 to about 80, or about 60 to about 70, or any and all subranges formed by any of these endpoints

[0115] In some embodiments, the Shore A hardness of the overmolded component and / or the thermoplastic elastomer material can be greater than or equal to about 1.0, or greater than or equal to about 1.1; and less than or equal to about 1.3, or less than or equal to about 1.2; for example, from about 1.0 to about 1.3, from about 1.0 to about 1.2, from about 1.1 to about 1.3, or from about 1.1 to about 1.2, or any and all subranges formed by any of these endpoints.

[0116] In some embodiments, the tensile strength of the overmolded component and / or the thermoplastic elastomer material can be greater than or equal to about 12 MPa, or greater than or equal to about 14 MPa; and less than or equal to about 19 MPa, or less than or equal to about 17 MPa; for example, from about 12 MPa to about 19 MPa, from about 12 MPa to about 17 MPa, from about 14 MPa to about 19 MPa, from about 14 MPa to about 17 MPa, or any and all subranges formed by any of these endpoints.

[0117] In some embodiments, the tensile elongation of the overmolded component and / or the thermoplastic elastomer material can be greater than or equal to about 550%, or greater than or equal to about 650%; and less than or equal to about 850%, or less than or equal to about 750%; for example, from about 550% to about 850%, from about 550% to about 750%, from about 650% to about 850%, or from about 650% to about 750%, or any and all subranges formed by any of these endpoints.

[0118] In some embodiments, the 300% tensile modulus of the overmolded component and / or the thermoplastic elastomer material may be: greater than or equal to about 0.07 MPa, greater than or equal to about 0.1 MPa, greater than or equal to about 0.5 MPa, greater than or equal to about 1 MPa, or greater than or equal to about 3 MPa; and less than or equal to about 15 MPa, less than or equal to about 12 MPa, less than or equal to about 10 MPa, less than or equal to about 8 MPa, or less than or equal to about 6 MPa; for example, about 0.07 MPa to about 15 MPa, about 0.07 MPa to about 12 MPa, about 0.07 MPa to about 10 MPa, about 0.07 MPa to about 8 MPa, about 0.07 MPa to about 6 MPa, about 0.1 MPa to about 15 MPa, about 0.1 MPa to about 12 MPa, about 0.1 MPa to about 10 MPa, about 0.1 MPa to about 8 MPa, about 0.1 MPa to about 6 MPa, about 0.5 MPa to about 15 MPa, about 0.5 MPa to about 12 MPa, about 0.5 MPa to about 10 MPa, about 0.5 MPa to about 8 MPa, about 0.5 MPa to about 6 MPa, about 1 MPa to about 15 MPa, about 1 MPa to about 12 MPa, about 1 MPa to about 10 MPa, about 1 MPa to about 8 MPa, about 1 MPa to about 6 MPa, about 3 MPa to about 15 MPa, about 3 MPa to about 12 MPa, about 3 MPa to about 10 MPa, about 3 MPa to about 8 MPa, or about 3 MPa to about 6 MPa, or any and all subranges formed by any of these endpoints.

[0119] Thermoplastic elastomer

[0120] In some embodiments, the thermoplastic elastomer material (as the recycled thermoplastic elastomer material, or the precursor thermoplastic elastomer material) may comprise a thermoplastic elastomer.

[0121] Suitable thermoplastic elastomers may include conventional or commercially available thermoplastic elastomers. The thermoplastic elastomers may be used alone or in combination with one or more other thermoplastic elastomers.

[0122] In some embodiments, the thermoplastic elastomer may be selected from: thermoplastic polyurethane (TPU) and styrenic block copolymers (SBC), wherein the styrenic block copolymers (SBC) are selected from: styrene-ethylene / butylene-styrene (SEBS) block copolymers, styrene-ethylene / propylene-styrene (SEPS), styrene-ethylene / ethylene / propylene-styrene (SEEPS), styrene-isobutylene-styrene (SIBS), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), and combinations thereof.

[0123] In some embodiments, the amount of the thermoplastic elastomer present in the thermoplastic elastomer material may be from about 50 wt% to about 99.9 wt%, based on the weight of the thermoplastic elastomer material, or any and all sub-ranges formed between these endpoints. For example, in some embodiments, the amount of the thermoplastic elastomer present in the thermoplastic elastomer material may be from about 60 wt% to about 99.9 wt%, or from about 70 wt% to about 99.9 wt%, or from about 80 wt% to about 99.9 wt%, or from about 90 wt% to about 99.9 wt%, or from about 95 wt% to about 99.9 wt%, based on the weight of the thermoplastic elastomer material, or any and all sub-ranges formed between any of these endpoints.

[0124] Polymeric chain extender

[0125] In some embodiments, the overmolded component and / or the thermoplastic elastomer material (as the virgin thermoplastic elastomer material or the recycled thermoplastic elastomer material) may further comprise a polymeric chain extender.

[0126] For example, in some embodiments, when the thermoplastic elastomer is selected from thermoplastic polyurethanes, the overmolded component and / or the thermoplastic elastomer material (as the virgin thermoplastic elastomer material or the recycled thermoplastic elastomer material) may further comprise a polymeric chain extender. In these embodiments, adding a polymeric chain extender to the thermoplastic elastomer material used to form the overmolded component 104 may improve the tensile strength of the overmolded component 104.

[0127] Suitable polymeric chain extenders may include conventional or commercially available polymeric chain extenders. The polymeric chain extender may be used alone or in combination with one or more other polymeric chain extenders.

[0128] For example, in some embodiments, the polymeric chain extender may be selected from functionalized styrene acrylic copolymers having epoxy groups.

[0129] In some embodiments, the amount of the polymeric chain extender present may be from about 0.2 wt% to about 1.0 wt%, based on the weight of the overmolded component 104, or based on the weight of the thermoplastic elastomer material (if applicable and as applicable).

[0130] In some embodiments, the amount of the polymeric chain extender in the overmolded component 104 can be greater than or equal to about 0.2 wt%, or greater than or equal to about 0.4 wt%, based on the weight of the overmolded component 104. In some embodiments, the amount of the polymeric chain extender in the overmolded component 104 can be less than or equal to about 2 wt%, less than or equal to about 1.5 wt%, less than or equal to about 1 wt%, or less than or equal to about 0.8 wt%, based on the total weight of the overmolded component 104. In some embodiments, the amount of the polymeric chain extender in the overmolded component 104 can be from about 0.2 wt% to about 2 wt%, from about 0.2 wt% to about 1.5 wt%, from about 0.2 wt% to about 1 wt%, from about 0.2 wt% to about 0.8 wt%, from about 0.4 wt% to about 2 wt%, from about 0.4 wt% to about 1.5 wt%, from about 0.4 wt% to about 1 wt%, or from about 0.4 wt% to about 0.8 wt%, or any and all subranges formed by any of these endpoints, based on the total weight of the overmolded component 104.

[0131] Suitable commercial embodiments of the polymeric chain extender are available from BASF under the brand JONCRYL, such as a functionalized styrene acrylic copolymer having epoxy groups, grade ADR 4400.

[0132] Other additives

[0133] In some embodiments, one or both of the rigid thermoplastic material and the thermoplastic elastomeric material can further include one or more optional other additives.

[0134] Suitable additives can include conventional or commercially available plastic additives. Those skilled in the art of thermoplastic compounding can select suitable additives from available references without undue experimentation, such as E.W. Flick, Plastics Design Library's Plastic additive database (Plastics Additives Database) (Elsevier 2004).

[0135] The optional other additives can be used in any amount sufficient to obtain the desired processing or performance properties for the material or the component formed from the material. The amount should not be wasteful of the additive and should not be detrimental to processing or performance.

[0136] For example, in some embodiments, one or more optional additional additives may be present in the material in an amount of from 0 wt% to about 40 wt%, or from about 0.01 wt% to about 20 wt%, or from about 0.1 wt% to about 10 wt%, based on the weight of the material, or any and all subranges formed between any of these endpoints.

[0137] Non-limiting examples of optional additional additives can include: adhesion promoters; antioxidants; biocides; antifogging agents; antistatic agents; adhesives and adhesive polymers; dispersants; fillers; flame retardants and smoke suppressants; impact modifiers; initiators; lubricants; mica; colorants (pigments and / or dyes); plasticizers; processing aids; mold release agents; silanes, titanates / esters, and zirconates / esters; slip agents and antiblocking agents; stearates / esters; ultraviolet light absorbers; viscosity modifiers; waxes; and combinations thereof.

[0138] In some embodiments, one or both of the rigid thermoplastic material and the thermoplastic elastomeric material may comprise an inorganic filler. For example, in some embodiments, the inorganic filler may be selected from: chopped glass fibers, glass beads, talc, clay, calcium carbonate, and combinations thereof.

[0139] In some embodiments, one or both of the rigid thermoplastic material and the thermoplastic elastomeric material may comprise an antioxidant. Suitable commercial embodiments of the antioxidant are available from BASF under the brand name IRGANOX, such as grade B225.

[0140] Photoluminescent marker

[0141] In some embodiments, the article may further comprise a photoluminescent marker.

[0142] In some embodiments, the photoluminescent marker may be fixed or applied to the outer surface of the article. Additionally or alternatively, in some embodiments, the photoluminescent marker may be incorporated into the substrate assembly (and / or the rigid thermoplastic material used to form the substrate assembly), and / or may be incorporated into the overmolded assembly (and / or the thermoplastic elastomeric material used to form the overmolded assembly).

[0143] In some embodiments, the photoluminescent marker may emit a spectrum visible to the human eye under normal lighting conditions. Similarly, in some embodiments, the photoluminescent marker may emit a spectrum that is visible to the human eye and / or detectable by a sensor when excited by an ultraviolet (UV) light source, visible light source, or near-infrared light source.

[0144] Accordingly, the photoluminescent marker can be used to facilitate the identification of an article as a "recycle friendly" article. For example, in some embodiments, the photoluminescent marker can include a brand, logo, or other identifier that is visible to the human eye and informs the consumer that the article is a "recycle friendly" article. Further, in some embodiments, the photoluminescent marker can be detected by an automated optical sorter during the recycling process, and thus the "recycle friendly" articles can be sorted out from other non-recycle friendly articles prior to the granulation step.

[0145] In some embodiments, the photoluminescent marker is thermally resistant, enabling it to withstand the repeated thermal exposures or thermal histories involved in recycling the article and forming new articles through extrusion and / or molding processes for multiple cycles.

[0146] In some embodiments, the photoluminescent marker can include a thermoplastic carrier and at least one inorganic fluorophore.

[0147] In some embodiments, the thermoplastic carrier can be the same as the thermoplastic resin or thermoplastic elastomer described above.

[0148] In some embodiments, the inorganic fluorophore can be selected from: lanthanide-doped silicates or aluminates, manganese-doped silicates or aluminates, up-converting inorganic nanocrystals, or lanthanide-doped nanoparticles (such as lanthanide-doped fluorides, or lanthanide-doped metal oxide nanoparticles), semiconductor quantum dots, and combinations thereof.

[0149] In some embodiments, the average particle size of the inorganic fluorophore ranges from about 5 nm to about 100 microns.

[0150] In some embodiments, the inorganic fluorophore is present in the photoluminescent marker at about 25 ppm to about 5000 ppm, based on the weight of the photoluminescent marker.

[0151] In some embodiments, the photoluminescent marker can be applied to the outer surface of the article by overmolding, mechanical interlocking, or direct printing without using an adhesive.

[0152] Additional component

[0153] In some embodiments, the article may further comprise additional components that include additional thermoplastic material, where the additional thermoplastic material (a) is the same as the rigid thermoplastic material, or (b) is the same as the recycled thermoplastic elastomeric material, or (c) is different from each of the rigid thermoplastic material and the recycled thermoplastic elastomeric material.

[0154] In some embodiments, at least a portion of the additional components may be fixed to at least a portion of the overmolded component, or at least a portion of the substrate component, or both.

[0155] In some embodiments, the additional components may include a separation additive that is the same as or different from the separation additive included in the rigid thermoplastic material.

[0156] Referring now Figures 3 - 5 , article 300 that includes substrate component 302 and overmolded component 304 may further comprise additional component 306. Substrate component 302 includes a rigid thermoplastic material. Overmolded component 304 includes a recycled thermoplastic elastomeric material. Additional component 306 includes additional thermoplastic material. Additional component 306 may be fixed to overmolded component 304, as shown in Figure 3 ; fixed to substrate component 302, as shown in Figure 4 ; or fixed to both substrate component 302 and overmolded component 304, as shown in Figure 5 . Non-limiting examples of methods of fixing component 306 may include: overmolding, gluing, and mechanical fastening.

[0157] Protective cover for electronic device, and its system

[0158] In some embodiments, the articles described herein may be protective cases or covers for electronic devices, where the electronic devices are capable of sending and / or receiving wireless communication signals having frequencies between about 1 GHz and about 50 GHz.

[0159] Non-limiting examples of such electronic devices include: mobile phones, smart phones, tablet computers, computers, and other devices connected via 5G broadband cellular networks.

[0160] In some embodiments, a lower dielectric constant may be preferred for high-quality communication applications. In these embodiments, the rigid thermoplastic material of the protective housing or cover may include a separation additive, where the separation additive is a magnetic separation additive, and where the magnetic separation additive is ferromagnetic stainless steel, magnetite, or a combination thereof. As exemplified in the Examples section, ferromagnetic stainless steel or magnetite may have a relatively low dielectric constant compared to other magnetic separation additives.

[0161] In some embodiments, a system includes an electronic device and a protective housing or cover, the electronic device being capable of transmitting and / or receiving wireless communication signals having frequencies between about 1 GHz and about 50 GHz, the protective housing or cover including the article as described herein. In these embodiments, the protective housing or cover encapsulates at least a portion of the electronic device and substantially does not interfere with the electronic device's transmission and / or reception of wireless communication signals.

[0162] Examples

[0163] Non-limiting examples of the various embodiments of the disclosed invention are provided.

[0164] Table 1 shows the ingredients used to form Comparative Examples C1 to C4 and Examples E1 to E15.

[0165] Table 1

[0166]

[0167]

[0168] Table 2 below shows Comparative Example C1 and Examples E1 to E3, which are regrinds of precursor articles that include a VERSAFLEX CE 3120-65 (i.e., a thermoplastic elastomer) component and a MAKROLON 2407 (i.e., a rigid thermoplastic) component, where the POLYMAG loading is different in either the VERSAFLEX CE 3120-65 component or the MAKROLON 2407 component, as shown in Table 2. The precursor articles of Comparative Example C1 and Examples E1-E3 are in the form of flat plates that are 100 mm x 100 mm x 3.2 mm. The VERSAFLEX CE 3120-65 component is co-extruded as a 1.6 mm thick layer onto one side of a previously formed 1.6 mm thick MAKROLON 2407 component such that the VERSAFLEX CE 3120-65 component completely covers the coated side of the MAKROLON 2407 component. In each of the precursor articles of Comparative Example C1 and Examples E1 to E3, the weight ratio of the VERSAFLEX CE 3120-65 component to the MAKROLON 2407 component is 48:52. The regrinds are produced by grinding the sheets of each precursor article into smaller particles having a transverse dimension between 0.5 mm and 5 mm, and collecting the smaller particles using a perforated metal screen in a grinder, where the diameter of the perforations is 5 mm.

[0169] Table 2

[0170]

[0171] Back to Figure 2 , a pilot scale magnetic pulley separator 200 (having a 20″ wide belt conveyor 202 and a POLYMAG magnetic roll 204) is used to separate the regrinds of Comparative Example C1 and Examples E1-E3. The roll 204 consists of a neodymium boron iron permanent magnet disk sandwiching steel pole pieces. The steel pole pieces are magnetized to a saturation point of approximately 24,000 gauss. The thickness of the belt 202 is about 0.25 mm. The separator 200 is provided with a diverter 206 and two collection bins 208, 210. Collection bin 208 primarily collects the regrind without POLYMAG, while collection bin 210 primarily collects the regrind with POLYMAG. The diverter position is adjustable and is set to achieve a high purity of the fraction rich in VERSAFLEX CE 3120-65. The feed rate is 300 lb / hr / foot of belt width. The belt speed is 160 feet per minute (ft / min). The samples are run in a one-pass test, and the results are shown in Table 3.

[0172] As used herein, the term "purity of the fraction rich in VERSAFLEX CE 3120-65" refers to the weight percentage of net VERSAFLEX CE 3120-65 in the fraction rich in VERSAFLEX CE 3120-65.

[0173] As used herein, the term "purity of the fraction rich in MAKROLON 2407" refers to the weight percentage of net MAKROLON 2407 in the fraction rich in MAKROLON 2407.

[0174] After separating each regrind, the recovery rate of net VERSAFLEX CE 3120-65 (i.e., the thermoplastic elastomer, denoted as VERSAFLEX in the equation) was calculated using the following equation and is listed in Table 3 in weight %. As described above, in Comparative Example C1 and Examples E1-E3, the VERSAFLEX CE 2130-65 component accounted for 48 wt% of the total weight of the regrind, which is why the total weight of the regrind was multiplied by 0.48.

[0175]

[0176] After separating each regrind, the recovery rate of net MAKROLON 2407 (i.e., the rigid thermoplastic, denoted as MAKROLON in the equation) was calculated using the following equation and is listed in Table 3 in weight %. As described above, in Comparative Example C1 and Examples E1-E3, the MAKROLON 2407 component accounted for 52 wt% of the total weight of the regrind, which is why the total weight of the regrind was multiplied by 0.52.

[0177]

[0178] Table 3

[0179]

[0180] As shown in Table 3, compared with Comparative Example C1 (regrind of a prior article in which POLYMAG is 0.5 wt% in the VERSAFLEX CE 3120-65 component), Examples E1 to E3 (regrinds of prior articles in which POLYMAG is 1.0 wt%, 0.5 wt%, and 0.2 wt% respectively in the MAKROLON 2407 component) resulted in significantly higher purity of the VERSAFLEX CE 3120-65-rich fraction. In addition, for the closed-loop recycling process, the net VERSAFLEX 3120-65 recovery rates for Examples E1 to E3 were acceptable (i.e., greater than 50%). As illustrated in Table 3, including the separation additive in the rigid thermoplastic material resulted in higher purity and acceptable recovery rates for the closed-loop recycling process compared to including the separation additive in the thermoplastic elastomer material.

[0181] Also as shown in Table 3, Examples E1 to E3 obtained purities of the VERSAFLEX CE 3120-65-rich fraction of 100%, 99%, and 97% respectively. The purity of the VERSAFLEX CE 3120-65-rich fraction of Example 1 was slightly higher than that of Example E2, and Example E2 was slightly higher than Example E3. Without wishing to be bound by theory, it is believed that a higher loading level of the magnetic separation additive in the polycarbonate component (i.e., the rigid thermoplastic component) results in higher purity of the thermoplastic elastomer-rich fraction substantially free of the magnetic separation additive.

[0182] Now referring to Table 4, Examples E2 and E3 were run through a three-pass test, the results of which are shown in Table 4. During the three-pass test, the VERSAFLEX CE 3120-65 (i.e., thermoplastic elastomer)-rich fraction obtained from the first pass was run through the magnetic separator for the second pass, and the VERSAFLEX CE 3120-65-rich fraction obtained from the second pass was run through the magnetic separator for the third pass. For the second and third passes, the feed rate was reduced to 177 pounds per hour per foot (lb / hr / foot) of belt, while the first pass still used a rate of 300 lb / hr / foot.

[0183] Table 4

[0184]

[0185] As shown in Table 4, there was a small improvement in the purity of the VERSAFLEX CE 3120-65-rich fraction from the first pass to the second and / or third passes.

[0186] Closed-loop recycling process of particulate-mimicking thermoplastic elastomers (collected from pre-coated articles, the pre-coated articles comprising a coating component based on VERSAFLEX CE3120-65 and a substrate component based on MAKROLON 2407), mixing and compounding the compositions of Comparative Example C3 and Examples E4 to E7 as shown in Table 5 using a twin-screw extruder, and then molding into 3.2 mm thick flat plates. Comparative Example C2 was directly molded into 3.2 mm thick flat plates. Subsequently, the flat plates of each example were die punched into standard ASTM D412 Type C tensile splines for tensile testing. The tensile strength at break of Comparative Examples C2 and C3 and Examples E4 to E7 was measured according to ASTM D412, as shown in Table 5. Note that the compositions in Table 5 are expressed in weight %, i.e., the weight percentage of each component relative to the total weight of each composition. VERSAFLEX CE 3120-65 regrind 1 and regrind 2 were intended to mimic VERSAFLEX-rich fractions with high purity of net VERSAFLEX CE3120-65 (99% and 97% respectively) collected from a magnetic separation process, as described above.

[0187] Table 5

[0188]

[0189] Table 5 (continued)

[0190]

[0191]

[0192] As shown in Table 5, compared with Comparative Example C3 [a plastic-coated component prepared without VERSAFLEX CE 3120-65 regrind in the compounding and molding processes], the tensile strength of Examples E4 to E6 [plastic-coated components made using VERSAFLEX CE 2120-65 regrind 1 or regrind 2 (containing 1 wt% or 3 wt% of MAKROLON 2407 contaminants, based on the total amount of each regrind)] was lower. Without wishing to be bound by theory, the higher contaminant levels in Examples E4 and E5 resulted in a tensile strength even lower than that of Example E6. However, compared with Example E5 (including the same weight percentage of VERSAFLEX CE 3120-65 regrind 2 as Example E7 but not including JONCRYL ADR 4400), the tensile strength of Example E7 (including 0.4 wt% of JONCRYL ADR 4400 used in the compounding step of the closed-loop recycling process) was improved. As shown in Table 5, including a polymeric chain extender with epoxy functionality in the compounding step of a plastic-coated component (which contains thermoplastic polyurethane) that has been recycled in a closed loop improved the tensile strength of the recycled plastic-coated component.

[0193] Referring now to Table 6, the dielectric constants of Comparative Example C4 and Examples E8 to E15 (which are substrate components (i.e., non-plastic-coated components) containing MAKROLON 2407 with different loadings of POLYMAG, MICROMAG5, or BAYFERROX 318M, as shown in Table 6) at 40 GHz are shown.

[0194] Table 6

[0195]

[0196]

[0197] As shown in Table 6, when up to 0.5 wt% of POLYMAG (i.e., ferromagnetic stainless steel powder) or MICROMAG 5 (i.e., magnetite powder) was added, the change in the dielectric constant of MAKROLON 2407 was less than 0.3%. At the same loading levels as POLYMAG and MICROMAG 5, BAYFERROX 318M (i.e., synthetic iron oxide) resulted in a higher dielectric constant increment. As shown in Table 7, ferromagnetic stainless steel and magnetite may be preferred as magnetic separation additives for such applications.

[0198] Unless otherwise indicated, each document cited herein is incorporated herein by reference in its entirety. The citation of any document is not to be construed as an admission that it is prior art with respect to any invention disclosed or claimed herein. When any meaning or definition of a term in this utility model conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition given to that term in this utility model shall prevail.

[0199] Obviously, modifications and variations can be made without departing from the scope of the disclosure defined in the appended claims. While some aspects of this disclosure are identified herein as preferred or particularly advantageous, it is contemplated that the disclosure is not necessarily limited to these aspects.

Claims

1. An article, the article comprising: (a) a substrate component, the substrate component comprising a rigid thermoplastic material; and (b) a coextruded component, the coextruded component comprising a recycled thermoplastic elastomer material; wherein the recycled thermoplastic elastomer material comprises: (i) greater than or equal to about 97 wt% of a precursor thermoplastic elastomer material, based on the weight of the recycled thermoplastic elastomer material; and (ii) less than or equal to about 3 wt% of a precursor rigid thermoplastic material, based on the weight of the recycled thermoplastic elastomer material.

2. The article according to claim 1, wherein the recycled thermoplastic elastomer material comprises: (i) greater than or equal to about 99 wt% of the precursor thermoplastic elastomer material, based on the weight of the recycled thermoplastic elastomer material; (ii) less than or equal to about 1 wt% of the precursor rigid thermoplastic material, based on the weight of the recycled thermoplastic elastomer material.

3. The article according to any one of the preceding claims, wherein the recycled thermoplastic elastomer material is substantially free of virgin thermoplastic elastomer and is obtained from a precursor separation process, wherein at least a portion of the precursor thermoplastic elastomer material is separated from the precursor rigid thermoplastic material to provide the recycled thermoplastic elastomer material.

4. The article according to claim 3, wherein the recycled thermoplastic elastomer material comprises regrind of a precursor article or precursor waste material from a precursor process used to manufacture or recycle the precursor article, wherein the precursor article or the precursor waste material comprises a precursor thermoplastic elastomer material coextruded onto the precursor rigid thermoplastic material, and wherein the regrind of the precursor article or the precursor waste material is subjected to the precursor separation process, wherein at least a portion of the precursor thermoplastic elastomer material is separated from the precursor rigid thermoplastic material to provide the recycled thermoplastic elastomer material.

5. The article according to any one of the preceding claims, wherein the rigid thermoplastic material comprises a separation additive, and wherein the separation additive is present in an amount of about 0.05 wt% to about 10 wt%, based on the weight of the rigid thermoplastic material.

6. The article as claimed in claim 5, wherein the separating additive is a magnetic separation additive, and the amount of the magnetic separation additive is about 0.05% to about 1.0% by weight, based on the weight of the rigid thermoplastic material; and the magnetic separation additive is selected from: iron, ferromagnetic steel alloy, ferromagnetic stainless steel alloy, synthetic iron oxide with the chemical formula Fe3O4, magnetite, ferrite, strontium ferrite, neodymium mixed oxide, alnico magnetic steel alloy, samarium-cobalt alloy, neodymium alloy, and combinations thereof.

7. The article as claimed in claim 6, wherein the recycled thermoplastic elastomer material or the overmolded component contains less than about 0.03% by weight of the magnetic separation additive, based on the weight of the recycled thermoplastic elastomer material or the overmolded component; or the recycled thermoplastic elastomer material or the overmolded component is substantially free of the magnetic separation additive.

8. The article as claimed in claim 5, wherein the separating additive is a density separation additive, and the amount of the density separation additive is about 5% to about 10% by weight, based on the weight of the rigid thermoplastic material, and the density separation additive is selected from: tungsten, tungsten oxide, barium sulfate, copper, ferromagnetic stainless steel, cerium oxide, and combinations thereof.

9. The article as claimed in any one of the preceding claims, wherein the overmolded component is formed of: greater than or equal to about 50% by weight, or greater than or equal to about 75% by weight of the recycled thermoplastic elastomer material, based on the weight of the overmolded component.

10. The article as claimed in any one of the preceding claims, wherein at least a part of the overmolded component is fixed to at least a part of the substrate component by interfacial adhesion.

11. The article as claimed in any one of the preceding claims, wherein: (a) The rigid thermoplastic material comprises: (i) a thermoplastic resin selected from: polycarbonate, thermoplastic polyester, polyamide, aliphatic polyketone, acrylonitrile-butadiene-styrene, polypropylene, and combinations thereof; and (ii) a separation additive; and (iii) optional other additives; and (b) The recycled thermoplastic elastomer material comprises: (i) a thermoplastic elastomer selected from thermoplastic polyurethane (TPU) and styrenic block copolymers (SBC), and wherein the styrenic block copolymers (SBC) are selected from: styrene-ethylene / butylene-styrene (SEBS) block copolymer, styrene-ethylene / propylene-styrene (SEPS), styrene-ethylene / ethylene / propylene-styrene (SEEPS), styrene-isobutylene-styrene (SIBS), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), and combinations thereof; (ii) optional polymeric chain extenders; and (iii) optional other additives; wherein the optional other additives in the rigid thermoplastic material and / or the recycled thermoplastic elastomer material are independently selected from one or more of the following: adhesion promoter; antioxidant; biocide; antifogging agent; antistatic agent; binder; dispersant; filler; flame retardant and smoke inhibitor; impact modifier; initiator; lubricant; mica; colorant (pigment and / or dye); plasticizer; processing aid; mold release agent; silane, titanate / ester and zirconate / ester; slip agent and anti-blocking agent; stearate / ester; ultraviolet light absorber; viscosity modifier; and wax.

12. The article according to claim 11, wherein the thermoplastic elastomer is selected from thermoplastic polyurethanes, and the overmolded component further comprises a polymeric chain extender, wherein the polymeric chain extender is selected from functionalized styrene-acrylic copolymers having epoxy groups, and wherein there is about 0.2% to about 2.0% by weight of the polymeric chain extender, based on the weight of the overmolded component.

13. The article according to any one of the preceding claims, wherein the rigid thermoplastic material comprises virgin thermoplastic resin, recycled thermoplastic resin, or a combination thereof.

14. The article according to any one of the preceding claims, wherein the article further comprises a photoluminescent marker.

15. The article according to claim 14, wherein the photoluminescent marker is fixed to the outer surface of the article.

16. The article according to claim 14, wherein the photoluminescent marker is incorporated into the rigid thermoplastic material used to form the base component, or into the recycled thermoplastic elastomer material used to form the overmolded component, or into both.

17. The article according to any one of claims 14 to 16, wherein the photoluminescent marker comprises at least one inorganic fluorophore selected from the group consisting of: lanthanide-doped silicates or aluminates; manganese-doped silicates or aluminates; lanthanide-doped nanoparticles; semiconductor quantum dots; and combinations thereof.

18. The article according to any one of the preceding claims, wherein the article is a protective chassis or cover for an electronic device, and the electronic device is capable of transmitting and / or receiving wireless communication signals having a frequency between about 1 GHz and about 50 GHz.

19. The article according to claim 15, wherein the rigid thermoplastic material comprises a separation additive, the separation additive is a magnetic separation additive, and the magnetic separation additive is ferromagnetic stainless steel, magnetite, or a combination thereof.

20. A system, the system comprising: (a) an electronic device capable of transmitting and / or receiving wireless communication signals having a frequency between about 1 GHz and about 50 GHz; and (b) a protective cover comprising the article according to any one of the preceding claims; wherein the protective cover encapsulates at least a portion of the electronic device and substantially does not interfere with the electronic device transmitting and / or receiving the wireless communication signals.

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