Patent Description:
Wearable devices are available in a variety of shapes and include components, for example, gaskets, seals, and ear tips that are made of soft materials, such as rubber. Components that made of rubber are vulnerable to dimensional changes (swelling) causing delamination or complete dissolution due to exposure to sebum (human skin oils). Some methods for improving resistance to sebum involve increasing the crosslink density in thermoset/vulcanized rubbers. However, increasing the crosslink density changes the bulk properties, such as hardness, tensile strength, elongation, etc. of the rubber. Moreover, increasing the crosslink density may not be suitable for wearable devices where comfort, softness, and elasticity are important. Other methods include adding protective coatings to the surface of rubbers. However, these coatings are deposited using expensive equipment, are time intensive operations, and may wear or abrade over time, rendering them ineffective.

Accordingly, there is a need in the art for inexpensive, efficient, and effective methods for treating surfaces of wearable devices for improved resistance to sebum.

<CIT>, <CIT>, <CIT>, <NPL>, and <NPL> all belong to the general state of the art, but are of limited or no relevance at all to the present invention.

The present invention relates to a method of treating a surface of a wearable device according to claim <NUM>, as well as to a wearable device having a surface treated to resist sebum according to claim <NUM>. Advantageous embodiments are set forth in the dependent claims <NUM> to <NUM>.

Wearable devices commonly employ soft materials (e.g., rubber). However, such soft materials tend to have an affinity to sebum, which leads to dimensional changes or complete dissolution. Such soft materials also tend to have a high surface tack, which leads to dust collection and prevents proper placement or presents difficulty in donning certain wearable devices. For some wearable devices, dust collection can also compromise an acoustic seal. The surface treatments described herein extend the long-term wearability of wearable devices by improving sebum resistance. The surface treatments described herein may also reduce tackiness and surface contaminants. The surface treatments simultaneously may reduce surface glare for improved appearance.

This disclosure is based, at least in part, on the realization that sebum is harmful to soft materials and that treating the surfaces of these materials can provide improved sebum resistance. Sebum is a waxy or oily substance that is excreted from sebaceous glands on the body. Chemically, sebum includes a mixture of long aliphatic chains with a polar aprotic end. Natural and synthetic rubbers have an affinity to sebum, leading to dimensional change (swelling) or complete dissolution of the polymer. Polymeric materials can be rendered oleophobic for improved sebum resistance, for example, by oxidation, to generate highly polar hydroxyl, carboxylic acid, ketone, and/or aldehyde functional groups, which resist sebum, on the polymeric backbone. In embodiments, at least a portion of an outer surface of a body made of an elastic polymeric material can be oxidized to generate a functional group which may be selected from a group consisting of a hydroxyl diol, a carboxylic acid, a ketone, or an aldehyde.

The embodiments and implementations disclosed or otherwise envisioned herein can be utilized with any suitable wearable device made of an elastic material, such as rubber, that has already been cured and/or shaped. Examples of suitable wearable devices include Bose QuietControl® headphones (manufactured by Bose Corporation of Framingham, Massachusetts), noise-blocking earplugs, and hearing aids. However, the disclosure is not limited to these enumerated devices, and thus the disclosure and embodiments disclosed herein can encompass any wearable device.

Referring to <FIG>, an example wearable device <NUM>, e.g., a Bose StayHear®+ tip (manufactured by Bose Corporation of Framingham, Massachusetts) is shown. The wearable device <NUM> in <FIG>, including a tip base <NUM> and a tip wing <NUM>, is commonly made of rubber. Depending on the nature of the rubber used, the tip may exhibit an affinity to sebum. As a result, wearable device <NUM> may exhibit a decrease in mechanical strength after prolonged exposure to sebum. In addition, due to the high tackiness of rubber, the wearable device <NUM> may attract dirt, which can compromise its acoustic seal and damage tissues of the wearer. Although wearable device <NUM> can be made of any suitable soft material, one suitable material is compounded polynorbornene (Norsorex® material available from D-NOV GmbH of Vienna, Austria, product number M040822-<NUM>). Polynorbornene is a hydrocarbon-based material containing carbon-carbon double bonds in the polymer backbone (unsaturation) as follows:
<CHM>.

Polynorbornene exhibits high performance in acoustic, passive attenuation, and comfort metrics and a high glass transition temperature which provides good damping properties and pseudo-custom fit properties. The "unsaturation" refers to the presence of at least one carbon-carbon double bond or carbon-carbon triple bond. Materials suitable for the surface chemistries described herein include any polymeric material containing some amount of unsaturation. The unsaturation may be present as a consequence of the material's formation, or the unsaturation may be introduced by any suitable process.

The methods described herein focus on surface chemistries occurring on the outer sub-micron level of the material so that bulk properties are not impacted. The surface chemistries are analyzed using Fourier-transform infrared spectrophotometry (FT-IR) and x-ray photoelectron spectroscopy (XPS). Through surface oxidation using the methods described herein, drastic improvements in sebum resistance are observed. For example, the IR-spectrum at the top of <FIG> shows the unsaturation of the Norsorex® material including intense absorption bands at ~<NUM>-<NUM> which indicate a number of carbon-carbon double bonds in the backbone. The out-of-plane bending of carbon-carbon double bonds of alkenes typically shows strong signals within the range of <NUM>-<NUM>-<NUM>. Silverstein, R. and Webster, F. Spectrometric Identification of Organic Compounds, <NUM>th Edition, John Whiley & Son <NUM>. XPS analysis of neat (untreated) Norsorex® material reveals <NUM>% of the material is composed of aliphatic hydrogen-carbon bonds (~285eV) and <NUM>% of the material is composed of C=O bonds (<NUM>.

The IR-spectrum at the bottom of <FIG> on the other hand represents the Norsorex® material after <NUM> minutes (front and back) of ultraviolet/ozone (UV/O) treatment (further discussed below). The reduced intensity of absorption bands at ~<NUM>-<NUM> corresponds to the conversion of the carbon-carbon double bonds and the new bands that emerge in the spectrum at ~<NUM>-<NUM> and ~<NUM>-<NUM> correspond to the oscillations of carbonyl and alcohol groups introduced into the polymer due to the UV/O treatment. The broad signals of hydroxyl groups of alcohols are typically between <NUM>-<NUM>-<NUM>, the signals of carbon-oxygen bonds of ketones are typically between <NUM>-<NUM>-<NUM>, and the signals of carbon-oxygen bonds of aldehydes and carboxylic acids are typically between <NUM>-<NUM>-<NUM> and at ~<NUM>-<NUM>, respectively. Silverstein, R. and Webster, F. Spectrometric Identification of Organic Compounds, <NUM>th Edition, John Whiley & Son <NUM>. As shown in <FIG>, UV/O treatment alters the surface chemistry of the Norsorex® material such that hydroxyl and carbonyl functional groups are incorporated on the backbone of the polymer. XPS analysis of the Norsorex® material treated with UV/O reveals <NUM>% of the material is composed of aliphatic hydrogen-carbon bonds (versus <NUM>% for the untreated Norsorex® material) and <NUM>% of the material is composed of C=O bonds (versus <NUM>% for the untreated Norsorex® material). In addition, XPS analysis of the Norsorex® material treated with UV/O reveals <NUM>% of the material consists of hydroxyl groups (-OH) (~<NUM>. 4eV), whereas the untreated Norsorex® material contained no hydroxyl groups. The treated modified surface exhibits an improved resistance to sebum, a reduced tackiness, and a reduced surface glare (or specular reflectance) as a result of the treatment.

The UV/O treatment, which creates the surface oxidation, can be conducted in any suitable gas chamber including oxygen, for example, a customized chamber which can be manufactured by Jelight Company, Inc. of Irvine, Ca. A schematic representation of an example UV/O chamber is shown in <FIG>. The UV/O chamber <NUM> includes a top UV lamp station <NUM> and a bottom UV lamp station <NUM>. Each lamp within each UV lamp station emits multiple wavelengths. The UV/O chamber <NUM> can be filled with atmospheric air or oxygen. Each of the top and bottom UV lamp stations <NUM> and <NUM> can include multiple UV lights. For example, the atmospheric oxygen in the chamber <NUM> can be irradiated with UV rays having a wavelength of <NUM> to form ozone (O<NUM>). Ozone decomposes through irradiation with UV rays having a wavelength of <NUM>. Atomic oxygen is generated during these processes. The UV/O chamber <NUM> can also include a fan or air pump to move the oxygen through the chamber. Although the embodiments and implementations disclosed or otherwise envisioned herein include UV lamps, any suitable source of light may be employed, such as, mercury lights, electric arcs, sunlight, lasers tuned to a suitable wavelength, flash tubes, etc., instead.

Although commercially available UV/O chambers have lamps only on the top (for example, to clean silicon wafers), in contrast, one or more wearable devices <NUM> can be arranged between the top and bottom UV lamp stations <NUM> and <NUM> of the UV/O chamber <NUM> as shown in <FIG>. The one or more wearable devices can be placed on top of a support member <NUM> arranged between the top and bottom UV lamp stations <NUM> and <NUM>. The support member <NUM> can be made of any suitable synthetic material that is transparent to UV or any other suitable alternative. The transparent support member <NUM> allows the UV rays from the lamps to reach <NUM> degrees around each wearable device <NUM>, reducing cycle time and labor in a production environment. Although <FIG> depicts each wearable device held in place without any additional components, such additional components, for example, pins, or any suitable alternative can be included in alternate embodiments. The wearable devices are arranged at a distance of less than <NUM> from the top and bottom UV lamp stations <NUM> and <NUM>, preferably less than <NUM>, and preferably at a distance between <NUM>-<NUM>. The wearable devices can be arranged along a plane that is equidistant between the top and bottom UV lamp stations <NUM> and <NUM>.

To achieve an improved resistance to sebum and/or a reduced tackiness, the wearable devices are exposed to the UV/O treatment for at least <NUM> minutes, and preferably at least <NUM>-<NUM> minutes at ambient temperature. Prolonged treating time and elevated temperature show increased surface chemistry change. Effective surface oxidation using the UV/O treatment is observed at <NUM> degrees Celsius, and even further surface oxidation is observed at <NUM> degrees Celsius. There is minimal impact on the surface chemistry from using different oxygen flow rates.

While the surface oxidation can be achieved using UV/O treatment without any solutions, the surface oxidation can also be achieved using a suitable solution of potassium permanganate and sodium hydroxide (KMnO<NUM>/NaOH), a sulfuric acid, or any other suitable oxidizing agent. Like the UV/O treatment, potassium permanganate surface treatment leads to improvements in mechanical properties after sebum exposure. For example, wearable devices <NUM> that are exposed to only one minute of potassium permanganate surface treatment and three days of sebum exposure thereafter show significant degradation. However, increasing the duration of potassium permanganate treatment from one minute to five minutes yields less degradation of the wearable devices <NUM> after the three days of sebum exposure. Increasing the duration of potassium permanganate treatment from five to ten minutes yields even less degradation after the three days of sebum exposure. The potassium permanganate surface treatment can involve immersing the wearable devices <NUM> in a high temperature potassium permanganate bath, preferably around <NUM> degrees Celsius. The three day sebum exposure can involve immersing the wearable devices <NUM> in a sebum bath for three days at <NUM> degrees Celsius. Critically, the wearable devices <NUM> having five minutes of potassium permanganate surface treatment can withstand the three days of sebum exposure and the devices having at least ten minutes of potassium permanganate surface treatment, preferably at least fifteen minutes of potassium permanganate surface treatment, and, more preferably at least thirty minutes of potassium permanganate surface treatment, can withstand at least five days of the sebum exposure.

Similarly, exposing the wearable devices <NUM> to potassium permanganate treatment at room temperature for one hour leads to improved mechanical properties post sebum testing. <FIG> shows a graph of the effect of potassium permanganate surface treatment on tear strength of example wearable devices <NUM>. The tear strength represents the ability of a material to resist tearing. Tear strength for rubber can be quantified by measuring the force required to tear a <NUM> thick specimen under the conditions outlined in ASTM D-<NUM>. Suitable testing systems are available from Instron® of Norwood, Massachusetts. The wearable devices <NUM> that are treated with potassium permanganate at room temperature for one hour and having no sebum exposure have the highest tear strength. In contrast, untreated wearable devices dissolve after one day of sebum exposure. However, the wearable devices <NUM> that are treated with potassium permanganate at room temperature for one hour still have an acceptable tear strength for the application, albeit a reduced tear strength, after one day of sebum exposure. Thus, the potassium permanganate treatment prevents the wearable devices from dissolving due to sebum exposure, thereby improving the mechanical properties. XPS analysis of the Norsorex® material treated with potassium permanganate and sodium hydroxide reveals <NUM>% of the material is composed of aliphatic hydrogen-carbon bonds (versus <NUM>% for the neat Norsorex® material) and <NUM>% of the material is composed of C=O bonds (versus <NUM>% for the neat Norsorex® material). In addition, XPS analysis of the Norsorex® material treated with potassium permanganate and sodium hydroxide reveals <NUM>% of the material consists of hydroxyl groups (-OH), whereas the untreated Norsorex® material contained no hydroxyl groups.

Exposing the wearable devices <NUM> to sulfuric acid treatment also leads to improved mechanical properties. The IR-spectrum at the top of <FIG> represents the untreated (neat) Norsorex® material. The IR-spectrum in the middle of <FIG> represents the Norsorex® material after <NUM> minutes of surface treatment with <NUM>% concentrated sulfuric acid and a post water boiling process. The increased intensity of the broad absorption bands between <NUM>-<NUM>-<NUM> indicates the incorporation of hydroxyl groups. The IR-spectrum at the bottom of <FIG> represents the Norsorex® material after <NUM> minutes of surface treatment with <NUM>% concentrated sulfuric acid and a post water boiling process. Similarly, there is an increased intensity of broad absorption bands between <NUM>-<NUM>-<NUM>. It is believed that the concentrated sulfuric acid breaks up the carbon-carbon double bonds and the post water boiling process converts the previously added sulfonate group into a hydroxyl group. As a result of the added hydroxyl group, the treated surface exhibits a 3x improvement in sebum resistance.

The following examples are provided as further illustrations and are not to be construed as limiting inasmuch as variations and modifications within the scope of the present disclosure will be readily apparent.

The UV/O surface treatment described herein is also effective on styrene-butadiene polymers (SB, SBS). For example, neat styrene-butadiene polymers (SB, SBS) dissolve in sebum after a few hours. However, SBS with UV/O treatment becomes soft after <NUM> day of sebum exposure but can maintain some mechanical strength. <FIG> shows absorbance spectra for neat SBS, SBS treated with UV/O, and SBS treated with KMnO<NUM>/NaOH. The IR-spectrum in the middle of <FIG> shows increased intensity of absorption bands at ~<NUM>-<NUM> and ~<NUM>-<NUM> indicating the incorporation of hydroxyl and carbonyl functional groups due to the UV/O treatment. In contrast, the IR-spectrum at the top of <FIG> showing the neat SBS lacks these absorption bands. The IR-spectrum in the middle also shows a reduced intensity of absorption bands at ~<NUM>-<NUM> corresponding to a decrease in the C=C double bonds. These same changes are not visible in the IR-spectrum at the bottom of <FIG> showing the SBS treated with KMnO<NUM>/NaOH.

Both UV/O and KMnO<NUM>/NaOH surface treatments described herein are also effective on a styrenic-based thermoplastic elastomer (TPE) available from PolyOne of Avon Lake, Ohio, product number <NUM>-047A9. The PolyOne® TPE has at least some unsaturation, preferably at least <NUM>% unsaturation. <FIG> shows absorbance spectra for the styrenic-based thermoplastic elastomer, neat, with UV/O treatment, and with KMnO<NUM>/NaOH treatment. While neat styrenic-based thermoplastic elastomer becomes very soft and breaks easily after <NUM> days in sebum, samples that are treated with UV/O and KMnO<NUM>/NaOH do not become very soft or break easily until <NUM>-<NUM> days in sebum. In addition, the styrenic-based thermoplastic elastomer devices treated with UV/O and KMnO<NUM>/NaOH show a reduced amount of sebum uptake. As shown in <FIG>, the bottom two IR-spectra show increased intensity of absorption bands at ~<NUM>-<NUM> indicating the incorporation of C=O functional groups. In addition, the bottom two IR-spectra show a reduced intensity of absorption bands at ~<NUM>-<NUM> corresponding to a decrease in the C=C double bonds.

<FIG> is a flowchart of an example method of treating a surface of a wearable device to resist sebum. At step <NUM>, a wearable device is provided, the wearable device having a body made of an elastic polymeric material, wherein a portion of the elastic polymeric backbone is unsaturated. The wearable device can be any device described or otherwise envisioned herein. For example, implementations of the body may include vulcanized polynorbornene, styrene-butadiene polymers, and styrenic-based thermoplastic elastomers.

At step <NUM>, at least one part of an outer surface of the body is oxidized such that the at least one part is more oleophobic than the body. The surface oxidation may generate one or more functional groups on the elastic polymeric backbone such as hydroxyls, carboxylic acids, ketones, and/or aldehydes.

Claim 1:
A method of treating a surface of a wearable device (<NUM>) to resist sebum so as to improve wearability of the wearable device by preventing potential degradation due to prolonged sebum exposure, the method comprising:
providing a body comprising an elastic material having a polymeric backbone, wherein a portion of the polymeric backbone is unsaturated, said material including one of: vulcanized polynorbornene, a styrene-butadiene polymer, or a styrenic-based thermoplastic elastomer, the body having an outer surface; and
oxidizing at least one part of the outer surface to incorporate at least one functional group on the polymeric backbone, the functional group consisting of a hydroxyl diol, a carboxylic acid, a ketone, and/or an aldehyde.