A functional package for an adhesive

Abstract

Disclosed herein is a package suitable for the storage and transportation of an adhesive (e.g., an enhanced sensation condom), which in certain embodiments permits ease of application of an enhanced sensation condom (ESC) by a user for use in sexual intercourse and / or removal of the package following application of the adhesive. Also disclosed is a packaged adhesive, as well as methods of using and manufacturing the package and packaged adhesive.

Description

A FUNCTIONAL PACKAGE FOR AN ADHESIVE TECHNICAL FIELD

[0001] Disclosed herein is a package suitable for the storage and transportation of an adhesive, which in certain embodiments permits ease of application of an enhanced sensation condom (ESC) by a user for use in sexual intercourse. Also disclosed is a packaged adhesive, as well as methods of using and manufacturing the package and packaged adhesive. CROSS-REFERENCE TO RELATED APPLICATION

[0002] This application claims priority to United States Provisional Patent Application No.63 / 512,802 filed on July 10, 2023 and entitled “A Functional Package for an Adhesive”, the content of which is hereby incorporated by reference. BACKGROUND

[0003] Adhesives have a variety of personal care and medical uses including tissue-tissue and tissue-medical device (e.g., catheter) bonding. They can also be used to promote healing, including by preventing egress of undesirable materials (e.g., bacteria, fluids) or absorbing fluids, or in some cases, by delivering one or more therapeutic agents.

[0004] There remains a need in the art for packaging that is suitable for transport and storage of such adhesives, as well as for application of the same. SUMMARY

[0005] Disclosed herein is a package suitable for protecting and optionally, applying (i.e., aligning, depositing) an adhesive (e.g., an enhanced sensation condom condom), as well as a packaged adhesive. Also disclosed are methods for manufacturing and using the package. Advantageously, the package and packaged adhesive disclosed herein provide one or more improvements over those known in the art, e.g., ease of use, ease of application.

[0006] In one aspect, a package suitable for protecting and optionally, applying an adhesive (e.g., enhanced sensation condom) is disclosed, comprising (i) a shaped receiving body comprising a peripheral flange, wherein the shaped receiving body comprises a wall defining an exterior surface and an interior surface and wherein the inner surface optionally comprises a retaining element; and (ii) aremovable film lid comprising a pull tab or tearable enclosure, wherein the receiving body and the removable lid are secured to form a package suitable for protecting a substrate comprising a barrier layer and adhesive (e.g., condom) or an adhesive simultaneously functioning as an adhesive and barrier layer.

[0007] The shape of the shaped receiving body may vary. In one embodiment, the shaped receiving body is selected from circular, elliptical, square, rectangular, polygonal, curvilinear polygonal, hemispherical, ellipsoidal, conical, generalized conical, tetrahedral, pyramidal, polyhedral, reflexive or otherwise substantially matches the shape of the contained adhesive (e.g., an enhanced sensation condom). In a particular embodiment, the shaped receiving body is circular or conical.

[0008] The thickness of the receiving body wall may vary. In one embodiment, the receiving body has a thickness of between about 0.001” and 1”, more preferably 0.005” and 0.8”, more preferably 0.01” and 0.6”, more preferably 0.015 and 0.4 “, more preferably 0.0175 and 0.2”, more preferably 0.0185 and 0.1”, more preferable 0.190 and 0.075”, more preferably 0.195 and 0.06”, more preferably.0.020” and 0.040”.

[0009] The physical characteristics of the receiving body may vary. In one embodiment, the received body is rigid. In a particular embodiment, the rigid receiving body comprises a thermoplastic polymer. In one embodiment, the thermoplastic polymer is polyethylene terephthalate glycol (PETG), polyethylene, polypropylene, polyethylene terephthalate, high density polyethylene, low density polyethylene, poly(vinyl chloride), poly(lactic acid), poly(hydroxy alkenoates), compostable and biobased plastics or thermoformable polyurethane. In another embodiment, the receiving body comprises a composite of a high surface energy liner film such as a low-density polyethylene film or poly(lactic acid) or poly(hydroyxy alkenoate) or compostable or bio-based plastic laminated to the interior surface of a rigid plastic such as PETG. In another embodiment, the receiving body is semi-rigid. In a particular embodiment, the semi-rigid receiving body comprises a PETG, a thermoplastic elastomer, a high-density polyethylene or a low-density polyethylene or a thermoformable polyurethane. In certain embodiments, the rigid or semi-rigid behavior is achieved through utilizing different thicknesses of the sheet of material used to manufacture the receiving body, an example is PETG.

[0010] The package may contain one or more additional features to facilitate use. In one embodiment, the outer wall of the receiving body comprises one or more features to assist in aligning the adhesive to the target site, e.g., a hole or pass- through. In one embodiment, the outer wall of the receiving body comprises one or more features to assist in removing the package following application of the adhesive, e.g., a lifting tag. In certain embodiments, the bottom of the package (opposed to the removable film lid) comprises one or more features to assist with in aligning the adhesive to the target site, e.g., a hole or pass-through.

[0011] In one embodiment, the outer wall of the receiving body comprises one or more features (e.g., ridges or ripples) to facilitate use or provide desired physical properties to the package.

[0012] In one embodiment, the package comprises a shell surrounding the outer wall of the receiving body, wherein the shell comprises an outer wall and an inner wall, where at least a portion of the inner wall is in contact with the outer wall of the receiving body. The shell is attached to the receiving body by a plastic adhesive or by plastic welding. The shell may be in contact with between 0.1 and 1.0% of the surface area of the receiving body, between 1 and 10% of the receiving body, between 10 and 50% of the receiving body, between 50 and 100% of the receiving body. The shell may be the same or a different shape than the receiving body. The shell may optionally include additional features, e.g., attachment features. The shell may be rigid or semi-rigid. In certain embodiments, the shell comprises one or more features to assist in aligning the adhesive to a target site. In a particular embodiment, the shell comprises a hole. In one embodiment, the outer wall of the shell comprises one or more features to assist in removing the package following application of the adhesive, e.g., a lifting tag.

[0013] The removable film lid may be comprised of any suitable material. In one embodiment, the removable film lid comprises paper, plastic, foil aluminum, mylar, or aluminum-backed mylar.

[0014] The retaining element may vary. In one embodiment, the retaining element comprises a thin layer of fluid film.

[0015] The fluid film may be any suitable fluid film. In one embodiment, the fluid film is selected from silicone-oils or silicone-based lubricants. In another embodiment, the fluid film is selected from water-based lubricants.

[0016] In another embodiment, the retaining element is a fluid film (1) impregnated in a porous application liner which functions to stabilize the fluid film. An example of a suitable porous application liner is paper. The porous application liner may have additional tabs to aide in removal and manipulation of the condom from the package.

[0017] In another embodiment, the retaining element comprises a pressure sensitive adhesive layer.

[0018] In another embodiment, the retaining element comprises a ridge that functions as a mechanical stop on the peripheral edge of the packaged adhesive (e.g., an enhanced sensation condom) of comparable height to the thickness of the packaged adhesive (thickness of barrier layer plus adhesive layer in the case of an enhanced sensation condom). The ridge is located on the inner surface of the package and is sufficiently large so as to constrain the condom within the package by mechanically stopping the adhesive from coming out of the package under its own weight or inertia when shaken, however not so large that it impedes the application of the adhesive. For example, the ridge is of comparable height to the thickness of the condom such that during application of the condom to the glans, the glans must pass through the opening of the package and contact the adhesive, and upon removal of the package from the glans, the ridge must not be so large as to either prevent the glans skin from making contact with the adhesive or preventing the now adhered condom from separating from the package / applicator. A rule of thumb for the thickness of this lip or ridge is comparable to the thickness of the condom wall (plus adhesive), which would provide a sufficient mechanical stop to prevent the condom from falling out of the package, yet not interfere with the glans skin contacting the adhesive surface.

[0019] In a further embodiment, the retaining element comprises an inner surface that possesses inherent tack matching with the adhesive containing substrate, such as that exhibited between PETG or polycarbonate plastic and natural dip coated latex, that is sufficient to secure the adhesive containing substrate to the retainingbody during transport and use, and then allow for release of the adhesive containing substrate when the adhesive containing substrate is applied to the target surface, e.g., the glans of the penis. The strength of the inherent tack matching should be strong enough to support the weight of the adhesive containing substrate when the package is inverted (opening facing down), yet sufficiently weaker than the adhesion strength between the adhesive containing substrate and the target surface to which it is applied, enabling the user to separate the receiving body from the adhesive containing substrate in use. In an embodiment, the maximum adhesion force of the retaining means is less than the tack force exhibited between the packaged adhesive and its target surface for the intended rate of delamination range of the adhesive to its target surface. It is desirable for the tack force to be between 1% and 90% of the tack force exhibited by the adhesive contained within to its intended application face, more preferably between 5% and 50% and most preferably between 10% and 25% at the intended rate of delamination range of the adhesive to its target surface. In general, the lower limit of the adhesion force is equal to the weight of the condom, in other words, sufficient to retain the condom when the package is inverted such that gravity is acting in a quasi-static manner to separate the condom from the package. It is preferable that the minimum adhesion force be a multiple of at least 1.5, and more preferably a multiple of 5, greater than this if possible to improve the packaged condom’s ability to survive being dropped from a height of between 1 and 2.5 meters (typical use case of handling by a human), vibrated (for example between 0.5 to 10 Hz such as when shipped), accelerations of 1.5 to 10 G’s (acceleration of gravity equal to 9.81 m / s^2; such as when shipped), all over a temperature range between - 10 and 70 C (to survive conditions when shipped or stored). This natural tack mechanism may be enhanced (increased) by modifying the surface energy of the package, the exterior of the adhesive, or both. Plasma (or corona discharge) treatment is the most promising treatment to achieve a sufficient and stable tack force. Plasma surface treatment is favorable as it is industrially scalable and economically efficient, while being applicable to natural rubber latex, polyurethane, and other thermoplastic elastomer barrier materials.

[0020] In another embodiment, the retaining element is a mechanical interference fit between the package geometry and the surface of the package, thus providing a friction force preventing the adhesive from separating from the packageunder its own weight when inverted and inertial loads up to 10 g or up to 5 g or up to 2 g or up to 1 g (where g is the acceleration due to gravity, 9.81 m / s^2). The interference fit is created by displacing the surface of the package inwards by between 0.000 and 0.005 inches to provide a small compressive surface to the outer surface of the adhesive to aide in retaining the adhesive within the device via slight mechanical compression, without compressing so much as to induce a buckling or wrinkling in the device. This effect may be enhanced by certain adhesive geometries that are constructed to provide additional resistance when compressed, such as a developable-adhesive-surface condom, wherein the adhesive resides in a frustrated state carrying an internal bending moment that is pushing outwards against and held in static equilibrium by the condom barrier layer.

[0021] In another embodiment, the retaining element comprises a fluid film and a ridge.

[0022] In another embodiment, the retaining element comprises a fluid film and an interference fit.

[0023] In another embodiment, the retaining element comprises a pressure sensitive adhesive and a ridge.

[0024] In another embodiment, the retaining element comprises a pressure sensitive adhesive and an interference fit.

[0025] In another embodiment, the retaining element comprises a tack matching package material and a ridge.

[0026] In another embodiment, the retaining element comprises a tack matching package material and an interference fit. The combination of a tack matching material and interference fit is a preferable embodiment as the interference fit ensures the outer surface of the adhesive (e.g., enhanced sensation condom) remains in good contact with the package surface, thus maximizing the efficacy of the inherent tack matching effect as the primary retaining element.

[0027] In an embodiment, a packaged adhesive is provided, comprising a package disclosed herein and an adhesive (e.g., a condom) enclosed within the package.

[0028] In one embodiment, the adhesive is an enhanced sensation condom.

[0029] In one embodiment, the adhesive is a medical adhesive, e.g., for protection or closure of a wound.

[0030] In one embodiment, the adhesive is rate responsive in a range relevant for human skin removal. For example, the adhesive might exhibit a work of adhesion in J / m2 change of 30x as retraction rate on a rheometer tack test under testing conditions described in the present invention is changed from 1 micrometer per second to 8000 micrometers per second. Rate responsive behavior could exhibit work of adhesion changes between 1 and 1.5 x in a retraction rate of 1 to 8000 micrometers per second, more optimally 1 to 2x, more optimally 1 to 3x, more optimally 1 to 4x, more optimally 1 to 5x, more optimally 1 to 7x, more optimally 1 to 10x, more optimally 1 to 12x, more optimally 1 to 13x, more optimally 1 to 15x, more optimally 1 to 16x, more optimally 1 to 20x, more optimally 1 to 23x, more optimally 1 to 25x, more optimally 1 to 27x, more optimally 1 to 30x or more.

[0031] An embodiment includes a method of using the packaged adhesive disclosed herein comprising (i) providing the packaged adhesive; (ii) opening the packaged adhesive and (ii) applying the adhesive (e.g., condom) to the target site (e.g., the glans of the penis).

[0032] In one embodiment, the adhesive is an enhanced sensation condom.

[0033] In one embodiment, the adhesive is a medical adhesive, e.g., for protection or closure of a wound.

[0034] In one embodiment, the adhesive is rate responsive in a range relevant for human skin removal. For example, the adhesive might exhibit a work of adhesion in J / m2 change of 30x as retraction rate on a rheometer tack test under testing conditions described in the present invention is changed from 1 micrometer per second to 8000 micrometers per second. Rate responsive behavior could exhibit work of adhesion changes between 1 and 1.5 x in a retraction rate of 1 to 8000 micrometers per second, more optimally 1 to 2x, more optimally 1 to 3x, more optimally 1 to 4x, more optimally 1 to 5x, more optimally 1 to 7x, more optimally 1 to 10x, more optimally 1 to 12x, more optimally 1 to 13x, more optimally 1 to 15x, more optimally 1 to 16x, more optimally 1 to 20x, more optimally 1 to 23x, more optimally 1 to 25x, more optimally 1 to 27x, more optimally 1 to 30x or more.

[0035] An embodiment includes a method of using the packaged adhesive disclosed herein is provided, comprising (i) opening the package; (ii) inverting the package to align, adhere and deposit the adhesive on a target substrate.

[0036] In one embodiment, the adhesive is an enhanced sensation condom.

[0037] In one embodiment, the adhesive is a medical adhesive, e.g., to protect or close a wound.

[0038] In one embodiment, the adhesive is rate responsive in a range relevant for human skin removal. For example, the adhesive might exhibit a work of adhesion in J / m2 change of 30x as retraction rate on a rheometer tack test under testing conditions described in the present invention is changed from 1 micrometer per second to 8000 micrometers per second. Rate responsive behavior could exhibit work of adhesion changes between 1 and 1.5 x in a retraction rate of 1 to 8000 micrometers per second, more optimally 1 to 2x, more optimally 1 to 3x, more optimally 1 to 4x, more optimally 1 to 5x, more optimally 1 to 7x, more optimally 1 to 10x, more optimally 1 to 12x, more optimally 1 to 13x, more optimally 1 to 15x, more optimally 1 to 16x, more optimally 1 to 20x, more optimally 1 to 23x, more optimally 1 to 25x, more optimally 1 to 27x, more optimally 1 to 30x or more.

[0039] In one embodiment, the method requires use of a single hand (or prosthetic aide).

[0040] An embodiment includes a method of manufacturing the packaged adhesive disclosed herein comprising (i) thermoforming a hot-melted sheet of thermoplastic over a form or an array of forms; (ii) pulling a vacuum to suction the malleable plastic sheet to the shape of the rigid form, thereby producing the receiving body; (iii) separating the receiving body from the excess plastic sheet by cutting or punching; (iv) optionally adding a retaining element to the receiving body; (v) adding an adhesive (e.g., condom, medical adhesive) to the receiving body; and (vi) adhering a removable film lid to the opening of the receiving body, thereby producing a packaged adhesive.

[0041] In one embodiment, the adhesive is an enhanced sensation condom.

[0042] In one embodiment, the adhesive is a medical adhesive, e.g., for protection or closure of a wound.

[0043] In one embodiment, the adhesive is rate responsive in a range relevant for human skin removal. For example, the adhesive might exhibit a work of adhesion in J / m2 change of 30x as retraction rate on a rheometer tack test under testing conditions described in the present invention is changed from 1 micrometer per second to 8000 micrometers per second. Rate responsive behavior could exhibit work of adhesion changes between 1 and 1.5 x in a retraction rate of 1 to 8000 micrometers per second, more optimally 1 to 2x, more optimally 1 to 3x, more optimally 1 to 4x, more optimally 1 to 5x, more optimally 1 to 7x, more optimally 1 to 10x, more optimally 1 to 12x, more optimally 1 to 13x, more optimally 1 to 15x, more optimally 1 to 16x, more optimally 1 to 20x, more optimally 1 to 23x, more optimally 1 to 25x, more optimally 1 to 27x, more optimally 1 to 30x or more.

[0044] An embodiment includes a method of manufacturing the package for a subsequent manufacturer to enclose an adhesive containing substrate disclosed herein comprising (i) thermoforming a hot-melted sheet of thermoplastic over a form or an array of forms; (ii) pulling a vacuum to suction the malleable plastic sheet to the shape of the rigid form, thereby producing the receiving body; (iii) separating the receiving body from the excess plastic sheet by cutting or punching; (iv) optionally adding a retaining element to the receiving body; and (v) optionally partially or fully adhering a removable or resealable film lid to the opening of the receiving body, thereby producing a package to contain an adhesive containing substrate.

[0045] In one embodiment, the adhesive containing substrate is an enhanced sensation condom.

[0046] In one embodiment, the adhesive is rate responsive in a range relevant for human skin removal. For example, the adhesive might exhibit a work of adhesion in J / m2 change of 30x as retraction rate on a rheometer tack test under testing conditions described in the present invention is changed from 1 micrometer per second to 8000 micrometers per second. Rate responsive behavior could exhibit work of adhesion changes between 1 and 1.5 x in a retraction rate of 1 to 8000 micrometers per second, more optimally 1 to 2x, more optimally 1 to 3x, more optimally 1 to 4x, more optimally 1 to 5x, more optimally 1 to 7x, more optimally 1 to 10x, more optimally 1 to 12x, more optimally 1 to 13x, more optimally 1 to 15x, more optimally 1 to 16x, more optimally 1 to 20x, more optimally 1 to 23x, more optimally 1 to 25x, more optimally 1 to 27x, more optimally 1 to 30x or more.

[0047] In one particular embodiment, the adhesive containing substrate is a developable surface enhanced sensation condom.

[0048] In one embodiment, the adhesive is a medical adhesive, e.g., for protection or closure of a wound.

[0049] In one embodiment, the adhesive is rate responsive in a range relevant for human skin removal. For example, the adhesive might exhibit a work of adhesion in J / m2 change of 30x as retraction rate on a rheometer tack test under testing conditions described in the present invention is changed from 1 micrometer per second to 8000 micrometers per second. Rate responsive behavior could exhibit work of adhesion changes between 1 and 1.5 x in a retraction rate of 1 to 8000 micrometers per second, more optimally 1 to 2x, more optimally 1 to 3x, more optimally 1 to 4x, more optimally 1 to 5x, more optimally 1 to 7x, more optimally 1 to 10x, more optimally 1 to 12x, more optimally 1 to 13x, more optimally 1 to 15x, more optimally 1 to 16x, more optimally 1 to 20x, more optimally 1 to 23x, more optimally 1 to 25x, more optimally 1 to 27x, more optimally 1 to 30x or more. BRIEF DESCRIPTION OF THE FIGURES

[0050] Features and advantages of embodiments of the present invention will become apparent from the appended claims, the following detailed description of one or more example embodiments, and the corresponding figures. Where considered appropriate, reference labels have been repeated among the figures to indicate corresponding or analogous elements.

[0051] Figures 1A and 1B present perspective and planar views of an embodiment of a package.

[0052] Figures 2A, 2B, 2C, 2D present an exemplary method of using a packaged condom.

[0053] Figure 3 presents a perspective view of an embodiment of a package.

[0054] Figures 4A-4B present perspective views of an embodiment of a package having a “back passthrough”.

[0055] Figures 5A, 5B, 5C present cross-sectional, plan, and cross-sectional views an embodiment of a packaged enhanced sensation condom.

[0056] Figures 6A-6C present perspective, planar, and cross-sectional views of an embodiment of a package disclosed herein.

[0057] Figures 7A, 7B, 7C present cross-sectional views of an exemplary embodiment of an internal shell of a package.

[0058] Figure 8 presents a cross-sectional view of an embodiment of a package.

[0059] Figure 9 presents a dimensioned computer model of the geometry form.

[0060] Figure 10 presents a dimensioned computer model of a geometry form.

[0061] Figure 11 presents a dimensioned computer model of a geometry form.

[0062] Figures 12A-12B present side and cross-sectional views of an embodiment of a package with a pronounced reservoir.

[0063] Figure 13 presents a cross-sectional view of a double shell cup style package embodiment.

[0064] Figure 14 presents a perspective view of embodiments of a package.

[0065] Figure 15 presents a perspective view of an embodiment of a package.

[0066] Figure 16 presents a cross-sectional view of an embodiment of a package with a porous application liner that stabilizes a fluid film retaining element.

[0067] Figure 17 presents a perspective view of an embodiment of an application liner.

[0068] Figures 18A-18C present side and perspective views of an embodiment of an application liner.

[0069] Figure 19 presents perspective views of an embodiment of an application liner.

[0070] Figures 20A-20E present cross-sectional views of embodiments of a receiving body having a reflexive geometry.

[0071] Figure 21 presents cross-section views of two embodiments of an enclosing cap for a reflexive geometry embodiment of the receiving body geometry.

[0072] Figure 22 includes a side view package and condom in an embodiment.

[0073] Figure 23 depicts frequency sweep plots for three different adhesives containing different crosslinkers.

[0074] Figure 24 depicts the tack profile of L6_1 adhesive film under variable debonding speeds.

[0075] Figure 25 depicts the work of adhesion results referenced in Figure 24.

[0076] Figure 26 depicts nominal stress as a function of strain for L6 adhesives with three different crosslinkers.

[0077] Figure 27 depicts work of adhesion of L6 Adhesives with three different crosslinkers.

[0078] Figure 28. depicts a frequency sweep plot comparing tan delta of L6 adhesive and a lightly crosslinked acrylate adhesive at 25°C.

[0079] Figure 29 depicts nominal stress as a function of strain comparing tack profile of L6 adhesive with the tack profile for a lightly crosslinked acrylate adhesive.

[0080] Figure 30 depicts work of adhesion of L6 Adhesive compared to the that of a lightly crosslinked acrylate adhesive (control).

[0081] Figure 31 depicts Frequency sweep plot comparing the Tan delta * complex modulus magnitude of L6 adhesive and a lightly crosslinked acrylate adhesive (control).

[0082] Figure 32 is a cross-sectional view of an embodiment of a condom.

[0083] Figure 33 is an embodiment of a method.

[0084] Figures 34A-B include side views of a developable surface in an embodiment.

[0085] Figures 34A-B include side views of a developable surface in an embodiment.

[0086] Figure 35 addresses a reinforcement rib in an embodiment.

[0087] Figures 36A-D include various views of a developable surface in an embodiment.

[0088] Figures 37A-D include various views of a developable surface in an embodiment.

[0089] Figures 38A-D include various views of a developable surface in an embodiment.DETAILED DESCRIPTION

[0090] Reference will now be made to the drawings wherein like structures may be provided with like suffix reference designations. In order to show the structures of various embodiments more clearly, the drawings included herein are diagrammatic representations of structures. Thus, the actual appearance of the fabricated structures, for example in a photo, may appear different while still incorporating the claimed structures of the illustrated embodiments (e.g., walls may not be exactly orthogonal to one another in actual fabricated devices). Moreover, the drawings may only show the structures useful to understand the illustrated embodiments. Additional structures known in the art may not have been included to maintain the clarity of the drawings. For example, not every layer of a device is necessarily shown. “An embodiment”, “various embodiments” and the like indicate embodiment(s) so described may include particular features, structures, or characteristics, but not every embodiment necessarily includes the particular features, structures, or characteristics. Some embodiments may have some, all, or none of the features described for other embodiments. “First”, “second”, “third” and the like describe a common object and indicate different instances of like objects are being referred to. Such adjectives do not imply objects so described must be in a given sequence, either temporally, spatially, in ranking, or in any other manner. “Connected” may indicate elements are in direct physical or electrical contact with each other and “coupled” may indicate elements co-operate or interact with each other, but they may or may not be in direct physical or electrical contact. Phrases such as “comprising at least one of A or B” include situations with A, B, or A and B.

[0091] “Adhesion” as used herein refers to the ability of a composition or material to adhere or “stick” to a substrate (e.g., the skin). Adhesion is measured as adhesive force in Newtons (N). The higher the adhesive force, the higher will be the number of Newtons required to peel one object from the other.

[0092] “Adhesive” as used herein refers to a composition or material that adheres to a substrate (e.g., the skin. The adhesive composition disclosed herein serve as the male diaphragm disclosed herein, i.e., either as a preformed membrane or film serving as a diaphragm or provided as a liquid which forms a membrane or film upon application to a substrate. In certain embodiments, the adhesive component of the package adhesive disclosed herein does not include cyanoacrylates or fibrin. Incertain embodiments, the adhesive is one component of a larger article or device. Multi-layer adhesives are within the scope of the adhesives disclosed herein. Therefore, the package disclosed herein is suitable for use in protecting, transporting and applying multi-layer adhesives, adhesives-containing articles, and adhesive- containing devices (e.g., medical devices).

[0093] “Bio-based” as used herein with reference to a composition or article disclosed herein means that a portion or all of the composition or article is derived from natural sources. In certain embodiments, one or more components of the package or packaged article are bio-based.

[0094] “Biodegradable” as used herein means used herein with reference to a composition or that can be degraded by living microorganisms like fungi or bacteria, without regard to a particular time frame. In certain embodiments, one or more components of the package or packaged article are biodegradable.

[0095] “Blended thermoplastic polymer” as used herein means the blending of two or more linear or branched polymers of the same or different monomeric constituencies by methods including but not limited to solution blending, melt blending, power blending, extrusion blending, centrifugal mixing.

[0096] “Compostable” as used herein means refers to a composition or article that require microorganisms, humidity, and heat to yield a finished compost product (CO2, water, inorganic compounds, and biomass). Compostable is distinguished from biodegradable in that compostable compositions and articles must break down into natural elements within a specific time frame. In one embodiment, the compositions and articles disclosed herein complies set forth by the U.S. Composting Council, Environmental Protection Agency, American Society for Testing and Materials (ASTM International), or Tüv Austria. In certain embodiments, one or more components of the package or packaged article are compostable.

[0097] “Controlled porosity “as used herein means pores that are normally closed are stimulated to open, allowing the passage of fluids as allowed by their rheological properties.

[0098] “Conventional condom” as used herein refers to a condom that comprises a continuous elastic tubular wall with a closed distal end (tip) and an open proximal end, typically made of a thin, soft material such as latex or polyurethane, that whenin use provides coverage on the penis head and shaft. The length of a conventional condom in use is typically between about 7 and about 8 inches, but with commercially available products up to 9 inches and down to about 6.3 inches. Numerous condom brand manufacturers and products are known in the art. See, e.g., https: / / www.trojanbrands.com / en / products / condoms and https: / / www.durexusa.com / collections / condoms, each incorporated herein by reference.

[0099] “Copolymer” as used herein refers to a polymer derived from more than a single species of monomer, and includes, for example, bipolymers, terpolymers and quaterpolymers. Copolymers may be, for example, block copolymers, graft copolymers, random copolymers, blends, mixtures, and / or adducts of any of the foregoing and other polymers.

[0100] “Curing” as used herein refers to the chemical process of converting a macromolecule into a higher molecular weight polymer via crosslinking reactions.

[0101] “Crosslink density,” as used herein, refers to average molecular weight between crosslinks. (https: / / www.pcimag.com / articles / 104955-calculation-of- crosslink-density-of-thermoset-polymers). Flory, et al., put forth theory in crosslink density in the 1940s.

[0102] “Debonding,” as used herein, refers the mechanism of debonding may vary and include, for example, phase changes, chemical reactions, cross-linking and volumetric expansion.

[0103] “Enhanced sensation or pleasure” as used herein refers to increased exposure of sensory neurons or increased exposed penile surface are (i.e., fractional coverage, or substantially less than a conventional condom) or increased sexual arousal or preference in use, or increased simulation of sensory neurons.

[0104] “ESC” as used herein is an abbreviation for enhanced sensation condom.

[0105] “Elastomeric behavior” as used herein refers to generally linear elastic or combined linear elastic and plastic deformation stress / strain behavior for a material as it is strained in a regime in a region above a key transition regime such that stress / strain hysteresis is generally conserved.

[0106] “Flexible behavior” as used herein refers to behavior of a rigid, viscoelastic or elastomeric material that can be described as compliant or deformable to fit the demands of a specific engineering application.

[0107] “Force responsive” as used herein means that the behavior of a solid, gel or fluid changes with the magnitude of the applied force.

[0108] “Fractional coverage” as used herein refers to substantially less coverage of the penis than a conventional condom. In certain embodiments, herein, the diaphragm does not cover the shaft of the penis.

[0109] “Frequency responsive “as used herein means the behavior of a material or fluid, changes under the application of a periodic or near-periodic force or displacement in time. This applied quantity can be called a “signal”. The applied signal has a defined amplitude and frequency, and optionally phase, all of which may be constant or varying in time and / or space.

[0110] G* refers to the square root of the sum of storage modulus squared and the and complex (loss) modulus squared of a polymer, G* = (G’^2 + G’’^2)^0.5, as measured by rheometry or dynamic mechanical analysis. The term may indicate the Resilience of an adhesive, a phenomenon described herein and defined herein, to fibrillate in a manner ideal for removal from surfaces where significant rate response at low frequency or at low shear rate is observed and high tack or high energy of removal is also observed across the low frequency or low shear rate spectrum (0 to 50 rad / s removal for frequency spectrum or 0 to 8000 microns / s for removal for shear rate spectrum) while minimal pain in removal from skin or minimal energy from a surface is observed.

[0111] “Resilience” refers herein to the integral of a plot of G* x tan delta versus angular frequency or shear rate in units of MPa multiplied by rad / s.

[0112] “Mechanically passive adhesive” refers to an adhesive that is that are designed to maintain their structural and mechanical properties after placement. Many pressure-sensitive adhesives are mechanically passive adhesives. In certain embodiments, the adhesive layer does not comprise a mechanically passive adhesive or pressure-sensitive adhesive.

[0113] “Tg” and “glass transition temperature” are used interchangeably herein to refer to . If measured, Tg values are determined by Differential Scanning Calorimetry(DSC) at a scan rate of 10°C / minute, unless otherwise indicated. Typically, Tg values for copolymers are not measured but are calculated using the well-known Fox Equation, using the monomer Tg values provided by the monomer supplier, as is understood by one of skill in the art.

[0114] “Heterogeneous network” as used herein means refers to a polymer network with non-uniform distribution of crosslink density.

[0115] “Gel Fraction” refers to the mass of a polymer remaining after washing with suitable solvent divided by initial mass. Means for determining the gel fraction are known in the art.

[0116] “Sol Fraction” refers to the mass of a polymer lost after washing with a substantial suitable solvent divided by initial mass. Means for determining the sol fraction are known in the art.

[0117] “Heterogeneous crosslinking,” as used herein, refers to crosslinking distributed in a polymer network or system that is non-uniform.

[0118] “Hot melt adhesive” refers to an adhesive that is processed (i.e., applied to its target substrate within which it performs intended adhesive function) at an elevated temperature to the temperature range of intended use for that adhesive.

[0119] “Interpenetrating network” or “IPN” as used here refers to a unique type of polymer material that comprises two or more independent polymer networks, which are physically entangled but not covalently bonded to each other. Each network maintains its distinct identity, but the networks are intertwined at the molecular level, forming a composite material with properties derived from the combination of the individual networks.

[0120] “Lightly crosslinked” refers to a crosslink density or network structure between that of a thermoplastic polymer and a thermoset polymer in which thermomechanical behavior is consistent with that not of a linear polymer that flows in polymer thermal processing techniques such as extrusion or injection molding or a fully covalently crosslinked network that exhibits the behavior of an ideal elastomer. A lightly crosslinked (meth)acrylate polymer of the present invention might comprise a (meth)acrylate and between 0.001 and 2 wt% crosslinker or might comprise other amounts of crosslinker that afford a rheological and thermomechanical profile that is not consistent with that of a melt processable thermoplastic that flows and also notconsistent with that of an ideal elastomer, which generally exhibits an upward sloping plot of storage modulus versus temperature in the rubbery regime in dynamic mechanical analysis plots of storage modulus versus temperature. Increased amounts of crosslinker might be required to form a lightly crosslinked polymer depending on polymerization pathways, efficiency and monomer conversion as well as polymerization kinetics, which may afford significantly different polymeric networks from a thermomechanical property standpoint despite identical compositions.

[0121] “Low molecular weight lightly crosslinked” refers to a lightly crosslinked polymer or polymer network that leaves little or no residue on a surface after removal and exhibits limited conversion or low chain length between crosslink sites on the order of tens to thousands to hundreds of thousands but not millions of Daltons, exhibits a high number of dangling chain ends, and exhibits a thermomechanical profile consistent with that of a polymeric network in which entanglements are less responsible for thermomechanical behavior, and instead side chain interactions, dangling chain ends and van der Waals forces and free volume drive thermomechanical behavior influence tack profile, including rate response and pain in removal of adhesives from skin.

[0122] “Monomer reactivity ratios” as used herein refers to parameters used in polymer chemistry to describe the relative reactivity of two monomers in a copolymerization reaction. A copolymerization reaction involves the simultaneous polymerization of two different monomers, forming a copolymer with varying monomer compositions.

[0123] “Network” as used herein with reference to a polymer refers to macromolecular architecture formed cross-linked polymer chains. Cross-links are covalent bonds or other strong interactions such as entanglements, supramolecular interactions or physical interactions such as polymer chain interactions with crystalline or glassy phases

[0124] “Nonlinear force “ as used herein refers to a type of force in which the relationship between the force and its effect on a system is not proportional or does not follow a simple, linear equation.

[0125] “On-demand” when used herein with reference to debonding or detachment refers to debonding that is quick, easy, and damage-free. On-demand delamination or release from the surface to which the adhesive composition or article is adhere occurs vis reversible or irreversible adhesive behavior triggered by exposure to a stimulus such as temperature changes, chemical changes, light, ultrasound, ionic strength change, pH change, magnetic, or mechanical forces as well as other stimuli.

[0126] “Room temperature" and "ambient temperature" are used interchangeably herein to refer to a temperature between about 20-25 ° C.

[0127] “Periodic: as used herein means occurring at intervals in time or space. This may be a repetition of the same feature or characteristic.

[0128] “Rate” as used herein means the magnitude at which a quantity varies in time, unless otherwise specified.

[0129] “Preventing” as used herein refers to reducing, minimizing, or eliminating the release of semen outside the barrier layer in the present invention in comparison to natural release during ejaculation.

[0130] “Plastic welding” as used herein refers to the process of joining two separate plastic components via the use of heat or solvents to create a permanent bond. The process may include heat sealing, hot gas or hot air welding, hot plate welding, infrared or non-contact welding, high-frequency welding, induction welding, injection welding, ultrasonic welding, friction welding, and solvent welding.

[0131] “Plasticizer” refers to an additive that when added to a polymer, polymer blend, copolymer, copolymer blend, polymer network or copolymer network results in thermomechanical behavior consistent with that understood to be associated with plasticization, namely, decrease in glass transition temperature, lowering of crystalline melting temperature, triggering of stress relaxation or resulting in increased or decreased adhesion strength. Plasticizers may be added in approximately about 1 wt%, about 2 wt%, about 3 wt% etc. increasing up to about 30 wt% or about 50 wt% or more to polymer, copolymer or network mixtures or blends. Examples of plasticizers for various polymer systems are known an include water, common solvents, small molecules such as phthalates, glycerol or fatty acid compounds, triacetin, poly(ethylene glycol) compounds that are liquid at roomtemperature with molecular weights ranging from 1 to 30 or more repeat units, vegetable oil, detergents and other common plasticizing agents.

[0132] “Polymer,” as used herein, refers substances composed of macromolecules, very large molecules with molecular weights ranging from a few thousand to as high as millions of grams / mole made up of simpler, repeating units, derived from lower molecular weight monomers. Polymer, as used herein, refers to both homopolymers and copolymers. Homopolymers are made from (i.e., they comprise) one type of monomer. Copolymers are made from (i.e., they comprise) two or more different kinds of monomers (e.g., a styrene-butadiene copolymer). The adhesive described herein may comprise one or more polymers, including but not limited to, stimuli-responsive polymers.

[0133] “Pressure sensitive”, as used herein with respect to adhesives refers to a viscoelastic material that meets appropriate Dahlquist criterion (e.g., the storage modulus of the material at 25° C. is less than 3×10^5 Pa at a frequency of 1 Hz) indicating it is sufficiently flowable when it is pressed against a surface.

[0134] “Reduce” or “reduction” as used herein refers to a decrease in a particular property. The reduction may be, for example, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90% or at least about 99% or more. The decrease can be measured by any suitable means, for example, by any suitable method known in the art. In the case of coverage of a condom of an erect penis, reduction may be decreased erect penis surface area of, for example, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90% or at least about 99% or more. In the case of coverage of a condom that primarily covers a portion of the head of the penis but exposes other sections of the head of the penis and the shaft of the penis, reduction may be decreased erect penis head surface area of, for example, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90% or at least about 99% or more. In all cases, reduction of erect penis coverage may include exposure of sections of the penis that have high sensation / sensory neuron presence, including the frenulum.

[0135] “Reflexive geometry”, as used herein, means exhibiting a three- dimensional shape with the region of the package in contact with the periphery of the adhesive contained within the package substantially upturned with respect to the center of the package in contact with the center (e.g., reservoir) of the adhesive. An example of a reflexive geometry is a sombrero hat. In cross-section, a reflexive geometry has a characteristic “W” shape or a broadened “U” shape over the area of the package in contact with the packaged adhesive.

[0136] “Rigid”, as used herein, means exhibiting glassy behavior or having the ability to maintain formed geometry without significant deformation (e.g., plastic deformation) occurring.

[0137] “Selectively permeable” as used herein means the membrane contains channels or passages that allow specific molecules to pass through, either passively or actively. Active transport through the membrane requires an energy input, which may be from a mechanical, acoustic, chemical, electrical, magnetic, pH change, ionic strength, thermal or optical source.

[0138] “Self-form” as used herein refers to natural expansion of barrier layer in the present invention upon forces resulting from ejaculation such that barrier layer expands but does not substantially release seminal fluid outside its boundaries.

[0139] “Self-healing “ as used herein means parameters used in polymer chemistry to describe the relative reactivity of two monomers in a copolymerization reaction. A copolymerization reaction involves the simultaneous polymerization of two different monomers, forming a copolymer with varying monomer compositions.

[0140] “Semi-interpenetrating network” or “Semi-IPN as used herein refers to a cross-linked or branched polymer network and an entangled linear or branched additional polymer or series of polymers.

[0141] “Semi-rigid”, as used herein, means having a flexible or pliable mechanical behavior while also having the ability to withstand deformation and maintain formed geometry without significant plastic deformation occurring. For clarification, semi-rigid behavior is not elastomeric behavior.

[0142] “Shear rate” as used herein means the rate with respect to time at which a shearing deformation occurs. A shearing deformation is one whereby parallel lamellae (layers) of a fluid, gel or solid material moves past one another in a slidingmanner. These layers may be discrete (possessing finite measurable thickness) or continuous (infinitesimally thin or not individually discernable). A shear rate may be a constant function in time, a monotonic function in time, a non-periodic non-monotonic or a periodic function in time. Periodic is understood to mean a function that is truly periodic in time, or is approximately periodic in time (e.g., a sync function).

[0143] “Shear rate responsive” as used herein means the behavior of a material (e.g., gel, solid, liquid) changes under the application of different shear displacements or shear rates. In the case of a shear rate responsive adhesive, an adhesive exhibits varying adhesive force when subjected to different shear or peel rates. In the case of an inverse pressure sensitive adhesive, an adhesive exhibits lower adhesive force when peeled away or removed from the surface to which it is adhered at a lower shear or peel rate versus at a higher shear or peel rate.

[0144] “Stimuli-responsive” as used herein refers to a change in physical, environmental, chemical, thermomechanical, mechanical, thermal, energetic or other properties of a composition or material arising from exposure to a stimulus including, for example, a change in temperature, pH, ionic strength, environmental conditions including moisture, water immersion, exposure or humidity, solvent exposure, exposure to electromagnetic radiation including gamma rays, x-rays, ultraviolet rays, visible light, infrared waves, radio waves, ultrasonic waves, high humidity, magnetism, electricity, as well as mechanical forces including shear forces or linear forces.

[0145] “Substantially less” used herein reference to fractional coverage of the penis refers to a reduction in covered penile surface area in comparison with that covered by a traditional condom such that enhanced sensation or pleasure occurs. Substantially less may be, for example, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80% or about 90% or less surface area.

[0146] “Thermoforming”, as used herein, refers to a forming process comprising heating a plastic sheet to a forming temperature at which it becomes pliable and forming it into a specific shape using a mold or rigid form. The shaped plastic cools or is cooled and is trimmed to result in the finished part. Thermoforming methods include vacuum thermoforming and pressure thermoforming. Vacuum thermoforminginvolves heating a sheet of plastic to a forming temperature, stretching it onto a single-surface mold, then forcing against the mold using a vacuum. A forming temperature for a given material is above its glass transition temperature and below its melting temperature.

[0147] “Thermoplastic”, as used herein with reference to a polymer, refers to a polymer that can be softened through heating and then processed using methods such as extrusion, injection molding, blow molding, thermoforming or the like.

[0148] “Viscosity”, as used herein, is a measure of a fluid’s resistance to deformation at a given rate. For liquids, it corresponds to the informal concept of "thickness.”

[0149] “Work of adhesion” is the (integral of a stress / strain plot of a tack test of an adhesive performed at a specific retraction rate, often by a stress controlled rheometer in strain controlled mode) multiplied by the thickness of the adhesive.

[0150] Various definitions related to “developable surfaces” now follow.

[0151] A “developable surface” means any surface that has zero Gaussian curvature https: / / en.wikipedia.org / wiki / Developable_surface. It is a surface that can be unrolled (i.e., “developed”) onto a flat plane without distortion (stretching or compression). An equivalent practical description that can be used for the purposes of evaluating the geometries described herein is a surface that may be constructed by bending, rolling and twisting an initially planar piece of paper without distorting it (stretching, tearing, compressing or wrinkling). For the purposes of this disclosure, a developable surface may have a crease or overlapping region when constructed out of real materials, but again fit the property that they can be constructed from rolling, bending, and folding a piece of paper.

[0152] A “doubly curved surface” is a surface that has a finite and non-zero Gaussian curvature at least in some locations, and therefore cannot be developed into a planar surface without distortion. Similarly, a planar sheet must be stretched or compressed at least in some locations to form the three-dimensional surface.

[0153] “Distortion” occurs when a of a planar or non-planar (three-dimensional) surface in an initial state of configuration is transformed into a second surface configuration (shape) and the original surface must be compressed or stretched to do so. If the surface may be thought of as a very thin membrane, the surface area ofthe membrane of the second configuration is different from the surface area in the initial configuration.

[0154] “Void volume” is the initial volume of an incompressible fluid that can be contained within a reservoir without straining the reservoir wall, i.e., the pressure differential between the inside and the outside of the reservoir across the wall is zero.

[0155] “Gaussian curvature” is the product of the two principal curvatures of a surface at any given point. The principal curvatures are the maximum and minimum values of curvature of the surface at a point. https: / / en.wikipedia.org / wiki / Principal_curvature

[0156] SELECT DETAILED DESCRIPTION OF FIGURES

[0157] Figures 1A and 1B depict an embodiment of a package disclosed herein, wherein the package has nominal circular geometry. Figure 1A discloses a film lid (4) attached to the receiving body (1) via a flange (3) or other mechanism. Figure 1B discloses on the underside (interior side) of the film lid (4), a release liner (e.g., silicone paper) (13) that may be affixed to reduce adhesion of the adhesive (e.g., condom) to the film lid. A ring of adhesive (12) may be used to attach the film lid (4) to flange (3).

[0158] Figures 2A, 2B, 2C, 2D depict an exemplary method of using a packaged enhanced sensation condom disclosed herein. Figure 2A addresses removing the film lid from the package. Figure 2B discloses inverting the package such that the package opening faces down. Figure 2C discloses pressing the package onto the glans penis. Figure 2D discloses pulling the package away. Fig.2A shows lid (4) partially coving package or receiving body (1), which includes adhesive containing substrate (5).

[0159] Figure 3 depicts an exemplary embodiment of a package disclosed herein, wherein the package has a lifting tag (6) affixed to the outer surface of the receiving body (1) to aid in the manual gripping and manipulation of the package. The lifting tag may be affixed to the receiving body, e.g., by a pressure sensitive or other standard adhesive.

[0160] Figures 4A-4B depict an exemplary embodiment of a package disclosed herein, wherein the package comprising a “back passthrough” (30) comprising asecondary film lid (31) on the opposite side of the package as the primary film lid ([4] shown in Figure 1). Optionally, a secondary flange (32) may be formed into the geometry to facilitate the attachment of the secondary film lid (31) over the back passthrough (30). The user then removes the primary lid (4) and the secondary film lid (31) (i.e., the film lid covering the back passthrough). As the user is applying the condom, the back passthrough (30) serves as a visual and tactile alignment aide, allowing the user to push the packaging over the glans, allowing the tip to protrude through the back passthrough. The adhesive containing substrate is denoted by (5).

[0161] This passthrough allows for the ejaculate reservoir and tip of the glans of the penis (20) to pass through the package, as the condom is applied, preventing adhesion and pressure on the urethra meatus (opening) during application, and mitigating collapse or pinching of the ejaculate reservoir.

[0162] Figures 5A, 5B, 5C depict an embodiment of a packaged enhanced sensation condom disclosed herein, wherein the rigid receiving body (1) and a semi- rigid (compliant) outer shell (6), which enables the user to press on the semi-rigid portion (6) directly over the adhesive, enable better compliance and conformation of the condom / adhesive system to the penis. Figure 5A provides a cross-sectional view. Figure 5B provides a plan view. Figure 5C depict application with applied pressure, causing the semi-rigid portion to deform to the position indicated by (6a).

[0163] Figures 6A-6C depict an exemplary embodiment of a package disclosed herein, whereby the package has a circular inner shell (1), and a rectangular flexible outer shell (7) that contains attachment features such as wings of the adhesive containing substrate (8). The flexible nature of the package allows the user to manipulate the wings to adhere to the penis, while the rigid section maintains the geometry of the primary portion of the condom, including the area covering the urethra meatus and a semen collection reservoir, if present.

[0164] Figures 7A, 7B, 7C depict an exemplary embodiment of an internal shell of a package disclosed herein. Figure 7A depicts an embodiment wherein the inner shell (1) is attached to the outer shell (50) near the flange (51) and at the pole of the shell (53), with a structure indicated by label (52). Figure 7B depicts an embodiment wherein the shell does not utilize a support at the pole. Figure 7C depicts deflection behavior of the inner shell (1) as the package containing the condom is pressed ontothe penis (20), until it makes contact with the inner surface of the outer shell as indicated by the position of the surface in position (1) compared to the pre- application position indicated by the dashed lines (1a).

[0165] Figure 8 depicts an exemplary embodiment of a package disclosed herein, wherein ridges or ripples (60) in the receiving body are present.

[0166] Figure 9 depicts a dimensioned computer model of the geometry form used to dip coat a barrier layer in Example 1 (Example Set. No.1).

[0167] Figure 10 depicts a dimensioned computer model of the geometry form used to thermoform the receiving body of a package in Example 1 (Example Set. No. 1).

[0168] Figure 11 depicts a dimensioned computer model of the geometry form used to thermoform the receiving body of a package in Example 2 (Example Set. No. 1).

[0169] Figures 12A-12B depict a package with a pronounced reservoir and steep-sided adhesive (such as a developable adhesive condom with a 1 mL reservoir) with a 0.030 inch thickness.

[0170] Figure 13 depicts a cross-section of a Double Shell cup style package with a compliant inner shell, and a rigid outer shell. The two are joined in the flange region. However, they could equivalently be joined along the wall adjacent to the opening that abuts the flange.

[0171] Figure 16 depicts a cross-sectional view of a package with a porous application liner that stabilizes a fluid film retaining element. Section view A depicts an embodiment of a package with a fluid film retaining means (100) securing the adhesive (5) to the inner face of the receiving body (1). Section view B depicts an embodiment of a package with a fluid film retaining means stabilized by a porous impregnated application liner (101) securing the adhesive (5) to the inner face of the receiving body (1). The thickness of the fluid film (100) and fluid film with impregnated application liner (101) are drawn with exaggerated thickness for visual clarity.

[0172] Figure 17 depicts an embodiment of an application liner (1701), which may optionally be impregnated with a fluid to stabilize the fluid film retaining means,if present. An overlapping region (1702) may be secured with a low tack adhesive to maintain a conical geometry of the application liner for applicable adhesive geometries (e.g., developable adhesive surface enhanced sensation condom). Optional pull tab (1703) aides in unwrapping and removal of the application liner once adhesive is applied to target surface (e.g., glans in the case of an enhanced sensation condom).

[0173] Figures 18A-18C depict an embodiment of an application liner (1701), which may optionally be impregnated with a fluid to stabilize a fluid film retaining means, if present. An overlapping region (1702) may be secured with a low tack adhesive to maintain a generalized conical geometry of the application liner for applicable adhesive geometries (e.g., developable adhesive surface enhanced sensation condom). Optional tab (1704) aides in removal of the device from the package receiving body (5, not depicted), enabling manipulation, alignment and application without contacting the adhesive or barrier layer, thereby mitigating contamination or fouling of the adhesive. Figures 18B and 18C depict perspective views of an ESC in the application liner and of the application liner-ESC assembly within the receiving body, respectively. Figures 18D-18F depict a foil membrane that closes the package.

[0174] Figure 19 depicts an embodiment of the application liner (1701) with an enhanced sensation condom as an exemplary adhesive (5). A force (1901) is applied in the downward direction (as drawn), while the application liner (1701) is supported to be fixed in space. This brings the outer surface of the enhanced sensation condom (1911) in contact with the inner surface of the application liner (1910) and provides a sufficient reaction force so as to prevent the condom surface (1911) from separating from the liner surface (1910) as the release liner (1902) is peeled away thus exposing the adhesive surface for application to the target surface without incurring wrinkles, folding or self-adhesion that would foul the adhesive and render the device unusable.

[0175] Figures 20A-20E depict embodiments of the receiving body having a reflexive geometry. Several cross-sectional variants are shows (Figures 20A-20C) as well as a perspective drawing (Figure 20D).

[0176] Figures 21A-21B depict cross section views of two variants of an enclosing cap for a reflexive geometry embodiment of the receiving body geometry. Figure 21A is a cap with vertical walls. Figure 21B is a cap with sloped or contoured walls.

[0177] Figure 23 depicts frequency sweep plots for three different adhesives containing different crosslinkers. All adhesives exhibit highly loss behavior indicated by high tan delta and highly rate dependent behavior.

[0178] Figure 24 depicts the tack profile of L6_1 adhesive film under variable debonding speeds. This adhesive exhibits a highly rate-dependent debonding behavior where, both, maximum stress and fibrillation process becomes larger with increasing probe retraction rate. As a result, work of adhesion increases significantly with increasing rate, depicted in figure 24.

[0179] Figure 25 depicts the work of adhesion results referenced in Figure 24 description, showing a 30x increase in work of adhesion for Nuceptive L6_1 adhesive across 1 to 8000 microns per second retraction rate in a tack test as described herein.

[0180] Figure 26 depicts nominal stress as a function of strain for L6 adhesives with three different crosslinkers. Tests are performed at 25°C and 100 µm / s crosshead speed. Mean stress values are plotted without error bars (n=3)

[0181] Figure 27 depicts work of adhesion of L6 Adhesives with three different crosslinkers. Error bars represent standard deviation. (n=3)

[0182] Figure 28. depicts a frequency sweep plot comparing tan delta of L6 adhesive and a lightly crosslinked acrylate adhesive at 25°C. Error bars represent standard deviation. (n=3)

[0183] Figure 29 depicts nominal stress as a function of strain comparing tack profile of L6 adhesive with the tack profile for a lightly crosslinked acrylate adhesive. Tests are performed at 25°C and 100 µm / s crosshead speed. Mean stress values are plotted without error bars (n=3)

[0184] Figure 30 depicts work of adhesion of L6 Adhesive compared to the that of a lightly crosslinked acrylate adhesive (control). Error bars represent standard deviation. (n=3)

[0185] Figure 31 depicts Frequency sweep plot comparing the Tan delta * complex modulus magnitude of L6 adhesive and a lightly crosslinked acrylate adhesive (control). Error bars represent standard deviation. (n=3)

[0186] Figures 36A (top view), 36B (perspective view), 36C (back view), and 36D (side view) illustrate a 3D developable adhesive surface.

[0187] Figures 37A (top view), 37B (perspective view), 37C (back view), and 37D (side view) illustrate a 3D developable adhesive surface with a reservoir atop the adhesive.

[0188] Figure 38A includes an exploded perspective view of two developable adhesive layers that couple to each other and to a reservoir to form the fully assembled condom. Figure 38B shows an exploded top view of the same. Figure 38C shows front, side, and back views of the fully assembled condom of Figure 38A.

[0189] Figure 38D shows a close up of the assembly of barrier and adhesion layers. The figure shows a cross-section of the developable adhesive ring geometry condom which consists of a barrier layer and an adhesive layer which covers a portion of the inner surface of the barrier layer, extending to the periphery and leaving exposed a section of the barrier layer with no adhesive thus forming a reservoir. The adhesive layer comprises two laminates of adhesive, in this rendering each 100 microns thick. The barrier layer depicted is also 100 microns thick.

[0190] Figure 32 includes a double-body construction of a condom with adhesive layer 1002. Primary barrier layer 10011 is planar and reservoir barrier layer 10012 joined at joining region 301 by a suitable means, such as an adhesive or plastic weld. A reservoir 1003 is formed by the two layers. Optionally in certain embodiments, the region between the upper surface of 10011 and inner surface of 10012, denoted by 309, may be filled with an absorbent material, such as a superabsorbent polymer pad, which swells, entraps, or gels ejaculate fluid. While shown in a planar configuration, either 10011, 10012 or 1002 may be curved. Barrier layers 10011 and 10012 are not required to be of the same material, and it may be preferable in certain embodiments for 10011 to be comprised of a thinner, more compliant layer for conforming to the shape of the glans, while 10012 is more elastic for expansion during ejaculation to contain fluid. The adhesive ring width (sum of distances 3101, 3102 and 3103) is approximately 10 mm in certain embodiments.Optionally, a different adhesive to 1002 is patterned underneath the attachment region 301 to provide increased adhesion in the normal direction to the skin surface (not depicted) to mitigate pull-up. The distances 3101, 3102 and 3103 should be selected for the specific barrier and adhesive materials selected to provide sufficient resistance to peel-up under expression of fluid or other mechanical forces. The attachment region 301 is located inset from the periphery (leftmost edge of 1011 as drawn) in order to provide more favorable orientation of the membrane stresses transmitted to the adhesive and the underlying attachment surface (skin).

[0191] PACKAGE

[0192] Disclosed herein is a package suitable for use in protecting and optionally, applying (e.g., aligning, depositing), an adhesive (e.g., a condom or medical adhesive). The package may be a hand-held, disposable package.

[0193] In one embodiment, the packaging comprises (a) a receiving body (e.g., a dome or cone), optionally comprising a flange, and (b) a sealing means (e.g., a film that seals the dome closed and that is adhered to the package, e.g., the flange). The package may optionally enclose a barrier layer (e.g., a barrier layer comprising latex, rubber or a combination thereof, having an outer and inner service, wherein an adhesive layer comprising a stimuli-responsive polymer is present on at least a portion of the inner surface of the barrier layer). In certain embodiments, the outer layer of the barrier layer is adhered to the inner surface of the receiving body, either directly or by a retaining means. In certain embodiments, the barrier layer remains adhered to the inner surface of the receiving body under the user applies the barrier layer. In certain embodiments, the barrier layer remains adhered under pre-use conditions, such as shaking or other perturbations.

[0194] The receiving body (e.g., dome or cone) may be formed of any suitable material, including any material described herein. In certain embodiments, the receiving body is formed of PETG or LDPE. The surface energy of the inner surface of the receiving body may vary. In certain embodiments, the surface energy is between about 25-55 dynes / cm, more particularly, about 30 and about 50, about 35 and about 35, or about 40, dynes / cm. In certain embodiments, the surface energy is about 25, about 28, about 30, about 32, about 35, about 38, about 40, about 42, about 45, about 48 or about 50 dynes / cm. In certain embodiments, the packagedoes not include grips, e.g., the outer surface of the package is smooth. The contact angle of the first package material with water may vary, In certain embodiments, the first package material has a contact angle of between about 60 and about 90 degrees with water, and more particularly, about 60 to about 70, about 70 and about 80, or about 80 and about 90 degrees with water, and even more particularly, about 70 and about 85 degrees with water.

[0195] The barrier layer may be formed of any suitable material, including any material described herein. In certain embodiments, the barrier layer is formed of latex, rubber or a combination thereof. In certain embodiments, the barrier layer consists essentially of later or essentially of rubber In certain embodiments, the latex or rubber is not chemically treated, e.g., unchlorinated, unpowdered or not treated with a lubricant. The thickness of the barrier layer may vary. In certain embodiments, The barrier layer is between 5 and 250 microns, or in some embodiments between 25 and 100 microns, or in some embodiments between 25 and 75 microns.

[0196] The barrier layer comprises an outer surface and an inner surface. In certain embodiments, the inner surface comprises an adhesive layer across at least a portion of the inner surface (e.g., substantially coextensive with the inner surface of the barrier layer). According to this embodiment, the inner adhesive layer adheres the barrier layer to the contact surface, for example skin and or particularly penile skin. The adhesive layer may comprise any suitable material, including any material described herein. In certain embodiments, the adhesive layer comprises at least one stimuli-responsive polymer, for example formed from one or more monomers and optionally one or more polyfunctional crosslinkers. The stimuli may be any suitable stimuli, e.g., physiochemical change or mechanical force, such as shear rate. In certain embodiments, the stimuli-responsive polymer has a lower peel strength at lower peel rates and a higher peel strength at higher peel rates. Optionally, a release liner may be coupled to the adhesive layer. However, in the certain embodiments, the adhesive layer is not coupled to a release liner. In certain embodiments, no portion of adhesive layer contacts any other portion of the adhesive layer. In certain embodiments, the barrier layer (e.g., condom) is not wrinkled, folded or rolled.

[0197] In certain embodiments, the stimuli responsive polymer comprises acrylate monomers, optionally crosslinked with one or more polyfunctional crosslinkers. In one embodiment, the stimuli responsive polymer comprises apoly(lauryl methacrylate) polymer, optionally crosslinked with one or more trifunctional crosslinkers (e.g., TMPTA).

[0198] In one embodiment, the stimuli responsive polymer comprises a lightly crosslinked polymer and more particularly, a lightly crosslinked low molecular weight polymer as defined herein.

[0199] In one embodiment, the weight ratio of the stimuli responsive polymer (e.g., lauryl methacrylate) to the one or more polyfunctional crosslinkers is from 98:2 to 99.9:0.1, e.g., from 98.5: 1.5 to 99.9: 0.1; from 99: 1 to 99.9:0.1, from 99.1:0.9 to 99.9:0.1, from 99.2: 0.8 to 99.9:0.1; from 99.3:0.7 to 99.9:0.1, from 99.4:0.6 to 99.9:0.1, from 99.5:0.5 to 99.9:0.1, from 99.6:0.4 to 99.9:0.1, from 99.7:0.3 to 99.9:0.1, or from 99.8:0.2 to 99.9:0.1.

[0200] In certain embodiments, the receiving body comprises a void. The void may be dehumidified in certain embodiments.

[0201] The barrier layer may be adhered to the inner layer of the receiving body (e.g., the dome comprising a first packaging material) directly or by a retaining means. Direct adhesion may be a function of tack matching and / or treatment of the first packaging material, the barrier layer or both, to increase tack). The treatment may be any suitable treatment, e.g., electrostatic treatment, plasma treatment, corona treatment or a combination thereof.

[0202] In certain embodiments, the barrier layer is retained within the package in part due to interference fit. In certain embodiments, the interference fit is attributable to the generalized conical geometry of the receiving body, for example, in the case of developable surface

[0203] In certain embodiments, the package further comprises a retaining means, which may be any suitable retaining means. In one embodiment, the retaining means is a lip, ridge, ripple or the like. In other embodiments, the retaining means is a fluid, e.g., adhered to or coating the first packaging material. The sizing of the retaining means is designed to permit retention of the

[0204] In certain embodiments, the barrier layer comprises a reservoir. The reservoir may be, for example, self-forming in response to ejaculation of semen.

[0205] The package may optionally be housed within an outer shell. The outer shell may be formed of any suitable material, including any material disclosed herein.

[0206] In one embodiment, the package comprises (i) a shaped receiving body (1), wherein the receiving body comprises a flange (2) and a thin layer of liquid disposed on the inner surface of the receiving body; and (ii) a removable film lid (3) comprising a pull tab, wherein the receiving body and the lid are adhered at the flange to form a package suitable for protecting an adhesive (Figure 1). These components are described in further detail below.

[0207] The receiving body may be any suitable, non-planar shape. In certain embodiments, the receiving body is a shape selected from circular, elliptical, square, rectangular, polygonal, curvilinear polygonal, hemispherical, ellipsoidal, conical, tetrahedral, pyramidal or polyhedral.

[0208] In certain embodiments, the receiving body is generally circular.

[0209] In certain embodiments, the receiving body is a dome.

[0210] The thickness of the receiving body wall may vary. In one embodiment, the thickness of the receiving body wall is between 0.005” and 0.010”, or between 0.010” and 0.020”, or between 0.020” and 0.040”.

[0211] The physical properties of the receiving body may vary. In one embodiment, the receiving body is rigid. In a particular embodiment, the rigid receiving body comprises a thermoplastic polymer. The thermoplastic polymer may be any suitable thermoplastic polymer, e.g., polypropylene (PP), PET, polyethylene terephthalate glycol (PET-G), poly-chloro-trifluoroethylene / polyethylene terephthalate glycol, and combinations thereof.

[0212] In one embodiment, the present invention comprises a thermoplastic film that is optionally thermoformed with the functional package. In one embodiment, the thermoplastic film is low density polyethylene. In other embodiments, the thermoplastic film is a polyolefin, including polyethylene, polypropylene, other common petroleum derived and bio based polyolefins, acrylics, vinyl esters, vinyl ethers and styrenics. In another embodiment, the thermoplastic film is a polyurethane, polyester including polyethylene terapthalate, poly carbonate, or polyether. The thermoplastic film has a molecular weight of 2k to 10M Daltons,preferably 100k to 500k Daltons. The film has a thickness of 0.01 to 2000 microns, preferably 20 to 150 microns. Optionally, the film is electrostatically treated.

[0213] The package is generally disposable. In some embodiments, the receiving body may be recyclable and form from a material selected from PP, PET, and combinations thereof. In some embodiments, the thermoformed portion is compostable. In some embodiments, the receiving body is bio-based, e.g., formed partially or totally from bio-based PET. In some embodiments, the receiving body comprises a biodegradable plastic, such as polylactic acid (PLA), polyhydroxyalkanoates (PHAs), polyglycolic acid (PGA), polybutylene succinate (PBS).

[0214] In certain embodiments, the receiving body comprises a rigid thermoplastic polymer (e.g., PET-G) and is formed in a generally circular shape.

[0215] In another embodiment, the rigid shell is made of pressed or stamped aluminum.

[0216] In certain embodiments, the receiving body is semi-rigid, e.g., made of a thermoplastic elastomer, a high-density polyethylene, a low-density polyethylene or a PETG. The semi-rigid nature enables the user to manually conform the condom / package assembly over the glans, aiding in compressing and adhering the condom to the skin. Additionally, the semi-rigid behavior allows user to bend, fold or squish the receiving body / package, such as when carrying in a pocket, a wallet or a bag. The semi-rigid body retains its formed shape when no external forces are applied. Thus. upon removing the external forces constraining the package, when for example bent or squished in a user’s pocket, the receiving body will rebound into its formed geometry.

[0217] In one embodiment, the outer wall of the receiving body (and / or optionally, the shell where the package further comprises a shell surrounding the receiving body) comprises one or more features to facilitate use, e.g., to assist with alignment of the adhesive or removal of the package following application of the adhesion to the target site.

[0218] In one embodiment, the package is clear.

[0219] In one embodiment, the package has a clear window to facilitate visual alignment, such as a reservoir portion of a packaged enhanced sensation condom with the urethra meatus (opening).

[0220] In a particular embodiment, the outer wall comprises a hole to assist in aligning the adhesive for application. The size of the hole may vary. In one embodiment, the center portion of the rigid shell is removed, for example with a die- punch.

[0221] In a particular embodiment, a flange or flat surface is molded into the geometry around the removed section, so that another film lid (a secondary film lid) may be affixed to the back of the package, as shown in Figures 4A-4B, creating a “back passthrough”. The user then removes the primary film lid and the secondary film lid, i.e., the film covering the back passthrough. As the user is applying the condom, the back passthrough serves as a visual and tactile alignment aide, allowing the user to push the packaging over the glans, allowing the tip to protrude through the back passthrough, now enrobed in the barrier.

[0222] In a particular embodiment, the outer wall comprises a lifting tag to assist in removing the package after the adhesive is applied. In one embodiment, a lift-peel tab, as depicted in an exemplary embodiment in Fig.3, may be affixed to the back of the shell to aide in the manual gripping and manipulation of the package. The lift- peel tab is affixed to the shell using a pressure sensitive or other standard adhesive.

[0223] In certain embodiments, a package further comprises a shell surrounding the outer wall of the receiving body, wherein the shell comprises an outer wall and an inner wall, where at least a portion of the inner wall is in contact with the outer wall of the receiving body.

[0224] The shell may be the same or a different shape than the receiving body (e.g., circular-circular, circular-rectangular). The shell may comprise one or more additional features to facilitate use, e.g., to assist with alignment of the adhesive or removal of the package following application of the adhesion to the target site. In a particular embodiment, the shell comprises a hole. In a particular embodiment, the shell comprises a lifting tag.

[0225] The shell may be rigid or semi-rigid, comprised of one or more of the materials disclosed herein with respect to the receiving body.

[0226] In a particular embodiment, the package comprises an exterior shell surrounding the receiving body wherein the exterior shell and the receiving body are formed of materials having different rigidity. For example, with the receiving body comprises a rigid plastic or aluminum and the shell comprises a semi-rigid thermoplastic (elastomer). According to this embodiment, the user is able manipulate and conform the exterior of the package to the glans geometry, promoting improved adhesion, without direct contact with the condom, as depicted in Fig.5.

[0227] In another embodiment utilizing rigid-semi-rigid package, the package comprises a circular receiving body, and a rectangular flexible outer shell that contains attachment features such as wings. The flexible nature of the package thus allows for the user to manipulate the wings to adhere to the penis, while the rigid section maintains the geometry of the primary portion of the condom, including the area covering the urethra meatus and a semen collection reservoir, if present.

[0228] In another embodiment, the package has an interior shell with a center hole removed for the semen collection reservoir. This inner shell is attached to the exterior shell at or near the flange used to attach the film lid, as shown in Figs.7A- 7B. The attachment may be made by joining the two pieces of plastic with an adhesive, or with thermal welding or ultrasonic welding. In the variation of Fig.7A of this design, a support exists as shown by tag 52, thus creating a well for the reservoir tip to reside within.

[0229] In the variant of Fig.7B, no support exists, allowing the inner shell wall to deflect as the user applies pressure to adhere the condom to the glans. The stiffness of the inner shell may be designed through selection of the material thickness and cutout diameter to provide a specific resistance necessary for proper adhesion. This may be programmed for between 0.01 and 0.1 N, 0.1 and 1 N, 1 and 2 N, 2 and 5N, 5 and 10N, 10 and 20N, or 20 and 50N of force. This therefore provides a minimum force indicator for applying the condom consistently. Additionally, it provides a tactile response when the inner shell is fully compressed against the interior surface of the outer shell to indicate to the user that the minimum force of application has been met, and the condom has been firmly pressed against the penis for proper sealing of the adhesive.

[0230] The deflection force may be further tuned by molding in ridges or ripples that permit deformation, as depicted in Fig.8.

[0231] To enhance the tactile response, a clicker feature may be molded into the inner shell, which can be a tensioned, compressed, or torqued section of the inner shell, in a manner similar to a pop-up metallic food jar lid or a dog clicker device. When pressed, it will provide a tactile or audible click, indicating the minimum application force has been achieved.

[0232] In certain embodiments, the package is collapsible or semi-collapsible, e.g., for ease of storage or disposal.

[0233] In certain embodiments, the receiving body (and / or the shell, where present) is collapsible or semi-collapsible. The receiving body may comprise one or more features to facilitate collapse.

[0234] An embodiment of a package comprises at least one film lid, i.e., a removable or attached “top” for the package to enclose the contents, i.e., the condom or medical adhesive. Note that the geometry of the film lid conforms to the geometry of the opening, which for the purposes of illustration in Fig.1 is circular, however it need not be.

[0235] In one embodiment, the opening of the receiving body is covered with a film lid adhered to a flange on the receiving body periphery.

[0236] The film lid may comprise any suitable material. In one embodiment, the film lid comprises paper, plastic, aluminum, mylar, or aluminum-backed mylar.

[0237] The film lid may comprise a pull tab. In certain embodiments, the pull-tab may be further embossed with dimpling to aide in grip due to the presence of bodily fluids, water, or personal lubricants.

[0238] On the interior of the film lid, a release liner (e.g., silicone paper) may be adhered to the lid to reduce any adhesion to the lid, as depicted in Fig.1A.

[0239] In some embodiments, the package further comprises a second film lid, i.e., a removable or attached film lid on the underside or bottom of the package (relative to the top lid) that permits alignment of the package for ease of application as describe further herein.

[0240] A retaining element may vary but is intended to retain the adhesive (e.g., condom or medical adhesive) within the package to prevent adherence, e.g., to the film lid or other structures or itself. The retaining element secures the adhesive containing substrate during transport, storage and application while also allowing for the adhesive containing substrate to release when desired.

[0241] In one embodiment, the retaining element comprises a thin fluid film coating the inner surface of the receiving body.

[0242] The fluid may be any suitable liquid or gel. In one embodiment, the fluid is water, water-based or silicone-based, e.g., silicone oils and silicone-based lubricants. The latter may be suitable for use in part due to their favorable wetting properties to both latex / polyisoprene (barrier substrate), and thermoplastics (e.g., PETG) and aluminum constituting the package. The fluid film may be between 0.001 and 1 mm thick, but is dependent on the fluid viscosity, surface tension and contact angle of the fluid to the package and adhesive containing substrate materials selected and will establish an equilibrium thickness naturally.

[0243] In certain embodiments, the fluid film comprises a low tack biocompatible adhesive.

[0244] In certain embodiments, the fluid film comprises a water-soluble adhesive or a water-soluble stimuli-responsive adhesive.

[0245] In certain embodiments, the fluid film comprises a petroleum jelly.

[0246] Viscous lubricants may add additional favorable behaviors as a viscous film mitigates sliding motions of the condom along the interior surface of the package. These effects, while sufficient to stably retain the adhesive containing substrate (e.g., condom, medical adhesive) during transportation, storage and application, are weak compared to the adhesion force of a properly applied adhesive containing substrate to the target site (e.g., body part such as the glans). Therefore, as the user pulls the packaging away, the adhesive containing substrate is left securely behind.

[0247] In another embodiment, the retaining element comprises a pressure sensitive adhesive layer. The adhesive strength of the pressure sensitive adhesive layer to the adhesive containing substrate should be less than that of the adhesive containing substrate to the surface to which the adhesive containing substrate willbond (e.g., an adhesive condom bonding to a penis head). The thickness may vary between 0.001 and 0.1 mm, but is preferably between 0.025 and 0.150 mm.

[0248] In a further embodiment, the retaining element comprises a layer that exhibits tack matching to the inner surface of the package to secure the adhesive while also allowing release upon use. The adhesive strength of the layer for the adhesive contained within the package is less than that of the target surface to which the adhesive will bond (e.g., an adhesive condom bonding to a penis head). For example, latex exhibits sufficient tack matching to a PETG or thermoformable polyurethane package to secure a condom in place while also allowing for the condom to release and adhere to a penis head. In this case, the retaining element is an inherent feature of the materials selected for the adhesive containing substrate and the package, and thus the thickness is zero. Alternatively, the inner wall of the receiving body and the adhesive exhibit tack matching.

[0249] If the adhesive (e.g., medical adhesive or condom) does not release from the package, it is an indicator that contamination, folding or other adverse application scenarios prevented a successful adhesion or seal to the body part (e.g., glans penis). This serves as an indicator for the user to discard the adhesive / package and start again with a new unopened device.

[0250] The application is mess-free and does not require the user to interact with or contact the adhesive nor the barrier layer directly during the application process. As a result, the potential for contamination is reduced.

[0251] Also disclosed is a packaged adhesive, i.e., an adhesive contained within the package disclosed herein. Advantageously, in certain embodiments, the package retains the adhesive within the receiving body even when the package is inverted, i.e., the film lid side pointed toward the ground, without folding or creasing edges. In such embodiments, the retaining element is sufficiently strong to support the weight of the adhesive containing substrate and prevent the adhesive containing substrate from inverting or folding on itself, but is weaker than the strength of the attachment between the adhesive containing substrate and its application target (e.g. glans of the penis). As such, the retaining element releases the adhesive containing substrate when the package is pulled away from the application target, facilitating ofthe adhesive containing substrate on the application target without folding or creasing.

[0252] In one embodiment, the top surface of the adhesive containing substrate is affixed to the interior surface of the receiving body via a capillary force mechanism attributable to the thin film of liquid coating the interior surface of the retaining body. The fluid film wets out the exterior barrier surface (adhesive), creating a thin film between, for example, about 25 to about 250 microns thick. Capillary (surface tension and viscosity) behavior of a fluid that wets both the barrier substrate and the package material then creates an attractive retaining force.

[0253] In another embodiment, the exterior surface of the barrier layer (adhesive) is affixed to the interior surface of the receiving body via an inherent tack matching behavior between the receiving body and the barrier layer.

[0254] The adhesive may be any suitable adhesive.

[0255] In one embodiment, the adhesive is a reversible and / or stimuli-responsive adhesive, i.e., the adhesive adheres to a target surface under one set of conditions but then delaminates from the surface under a different set of conditions. According to this embodiment, the adhesive exhibits reversible and / or stimuli-responsive in response to stimuli that include, for example, temperature change, peeling rate change, dissolution, light exposure, exposure to electromagnetic fields, chemical exposure including exposure to water or pH change, and subjection to mechanical forces including shear forces or forces that drive crack propagation in adhesive or adhesive barrier.

[0256] In one embodiment, the adhesive is reversible in response to a stimulus and becomes less adhesive. The stimulus may be, for example, temperature change, chemical change, light, ultrasound, ionic strength change, peel shear or peel rate change, pH change, magnetic, or mechanical forces.

[0257] In a particular embodiment, the adhesive barrier exhibits semi-permeable or selectively-permeable behavior that permits a stimulus (e.g., a temperature or chemical stimulus) to permeate the adhesive used to induce a stimuli-response effect.

[0258] In another particular embodiment, the adhesive barrier exhibits a stimuli- responsive behavior that enables selective permeability or controlled permeability orcontrolled porosity. On-demand permeation of an arbitrary substance is controlled by exposure to temperature changes, chemical changes, light, ultrasound, ionic strength change, pH change, magnetic, or mechanical forces as well as other stimuli. The arbitrary substance may be a stimulus for an inner adhesive layer, which may experience a stimuli-response effect, or it may be a solvent capable of delaminating the inner adhesive layer. Mechanical forces for delamination include shear and / or peeling or pulling off at different frequencies or amplitudes. In another embodiment, the adhesive layer is frequency or force responsive and remains functionally adhered at higher forces or frequencies and can be removed using lower frequencies or forces of removal, for example, by lightly peeling or light pulling. In another embodiment, removal occurs with minimal or no pain, including light peeling or pulling.

[0259] In one embodiment, the adhesive converts from tacky to a non-tacky response to a stimulus (e.g., temperature, light).

[0260] In a particular embodiment, the adhesive adheres to a surface (e.g., a tissue) at body temperature (about 37 C) and also enables lowered adhesive force or delamination upon cooling below body temperature to about 25 C, about 20 C, about 15 C, about 10 C, about 5 C, about 0 C or lower.

[0261] In another particular embodiment, the adhesive adheres to a surface (e.g., a tissue) upon application of external heat. According to this embodiment, the adhesive exhibits increased adhesive force upon heating to about 30, about 35, about 37, about 40, about 45, about 55, about 60 or about 65 C or greater.

[0262] In a particular embodiment, the adhesive delaminates from a surface (e.g., a tissue) upon exposure to water or a solvent.

[0263] In another particular embodiment, the adhesive delaminates from a surface in response to a change in pH, e.g., by exposure to a substrate impregnated a pH suitable for physiologic use.

[0264] In one embodiment, delamination from human skin occurs in about 0.1 s, 1 s, about 2 s, about 5 s, about 10 s, 15 s, about 30 s, about 45 s, or about 60 s or more and is achievable by a combination of thermal, chemical, physical, or mechanical stimulus.

[0265] In one embodiment, the adhesive comprises a frequency- or shear- responsive adhesive that provides sufficient adhesive force for functional use and can be removed with minimal or no pain from skin by peeling or light removal effort. In another embodiment, any residual adhesive on skin can be removed with minimal or no pain by rubbing or repeated wiping.

[0266] In one embodiment, the adhesive exhibits elastomeric or flexible thermomechanical behavior.

[0267] Embodiments disclosed herein have a variety of end uses, in terms of the product to be packaged. The product may be, for example, an adhesive or an article or device comprising an adhesive as one component. The adhesive may be, for example, a single or multi-layer adhesive.

[0268] In one embodiment, the adhesive is an enhanced sensation condom or male diaphragm. In certain embodiments, the condom or diaphragm provides: (a) fractional coverage of the penis; (b) a barrier layer capable of preventing the flow of semen outside the diaphragm; (c) on-demand delamination in response to a stimulus; (d) produces substantially no pain to the user upon delamination; and (e) substantially no residue upon removal or only that residue which is easily removable.

[0269] In one embodiment, the barrier layer comprises a polymer membrane or film that exhibits elastomeric, soft but tough, or flexible thermomechanical behavior. In one embodiment, the fractional coverage is limited to the tip of the penis. In another embodiment, the fractional coverage is limited to the head of the penis. In a further embodiment, the fractional coverage does not include the shaft of the penis. In a further embodiment, the fractional coverage includes the base of the penis or below the base of the penis.

[0270] In certain embodiments, the diaphragm further comprises a reservoir. The location of the reservoir may vary and include, for example, the tip of the diaphragm, along the side or the diaphragm, at the base of the diaphragm or below the section of the diaphragm below the penile head.

[0271] The adhesive may have more than one layer. In one embodiment, the barrier layer further comprises an inner adhesive layer, wherein the inner adhesives adhere the barrier layer to penile skin.

[0272] In one embodiment, the inner adhesive layer exhibits stimuli- reversible or irreversible adhesive behavior that permits on-demand delamination.

[0273] In one embodiment, the stimulus is selected from temperature changes, chemical changes, light, ultrasound, ionic strength change, peeling rate change, dissolution, pH change, magnetic, or mechanical forces as well as other stimuli.

[0274] In one embodiment, the diaphragm does not delaminate in response to bodily fluids.

[0275] In another embodiment, the inner adhesive layer of the diaphragm is coated with a polymer which swells and / or gels in the presence of sperm, semen or seminal fluid, thereby retain sperm, semen or seminal fluid within the diaphragm.

[0276] In another embodiment, the diaphragm is coated on the outside with a spermicide and / or lubricant.

[0277] In another embodiment, the barrier layer exhibits semi-permeable, selectively-permeable or controlled porosity behavior that permits a chemical or temperature stimulant to permeate the membrane, thereby inducing a stimuli- response effect on the diaphragm.

[0278] In another embodiment, the barrier layer exhibits a stimuli-responsive behavior that enables selective permeability or controlled permeability or controlled porosity that may be induced on demand. On-demand permeation of a substance capable of permeating the barrier layer (i.e., a permeating substance) is controlled by exposure to temperature changes, chemical changes, light, ultrasound, ionic strength change, pH change, magnetic, or mechanical forces as well as other stimuli. The permeating substance may be a stimulus for an inner adhesive layer, which may experience a stimuli-response effect, or it may be a solvent capable of delaminating the inner adhesive layer.

[0279] The barrier layer may vary in thickness and may have a thickness of for example about 0.01, about 0.05, about 0.10. about 0.15, about 0.25, about 0.3 or about 0.5 mm or greater.

[0280] The reservoir may be roughly spherical in nature and may have a radius of for example about 0.1 mm, about 0.25 mm, about 0.5 mm, about 0.75 mm, about 1.0 mm, about 2.0 mm, about 5.0 mm or greater.

[0281] The reservoir may be roughly cylindrical in nature and may have a radius of about 0.1 mm, about 0.25 mm, about 0.5 mm, about 0.75 mm, about 1.0 mm, or about 2.0 mm or greater and a length of about 1.0 mm, about 2.0 mm, about 5.0 mm or about 10.0 mm or greater.

[0282] The reservoir may self-form when subjected to pressure from ejaculation and may not have a pre- defined geometry.

[0283] The reservoir may contain a polymer coating which swells or gels in the presence of sperm to retain the sperm within the reservoir. Polymer included but not limited to include chitosan, alginate, polyacrylic acid, crosslinked polyacrylic acid, sodium polyacrylate, crosslinked sodium polyacrylate etc.

[0284] In another embodiment, the barrier layer covers substantially less of the penis than existing condoms. Condom coverage may include fractional or entire coverage of the head of the penis and may extend to the base of the penis or below the base of the penis, and a reservoir may exist at the tip of the penis, along the side or the head of the penis, at the base of the penile head or below the penile head.

[0285] The barrier layer may be circular or ovular or of other geometries and may include protruding arms that extent to, around or below the base of the penile head and may cover partially the shaft of the penis. Protruding arms may have an adhesive later or may secure the diaphragm by mechanical force. A circular barrier layer may have a radius of about 0.5 cm, about 1.0 cm, about 2.0 cm, about 3.0 cm, about 5.0 cm or about 10.0 cm or greater. An ovular barrier layer may have a primary radius of about 0.5 cm, about 1.0 cm, about 2.0 cm, about 3.0 cm, about 5.0 cm or about 10.0 cm and a separate secondary radius of about 0.5 cm, about 1.0 cm, about 2.0 cm, about 3.0 cm, about 5.0 cm or about 10.0 cm or greater. Protruding arms may have an aspect ratio of about 1:1, about 1:2, about 1:5, about 1:10, about 1:20 or about 1:100 or greater, may be 1, 2, 3, 4, 5, 6 or more in number, may have lengths of about 0.5 cm, about 1.0 cm, about 2.0 cm, about 3.0 cm, about 5.0 cm or more and widths of about 0.1, about 0.2, about 0.5, about 1.0 or about 2.0 cm or more. An elastomeric ring may encircle the base of the barrier layer and may be expandable by stretching to encompass and secure the barrier layer to the base of the penile head and may optionally exert contractile force that enhances adhesion of the condom to the penis and prevents stress concentrations or shear forces fromremoving the adhered barrier layer during mechanical perturbation such as that associated with sexual activity. Optionally, an elastomeric ring may be attached to the end of one or more protruding arms and may be expandable by stretching to encompass and secure the barrier layer to the base of the penile head and may optionally exert contractile force that enhances adhesion of the condom to the penis and prevents stress concentrations or shear forces from removing the adhered barrier layer during mechanical perturbation such as that associated with sexual activity. Optionally, the elastomeric ring may enhance sexual sensation or pleasure as well and may be comprised of the same or other materials as the barrier layer or adhesive layer and may have raised rings or studs. Optionally, the barrier layer may have a lubricant on the external side opposite the adhesive layer. The lubricant may be, for example a water- based, silicon-based or oil-based lubricant. Optionally, the barrier layer may have a spermicide on the external side opposite the adhesive layer. The spermicide may be for example, Nonoxynol-9, octoxynol-9, benzalkonium chloride, lactic acid, menfegol, and others known in the art.

[0286] The barrier layer may also be square, oval, spherical, rectangular, polygonal or curvilinear polygonal, conical, tetrahedral, pyramidal or polyhedral in geometry and may have primary dimensions of about 0.5 x 0.5 cm, about 1.0 x 1.0 cm, about 1.5 x 1.5 cm, about 2.5 x 2.5 cm, about 3.0 x 3.0 cm, or about 5.0 x 5.0 cm or any combination thereof in the case of a rectangular barrier layer and may optionally comprise protruding arms from the corners or edges of squares, rectangles, and polygonal or curvilinear polygonal. Protruding arms may have an aspect ratio of about 1:1, about 1:2, about 1:5, about 1:10, about 1:20 or about 1:100 or greater, may be 1, 2, 3, 4, 5, 6 or more in number, may have lengths of about 0.5 cm, about 1.0 cm, about 2.0 cm, about 3.0 cm, about 5.0 cm or more and widths of about 0.1, about 0.2, about 0.5, about 1.0 or about 2.0 cm or more. The optional ring may have a ring cross-sectional diameter of about 0.1, about 0.5, about 1.0. about 2.0 mm, about 3.0 mm or more and may have an overall diameter approximately 0.25x, 0.50x, 0.75x or 1.0x that of the barrier layer diameter.

[0287] In one embodiment, the barrier layer is not tubular.

[0288] In another embodiment, the barrier layer is one geometry or shape and then transforms to a second geometry or shape when applying it to the penis.

[0289] In another embodiment, the barrier layer comprises an inner adhesive layer that adheres the barrier layer to penile skin located on the penile head, penile head base or below the base of the penile head. The adhesive layer may extend to the ring or protruding arm sections of the diaphragm.

[0290] In another embodiment, the inner adhesive layer exhibits stimuli- responsive reversible or irreversible adhesive behavior that enables selective delamination (i.e., on-demand delamination) of the diaphragm from penile skin. Reversible or irreversible adhesive behavior can be triggered by exposure to temperature changes (e.g., a decrease in temperature), chemical changes, light, ultrasound, ionic strength change, pH change, magnetic, electrical, or mechanical forces as well as other stimuli or any combination thereof. Mechanical forces for delamination include shear and / or peeling or pulling off at different frequencies or rates. In another embodiment, the adhesive layer is frequency or force responsive and remains functionally adhered at higher forces or frequencies or shear rates and can be removed using lower frequencies or forces or shear rates of removal, for example, by lightly peeling or light pulling. In another embodiment, removal occurs with minimal or no pain, including light peeling or pulling. Higher and lower are taken with respect to a threshold about which a change in behavior is observed. For force, this may be between 0.01 and 0.1 N, between 0.1 and 1.0 N, between 1.0 and 10.0 N, between 10.0 and 100.0 N, or between 100.0 and 1000.0 N, or 1 and 10 Pa, 10 and 100 Pa, 0.1 and 1 kPa, 1 and 10 kPa, 10 and 100 kPa, 0.1 and 1 MPa. For shear rate this may be between 0.1 and 1 sec-1, between 1.0 and 10 sec-1, between 10 and 100 sec-1, between 100 and 1000 sec-1, 1000 and 10000 sec-1, or between 10000 and 100000 sec-1. For frequency this may be between 0.01 Hz and 0.1 Hz, between 0.1 and 1.0 Hz, between 1.0 and 10.0 Hz, between 10.0 and 100.0 Hz, or between 100.0 and 1000.0 Hz. Light pulling or light peeling means performing a removal action with a lower amount of force, a lower shear rate or a lower frequency than the threshold about which the behavior change occurs.

[0291] In another embodiment, the inner adhesive layer may be comprised of two or three or more adhesive regions which may exhibit different mechanical, chemical and biological properties. These may include different solubility parameters in various solvents including water or vaginal fluids or ejaculate fluids. Reversible or irreversible adhesive behavior can be triggered by an exposure to temperaturechanges, chemical changes, light, ultrasound, ionic strength change, pH change, magnetic, electrical or mechanical forces as well as other stimuli or any combination thereof, either simultaneously or sequentially.

[0292] Adhesive layer may be nanometer scale or micron scale in thickness, with adhesive layer thickness ranging from about 0.01 microns to about 0.1 microns to about 1.0 microns to about 5.0 microns to about 10.0 microns to about 20.0 microns to about 30.0 microns to about 50.0 microns to about 100.0 microns to about 200 microns to about 300 microns to about 400 microns to about 600 microns to about 750 microns to about 1000 microns to about 2000 microns to about 3000 microns or more and may be configured on the barrier uniformly or in a patterned configuration. Patterned configuration may cover about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75% or about 100% or any combination thereof of the overall adhesive area within the barrier layer, and the adhesive area of the barrier layer may cover about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75% or about 100% of the overall barrier layer. Pattered configurations of adhesive may be ringlike with single or multiple ring layers varying in thickness of about 0.1, about 0.25, about 0.5 or about 1.0 mm or more, may be dot-patterned as square, rectangular or circular dots that cover about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75% or about 100% or any combination thereof of the overall adhesive area within the barrier layer. Patterned configuration may also be stripe-like with stripe layers varying in thickness of about 0.1, about 0.25, about 0.5 or about 1.0 mm or more and stripe layers covering about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75% or about 100% or any combination thereof of the overall adhesive area within the barrier layer. Patterning may be uniform, non- uniform or random in shape or size or location, or any combination thereof. Adhesive layers may be uniform, non-uniform, circular, spherical, elliptical or ellipsoidal in cross-section, illustrated in Fig.3. Adhesive layer may only cover a fraction of the head of the penis and leave high sensation areas of the penis exposed such as the frenulum and may have a reservoir that allows for flow of semen below the head of the penis to and around the base of the penis.

[0293] In another embodiment, adhesive patterning may facilitate adhesive crack propagation or shear-responsive pressure sensitive adhesive delamination. Forexample, adhesive patterning may enable sufficient adhesion of barrier to penis head while also enabling barrier to be peeled with minimal or sufficient pain for user experience. Such patterning includes but is not limited to a continuous ring or repeating dot ring layer at the base of the barrier ranging from 0.1 to 3000 micrometers in length, more optimally 1 to 2000 micrometers in length, more optimally 20 to 2000 micrometers in length, and ranging from 0.1 to 3000 micrometers thick, more optimally 1 to 2000 micrometers thick, more optimally 5 to 1000 micrometers thick, more optimally 10 to 600 micrometers thick, with dot patterns covering between 10 and 100% of available adhesive area in base ring area, more optimally 20 and 100% of available adhesive area in base ring area, more optimally 30 and 100% of available area in base ring area. Additional dot patterns, ring-link configurations, stripes or other adhesive configurations may be patterned along the inside of the barrier to facilitate delamination via peeling (pressure sensitive adhesive behavior).

[0294] In one embodiment, the adhesive layer may achieve delamination by swelling by about 1% by volume, about 2%, about 5%, about 10%, about 25%, about 40%, about 50%, about 75%, about 100%, about 150%, about 200%, about 500%, about 1000%, about 1500%, about 2000%, about 3000%, about 5000%, about 10,000%, about 100,000% or more by volume or may become soluble in a solvent for delamination to be achieved, including solvent including water based solvent or chemical solution that is applied by a wipe. In another embodiment, the wipe denatures protein to achieve delamination such as water and PEG-doped (i.e., nonvolatile plasticizer) albumin via chemical denaturation by introduction of solvents that include ethanol or isopropanol. In another embodiment, the wipe contains a volatile solvent that diffuses through the diaphragm barrier to achieve delamination by chemical reaction, dissolution, denaturation or swelling of adhesive layer. In another embodiment. In another embodiment, the wipe contains a volatile additive that cools the wipe upon evaporation to enable temperature-based delamination)

[0295] In another embodiment, the adhesive is a medical adhesive. In one embodiment, the adhesive permits closure, fills a space, covers a surface, promotes healing (e.g., wound healing), promotes tissue regeneration, fill a space, cover a surface, supports an injured body part, immobilizes two structures. or secures a medical device to the body- in each case partially or totally.

[0296] In one embodiment, the adhesive is suitable for external medical use, internal medical use or both internal and external medical use. In certain embodiment, the adhesive is formulated to form a bandage, sealant, covering, dressing or the like.

[0297] In a particular embodiment, the adhesive is suitable for use in preventing securing tissue or organ adhesion which are damaged.

[0298] In a particular embodiment, the adhesive is a dental adhesive.

[0299] In a particular embodiment, the adhesive is transparent.

[0300] The adhesive composition may be provided, for example, as a membrane or film. The membrane or film may comprise a continuous layer of adhesive having an opposed first and second surface.

[0301] The membrane or film may be nanometer scale or micron scale in thickness, with adhesive layer thickness ranging from about 0.01 microns to about 0.1 microns to about 1.0 microns to about 5.0 microns to about 10.0 microns to about 20.0 microns to about 30.0 microns to about 50.0 microns to about 100.0 microns to about 200 microns to about 300 microns to about 400 microns to about 600 microns to about 750 microns to about 1000 microns to about 2000 microns to about 3000 microns or more and may be configured on the barrier uniformly or in a patterned configuration. Patterned configuration may cover about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75% or about 100% or any combination thereof of the overall adhesive area within the barrier layer, and the adhesive area of the barrier layer may cover about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75% or about 100% of the overall layer. Pattered configurations of adhesive may be annular with single or multiple concentric annular patterns. in the case of medical adhesive use cases that employ three dimensional geometries such as adhesive contraceptive devices or may utilize combinations of continuous lines and dots in the case of planar device geometries such as medical barrier adhesives for securing intravenous (IV) needles or tubes, catheters, bandages, wound dressings or other use cases that utilizes medical adhesives varying in thickness of about 0.1, about 0.25, about 0.5 or about 1.0 mm or more, may be dot-patterned as square, rectangular or circular dots that cover about 1%, about 5%, about 10%, about 25%, about 33%, about 50%,about 66%, about 75% or about 100% or any combination thereof of the overall adhesive area within the film or membrane Patterned configuration may also be stripe-like with stripe layers varying in thickness of about 0.1, about 0.25, about 0.5 or about 1.0 mm or more and stripe layers covering about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75% or about 100% or any combination thereof of the overall adhesive area within the film or membrane. Patterning may be uniform, non-uniform or random in shape or size or location, or any combination thereof. Adhesive layers may be uniform, non-uniform, circular, spherical, elliptical or ellipsoidal in cross-section,

[0302] In another embodiment, adhesive patterning may facilitate adhesive crack propagation or shear-responsive pressure sensitive adhesive delamination. For example, adhesive patterning may enable sufficient adhesion of barrier to target site while also enabling barrier to be peeled with minimal or sufficient pain for user experience. Such patterning includes but is not limited to a continuous ring or repeating dot ring layer at the base annulus or edge annulus of the barrier ranging from 0.1 to 3000 micrometers in length, more optimally 1 to 2000 micrometers in length, more optimally 20 to 2000 micrometers in length, and ranging from 0.1 to 3000 micrometers thick, more optimally 1 to 2000 micrometers thick, more optimally 5 to 1000 micrometers thick, more optimally 10 to 600 micrometers thick, with dot patterns covering between 10 and 100% of available adhesive area in the annular area, more optimally 20 and 100% of available adhesive area in annular area, more optimally 30 and 100% of available area in base annulus area in the case of medical adhesive use cases that employ three dimensional geometries such as adhesive contraceptive devices or may utilize combinations of continuous lines and dots in the case of planar device geometries such as medical barrier adhesives for securing intravenous (IV) needles or tubes, catheters, bandages, wound dressings or other use cases that utilizes medical adhesives. Additional dot patterns, ring-link configurations, stripes or other adhesive configurations may be patterned along the inside of the membrane or film to facilitate delamination via peeling (pressure sensitive adhesive behavior).

[0303] The size of the membrane or film can be tailored for specific intended uses, or it can be provided in a sheet or roll form. In one embodiment, the adhesive composition is provided as a tape.

[0304] In one embodiment, the membrane or film ranges in size from about ¼ inch to about 2 or 3 inches or more, although preferred widths in embodiments may be from about ½ to about 1 or 1½ inches and can range in length from about ½ inch to about 4 or 5 inches or more, although preferred lengths in embodiments may be from about 1 to about 2 or 3 inches. In another embodiment, the membrane or film ranges in size from about 5 to about 8 inches or more.

[0305] The shape of the membrane or film may vary. In one embodiment, the membrane or Film is square, oval, spherical, rectangular, polygonal or curvilinear polygonal in geometry.

[0306] In one embodiment, the adhesive composition comprises a proximal adhesive layer that adheres to a target substrate, e.g., the skin or a mucus membrane. In one embodiment, the inner adhesive layer exhibits stimuli-responsive reversible or irreversible adhesive behavior that enables selective delamination of the adhesive composition from the surface to which it is adhered.

[0307] In another embodiment, the adhesive is not in contact with or provided with any final barrier and instead is provided in solid, liquid or other forms and is provided to facilitate adhesion between skin, mucosal tissue or other biomass and an additional barrier that includes polyurethane, poly(vinyl chloride), polymeric, latex or other barriers.

[0308] In a particular embodiment, the adhesive is applied as a solid film that is adhesive on both sides, after which an additional barrier is applied.

[0309] In a particular embodiment, the inner adhesive layer may be comprised of two or three or more adhesive regions which may exhibit different mechanical, chemical and biological properties. These may include different solubility parameters in various solvents including water or biological fluids. Reversible or irreversible adhesive behavior can be triggered by an exposure to temperature changes, chemical changes, light, ultrasound, ionic strength change, pH change, magnetic, electrical or mechanical forces as well as other stimuli or any combination thereof, either simultaneously or sequentially.

[0310] In one embodiment, the adhesive layer may swell by about 1% by volume, about 2%, about 5%, about 10%, about 25%, about 40%, about 50%, about 75%, about 100%, about 150%, about 200%, about 500%, about 1000%, about 1500%,about 2000%, about 3000%, about 5000%, about 10,000%, about 100,000% or more by volume or may become soluble in a solvent for delamination to be achieved, including solvent including water based solvent or chemical solution that is applied by a wipe. In another embodiment, the wipe denatures protein to achieve delamination such as water and PEG-doped (i.e., nonvolatile plasticizer) albumin via chemical denaturation by introduction of solvents that include ethanol or isopropanol. In another embodiment, the wipe contains a volatile solvent that diffuses through the diaphragm barrier to achieve delamination by chemical reaction, dissolution, denaturation or swelling of adhesive layer. In another embodiment. In another embodiment, the wipe contains a volatile additive that cools the wipe upon evaporation to enable temperature-based delamination.

[0311] Adhesive layer may be comprised of one or more linear or crosslinked polymers that include, for example, poly(2- ethylhexyl acrylate), poly(butyl acrylate), poly(propyl acrylate), poly(ethyl acrylate), poly(methyl acrylate), poly(octyl acrylate), poly(nonyl acrylate) poly(decyl acrylate), poly(isodecyl acrylate), poly(isotridecyl acrylate), poly(isodecyl methacrylate), poly(iso tridecyl methacrylate), poly(lauryl methacrylate), poly(undecyl acrylate), poly(dodecyl acrylate), poly(tridecyl acrylate), poly(C14 acrylate), poly (C15 acrylate), poly(C16 acrylate), poly (C17 acrylate), poly(C18 acrylate), poly(C19 acrylate), poly(methacrylates) of any of the aforementioned acrylates, poly(C20-C100 or more acrylates, methacrylates and acrylamides thereof), poly(2-hydroxyethyl acrylate), poly(butoxymethyl acrylate), poly(butoxyethyl acrylate), poly(butoxypropyl acrylate), poly(butoxybutyl acrylate), poly(fin(ding)-nemo-acrylate), poly(octadecyl acrylate), poly(octadecyl 52ethacrylate), poly(acrylic acid), and polyacrylates or polymethacrylates with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or up to 100 carbons in the side chain and 0, 1, 2, 3, 4, 5, 6, 7, 8, 910 or up to 100 or more oxygens in the side chain, poly(methacrylate), poly(acrylamide) such as poly(n-isopropyl acrylamide), poly(dimethyl acrylamide), poly(methacrylamide) versions of the aforementioned acrylates, amorphous or semi- crystalline polyurethanes, polyethers including poly(ethylene glycol( (PEG) compounds and acrylated or polyurethane containing PEG compounds, epoxies, silicones or other adhesives suitable to human skin contact. In one embodiment, the adhesive may by comprised of a linear or crosslinked polymer with a side chain that optionally undergoes crystallization and / or melting in the region around body androom temperature, in the range of 0 C to 50 C, more particularly in the range of 5 C to 45 C, more particularly in the range of 10 C to 40 C, more particularly in the range of 15 C to 35 C. For clarity, side chain crystallization is optional. In another embodiment, the adhesive may be comprised of a complex homogenous or heterogenous blend comprising (1) a primary side chain optionally crystallizable side chain adhesive polymer, (2) optionally a secondary optionally crystallizable side chain, (3) optional tackifiers or plasticizers such as glyceryl, phthalates, polyethylene glycol derivatives with molecular weights ranging from 1 to 1000 or more repeat units, C10-C40 linear or branched wax or modified wax constituents such as n-butyl stearate or ethyl decanoate, (4) optionally additional amorphous polymer blended phases or heterophases, and (5) optionally crosslinkers, which optionally are incorporated into polymer network uniformly and optionally are aggregated and serve as high stress concentration network sites to facilitate adhesive failure when desirable.

[0312] In certain embodiments, ranges for primary side chain optionally crystallizable polymer range from about 40 to about 100%, more particularly, about 50 to 100%. In a particular embodiment, the range is from about 40 to about 50%, about 50 to about 60%, about 60 to about 70%, about 70 to about 80%, about 80 to about 90% or about 90% or more or any range or value subsumed therein.

[0313] In certain embodiments, ranges for secondary side chain optionally crystallizable polymer range from about 0 to about 50%, more particularly 1 to about 49%, more particularly about 2 to about 48%, more particularly about 3 to 47%, more particularly about particularly 5 to about 45% or any additional range or value subsumed therein.

[0314] In certain embodiments, ranges for tackifiers or plasticizers range from 0 to 60%, more particularly 0.01% to 60%.

[0315] In certain embodiments, ranges for amorphous polymer blend range of 0 to 60%. In one embodiment, ranges of crosslinkers range from 0 to 30 wt %, more optionally 0.001 to 29 wt%, more particularly 0.005 to 28 wt%, more particularly 0.0075 to 28 wt%, more particularly 0.01 to 27 wt%, more particularly 0.02 to 26 wt%, more particularly 0.05 to 26 wt%, more particularly 0.1 to 25 wt%, more particularly 0.15 to 24 wt%, more optimally 0.15 to 10 wt%, more optimally 0.15 to 2wt%, more optimally 0.15 to 1.5 wt%, including ranges within. Crosslinkers may exhibit functionality greater than n=1 reactive site statistically, for example, statistical averages of n = 2, 3, 4, 5, 6, 7, 8, 9, 10 or more reactive sites and may facilitate branching, hyperbranching, interpenetrating networks, semi-interpenetrating networks and generally homogeneous or partially homogeneous and partially heterogeneous or generally heterogeneous networks with respect to phase blending or concentration of crosslink density. For example, favorable adhesive failure or delamination from skin, including residual adhesive removal after peeling away of adhesive, may be achieved by heterogeneous crosslinking distribution to concentrate failure sites within network or a “swollen network” formed by polymerization of a crosslinker and a monomer with different reactivity ratios, for example, a blend of lauryl methacrylate and trimethylolpropane triacrylate, TMPTA, comprising 0.5 wt% TMPTA and 1.0 wt% DMPA photoinitiator. In one embodiment, TMPTA may form a swollen gelled network permeated by lauryl methacrylate monomer that then is polymerized to form a complex swollen network or semi-IPN such that polymer flow of cured network occurs at different shear rates or frequencies or force modalities and enables adhesive behavior such that an adhesive barrier can stick to skin or other surfaces in a functional manner and be removed using low shear rate or low frequency deformation or peeling such that polymer flow dissipates energy and does not cause pain upon removal. Representative crosslinkers include poly(ethylene glycol) diacrylate with internal repeat units ranging from 1 to 1000 or more, trimethylolpropane triacrylate,, trimethylolpropane trimethacrylate ethoxylated trimethyolpropane triacrylate or trimethacrylate with repeat units ranging from 1 to 1000 or more, pentaerithitol tetraacrylate, ethoxylated pentaerythritol tetraacrylate or tetramethacrylate with repeat units ranging from 1 to 1000 or more, penta and hexafunctional acrylates or methacrylates and ethoxylated versions as described above including dipentaerithrotol hexaacrylate and ethoxylated dipentaerithrotol hexaacrylate with repeat units ranging from 1 to 1000 or more, di, tri, tetra, penta, hexa more expoxide monomers, polythiols, polyalkenes cured by UV light, visible light, gamma or e-beam irradiation, heat or hydrosilation. In another embodiment linear or branched polymers with repeat units ranging from 1 to 1000 or more wherein the repeat unit may or may not contain an acrylate, cured by UV light, visible light, gama or e-beam irradiation, heat or hydrosilation, metal coordination including titanium to polymeric acid sidechain coordination, In one embodiment, UV curable compositions for adhesives in the present invention comprise a photoinitiator in the range of 0.001 to 10 wt %, more particularly 0.01 to 5 wt%, more particularly 0.1 to 5 wt%. In another embodiment, photoinitiators include 2,2-dimethoxy-2-phenylacetophenone (DMPA), Eosin y, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), lithium phenyl- 2,4,6-trimethylbenzoylphosphinate (LAP), biocompatible photoinitiators.

[0316] In another embodiment, the adhesive comprises polymeric components that include linear, branched and crosslinked polymers comprising (1) backbone chemistry, (2) side chain chemistry, (3) crosslinking, (4) additives.

[0317] Backbone chemistries include polymers made from monomers that include acrylate, methacrylate, thiol-acrylate Michael Addition, acrylate amine Michael Addition, epoxy thiol, epoxy amine, polyethylenimine (PEI), thiol-ene, alternating copolymers made from C=C electron poor + C=C electron rich monomers, urethane, urea, acrylamide, methacrylamide, polyester, polycarbonate, polyamide, peptoid, peptide, Diels-alder, lactides and lactams, and ring opening metathesis polymerization or olefin metathesis reactions

[0318] Side chain chemistries include linkages made from monomers that include acrylate, methacrylate, thiol-acrylate Michael Addition, acrylate amine Michael Addition, epoxy thiol, epoxy amine, polyethylenimine (PEI), thiol-ene, alternating copolymers made from C=C electron poor + C=C electron rich monomers, urethane, urea, acrylamide, methacrylamide, polyester, polycarbonate, polyamide, peptoid, peptide, Diels-alder, lactides and lactams, and ring opening metathesis polymerization or olefin metathesis reactions. Side chain chemistries include C1- C100 side chain linkages achieved by synthetic pathways disclosed herein.

[0319] Crosslinking chemistries include linkages made from monomers that include acrylate, methacrylate, thiol-acrylate Michael Addition, acrylate amine Michael Addition, epoxy thiol, epoxy amine, polyethylenimine (PEI), thiol-ene, alternating copolymers made from C=C electron poor + C=C electron rich monomers, urethane, urea, acrylamide, methacrylamide, polyester, polycarbonate, polyamide, peptoid, peptide, Diels-alder, lactides and lactams, and ring opening metathesis polymerization or olefin metathesis reactions

[0320] Acrylate monomers include Methyl acrylate, Ethyl acrylate, Butyl acrylate, 2-Ethylhexyl acrylate, Isobutyl acrylate, Methoxyethyl acrylate, Hydroxyethyl acrylate, Hydroxypropyl acrylate, Ethoxylated (2) hydroxyethyl acrylate, N-Vinyl pyrrolidone, Glycidyl acrylate, Methacrylic acid, Methyl methacrylate, Ethyl methacrylate, Butyl methacrylate, 2-Hydroxyethyl methacrylate, Cyclohexyl methacrylate, N-Isopropylacrylamide, Poly(ethylene glycol) methacrylate, Poly(ethylene glycol) diacrylate, Poly(ethylene glycol) dimethacrylate, Trimethylolpropane triacrylate, Triethylene glycol diacrylate, Tetraethylene glycol diacrylate, Neopentyl glycol diacrylate, Diethylene glycol diacrylate, Dipentaerythritol hexaacrylate, Ethoxylated trimethylolpropane triacrylate, Propoxylated glycerol triacrylate, Stearyl acrylate, Lauryl acrylate, Isodecyl acrylate, Acrylic acid, N,N- dimethylacrylamid, Ethylene glycol diacrylate (EGDA), Triethylene glycol diacrylate (TEGDA), Propylene glycol diacrylate (PGDA), Butanediol diacrylate (BDDA), Neopentyl glycol diacrylate (NPGDA), Pentaerythritol tetraacrylate (PETA), 1,4- Butanediol diacrylate (BDA), Di(trimethylolpropane) tetraacrylate (DTMPTA), Bisphenol A ethoxylate diacrylate (BPAEDA), Ethoxylated bisphenol A diacrylate (EBPA), Decanediol diacrylate, Polyethylene glycol diacrylate (PEGDA), Trimethylolpropane triacrylate (TMPTA), Diethylene glycol diacrylate (DEGDA), and 1,6-Hexanediol diacrylate (HDDA), Trimethylolpropane triacrylate (TMPTA), Tripropylene glycol diacrylate (TPGDA), Pentaerythritol triacrylate (PETA), Dipentaerythritol pentaacrylate (DPEPA), Tris(2-hydroxyethyl) isocyanurate triacrylate (THEIC-TA), Triethylene glycol dimethacrylate (TEGDMA), Triallyl isocyanurate (TAIC), Triethylene glycol diacrylate (TEGDA), Ethoxylated trimethylolpropane triacrylate (ETMPTA), Triallyl cyanurate (TAC)

[0321] Vinyl ether monomers include divinyl ether of ethylene glycol, divinyl ether of diethylene glycol, divinyl ether of triethylene glycol, divinyl ether of polyethylene glycol (DVE-PEG), divinyl ether of polypropylene glycol (DVE-PPG),Divinyl ether of poly(ethylene glycol) methyl ether (DVE-PEGME), divinyl ether of poly(ethylene glycol) butyl ether (DVE), Divinyl ether of poly(ethylene glycol) phenyl ether (DVE- PEGPhE) Divinyl ether of glycerol (DVE-Gly),Divinyl ether of 1,4- cyclohexanedimethanol (DVE-CHDM), Divinyl ether of neopentyl glycol (DVE-NPG)

[0322] Allyl monomers include Diallyl phthalate (DAP), Diallyl maleate (DAM), Diallyl succinate (DAS), Diallyl fumarate (DAF), Diallyl adipate (DAA), Diallylsebacate (DAS), Diallyl terephthalate (DAT), Diallyl isophthalate (DAI), Diallyl itaconate (DAI), Diallyl carbonate (DAC), Diallyl diglycolate (DADG), Diallyl tris(2- hydroxyethyl) isocyanurate (DATHEIC), Triallyl cyanurate (TAC), Triallyl isocyanurate (TAIC), Triallyl trimellitate (TATM), Triallyl citrate (TAC), Triallyl phosphate (TAP), Triallylamine (TAA), Triallyl cyanide (TACN), Triallyl benzene- 1,2,4-tricarboxylate (TABTC), Triallyl trimesate (TATM), Tris(2-hydroxyethyl) isocyanurate triallyl ether (THEIC-TAE)

[0323] Methyl methacrylate, Ethyl methacrylate, Butyl methacrylate, 2- Hydroxyethyl methacrylate, Cyclohexyl methacrylate, Isobornyl methacrylate, Stearyl methacrylate, Lauryl methacrylate, Isodecyl methacrylate, Tetrahydrofurfuryl methacrylate, Glyceryl methacrylate, Trimethylolpropane trimethacrylate, Trimethylolpropane triacrylate, Pentaerythritol triacrylate, Pentaerythritol tetramethacrylate, Poly(ethylene glycol) monomethyl ether methacrylate, Poly(ethylene glycol) monomethyl ether acrylate, Poly(ethylene glycol) diacrylate, Poly(ethylene glycol) dimethacrylate, Poly(ethylene glycol) monoacrylate, Ethoxylated bisphenol A dimethacrylate, Ethoxylated bisphenol A diacrylate, Ethoxylated trimethylolpropane triacrylate, Hydroxypropyl methacrylate, Methacrylic acid, Acryloyloxyethyltrimethylammonium chloride, Diethylaminoethyl methacrylate, Butylaminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, Methacryloyloxyethyl phthalate, N-Vinyl pyrrolidone, N-Isopropylacrylamide, and Cyclopropyl methacrylate

[0324] Thiol monomers include 3-Mercaptopropionic acid, Thioglycolic acid, 3- Mercapto-1-propanol, 2-Mercaptoethanol, 2-(2-Mercaptoethoxy)ethanol, 2-(2- Mercaptopropionylamino)ethanol, 2-(2-Mercaptosuccinyl)ethyl acrylate, 3-(2- Mercaptopropionylamino)propionic acid, 3-(Mercaptopropyl)trimethoxysila’e, 2,2'- (Ethylenebis(thio))diethanol, 3-Mercaptopropyltrimethoxysilane, 3- Mercaptopropylmethyldimethoxysilane, 3-(2,2- Dithiobis(ethylthio)propionylamino)propionic acid, 3,6,9-Trioxadecanethiol, 3- Mercapto-1,2-propanedi’l, 2,2'-Dithiodiethanol, N-Acetyl-L-cysteine, L-Cysteine, 2-(2- Mercaptoethyl)pyridine, 4-(2-Mercaptoethyl)morpholine, 3-Mercapto-1,2,4-triazole, Thiophenol, Pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), Trimethylolpropane tris(3-mercaptopropionate) (TMPMP), Triethanolamine tris(3- mercaptopropionate) (TEAMP), Tris(2-hydroxyethyl) isocyanurate tris(3-mercaptopropionate) (THEICMP), Bis(3-mercaptopropyl) sulfide (BMPS), 1,2- ethanedithiol (EDT), 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and 1,8- octanedithiol.

[0325] Epoxy monomers include Bisphenol A diglycidyl ether (BADGE), Bisphenol F diglycidyl ether (BFDGE), Novolac diglycidyl ether (NGDE), Phenol novolac diglycidyl ether (PNGDE), Cycloaliphatic epoxy resins, Glycidyl ethers of aliphatic alcohols, Glycidyl ethers of aromatic alcohols, Triglycidyl isocyanurate (TGIC), Diglycidyl ether of 1,4-butanediol (BDDGE), Diglycidyl ether of neopentyl glycol (NPGDGE), Diglycidyl ether of propylene glycol (PGDGE), Epoxidized soybean oil (ESO), Epoxidized linseed oil (ELO), Dicyclopentadiene-based epoxy resins, Tetrafunctional epoxy resins, and Epoxy phenolic novolac resins

[0326] Amine monomers include Ethylenediamine, Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine, Polyethyleneimine, Diaminopropane, Diaminobutane, Diaminopentane, Diethylenetriaminepentaacetic acid (DTPA), Tris(2-aminoethyl)amine, N-(2-Aminoethyl)piperazine, N-(3-Aminopropyl)morpholine, N,N-Dimethylaminopropylamine, N,N-Dimethylethylenediamine, 1,3- Diaminopropane, Isophoronediamine, Jeffamine D-230, Jeffamine T-403, Jeffamine M-207, Jeffamine EDR-148

[0327] Electron rich monomers Vinyl ethers (e.g. vinyl methyl ether, vinyl ethyl ether), Vinyl acetate, Allyl alcohol, Allyl amine, N-Methylolacrylamide, N- Methylolmethacrylamide, N-Methylolallylamine, N-Methylolvinylacetamide, Acrolein diethyl acetal, Acrolein diethyl ketal, Diacetone acrylamide, 2-Hydroxyethyl acrylate, 2-Hydroxyethyl methacrylate, 2-Hydroxypropyl acrylate, 2-Hydroxypropyl methacrylate, 2,3-Dihydroxypropyl methacrylate, Glycidyl methacrylate, Glycidyl acrylate, Tetrahydrofurfuryl methacrylate, and N-Vinylpyrrolidone, n-vinylformamide, n-vinyl pyridine, styrene, styrene derivitves

[0328] Electron poor monomers include Acrylonitrile, Methacrylonitrile, Methyl methacrylate, Acrylic acid, Methacrylic acid, Maleic anhydride, Itaconic acid, Fumaric acid, Acrylamide, Methacrylamide, N-Vinylcarbazole, Vinylidene chloride, Vinyl chloride, Vinyl sulfonic acid, Vinyl acetate, Styrene, Alpha-methylstyrene, Maleimide, N-Phenylmaleimide, and N-Butylmaleimide, maleic anhydride

[0329] Alternating copolymer monomer combinations include but are not limited to Styrene / maleic anhydride, Styrene / maleimide, Styrene / acrylonitrile, Styrene / butadiene, Acrylonitrile / methyl methacrylate, Acrylonitrile / styrene, Acrylonitrile / butadiene / styrene, Vinylidene chloride / methyl acrylate, Vinylidene chloride / methyl methacrylate, Vinylidene fluoride / hexafluoropropylene, Vinyl chloride / vinylidene chloride, Ethylene / propylene, Ethylene / propylene / diene, Cyclohexene oxide / styrene, Isoprene / styrene, Butadiene / maleic anhydride, Methacrylic acid / maleic anhydride, Vinyl acetate / maleic anhydride, and Glycidyl methacrylate / maleic anhydride

[0330] Lactam monomers include Caprolactam, Valerolactam, Enantholactam, Capryllactam, Laurinlactam, Prolactam, Butyrolactam, Methionyl lactam, Methoxyethyl lactam, Methoxyethyl methionyl lactam, Dimethylaminoethyl lactam, Dimethylaminoethyl methionyl lactam, Dimethylaminoethyl acryloyl lactam, Dimethylaminoethyl methacryloyl lactam, N-vinylpyrrolidone, N-methylpyrrolidone, and N-ethylpyrrolidone

[0331] Lactone monomers include β-propiolactone, γ-butyrolactone, δ- valerolactone, ε-caprolactone, ω-pentadecalactone, β-butyrolactone, δ-decalactone, ε-decalactone, γ-decalactone, δ-dodecalactone, γ-dodecalactone, α-methylene-γ- butyrolactone, β-methyl-γ-butyrolactone, β-methyl-γ-valerolactone, and γ- hexalactone

[0332] Alcohol monomers include Ethylene glycol, Propylene glycol, 1,3- Butanediol, 1,4-Butanediol, 1,5-Pentanediol, 1,6-Hexanediol, 1,10-Decanediol, Neopentyl glycol, Diethylene glycol, Triethylene glycol, Tetraethylene glycol, Polyethylene glycol (PEG), Polypropylene glycol (PPG), Polycaprolactone diol, Polymethylolpropane, HPHMB (Hydroxypivalyl hydroxymethylbutyrate), and 1,4- Cyclohexanedimethanol

[0333] Carboxylic acid monomers include Adipic acid, Succinic acid, Glutaric acid, Sebacic acid, Malonic acid, Phthalic acid, Isophthalic acid, Terephthalic acid, Fumaric acid, Maleic acid, Itaconic acid, Citric acid, 1,4-Cyclohexanedicarboxylic acid, 1,3-Cyclohexanedicarboxylic acid, and Dodecanedioic acid

[0334] Isocyanate monomers include Toluene diisocyanate (TDI), Diphenylmethane diisocyanate (MDI), Hexamethylene diisocyanate (HDI),Isophorone diisocyanate (IPDI), 1,6-Hexamethylene diisocyanate (HMD’), 4,4'- Methylenebis(cyclohexyl isocyanate) (H12MDI), Naphthalene diisocyanate (NDI), 2,4-Toluene diisocyanate (2,4-TDI), 2,6-Toluene diisocyanate (2,6-TDI), Polymethylene polyphenyl isocyanate (PAPI), Desmodur N-100, Desmodur L-75, Desmodur HL, Desmodur H, Desmodur VP, and Desmodur Z

[0335] Diels Alder monomers include Maleic anhydride, Furan, Cyclopentadiene, N-phenylmaleimide, Anthracene, N-ethylmaleimide, N-phenylnorbornene, N,N- dimethyl maleimide, 2,5-dimethylfuran, Tetracyanoethylene, Methyl vinyl ketone

[0336] Ring opening metathesis monomers include Norbornene, Dicyclopentadiene (DCPD), Cyclooctene, Tetracyclododecene (TCD), Cyclopentene, Cycloheptene, Cyclohexene, Bicyclo[2.2.1]hept-2-ene, Bicyclo[2.2.2]oct-5-ene, Tricyclo[5.2.1.0(2,6)]dec-8-ene (TCD-Diene)

[0337] Additives include plasticizers. Plasticizers include Glyceryl triacetate (triacetin), Glyceryl monooleate (GMO), Glyceryl monostearate (GMS), Glyceryl tristearate (tristearin), Glyceryl tributyrate (tributyrin), Glyceryl tripropionate (triproprionin), Glyceryl trioleate (triolein), Glyceryl dilaurate (GDL), Glyceryl dimyristate (GDM), Glyceryl distearate (GDS), Diethylhexyl phthalate (DEHP), Diisononyl phthalate (DINP), Dibutyl phthalate (DBP), Diisodecyl phthalate (DIDP), Butyl benzyl phthalate (BBP), Dimethyl phthalate (DMP), Di-n-octyl phthalate (DnOP), Diisobutyl phthalate (DIBP), Diethyl phthalate (DEP), Dicyclohexyl phthalate (DCHP), Methyl decanoate, Ethyl decanoate, Propyl decanoate, Isopropyl decanoate, Butyl decanoate, Isobutyl decanoate, Pentyl decanoate, Hexyl decanoate, Heptyl decanoate, Octyl decanoate, Decyl decanoate, C1-C20 anoates on either side of ester,

[0338] Additives include tackifiers. Tackifiers include Rosin esters, Hydrocarbon resins, Terpene resins, Styrene resins, Polyterpene resins, Coumarone-indene resins, Phenolic resins, Tall oil rosin, Aliphatic resins, Aromatic resins

[0339] Additives include fillers. Fillers include Calcium carbonate, Talc, Silica, Glass fibers, Carbon black, Barium sulfate, Kaolin, Mica, Wollastonite, Alumina, Titanium dioxide, Cellulose, Wood flour, Fly ash, Graphite

[0340] In one embodiment, Michael Addition reactions under base catalyzed conditions may be used to form polymers, prepolymers, monomers, or curablemixtures. In one embodiment thiol-acrylate or amine-acrylate reactions may be used. In one embodiment, these reactions may be catalyzed by any amines mentioned herein, tertiary amines, DABCO, dipropylamine, triethylamine. In one embodiment, Thiol / epoxy reactions may be used under similar catalytic conditions to form polymers, prepolymers, monomers or curable mixtures. In one embodiment, mixtures are prepared in a one-pot manner.

[0341] In one embodiment, compostable, bio-based or degradable adhesives are prepared from constituents described herein. In one embodiment, compostable adhesives are prepared from plasticized polycaprolactone or plasticized poly(lactic acid). In another embodiment, plasticization is carried out to lower glass transition or increase tack. In one embodiment, adhesive is suitable for use in food grade applications such as fruit produce stickers.

[0342] In one embodiment, polymers with side chains or dangling chain ends between C6 and C30 carbons are preferable, with alkyl linkages further preferable, with C7, C8, C9 up to C18 linkages preferable, with C12 to C18 further preferable. In one embodiment, polymers with greater than 80 wt% side chain (same C linkage preference) are preferred. In a further embodiment, polymers with C6 to C18 side chains or dangling chain ends are prepared from acrylate, methacrylate, alcohol, carboxylic acid, electron rich alkene, electron poor alkene, epoxy, amine, ROMP, Diels-Alder, Lactone, Lactam, Peptide, Peptoid, acrylamide, methacrylamide, thiol, vinyl and allyl monomers. In a further embodiment, light crosslinking such as the netpoint concentration afforded by a range including but not limited to 0.4wt%, 0.6 wt%, 0.75 wt%, 0.95 wt% trimethylolpropane triacrylate in a poly(lauryl) or poly(stearyl methacrlate polymer (including but not limited to 99.6 wt%, 99.4 wt%, 99.25 wt%, 99,05 wt%) lauryl or stearyl methacrylate) is preferable to afford a shear rate responsive polymer that is tacky to human skin and that subsequently can be removed from human skin with minimal pain, and residual adhesive that remains on human skin can be removed by light rubbing with minimal pain. In another embodiment, these long side chain / low crosslink density polymers can be prepared by any monomers, crosslinkers or other constituents described herein by any reaction process described herein. For example, linear or branched poly(ethyeneimine, PEI) can be modified on side chain and chain ends using laurl or octadecyl acrylate inder base catalyzed conditions via Michael addition or lauryl oroctacecyl isocyanate using isocyanate / amine reaction. In another embodiment, off or on stoichiometric thiolenes can be prepared using combinations of mono, di, tri and tetrafuctional thiol and alkene monomers with monofuctional constituent such as lauryl mercaptopropionate or dodecyl vinyl ether such that monofuctional constituent comprises 0.1, 0.2, 0.3, 0.4 or 0.5 or more mole % of overall thiolene constituency. In another representative embodiment, an alternating copolymer comprising maleimide or n-butyl maleimide and docecyl vinyl ether is prepared using radical alternating polymerization and can be lightly crosslinked by dodecyl vinyl ether with less than wt% or a polymethacrylate or acrylate to form hetereogeneous crosslinked networks with low crosslink density and high C12 side chain wt % (60, 70, 80, 90 or more wt% alkyl side chain C6 or greater with C12C18 preferred). In another embodiment, octadecyl amine is polymerizered with a Michael addition co-monomer such as ethylene glycol diacrylate or hexanediol diacrylate under base catalized conditions. In one embodiment, the resulting poly(beta aminoester) is prepared with 1:25 : 1.0 C=C : NH2 (double NH2 reaction with acrylate) reaction such that acrylate end capped groups result, and acrylate end-capped poly(betamino ester) reaction products can be photcured using UV light, and crosslink density can be reduce by the addition of monofuctional acrylates or methacylates such as stearyl or lauryl methacrlate or acrylate or by adding thiol chain transfer or capping agents such as PETMP or IOMP or EGBMP or 1,10-decanediothiol or PETMP. In another embodiment, a similar Michael addition synthetic process can be used for thiol / acrylate Michael addition reaction products, with excess acrylate preferred.

[0343] In another embodiment, the adhesive is a semicrystalline polyurethane elastomer either linear or crosslinked as described above or by other methods with segments that include polyether, polyester, polyurethane, polyurethane urea, poly(isoprene), poly(butadiene) or other crystalline segments.

[0344] In another embodiment, adhesive is crosslinked after processing onto diaphragm by latent reaction using the aforementioned crosslinking chemistries or others. For example, residual epoxide and alcohol or amine chemistries could be used to achieve crosslinking after dip coating an adhesive onto a diaphragm barrier layer or applying via spray or in a roll-to-roll coating method.

[0345] In another embodiment, adhesive is self-healing, in that it can be prepared separately from a barrier layer, applied to a barrier layer in an additional step andoptionally be made to undergo regenerative adhesive capability after removal from skin or other application surface. An example of a transfer process to apply a separately prepared adhesive layer to a barrier layer is pad printing. Another example is the adhesive may be prepared separately from a barrier layer and extruded through an orifice or nozzle and transferred to a barrier layer. Another example is the adhesive may be prepared on a form or mold separately from the barrier, and the barrier transferred to the adhesive a solid layer or a liquid deposited via dip coating, spray, brush, painting or rolling transfer.

[0346] In another embodiment, the adhesive is a liner or branched crosslinked polymer network wherein the crosslinked polymer network contains 10 or more ester to thiolester linkages which hydrolyze in the presence of an added base or a compound containing a thiol, or a compound containing an amino wherein hydrolysis results in dissolution of the adhesive and delamination from penile skin.

[0347] In another embodiment, adhesive layer may be a liner or branched polymer comprising the reaction product by free radical addition polymerization of mono-, di- try- tetra-, penta, and hexa-functional thiol-ene constituents including triallyl isocyanurate pentaerythritol tetrakis (3-mercaptopropionate) or any of the thiol-ene monomeric constituents disclosed herein. One embodiment, thiol-ene adhesive may exhibit stimuli-responsive adhesive behavior upon cooling below its glass transition. In another embodiment, thiol-ene adhesive layer may exhibit chemically-responsive adhesive behavior such as oxidation of thioether linkages by common oxidizing agents such as hydrogen peroxide to form reversibly clearable disulfide linkages.

[0348] In another embodiment, adhesive layer may comprise additives that offer physical pathways to delamination such as water or solvent chemically swellable particulate additives such as poly(sodium acrylate) molecular weight ranging from 100 to 5 million Daltons, more particularly 100 to 1 million Daltons, more particularly 1000 to 1 million Daltons, with particle sizes ranging from 1 micron to 1000 microns, more particularly 20 microns to 800 microns, more particularly 20 to 300 microns, in concentrations ranging from 0.01 to 95 wt,%, more particularly 0.1 to 75 wt%, more particularly 1 to 60 wt %, more particularly 2 to 55 wt%.

[0349] In another embodiment, particulate additives may decrease diffusion of water or other solvents into adhesive layer and may be hydrophobic constituents such as steric acid, hydrophobic fumed silica or polyethylene waxes molecular weight ranging from 100 to 5 million Daltons, more particularly 100 to 1 million Daltons, more particularly 200 to 1 million Daltons, with particle sizes ranging from 1 micron to 1000 microns, more particularly 20 microns to 800 microns, more particularly 20 to 300 microns, in concentrations ranging from 0.01 to 95 wt,%, more particularly 0.1 to 75 wt%, more particularly 1 to 60 wt %, more particularly 2 to 55 wt%.

[0350] In another embodiment, particulate additives may create physical sites for increased or reduced adhesion to skin and may be stimuli-responsive in nature. Constituents that create physical sites for enhanced or reduced adhesion to skin may be ceramic additives such as fumed silica, zinc oxide or titanium dioxide or may be polymers that have molecular weight ranging from 100 to 5 million Daltons, more particularly 100 to 1 million Daltons, more particularly 200 to 1 million Daltons, with particle sizes ranging from 1 micron to 1000 microns, more particularly 20 microns to 800 microns, more particularly 20 to 300 microns, in concentrations ranging from 0.01 to 95 wt,%, more particularly 0.1 to 75 wt%, more particularly 1 to 60 wt %, more particularly 2 to 55 wt%.

[0351] In another embodiment, adhesive layer may comprise multiple adhesives, blended together or applied separately to barrier layer. For example, adhesive layer may include a hydrophobic, water-insoluble layer at its outer edges along the circumference of the diaphragm approximately 0.1 to 2 cm in length, more particularly 0.2 to 1 cm in length, more particularly 0.25 to 1 cm in length, and a hydrophilic, water-soluble layer above the hydrophobic adhesive layer as illustrated in Figure 2. One embodiment, the hydrophobic outer adhesive layer may be stimuli- responsive.

[0352] In another embodiment additives of the present invention may serve as nucleating agents for stimuli-responsive adhesives undergo change in adhesive behavior upon crystallization by cooling. The addition of nucleating agents such as nano-scale fumed silica and polyethylene waxes could be used to tune crystallization temperature of adhesives that exhibit crystalline transitions such as poly(octadecyl methacrylate). Nucleation-inducing additives include additives ranging in particlesize from 1 nm to 1000 microns, more particularly 10 nm to 500 microns, more particularly 10 nm to 250 microns. Nucleation-inducing additives may be blended with adhesive in solution blending, high-shear mixing or other blending technique or may be generated in situ during adhesive preparation or diaphragm formation through techniques that include precipitation or phase separation. For example, stearic acid could be mixed with adhesive solutions under high shear conditions to form nanophases that remain dispersed in adhesive blends such as poly(stearyl) methacrylate.

[0353] In another embodiment additives may serve as crack propagating agents to facilitate adhesive failure upon removal via mechanical peeling.

[0354] Styrene-butadiene rubbers (SBRs) suitable for use in the present invention include those used in the manufacture of pressure sensitive tapes, including synthetic elastomers derived from styrene and butadiene. SBRs, whether solvent borne or waterborne suitable for use in the present invention include SBRs with varying percent of bound styrene, average molecular weight and its distribution, and the presence of functional groups introduced during polymerization.

[0355] Adhesive layer may be comprised of linear or crosslinked polymers that include liquid crystalline polymers with thermal transitions in the range of -10 C to 50 C, more particularly 0 C to 40 C, more particularly 5 C to 35 C, more particularly 5 C to 20 C. Liquid crystalline polymer compositions suitable for use in the present invention include thiol-ene and thiol-acrylate polymers prepared via base catalyzed Michael addition or free radical polymerization processes, including those prepared from thiol building blocks such as 1,6-hexanedithiol, 1,8-octanedithol, 1,10- decanedithiol, 1,12-dodecanedithiol, hexanediol diacrylate, octanediol diacrylate, decanediol diacrylate and diacrylate species containing mesogens such as–RM105 - 4-(6-Acryloyloxyhexyloxy)-benzoic acid (4-cyanophenyl ester), RM 23 – 4- Methoxyphenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate, CB3A – 3-[(3′-Cyanobiphenyl- 3-yl)oxy]propylacrylate.

[0356] Di-acrylate mesogens include but are not limited to –M 257 - 4-(3- acryloyoxy-propyloxy) benzoic acid 2-methyl-1,4-phenylene ester,–RM 82 - 1,4- Bis[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene

[0357] In one embodiment, free-radical polymerization can be used to crosslink acrylate-functionalized liquid-crystal networks. Click chemistry reactions such as Michael addition reactions may also be used to incorporate soft flexible segments in between mesogenic monomers to decrease Tg and enable elastomeric behavior at ambient conditions. In one embodiment, dithiols can be used as flexible spacers and include but are not limited to: ethane dithiol, propane dithiol, or any other dithiol with an all-carbon backbone, 2,2′-(ethylenedioxy)diethanethiol or any other dithiol with a polyethylene glycol backbone, 1,4-benzenedithiol, 4,4’-biphenyldithiol, ethylene bis(thioglycolate), glycol dimercaptopropionate.

[0358] In another embodiment, in addition to thiols, amine-functionalized monomers may be used in a similar fashion. For example, n-butylamine can be used as a flexible chain extender or spacer for mesogenic monomers. Using a Michael addition catalyst such as triethyl amine or dipropyl amine, acrylate-functionalized mesogenic oligomers can be created by combining a non-stoichiometric ratio of diacrylate mesogens to dithiol monomers or diacrylate mesogens to di-functional amines. In either case, an excess of acrylate functional groups is optionally preferred. These oligomers can then be photo-crosslinked to form an LCE network.

[0359] In one embodiment, LCEs can be synthesized in a one-pot manner by utilizing thiol or amine functionalized crosslinkers with a functionality of 2 or greater. This one-pot approach can be used with both free-radical and Michael-addition polymerization methods. Examples include but are not limited to pentaerythritol tetramercaptoacetate (PETMA), trimethylolpropane tri(3- mercaptopropionate), pentaerythritol tetra(3- mercaptopropionate), di-pentaerythritol tetra(3- mercaptopropionate)

[0360] The adhesive described herein comprises a stimuli-responsive polymer, and optionally, one or more additional polymers.

[0361] In some embodiments, the stimuli-responsive polymer has a glass transition temperature (Tg) from 0 °C to 50 °C, such as, for example, from 0 °C to 40 °C, from 0 °C to 30 °C, from 0 °C to 20 °C, from 0 °C to 10 °C, from 5 °C to 50 °C, from 5 °C to 40 °C, from 5 °C to 30 °C, from 5 °C to 20 °C, from 5 °C to 10 °C, from 10 °C to 50 °C, from 10 °C to 40 °C, from 10 °C to 30 °C, from 10 °C to 20 °C, from20 °C to 50 °C, from 20 °C to 40 °C, from 20 °C to 30 °C, from 30 °C to 50 °C, from 30 °C to 40 °C, or from 40 °C to 50 °C.

[0362] In some embodiments, the stimuli-responsive polymer has a glass transition below ambient temperature, such as, for example, a glass transition from - 90 °C to 20 °C, from -90 °C to -80 °C, from -80 °C to -70 °C, from -70 °C to -60 °C, from -60 °C to -50 °C, from -50 °C to -40 °C, from -40 °C to -30 °C, from -30 °C to - 20 °C, from -20 °C to -10 °C, from -10 °C to 0 °C, from 0 °C to 10 °C, or from 20 °C to 20 °C.

[0363] In some embodiments, the stimuli-responsive polymer has a crystalline melt transition below ambient temperature, such as, for example, a crystalline melt transition from -90 °C to 20 °C, from -90 °C to -80 °C, from -80 °C to -70 °C, from -70 °C to -60 °C, from -60 °C to -50 °C, from -50 °C to -40 °C, from -40 °C to -30 °C, from -30 °C to -20 °C, from -20 °C to -10 °C, from -10 °C to 0 °C, from 0 °C to 10 °C, or from 20 °C to 20 °C.

[0364] In some embodiments, the stimuli-responsive polymer comprises a single copolymer. In some embodiments, the stimuli-responsive polymer comprises a blend of two or more homopolymers or copolymers, which includes copolymer architecture of block, gradient, and random copolymers of two or more.

[0365] In some embodiments, the one or more polymers are selected from, for example, polyacrylates, polymethacrylates, polyurethanes, polyolefins, polyethers, silicones, polyepoxies, synthetic rubbers or other adhesives suitable for use with human skin, including derivatives, copolymers, and mixtures thereof.

[0366] In some embodiments, the stimuli-responsive polymer comprises one or more polyacrylate or polymethacrylate polymers.

[0367] In some embodiments, the stimuli-responsive polymer comprises one or more polyacrylates or polymethacrylates with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or up to 100 carbons in the side chain and 0, 1, 2, 3, 4, 5, 6, 7, 8, 910 or up to 100 or more oxygens in the side chain.

[0368] Representative, non-limiting polymers include poly(2- ethylhexyl acrylate), poly(butyl acrylate), poly(propyl acrylate), poly(ethyl acrylate), poly(methyl acrylate), poly(octyl acrylate), poly(nonyl acrylate) poly(decyl acrylate), poly(undecyl acrylate), poly(dodecyl acrylate), poly(tridecyl acrylate), poly(C14 acrylate), poly (C15acrylate), poly(C16 acrylate), poly (C17 acrylate), poly(C18 acrylate), poly(C19 acrylate), poly(C20-C100 or more acrylates, methacrylates and acrylamides thereof), poly(2-hydroxyethyl acrylate), poly(butoxymethyl acrylate), poly(butoxyethyl acrylate), poly(butoxypropyl acrylate), poly(butoxybutyl acrylate), poly(fin(ding)- nemo-acrylate), poly(octadecyl acrylate), poly(octadecyl methacrylate), and poly(acrylic acid).

[0369] In some embodiments, the stimuli-responsive polymer comprises polymethacrylate, a polymethacrylate copolymer or blend thereof. The copolymer is derived least one methacrylate monomer and at least one polymerizable comonomer, including any monomer disclosed herein.

[0370] In some embodiments, the stimuli-responsive polymer comprises a crosslinked polymethacrylate. The crosslinker can be polyfunctional. In one embodiment, the stimuli-responsive polymer comprises a polymethacrylate crosslinked by an acrylate. In some embodiments, the polymethacrylate is poly(lauryl) methacrylate and the acrylate crosslinker is TMPTA. The weight ratio of the lauryl methacrylate and TMPTA may vary.

[0371] In some embodiments, the weight ratio is 98:2, 98.5:1.5, or 99:1, or more particularly, 99.1:0.9, 99.2:0.8, 99.3:0.7, 99.4:0.6, 99.6:0.4, or 99.8:0.2, 99.0:0.1 or any range therein.

[0372] In some embodiments, the stimuli-responsive polymer does not comprise polyacrylates or polymethacrylates.

[0373] In some embodiments, the stimuli-responsive polymer comprises one or more amorphous or semi-crystalline polyurethanes.

[0374] In some embodiments, the stimuli-responsive polymer comprises a semicrystalline polyurethane elastomer with segments that include polyether, polyester, polyurethane, polyurethane urea, poly(isoprene), poly(butadiene) or other crystalline segments.

[0375] In some embodiments, the stimuli-responsive polymer comprises semicrystalline polyurethane elastomer either linear or crosslinked with segments that include polyether, polyester, polyurethane, polyurethane urea, poly(isoprene), poly(butadiene) or other crystalline segments.

[0376] In some embodiments, the stimuli-responsive polymer does not comprise polyurethane.

[0377] In some embodiments, the stimuli-responsive polymer comprises a polyolefin. In some embodiments, the polyolefin is a polyisoprene.

[0378] In some embodiments, the stimuli-responsive polymer comprises at least one polyether, for example, poly(ethylene glycol) (PEG) compounds and acrylated or polyurethane-containing PEG compounds.

[0379] In some embodiments, the stimuli-responsive polymer comprises at least one polyepoxy. In some embodiments, the polyepoxy comprises one or more epoxy monomers disclosed herein. In some embodiments, the stimuli-responsive polymer does not comprise polyepoxy. In some embodiments, the polyepoxy comprises one or more silicone monomers disclosed herein.

[0380] In some embodiments, the stimuli-responsive polymer comprises at least one silicone polymer. In some embodiments, the silicone polymer is a high molecular weight, linear siloxane polymer and a highly condensed, silicate tackifying resin.

[0381] In some embodiments, the stimuli-responsive polymer does not comprise a silicone polymer.

[0382] In some embodiments, the stimuli-responsive polymer comprises at least one synthetic rubber.

[0383] In some embodiments, the stimuli-responsive polymer comprises styrene- butadiene rubber (SBR). Examples of SBRs include those used in the manufacture of pressure sensitive tapes, including synthetic elastomers derived from styrene and butadiene. SBRs, whether solvent borne or waterborne suitable for use in the present disclosure include SBRs with varying percent of bound styrene, average molecular weight and its distribution, and the presence of functional groups introduced during polymerization. Molecular weights of SBRs range from 10 to 1,000,000 g / mol, more specifically 25,000 to 750,000 g / more, more specifically 50,000 to 500,000 g / mol. SBRs generally exhibit low water uptake, less than 1 wt% water, more specifically less than 0.5 wt% water, more specifically 0.1 wt% water, more specifically less than 0.05 wt% water.

[0384] In some embodiments, the stimuli-responsive polymer does not comprise synthetic rubber.

[0385] In some embodiments, the stimuli-responsive polymer comprises thiol monomers. Exemplary thiol monomers include, but are not limited to, 3- Mercaptopropionic acid; Thioglycolic acid; 3-Mercapto-1-propanol; 2- Mercaptoethanol; 2-(2-Mercaptoethoxy)ethanol; 2-(2- Mercaptopropionylamino)ethanol; 2-(2- Mercaptosuccinyl)ethyl acrylate; 3-(2- Mercaptopropionylamino)propionic acid; 3- (Mercaptopropyl)trimethoxysilane; 2,2'- (Ethylenebis(thio))diethanol; 3-Mercaptopropyltrimethoxysilane; 3- Mercaptopropylmethyldimethoxysilane; 3-(2,2- Dithiobis(ethylthio)propionylamino)propionic acid; 3,6,9- Trioxadecanethiol; 3- Mercapto-1,2-propanediol; 2,2'-Dithiodiethanol; N-Acetyl-L-cysteine; L-Cysteine; 2- (2- Mercaptoethyl)pyridine; 4-(2-Mercaptoethyl)morpholine; 3-Mercapto-1,2,4- triazole; Thiophenol; Pentaerythritol tetrakis(3-mercaptopropionate) (PETMP); Trimethylolpropane tris(3-mercaptopropionate) (TMPMP); Triethanolamine tris(3- mercaptopropionate) (TEAMP); Tris(2-hydroxyethyl) isocyanurate tris(3- mercaptopropionate) (THEICMP); Bis(3-mercaptopropyl) sulfide (BMPS); 1,2- ethanedithiol (EDT); 1,3- propanedithiol; 1,4-butanedithiol; 1,6-hexanedithiol; 1,8- octanedithiol and combinations thereof.

[0386] In some embodiments, the stimuli-responsive polymer is a linear or branched crosslinked polymer network wherein the crosslinked polymer network contains 10 or more ester to thiolester linkages which hydrolyze in the presence of an added base or a compound containing a thiol, or a compound containing an amino wherein hydrolysis results in dissolution of the adhesive and delamination from penile skin.

[0387] In another embodiment, the stimuli-responsive polymer may be a linear or branched polymer comprising the reaction product by free radical addition polymerization of mono-, di- try- tetra-, penta, and hexafunctional thiol-ene constituents including triallyl isocyanurate pentaerythritol tetrakis (3- mercaptopropionate) or any of the thiol-ene monomeric constituents disclosed herein. In some embodiments, thiol-ene adhesives may exhibit stimuli-responsive adhesive behavior upon cooling below its glass transition. In some embodiments, thiol-ene adhesive layer may exhibit chemically-responsive adhesive behavior suchas oxidation of thioether linkages by common oxidizing agents such as hydrogen peroxide to form reversibly clearable disulfide linkages.

[0388] In some embodiments, the stimuli-responsive polymer comprises linear or crosslinked polymers that include liquid crystalline polymers with thermal transitions in the range of -10 °C to 50 °C, more particularly 0 °C to 40 °C, more particularly 5 °C to 35 °C, more particularly 5 °C to 20 °C. Liquid crystalline polymer compositions suitable for use include thiol-ene and thiol-acrylate polymers prepared via base catalyzed Michael addition or free radical polymerization processes, including those prepared from thiol building blocks such as 1,6-hexanedithiol, 1,8-octanedithol, 1,10- decanedithiol, 1,12-dodecanedithiol, hexanediol diacrylate, octanediol diacrylate, decanediol diacrylate and diacrylate species containing mesogens such as RM105 - 4-(6- Acryloyloxyhexyloxy)-benzoic acid (4-cyanophenyl ester), RM 23 - 4- Methoxyphenyl 4-((6- (acryloyloxy)hexyl)oxy)benzoate, CB3A - 3-[(3'-Cyanobiphenyl- 3-yl)oxy]propylacrylate. Di-acrylate mesogens include but are not limited to RM 257 - 4-(3- acryloyoxy-propyloxy) benzoic acid 2-methyl-1,4-phenylene ester, RM 82 - 1,4- Bis[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2- methylbenzene.

[0389] In some embodiments, free-radical polymerization can be used to crosslink acrylate-functionalized liquid crystal networks. Click chemistry reactions such as Michael addition reactions may also be used to incorporate soft flexible segments in between mesogenic monomers to decrease Tg and enable elastomeric behavior at ambient conditions. In some embodiments, dithiols can be used as flexible spacers and include but are not limited to: ethane dithiol, propane dithiol, or any other dithiol with an all-carbon backbone, 2,2'-(ethylenedioxy)diethanethiol or any other dithiol with a polyethylene glycol backbone, 1,4- benzenedithiol, 4,4’- biphenyldithiol, ethylene bis(thioglycolate), glycol dimercaptopropionate.

[0390] In some embodiments, in addition to thiols, amine-functionalized monomers may be used in a similar fashion. For example, n-butylamine can be used as a flexible chain extender or spacer for mesogenic monomers. Using a Michael addition catalyst such as triethyl amine or dipropyl amine, acrylate- functionalized mesogenic oligomers can be created by combining a non-stoichiometric ratio of diacrylate mesogens to dithiol monomers or diacrylate mesogens to di-functional amines. In either case, an excess of acrylate functional groups is optionally preferred. These oligomers can then be photo-crosslinked to form an LCE network.

[0391] In some embodiments, LCEs can be synthesized in a one-pot manner by utilizing thiol or amine functionalized crosslinkers with a functionality of 2 or greater. This one-pot approach can be used with both free-radical and Michael-addition polymerization methods. Examples include but are not limited to pentaerythritol tetramercaptoacetate (PETMA), trimethylolpropane tri(3- mercaptopropionate), pentaerythritol tetra(3- mercaptopropionate), di-pentaerythritol tetra(3- mercaptopropionate).

[0392] In some embodiments, the stimuli-responsive polymer comprises linear or crosslinked polymers that include silicone polymers, for example, a high molecular weight, linear siloxane polymer and a highly condensed, silicate tackifying resin. Tackifying resins or tackifiers include low-molecular weight compounds with high glass transition temperature used in formulating adhesives to increase the tack, the stickiness of the surface of the adhesive. Tackifiers include resins (e.g., rosins and their derivates, terpenes and modified terpenes, aliphatic, cycloaliphatic and aromatic resins (C5 aliphatic resins, C9 aromatic resins, and C5 / C9 aliphatic / aromatic resins), hydrogenated hydrocarbon resins, and their mixtures, terpenephenol resins (TPR, used often with ethylene-vinyl acetate adhesives)), novolacs. Silicone rubber-based pressure-sensitive adhesives suitable for use include special tackifiers based on "MQ" silicate resins, composed of a monofunctional trimethyl silane ("M") reacted with quadrafunctional silicon tetrachloride ("Q").

[0393] In some embodiments, the stimuli-responsive polymer exhibits one or more glass transition (Tg), crystallization temperature (Tc), melting temperature (Tm) or other thermal transition ranging from -100 to 100 °C or about - 40 °C, about -30 °C, about -20 °C, about -10 °C, about 10 °C, about 0 °C, about 10 °C, about 15 °C, about 20 °C, about 25 °C, about 30 °C, about 35 °C, about 40 °C, about 45 °C, about 50 °C, about 55 °C, about 60 °C, or about 65 °C or more as measured by differential scanning calorimetry (DSC) Tg, Tc, Tm peak inflection point or dynamic mechanical analysis loss modulus or tan delta peak at 1 Hz.

[0394] In some embodiments, the stimuli-responsive polymer may be a linear, brush, star, dendritic, or branched polymer with weight average molecular weight (Mw) of approximately 1 kDa, about 5 kDa, about 10 kDa, about 15 kDa, about 20 kDa, about 30 kDa, about 50kDa, about 75 kDa, about 90 kda, about 100 kDa, about110 kDa, about 200 kDa, about 300 kDa, about 400 kDa, about 500 kDa, or about 1000 kDa or more.

[0395] In some embodiments, the stimuli-responsive polymer is a crosslinked polymer that provides a semi-interpenetrating network or is an interpenetrating network.

[0396] In some embodiments, the stimuli-responsive polymer is petroleum- based.

[0397] In some embodiments, the stimuli-responsive polymer is bio-based, in whole or in part.

[0398] In some embodiments, the stimuli-responsive polymer is a compostable, bio-based or degradable polymer prepared, for example from plasticized polycaprolactone or plasticized poly(lactic acid). In some embodiments, plasticization is carried out to lower glass transition or increase tack.

[0399] In some embodiments, the stimuli-responsive polymer is suitable for use in food grade applications such as stickers used for produce or fruit.

[0400] The amount of stimuli-responsive polymer present in the adhesive may vary. In some embodiments, the stimuli-responsive polymer comprises at least 70 wt% of the adhesive, such as, for example, at least about 80 wt%, at least 90 wt%, or at least 95 wt%.

[0401] In some embodiments, the stimuli-responsive polymer comprises at least 90 wt% of the adhesive, such as, for example, at least 91 wt%, at least 92 wt%, at least 93 wt%, at least 94 wt%, at least 95 wt%, at least 96 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt%.

[0402] In some embodiments, the linear and crosslinked polymers comprise (i) a main chain; (ii) at least one side chain; (iii) crosslinking; and (iv) additives. The main chain (i), side chain (ii) and / or crosslinkers (iii) may comprise one or more monomers.

[0403] In some embodiments, the monomers comprising (i), (ii) and (iii) may be the same monomers or different monomers.

[0404] The monomers may be any suitable monomers. In one embodiment, the monomers are selected from acrylate monomers, allyl monomers, thiol monomers,epoxy monomers, amine monomers, electron-rich monomers, electron-poor monomers, lactam monomers, lactone monomers, alcohol monomers, carboxylic monomers, isocyanate monomers, Diels Alder monomers, ring opening metathesis monomers or the like.

[0405] In some embodiments, the stimuli-responsive polymer does not comprise an acrylic-based adhesive which contains an unreacted polyol plasticizer.

[0406] In some embodiments, the stimuli-responsive polymer does not comprise a hydrophobic polyoxyalkylene-based adhesive derived from poly(ethylene glycol) prepared in the presence of a plasticizer.

[0407] In some embodiments, the stimuli-responsive polymer does not comprise an acrylic pressure-sensitive adhesive and (i) an elastomer with a tackifying resin or (b) a thermoplastic elastomer. In some embodiments, the adhesive does not comprise an acrylic pressure-sensitive adhesive and (i) an elastomer with a tackifying resin or (b) a thermoplastic elastomer.

[0408] The adhesive described herein may be utilized as the adhesive layer in the contraceptive device disclosed herein, e.g., the non-rigid fractional condom described herein, for example, a rigid, non-rolling fractional condom comprising a first adhesive layer (e.g., a stimuli responsive polymer, such as a stimuli-responsive polymer described herein) and a second layer comprising a barrier and reservoir, wherein the condom does not contact the shaft or corona of the penis; wherein the adhesive layer is (a) coextensive with the barrier layer; (b) thicker than the barrier layer and / or (c) the only securing means. The adhesive may be, for example, a stimuli-responsive polymer comprising one or more methacrylate monomers and a tri-functional crosslinker (e.g., TMPTA), providing a low density heterogenous crosslinked polymer. The weight ratio of the polymer to the tri-functional crosslinker may be, for example, about 99.4:06. The non-rigid, fractional condom may exhibit one or more properties disclosed herein, e.g., pain-free removal, low peel strength at low peel rate, high peel strength at high peel rate, loss modulus, etc.

[0409] In some embodiments, the stimuli-responsive polymer, and optionally, one or more other polymers present in the adhesive, is formed from (i.e., comprises) monomers selected from acrylate monomers, methacrylate monomers, vinyl ether monomer, allyl monomers, thiol monomers, epoxy monomers, amine monomers,electron rich monomers, electron poor monomers, lactam monomers, lactone monomers, alcohol monomers, carboxylic acid monomers, isocyanate monomers, Diels-Alder monomers, ring opening metathesis monomers, or a combination thereof.

[0410] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises acrylate monomers. In some embodiments, the acrylate monomers are C6-C30 alkyl acrylate monomers, such as, for example, C8-C30 alkyl acrylate monomers, C8-C20 alkyl acrylate monomers, C8-C16 alkyl acrylate monomers, C8-C12 alkyl acrylate monomers, C12- C30 alkyl acrylate monomers, C12-C20 alkyl acrylate monomers, or C12-C16 alkyl acrylate monomers.

[0411] Exemplary acrylate monomers include, but are not limited to, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate, nonadecyl acrylate, eicosyl acrylate, heneicosyl acrylate, docosyl acrylate, tricosyl acrylate, tetracosyl acrylate, pentacosyl acrylate, isodecyl acrylate, isotridecyl acrylate, hexacosyl acrylate, heptacosyl acrylate, octacosyl acrylate, nonacosyl acrylate, triacontyl acrylate, methyl acrylate, ethyl acrylate, Butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, Methoxyethyl acrylate, Hydroxyethyl acrylate, Hydroxypropyl acrylate, Ethoxylated hydroxyethyl acrylate, Glycidyl acrylate, Methacrylic acid, Methyl methacrylate, Ethyl methacrylate, Butyl methacrylate, 2-Hydroxyethyl methacrylate, Cyclohexyl methacrylate, Poly(ethylene glycol) methacrylate, Poly(ethylene glycol) diacrylate, Poly(ethylene glycol) dimethacrylate, Trimethylolpropane triacrylate, Triethylene glycol diacrylate, Tetraethylene glycol diacrylate, Neopentyl glycol diacrylate, Diethylene glycol diacrylate, Dipentaerythritol hexaacrylate, Ethoxylated trimethylolpropane triacrylate, Propoxylated glycerol triacrylate, Stearyl acrylate, Lauryl acrylate, Isodecyl acrylate, Acrylic acid, Ethylene glycol diacrylate (EGDA), Triethylene glycol diacrylate (TEGDA), Propylene glycol diacrylate (PGDA), Butanediol diacrylate (BDDA), Neopentyl glycol diacrylate (NPGDA), Pentaerythritol tetraacrylate (PETA), 1,4-Butanediol diacrylate (BDA), Di(trimethylolpropane) tetraacrylate (DTMPTA), Bisphenol A ethoxylate diacrylate (BPAEDA), Ethoxylated bisphenol A diacrylate (EBPA), Decanediol diacrylate, Polyethylene glycol diacrylate(PEGDA), Trimethylolpropane triacrylate (TMPTA), Diethylene glycol diacrylate (DEGDA), and 1,6-Hexanediol diacrylate (HDDA), Trimethylolpropane triacrylate (TMPTA), Tripropylene glycol diacrylate (TPGDA), Pentaerythritol triacrylate (PETA), Dipentaerythritol pentaacrylate (DPEPA), Tris(2-hydroxyethyl) isocyanurate triacrylate (THEIC-TA), Triethylene glycol dimethacrylate (TEGDMA), Triallyl isocyanurate (TAIC), Triethylene glycol diacrylate (TEGDA), Ethoxylated trimethylolpropane triacrylate (ETMPTA), Triallyl cyanurate (TAC), and combinations thereof.

[0412] In certain embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises acrylate monomers selected from octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate, nonadecyl acrylate, eicosyl acrylate, heneicosyl acrylate, docosyl acrylate, tricosyl acrylate, tetracosyl acrylate, pentacosyl acrylate, hexacosyl acrylate, heptacosyl acrylate, octacosyl acrylate, nonacosyl acrylate, triacontyl acrylate, and combinations thereof.

[0413] In some embodiments, the acrylate monomer is TMPTA.

[0414] In some embodiments, the stimuli-responsive polymer comprises at least 10 wt% acrylate monomers, such as, for example, at least 50 wt%, at least 75 wt%, or at least 90 wt%. In some embodiments, the stimuli-responsive polymer comprises at least 95 wt% acrylate monomers, e.g., at least 96 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt%.

[0415] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises methacrylate monomers. In some embodiments, the methacrylate monomers are C6-C30 alkyl methacrylate monomers, such as, for example, C8-C30 alkyl methacrylate monomers, C8-C20 alkyl methacrylate monomers, C8-C16 alkyl methacrylate monomers, C8-C12 alkyl methacrylate monomers, C12-C30 alkyl methacrylate monomers, C12-C20 alkyl methacrylate monomers, or C12-C16 alkyl methacrylate monomers.

[0416] Exemplary methacrylate monomers include, but are not limited to, hexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate,pentadecyl methacrylate, hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, eicosyl methacrylate, heneicosyl methacrylate, docosyl methacrylate, tricosyl methacrylate, tetracosyl methacrylate, pentacosyl methacrylate, hexacosyl methacrylate, heptacosyl methacrylate, octacosyl methacrylate, nonacosyl methacrylate, triacontyl methacrylate, Ethyl methacrylate, Butyl methacrylate, 2-Hydroxyethyl methacrylate, Cyclohexyl methacrylate, Isobornyl methacrylate, Stearyl methacrylate, Lauryl methacrylate, Isodecyl methacrylate, isotridecytl methacrylate, Tetrahydrofurfuryl methacrylate, Glyceryl methacrylate, Trimethylolpropane trimethacrylate, Trimethylolpropane triacrylate, Pentaerythritol triacrylate, Pentaerythritol tetramethacrylate, Poly(ethylene glycol) monomethyl ether methacrylate, Poly(ethylene glycol) monomethyl ether acrylate, Poly(ethylene glycol) diacrylate, Poly(ethylene glycol) dimethacrylate, Poly(ethylene glycol) monoacrylate, Ethoxylated bisphenol A dimethacrylate, Ethoxylated bisphenol A diacrylate, Ethoxylated trimethylolpropane triacrylate, Hydroxypropyl methacrylate, Methacrylic acid, Acryloyloxyethyltrimethylammonium chloride, Diethylaminoethyl methacrylate, Butylaminoethyl methacrylate, N,N- dimethylaminoethyl methacrylate, Methacryloyloxyethyl phthalate, Cyclopropyl methacrylate, and combinations thereof.

[0417] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises methacrylate monomers selected from hexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, eicosyl methacrylate, heneicosyl methacrylate, docosyl methacrylate, tricosyl methacrylate, tetracosyl methacrylate, pentacosyl methacrylate, hexacosyl methacrylate, heptacosyl methacrylate, octacosyl methacrylate, nonacosyl methacrylate, triacontyl methacrylate, and combinations thereof. In some embodiments, the stimuli- responsive polymer comprises undecyl methacrylate monomers, i.e., lauryl methacrylate monomers. In some embodiments, the stimuli-responsive polymer comprises octadecyl methacrylate monomers, i.e., stearyl methacrylate monomers.

[0418] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises at least 10 wt%methacrylate monomers, such as, for example, at least 50 wt%, at least 75 wt%, or at least 90 wt%. In some embodiments, the stimuli-responsive polymer comprises at least 95 wt% methacrylate monomers, e.g., at least 96 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt%.

[0419] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises vinyl ether monomers. Exemplary vinyl ether monomers include, but are not limited to, divinyl ether of ethylene glycol, divinyl ether of diethylene glycol, divinyl ether of triethylene glycol, divinyl ether of polyethylene glycol (DVE-PEG), divinyl ether of polypropylene glycol (DVE-PPG), Divinyl ether of poly(ethylene glycol) methyl ether (DVE-PEGME), divinyl ether of poly(ethylene glycol) butyl ether (DVE), Divinyl ether of poly(ethylene glycol) phenyl ether (DVE-PEGPhE), Divinyl ether of glycerol (DVE-Gly), Divinyl ether of 1,4-cyclohexanedimethanol (DVE-CHDM), Divinyl ether of neopentyl glycol (DVE-NPG), and combinations thereof.

[0420] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises allyl monomers. Exemplary allyl monomers include, but are not limited to, Diallyl phthalate (DAP), Diallyl maleate (DAM), Diallyl succinate (DAS), Diallyl fumarate (DAF), Diallyl adipate (DAA), Diallyl sebacate (DAS), Diallyl terephthalate (DAT), Diallyl isophthalate (DAI), Diallyl itaconate (DAI), Diallyl carbonate (DAC), Diallyl diglycolate (DADG), Diallyl tris(2- hydroxyethyl) isocyanurate (DATHEIC), Triallyl cyanurate (TAC), Triallyl isocyanurate (TAIC), Triallyl trimellitate (TATM), Triallyl citrate (TAC), Triallyl phosphate (TAP), Triallylamine (TAA), Triallyl cyanide (TACN), Triallyl benzene- 1,2,4-tricarboxylate (TABTC), Triallyl trimesate (TATM), Tris(2-hydroxyethyl) isocyanurate triallyl ether (THEIC-TAE), and combinations thereof.

[0421] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises thiol monomers. Exemplary thiol monomers include, but are not limited to, 3-Mercaptopropionic acid; Thioglycolic acid; 3-Mercapto-1-propanol; 2- Mercaptoethanol; 2-(2- Mercaptoethoxy)ethanol; 2-(2-Mercaptopropionylamino)ethanol; 2-(2- Mercaptosuccinyl)ethyl acrylate; 3-(2-Mercaptopropionylamino)propionic acid; 3- (Mercaptopropyl)trimethoxysilane; 2,2'-(Ethylenebis(thio))diethanol; 3- Mercaptopropyltrimethoxysilane; 3-Mercaptopropylmethyldimethoxysilane; 3-(2,2-Dithiobis(ethylthio)propionylamino)propionic acid; 3,6,9- Trioxadecanethiol; 3- Mercapto-1,2-propanediol; 2,2'-Dithiodiethanol; N-Acetyl-L-cysteine; L-Cysteine; 2- (2- Mercaptoethyl)pyridine; 4-(2-Mercaptoethyl)morpholine; 3-Mercapto-1,2,4- triazole; Thiophenol; Pentaerythritol tetrakis(3-mercaptopropionate) (PETMP); Trimethylolpropane tris(3-mercaptopropionate) (TMPMP); Triethanolamine tris(3- mercaptopropionate) (TEAMP); Tris(2-hydroxyethyl) isocyanurate tris(3- mercaptopropionate) (THEICMP); Bis(3-mercaptopropyl) sulfide (BMPS); 1,2- ethanedithiol (EDT); 1,3- propanedithiol; 1,4-butanedithiol; 1,6-hexanedithiol; 1,8- octanedithiol and combinations thereof.

[0422] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises epoxy monomers. Exemplary epoxy monomers include, but are not limited to, Bisphenol A diglycidyl ether (BADGE), Bisphenol F diglycidyl ether (BFDGE), Novolac diglycidyl ether (NGDE), Phenol novolac diglycidyl ether (PNGDE), Cycloaliphatic epoxy resins, Glycidyl ethers of aliphatic alcohols, Glycidyl ethers of aromatic alcohols, Triglycidyl isocyanurate (TGIC), Diglycidyl ether of 1,4-butanediol (BDDGE), Diglycidyl ether of neopentyl glycol (NPGDGE), Diglycidyl ether of propylene glycol (PGDGE), Epoxidized soybean oil (ESO), Epoxidized linseed oil (ELO), Dicyclopentadiene- based epoxy resins, Tetrafunctional epoxy resins, Epoxy phenolic novolac resins, and combinations thereof.

[0423] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises amine monomers. Exemplary amine monomers include, but are not limited to, Ethylenediamine; Diethylenetriamine; Triethylenetetramine; Tetraethylenepentamine; Polyethyleneimine; Diaminopropane; Diaminobutane; Diaminopentane; Diethylenetriaminepentaacetic acid (DTPA); Tris(2-aminoethyl)amine; N-(2- Aminoethyl)piperazine; N-(3- Aminopropyl)morpholine; N,N- Dimethylaminopropylamine; N,N-Dimethylethylenediamine; 1,3- Diaminopropane; Isophoronediamine; Jeffamine D-230; Jeffamine T-403; Jeffamine M-207; Jeffamine EDR- 148; and combinations thereof.

[0424] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises electron rich monomers. Exemplary electron rich monomers include, but are not limited to, Vinyl ethers (e.g.vinyl methyl ether, vinyl ethyl ether), Vinyl acetate, Allyl alcohol, Allyl amine, N- Methylolacrylamide, N-Methylolmethacrylamide, N-Methylolallylamine, N- Methylolvinylacetamide, Acrolein diethyl acetal, Acrolein diethyl ketal, Diacetone acrylamide, 2- Hydroxyethyl acrylate, 2-Hydroxyethyl methacrylate, 2-Hydroxypropyl acrylate, 2-Hydroxypropyl methacrylate, 2,3-Dihydroxypropyl methacrylate, Glycidyl methacrylate, Glycidyl acrylate, Tetrahydrofurfuryl methacrylate, and N- Vinylpyrrolidone, n-vinylformamide, n-vinyl pyridine, styrene, styrene derivatives, and combinations thereof.

[0425] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises electron poor monomers. Exemplary electron poor monomers include, but are not limited to, Acrylonitrile, Methacrylonitrile, Methyl methacrylate, Acrylic acid, Methacrylic acid, Maleic anhydride, Itaconic acid, Fumaric acid, Acrylamide, Methacrylamide, N- Vinylcarbazole, Vinylidene chloride, Vinyl chloride, Vinyl sulfonic acid, Vinyl acetate, Styrene, Alpha¬methylstyrene, Maleimide, N-Phenylmaleimide, and N- Butylmaleimide, maleic anhydride, and combinations thereof.

[0426] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises lactam monomers. Exemplary lactam monomers include, but are not limited to, Caprolactam, Valerolactam, Enantholactam, Capryllactam, Laurinlactam, Prolactam, Butyrolactam, Methionyl lactam, Methoxyethyl lactam, Methoxyethyl methionyl lactam, Dimethylaminoethyl lactam, Dimethylaminoethyl methionyl lactam, Dimethylaminoethyl acryloyl lactam, Dimethylaminoethyl methacryloyl lactam, N- vinylpyrrolidone, N-methylpyrrolidone, N- ethylpyrrolidone, and combinations thereof.

[0427] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises lactone monomers. Exemplary lactone monomers include, but are not limited to, β-propiolactone, γ- butyrolactone, 8-valerolactone, ε-caprolactone, ω- pentadecalactone, β- butyrolactone, 8-decalactone, ε -decalactone, γ-decalactone, 8-dodecalactone, γ- dodecalactone, α-methylene- γ-butyrolactone, β-methyl-y-butyrolactone, β-methyl-γ- valerolactone, γ-hexalactone, and combinations thereof.

[0428] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises alcohol monomers. Exemplary alcohol monomers include, but are not limited to, Ethylene glycol; Propylene glycol;1,3-Butanediol; 1,4-Butanediol; 1,5- Pentanediol; 1,6-Hexanediol; 1,10-Decanediol; Neopentyl glycol; Diethylene glycol; Triethylene glycol; Tetraethylene glycol; Polyethylene glycol (PEG); Polypropylene glycol (PPG); Polycaprolactone diol; Polymethylolpropane; Hydroxypivalyl hydroxymethylbutyrate (HPHMB); 1,4-Cyclohexanedimethanol; and combinations thereof.

[0429] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises carboxylic acid monomers. Exemplary carboxylic acid monomers include, but are not limited to, Adipic acid, Succinic acid, Glutaric acid, Sebacic acid, Malonic acid, Phthalic acid, Isophthalic acid, Terephthalic acid, Fumaric acid, Maleic acid, Itaconic acid, Citric acid, 1,4- Cyclohexanedicarboxylic acid, 1,3-Cyclohexanedicarboxylic acid, Dodecanedioic acid, and combinations thereof.

[0430] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises isocyanate monomers. Exemplary isocyanate monomers include, but are not limited to, Toluene diisocyanate (TDI), Diphenylmethane diisocyanate (MDI), Hexamethylene diisocyanate (HDI), Isophorone diisocyanate (IPDI), 1,6-Hexamethylene diisocyanate (HMDI), 4,4'-Methylenebis(cyclohexyl isocyanate) (H12MDI), Naphthalene diisocyanate (NDI), 2,4-Toluene diisocyanate (2,4-TDI), 2,6-Toluene diisocyanate (2,6-TDI), Polymethylene polyphenyl isocyanate (PAPI), Desmodur N-100, Desmodur L-75, Desmodur HL, Desmodur H, Desmodur VP, Desmodur Z, and combinations thereof.

[0431] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises Diels-Alder monomers. Exemplary Diels-Alder monomers include, but are not limited to, Maleic anhydride, Furan, Cyclopentadiene, N-phenylmaleimide, Anthracene, N-ethylmaleimide, N- phenylnorbornene, N,N-dimethyl maleimide, 2,5-dimethylfuran, Tetracyanoethylene, Methyl vinyl ketone, and combinations thereof.

[0432] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, comprises ring opening metathesis monomers. Exemplary ring opening metathesis monomers include, but are not limited to, Norbornene, Dicyclopentadiene (DCPD), Cyclooctene, Tetracyclododecene (TCD), Cyclopentene, Cycloheptene, Cyclohexene, Bicyclo[2.2.1]hept-2-ene, Bicyclo[2.2.2]oct-5-ene, Tricyclo[5.2.1.0(2,6)]dec-8-ene (TCD-Diene), and combinations thereof.

[0433] In some embodiments, the stimuli-responsive polymer comprises two or more side chains.

[0434] In some embodiments, the stimuli-responsive polymer comprises C6 to C30 side chains or C6 to C30 dangling chain ends. In some embodiments, the C6 to C30 side chains or C6 to C30 dangling chain ends are C6 to C30 alkyl side chains, preferably C12 to C18 alkyl side chains.

[0435] In some embodiments, stimuli-responsive polymers comprise at least 80 wt% side chains, such as, for example, at least 85 wt%, at least 90 wt%, or at least 95 wt%. In some embodiments, the side chains are the same. In some embodiments, the side chains are different.

[0436] In some embodiments, the side chain comprises linkages made from monomers selected from acrylate, methacrylate, thiol-acrylate Michael Addition, acrylate amine Michael Addition, epoxy thiol, epoxy amine, polyethylenimine (PEI), thiol-ene, alternating copolymers made from C=C electron poor + C=C electron rich monomers, urethane, urea, acrylamide, methacrylamide, polyester, polycarbonate, polyamide, peptoid, peptide, Diels- alder, lactides and lactams, and ring opening metathesis polymerization or olefin metathesis reactions.

[0437] In some embodiments, side chain chemistries include C1-C100 side chain linkages achieved by synthetic pathways disclosed herein.

[0438] In some embodiments, stimuli-responsive polymers with C6 to C18 side chains or dangling chain ends are prepared from acrylate, methacrylate, alcohol, carboxylic acid, electron rich alkene, electron poor alkene, epoxy, amine, ROMP, Diels-Alder, Lactone, Lactam, Peptide, Peptoid, acrylamide, methacrylamide, thiol, vinyl and allyl monomers.

[0439] In some embodiment, the stimuli-responsive polymer comprises a linear or crosslinked polymer with a side chain that optionally undergoes crystallization and / or melting in the region around body and room temperature, in the range of 0 °C to 50 °C, more particularly in the range of 5 °C to 45 °C, more particularly in the range of 10 °C to 40 °C, more particularly in the range of 15 °C to 35 °C. For clarity, side chain crystallization is optional.

[0440] In some embodiments, ranges for the linear or crosslinked polymer range from about 40 to about 100%, more particularly, about 50 to 100%. In some embodiments, the range is from about 40 to about 50%, about 50 to about 60%, about 60 to about 70%, about 70 to about 80%, about 80 to about 90% or about 90% or more or any range or value subsumed therein.

[0441] In some embodiments, ranges for secondary side chain optionally crystallizable polymer range from about 0 to about 50%, more particularly 1 to about 49%, more particularly about 2 to about 48%, more particularly about 3 to 47%, more particularly about particularly 5 to about 45% or any additional range or value subsumed therein.

[0442] In some embodiments, the stimuli-responsive polymer, or optionally, one or more other polymers present in the adhesive, is a crosslinked polymer. Crosslinked polymers are prepared using one or more polyfunctional crosslinkers. Crosslinkers may exhibit functionality greater than n=1 reactive site statistically, for example, statistical averages of n = 2, 3, 4, 5, 6, 7, 8, 9, 10 or more reactive sites and may facilitate branching, hyperbranching, interpenetrating networks, semi- interpenetrating networks and generally homogeneous or partially homogeneous and partially heterogeneous or generally heterogeneous networks with respect to phase blending or concentration of crosslink density.

[0443] In some embodiments, the polyfunctional crosslinker is selected from a difunctional crosslinker, a trifunctional crosslinker, or a tetrafunctional crosslinker. In some embodiments, the polyfunctional crosslinker is a trifunctional crosslinker.

[0444] In some embodiments, the polyfunctional crosslinker is a trifunctional crosslinker. In some embodiments, the trifunctional crosslinker is a trifunctional acrylate crosslinker.

[0445] In some embodiments, the polyfunctional crosslinker is selected from poly(ethylene glycol) diacrylate, trimethylolpropane triacrylate (TMPTA); ethoxylated trimethyolpropane triacrylate; pentaerythritol tetraacrylate; ethoxylated pentaerythritol tetraacrylate; dipentaerythritol hexaacrylate; ethoxylated dipentaerythritol hexaacrylate; di-, tri-, tetra-, penta-, or hexa- epoxides; polythiols; polyalkenes; tris(2- acryloxyethyl) isocyanurate, ε-caprolactone modified tris(2-acryloxyethyl) isocyanurate, ethoxylated glycerine triacrylate, pentaerythritol triacrylate, and combinations thereof.

[0446] In some embodiments, the polyfunctional crosslinker is poly(ethylene glycol) diacrylate with internal repeat units ranging from 1 to 1000 or more, trimethylolpropane triacrylate (TMPTA), ethoxylated trimethyolpropane triacrylate with repeat units ranging from 1 to 1000 or more, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate with repeat units ranging from 1 to 1000 or more, penta and hexafunctional acrylates and ethoxylated versions as described above including dipentaerythritol hexaacrylate and ethoxylated dipentaerythritol hexaacrylate with repeat units ranging from 1 to 1000 or more, di, tri, tetra, penta, hexa more expoxide monomers, polythiols, polyalkenes cured by UV light, visible light, gamma or e-beam irradiation, heat or hydrosilation.

[0447] In some embodiments, the polyfunctional crosslinker is selected from trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, hexanediol diacrylate, and combinations thereof. In some embodiments, the polyfunctional crosslinker is trimethylolpropane triacrylate (TMPTA).

[0448] In some embodiments, the stimuli-responsive polymer is a crosslinked polymer having a homogeneous crosslinked network density. In some embodiments, the stimuli-responsive polymer is a crosslinked polymer having a heterogeneous crosslink network. For example, favorable adhesive failure or delamination from skin, including residual adhesive removal after peeling away of adhesive, may be achieved by heterogeneous crosslinking distribution to concentrate failure sites within network or a “swollen heterogeneous network” formed by polymerization of a crosslinker and a monomer with different reactivity ratios.

[0449] In some embodiments, the stimuli-responsive polymer is characterized by low-density crosslinking.

[0450] In some embodiments, the crosslinker is incorporated into the stimuli- responsive polymer network uniformly.

[0451] In some embodiments, the crosslinker is aggregated within the stimuli- responsive polymer network. This embodiment creates high stress concentration network sites and / or drives rheological behavior and enables energy dissipation (high tan delta and high loss modulus in comparison with those in a more uniform network) to facilitate adhesive failure when desirable.

[0452] The amount of the crosslinker in the stimuli-responsive polymer, or optionally, one or more additional polymers, may vary. In some embodiments, the polymer comprises from 0 to 30 wt % of the crosslinker, such as, for example, from 0.001 to 29 wt%, more particularly 0.005 to 28 wt%, more particularly 0.0075 to 28 wt%, more particularly 0.01 to 27 wt%, more particularly 0.02 to 26 wt%, more particularly 0.05 to 26 wt%, more particularly 0.1 to 25 wt%, more particularly 0.15 to 24 wt%.

[0453] In some embodiments, the stimuli-responsive polymer comprises a crosslinker in an amount selected from about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 7.5 wt%, about 0.8 wt%, about 0.9 wt%, about 9.5 wt% or about 1.0 wt% or more, in each case with respect to the weight of the polymer.

[0454] In a particular embodiment, the stimuli-responsive polymer comprises a crosslinker in an amount from about 0.1 wt% and about 1 wt%, from about 0.2 wt% to about 0.8 wt%, from about 0.3 wt% to about 0.7 wt%, or from about 0.4 wt% to about 0.6 wt%, in each case with respect to the weight of the polymer.

[0455] In some embodiments, the stimuli-responsive polymer comprises from 0.1 wt% to 2.5 wt% polyfunctional crosslinker, such as, for example, from 0.1 wt% to 2 wt%, from 0.1 to 1.5 wt%, from 0.1 wt% to 1 wt%, from 0.1 wt% to 0.9 wt, from 0.1 wt% to 0.8 wt%, from 0.1 wt% to 0.7 wt%, from 0.1 wt% to 0.6 wt%, from 0.1 wt% to 0.5 wt%, from 0.1 wt% to 0.4 wt%, from 0.1 wt% to 0.3 wt% from 0.1 wt% to 0.2 wt%, from 0.2 wt% to 1.5 wt%, from 0.2 wt% to 1 wt%, from 0.3 wt% to 1.5 wt%, from 0.3 wt% to 1 wt%, from 0.4 wt% to 1.5 wt%, from 0.4 wt% to 1 wt%, from 0.5 wt% to 1.5wt%, from 0.5 wt% to 1 wt%, from 0.6 wt% to 1.5 wt%, from 0.6 wt% to 1 wt%, from 0.7 wt% to 1.5 wt%, from 0.7 wt% to 1 wt%, from 0.8 wt% to 1.5 wt%, from 0.8 wt% to 1 wt%, from 0.9 wt% to 1.5 wt% or from 0.9 wt% to 1 wt%.

[0456] In some embodiments, the stimuli-responsive polymer comprises from 0.4 wt% to 0.8 wt% polyfunctional crosslinker, such as, for example, from 0.4 wt% to 0.7 wt%, from 0.4 wt% to 0.6 wt%, from 0.4 wt% to 0.5 wt%, from 0.5 wt% to 0.8 wt%, from 0.5 wt% to 0.7 wt%, from 0.5 wt% to 0.6 wt%, from 0.6 wt% to 0.8 wt%, from 0.6 wt% to 0.7 wt%, or from 0.7 wt% to 0.8 wt%. In some embodiments, the polyfunctional crosslinker is trimethylolpropane triacrylate (TMPTA).

[0457] In some embodiment, the weight ratio of the one or more monomers to the one or more polyfunctional crosslinkers is 99:1, 98: 2, 97:3, 96:4, 95.3, 94:6, 93.7: 92:8, 91:9, 90:10, 89:11, 88:12, 87:13, 86:14; 85: 15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71: 29, 70:30, 69:31, 68:32, 67:33, 66:34, 65:35, 64:36, 63:37, 62:38, 61:39, 60:40, 59:41, 58:42, 57:43, 56:44, 55:45, 54:46, 53:47, 52:48, 51:49 or 50:50.

[0458] In some embodiments, the weight ratio of the one or more monomers to the one or more polyfunctional crosslinkers is from 98:2 to 99.9:0.1, e.g., from 98.5:1.5 to 99.9: 0.1; from 99:1 to 99.9:0.1, from 99.1:0.9 to 99.9:0.1, from 99.2: 0.8 to 99.9:0.1; from 99.3:0.7 to 99.9:0.1, from 99.4:0.6 to 99.9:0.1, from 99.5:0.5 to 99.9:0.1, from 99.6:0.4 to 99.9:0.1, from 99.7:0.3 to 99.9:0.1, or from 99.8:0.2 to 99.9:0.1.

[0459] In some embodiments, the adhesive further comprises one or more additives. Exemplary additives include tackifiers, plasticizers, pigments, fillers, fluorescents, flow agents, wetting agents, surfactants, anti-foaming agents, rheology modifiers, colorants, permeation enhancers, stabilizers, antioxidants, and combinations thereof. In some embodiments, adhesion may be enhanced or decreased through the addition of an additive.

[0460] Exemplary plasticizers include, are not limited to, Glyceryl triacetate (triacetin), Glyceryl monooleate (GMO), Glyceryl monostearate (GMS), Glyceryl tristearate (tristearin), Glyceryl tributyrate (tributyrin), Glyceryl tripropionate (triproprionin), Glyceryl trioleate (triolein), Glyceryl dilaurate (GDL), Glyceryl dimyristate (GDM), Glyceryl distearate (GDS), Diethylhexyl phthalate (DEHP),Diisononyl phthalate (DINP), Dibutyl phthalate (DBP), Diisodecyl phthalate (DIDP), Butyl benzyl phthalate (BBP), Dimethyl phthalate (DMP), Di-n-octyl phthalate (DnOP), Diisobutyl phthalate (DIBP), Diethyl phthalate (DEP), Dicyclohexyl phthalate (DCHP), Methyl decanoate, Ethyl decanoate, Propyl decanoate, Isopropyl decanoate, Butyl decanoate, Isobutyl decanoate, Pentyl decanoate, Hexyl decanoate, Heptyl decanoate, Octyl decanoate, Decyl decanoate, and C1-C20 anoates on either side of ester.

[0461] In some embodiments, a plasticizer may be added to lower glass transition of a polymer to tune adhesive regime. Plasticizers suitable for use include glycerol, 1,-butanol 1-octanol, stearic acid, n-butyl stearate, poly(ethylene glycol), Mw varying from 100 to 200 to 400 to 1000 to 2000 to 4000 to 10000 Daltons or more, water, various organic solvents, 1-decanoate, and 1-octanoate.

[0462] In some embodiments, the additives are stimuli-responsive. For example, an additive such as poly(ethylene glycol) Mw 400 Daltons or glycerol could be used in blending ratios from 1 wt% 90 wt% with an adhesive layer constituent such as poly(n-dimethyl acylamide), such that the additive plasticizes an adhesive layer above the crystallization temperature of the additive and no longer plasticizes the adhesive layer below the crystallization temperature of the additive.

[0463] In some embodiments, stimuli-responsive additives may exhibit crystallization, glass transition, or other thermal transition in the range of 0 °C to 50 °C, more particularly 5 °C to 40 °C, more particularly 10 °C to 30 °C, and further particularly 12 °C to 25 °C.

[0464] Adhesive layer may be comprised of linear or crosslinked polymers that include silicone polymers, for example, a high molecular weight, linear siloxane polymer and a highly condensed, silicate tackifying resin. Tackifying resins or Tackifiers suitable for use in the present invention include low-molecular weight compounds with high glass transition temperature used in formulating adhesives to increase the tack, the stickiness of the surface of the adhesive. Tackifiers suitable for use in the present invention include resins (e.g., rosins and their derivates, terpenes and modified terpenes, aliphatic, cycloaliphatic and aromatic resins (C5 aliphatic resins, C9 aromatic resins, and C5 / C9 aliphatic / aromatic resins), hydrogenated hydrocarbon resins, and their mixtures, terpene-phenol resins (TPR, used often withethylene-vinyl acetate adhesives)), novolacs. Silicone rubber–based pressure- sensitive adhesives suitable for use in the present invention include special tackifiers based “on "MQ" silicate resins, composed of a monofunctional trimethyl silane ("M") reacted with quadrafunctional silicon tetrachloride("Q").

[0465] Adhesive layer may be comprised of a blend of two or more homopolymers or copolymers, which includes copolymer architecture of block, gradient, and random copolymers of two or more different repeating units. Adhesive layer may be comprised of a single copolymer as described above. Adhesive layer may exhibit a one or more glass transition (Tg), crystallization temperature (Tc), melting temperature (Tm) or other thermal transition ranging from –100 to 100 – or about - 40 C, about -30 C, about -20 C, about -10 C, about 10 C, about 0 C, about 10 C, about 15 C, about 20 C, about 25 C, about 30 C, about 35 C, about 40 C, about 45 C, about 50 C, about 55 C, about 60 C, or about 65 C or more as measured by differential scanning calorimetry (DSC) Tg, Tc, Tm peak inflection point or dynamic mechanical analysis loss modulus or tan delta peak.

[0466] Adhesive layer may be a linear, brush, star, dendritic, or branched polymer with weight average molecular weight (Mw) of approximately 1 kDa, about 5 kDa, about 10 kDa, about 15 kDa, about 20 kDa, about 30 kDa, about 50kDa, about 75 kDa, about 90 kda, about 100 kDa, about 110 kDa, about 200 kDa, about 300 kDa, about 400 kDa, about 500 kDa, or about 1000 kDa or more.

[0467] Adhesive layer may be crosslinked, a blend of multiple aforementioned linear polymers or a copolymer of aforementioned polymers and may also be a semi- interpenetrating network or interpenetrating network of two or more polymer or copolymers.

[0468] Adhesive layer may exhibit thermally-responsive stimuli responsive behavior that enables adhesion to penile skin at body temperature (about 37 C) and also enables lowered adhesive force or delamination upon cooling below body temperature to about 25 C, about 20 C, about 15 C, about 10 C, about 5 C, about 0 C or lower. Cooling may be achieved, for example, by accelerated heat transfer by rubbing a wet substrate such as a water-impregnated towel or paper towel on the diaphragm or at the interface of the adhered barrier layer while adhered to the penis or by running water from a source such as a shower or a cloth or tissue wipe whichcontain a reagent which causes cooling (alcohol evaporation or dissolution of aammonium nitrate) to cool the diaphragm through a thermal transition such that delamination is achievable more easily than if the diaphragm were to be removed at body temperature.

[0469] Adhesive layer may exhibit chemically responsive behavior and may be water or solvent soluble in nature and may be removed by pulling back edges and flowing water or solvent or rubbing a substrate impregnated with water or solvent until diaphragm is removed by weakening of adhesive later or dissolution by water or solvent. Chemical delamination may also be achieved in this manner by pH- triggerable delamination by flowing or wiping in this manner with a substrate impregnated with a fluid with a pH suitable for skin contact that also achieves delamination of diaphragm from skin. Alternatively, chemical delamination may also be achieved by dissolution of the adhesive by flowing or wiping in this manner with a substrate impregnated with a fluid that achieves delamination of the diaphragm from skin.

[0470] ADHESIVE AND STIMULI RESPONSIVE POLYMER PROPERTIES

[0471] In some embodiments, the stimulus is selected from a temperature change, a physico-chemical change, light, ultrasound, an ionic strength change, a pH change, magnetism, a mechanical force, or mechanical action.

[0472] In some embodiments, the stimulus is a mechanical action, e.g., shear rate. In some embodiments, the shear rate is induced by peeling or pulling on the contraceptive device at different rates or frequencies.

[0473] In some embodiments, the adhesive is shear-rate responsive. In some embodiments, the stimuli-responsive polymer is shear-rate responsive. In such embodiments, the adhesive remains adhered upon application of higher shear rates and becomes less adhesive at lower shear rates. Exemplary higher shear rates include hard peeling or hard pulling. Exemplary lower shear rates include light peeling or light pulling. Higher and lower are taken with respect to a threshold about which a change in behavior is observed. In this manner, the adhesive layer and the contraceptive device can be easily removed from the penis or vagina following application of a stimulus to the contraceptive device.

[0474] In some embodiments, light peeling corresponds to a peel rate of 500 mm / min or less, such as, for example, 400 mm / min or less, 300 mm / min or less, 200 mm / min or less, 100 mm / min or less, or 50 mm / min or less. In some embodiments, light peeling corresponds to a peel rate of 50 mm / min to 500 mm / min, such as, for example, from 50 mm / min to 400 mm / min, from 50 mm / min to 300 mm / min, from 50 mm / min to 200 mm / min, from 50 mm / min to 100 mm / min, from 100mm / min to 500 mm / min, from 100 mm / min to 400 mm / min, from 100 mm / min to 300 mm / min, from 100 mm / min to 200 mm / min, from 200 mm / min to 500 mm / min, from 200 mm / min to 400 mm / min, from 200 mm / min to 300 mm / min, from 300 mm / min to 500 mm / min, from 300 mm / min to 400 mm / min, or from 400 mm / min to 500 mm / min.

[0475] In some embodiments, light peeling corresponds to a peel rate of 25 mm / s or less, such as, for example, 10 mm / s or less, 5 mm / s or less, 1 mm / s or less, 0.5 mm / s or less, 0.3 mm / s or less, or 0.1 mm / s or less. In some embodiments, light peeling corresponds to a peel rate from 0.01 mm / s to 25 mm / s, such as, for example, from 0.01 mm / s to 10 mm / s, from 0.01 mm / s to 5 mm / s, from 0.01 mm / s to 1 mm / s, from 0.01 mms / to 0.5 mm / s, from 0.01 mm / s to 0.3 mm / s, from 0.01 mm / s to 0.1 mm / sec, from 0.1 mm / s to 25 mm / s, from 0.1 mm / s to 10 mm / s, from 0.1 mm / s to 5 mm / s, from 0.1 mm / s to 1 mm / s, from 0.1 mms / to 0.5 mm / s, from 0.1 mm / s to 0.3 mm / s, from 1 mm / s to 25 mm / s, from 1 mm / s to 10 mm / s, or from 1 mm / s to 5 mm / s.

[0476] In some embodiments, the stimulus is a mechanical force. In some embodiments, the adhesive is force responsive. In some embodiments, the stimuli- responsive polymer is force responsive. In such embodiments, the adhesive remains adhered upon application of higher forces and becomes less adhesive upon application of lower forces. Higher and lower are taken with respect to a threshold about which a change in behavior is observed.

[0477] In some embodiments, the applied force that results in delamination of the stimuli-responsive polymer is, for example, from 0.01 to 0.1 N, from 0.1 to 1 N, from 1 to 10 N, from 10 to 100 N, or from 100 and 1000 N. In some embodiments, the applied force that results in delamination of the stimuli-responsive polymer is, for example, from 1 to 10 Pa, from 10 to 100 Pa, from 0.1 to 1 kPa, from 1 to 10 kPa, from 10 to 100 kPa, or from 0.1 to 1 MPa.

[0478] In some embodiments, the applied force that results in delamination of the adhesive is, for example, from 0.01 to 0.1 N, from 0.1 to 1 N, from 1 to 10 N, from 10 to 100 N, or from 100 and 1000 N. In some embodiments, the applied force that results in delamination of the adhesive is, for example, from 1 to 10 Pa, from 10 to 100 Pa, from 0.1 to 1 kPa, from 1 to 10 kPa, from 10 to 100 kPa, or from 0.1 to 1 MPa.

[0479] In some embodiments, the stimuli-responsive polymer has a lower peel strength at lower peel rates and a higher peel strength at higher peel rates. In some embodiments, the stimuli-responsive polymer has at least a 5% lower peel strength at a lower peel rate compared to the peel strength at a higher peel rate, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0480] In some embodiments, the stimuli-responsive polymer has a lower peel strength at a peel rate of 100 mm / min than at 200 mm / min. In some embodiments, the stimuli-responsive polymer has a lower peel strength at a peel rate of 100 mm / min than at 300 mm / min. In some embodiments, the stimuli-responsive polymer has a lower peel strength at a peel rate of 100 mm / min than at 400 mm / min. In some embodiments, the stimuli-responsive polymer has a lower peel strength at a peel rate of 100 mm / min than at 500 mm / min.

[0481] In some embodiments, the stimuli-responsive polymer has a lower peel strength at a peel rate of 1 mm / s than at 3 mm / s. In some embodiments, the stimuli- responsive polymer has a lower peel strength at a peel rate of 1 mm / s than at 5 mm / s. In some embodiments, the stimuli-responsive polymer has a lower peel strength at a peel rate of 1 mm / s than at 7 mm / s. In some embodiments, the stimuli- responsive polymer has a lower peel strength at a peel rate of 1 mm / s than at 10 mm / s.

[0482] In some embodiments, the stimuli-responsive polymer has at least a 5% lower peel strength at a peel rate of 100 mm / min than at 200 mm / min, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0483] In some embodiments, the stimuli-responsive polymer has at least a 5% lower peel strength at a peel rate of 100 mm / min than at 300 mm / min, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0484] In some embodiments, the stimuli-responsive polymer has at least a 5% lower peel strength at a peel rate of 100 mm / min than at 400 mm / min, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0485] In some embodiments, the stimuli-responsive polymer has at least a 5% lower peel strength at a peel rate of 100 mm / min than at 500 mm / min, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0486] In some embodiments, the stimuli-responsive polymer has at least a 5% lower peel strength at a peel rate of 1 mm / s than at 3 mm / s, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0487] In some embodiments, the stimuli-responsive polymer has at least a 5% lower peel strength at a peel rate of 1 mm / s than at 5 mm / s, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0488] In some embodiments, the stimuli-responsive polymer has at least a 5% lower peel strength at a peel rate of 1 mm / s than at 7 mm / s, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0489] In some embodiments, the adhesive has a lower peel strength at lower peel rates and a higher peel strength at higher peel rates. In some embodiments, theadhesive has at least a 5% lower peel strength at a lower peel rate compared to the peel strength at a higher peel rate, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0490] In some embodiments, the adhesive has a lower peel strength at a peel rate of 100 mm / min than at 200 mm / min. In some embodiments, the adhesive has a lower peel strength at a peel rate of 100 mm / min than at 300 mm / min. In some embodiments, the adhesive has a lower peel strength at a peel rate of 100 mm / min than at 400 mm / min. In some embodiments, the adhesive has a lower peel strength at a peel rate of 100 mm / min than at 500 mm / min.

[0491] In some embodiments, the adhesive has a lower peel strength at a peel rate of 1 mm / s than at 3 mm / s. In some embodiments, the adhesive has a lower peel strength at a peel rate of 1 mm / s than at 5 mm / s. In some embodiments, the adhesive has a lower peel strength at a peel rate of 1 mm / s than at 7 mm / s. In some embodiments, the adhesive has a lower peel strength at a peel rate of 1 mm / s than at 10 mm / s.

[0492] In some embodiments, the adhesive has at least a 5% lower peel strength at a peel rate of 100 mm / min than at 200 mm / min, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0493] In some embodiments, the adhesive has at least a 5% lower peel strength at a peel rate of 100 mm / min than at 300 mm / min, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0494] In some embodiments, the adhesive has at least a 5% lower peel strength at a peel rate of 100 mm / min than at 400 mm / min, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0495] In some embodiments, the adhesive has at least a 5% lower peel strength at a peel rate of 100 mm / min than at 500 mm / min, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0496] In some embodiments, the adhesive has at least a 5% lower peel strength at a peel rate of 1 mm / s than at 3 mm / s, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0497] In some embodiments, the adhesive has at least a 5% lower peel strength at a peel rate of 1 mm / s than at 5 mm / s, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0498] In some embodiments, the adhesive has at least a 5% lower peel strength at a peel rate of 1 mm / s than at 7 mm / s, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0499] In some embodiments, the stimuli-responsive polymer has a peel strength from 1 to 400 N / m at a peel rate of 100 mm / sec, such as, for example, from 1 to 300 N / m, from 1 to 200 N / m, from 1 to 100 N / m, or from 1 to 50 N / m. Peel strength can be determined by a 180° peel test using a human skin substrate analog as described hereinbelow.

[0500] In some embodiments, the adhesive has a peel strength from 1 to 400 N / m at a peel rate of 100 mm / sec, such as, for example, from 1 to 300 N / m, from 1 to 200 N / m, from 1 to 100 N / m, or from 1 to 50 N / m. Peel strength can be determined by a 180° peel test using a human skin substrate analog as described hereinbelow.

[0501] In some embodiments, the stimuli-responsive polymer has a tack strength at 25 °C of at least 1 N, such as, for example, from 1 N to 5 N, from 1 N to 4 N, from 1 N to 3 N, or from 1 N to 2 N. Tack strength can be measured as described hereinbelow, e.g., compressing an aluminum-tipped rheometer containing thepolymer to an aluminum base plate for 60 s, withdrawing the rheometer at 100 micrometers per second, and measuring the axial force in N.

[0502] In some embodiments, the adhesive has a tack strength at 25 °C of at least 1 N, such as, for example, from 1 N to 5 N, from 1 N to 4 N, from 1 N to 3 N, or from 1 N to 2 N.

[0503] In some embodiments, the stimuli-responsive polymer has an adhesive strength at 25 °C of a least 20 N*s, such as, for example, at least 30 N*s, at least 40 N*s, at least 50 N*s, at least 60 N*s, at least 70 N*s, at least 80 N*s, at least 90 N*s, at least 100 N*s, at least 150 N*s, at least 200 N*s, at least 300 N*s, at least 400 N*s, or at least 500 N*s. Adhesive strength is calculated by integrating the area under the axial force vs time measurements for a sample.

[0504] In some embodiments, the adhesive has an adhesive strength at 25 °C of a least 20 N*s, such as, for example, at least 30 N*s, at least 40 N*s, at least 50 N*s, at least 60 N*s, at least 70 N*s, at least 80 N*s, at least 90 N*s, at least 100 N*s, at least 150 N*s, at least 200 N*s, at least 300 N*s, at least 400 N*s, or at least 500 N*s.

[0505] In some embodiments, the stimuli-responsive polymer has a storage modulus of from 0.01 MPa to 1 MPa, such as, for example, from 0.1 MPa to 1 MPa, from 0.1 MPa to 0.8 MPa or from 0.1 MPa to 0.5 MPa.

[0506] In some embodiments, the adhesive has a storage modulus of from 0.01 to 1 MPa, such as, for example, from 0.1 MPa to 1 MPa, from 0.1 MPa to 0.8 MPa or from 0.1 MPa to 0.5 MPa.

[0507] In some embodiments, the stimuli-responsive polymer has a loss modulus of from 0.1 MPa to 1 MPa, such as, for example, from 0.1 MPa to 0.8 MPa or from 0.1 MPa to 0.5 MPa.

[0508] In some embodiments, the adhesive has a loss modulus of from 0.1 MPa to 1 MPa, such as, for example, from 0.1 MPa to 0.8 MPa or from 0.1 MPa to 0.5 MPa.

[0509] In some embodiments, the stimuli-responsive polymer has a tan(δ) (ratio of storage modulus (G’’) to loss modulus (G’)) at 25 °C and 1 Hz (2*pi radian / s) of at least 0.1, such as, for example, at least 0.2, at least 0.3, at least 0.4 at least 0.5, atleast 0.6, at least 0.7, at least 0.8, at least 0.9, at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9, at least 2.0, at least 3.0, at least 4.0, or at least 5.0. In some embodiments, the stimuli-responsive polymer has a tan(δ) from 0.1 to 5, such as, for example, from 0.1 to 4, 0.1 to 3, 0.1 to 2, 0.1 to 1, 0.5 to 5, 0.5 to 4, 0.5 to 3, 0.5 to 3, 0.5 to 2, 0.5 to 1, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 5, 2 to 4, 2 to 3, 3 to 5, 3 to 4, or 4 to 5. In certain embodiments, the stimuli-responsive polymer has a tan(δ) of 0.2 to 2, e.g., 0.1 to 1.5, 0.1 to 1, 0.1 to 0.5, 0.3 to 1, or 0.5 to 1.

[0510] In some embodiments, the adhesive has a tan(δ) (ratio of storage modulus (G’’) to loss modulus (G’)) at 25 °C and 1 Hz (2* pi radian / s) of at least 0.1, such as, for example, at least 0.2, at least 0.3, at least 0.4 at least 0.5, at least 0.6, at least 0.7, at least 0.8, at least 0.9, at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9, at least 2.0, at least 3.0, at least 4.0, or at least 5.0. In some embodiments, the adhesive has a tan(δ) from 0.1 to 5, such as, for example, from 0.1 to 4, 0.1 to 3, 0.1 to 2, 0.1 to 1, 0.5 to 5, 0.5 to 4, 0.5 to 3, 0.5 to 3, 0.5 to 2, 0.5 to 1, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 5, 2 to 4, 2 to 3, 3 to 5, 3 to 4, or 4 to 5. In certain embodiments, the adhesive has a tan(δ) of 0.2 to 2, e.g., 0.1 to 1.5, 0.1 to 1, 0.1 to 0.5, 0.3 to 1, or 0.5 to 1.

[0511] In some embodiments, the stimuli-responsive polymer has less tack when wet compared to when dry. In some embodiments, the adhesive has less tack when wet compared to when dry.

[0512] In some embodiments, the stimuli-responsive polymer is a crosslinked polymer is a low-density crosslinked polymer or a polymer with limited, heterogeneous crosslinking.

[0513] In some embodiments, the stimuli-responsive polymer is Lightly Crosslinked as defined herein

[0514] In some embodiments, the stimuli-responsive polymer is Low Molecular Weight Lightly Crosslinked as defined herein

[0515] In some embodiments, the adhesive comprises a polymer that is Lightly Crosslinked as defined herein

[0516] In some embodiments, the adhesive comprises a polymer that is is Low Molecular Weight Lightly Crosslinked as defined herein

[0517] In some embodiments, the stimuli-responsive polymer has gel fraction consistent with that of a lightly crosslinked polymer network when analyzed by sol- gel analysis. In some embodiments, the stimuli-responsive polymer has a gel fraction from 0.0001 to 0.99, such as, for example, from 0.001 to 0.98, from 0.01 to 0.95, from 0.015 to 0.95, from 0.02 to 0.96, from 0.05 to 0.95, from 0.1 to 0.95, from 0.175 to 0.95, from 0.2 to 0.95, from 0.25 to 0.95, from 0.3 to 0.95, from 0.35 to 0.95, from 0.4 to 0.95, from 0.5 to 0.95, from 0.6 to 0.95, from 0.7 to 0.95, from 0.8 to 0.95, from 0.5 to 0.95, from 0.6 to 0.93, from 0.6 to 0.65 to 0.92, from 0.7 to 0.9, or from 0.7 to 0.89.

[0518] In some embodiments, the adhesive has gel fraction consistent with that of a lightly crosslinked polymer network when analyzed by sol-gel analysis. In some embodiments, the adhesive has a gel fraction from 0.0001 to 0.99, such as, for example, from 0.001 to 0.98, from 0.01 to 0.95, from 0.015 to 0.95, from 0.02 to 0.96, from 0.05 to 0.95, from 0.1 to 0.95, from 0.175 to 0.95, from 0.2 to 0.95, from 0.25 to 0.95, from 0.3 to 0.95, from 0.35 to 0.95, from 0.4 to 0.95, from 0.5 to 0.95, from 0.6 to 0.95, from 0.7 to 0.95, from 0.8 to 0.95, from 0.5 to 0.95, from 0.6 to 0.93, from 0.6 to 0.65 to 0.92, from 0.7 to 0.9, or from 0.7 to 0.89.

[0519] In some embodiments, following adhesion of the adhesive layer to the penis or vagina, removal of the contraceptive device by light peeling does not cause pain in the subject. In some embodiments, following adhesion of the adhesive layer to the glans of the penis, removal of the condom by light peeling causes minimal or no pain to the subject. Any suitable method can be utilized to determine the existence or absence of pain. There are several validated instruments for the measurement of pain. The instruments can be unidimensional, measuring only the intensity of pain, such as pain Wong-Baker Qualitative Pain Assessment (WBQPA), Numeric Pain Rating Scale (NRPS), visual analogue scale (VAS) and verbal rating scale. Multidimensional instruments measure the intensity, character and impact of pain, for example, the McGill Pain Questionnaire (MPQ) and Brief Pain Inventory (BPI).

[0520] In some embodiments, pain is measured using the WBQPA on a scale of 0 (no pain) to 10 (maximum pain). In some embodiments, the pain is less than 4 on the WBQPA scale when the adhesive layer is removed by light peeling, e.g., less than 3, less than 2, less than 1 or 0. In some embodiments, a WBQPA score of 0 isreported upon removal of the contraceptive device by light peeling. As discussed above, in some embodiments, light peeling corresponds to a user peel rate of the contraceptive device (e.g., condom) of 25 mm / s or less, such as, for example, 10 mm / s or less, 5 mm / s or less, 1 mm / s or less, 0.5 mm / s or less, 0.3 mm / s or less, or 0.1 mm / s or less. In some embodiments, light peeling corresponds to a peel rate from 0.01 mm / s to 25 mm / s, such as, for example, from 0.01 mm / s to 10 mm / s, from 0.01 mm / s to 5 mm / s, from 0.01 mm / s to 1 mm / s, from 0.01 mms / to 0.5 mm / s, from 0.01 mm / s to 0.3 mm / s, from 0.01 mm / s to 0.1 mm / sec, from 0.1 mm / s to 25 mm / s, from 0.1 mm / s to 10 mm / s, from 0.1 mm / s to 5 mm / s, from 0.1 mm / s to 1 mm / s, from 0.1 mms / to 0.5 mm / s, from 0.1 mm / s to 0.3 mm / s, from 1 mm / s to 25 mm / s, from 1 mm / s to 10 mm / s, or from 1 mm / s to 5 mm / s.

[0521] In some embodiments, light peeling corresponds to a user peel rate of the contraceptive device (e.g., condom) of 500 mm / min or less, such as, for example, 400 mm / min or less, 300 mm / min or less, 200 mm / min or less, 100 mm / min or less, or 50 mm / min or less, or 25 mm / min or less, or 10 mm / min or less, or 5 mm / min or less, or 1 mm / min or less, or 0.5 mm / min or less, or 0.3 mm / min or less, or 0.1 mm / min or less. In some embodiments, light peeling corresponds to a peel rate of 50 mm / min to 500 mm / min, such as, for example, from 50 mm / min to 400 mm / min, from 50 mm / min to 300 mm / min, from 50 mm / min to 200 mm / min, from 50 mm / min to 100 mm / min, from 100 mm / min to 500 mm / min, from 100 mm / min to 400 mm / min, from 100 mm / min to 300 mm / min, from 100 mm / min to 200 mm / min, from 200 mm / min to 500 mm / min, from 200 mm / min to 400 mm / min, from 200 mm / min to 300 mm / min, from 300 mm / min to 500 mm / min, from 300 mm / min to 400 mm / min, or from 400 mm / min to 500 mm / min.

[0522] In some embodiments, the adhesive is rate responsive in a range relevant for human skin removal. For example, the adhesive might exhibit a work of adhesion in J / m2 change of 30x as retraction rate on a rheometer tack test under testing conditions described in the present invention is changed from 1 micrometer per second to 8000 micrometers per second. Rate responsive behavior could exhibit work of adhesion changes between 1 and 1.5 x in a retraction rate of 1 to 8000 micrometers per second, more optimally 1 to 2x, more optimally 1 to 3x, more optimally 1 to 4x, more optimally 1 to 5x, more optimally 1 to 7x, more optimally 1 to 10x, more optimally 1 to 12x, more optimally 1 to 13x, more optimally 1 to 15x, moreoptimally 1 to 16x, more optimally 1 to 20x, more optimally 1 to 23x, more optimally 1 to 25x, more optimally 1 to 27x, more optimally 1 to 30x or more.

[0523] In some embodiments, the stimuli-responsive polymer is rate responsive in a range relevant for human skin removal. For example, the adhesive might exhibit a work of adhesion in J / m2 change of 30x as retraction rate on a rheometer tack test under testing conditions described in the present invention is changed from 1 micrometer per second to 8000 micrometers per second. Rate responsive behavior could exhibit work of adhesion changes between 1 and 1.5 x in a retraction rate of 1 to 8000 micrometers per second, more optimally 1 to 2x, more optimally 1 to 3x, more optimally 1 to 4x, more optimally 1 to 5x, more optimally 1 to 7x, more optimally 1 to 10x, more optimally 1 to 12x, more optimally 1 to 13x, more optimally 1 to 15x, more optimally 1 to 16x, more optimally 1 to 20x, more optimally 1 to 23x, more optimally 1 to 25x, more optimally 1 to 27x, more optimally 1 to 30x or more.

[0524] In some embodiments, the stimuli-responsive polymer exhibits a Resilience, or integrated value of a plot of tan delta multiplied by G* versus angular frequency over the angular frequency range of 0 to 50 rad / s of 2.5 [MPa*(rad / s)]. Integrated value of a plot of tan delta x G* versus angular frequency over the angular frequency range of 0 to 50 rad / s for the stimuli responsive polymer of the present invention could be 0.1 to 0.2, 0.2 to 0.4, 0.4 to 0.7, 0.8 to 0.9, 1.0 to 1.3, 1.4 to 1.8, 1.9 to 2.1, 2.2 to 2.5, 3.0 to 3.5 or higher.

[0525] In some embodiments, the adhesive exhibits a Resilience, or integrated value of a plot of tan delta multiplied by G* versus angular frequency over the angular frequency range of 0 to 50 rad / s of 2.5 [MPa*(rad / s)]. Integrated value of a plot of tan delta x G* versus angular frequency over the angular frequency range of 0 to 50 rad / s for the adhesive comprising a polymer of the present invention could be 0.1 to 0.2, 0.2 to 0.4, 0.4 to 0.7, 0.8 to 0.9, 1.0 to 1.3, 1.4 to 1.8, 1.9 to 2.1, 2.2 to 2.5, 3.0 to 3.5 or higher.

[0526] In some embodiments, following adhesion of the adhesive layer to the penis or vagina, removal of the contraceptive device by light peeling causes minimal or no pain in the subject when removed in less than 15 seconds, e.g., less than 10 seconds, less than 8 seconds or less than 5 seconds.

[0527] In some embodiments, the site of adhesion exhibits limited or no irritation upon removal of the contraceptive device. Various methods are known in research settings for quantitatively assessing skin damage. Certain of these models are based on measurement of baseline skin properties that change when skin is stressed. Measurable parameters such as skin hydration, trans-epidermal water low (TEWL), and irritation, among others, will provide information differentiating damaged skin from healthy skin. See, e.g., Bernatchez, S. et al, ADVANCES IN WOUND CARE, Vol.2, No.4 (2022), which is incorporated herein by reference. Reconstructed human epidermis models are also available that demonstrate reasonable similarities to the native human tissue in terms of morphology, lipid composition and biochemical markers. See, e.g., EpiSkin, SkinEthic and EpiDerm. Animal models of skin injury are also known in the art, including pigs and rodents. See, e.g., Summerfield, A. et al., Molecular Immunology, Vol.66, Issue 1, July 2015, p.14-21.

[0528] Also disclosed is a method of using the package or packaged adhesives disclosed herein.

[0529] In one embodiment, a method is provided of packaging an adhesive, comprising (i) providing a package as disclosed herein and (ii) introducing the adhesive (e.g., condom, medical adhesive) into the package.

[0530] In another embodiment, a method of using the packaged adhesive disclosed herein is provided, comprising (i) providing the packaged adhesive; (ii) opening the packaged adhesive and (ii) applying the adhesive to the target site. In certain embodiments, the adhesive is an enhanced sensation condom, e.g., as disclosed herein. See FIGURE 2. In certain embodiments, the adhesive is a medical adhesive, e.g., as disclosed herein.

[0531] In another embodiment, a method of using the packaged adhesive disclosed herein is provided, comprising (i) opening the package; (ii) inverting the package to align, adhere and deposit the adhesive on a target substrate. In certain embodiments, the adhesive is an enhanced sensation condom. In certain embodiments, the adhesive is a medical adhesive, e.g., to protect or close a wound.

[0532] In one embodiment, the method requires use of a single hand (or prosthetic aide).

[0533] Also disclosed is a method of manufacturing the package and / or packaged adhesive disclosed herein.

[0534] In one embodiment, a method of manufacturing the package disclosed herein is provided, comprising (i) thermoforming a hot-melted sheet of thermoplastic or thermoset material over a rigid form or an array of rigid forms; (ii) pulling a vacuum to suction the malleable plastic sheet to the shape of the rigid form or applying a positive pressure to push the malleable plastic sheet onto the shape of the rigid form, and allowing the malleable plastic sheet to cool, thereby producing the receiving body of the package; (iii) separating the receiving body from the excess plastic sheet by cutting or punching; (iv) optionally adding a thin layer of liquid to the receiving body; (v) adding an adhesive to the receiving body; and (vi) sealing the package by adhering a removable film lid to the opening of the receiving body.

[0535] In certain embodiments, the thin layer of liquid is added in (iv) at an elevated temperature or while the plastic packaging has yet to full cool to ambient temperature following thermoforming to permit easier wetting out of the interior surface of the package.

[0536] In one embodiment, the adhesive is an enhanced sensation condom, e.g., as disclosed herein.

[0537] In one embodiment, the adhesive is a medical adhesive, e.g., for protection or closure of a wound.

[0538] In one embodiment, the adhesive is sterilized before added to the receiving body in (iv), e.g., by treatment with e-beam or gamma irradiation.

[0539] In one embodiment, an enhanced sensation condom or other adhesive containing substrate such as a medical skin adhesive that is manufactured from a roll-to-roll, thermoforming or other planar process may be deposited into the packaging by means of die-punching or cutting of the condom out of the manufactured sheet, and either drop-deposition using gravity or pick-and-place deposition using suction or a transfer liner (such as silicone paper or other appropriate release liner). The optional liquid capillary film is assumed to have been deposited in the packaging prior to condom insertion.

[0540] In another embodiment, the condom may be transferred to the package using a deformable transfer pad made of silicone or another (non)linear elastomeric material.

[0541] In another embodiment, the condom may be made by inverse dip coating or conventional dip coating, enabling the condom to be slid directly off the dipping form into the package (if dipped with the adhesive on the inside, inverse dip coating), or inverted as it is removed from the dipping form (conventional dip coating with the adhesive on the exterior). The removal device may be a rigid or compliant arm, or a jet of air.

[0542] In another embodiment of the package insertion process, the condoms are placed in the package, they may be vibrated, or rotated about their axis in order to remove any trapped air bubbles and assist in settling them into a stable position within the package.

[0543] Also disclosed is a method of manufacturing the package without an adhesive containing substrate, which may be added at a later time disclosed herein.

[0544] An embodiment includes a method of manufacturing the package for a subsequent manufacturer to enclose an adhesive containing substrate disclosed herein is provided, comprising (i) thermoforming a hot-melted sheet of thermoplastic over a form or an array of forms; (ii) pulling a vacuum to suction the malleable plastic sheet to the shape of the rigid form, thereby producing the receiving body; (iii) separating the receiving body from the excess plastic sheet by cutting or punching; (iv) optionally adding a retaining element to the receiving body; and (v) optionally partially or fully adhering a removable or resealable film lid to the opening of the receiving body, thereby producing a package to contain an adhesive containing substrate.

[0545] In certain embodiments, the thin layer of liquid is added in (iv) at an elevated temperature or while the plastic packaging has yet to full cool to ambient temperature following thermoforming to permit easier wetting out of the interior surface of the package.

[0546] In certain embodiments, the retaining element added in (iv) may be covered with a suitable release liner, such as silicone impregnated paper, or otherprotective barrier to prevent contamination of the retaining element prior to addition of the adhesive containing substrate at a later time.

[0547] In certain embodiments, the retaining element added in (iv) may be added in a later step after the package is re-opened, prior to adding the adhesive containing substrate to the receiving body.

[0548] In one embodiment, the film lid may be attached to the opening of the receiving body at a single point or over a small area of the flange of the receiving body by less than 1% of the flange area, by between 1 and 10% of the flange area, between 10 and 50% of the flange area or between 50 and 100% of the flange area, such that an adhesive containing substrate may be deposited or placed in the package at a later time, after which the remainder of the film lid is adhered to the opening of the receiving body.

[0549] In another embodiment, the film lid may be attached to the opening of the receiving body with an adhesive that may be opened and re-sealed one or more times, such that the film lid may be removed at a later time, an adhesive containing substrate may be placed within the receiving body, and the lid re-attached or re- sealed to the opening of the receiving body.

[0550] In certain embodiments, the package may be enclosed in a plastic bag or wrap to prevent contamination of the package prior to addition of an adhesive containing substrate at a later time.

[0551] DEVELOPABLE SURFACES

[0552] Developable surfaces are a known class of surfaces in the fields of differentiable geometry. A developable surface is a smooth surface (without kinks, corners or creases) that has zero Gaussian curvature.

[0553] Developable surfaces have found value in the domain of shipbuilding, building architecture, and automotive design. A developable surface may be constructed by bending and rolling an initially planar piece of material into the desired three-dimensional shape without local stretching or compression of the material. This is particularly advantageous when considering construction materials which do not distort (stretch or compress) easily. Common examples of such materials are paper and plywood, which can be readily bent, creased, or rolled. However, when these materials are put under tension beyond a threshold load, theytend to tear or fracture, rather than undergo a large elastic or plastic deformation. And when they are loaded under compression beyond a threshold, they often buckle.

[0554] In ship hull design, it is rare to be able to form a hull geometry entirely from a single developable surface, so typically several are joined together, where each “patch” may be regarded as a developable surface, joined together into the ship hull, which may be regarded as a “polysurface”. A polysurface is typically watertight, however the junction or boundary between adjacent surfaces need not be continuous, smooth (e.g., corners or chines), or endowed with the same or continuous properties. These joints are typically secured with glue / adhesives, fillers, weldments, or other methods.

[0555] A material having a developable surface has a 3D surface that can be “unrolled” into a flat surface without locally stretching or compressing the material. Common examples may include any ring or cone one can make from a piece of paper by rolling and bending the paper and then taping / gluing the paper ends together. This would constitute a developable surface because paper cannot be stretched or compressed—the paper will just tear. As another example, one can cover half of a sphere (e.g., a globe) by stretching a sheet of latex over the sphere without wrinkling, folding, or tearing the latex. But this cannot be done with a sheet of flat paper.

[0556] Embodiments include an enhanced sensation condom (ESC) for containing ejaculate fluids and when used as a contraceptive, preventing the passage of sperm to a receiving partner, thereby preventing pregnancy during vaginal intercourse. It may also be used for containing ejaculate fluids (i.e., semen and understood to also include pre-ejaculate fluids, particularly those that may contain sperm) and preventing their passage to a receiving user during penetrative or non-penetrative vaginal, anal or oral intercourse to mitigate transmission of sexually transmitted infections (STI prevention), avoid undesirable ingestion of ejaculate fluids by a receiving partner, or to otherwise contain ejaculate fluids such as in the hopes of reducing clean up or mess.

[0557] An embodiment of the ESC is comprised of a barrier body (sometimes referred to as a “barrier layer”) for containing the ejaculate fluid which is secured to the penis glans (hereafter referred to simply as the “glans”) by the secondcomponent, an adhesive layer, which also functions to provide a seal between the barrier body and the user’s skin. The adhesive layer is designed to secure to the glans, however due to the variation in human anatomy, some users may find parts of the adhesive region may wrap over portions of the glans corona, the frenulum and may contact small portions of the surrounding shaft skin. However, it should be understood that these are due to the naturally vast variations in human anatomy and should not be interpreted as functioning in a manner different from that of exemplary modes described in this disclosure, and geometric designs, mechanical properties of the barrier layer and adhesive layer properties have been selected to optimize performance without compromising the intended purpose of remaining affixed to a male user during intercourse, and containing ejaculate fluids. By affixing to the glans of the penis, most of the shaft remains exposed to natural naked contact for sexual stimulation, in contrast to the total penile skin coverage afforded by a conventional condom.

[0558] In an embodiment, the barrier body comprises one, two or more pieces of an elastomeric or plastic material that conform in a facile manner or drape to the shape of the user’s glans geometry and expand under the pressure of human ejaculation to contain the expelled fluid within a reservoir that has a three- dimensional shape and for the adhesive layer to join the reservoir with an angle that mitigates the peel up of the adhesive layer from the glans skin by primarily loading the adhesive layer in shear.

[0559] In an embodiment, the adhesive layer comprises an adhesive material that exhibits a stimuli-responsive or dynamically varying material behavior. Such adhesives are tacky when applied to the skin and remain affixed throughout intercourse. When an appropriate stimulus is applied to the adhesive, the stimuli- responsive adhesive exhibits a lower peel force such that it is easier and less painful to remove than without the specific stimuli applied, particularly when compared to medical and household adhesives known in the art, such as 3M Tegaderm™. Several embodiments and compositions are disclosed herein, with the most favorable being a shear-rate responsive adhesive where the stimulus is a continuous variation in the applied shear peel rate of the adhesive, and the measured peel force varies dynamically in response.

[0560] Embodiments of adhesive compositions disclosed herein exhibit several properties that are novel to the art. Embodiments of compositions are crosslinked or lightly crosslinked polymeric network materials that live minimal or no residual residue on skin after removal in manners that include peeling. Embodiments of adhesives exhibit an energy-dissipating viscoelastic behavior with strain capacities consistent with or greater than that of human skin, and glans skin in particular, so they comply with skin and bodily motions. The favorable compositions disclosed herein exhibit very low to no tack to naturally moist tissues or mucosa membranes, such as the tissue that makes up the urethra, the vaginal wall, the rectum, and the oral cavity. This behavior mitigates problems that arise from adhesives and adhesive condoms known in the art, where the adhesive may either block or seal the urethra meatus (opening) shut or adhere to the inner surface, causing significant pain on removal. Furthermore, the adhesive disclosed herein mitigates the risk of adhering to the vaginal wall or oral cavity, causing pain or discomfort for one or both users, or loss of the device within the receiving user’s body. However, these compositions are hydrophobic and their adhesive behavior is not reduced due to exposure to water once dried, nor are they dissolved or washed away from a substrate to which they are applied by water.

[0561] Exemplary adhesives comprise compositions formed into polymeric adhesives using roll to roll or sheet coating processes known in the art. However, the manipulation of crosslinked or lightly crosslinked adhesives from planar sheets or films into more complex surfaces poses a significant challenge. A novel developable three-dimensional ring-like or encompassing adhesive layer geometry and a novel method of manufacture of such a three-dimensional adhesive ring comprising an adhesive, including a crosslinked or lightly crosslinked adhesive, is disclosed herein The combination of the developable ring geometry and manufacturing process enable the manipulation of a crosslinked adhesive while attached to a release liner, most typically a siliconized paper or surface-treated thermoset plastic film, by a machine to fabricate an ESC. While not exhaustive, this method may be preferable when the barrier body is composed of a material that is not a thermoplastic, such as natural rubber latex—a ubiquitous material in the condom and medical barrier space.

[0562] For embodiments in which natural rubber latex allergies are a concern, alternative methods of manufacture are disclosed to be used with barrier bodies withthermoplastic alternative compositions, including thermoplastic polyurethane, thermoplastic elastomers, polyisoprene and nitrile rubber.

[0563] Embodiments describe a solution for the unmet societal demand for pleasurable of contraceptive solutions. The solution of an adhesive condom that adheres to the tip of the penis (glans) is an impactful innovation that embodies novel adhesives strong and robust enough to stay adhered to the penis during sexual intercourse, contain a volume of semen upon ejaculation, and not damage penile skin tissue or otherwise cause pain is also described in the background above, including not damaging mucosal tissue in the urethra by not adhering to wet or aqueous tissue.

[0564] Embodiments highlight the difference between a planar (flat) adhesive surface and a three-dimensional surface that may be developed (unrolled) into a planar surface without distortion. It is important to note the difference between “developing” a 3D surface into a planar (2D) surface (best stated as “unrolled” in layman’s terms) and “projecting” a 3D surface onto a planar (2D) surface. Any surface can be projected onto any plane, but the ability for a given surface to be developed into its planar representation is a special property of this special family of 3D surfaces.

[0565] The geometries presented herein are referred to three-dimensional rings. As used herein, a developable three-dimensional ring is a surface with infinitesimal or finite thickness and two edges, each transversable by an edge walk terminating at the starting location, and optionally may have corners, curves, or kinks. If these geometries exist in a plane, they are a form of generalized annulus, whereby the region of note spans the area between two planar polygons or curvilinear polygons. For example, see Figure 43 (a cross-section), 49 (a fabricated example).

[0566] Embodiments provide solutions to problems of implementing an adhesive condom in a manner that is robust in its performance in use (sexual intercourse, securing and / or sealing to body appendages such as the penis) and can be manufactured economically at scale.

[0567] In one embodiment, the condom is suitable for conforming to and surviving sex for penis geometries and anatomies that vary widely amongst users— in shape, size, and location of the urethra meatus (opening) on the glans (head ofthe penis). Embodiments solve these problems through geometric design innovations. Geometries described herein have novel varying ability to conform to diverse penis geometries and locations of urethra meatuses, namely in the three- dimensional geometries.

[0568] Embodiments are differentiated from prior art in the space of adhesive or fractional condoms in that, for example, they do not require the user to use both hands or fine dexterity, or both, to either apply or remove the device, enabling a broader audience of users to use the device, and to increase the robustness of the device when used for any user to mitigate the likelihood of failure.

[0569] The geometries of various embodiments conform to the penises on the smaller side of the distribution of penis geometries with minimal wrinkling or folding. As the curvature of the adhesive layer geometries matches the smaller radius of curvature of a smaller-than-average penis geometry in comparison to an initially flat geometry that must be bent significantly by the user to match the radius of a smaller glans, less wrinkling is likely to be introduced during application. Reducing wrinkling or folding reduces the risk of poor adhesion attachment and thus delamination either during intercourse, upon ejaculation or when inflated with semen. Reducing wrinkling or folding also reduces the likelihood of channels that would permit the flow of semen or pre-ejaculate fluids from the male user to the receiving user. Small geometry users are proposed by the inventor to be the limiting factor in an ESC or traditional condom’s functional performance.

[0570] Furthermore, the novel geometries presented herein accommodate larger penises by simply “riding higher” on the glans of the penis. In some non-limiting embodiments, condoms in embodiments exhibit performance advantages over other fractional condoms because embodiments of condoms adhere substantially to the glans skin, which exhibits greater surface roughness and higher surface area for adhesion to the condoms of the embodiments described herein and skin mechanical behavior and chemistry to enable adhesion suitable for the condoms in embodiments described herein to survive sex in contrast to those of shaft skin, to which some fractional condoms adhere. And the glans geometry will appear milder in the sense that the adhesive or the device in general will not need to bend or crease to an undesirable extent because the penis dimensions (particularly its principal curvatures over the glans) are small in comparison to those of the condom—i.e., the penisappears “flatter” to the adhesive. This relative “flatness” is favorable with respect to reducing adverse internal strains and bending moments that may contribute to delamination behavior or adverse (peeling) stresses.

[0571] In the case of a compressive “hoop stress” that may be induced by the response of the adhesive condom to a larger penis as the adhesive portion of the condom is stretched (along with the barrier layer in certain embodiments) over the glans. In this case, this compressive hoop stress can provide an additional favorable mechanism to help the condom seal and stay attached to the penis and enhance the seal for containing semen in a similar manner to how a traditional condom compressively seals against the base of penis shaft (when the condom is appropriately sized for its user).

[0572] One embodiment addresses challenges in scaled manufacturing of adhesives- including, but not limited to, adhesives that adhere to human skin. Certain adhesives are prepared or formed by coating and / or drying / curing a liquid resin (either neat or solvent based resin) onto a substrate, tape, or release liner. In some embodiments, heat or UV curing technology is utilized to cure adhesives from monomers, prepolymers or oligomers. In some embodiments, UV curable adhesives are coated onto a release liner, or between two release liners and subsequently transferred or mated to a substrate at a later step. In some of embodiments, a suitable release liner is a paper-based substrate (e.g., siliconized paper). In other embodiments, a suitable release liner comprises an optically and UV transparent film. In other embodiments, the optical or UV transparent film is polyethylene terephthalate coated in fluoropolymer or silicone.

[0573] One embodiment improves upon difficulties associated with making a three-dimensional shape from these adhesives. Processable lightly crosslinked, branched, hyperbranched or liner adhesive can be formed into a layer and processed to conform to or mate to another shape, and are coated onto a distortable (e.g. compliant, plastically deformable, or highly elastic) release liner, then they may be transferred or matted to general 3D geometric substrates (whether those also be rigid or compliant to whatever arbitrary degree). However, if they are coated on a non-distortable release liner (e.g., siliconized paper), then the construction methods to achieve a 3D geometry or transfer are limited to non-distortive operations. The adhesive can also be coated onto a compliant barrier material (i.e. latex,thermoplastic (elastomer), or thermoplastic polyurethane), which will allow the construct to be configured into a 3D geometry.

[0574] In certain embodiments, when trying to achieve a smooth and continuous adhesive layer when transferred, manipulated, or otherwise transformed into a 3D shape, bending, and “rolling” into (generalized) cylinders, (generalized) cones, (generalized) helices and tangent curves, are the only option. These specific shapes permit the adhesive to stay affixed to the release liner, facilitating manipulation and handling of the adhesive (and preventing it from being contaminated until ready for use). In one embodiment, utilizing this geometry enables the performance required by the problem and solution above, while also satisfying the adhesive manufacturing constraint. Note that these requirements for non-distortion are typically driven by the release liner but may also be driven by the adhesive.

[0575] In certain embodiments, it is desirable to add a texture to the outer surface of the barrier layer, such as one to enhance the sensation experienced by one or both users, or to the inner surface of the barrier layer to enhance the sensation of one or both users. Examples of such textures are bumps, dots, ribs, diamonds, or random roughness. Additional enhancements may also be added to enhance the use of using the product, such as colorations, printed decorative or instructional patterns and markings, scent additives, flavoring additives, stimulant additives (e.g., those that may induce a cooling / icy or warming sensation), or lubricants.

[0576] In certain embodiments, these shapes may have internal stresses limited to internal bending moments. Limited stretching or compressive stresses are present when integrating through the thickness (measured at any point on the surface).

[0577] ENHANCED SENSATION CONDOM – SINGLE BODY

[0578] In some embodiments, ESC is a single body comprising two components—a barrier body which itself consists of a single barrier layer, and an adhesive layer. The barrier layer is a compliant membrane or film that functions as the main body of the condom to contain the ejaculate fluid. The barrier layer is affixed to the penis glans via the adhesive layer. The adhesive layer of the condom has a ring-shaped (annular) region for attaching to the glans of the penis, morespecifically a three-dimensional ring shape. In exemplary embodiments, the three- dimensional ring shape is a developable surface.

[0579] In some embodiments, the non-rigid, non-rolled, fractional condom may be removed with little or no pain, e.g., as measured using the Wong-Baker Qualitative Pain Assessment (WBQPA) on a scale of 0 (no pain) to 10 (maximum pain). In some embodiments, the pain is less than 4 on the WBQPA scale when the adhesive layer is removed by light peeling, e.g., less than 3, less than 2, less than 1 or 0. In some embodiments, the non-rigid, non-rolled, fractional condom may have a loss modulus from 0.1 MPa to 0.5 MPa.

[0580] In certain embodiments, the non-rigid, non-rolled, fractional condom described above leaves little or no residue on the skin after removal, e.g., less than about 10%, less than about 5%, less than about 1% or 0 residue.

[0581] In some embodiments, the rate of contraceptive device failure (clinical or nonclinical) when measured a subject or a group of subjects is less than about 10%, less than about 8%, less than about 6%, less than about 4%, less than about 2%, less than about 1.5%, less than about 1%, less than about 0.9%, less than about 0.8%, less than about 0.7%, less than about 0.6%, less than about 0.5%, less than about 0.4%, less than about 0.3%, less than about 0.2% or about 0.1% or less. Clinical failure refers to contraceptive devices, e.g., condoms, that break, tear, leak, or slip off completely after initial penetration and before final complete withdrawal. Nonclinical failure refers to contraceptive devices, e.g., condoms, that break, tear, leak, or partially slip.

[0582] In some embodiments, the leakage rate of the condom is less than about 6%, such as, for example, less than about 5%, less than about 4%, less than about 3%, less than about 2%, or less than about 1%.

[0583] BARRIER LAYER

[0584] The barrier layer has an inner surface and an outer surface to contain semen between the inner surface and the surface of the penis of the user. The barrier layer is between 5 and 250 microns, or in some embodiments between 25 and 100 microns, or in some embodiments between 25 and 75 microns.

[0585] In some embodiments, the barrier layer comprises a polymer membrane or film that exhibits elastomeric or flexible thermomechanical behavior. In some embodiments, the barrier layer is a membrane or film.

[0586] In some embodiments, the barrier layer comprises natural latex rubber, synthetic rubber, amorphous polyurethane, semi-crystalline polyurethanes including various thermoplastic polyurethanes, polyethylene, polypropylene, polydimethylsiloxane and other silicone rubbers, polyethylene terephthalate, poly(vinyl chloride), polyisoprene, vulcanized polyisoprene and other vulcanized or crosslinked rubbers, ethylene vinyl acetate, poly(vinyl acetate), elastomeric or flexible materials, or blends thereof. In some embodiments, the barrier layer comprises natural latex rubber, synthetic rubber, or polyurethanes.

[0587] In some embodiments, the barrier layer is not polyurethane.

[0588] In some embodiments, the barrier layer is not loose fitting.

[0589] In some embodiments, the barrier layer exhibits a stimuli-responsive behavior that enables selective permeability, controlled permeability, or controlled porosity. Exemplary stimuli of the stimuli-responsive barrier layer include temperature change, physico-chemical change, light, ultrasound, ionic strength change, pH change, magnetism, and mechanical force. In some embodiments, the stimulus of the stimuli-responsive barrier layer is different than the stimulus of the stimuli-responsive polymer of the adhesive layer. In some embodiments, the stimulus of the stimuli-responsive barrier layer is the same as the stimulus of the stimuli-responsive polymer of the adhesive layer.

[0590] In some embodiments, the barrier layer further comprises one or more additives, e.g., to enhance its properties. Exemplary additives include, but are not limited to, a polymer, ceramic, metal material or spherical, rod, disc, or other shaped structures. Additive materials include silicon oxide, metal oxides, iron oxides, metals, nitinol, ceramics, conducting polymers, etc. Additive materials maybe uniformly or non-uniformly dispersed or crosslinked within the material.

[0591] In some embodiments, the barrier layer has a thickness from 0.001 mm to 2 mm, such as, for example, from 0.001 mm to 1.5 mm, from 0.001 mm to 1 mm, from 0.001 mm to 0.5 mm, from 0.001 mm to 0.1 mm, from 0.001 mm to 0.01 mm. In some embodiments, the barrier layer has a thickness from 0.025 mm to 0.25 mm,such as, for example, from 0.025 mm to 0.2 mm, from 0.025 mm to 0.15 mm, from 0.025 mm to 0.1 mm, or from 0.025 mm to 0.05 mm. In some embodiments, the barrier layer has thickness of at least 0.01 mm, e.g., at least 0.05 mm, at least 0.10 mm, at least 0.15 mm, at least 0.25 mm, at least 0.3 mm, or at least 0.5 mm.

[0592] In some embodiments, the barrier layer has a thickness of less than about 200 microns, such as, for example, from about 40 to 100 microns, or about 40 microns, about 50 microns, about 60 microns, about 70 microns, about 80 microns, about 90 microns, or about 100 microns.

[0593] In some embodiments, the barrier layer has a thickness of less than about 180 microns, such as, for example, less than about 160 microns, less than about 140 microns, less than about 120 microns, less than about 100 microns, less than about 80 microns, less than about 60 microns, less than about 40 microns, or less than about 20 microns, but in each case greater than zero.

[0594] In some embodiments, the barrier layer has a planar or curved geometry selected from a square, circle, oval, hemisphere, rectangle, polygon, or curvilinear polygon. In some embodiments, the barrier layer is not tubular.

[0595] In some embodiments, the barrier layer has a first geometry before adhering to the penis and transforms to a second geometry upon application to the penis.

[0596] In some embodiments, the barrier layer has a circle geometry. In some embodiments, the radius of the circle is at least about 0.5 cm, e.g., about 1.0 cm, about 2.0 cm, about 3.0 cm, or about 5.0 cm. In some embodiments, the radius of the circle is about 0.5 cm, about 1.0 cm, about 2.0 cm, about 3.0 cm, about 5.0 cm or about 10.0 cm or greater.

[0597] In some embodiments, the barrier layer has a rectangle geometry. In some embodiments, the rectangle has a length from 0.5 cm to 5 cm and a width from 0.5 cm to 5 cm. In some embodiments, the rectangle has a length from 0.5 cm to 4 cm, from 0.5 cm to 3 cm, from 0.5 cm to 2 cm, from 0.5 cm to 1 cm, from 1 cm to 5 cm, from 1 cm to 4 cm, from 1 cm to 3 cm, from 1 cm to 2 cm, from 2 cm to 5 cm, from 2 cm to 4 cm, from 2 cm to 3 cm, from 3 cm to 5 cm, or from 4 cm to 5. In some embodiments, the rectangle has a width from 0.5 cm to 4 cm, from 0.5 cm to 3 cm, from 0.5 cm to 2 cm, from 0.5 cm to 1 cm, from 1 cm to 5 cm, from 1 cm to 4 cm,from 1 cm to 3 cm, from 1 cm to 2 cm, from 2 cm to 5 cm, from 2 cm to 4 cm, from 2 cm to 3 cm, from 3 cm to 5 cm, or from 4 cm to 5.

[0598] In some embodiments, the barrier layer has an oval geometry. In some embodiments, the oval has a primary radius of about 0.5 cm, about 1.0 cm, about 2.0 cm, about 3.0 cm, about 5.0 cm, or about 10.0 cm and a separate secondary radius of about 0.5 cm, about 1.0 cm, about 2.0 cm, about 3.0 cm, about 5.0 cm, or about 10.0 cm or greater.

[0599] In some embodiments, the barrier layer has primary dimensions of about 0.5 x 0.5 cm, about 1.0 x 1.0 cm, about 1.5 x 1.5 cm, about 2.5 x 2.5 cm, about 3.0 x 3.0 cm, or about 5.0 x 5.0 cm or any combination thereof in the case of a rectangular barrier layer.

[0600] In some embodiments, the barrier layer does not comprise one or more protrusions. Rather, according to this embodiment, the barrier layer is a conventional, simple geometric form (e.g., rectangle, oval, or circle).

[0601] In some embodiments, the barrier layer does not comprise one or more protrusions. Rather, according to this embodiment, the barrier layer is a conventional, simple geometric form (e.g., rectangle, oval, or circle). This is contrast, for example, to the protruding wings disclosed in WO2014178661A1.

[0602] In some embodiments, the barrier layer comprises a lubricant on the outer surface, e.g., the outer surface of the contraceptive device (condom or diaphragm). In some embodiments, the lubricant is selected from a water-based lubricant, silicon- based lubricant, and oil-based lubricant.

[0603] In some embodiments, the barrier layer comprises a spermicide on the outer surface of the barrier layer, i.e., the outer surface of the condom. In some embodiments, the spermicide is selected from Nonoxynol-9, octoxynol-9, benzalkonium chloride, lactic acid, menfegol, and combinations thereof.

[0604] In some embodiments, a condom further comprises a reservoir sized and shaped suitably for collecting semen ejaculated from the penis. In some embodiments, the reservoir is configured for distal to the urethral opening of the penis. In some embodiments, the reservoir is configured on the tip, along the side, or at the base, or below the base of the condom.

[0605] In some embodiments, the reservoir is continuous with the barrier layer, i.e., the reservoir and the barrier layer are part of the same structure / not separate structures and not adhered or otherwise connected by a connecting means.

[0606] In some embodiments, the reservoir self-forms when subjected to pressure from ejaculation by the penis and does not have a pre-defined geometry.

[0607] In some embodiments, the reservoir comprises a polymer coating that swells or gels when contacted with semen. In some embodiment, such swelling or gelling retains the sperm within the reservoir. Exemplary polymer coatings include, but are not limited to, chitosan, alginate, polyacrylic acid, crosslinked polyacrylic acid, sodium polyacrylate, crosslinked sodium polyacrylate, and combinations thereof.

[0608] In some embodiments, the reservoir is roughly spherical in nature and has a radius of, e.g., about 0.1 mm, about 0.25 mm, about 0.5 mm, about 0.75 mm, about 1.0 mm, about 2.0 mm, or about 5.0 mm or greater.

[0609] In some embodiments, the reservoir is roughly cylindrical in nature and has a radius of, e.g., about 0.1 mm, about 0.25 mm, about 0.5 mm, about 0.75 mm, about 1.0 mm, or about 2.0 mm or greater and a length of about 1.0 mm, about 2.0 mm, about 5.0 mm or about 10.0 mm or greater.

[0610] In some embodiments, a condom further comprises an elastomeric ring affixed to the outer portion of the inner surface of the barrier layer or the edge of the barrier layer. In some embodiments, the elastomeric ring encircles the base of the barrier layer and may be expandable by stretching to encompass and secure the barrier layer to the base of the penile head and may optionally exert contractile force that enhances adhesion of the condom to the penis and prevents stress concentrations or shear forces from removing the adhered barrier layer during mechanical perturbation such as that associated with sexual activity.

[0611] In some embodiments, the elastomeric ring has a cross-sectional diameter of at least 0.1 mm, such as, for example, at least 0.5 mm, at least 1.0 mm, at least 2.0 mm, or at least 3.0 mm or more. In some embodiments, the elastomeric ring has an overall diameter of at least 0.25 times (0.25x) the diameter of the barrier layer, such as, for example, from 0.25x to 1x, or 0.25x, 0.50x, 0.75x, or 1.0x.

[0612] In some embodiments, the elastomeric ring comprises raised rings or studs to enhance sexual sensation or pleasure.

[0613] In some embodiments, the condom further comprises one or more protruding arms connected to the elastomeric ring or the barrier layer. In some embodiments, the more protruding arms may be expandable by stretching to encompass and secure the barrier layer to the base of the penile head and may optionally exert contractile force that enhances adhesion of the condom to the penis and prevents stress concentrations or shear forces from removing the adhered barrier layer during mechanical perturbation such as that associated with sexual activity.

[0614] In some embodiments, the protruding arms may have an aspect ratio of about 1:1, about 1:2, about 1:5, about 1:10, about 1:20 or about 1:100 or greater. In some embodiments, there may be 1, 2, 3, 4, 5, 6 or more protruding arms present. In some embodiments, a protruding arm has a length of about 0.5 cm, about 1.0 cm, about 2.0 cm, about 3.0 cm, or about 5.0 cm or more, and a width of about 0.1 cm, about 0.2 cm, about 0.5 cm, about 1.0 cm or about 2.0 cm or more.

[0615] A portion of the inner surface of the barrier layer is covered by the adhesive layer, which extends to the free edges (peripheral edge) of the inner surface of the barrier layer to prevent unintended peel-up of the device during use. One embodiment solves a notable problem associated with that of a free-hanging edge that is not sufficiently adhered to the user’s penis may result in a partial or complete delamination of the device, reducing and possibly compromising its function to contain semen. The fraction of the area of the barrier layer covered by the adhesive layer may be up to 100%, up to 90%, up to 80%, up to 70%, up to 60%, up to 50%, up to 40%, up to 30%, or up to 20% of the inner surface area of the barrier layer. The portion of the inner surface of the barrier layer covered by the adhesive layer has either a planar geometry, a developable three-dimensional closed ring geometry or a doubly curved three-dimensional closed ring geometry that conforms to the geometry of the adhesive layer without wrinkling, folding or voids between the two layers.

[0616] The barrier layer is an elastic or plastic film that is impervious to the passage of sperm and is sufficiently compliant to conform to the shape of the glansand surrounding anatomy in a facile manner. Suitable materials include natural rubber latex, thermoplastic elastomers, and thermoplastic polyurethane, polyurethane, polyethylene, polypropylene, polyester. Favorable materials have a strain capacity (maximum strain before rupture or leaking failure) between 50 and 2000%, or in some embodiments between 100 and 800%, or in some embodiments between 125 and 700%. As a non-limiting rule of thumb, for a hemispherical reservoir, the strain capacity to accommodate a given volume increase over the unstrained initial reservoir volume, scales approximately as the two-thirds power of the ratio of the final volume divided by the initial void volume.

[0617] Both elastically and plastically deforming materials are suitable. If the barrier material is elastic, the elastic modulus measured at 0% or 100% strain is between 0.1 and 10 MPa, or in some embodiments between 0.2 and 5 MPa, or in some embodiments between 0.5 and 2.5 MPa. If the material plastically deforms, the yield stress should be between the same limits. Non-limiting suitable materials may have a Shore-A durometer measure of between 30A and 100A.

[0618] The reservoir for containing semen comprises the area of the barrier layer not adhered to the glans of the user.

[0619] In one embodiment, the reservoir comprises pre-formed portion of the barrier layer with a void volume between 0.1 and 10 mL, or in some embodiments between 0.5 and 3.5 mL, or in some embodiments between 1.0 and 3.0 mL. In another embodiment, the reservoir is self-forming, such that the void volume is 0 mL.

[0620] In some embodiments, a fraction of the inner surface area of the adhesive layer (the face directly in contact with the glans when in use) near the center of the device is passivated such that it does not adhere to the skin, to the barrier layer or to itself. The fraction of the adhesive layer surface that is passivated may be up to 60%, up to 50%, up to 40%, up to 30%, up to 20%, up to 10%, or up to 5% of the adhesive layer surface area. Exemplary methods for passivating the adhesive layer comprises covering the area with an elastomeric or plastic film such as natural rubber latex, polyurethane, polyisoprene, or thermoplastic elastomer.

[0621] The reservoir for containing semen comprises the volume bounded between the glans and by the area of the barrier layer not covered by the adhesive layer plus the area of the adhesive layer that has been passivated.

[0622] In some embodiments, the reservoir is preformed and has an absorbent material, such as super-absorbing polymer contained within a thin ejaculate- permeable polyethylene covering, attached to a portion of the inner surface of the reservoir that absorbs or gels ejaculate fluids to the likelihood of leaking. The absorbent material may have a thickness between 50 and 150 microns. The portion of the reservoir covered by the absorbent material may be between 10% and 90%.

[0623] In some embodiments, the reservoir is self-forming and has an absorbent material, such as super-absorbing polymer contained within a thin ejaculate- permeable polyethylene covering, attached to a portion of the inner surface of the reservoir that absorbs or gels ejaculate fluids to the likelihood of leaking. The absorbent material may have a thickness between 50 and 150 microns. The portion of the reservoir covered by the absorbent material may be between 10% and 90%.

[0624] RESERVOIR

[0625] In certain embodiments, the reservoir is pre-formed prior to use with a volume between 0.1 and 10 mL, or in some embodiments between 0.5 and 3.5 mL, or in some embodiments between 1.0 and 3.0 mL, or in some embodiments between 1.5 and 2.5 mL.

[0626] In other embodiments, the reservoir is self-forming, and not visibly distinguishable from the rest of the barrier layer prior to use.

[0627] In yet other embodiments, the reservoir is self-forming, and is distinguishable from the barrier layer by the absence of adhesive on the inner surface of the barrier layer.

[0628] In some embodiments, the reservoir has absorbable materials such as super absorbable polymer with a thin polyethylene covering mated to the inner surface of the barrier layer covering a portion of the inner surface of the reservoir.

[0629] In some embodiments, the surface that comprises the reservoir may be a doubly curved surface.

[0630] REINFORCEMENT RIB

[0631] In some embodiments, the reservoir has a reinforcement rib that aides in semen retention by creating a neck in the reservoir for the user to pinch upon removal, and mitigates creep delamination of the adhesive after ejaculation byconstraining the expansion of the reservoir where it meets the adhesive layer, therefore keeping the angle small and thus reducing peel-up effects causing undesirable delamination of the adhesive that may lead to partial or complete failure of semen retention. The reinforcement rib comprises a thin rib of a suitable material that has a stiffening effect to the reservoir area. One such suitable material is natural rubber latex, polyisoprene or polyurethane in embodiments where the barrier layer comprises a natural rubber latex, polyisoprene or polyurethane layer, respectively, and in such embodiments, the reinforcement rib is molded into the barrier layer. Another suitable material is a plastic filament, such as a nylon, whereby the filament is adhered to the outer or inner surface of the barrier layer.

[0632] In certain embodiments where the reinforcement rib is a filament, the filament is adhered to the outer surface of the barrier layer and one end is free with sufficient length to be grasped between two fingers, and may have a small knot or loop in the free end to aide in grasping. In an exemplarily embodiment, the free end is between 1 and 2 centimeters long.

[0633] A method of use of a reinforcement rib with a free end is disclosed herein (e.g., a thread or filament coupled to the rib). Following ejaculation, the free end of the reinforcement rib (e.g., filament) may be grasped by the user (e.g., using the fingers or suitable tool such as tweezers, which may be supplied in the packaging) and either wrapped around the expanded semen-containing reservoir or pulled to constrict the outer edge of the reservoir, helping to entrap the semen within the device as the adhesive portion is peeled away from the skin during removal.

[0634] In certain embodiments where a barrier layer or barrier-adhesive composite is formed via a thermoforming process, the reinforcement rib or filament may be positioned to the adhesive or barrier layers prior to the thermoforming step, as shown in the figure below. In other embodiments it is positioned and affixed / secured following the thermoforming step if a thermoforming step is used.

[0635] FIGURE 34A: Condom comprised of a barrier layer 1001 and a developable adhesive layer 1002 which can be split along an (approximately) vertical seam (as depicted) and unrolled into a planar sheet without local stretching or compression (without distortion). A reservoir 1003 is formed between the barrier layer and the glans, where in this embodiment, no adhesive layer is present. Thereservoir region is not required to be developable. The condom is affixed entirely to the glans 1101 of the penis in this embodiment, leaving the entirety of the shaft 1100 exposed. A reinforcement rib 1004 is affixed to the barrier layer a distance of 1010 from the upper edge of the adhesive layer, as depicted in this figure. In some embodiments the distance 1010 is between 0 and 10 mm, or in some embodiments between 0 and 4 mm.

[0636] FIGURE 34B: Condom showing ejaculate (volume 1011) expressed through the urethra meatus (opening) 1102 contained within the reservoir 1003. Fluid flow lines are for illustrative purposes only. The reservoir 1003 expands to contain the ejaculate volume 1011, with the reinforcement rib 1004 constraining the barrier layer so as to mitigate the peel up force and peel up angle imparted onto the adhesive layer 1002 on the inner edge of the adhesive layer (upper edge of the adhesive layer as depicted here).

[0637] FIGURE 35: Schematic of an embodiment of a manufacturing process using thermoforming of the barrier layer 1001 over a rigid form, with a reinforcement ring 1004 and an annular adhesive layer 1002 placed on the surface of the thermoformable barrier layer. Heat is first added to the composite layer as illustrated by the arrows labeled with Q-dot. Air flow from the vacuum is depicted on the bottom part of the sketch to draw the heated materials over the form.

[0638] ADHESIVE LAYER

[0639] The adhesive layer comprises an adhesive comprising a stimuli- responsive polymer and optionally, one or more additional polymers, crosslinkers and / or additives that adheres substantially to the glans surface of the user and delaminates from the user upon application of a stimulus to the ESC. The adhesive layer may be constructed from one or more laminae of adhesive. In some embodiments, the adhesive is preferably a shear-rate responsive adhesive where the stimulus is mechanical action or a force-responsive polymer where the stimulus is a mechanical action.

[0640] The total adhesive layer thickness is between 10 and 1500 microns, or in some embodiments between 25 and 750 microns, or in some embodiments between 50 and 500 microns, more specifically between 50 and 400 microns. In some embodiments the adhesive layer is comprised of a composite of thinner adhesivelaminae. For example, an adhesive layer having a total thickness of 200 microns may be comprised of two 100-micron thick laminae, or by a 50-micron thick lamina and a 150-micron thick lamina. In some embodiments, the peripheral boundaries of laminae are offset so as to provide a stair-step tapering effect of the adhesive thickness at the peripheral edge of the adhesive layer, so that the peripheral edge of the device transitions more gradually to the user’s skin so as to minimize the peeling effects imparted on the edge of the device during intercourse.

[0641] In some embodiments where the adhesive layer is a composite of thinner laminates, seems between adjacent pieces of adhesive of the same stratum of the composite may be coincident or offset. For example, if a rectangular adhesive strip is joined together at the edge to form an open cylindrical surface, and a second adhesive strip is laminated on top to increase the wall thickness of the resulting cylindrical surface, the seams between the two ends of a single rectangular strip may be aligned between the inner and outer layer, or they may be offset in some manner.

[0642] In certain other embodiments, the adhesive layer is patterned. In certain embodiments, a second adhesive is used at the peripheral edge of the adhesive layer (the free edge of the device). The width of this adhesive may be less than 50%, less than 40%, less than 30%, less than 20%, less than 10%, less than 5%, less than 2%, less than 1%, less than 0.1% of the primary adhesive layer width. In certain other embodiments, a secondary adhesive is used at the inner edge of the adhesive layer (the edge adjoining the reservoir). The thickness of the secondary adhesive region may be the same as the primary adhesive or may be between 10% and 500% of the thickness of the primary adhesive. For example, see Fig.2 illustrating a primary adhesive 0202 and secondary adhesive 0203 at both the peripheral and interior edge of the primary adhesive.

[0643] DEVELOPABLE GEOMETRY

[0644] The adhesive layer comprises a ring-shaped contact area over which the adhesive secures the ESC to the glans and functions as a seal to contain ejaculate fluids. In an embodiment, the contact area is a three-dimensional ring prior to application the glans. The portion of the barrier layer that mates to the adhesive layer has the complementary geometry so that there are no wrinkles, voids, folds or gaps present in the adhesive layer or the barrier layer.

[0645] In one embodiment, the adhesive layer geometry is a developable surface which satisfy the generalized cone equation: ^^^^(^^^^, ^^^^)= ^^^^ + ^^^^ ^^^^( ^^^^) where capital symbols denote vectors in 3D space, P is a fixed point, and lowercase (u,v) are scalar parameters, in an embodiment the surfaces may be cones that have a left- right symmetry plane passing through P. In various embodiments, adhesives may be fabricated in planar forms by roll-to-roll or sheet coating processes known in the art. Adhesive materials are frequently coated on or covered with a release liner to aide in manipulation of the adhesive during subsequent manufacturing processes. Common release liners are paper or plastic films with silicone or fluoropolymer surface treatments. Such exemplary release liners are not distortable—they can bend, roll and fold but cannot be stretched or compressed into a doubly-curved surface. The family of developable shapes are those that can be formed by rolling and bending initially planar surfaces into three-dimensional geometries.

[0646] In some embodiments, the three-dimensional adhesive ring is a developable surface that is a section of a circular cone. In certain non-limiting embodiments, the three-dimensional adhesive ring is a developable surface that is a section of a circular cone, with an adhesive width of between 0.1 and 25 mm, or in some embodiments between 5 and 20 mm, or in some embodiments between 10 and 15 m, and a peripheral diameter between 2 and 6 cm, or in some embodiments between 3 and 5 cm, or in some embodiments between 4 and 5 cm.

[0647] In some specific embodiments, the three-dimensional adhesive ring is a developable surface that is a section of an elliptical cone. In certain non-limiting embodiments, the three-dimensional adhesive ring is a developable surface that is a section of an elliptical cone, with an adhesive width of between 0.1 and 25 mm, or in some embodiments between 5 and 20 mm, or in some embodiments between 10 and 15 mm. The major axis of the peripheral edge is between 2 and 6 cm, or in some embodiments between 3 and 5 cm, or in some embodiments between 4 and 5 cm. The minor axis of the peripheral edge is between 2 and 6 cm, or in some embodiments between 2 and 5 cm, or in some embodiments between 2 and 4 cm.

[0648] In some specific embodiments, the three-dimensional adhesive ring is a developable surface that is a section of a cardioid, limacon or epitrochoid cone. In certain non-limiting embodiments, the three-dimensional adhesive ring is a developable surface that is a section of a cardioid, limacon or epitrochoid cone, withan adhesive width of between 0.1 and 25 mm, or in some embodiments between 5 and 20 mm, or in some embodiments between 10 and 15 mm, and a peripheral diameter between 2 and 6 cm, or in some embodiments between 3 and 5 cm, or in some embodiments between 4 and 5 cm.

[0649] The developable three-dimensional ring surface adhesive layer must be formed by joining together the free ends 3813 and 3814 of the developed (i.e., unrolled) planar form of the adhesive using a suitable reinforcement means in Figure 38. One such suitable means is an overlapping region whereby edge 3813 overlaps the adhesive layer area from which 3814 is the boundary, and vice versa. Another such means is to bring edge 3813 in contact with edge 3814 so that they abut precisely in the thickness direction thus forming a seam, and the barrier layer which is a continuous material serves as the primary means to secure the edges 3813 and 3814 in abutment to one another. A means is to construct the adhesive layer from two or more adhesive laminae. In an exemplary optimum embodiment, the adhesive layer consists of two laminae Fig 38B 3821 and 3822 are folded / rolled in such a way to bring edges 3813 and 3814 of the outer lamina 3821 in abutment along 3812, and to bring edges 3815 and 3816 of the inner lamina 3822 into abutment along 3811. The laminae are then brought into contact such that the inner face of the 3D ring formed by lamina 3821 comes into contact with the outer face of lamina 3822, and their inner and outer free edges are aligned, as depicted. In doing so, lamina 3821 serves as the reinforcement means for the seam between edges 3815 and 3816 of lamina 3822, and lamina 3822 serves as the reinforcement means for the seam between edges 3813 and 3814 of lamina 3821. By offsetting the seams, the likelihood of a channel opening between the edges and serving as either an initiation location for partial or complete delamination or as a channel for the leakage of ejaculate fluid are mitigated. It is understood that the shape of the edges 3813, 3814, 3815 and 3816, and therefore the respective seams of the manufactured adhesive layer are depicted as straight but may be wavy, crenelated, saw-toothed, curvilinear or another edge shape.

[0650] In one embodiment, the adhesive layer is a developable surface taken from the family of generalized cones, which satisfy the equation: ^^^^(^^^^, ^^^^)= ^^^^ + ^^^^ ^^^^( ^^^^) where capital symbols denote vectors in 3D space, P is a fixed point, and lowercase (u, v) are scalar parameters. This constraint is introduced as mostadhesives are manufactured on roll-to-roll or sheet coating applications, whereby an adhesive is fabricated on a release liner. Suitable release liners are often siliconized paper or surface treated plastic films. Paper and common plastic release liner films are not distortable—the material can bend and fold but cannot be locally stretched or compressed into a doubly-curved surface. The family of developable shapes are those that can be formed by rolling and bending initially planar surfaces into three- dimensional geometries. The adhesives are open truncations of these surfaces. The surfaces that truncate the generalized cone need not be planar or parallel.

[0651] In one embodiment, the developable surface is a circular cone. In some embodiments, the generalized cone is a circular cone, with an adhesive width of between 0.1 and 25 mm, or in some embodiments between 5 and 20 mm, or in some embodiments between 10 and 15 mm. In one embodiment, the developable surface is an elliptical cone.

[0652] In one embodiment, the developable surface is a cardioid cone. In one embodiment, the generalized cone is truncated by parallel planes, forming an open frustum.

[0653] In one embodiment, the generalized cone is truncated by oblique planes, that is nonparallel with an angle between them greater than zero degrees and less than 30 degrees or less than 25 degrees or less than 20 degrees or less than 15 degrees or less than 10 degrees or less than 5 degrees or less than 2 degrees or less than 1 degree.

[0654] In one embodiment, the generalized cone is truncated by a left-right symmetric curved surface on the top edge, and the same or different left-right symmetric curved surface on the bottom edge.

[0655] Figures 36A (top view), 36B (perspective view), 36C (back view), and 36D (side view) illustrate a 3D developable adhesive surface.

[0656] Figures 36A (top view), 36B (perspective view), 36C (back view), and 36D (side view) illustrate a 3D developable adhesive surface with a reservoir atop the adhesive.

[0657] Figure 38A includes an exploded perspective view of two developable adhesive layers that couple to each other and to a reservoir to form the fullyassembled condom. Figure 38B shows an exploded top view of the same. Figure 38C shows front, side, and back views of the fully assembled condom of Figure 38A.

[0658] Figure 38D shows a close up of the assembly of barrier and adhesion layers. The figure shows a cross-section of the developable adhesive ring geometry condom which consists of a barrier layer and an adhesive layer which covers a portion of the inner surface of the barrier layer, extending to the periphery and leaving exposed a section of the barrier layer with no adhesive thus forming a reservoir. The adhesive layer comprises two laminates of adhesive, in this rendering each 100 microns thick. The barrier layer depicted is also 100 microns thick.

[0659] Figure 32 includes a double-body construction of a condom with adhesive layer 1002. Primary barrier layer 10011 is planar and reservoir barrier layer 10012 joined at joining region 301 by a suitable means, such as an adhesive or plastic weld. A reservoir 1003 is formed by the two layers. Optionally in certain embodiments, the region between the upper surface of 10011 and inner surface of 10012, denoted by 309, may be filled with an absorbent material, such as a superabsorbent polymer pad, which swells, entraps, or gels ejaculate fluid. While shown in a planar configuration, either 10011, 10012 or 1002 may be curved. Barrier layers 10011 and 10012 are not required to be of the same material, and it may be preferable in certain embodiments for 10011 to be comprised of a thinner, more compliant layer for conforming to the shape of the glans, while 10012 is more elastic for expansion during ejaculation to contain fluid. The adhesive ring width (sum of distances 3101, 3102 and 3103) is approximately 10 mm in certain embodiments. Optionally, a different adhesive to 1002 is patterned underneath the attachment region 301 to provide increased adhesion in the normal direction to the skin surface (not depicted) to mitigate pull-up. The distances 3101, 3102 and 3103 should be selected for the specific barrier and adhesive materials selected to provide sufficient resistance to peel-up under expression of fluid or other mechanical forces. The attachment region 301 is located inset from the periphery (leftmost edge of 1011 as drawn) in order to provide more favorable orientation of the membrane stresses transmitted to the adhesive and the underlying attachment surface (skin).

[0660] MANUFACTURING PROCESS

[0661] Well-Mandrel Method

[0662] The adhesive is to be manufactured using an industrial roll-to-roll or sheet coating processes, whereby the adhesive is coated onto a release liner or transfer release liner. In some embodiments, it may be sandwiched between two release liners.

[0663] In one embodiment, the adhesive is a developable surface. The developed (planar form) of the geometry is cut out of a planar sheet of adhesive, while still affixed to the release liner on both sides. If the adhesive is coated on only a single release liner, it may be sandwiched with another release liner either before or after cutting.

[0664] In one embodiment, this requires the identification and insertion of a seam for an abutting seam for a monolaminate non-overlapping adhesive layer. In another embodiment, this requires identifying an amount of overlap between one side and another, for a monolaminate overlapping adhesive layer. In another embodiment, this requires identifying two seams which may be coincident or offset, with the offset to provide redundant sealing capability over the seams, on opposite sides of the device in some embodiments (e.g., the front and rear centerlines, or the left and right midlines), to construct a bilaminate device. In another embodiment, more than two seams need to be identified for a polylaminate device, however bilaminate may be used instead of layers with greater than two laminates for manufacturing ease.

[0665] The cut planar adhesives are formed into the three-dimensional developable surface through a suitable folding process. One such folding process is as follows. First, the adhesive is aligned with a well whose shape has the final form of the adhesive layer. Tabs in the adhesive, release liner or both, may be used to align or clamp the adhesive to the well, or both. Next a male mandrel contacts the surface of the adhesive opposite the well, and presses it into the mold, allowing the release liner sandwiching the adhesive to slide along both the well surface and the mandrel surface. Optionally a vacuum may be continuously or intermittently applied to either the mandrel or the well to both aide in drawing the adhesive layer into the well and to selectively change the relative friction force between the mandrel- adhesive interface and the well-adhesive interface, so as to control the sliding and folding motion.

[0666] Once the adhesive is in the final position, if the adhesive is a monolaminate, then the well vacuum is switched off if it is on and a mandrel vacuum is switched on to affix the adhesive to the mandrel and allowing it to be removed. Alternatively, adhesive may be extracted from the well through other means. One side of the release liner may be removed by applying vacuum to both the well and the mandrel, and selecting differential release liner surface energies such that the release liner desired to be removed is lower than the release liner on the other side of the adhesive. Additionally, the vacuum on that release liner should have a force greater than the peel force between the release liner and the adhesive. And the vacuum force on the opposite release liner to the one intended to be removed should also be stronger than the peel force required to separate the adhesive from the release liner intended to be removed.

[0667] If the adhesive is a bilayer, then the release liner on side of the adhesive should be removed, and the process repeated for another piece of adhesive with additional tooling as needed, with the opposite release liner removed, and affixed to the opposite tooling. In other words, once this is complete, a well should have an adhesive layer laminate affixed to it with the release liner on the side opposite the well surface removed, and a mandrel should have an adhesive layer laminate affixed to it with the release liner on the side opposite the mandrel surface removed, thereby exposing two adhesive surfaces. The two adhesives are brought into contact with one another, and optionally compressed together to ensure good lamination and adhesion between the two laminates, forming a bilaminate adhesive layer. The adhesive layer may be separated from the tooling and retained on either the well or mandrel side by activating only the vacuum on the well or mandrel, respectively. Optionally, the well-side release liner may be removed in this step by selecting a release liner with a lower surface affinity than the release liner on the mandrel side, just as in the monolaminate described above, and performing the same removal process as well. Thereby, the bilayer adhesive layer is retained on the mandrel, with the outer surface of the adhesive layer exposed, prepared to be mated to a barrier layer.

[0668] PROCESS FOR APPLICATION

[0669] In one embodimen...

Claims

CLAIMS 1. A system comprising: a fractional condom that comprises a condom material, the condom material includes at least one of rubber, latex, polyurethane, polyisoprene, thermoplastic elastomer, or combinations thereof; a package that comprises a first package material, the first package material including at least one of polyethylene, polyethylene terephthalate (PET), polyethylene terephthalate glycol-modified (PETG), polypropylene, acrylic, polyethylene, high density polyethylene (HDPE), polycarbonate, poly(lactic acid), poly(hydroxyl alkenoate), thermoplastic polymer, or combinations thereof; wherein the package includes: (a) a dome having a flange, and (b) a film that seals the dome closed and that is adhered to the flange; wherein: (a) the film is disposed in a plane, (b) an axis is parallel to the plane and traverses the dome at first and second dome locations, (c) the axis traverses the condom at first and second condom locations that are between the first and second dome locations, and (d) the axis traverses an empty void that is between the first and second condom locations; wherein: (a) the condom is included in the package, (b) the condom material is adhered directly to the first package material.

2. The system of claim 1, wherein the condom material is adhered directly to the first package material via tack adhesion.

3. The system according to any of claims 1-2, wherein the condom material is unchlorinated.

4. The system according to any of claims 1-3, wherein the condom material is unpowdered.

5. The system according to any of claims 1-4, wherein the condom material consists essentially of rubber.

6. The system according to any of claims 1-4, wherein the condom material consists essentially of latex.

7. The system according to any of claims 1-6, wherein the first package material includes at least one of PET, PETG, or combinations thereof.

8. The system according to any of claims 1-7, wherein the first package material has a surface energy of between approximately 40-45 dynes / cm.

9. The system according to any of claims 1-8, wherein the first package material has a contact angle of between 75-80 degrees with water.

10. The system according to any of claims 1-6, wherein the first package material includes polypropylene.

11. The system according to any claim 1-6, 10, wherein the first package material has a surface energy of between approximately 28-32 dynes / cm.

12. The system according to any of claims 1-6, 10, wherein the first package material has a contact angle of between 85-90 degrees with water.

13. The system according to any of claims 1-6, wherein the first package material includes polypropylene and polyethylene.

14. The system of claim 13, wherein the first package material includes at least one of PET, PETG, or combinations thereof.

15. The system according to any of claims 1-14, wherein the condom is retained within the package via a resistive fit.

16. The system according to any of claims 15, wherein the condom is resiliently biased outward away from the empty void and towards the package.

17. The system according to any of claims 15-16 wherein the package is resiliently biased inward toward the empty void.

18. The system of claim 17 wherein the package is in compression and compresses the condom towards the void.

19. The system according to any of claims 1-18, wherein: the condom has a weight; the condom material is adhered directly to the first package material at a force level greater than the weight of the condom.

20. The system according to any of claims 1-19, wherein the condom includes a plasma-treated outer surface that directly contacts the package.

21. The system according to any of claims 1-19, wherein the condom includes a corona discharge-treated inner surface that directly contacts the package.

22. The system according to any of claims 1-6, 10, wherein the first package material has a contact angle 23. The system according to any of claims 1-21, wherein the package includes a plasma-treated inner surface that directly contacts the condom.

24. The system according to any of claims 1-21, wherein the package includes an corona discharge-treated inner surface that directly contacts the condom.

25. The system according to any of claims 20-23, wherein the empty void of the package is dehumidified.

26. The system according to any of claims 20-23, wherein: the empty void of the package has a first humidity level; an atmosphere immediately surrounding the package has a second humidity level that is more humid than the first humidity level.

27. The system according to any of claims 1-26 comprising a release liner coupled to an inner surface of the condom.

28. The system according to any of claims 1-26 wherein no release liner is coupled to the inner surface.

29. The system according to any of claims 1-28 comprising an additional shell, wherein: the additional shell includes the package and the condom; the package is between the additional shell and the condom.

30. The system of claim 29, wherein the additional shell is less compliant than the package.

31. The system according to any of claims 1-30, wherein: the package includes first and second apertures that are on opposite ends of the package from one another; the film covers the first aperture but not the second aperture.

32. The system of claim 31, wherein the condom includes a semen receptable directly adjacent the second aperture.

33. The system according to any of claims 31-32 comprising an additional film that covers the second aperture.

34. The system according to any of claims 1-33, wherein: the package includes a package wall directly contacting the condom; the package wall includes a thickness between 0.015 and 0.055 inches.

35. The system according to any of claims 1-34, wherein the axis only traverses the condom at the first and second condom locations and does not traverse the condom at any additional condom location.

36. The system according to any of claims 1-35 wherein the condom does not contact the film and the condom does not contact the flange.

37. The system according to any of claims 1-36, wherein: the condom includes an inner surface and an outer surface; no portion of the inner surface of the condom contacts any other portion of the inner surface of the condom.

38. The system according to any of claims 1-37, wherein no portion of the condom is folded, wrinkled, or rolled.

39. The system according to any of claims 1-37, wherein: the condom is divided into a first third, a second third, and a third third; the second third is between the first and third thirds; the first third is between the film and the second third; no portion of the first third is folded, wrinkled, or rolled.

40. The system according to any of claims 1-37, wherein: the condom is divided into a first third, a second third, and a third third; the second third is between the first and third thirds; the first third is between the film and the second third; no portion of the second third is folded, wrinkled, or rolled.

41. The system according to any of claims 1-40, wherein: the first package material is included in a first layer of the package; the package comprises a second package material; the second package material is included in a second layer of the package.

42. The system of claim 41, wherein the condom directly contacts the first layer.

43. The system according to any claims 41-42, wherein the first layer includes polyethylene and the second layer includes PETG.

44. The system of claim 41, wherein the second layer is a thermoplastic film that includes the second package material.

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