Functional packaging for adhesives

Abstract

Disclosed herein are packages suitable for storing and transporting adhesives (e.g., enhanced feel condoms) that, in certain embodiments, allow for convenient application of enhanced feel condoms (ESC) for sexual intercourse by a user, and / or removal of the packages after application of the adhesive. Also disclosed are packaged adhesives, as well as methods of using and making the packages and packaged adhesives.

Description

Technical Field

[0001] This document discloses packaging suitable for the storage and transport of adhesives, which in some embodiments allows for convenient application by a user using an enhanced sensation condom (ESC) for sexual intercourse. Also disclosed are packaged adhesives, and methods for using and manufacturing said packaging and packaged adhesives.

[0002] Cross-references to related applications

[0003] This application claims priority to U.S. Provisional Patent Application No. 63 / 512802, filed July 10, 2023, entitled “A Functional Package for an Adhesive,” the contents of which are incorporated herein by reference.

[0004] background

[0005] Adhesives have a wide range of personal care and medical uses, including bonding tissue to tissue and tissue to medical devices such as catheters. They can also be used to promote healing, including by preventing the seepage of unwanted substances such as bacteria or fluids or absorbing fluids, or in some cases by delivering one or more therapeutic agents.

[0006] There is still a need in the art for the transport and storage of such adhesives, as well as the packaging to which they are applied.

[0007] Overview

[0008] This document discloses packaging suitable for protecting and optionally applying (i.e., aligning, depositing) adhesives (e.g., sensation-enhancing condoms), as well as packaged adhesives. Methods for manufacturing and using said packaging are also disclosed. Advantageously, the packaging and packaged adhesives disclosed herein offer one or more improvements over those known in the art, such as ease of use and ease of application.

[0009] On the one hand, packaging suitable for protecting and optionally applying adhesives (e.g., sensation-enhancing condoms) is disclosed, comprising (i) a shaped receptacle including a peripheral flange, wherein the shaped receptacle includes a wall defining an outer surface and an inner surface, and wherein the inner surface optionally includes a retaining element; and (ii) a removable cap including a pull tab or a tear-away seal, wherein the receptacle and the removable cap are secured to form packaging suitable for protecting a substrate comprising a barrier layer and an adhesive (e.g., a condom), or an adhesive that simultaneously functions as an adhesive and a barrier layer.

[0010] The shape of the shaped receptacle can vary. In one embodiment, the shaped receptacle is selected from circular, elliptical, square, rectangular, polygonal, curved polygonal, hemispherical, ellipsoidal, conical, generalized conical, tetrahedral, pyramidal, polyhedral, reflexive, or otherwise substantially matches the shape of the contained adhesive (e.g., a sensation-enhancing condom). In a particular embodiment, the shaped receptacle is circular or conical.

[0011] The thickness of the walls of the container can vary. In one embodiment, the thickness of the container is from about 0.001 inches to 1 inch, more preferably from 0.005 inches to 0.8 inches, more preferably from 0.01 inches to 0.6 inches, more preferably from 0.015 inches to 0.4 inches, more preferably from 0.0175 inches to 0.2 inches, more preferably from 0.0185 inches to 0.1 inches, more preferably from 0.190 inches to 0.075 inches, more preferably from 0.195 inches to 0.06 inches, and more preferably from 0.020 inches to 0.040 inches.

[0012] The physical properties of the containment can vary. In one embodiment, the containment is rigid. In a particular embodiment, the rigid containment comprises a thermoplastic polymer. In one embodiment, the thermoplastic polymer is glycol-modified polyethylene terephthalate (PETG), polyethylene, polypropylene, polyethylene terephthalate, high-density polyethylene, low-density polyethylene, poly(vinyl chloride), poly(lactic acid), poly(hydroxyalkenoates), compostable and bio-based plastics, or thermoformable polyurethane. In another embodiment, the containment comprises a high surface energy liner film composite, such as a low-density polyethylene film laminated to the inner surface of a rigid plastic (e.g., PETG), or poly(lactic acid), poly(hydroxyalkenoates), or compostable or bio-based plastic. In another embodiment, the containment is semi-rigid. In a particular embodiment, the semi-rigid containment comprises PETG, a thermoplastic elastomer, high-density polyethylene, low-density polyethylene, or thermoformable polyurethane. In some embodiments, rigid or semi-rigid behavior is achieved by utilizing different thicknesses of the material sheets used to manufacture the containment, for example, PETG.

[0013] The packaging may include one or more additional features to facilitate use. In one embodiment, the outer wall of the container includes one or more features to assist in aligning the adhesive with a target area, such as a hole or through-hole. In one embodiment, the outer wall of the container includes one or more features to assist in removing the packaging after the adhesive has been applied, such as a pull-tab. In some embodiments, the bottom of the packaging (opposite to the removable film cap) includes one or more features to assist in aligning the adhesive with a target area, such as a hole or through-hole.

[0014] In one embodiment, the outer wall of the container includes one or more features (e.g., ridges or ripples) to facilitate use or to provide the desired physical properties to the packaging.

[0015] In one embodiment, the packaging includes a shell surrounding the outer wall of the container, wherein the shell includes an outer wall and an inner wall, and at least a portion of the inner wall contacts the outer wall of the container. The shell is attached to the container by a plastic adhesive or by plastic welding. The shell may contact 0.1 to 1.0% of the surface area of ​​the container, 1 to 10% of the container, 10 to 50% of the container, or 50 to 100% of the container. The shell may have the same or different shape as the container. The shell may optionally include additional features, such as attachment features. The shell may be rigid or semi-rigid. In some embodiments, the shell includes one or more features to assist in aligning the adhesive with a target area. In a particular embodiment, the shell includes a hole. In one embodiment, the outer wall of the shell includes one or more features to assist in removing the packaging after the adhesive has been applied, such as a pull-tab label.

[0016] The removable film cover may contain any suitable material. In one embodiment, the removable film cover comprises paper, plastic, aluminum foil, polyester film (mylar), or aluminum-backed polyester film.

[0017] The retaining element can be varied. In one embodiment, the retaining element comprises a thin layer of a fluid membrane.

[0018] The fluid membrane can be any suitable fluid membrane. In one embodiment, the fluid membrane is selected from silicone oil or silicone-based lubricants. In another embodiment, the fluid membrane is selected from water-based lubricants.

[0019] In another embodiment, the retaining element is a fluid membrane (1) impregnated in a porous application liner, which serves to stabilize the fluid membrane. A suitable example of a porous application liner is paper. The porous application liner may have an additional tab to assist in the removal and handling of the condom from the packaging.

[0020] In another embodiment, the retaining element includes a pressure-sensitive adhesive layer.

[0021] In another embodiment, the retaining element includes a ridge that acts as a mechanical limiter at the peripheral edge of the packaged adhesive (e.g., a sensation-enhancing condom), its height being comparable to the thickness of the packaged adhesive (in the case of a sensation-enhancing condom, the thickness of the barrier layer plus the adhesive layer). The ridge is located on the inner surface of the package and is large enough to restrain the condom within the package by mechanically preventing the adhesive from dislodging from the package due to its own weight or inertia during shaking, but not so large that the ridge hinders the application of the adhesive. For example, the height of the ridge is comparable 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 when removing the package from the glans, the ridge must not be so large that it prevents the glans skin from contacting the adhesive, or prevents the already adhered condom from separating from the package / applier. A rule of thumb regarding the thickness of the lip or ridge is that it should be comparable to the thickness of the condom wall (plus the adhesive), which will provide sufficient mechanical restraint to prevent the condom from falling out of the packaging without interfering with the skin of the glans penis in contact with the adhesive surface.

[0022] In another embodiment, the retaining element includes an inner surface having an inherent adhesiveness that matches the adhesive-containing substrate, such as that exhibited between PETG or polycarbonate plastic and natural dip-coated latex, sufficient to hold the adhesive-containing substrate to the retainer during transport and use, and subsequently allowing release of the adhesive-containing substrate when applied to a target surface (e.g., the glans of a penis). The inherent adhesiveness matching strength should be strong enough to support the weight of the adhesive-containing substrate when the package is inverted (opening downwards), but sufficiently weaker than the adhesive strength between the adhesive-containing substrate and the target surface to which it is applied, allowing the user to detach the receptacle from the adhesive-containing substrate during use. In an embodiment, the maximum adhesive force of the retaining device is less than the adhesion force exhibited between the packaged adhesive and its target surface for a range of expected delamination rates of the adhesive relative to its target surface. The desired adhesive force is between 1% and 90%, more preferably between 5% and 50%, and most preferably between 10% and 25%, of the adhesive force exhibited by the contained adhesive on its intended application surface, within the range of the expected delamination rate of the adhesive relative to its target surface. Typically, the lower limit of the adhesive force is equal to the weight of the condom, in other words, sufficient to hold the condom when the packaging is inverted (so that gravity acts in a quasi-static manner, causing the condom to detach from the packaging). Preferably, the minimum adhesive force is at least 1.5 times, more preferably 5 times, and if possible, greater than this, to improve the ability of the packaged condom to withstand drops from a height of 1 to 2.5 meters (typical human-handled use), vibrations (e.g., between 0.5 and 10 Hz, e.g., during transport), and accelerations of 1.5 to 10 G (gravitational acceleration equal to 9.81 m / s²; e.g., during transport), all within a temperature range of -10 to 70°C (to withstand transport or storage conditions). Such natural adhesion mechanisms can be enhanced (increased) by altering the surface energy of the packaging, the exterior of the adhesive, or both. Plasma (or corona discharge) treatment is the most promising treatment for achieving sufficient and stable adhesion. Plasma surface treatment is advantageous because it is industrially scalable and cost-effective, and applicable to natural rubber latex, polyurethane, and other thermoplastic elastomer barrier materials.

[0023] In another embodiment, the retaining element is a mechanical interference fit between the packaging geometry and the packaging surface, thus providing friction to prevent the adhesive from separating from the packaging when inverted due to its own weight and inertial loads of up to 10 g, 5 g, 2 g, or 1 g (where g is the acceleration due to gravity, 9.81 m / s²). This interference fit is created by displacing the packaging surface inward by 0.000 to 0.005 inches to provide a small compressible surface to the outer surface of the adhesive, thereby assisting in retaining the adhesive within the device through slight mechanical compression, without the compression being too great to cause buckling or wrinkling within the device. Certain adhesive geometries configured to provide additional resistance when compressed can enhance this effect, such as unfoldable adhesive-surface condoms, where the adhesive is in a frustrated state with an internal bending moment that pushes outward against the condom barrier layer and is held in static equilibrium by the barrier layer.

[0024] In another embodiment, the retaining element includes a fluid membrane and ridges.

[0025] In another embodiment, the retaining element includes a fluid membrane and an interference fit.

[0026] In another embodiment, the retaining element includes a pressure-sensitive adhesive and a raised ridge.

[0027] In another embodiment, the retaining element includes a pressure-sensitive adhesive and an interference fit.

[0028] In another embodiment, the retaining element includes adhesively matched packaging material and a raised ridge.

[0029] In another embodiment, the retaining element comprises an adhesively matched packaging material and an interference fit. The combination of the adhesively matched material and the interference fit is a preferred embodiment because the interference fit ensures that the outer surface of the adhesive (e.g., a sensation-enhancing condom) remains in good contact with the packaging surface, thereby maximizing the effectiveness of the inherent adhesive matching effect as the primary retaining element.

[0030] In one embodiment, a packaged adhesive is provided, which includes the packaging disclosed herein and an adhesive (e.g., a condom) enclosing the package.

[0031] In one implementation, the adhesive is a condom that enhances sensation.

[0032] In one embodiment, the adhesive is a medical adhesive, such as one used for wound protection or closure.

[0033] In one embodiment, the adhesive is rate-responsive within a range relevant to human skin removal. For example, when the retraction rate of the rheometer adhesion test under the test conditions described in this invention changes from 1 micrometer per second to 8000 micrometers per second, the adhesive can exhibit a 30-fold change in adhesive work in J / m². The rate-responsive behavior can be characterized by a change in adhesive work of 1 to 1.5 times, more preferably 1 to 2 times, more preferably 1 to 3 times, more preferably 1 to 4 times, more preferably 1 to 5 times, more preferably 1 to 7 times, more preferably 1 to 10 times, more preferably 1 to 12 times, more preferably 1 to 13 times, more preferably 1 to 15 times, more preferably 1 to 16 times, more preferably 1 to 20 times, more preferably 1 to 23 times, more preferably 1 to 25 times, more preferably 1 to 27 times, more preferably 1 to 30 times or more.

[0034] The implementation includes a method of using a packaged adhesive disclosed herein, comprising (i) providing the packaged adhesive; (ii) opening the packaged adhesive; and (iii) applying the adhesive (e.g., a condom) to a target site (e.g., the glans penis).

[0035] In one implementation, the adhesive is a condom that enhances sensation.

[0036] In one embodiment, the adhesive is a medical adhesive, such as one used for wound protection or closure.

[0037] In one embodiment, the adhesive is rate-responsive within a range relevant to human skin removal. For example, when the retraction rate of the rheometer adhesion test under the test conditions described in this invention changes from 1 micrometer per second to 8000 micrometers per second, the adhesive can exhibit a 30-fold change in adhesive work in J / m². The rate-responsive behavior can be characterized by a change in adhesive work of 1 to 1.5 times, more preferably 1 to 2 times, more preferably 1 to 3 times, more preferably 1 to 4 times, more preferably 1 to 5 times, more preferably 1 to 7 times, more preferably 1 to 10 times, more preferably 1 to 12 times, more preferably 1 to 13 times, more preferably 1 to 15 times, more preferably 1 to 16 times, more preferably 1 to 20 times, more preferably 1 to 23 times, more preferably 1 to 25 times, more preferably 1 to 27 times, more preferably 1 to 30 times or more.

[0038] The implementation includes providing a method of using the packaged adhesive disclosed herein, comprising (i) opening the package; and (ii) inverting the package to align, adhere, and deposit the adhesive on a target substrate.

[0039] In one implementation, the adhesive is a condom that enhances sensation.

[0040] In one embodiment, the adhesive is a medical adhesive, for example, used to protect or close a wound.

[0041] In one embodiment, the adhesive is rate-responsive within a range relevant to human skin removal. For example, when the retraction rate of the rheometer adhesion test under the test conditions described in this invention changes from 1 micrometer per second to 8000 micrometers per second, the adhesive can exhibit a 30-fold change in adhesive work in J / m². The rate-responsive behavior can be characterized by a change in adhesive work of 1 to 1.5 times, more preferably 1 to 2 times, more preferably 1 to 3 times, more preferably 1 to 4 times, more preferably 1 to 5 times, more preferably 1 to 7 times, more preferably 1 to 10 times, more preferably 1 to 12 times, more preferably 1 to 13 times, more preferably 1 to 15 times, more preferably 1 to 16 times, more preferably 1 to 20 times, more preferably 1 to 23 times, more preferably 1 to 25 times, more preferably 1 to 27 times, more preferably 1 to 30 times or more.

[0042] In one implementation, the method requires the use of a single hand (or prosthetic assistance).

[0043] The implementation includes a method for manufacturing the packaged adhesive disclosed herein, comprising (i) thermoforming a hot-melt thermoplastic sheet on a molding die or array of molding dies; (ii) vacuuming to draw the stretchable plastic sheet into the shape of a rigid molding die, thereby producing a receptacle; (iii) separating the receptacle from excess plastic sheet by cutting or punching; (iv) optionally adding a retaining element to the receptacle; (v) adding an adhesive (e.g., a condom, a medical adhesive) to the receptacle; and (vi) adhering a removable cap to an opening in the receptacle, thereby producing a packaged adhesive.

[0044] In one implementation, the adhesive is a condom that enhances sensation.

[0045] In one embodiment, the adhesive is a medical adhesive, such as one used for wound protection or closure.

[0046] In one embodiment, the adhesive is rate-responsive within a range relevant to human skin removal. For example, when the retraction rate of the rheometer adhesion test under the test conditions described in this invention changes from 1 micrometer per second to 8000 micrometers per second, the adhesive can exhibit a 30-fold change in adhesive work in J / m². The rate-responsive behavior can be characterized by a change in adhesive work of 1 to 1.5 times, more preferably 1 to 2 times, more preferably 1 to 3 times, more preferably 1 to 4 times, more preferably 1 to 5 times, more preferably 1 to 7 times, more preferably 1 to 10 times, more preferably 1 to 12 times, more preferably 1 to 13 times, more preferably 1 to 15 times, more preferably 1 to 16 times, more preferably 1 to 20 times, more preferably 1 to 23 times, more preferably 1 to 25 times, more preferably 1 to 27 times, more preferably 1 to 30 times or more.

[0047] The implementation includes a method for manufacturing a package for subsequent manufacturers to encapsulate the adhesive-containing substrate disclosed herein, comprising (i) thermoforming a hot-melt thermoplastic sheet on a molding die or array of molding dies; (ii) vacuuming to draw the stretchable plastic sheet into the shape of a rigid molding die, thereby producing a receptacle; (iii) separating the receptacle from excess plastic sheet by cutting or punching; (iv) optionally adding a retaining element to the receptacle; and (v) optionally partially or completely adhering a removable or resealable film cap to an opening in the receptacle, thereby producing a package for containing an adhesive-containing substrate.

[0048] In one embodiment, the substrate containing the adhesive is a condom that enhances sensation.

[0049] In one embodiment, the adhesive is rate-responsive within a range relevant to human skin removal. For example, when the retraction rate of the rheometer adhesion test under the test conditions described in this invention changes from 1 micrometer per second to 8000 micrometers per second, the adhesive can exhibit a 30-fold change in adhesive work in J / m². The rate-responsive behavior can be characterized by a change in adhesive work of 1 to 1.5 times, more preferably 1 to 2 times, more preferably 1 to 3 times, more preferably 1 to 4 times, more preferably 1 to 5 times, more preferably 1 to 7 times, more preferably 1 to 10 times, more preferably 1 to 12 times, more preferably 1 to 13 times, more preferably 1 to 15 times, more preferably 1 to 16 times, more preferably 1 to 20 times, more preferably 1 to 23 times, more preferably 1 to 25 times, more preferably 1 to 27 times, more preferably 1 to 30 times or more.

[0050] In one particular embodiment, the substrate containing the adhesive is a deployable, surface-enhancing condom.

[0051] In one embodiment, the adhesive is a medical adhesive, such as one used for wound protection or closure.

[0052] In one embodiment, the adhesive is rate-responsive within a range relevant to human skin removal. For example, when the retraction rate of the rheometer adhesion test under the test conditions described in this invention changes from 1 micrometer per second to 8000 micrometers per second, the adhesive can exhibit a 30-fold change in adhesive work in J / m². The rate-responsive behavior can be characterized by a change in adhesive work of 1 to 1.5 times, more preferably 1 to 2 times, more preferably 1 to 3 times, more preferably 1 to 4 times, more preferably 1 to 5 times, more preferably 1 to 7 times, more preferably 1 to 10 times, more preferably 1 to 12 times, more preferably 1 to 13 times, more preferably 1 to 15 times, more preferably 1 to 16 times, more preferably 1 to 20 times, more preferably 1 to 23 times, more preferably 1 to 25 times, more preferably 1 to 27 times, more preferably 1 to 30 times or more. Attached Figure Description

[0053] The features and advantages of the embodiments of the present invention will become apparent upon reading the following detailed description of one or more exemplary embodiments in conjunction with the accompanying drawings. Reference numerals are repeated in the drawings where deemed appropriate to indicate corresponding or similar elements.

[0054] Figure 1A and 1B The three-dimensional and two-dimensional diagrams of the packaging implementation plan are presented.

[0055] Figure 2A , 2B Examples of methods for using packaged condoms are presented in 2C and 2D.

[0056] Figure 3 A three-dimensional diagram of the packaging implementation plan is presented.

[0057] Figures 4A-4B A perspective view of a packaging implementation scheme with a "rear through-hole" is presented.

[0058] Figure 5A , 5B 5C presents cross-sectional, plan, and cross-sectional views of an implementation scheme for a packaged condom that enhances the senses.

[0059] Figures 6A-6C Perspective, plan, and cross-sectional views of the packaging implementation scheme disclosed herein are presented.

[0060] Figure 7A , 7B Figure 7C shows a cross-sectional view of an exemplary embodiment of the inner shell of the packaging.

[0061] Figure 8 A cross-sectional view of the packaging implementation plan is presented.

[0062] Figure 9 A computer model with dimensioned geometric shapes.

[0063] Figure 10 A computer model with dimensioned geometric shapes.

[0064] Figure 11 A computer model with dimensioned geometric shapes.

[0065] Figure 12A-12B The side view and cross-sectional view of the packaging implementation scheme with a prominent storage container are presented.

[0066] Figure 13 A cross-sectional view of the double-shell cup packaging implementation scheme is presented.

[0067] Figure 14 A three-dimensional diagram of the packaging implementation plan is presented.

[0068] Figure 15 A three-dimensional diagram of the packaging implementation plan is presented.

[0069] Figure 16 A cross-sectional view of a packaging embodiment is presented, which has a porous application liner for a stable fluid membrane retention element.

[0070] Figure 17 A perspective view of the proposed padding implementation scheme is presented.

[0071] Figures 18A-18C The side view and perspective view of the padding implementation scheme are presented.

[0072] Figure 19 A perspective view of the proposed padding implementation scheme is presented.

[0073] Figures 20A-20E A cross-sectional view of an embodiment of a container with a reflexive geometry is presented.

[0074] Figure 21 shows cross-sectional views of two embodiments of the closed cap used to accommodate the reflexive geometry of the body geometry.

[0075] Figure 22 Includes a side view of the packaging and condom in the implementation plan.

[0076] Figure 23 Frequency sweep plots of three different adhesives containing different crosslinking agents were depicted.

[0077] Figure 24The adhesive properties of the L6_1 adhesive film under variable debonding speed were depicted.

[0078] Figure 25 Depicting Figure 24 The adhesion work results cited in the paper.

[0079] Figure 26 The nominal stress as a function of strain is depicted for L6 adhesives with three different crosslinking agents.

[0080] Figure 27 The adhesion work of L6 adhesive with three different crosslinking agents was described.

[0081] Figure 28 A sweep spectrum of Tan δ was plotted to compare L6 adhesive and slightly cross-linked acrylic adhesive at 25°C.

[0082] Figure 29 The nominal stress as a function of strain is depicted to compare the adhesion profile of L6 adhesive with that of a slightly cross-linked acrylic adhesive.

[0083] Figure 30 The adhesive work of L6 adhesive was described compared with that of a mildly cross-linked acrylate adhesive (control group).

[0084] Figure 31 The Tan δ values ​​were depicted to compare L6 adhesive with those of a mildly crosslinked acrylic adhesive (control group). Frequency sweep plot of complex modulus amplitude.

[0085] Figure 32 This is a cross-sectional view of a condom implementation scheme.

[0086] Figure 33 It is the implementation plan of the method.

[0087] Figure 34A -B includes a side view of the deployable surface in the implementation scheme.

[0088] Figure 34A -B includes a side view of the deployable surface in the implementation scheme.

[0089] Figure 35 The reinforcing ribs involved in the implementation plan.

[0090] Figures 36A-D include various views of the deployable surface in the implementation scheme.

[0091] Figures 37A-D include various views of the deployable surface in the implementation scheme.

[0092] Figure 38A -D includes various views of the deployable surface in the implementation scheme.

[0093] Detailed description

[0094] Reference will now be made to the accompanying drawings, wherein the same structures may be provided with the same suffix reference numerals. To illustrate the structures of the various embodiments more clearly, the drawings included herein are schematic representations of the structures. Therefore, the actual appearance of the manufactured structures (e.g., in photographs) may differ, but still incorporate the claimed structures of the illustrated embodiments (e.g., in an actual manufactured device, walls may not be perfectly orthogonal to each other). Furthermore, the drawings may only show structures that aid in understanding the illustrated embodiments. To maintain clarity of the drawings, additional structures known in the art may not be included. For example, not every layer of the device may be shown. Terms such as “one embodiment,” “various embodiments,” etc., indicate that the embodiments(s) described so far may include specific features, structures, or characteristics, but not every embodiment must include said specific features, structures, or characteristics. Some embodiments may have some, all, or none of the features described for other embodiments. Terms such as “first,” “second,” “third,” etc., describe common objects and indicate reference to different instances of the same object. Such adjectives do not imply that the objects described so far must be in a given order in time, space, ranking, or any other way. "Connection" can mean that elements are in direct physical or electrical contact with each other, while "combination" can mean that elements cooperate or interact with each other, but they may or may not be in direct physical or electrical contact. Phrases such as "containing at least one of A or B" include cases where A is present, B is present, or both A and B are present.

[0095] As used in this article, “adhesion” refers to the ability of a composition or material to adhere to or “stick” to a substrate (such as skin). Adhesion is measured in Newtons (N) and is a measure of adhesive force. The higher the adhesive force, the more Newtons are required to peel one object from another.

[0096] As used herein, “adhesive” refers to a composition or material that adheres to a substrate (e.g., skin). The adhesive compositions disclosed herein are used as the male contraceptive diaphragm disclosed herein, either as a pre-formed diaphragm or membrane used as a contraceptive diaphragm, or as a liquid that forms a diaphragm or membrane upon application to a substrate. In some embodiments, the adhesive component of the packaging adhesives disclosed herein does not contain cyanoacrylates or fibrous materials. In some embodiments, the adhesive is a component of a larger article or device. Multilayer adhesives are within the scope of the adhesives disclosed herein. Therefore, the packaging disclosed herein is suitable for protecting, transporting, and applying multilayer adhesives, adhesive-containing articles, and adhesive-containing devices (e.g., medical devices).

[0097] As used herein, "bio-based" means, in connection with the use of the compositions or articles disclosed herein, that some or all of the compositions or articles are derived from natural sources. In some embodiments, one or more components of the packaged or packaged articles are bio-based.

[0098] As used herein, "biodegradable" means, when the composition is used, that it can be degraded by living microorganisms (such as fungi or bacteria), without regard to a specific time frame. In some embodiments, one or more components of the packaging or packaged article are biodegradable.

[0099] As used in this article, “blended thermoplastic polymers” refers to the blending of two or more linear or branched polymers with the same or different monomer compositions by methods including but not limited to solution blending, melt blending, powder blending, extrusion blending, and centrifugal blending.

[0100] As used herein, “compostable” means a composition or article that requires microorganisms, moisture, and heat to produce a final compost product (carbon dioxide, water, inorganic compounds, and biomass). The difference between compostable and biodegradable is that compostable compositions and articles must decompose into natural elements within a specific timeframe. In one embodiment, the compositions and articles disclosed herein comply with the standards of the U.S. Composting Council, the Environmental Protection Agency, the American Society for Testing and Materials (ASTM International), or TÜV Austria. In some embodiments, one or more components of the packaged or packaged article are compostable.

[0101] As used in this article, “controlled porosity” means that normally closed pores are stimulated to open, allowing fluid to pass through, as permitted by their rheological properties.

[0102] As used herein, "regular condom" refers to a condom comprising a continuous elastic tubular wall having a closed distal end (tip) and an open proximal end, typically made of a thin, soft material such as latex or polyurethane, providing coverage of the glans and shaft of the penis during use. Regular condoms in use are typically between approximately 7 and 8 inches in length, but commercially available products can be up to 9 inches long and as short as approximately 6.3 inches. Many condom brand manufacturers and products are known in the art. See, for example, https: / / www.trojanbrands.com / en / products / condoms and https: / / www.durexusa.com / collections / condoms, each incorporated herein by reference.

[0103] As used herein, “copolymer” refers to a polymer derived from more than one class of monomers, and includes, for example, binary copolymers, ternary copolymers, and quaternary copolymers. Copolymers can be, for example, block copolymers, graft copolymers, random copolymers, blends, mixtures, and / or adducts of any of the above polymers and other polymers.

[0104] The term "curing" as used in this article refers to the chemical process of converting macromolecules into higher molecular weight polymers through cross-linking reactions.

[0105] The term "crosslink density" used in this article refers to the average molecular weight between crosslinking points. (https: / / www.pcimag.com / articles / 104955-calculation-of-crosslink-density-of-thermoset-polymers). The theory of crosslink density was proposed by Flory et al. in the 1940s.

[0106] The term "debonding" as used in this article refers to the fact that the mechanism of debonding can vary and includes, for example, phase transitions, chemical reactions, cross-linking, and volume expansion.

[0107] As used in this article, “enhanced sensation or pleasure” refers to increased exposure of sensory neurons or increased exposed penile surface area (i.e., partial coverage, or significantly less than with a regular condom), or increased sexual arousal or preference during use, or increased stimulation of sensory neurons.

[0108] The term "ESC" used in this article is an abbreviation for Sensation Enhanced Condom.

[0109] The “elastic body behavior” used in this paper refers to the approximate linear elastic or combined linear elastic and plastic deformation stress / strain behavior of a material when it is strained in a state above the critical transition region, such that the stress / strain hysteresis remains approximately constant.

[0110] As used in this article, “flexible behavior” refers to the behavior of rigid, viscoelastic, or elastomeric materials, which can be described as compliant or deformable to meet the needs of specific engineering applications.

[0111] As used in this article, “force response” refers to the behavior of a solid, gel, or fluid that changes with the magnitude of the applied force.

[0112] As used herein, "partial coverage" refers to significantly less penile coverage than a conventional condom. In some embodiments described herein, the diaphragm does not cover the penile shaft.

[0113] As used in this article, “frequency response” refers to the change in behavior of a material or fluid when a periodic or near-periodic force or displacement (over time) is applied. This applied quantity may be referred to as a “signal.” The applied signal has a defined amplitude and frequency, and optionally a phase, all of which may be constant or vary with time and / or space.

[0114] G It refers to the square root of the sum of the square of the polymer's storage modulus and the square of its complex (loss) modulus, i.e., G. =(G'^2 + G''^2)^0.5, as measured by rheological determination or dynamic mechanical analysis. This term can indicate the resilience of an adhesive (a phenomenon described and defined herein) to fibrillate in a manner ideal for removal from a surface where a significant rate response at low frequencies or low shear rates is observed, and high adhesion or high removal energy is also observed across low frequency or low shear rate spectra (for removal with a frequency spectrum of 0 to 50 rad / s, or for removal with a shear rate spectrum of 0 to 8000 μm / s), while minimal pain is observed when removed from the skin or minimal energy is observed when removed from the surface.

[0115] "Resilience" in this article refers to G x Tanδ is the integral of the graph of angular frequency or shear rate, in MPa multiplied by rad / s.

[0116] "Mechanically passive adhesives" are adhesives designed to maintain their structural and mechanical properties after placement. Many pressure-sensitive adhesives are mechanically passive adhesives. In some embodiments, the adhesive layer does not contain either mechanically passive or pressure-sensitive adhesives.

[0117] “Tg” and “glass transition temperature” are used interchangeably herein. If measured, Tg values ​​are determined by differential scanning calorimetry (DSC) at a scan rate of 10 °C / min, unless otherwise stated. Typically, the Tg values ​​of copolymers are not measured, but are calculated using the monomer Tg values ​​provided by the monomer supplier, using the well-known Fox equation, as will be understood by those skilled in the art.

[0118] The term "heterogeneous network" as used in this article refers to a polymer network with a non-uniformly distributed crosslinking density.

[0119] "Gel fraction" refers to the mass of polymer remaining after washing with a suitable solvent divided by the initial mass. Methods for determining gel fraction are known in the art.

[0120] "Soluble fraction" refers to the mass of polymer lost after washing with a sufficient amount of suitable solvent divided by the initial mass. Methods for determining sol fraction are known in the art.

[0121] The term "heterogeneous crosslinking" as used in this article refers to non-uniform crosslinking distributed in a polymer network or system.

[0122] "Hot melt adhesive" refers to an adhesive that is processed (i.e., applied to a target substrate where it performs its intended adhesive function) at a temperature above the temperature range of the adhesive's intended use.

[0123] As used herein, “interpenetrating network” or “IPN” refers to a unique type of polymer material comprising two or more independent polymer networks that are physically entangled but not covalently bonded to each other. Each network retains its unique properties, but the networks interweave at the molecular level to form a complex that possesses properties derived from the combination of the individual networks.

[0124] "Lightly crosslinked" refers to a crosslinking density or network structure intermediate between thermoplastic and thermosetting polymers, where the thermomechanical behavior does not conform to the behavior of linear polymers flowing in polymer thermal processing techniques (such as extrusion or injection molding), nor to the behavior of fully covalently crosslinked networks exhibiting ideal elastomer behavior. The lightly crosslinked (meth)acrylate polymers of this invention may comprise (meth)acrylates and 0.001 to 2 wt% of a crosslinking agent, or may comprise other amounts of crosslinking agent providing rheological and thermomechanical property characteristics that do not conform to the properties of flowing melt-processable thermoplastics, nor to the properties of ideal elastomers, which typically exhibit an upward-sloping curve of storage modulus versus temperature in the rubbery region of a dynamic mechanical analysis plot of storage modulus versus temperature. Depending on the polymerization pathway, efficiency, monomer conversion, and polymerization kinetics, it may be necessary to increase the amount of crosslinking agent to form lightly crosslinked polymers, which, despite the same composition, may provide significantly different polymer networks from a thermomechanical property perspective.

[0125] "Low molecular weight, lightly crosslinked" refers to lightly crosslinked polymers or polymer networks that leave little or no residue on the surface after removal and exhibit limited conversion or low chain lengths (approximately tens to hundreds of thousands, but not millions of Daltons) between crosslinking sites, a large number of dangling chain ends, and thermomechanical properties consistent with polymer networks in which entanglement has little effect on thermomechanical behavior. Instead, side chain interactions, dangling chain ends and van der Waals forces, and free volume drive thermomechanical behavior that influence adhesive properties, including rate response and pain when removing the adhesive from the skin.

[0126] The term "monomer reactivity ratio" used in this article refers to a parameter in polymer chemistry used to describe the relative reactivity of two monomers in a copolymerization reaction. Copolymerization involves the simultaneous polymerization of two different monomers to form copolymers with different monomer compositions.

[0127] When referring to polymers, the term "network" in this article refers to a macromolecular structure formed by cross-linked polymer chains. Cross-linking is a covalent bond or other strong interaction, such as entanglement, supramolecular interaction, or physical interaction (e.g., the interaction between polymer chains and a crystalline or glassy phase).

[0128] The term "nonlinear force" as used in this paper refers to a type of force in which the relationship between the force and its effect on the system is not proportional or follows a simple linear equation.

[0129] As used in this article, “on-demand” in the context of debonding or separation refers to rapid, easy, and non-destructive debonding. On-demand delamination or release from the surface to which the adhesive composition or article adheres occurs via reversible or irreversible adhesive behavior triggered by exposure to stimuli such as temperature changes, chemical changes, light, ultrasound, changes in ionic strength, pH changes, magnetic or mechanical forces, and other stimuli.

[0130] The terms “room temperature” and “ambient temperature” used interchangeably in this article refer to temperatures between approximately 20 and 25°C.

[0131] As used in this article, "periodic" refers to events that occur at intervals in time or space. This can be a repetition of the same feature or characteristic.

[0132] Unless otherwise stated, “rate” as used in this article refers to the magnitude of change of a quantity over time.

[0133] As used herein, “prevention” means reducing, minimizing, or eliminating the release of semen outside the barrier layer of this invention compared to the natural release during ejaculation.

[0134] As used herein, “plastic welding” refers to the process of joining two separate plastic parts by using heat or solvents to create a permanent bond. This 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.

[0135] "Plasticizer" refers to an additive that, when added to a polymer, polymer blend, copolymer, copolymer blend, polymer network, or copolymer network, causes thermomechanical behavior consistent with that understood to be associated with plasticizing, namely, lowering the glass transition temperature, lowering the crystallization melting temperature, inducing stress relaxation, or causing an increase or decrease in adhesive strength. Plasticizers can be added to polymer, copolymer, or network mixtures or blends in amounts from about 1 wt%, about 2 wt%, about 3 wt%, up to a maximum of about 30 wt% or about 50 wt% or more. Examples of plasticizers used in various polymer systems are known and include water, common solvents, small molecules such as phthalates, glycerol or fatty acid compounds, triacetin, poly(ethylene glycol) compounds with a molecular weight ranging from 1 to 30 or more repeating units that are liquid at room temperature, vegetable oils, detergents, and other common plasticizers.

[0136] As used herein, "polymer" refers to a substance composed of macromolecules, which are very large molecules with molecular weights ranging from several thousand to several million grams per mole, and which are composed of simpler repeating units derived from lower molecular weight monomers. Polymers as used herein refer to homopolymers and copolymers. Homopolymers are made from one type of monomer (i.e., they contain one type of monomer). Copolymers are made from two or more different types of monomers (i.e., they contain two or more different types of monomers) (e.g., styrene-butadiene copolymers). The adhesives described herein may contain one or more polymers, including but not limited to stimulus-responsive polymers.

[0137] The term "pressure-sensitive" in this article refers to viscoelastic materials that meet appropriate Dahlquist criteria (e.g., the material has a storage modulus of less than 3 × 10⁵ Pa at 1 Hz at 25°C), indicating that it has sufficient flowability when pressed against a surface.

[0138] As used herein, “reduction” or “lowering” refers to a reduction of a specific quality. This 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 reduction can be measured by any suitable method, for example, by any suitable method known in the art. In the case of a condom covering an erect penis, the reduction may be a reduction in the surface area of ​​the erect penis, 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 a condom primarily covering a portion of the glans penis but exposing the other portions of the glans penis and the penile shaft, the reduction may be a reduction in the surface area of ​​the erect glans penis, 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, a reduction in the coverage of the erect penis may include exposure of penile portions with high sensory / sensory neuron activity, including the frenulum.

[0139] As used in this article, "reflexive geometry" refers to a three-dimensional shape in which the area of ​​the packaging in contact with the periphery of the adhesive contained within it is substantially flipped upwards relative to the center of the packaging in contact with the center of the adhesive (e.g., the reservoir). An example of reflexive geometry is the somrero hat. In cross-section, reflexive geometry has a characteristic "W" shape or a widened "U" shape on the packaging area in contact with the adhesive.

[0140] As used in this article, “rigidity” refers to exhibiting glassy behavior or having the ability to maintain the shaped geometry without significant deformation (e.g., plastic deformation).

[0141] The term "selective osmosis" as used in this article refers to membranes that include channels or pathways that allow specific molecules to pass through passively or actively. Active transport across a membrane requires energy input, which can come from mechanical, acoustic, chemical, electrical, magnetic, pH changes, ionic strength, heat, or light sources.

[0142] As used herein, “self-forming” refers to the natural expansion of the barrier layer in this invention under the force generated by ejaculation, which causes the barrier layer to expand but does not substantially prevent it from releasing semen outside the boundary.

[0143] The term "self-healing" as used in this article refers to a parameter in polymer chemistry used to describe the relative reactivity of two monomers in a copolymerization reaction. Copolymerization involves the simultaneous polymerization of two different monomers to form copolymers with different monomer compositions.

[0144] As used in this article, “semi-interpenetrating network” or “Semi-IPN” refers to a cross-linked or branched polymer network with entangled linear or branched additional polymers or polymer series.

[0145] As used in this article, "semi-rigid" refers to mechanical behavior that is flexible or pliable while also possessing the ability to withstand deformation and maintain its shaped geometry without significant plastic deformation. For clarity, semi-rigid behavior is not the same as elastic behavior.

[0146] As used in this paper, "shear rate" refers to the rate at which shear deformation occurs over time. Shear deformation refers to the sliding movement of parallel sheets (layers) of a fluid, gel, or solid material across each other. These layers can be discrete (with a finite measurable thickness) or continuous (infinitely thin or indistinguishable individually). The shear rate can be a constant function over time, a monotonic function over time, a non-periodic non-monotonic function, or a periodic function over time. Periodicity is understood to refer to a function that is truly periodic over time, or a function that is approximately periodic over time (e.g., a sinc function).

[0147] As used in this article, "shear rate response" refers to the change in the behavior of a material (e.g., gel, solid, liquid) under different shear displacements or shear rates. In the case of shear rate responsive adhesives, the adhesive exhibits varying adhesive strength when subjected to different shear or peel rates. In the case of reverse pressure-sensitive adhesives, the adhesive exhibits lower adhesive strength when peeled or removed from its adhered surface at lower shear or peel rates compared to higher shear or peel rates.

[0148] As used herein, “stimulus response” refers to a change in the physical, environmental, chemical, thermomechanical, mechanical, thermal, energy, or other properties of a composition or material caused by exposure to a stimulus, such as changes 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, and radio waves), ultrasound, high humidity, magnetism, electricity, and mechanical forces (including shear forces or linear forces).

[0149] When referring to fractional coverage of the penis, the term "significantly less" in this article means a reduction in the surface area of ​​the penis compared to that covered by a conventional condom, resulting in enhanced sensation or pleasure. Significantly less can be, for example, approximately 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% or less of the surface area.

[0150] As used herein, "thermoforming" refers to a molding process that involves heating a plastic sheet to a molding temperature (at which it becomes flexible) and shaping it into a specific form using a mold or rigid molding die. The molded plastic is then cooled or cooled and trimmed to produce the final part. Thermoforming methods include vacuum thermoforming and pressure thermoforming. Vacuum thermoforming involves heating a plastic sheet to a molding temperature, stretching it onto a single-surface mold, and then pressing it against the mold using a vacuum. For a given material, the molding temperature is above its glass transition temperature and below its melting temperature.

[0151] When referring to polymers, the term "thermoplastic" in this article means polymers that can be softened by heating and then processed using methods such as extrusion, injection molding, blow molding, and thermoforming.

[0152] The “viscosity” used in this article is a measure of a fluid’s resistance to deformation at a given rate. For liquids, it corresponds to the informal concept of “consistency.”

[0153] "Adhesion work" is the integral of the stress / strain diagram of an adhesive adhesion test performed at a specific retraction rate, typically by a stress-controlled rheometer in strain-controlled mode, multiplied by the thickness of the adhesive.

[0154] This is followed by various definitions related to "developable surface".

[0155] A “developable surface” refers to any surface with zero Gaussian curvature (https: / / en.wikipedia.org / wiki / Developable_surface). It is a surface that can be flattened (i.e., “unfolded”) onto a plane without deformation (stretching or compression). For the purpose of evaluating the geometry described herein, an equivalent practical description that can be used is a surface that can be constructed by bending, rolling, and twisting an initially flat sheet of paper without deforming it (stretching, tearing, compressing, or wrinkling). For the purposes of this disclosure, developable surfaces may have folded or overlapping areas when constructed from real materials, but again conform to their property of being constructed from rolled, bent, and folded sheets of paper.

[0156] A hyperbolic surface is a surface that has a finite and non-zero Gaussian curvature at least some locations, and therefore cannot be unfolded into a planar surface without deformation. Similarly, a planar sheet must be stretched or compressed at least in some locations to form a three-dimensional surface.

[0157] "Deformation" occurs when a planar or non-planar (three-dimensional) surface in its initial configuration is transformed into a second surface configuration (shape) and the original surface must be compressed or stretched to do so. If the surface is considered as a very thin diaphragm, the diaphragm surface area in the second configuration differs from the surface area in the initial configuration.

[0158] "Void volume" is the initial volume of an incompressible fluid that can be contained within a reservoir without straining the reservoir walls; that is, the pressure difference between the inside and outside of the reservoir across the walls is zero.

[0159] "Gaussian curvature" is the product of the two principal curvatures at any given point on the surface. The principal curvatures are the maximum and minimum values ​​of curvature at a point on the surface.

[0160] https: / / en.wikipedia.org / wiki / Principal_curvature

[0161] Detailed description of the selected figures

[0162] Figure 1A and 1B An embodiment of the packaging disclosed herein is depicted, wherein the packaging has a nominal circular geometry. Figure 1A A membrane cover (4) is disclosed that is attached to a receiver (1) via a flange (3) or other means. Figure 1B It is disclosed that a release liner (e.g., silicone paper) (13) can be fixed on the underside (inner side) of the membrane cap (4) to reduce the adhesion of adhesives (e.g., condoms) to the membrane cap. The membrane cap (4) can be attached to the flange (3) using an adhesive ring (12).

[0163] Figure 2A , 2B Examples of methods for using the packaged, sensation-enhancing condoms disclosed herein are depicted in 2C and 2D. Figure 2A This involves removing the film cover from the packaging. Figure 2B The packaging was shown to be inverted so that the opening faced downwards. Figure 2C It was revealed that the packaging was pressed onto the glans penis. Figure 2D The packaging was opened. Figure 2A The film cover (4) partially covers the package or receiver (1), which includes an adhesive substrate (5).

[0164] Figure 3 An exemplary embodiment of the packaging disclosed herein is depicted, wherein the packaging has a pull tab (6) attached to the outer surface of a receiver (1) to assist in manual gripping and handling of the packaging. The pull tab may be attached to the receiver, for example, by pressure-sensitive adhesive or other standard adhesive.

[0165] Figures 4A-4BAn exemplary embodiment of the packaging disclosed herein is depicted, wherein the packaging includes a “rear through-hole” (30) comprising a secondary cover (31) on the side of the packaging opposite to the main cover (shown in FIG. 1 [4]). Optionally, a secondary flange (32) may be formed in the geometry to facilitate attachment of the secondary cover (31) to the rear through-hole (30). The user then removes the main cover (4) and the secondary cover (31) (i.e., the cover covering the rear through-hole). When the user applies a condom, the rear through-hole (30) acts as a visual and tactile alignment aid, allowing the user to push the packaging toward the glans, allowing the tip to protrude through the rear through-hole. The substrate containing the adhesive is indicated by (5).

[0166] The through-hole allows the tip of the ejaculation reservoir and the glans penis (20) to pass through the packaging when the condom is applied, thereby preventing adhesion and pressure on the urethral opening (orifice) during application and reducing the collapse or compression of the ejaculation reservoir.

[0167] Figure 5A , 5B 5C describes an embodiment of the packaged, enhanced-feel condom disclosed herein, wherein a rigid receiver (1) and a semi-rigid (compliant) outer shell (6) (allowing the user to press the semi-rigid portion (6) directly over the adhesive) enable the condom / adhesive system to better conform to and fit the penis. Figure 5A A cross-sectional view is provided. Figure 5B A floor plan was provided. Figure 5C The application of pressure is depicted, causing the semi-rigid portion to deform to the position shown in (6a).

[0168] Figures 6A-6C An exemplary embodiment of the packaging disclosed herein is depicted, wherein the packaging has a circular inner shell (1) and a rectangular flexible outer shell (7) including attachment features such as wings containing an adhesive substrate (8). The flexible nature of the packaging allows a user to manipulate the wings to adhere to the penis, while the rigid portion maintains the geometry of the main parts of the condom, including the area covering the urethral opening and the semen collection reservoir (if present).

[0169] Figure 7A , 7B 7C describes an exemplary embodiment of the inner shell of the packaging disclosed herein. Figure 7A An embodiment is described in which the inner housing (1) is attached to the outer housing (50) near the flange (51) and at the pole (53) of the housing, having the structure shown by reference numeral (52). Figure 7B An implementation scheme is described in which the shell does not utilize supports at the poles. Figure 7CThe deflection behavior of the inner shell (1) when the package containing the condom is pressed onto the penis (20) is depicted until it contacts the inner surface of the outer shell, as shown by the surface position (1) compared to the pre-application position shown by the dashed line (1a).

[0170] Figure 8 An exemplary embodiment of the packaging disclosed herein is depicted, wherein there are ridges or corrugations (60) in the receiver.

[0171] Figure 9 A computer model depicting the dimensioned geometry of the barrier layer used for impregnation in Example 1 (Example Group 1) is provided.

[0172] Figure 10 A computer model depicting the dimensioned form of the geometry of the thermoformed packaging receiver in Example 1 (Example Group 1) is provided.

[0173] Figure 11 A computer model depicting the dimensioned form of the geometry of the thermoformed packaging receiver in Example 2 (Example Group 1) is provided.

[0174] Figure 12A-12B The packaging is described as having a protruding reservoir and steep side adhesive (e.g., an expandable adhesive condom with a 1 mL reservoir) and a thickness of 0.030 inches.

[0175] Figure 13 A cross-section of a double-shell cup-shaped package with a compliant inner shell and a rigid outer shell is depicted. The two shells join at the flange region. However, they can also be equivalently joined along the wall near the opening adjacent to the flange.

[0176] Figure 16 A cross-sectional view of a package with a porous application liner having a stable fluid film holding element is depicted. Sectional view A depicts a package embodiment having a fluid film holding device (100) that holds the adhesive (5) to the inner surface of the receiver (1). Sectional view B depicts a package embodiment having a fluid film holding device stabilized by a porous impregnated application liner (101) that holds the adhesive (5) to the inner surface of the receiver (1). The thicknesses of the fluid film (100) and the fluid film with the impregnated application liner (101) are exaggerated for visual clarity.

[0177] Figure 17An embodiment of the application pad (1701) is depicted, which may optionally be impregnated with fluid to stabilize the fluid membrane retention device (if present). The overlapping area (1702) may be secured with a low-tack adhesive to maintain the conical geometry of the application pad, which is suitable for the adhesive geometry (e.g., a condom with an expandable adhesive surface for enhanced sensation). An optional pull tab (1703) facilitates the unfolding and removal of the application pad once the adhesive has been applied to the target surface (e.g., the glans penis in the case of an enhanced sensation condom).

[0178] Figures 18A-18C An embodiment of the application pad (1701) is depicted, which may optionally be impregnated with fluid to stabilize the fluid membrane holding device (if present). The overlapping area (1702) may be secured with a low-tack adhesive to maintain the generalized conical geometry of the application pad, which is suitable for the adhesive geometry (e.g., a condom with an expandable adhesive surface for enhanced sensation). An optional tongue (1704) facilitates removal of the device from the packaging receiver (5, not depicted), thereby enabling operation, alignment, and application without contact with the adhesive or barrier layer, thus reducing adhesive contamination or soiling. Figure 18B and 18C A three-dimensional view is depicted of the ESC in the application pad and the application pad-ESC assembly in the receiver body. Figure 18D-18F The foil separator of the sealed packaging is depicted.

[0179] Figure 19 An embodiment of an application pad (1701) for a condom with enhanced sensation as an exemplary adhesive (5) is depicted. A force (1901) is applied in a downward direction (as shown in the drawing) while the application pad (1701) is supported to hold it in place. This allows the outer surface (1911) of the enhanced-sensory condom to contact the inner surface (1910) of the application pad and provides sufficient reaction force to prevent the condom surface (1911) from separating from the pad surface (1910) when the release pad (1902) is peeled off to expose the adhesive surface for application to the target surface, without causing wrinkles, folds, or self-adhesion that would contaminate the adhesive and render the device unusable.

[0180] Figures 20A-20E An embodiment of a receiver with a reflexive geometry is depicted. Several cross-sectional variations are shown. Figures 20A-20C ) and 3D diagram ( Figure 20D ).

[0181] Figures 21A-21B Cross-sectional views of two variants of the closed cap for a reflexive geometry implementation of the receiver geometry are depicted. Figure 21A It is a cap with vertical walls. Figure 21B It is a cap with sloping or contoured walls.

[0182] Figure 23 Frequency sweep plots of three different adhesives containing different crosslinking agents were depicted. All adhesives exhibited high loss behavior, indicated by high tan δ and highly rate-dependent behavior.

[0183] Figure 24 The adhesive properties of the L6_1 adhesive film under variable debonding rates were plotted. The adhesive exhibits highly rate-dependent debonding behavior, where both maximum stress and fibrillation increase with increasing probe retraction rate. Consequently, the adhesion work increases significantly with increasing rate, such as... Figure 24 As shown.

[0184] Figure 25 Depicting Figure 24 The adhesion work results cited in the description show that, in the adhesion tests described herein, Nuceptive L6_1 adhesive increases adhesion work by 30-fold over a retraction rate range of 1 to 8000 micrometers per second.

[0185] Figure 26 The nominal stress as a function of strain was plotted for L6 adhesives with three different crosslinking agents. Tests were conducted at 25 °C and a crosshead speed of 100 µm / s. Mean stress values ​​were plotted without error bars (n=3).

[0186] Figure 27 The adhesive work of L6 adhesive with three different crosslinking agents is depicted. Error bars represent standard deviations. (n=3)

[0187] Figure 28 A sweep spectrum of tan δ was plotted to compare L6 adhesive and slightly crosslinked acrylic adhesive at 25°C. Error bars represent standard deviations. (n=3)

[0188] Figure 29 The nominal stress as a function of strain was plotted to compare the tack profile of L6 adhesive with that of a slightly crosslinked acrylic adhesive. Tests were conducted at 25°C and a crosshead speed of 100 µm / s. Mean stress values ​​were plotted without error bars (n=3).

[0189] Figure 30 The adhesive work of L6 adhesive is depicted compared to that of a mildly cross-linked acrylic adhesive (control group). Error bars represent standard deviations (n=3).

[0190] Figure 31 The tan δ values ​​were plotted to compare L6 adhesive and a mildly crosslinked acrylic adhesive (control group). A sweep spectrum of the complex modulus amplitude. The error bars represent the standard deviation (n=3).

[0191] Figures 36A (top view), 36B (perspective view), 36C (rear view), and 36D (side view) illustrate a 3D unfoldable adhesive surface.

[0192] Figures 37A (top view), 37B (perspective view), 37C (rear view), and 37D (side view) illustrate a 3D deployable adhesive surface with a reservoir on top of the adhesive.

[0193] Figure 38A An exploded perspective view of two deployable adhesive layers that are joined together and attached to a reservoir to form a fully assembled condom. Figure 38B It shows its exploded top view. Figure 38C Showing Figure 38A Front, side, and back views of a fully assembled condom.

[0194] Figure 38D A close-up of the barrier layer and adhesive layer assembly is shown. The figure shows a cross-section of a condom with an expandable adhesive ring geometry, consisting of a barrier layer and an adhesive layer covering a portion of the inner surface of the barrier layer. The adhesive layer extends to the periphery, exposing the unadhesive portion of the barrier layer, thus forming a reservoir. The adhesive layer comprises two adhesive laminates, each 100 micrometers thick in this rendering. The depicted barrier layer is also 100 micrometers thick.

[0195] Figure 32The condom includes a two-part structure with an adhesive layer 1002. The main barrier layer 10011 is planar, and the reservoir barrier layer 10012 is joined at the engagement area 301 by a suitable method (e.g., adhesive or plastic welding). The reservoir 1003 is formed by these two layers. Optionally, in some embodiments, the area between the upper surface of 10011 (represented by 309) and the inner surface of 10012 may be filled with an absorbent material, such as a superabsorbent polymer pad, which swells, traps, or gels ejaculatory fluid. Although shown in a planar configuration, any of 10011, 10012, or 1002 can be curved. The barrier layers 10011 and 10012 do not need to be the same material, and in some embodiments, 10011 preferably comprises a thinner, more compliant layer to conform to the shape of the glans penis, while 10012 is more elastic to expand during ejaculation to accommodate fluid. In some embodiments, the adhesive ring width (the sum of distances 3101, 3102, and 3103) is approximately 10 mm. Optionally, an adhesive different from 1002 is patterned below the attachment area 301 to provide increased adhesion to the skin surface (not depicted) in the normal direction to mitigate pull-up. Distances 3101, 3102, and 3103 should be selected for the specific barrier layer and adhesive material chosen to provide sufficient resistance to peel-up under fluid pressure or other mechanical forces. The attachment area 301 is located inset from the periphery (such as the leftmost edge of 1011 as depicted) to provide a more favorable orientation for the transfer of diaphragm stress to the adhesive and the underlying attachment surface (skin).

[0196] Package

[0197] This document discloses packaging suitable for protecting and optionally applying (e.g., aligning, depositing) adhesives (e.g., condoms or medical adhesives). The packaging may be handheld or disposable.

[0198] In one embodiment, the package includes (a) a receiver (e.g., a dome or cone), optionally including a flange, and (b) a sealing device (e.g., a film that seals the dome and adheres 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 surface and an inner surface, wherein an adhesive layer of a stimulus-responsive polymer is present on at least a portion of the inner surface of the barrier layer). In some embodiments, the outer layer of the barrier layer is adhered directly to or via a retaining device to the inner surface of the receiver. In some embodiments, the barrier layer remains adhered to the inner surface of the receiver when applied by a user. In some embodiments, the barrier layer remains adhered under pre-use conditions such as shaking or other disturbances.

[0199] The receiver (e.g., a dome or cone) can be formed of any suitable material, including any of the materials described herein. In some embodiments, the receiver is formed of PETG or LDPE. The surface energy of the inner surface of the receiver can vary. In some embodiments, the surface energy is between about 25-55 dynes / cm, more specifically, about 30 to about 50, about 35 to about 35, or about 40 dynes / cm. In some 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 some embodiments, the packaging does not include a grip; for example, the outer surface of the packaging is smooth. The contact angle between the first packaging material and water can vary. In some embodiments, the first packaging material has a water contact angle of about 60 to about 90 degrees, more specifically, about 60 to about 70, about 70 and about 80, or about 80 and about 90 degrees, or even more specifically, about 70 and about 85 degrees.

[0200] The barrier layer can be formed of any suitable material, including any of the materials described herein. In some embodiments, the barrier layer is formed of latex, rubber, or a combination thereof. In some embodiments, the barrier layer is substantially composed of latex or substantially of rubber. In some embodiments, the latex or rubber is untreated, for example, unchlorinated, unpowdered, or untreated with lubricants. The thickness of the barrier layer can vary. In some embodiments, the barrier layer is between 5 and 250 micrometers, or in some embodiments between 25 and 100 micrometers, or in some embodiments between 25 and 75 micrometers.

[0201] The barrier layer comprises an outer surface and an inner surface. In some embodiments, the inner surface comprises an adhesive layer that extends at least partially across the inner surface (e.g., substantially co-extended with the inner surface of the barrier layer). According to this embodiment, the inner adhesive layer adheres the barrier layer to a contact surface, such as skin and / or particularly penile skin. The adhesive layer may comprise any suitable material, including any of the materials described herein. In some embodiments, the adhesive layer comprises at least one stimulus-responsive polymer, for example formed from one or more monomers and optionally one or more multifunctional crosslinkers. The stimulus may be any suitable stimulus, such as a physicochemical change or a mechanical force, such as a shear rate. In some embodiments, the stimulus-responsive polymer has lower peel strength at lower peel rates and higher peel strength at higher peel rates. Optionally, a release liner may be bonded to the adhesive layer. However, in some embodiments, the adhesive layer is not bonded to the release liner. In some embodiments, no portion of the adhesive layer contacts any other portion of the adhesive layer. In some embodiments, the barrier layer (e.g., a condom) is not wrinkled, folded, or rolled up.

[0202] In some embodiments, the stimulus-responsive polymer comprises an acrylate monomer, optionally crosslinked with one or more multifunctional crosslinking agents. In one embodiment, the stimulus-responsive polymer comprises a poly(laurate methacrylate) polymer, optionally crosslinked with one or more trifunctional crosslinking agents (e.g., TMPTA).

[0203] In one embodiment, the stimulus-responsive polymer comprises a lightly cross-linked polymer, more specifically, a lightly cross-linked low molecular weight polymer as defined herein.

[0204] In one embodiment, the weight ratio of the stimulus-responsive polymer (e.g., lauryl methacrylate) to one or more multifunctional crosslinkers is 98:2 to 99.9:0.1, for example, 98.5:1.5 to 99.9:0.1; 99:1 to 99.9:0.1, 99.1:0.9 to 99.9:0.1, 99.2:0.8 to 99.9:0.1; 99.3:0.7 to 99.9:0.1, 99.4:0.6 to 99.9:0.1, 99.5:0.5 to 99.9:0.1, 99.6:0.4 to 99.9:0.1, 99.7:0.3 to 99.9:0.1, or 99.8:0.2 to 99.9:0.1.

[0205] In some embodiments, the receiver includes a void. In some embodiments, the void is dehumidified.

[0206] The barrier layer can be adhered directly or via a retaining device to the inner layer of the receiver (e.g., a dome containing the first packaging material). Direct adhesion can depend on adhesive matching and / or treatment of the first packaging material, the barrier layer, or both (to increase adhesion). Treatment can be any suitable treatment, such as electrostatic treatment, plasma treatment, corona treatment, or a combination thereof.

[0207] In some embodiments, the barrier layer is partially retained within the package due to an interference fit. In some embodiments, the interference fit is due to the generalized conical geometry of the receiver, for example, in the case of a deployable surface.

[0208] In some embodiments, the packaging also includes a retaining device, which can be any suitable retaining device. In one embodiment, the retaining device is a lip, ridge, corrugation, etc. In other embodiments, the retaining device is a fluid, such as one that adheres to or coats the first packaging material. The retaining device is sized to allow for retention.

[0209] In some implementations, the barrier layer includes a reservoir. The reservoir may be self-formed, for example, in response to ejaculation of semen.

[0210] The packaging may optionally be housed within an outer casing. The outer casing may be formed of any suitable material, including any of the materials disclosed herein.

[0211] In one embodiment, the package includes (i) a shaped receiver (1) having a flange (2) and a liquid thin layer disposed on the inner surface of the receiver; and (ii) a removable film cap (3) having a pull tab, wherein the receiver and the cap are adhered at the flange to form a package suitable for protecting the adhesive (Figure 1). These components will be described in further detail below.

[0212] The receiver can be any suitable non-planar shape. In some embodiments, the receiver is a shape selected from circles, ellipses, squares, rectangles, polygons, curved polygons, hemispheres, ellipsoids, cones, tetrahedrons, pyramids, or polyhedra.

[0213] In some implementations, the receiver is approximately circular.

[0214] In some implementations, the receiver is a dome.

[0215] The thickness of the receiver wall can vary. In one embodiment, the thickness of the receiver wall is between 0.005 inches and 0.010 inches, or between 0.010 inches and 0.020 inches, or between 0.020 inches and 0.040 inches.

[0216] The physical properties of the receiver can vary. In one embodiment, the receiver is rigid. In a particular embodiment, the rigid receiver comprises a thermoplastic polymer. The thermoplastic polymer can be any suitable thermoplastic polymer, such as polypropylene (PP), PET, glycol-modified polyethylene terephthalate (PET-G), polychlorotrifluoroethylene / glycol-modified polyethylene terephthalate, and combinations thereof.

[0217] In one embodiment, the invention includes a thermoplastic film, optionally thermoformed together with functional packaging. 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 styrene. In yet another embodiment, the thermoplastic film is a polyurethane, polyester (including polyethylene terephthalate), polycarbonate, or polyether. The molecular weight of the thermoplastic film is from 2k to 10M Daltons, preferably from 100k to 500k Daltons. The thickness of the film is from 0.01 to 2000 micrometers, preferably from 20 to 150 micrometers. Optionally, the film is electrostatically treated.

[0218] The packaging is typically single-use. In some embodiments, the receiver may be recyclable and formed from materials selected from PP, PET, and combinations thereof. In some embodiments, the thermoformed portion is compostable. In some embodiments, the receiver is bio-based, for example, formed partially or entirely from bio-based PET. In some embodiments, the receiver comprises biodegradable plastics such as polylactic acid (PLA), polyhydroxyalkanoate (PHA), polyglycolic acid (PGA), and polybutylene succinate (PBS).

[0219] In some embodiments, the receiver comprises a rigid thermoplastic polymer (e.g., PET-G) and is formed in a generally circular shape.

[0220] In another embodiment, the rigid housing is made of pressed or stamped aluminum.

[0221] In some implementations, the receiver is semi-rigid, for example, made of thermoplastic elastomer, high-density polyethylene, low-density polyethylene, or PETG. This semi-rigid nature allows the user to manually conform the condom / packaging assembly to the glans penis, aiding in compression and adhesion of the condom to the skin. Furthermore, the semi-rigid behavior allows the user to bend, fold, or squeeze the receiver / packaging, for example, when carried in a pocket, purse, or bag. The semi-rigid body maintains its shaped form when no external force is applied. Therefore, when the external force restricting the packaging is removed (e.g., when bent or squeezed in a user's pocket), the receiver will spring back to its shaped geometry.

[0222] In one embodiment, the outer wall of the receiver (and / or optionally, in the case where the packaging also includes a housing surrounding the receiver) includes one or more features to facilitate use, such as assisting in the alignment of the adhesive or removing the packaging after the adhesive has been applied to the target site.

[0223] In one implementation, the packaging is transparent.

[0224] In one embodiment, the packaging has a transparent window to facilitate visual alignment, such as the alignment of the reservoir portion of a packaged, enhanced-feel condom with the urethral opening.

[0225] In one particular embodiment, the outer wall includes holes to assist in aligning the adhesive used for application. The size of the holes can vary. In one embodiment, the central portion of the rigid housing is removed, for example, by stamping with a die.

[0226] In one particular embodiment, the flange or flat surface is molded into the geometry around the removed portion, such that another film cap (sub-film cap) can be secured to the back of the packaging, as shown below. Figures 4A-4BAs shown, this creates a "rear through-hole". The user then removes the main and secondary membrane caps, which are the membranes covering the rear through-hole. When the user applies the condom, the rear through-hole acts as a visual and tactile alignment aid, allowing the user to push the packaging onto the glans, allowing the tip to protrude through the rear through-hole now encased in the barrier layer.

[0227] In one particular embodiment, the outer wall includes a pull tab to assist in removing the packaging after adhesive has been applied. In one embodiment, such as... Figure 3 The pull-out tongue shown in the exemplary embodiment can be attached to the back of the housing to aid in manual gripping and handling of the packaging. The pull-out tongue is attached to the housing using pressure-sensitive adhesive or other standard adhesives.

[0228] In some embodiments, the packaging further includes a housing surrounding the outer wall of the receiver, wherein the housing includes an outer wall and an inner wall, wherein at least a portion of the inner wall contacts the outer wall of the receiver.

[0229] The housing may be the same as or different in shape from the receiver (e.g., circular-circular, circular-rectangular). The housing may include one or more additional features to facilitate use, such as assisting in the alignment of the adhesive or removing the packaging after the adhesive has been applied to the target area. In one particular embodiment, the housing includes a hole. In one particular embodiment, the housing includes a pull-tab.

[0230] The housing may be rigid or semi-rigid and may contain one or more materials disclosed herein with respect to the receiver.

[0231] In one particular embodiment, the packaging includes an outer shell surrounding the receiver, wherein the outer shell and the receiver are formed of materials with different stiffnesses. For example, the receiver comprises rigid plastic or aluminum, while the shell comprises a semi-rigid thermoplastic (elastomer). According to this embodiment, the user can manipulate and conform the exterior of the packaging to the geometry of the glans penis, promoting improved adhesion without direct contact with the condom, as shown in Figure 5.

[0232] In another embodiment utilizing rigid-semi-rigid packaging, the packaging comprises a circular receiver and a rectangular flexible outer shell including attachment features such as wings. Thus, the flexible nature of the packaging allows the user to manipulate the wings to adhere to the penis, while the rigid portion maintains the geometry of the main part of the condom, including an area covering the urethral opening and a semen collection reservoir (if present).

[0233] In another embodiment, the packaging has an inner shell with a central hole removed for a semen collection reservoir. The inner shell is attached to the outer shell at or near a flange for attaching a membrane cap, as shown below. Figures 7A-7BAs shown. Attachment can be achieved by bonding the two plastic pieces with an adhesive, or by thermal welding or ultrasonic welding. In this design... Figure 7A In some variants, there is a support as indicated by reference numeral 52, which creates a well in which the tip of the reservoir resides.

[0234] exist Figure 7B In this variant, there is no support, 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 can be designed by selecting the material thickness and cutout diameter to provide the specific resistance required for proper adhesion. This can be set to forces of 0.01 to 0.1 N, 0.1 to 1 N, 1 to 2 N, 2 to 5 N, 5 to 10 N, 10 to 20 N, or 20 to 50 N. Therefore, this provides an indicator of the minimum force required for consistent condom application. Furthermore, it provides a tactile response as the inner shell presses firmly against the inner surface of the outer shell, indicating to the user that the minimum applied force has been met and the condom has been securely pressed against the penis for a proper seal of the adhesive.

[0235] The deflection force can be further adjusted by molding ridges or corrugations that allow deformation, such as... Figure 8 As shown.

[0236] To enhance tactile response, a clicker feature can be molded into the inner housing. This could be a tensioned, compressed, or torsional section of the inner housing, similar to a pop-out metal food can lid or a dog clicker device. When pressed, it will provide a tactile or audible click, indicating that minimal applied force has been applied.

[0237] In some implementations, the packaging is foldable or semi-foldable, for example, to facilitate storage or disposal.

[0238] In some embodiments, the receiver (and / or housing, if present) is foldable or semi-foldable. The receiver may include one or more features to facilitate folding.

[0239] The packaging embodiment includes at least one membrane cap, which is a removable or attached "top" of the packaging for sealing the contents (i.e., a condom or medical adhesive). Note that the geometry of the membrane cap corresponds to the geometry of the opening, which is circular for illustrative purposes in Figure 1, but it does not have to be circular.

[0240] In one embodiment, the opening of the receiver is covered by a membrane cap that is adhered to a flange on the periphery of the receiver.

[0241] The membrane cover may comprise any suitable material. In one embodiment, the membrane cover comprises paper, plastic, aluminum, polyester film, or an aluminum-backed polyester film.

[0242] The membrane cover may include a pull tab. In some embodiments, the pull tab may be further embossed with indentations to aid gripping due to the presence of body fluids, water, or personal lubricant.

[0243] Inside the membrane cover, a release liner (e.g., silicone paper) can be adhered to the cover to reduce any adhesion to the cover, such as... Figure 1A As shown.

[0244] In some embodiments, the packaging also includes a second film cover, i.e., a removable or attached film cover located on the underside or bottom of the packaging (relative to the top cover), which allows the packaging to be aligned for application, as further described herein.

[0245] The retaining element may vary, but is designed to hold the adhesive (e.g., a condom or medical adhesive) within the packaging to prevent adhesion to, for example, a membrane cap or other structure or itself. The retaining element secures the adhesive-containing substrate during transport, storage, and application, while also allowing the adhesive-containing substrate to be released when needed.

[0246] In one embodiment, the retaining element comprises a thin fluid membrane coated on the inner surface of the receiver.

[0247] The fluid can be any suitable liquid or gel. In one embodiment, the fluid is water, water-based, or silicone-based, such as silicone oil and silicone-based lubricants. The latter may be suitable for use, in part because of its favorable wettability to latex / polyisoprene (barrier substrate) as well as thermoplastics (e.g., PETG) and aluminum that constitute the packaging. The fluid film can be between 0.001 and 1 mm thick, but this depends on the fluid's viscosity, surface tension, and the contact angle of the fluid with the selected packaging and adhesive-containing substrate materials, and an equilibrium thickness will naturally be established.

[0248] In some embodiments, the fluid membrane comprises a low-adhesion biocompatible adhesive.

[0249] In some embodiments, the fluid membrane comprises a water-soluble binder or a water-soluble stimuli-responsive binder.

[0250] In some implementations, the fluid membrane contains petrolatum.

[0251] The adhesive lubricant can enhance the additional beneficial behavior because the adhesive film reduces the sliding motion of the condom along the inner surface of the packaging. While these effects are sufficient to stably hold the adhesive-containing substrate (e.g., condoms, medical adhesives) during transport, storage, and application, they are weaker than the adhesion of a properly applied adhesive-containing substrate to a target site (e.g., a body part, such as the glans penis). Therefore, when the user opens the packaging, the adhesive-containing substrate remains firmly in place.

[0252] 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 the adhesive strength of the adhesive-containing substrate to the surface to which the adhesive-containing substrate will be bonded (e.g., an adhesive condom bonded to the glans penis). The thickness can vary between 0.001 and 0.1 mm, but is preferably between 0.025 and 0.150 mm.

[0253] In another embodiment, the retaining element comprises a layer that exhibits an adhesive match to the inner surface of the packaging to secure the adhesive while also allowing release during use. The adhesive strength of this layer to the adhesive contained within the packaging is less than the adhesive strength to the target surface to which the adhesive will bond (e.g., an adhesive condom bonded to the glans penis). For example, latex exhibits a sufficient adhesive match to PETG or thermoformable polyurethane packaging to hold the condom in place while also allowing it to release and adhere to the glans penis. In such cases, the retaining element is an inherent feature of both the adhesive-containing substrate and the chosen packaging material, and therefore has zero thickness. Alternatively, the inner wall of the receiver and the adhesive exhibit an adhesive match.

[0254] If the adhesive (such as medical adhesive or condom adhesive) is not released from the packaging, it indicates that contamination, folding, or other adverse application conditions prevented successful adhesion or sealing to body parts (such as the glans penis). This serves as an indication to the user to discard the adhesive / packaging and begin using a new, unopened device.

[0255] The application process requires no cleaning and does not require the user to directly interact with or come into contact with the adhesive or barrier layer during application. As a result, the possibility of contamination is reduced.

[0256] Also disclosed is a packaged adhesive, i.e., an adhesive contained within the packaging disclosed herein. Advantageously, in some embodiments, the packaging retains the adhesive within the receiver even when the packaging is inverted, i.e., with the cap side facing the ground, without folding or wrinkling the edges. In such embodiments, the retaining element is strong enough to support the weight of the adhesive-containing substrate and prevent the adhesive-containing substrate from being inverted or folding itself, but weaker than the adhesion strength between the adhesive-containing substrate and its application target (e.g., the glans penis). Therefore, when the packaging is pulled away from the application target, the retaining element releases the adhesive-containing substrate, facilitating application of the adhesive-containing substrate to the application target without folding or wrinkling.

[0257] In one embodiment, the top surface of the substrate containing the adhesive is held to the inner surface of the receiver by a capillary mechanism attributable to the coating of a liquid film that retains the inner surface. The fluid film completely wets the outer barrier surface (adhesive), creating a film, for example, about 25 to about 250 micrometers thick. The capillary (surface tension and viscosity) behavior of the fluid wetting both the barrier substrate and the packaging material subsequently generates an attractive retaining force.

[0258] In another embodiment, the outer surface of the barrier layer (adhesive) is fixed to the inner surface of the receiver by the inherent adhesive matching behavior between the receiver and the barrier layer.

[0259] The adhesive can be any suitable adhesive.

[0260] In one embodiment, the adhesive is a reversible and / or stimulus-responsive adhesive, meaning that the adhesive adheres to a target surface under one set of conditions but delaminates from the surface under another set of different conditions. According to this embodiment, the adhesive exhibits a reversible and / or stimulus-responsive behavior, including stimuli such as temperature changes, peel rate changes, dissolution, light exposure, exposure to electromagnetic fields, chemical exposure (including exposure to water or pH changes), and exposure to mechanical forces (including shear forces or forces that drive crack propagation in the adhesive or adhesive barrier layer).

[0261] In one embodiment, the adhesive's response to a stimulus is reversible and it becomes less viscous. The stimulus can be, for example, a change in temperature, a chemical change, light, ultrasound, a change in ionic strength, a change in peel shear or peel rate, a change in pH, magnetic force, or mechanical force.

[0262] In one particular embodiment, the adhesive barrier layer exhibits semi-permeable or selective permeable behavior, which allows stimuli (such as temperature or chemical stimuli) to permeate the adhesive used to induce a stimulus response effect.

[0263] In another specific embodiment, the adhesive barrier layer exhibits stimulus-responsive behavior that achieves selective or controlled permeability or controlled porosity. On-demand permeation of any substance is controlled by exposure to temperature changes, chemical changes, light, ultrasound, changes in ionic strength, pH changes, magnetic or mechanical forces, and other stimuli. This arbitrary substance can be a stimulus for the inner adhesive layer (which may experience a stimulus-responsive effect), or it can be a solvent capable of delaminating the inner adhesive layer. Mechanical forces used for delamination include shearing and / or peeling or pulling at different frequencies or amplitudes. In another embodiment, the adhesive layer is frequency- or force-responsive and maintains functional adhesion at higher forces or frequencies, and can be removed using lower frequencies or removal forces (e.g., by gentle peeling or pulling). In another embodiment, removal occurs with minimal or no pain, including gentle peeling or pulling.

[0264] In one implementation, the adhesive changes from viscous to non-viscous in response to stimuli such as temperature or light.

[0265] In one particular embodiment, the adhesive adheres to a surface (e.g., tissue) at body temperature (about 37°C) and is able to reduce adhesion or delamination when cooled to below body temperature to about 25°C, about 20°C, about 15°C, about 10°C, about 5°C, about 0°C or lower.

[0266] In another specific embodiment, the adhesive adheres to a surface (e.g., tissue) when external heat is applied. According to this embodiment, the adhesive exhibits increased adhesive strength when heated to about 30, about 35, about 37, about 40, about 45, about 55, about 60, or about 65°C or higher.

[0267] In one particular embodiment, the adhesive delaminates from a surface (e.g., tissue) upon exposure to water or solvent.

[0268] In another specific embodiment, the adhesive delaminates from the surface in response to changes in pH, for example, by exposure to a substrate impregnated with a pH suitable for physiological use.

[0269] In one implementation, delamination from human skin occurs within a time frame of approximately 0.1 seconds, 1 second, approximately 2 seconds, approximately 5 seconds, approximately 10 seconds, 15 seconds, approximately 30 seconds, approximately 45 seconds, or approximately 60 seconds or longer, and can be achieved by a combination of thermal, chemical, physical, or mechanical stimulation.

[0270] In one embodiment, the adhesive comprises a frequency- or shear-responsive adhesive that provides sufficient adhesive force for functional use and can be removed from the skin with minimal or no pain by peeling or slight removal effort. In another embodiment, any residual adhesive on the skin can be removed with minimal or no pain by rubbing or repeated wiping.

[0271] In one embodiment, the adhesive exhibits elastomeric or flexible thermomechanical behavior.

[0272] The embodiments disclosed herein have a variety of end uses for products to be packaged. The product may be, for example, an adhesive or an article or device containing an adhesive as a component. The adhesive may be, for example, a single-layer or multi-layer adhesive.

[0273] In one embodiment, the adhesive is a sensation-enhancing condom or male diaphragm. In some embodiments, the condom or diaphragm provides: (a) partial coverage of the penis; (b) a barrier layer capable of preventing semen leakage from the diaphragm; (c) on-demand delamination in response to stimulation; (d) substantially painless to the user during delamination; and (e) substantially no residue or only easily removable residue upon removal.

[0274] In one embodiment, the barrier layer comprises a polymer diaphragm or membrane exhibiting elastomeric, soft yet tough, or flexible thermomechanical behavior. In one embodiment, the partial cover is limited to the tip of the penis. In another embodiment, the partial cover is limited to the head of the penis. In yet another embodiment, the partial cover does not include the body of the penis. In yet another embodiment, the partial cover includes the base of the penis or below the base of the penis.

[0275] In some embodiments, the contraceptive diaphragm also includes a reservoir. The location of the reservoir can vary, including, for example, at the tip of the contraceptive diaphragm, along the side of the contraceptive diaphragm, at the base of the contraceptive diaphragm, or below the portion of the contraceptive diaphragm below the glans penis.

[0276] The adhesive may have more than one layer. In one embodiment, the barrier layer further comprises an inner adhesive layer, wherein the inner adhesive adheres the barrier layer to the penile skin.

[0277] In one embodiment, the inner adhesive layer exhibits stimuli-reversible or irreversible adhesive behavior that allows for on-demand delamination.

[0278] In one implementation, the stimulus is selected from temperature changes, chemical changes, light, ultrasound, changes in ionic strength, changes in peeling rate, dissolution, pH changes, magnetic or mechanical forces, and other stimuli.

[0279] In one implementation, the contraceptive diaphragm does not delaminate in response to bodily fluids.

[0280] In another embodiment, the inner adhesive layer of the contraceptive diaphragm is coated with a polymer that swells and / or gels in the presence of sperm, semen, or semen fluid, thereby retaining sperm, semen, or semen fluid within the contraceptive diaphragm.

[0281] In another embodiment, the contraceptive diaphragm is externally coated with a spermicide and / or lubricant.

[0282] In another embodiment, the barrier layer exhibits semi-permeable, selectively permeable, or controlled porosity behavior, which allows chemical or temperature stimuli to permeate the diaphragm, thereby inducing a stimulus-response effect on the contraceptive diaphragm.

[0283] In another embodiment, the barrier layer exhibits stimulus-responsive behavior that enables selective permeability, controlled permeability, or controlled porosity that can be induced on demand. The on-demand permeation of the substance capable of permeating the barrier layer (i.e., the permeating material) is controlled by exposure to temperature changes, chemical changes, light, ultrasound, changes in ionic strength, pH changes, magnetic or mechanical forces, and other stimuli. The permeating material can be a stimulus for the inner adhesive layer (which may undergo a stimulus-responsive effect), or it can be a solvent capable of delaminating the inner adhesive layer.

[0284] The thickness of the barrier layer can vary and can have, for example, a thickness of 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.

[0285] The reservoir may be substantially spherical in shape 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 larger.

[0286] The reservoir may be substantially cylindrical in shape 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.

[0287] The reservoir can self-form under ejaculation pressure and may not have a predefined geometry.

[0288] The reservoir may contain a polymer coating that swells or gels in the presence of sperm to retain sperm within the reservoir. Polymers include, but are not limited to, chitosan, alginate, polyacrylic acid, cross-linked polyacrylic acid, sodium polyacrylate, and cross-linked sodium polyacrylate.

[0289] In another embodiment, the barrier layer covers significantly less of the penis than existing condoms. The condom coverage may include partial or complete coverage of the glans penis and may extend to or below the base of the penis, and the reservoir may be present at the tip of the penis, along the side or head of the penis, at the base of the glans penis, or below the glans penis.

[0290] The diaphragm can be circular, oval, or other geometrically shaped, and may include protruding arms extending to, surrounding, or below the base of the glans penis, and may partially cover the penile body. The protruding arms may have an adhesive layer or may be mechanically secured to the diaphragm. Circular diaphragms may have radii of approximately 0.5 cm, 1.0 cm, 2.0 cm, 3.0 cm, 5.0 cm, or 10.0 cm or greater. Oval diaphragms may have a primary radius of approximately 0.5 cm, 1.0 cm, 2.0 cm, 3.0 cm, 5.0 cm, or 10.0 cm, and independent secondary radii of approximately 0.5 cm, 1.0 cm, 2.0 cm, 3.0 cm, 5.0 cm, or 10.0 cm or greater. The protruding arms may have an aspect ratio of approximately 1:1, 1:2, 1:5, 1:10, 1:20, or 1:100 or greater, and may be 1, 2, 3, 4, 5, 6, or more. They may have a length of approximately 0.5 cm, 1.0 cm, 2.0 cm, 3.0 cm, or 5.0 cm or longer, and a width of approximately 0.1, 0.2, 0.5, 1.0, or 2.0 cm or wider. The elastomeric ring may surround the base of the barrier layer and may be stretched to enclose and secure the barrier layer to the base of the glans penis. Optionally, a contractile force may be applied to enhance the adhesion of the condom to the penis and prevent stress concentration or shear force from removing the adhered barrier layer during mechanical disturbances, such as those associated with sexual activity. Optionally, the elastomeric ring may be attached to the end of one or more protruding arms and may be stretched to surround and secure the barrier layer to the base of the glans penis. Optionally, a contractile force may be applied to enhance the adhesion of the condom to the penis and prevent stress concentration or shear forces from removing the adhered barrier layer during mechanical disturbances, such as those associated with sexual activity. Optionally, the elastomeric ring may also enhance sexual sensation or pleasure and may comprise 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 outer side opposite the adhesive layer. The lubricant may be, for example, a water-based, silicone-based, or oil-based lubricant. Optionally, the barrier layer may have a spermicide on the outer side opposite the adhesive layer. The spermicide may be, for example, nonoxynol-9, octylphenylene glycol-9, benzalkonium chloride, lactic acid, methylphenidate, and other spermicides known in the art.

[0291] The geometry of the barrier layer can also be square, elliptical, spherical, rectangular, polygonal or curved polygonal, conical, tetrahedral, pyramidal or polyhedral, and can have a main dimension 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 can optionally include protruding arms extending from the corners or edges of the square, rectangular and polygonal or curved polygonal. The projecting arms may have an aspect ratio of approximately 1:1, 1:2, 1:5, 1:10, 1:20, or 1:100 or greater, and may be 1, 2, 3, 4, 5, 6, or more. They may have a length of approximately 0.5 cm, 1.0 cm, 2.0 cm, 3.0 cm, or 5.0 cm or longer, and a width of approximately 0.1, 0.2, 0.5, 1.0, or 2.0 cm or wider. Optional rings may have a ring cross-sectional diameter of approximately 0.1, 0.5, 1.0, 2.0 mm, or 3.0 mm or greater, and may have a total diameter approximately 0.25, 0.50, 0.75, or 1.0 times the diameter of the barrier layer.

[0292] In one implementation, the barrier layer is not tubular.

[0293] In another embodiment, the barrier layer is a geometry or shape that is then deformed into a second geometry or shape when applied to the penis.

[0294] In another embodiment, the barrier layer includes an inner adhesive layer that adheres the barrier layer to the penile skin located at or below the glans penis, the base of the glans penis, or below the base of the glans penis. The adhesive layer may extend to the ring or protruding arm portion of the diaphragm.

[0295] In another embodiment, the inner adhesive layer exhibits reversible or irreversible adhesive behavior in response to stimulation, enabling the diaphragm to selectively detach from the penile skin (i.e., detach on demand). Reversible or irreversible adhesive behavior can be triggered by exposure to temperature changes (e.g., temperature decreases), chemical changes, light, ultrasound, changes in ionic strength, pH changes, magnetic, electrical, or mechanical forces, and other stimuli or any combination thereof. Mechanical forces used for detachment include shearing and / or peeling or pulling at different frequencies or rates. In another embodiment, the adhesive layer is frequency- or force-responsive and maintains functional adhesion at higher forces or frequencies or shear rates, and can be removed using lower removal frequencies or forces or shear rates (e.g., by gentle peeling or pulling). In another embodiment, removal occurs with minimal or no pain, including gentle peeling or pulling. "Higher" and "lower" are relative to thresholds at which behavioral changes are observed. For force, this can be between 0.01 and 0.1 N, 0.1 and 1.0 N, 1.0 and 10.0 N, 10.0 and 100.0 N, or 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, or 0.1 and 1 MPa. For shear rate, this can be between 0.1 and 1 se Between ¹ and 1.0 and 10 se Between ¹ and 10 to 100 se Between ¹ and 100 to 1000 se Between ¹ and 1000 to 10000 se Between ¹ and 10,000, or between 100,000 and 100,000 se ¹ For frequency, this can be between 0.01 Hz and 0.1 Hz, 0.1 to 1.0 Hz, 1.0 to 10.0 Hz, 10.0 to 100.0 Hz, or 100.0 to 1000.0 Hz. Slight pulling or slight peeling refers to a removal action performed with a force, shear rate, or frequency below a threshold at which a change in behavior occurs.

[0296] In another embodiment, the inner adhesive layer may include two, three, or more adhesive regions that may exhibit different mechanical, chemical, and biological properties. These may include varying solubility parameters in various solvents, including water, vaginal fluid, or ejaculate fluid. Reversible or irreversible adhesive behavior can be triggered by simultaneous or sequential exposure to temperature changes, chemical changes, light, ultrasound, changes in ionic strength, pH changes, magnetic, electrical, or mechanical forces, and other stimuli or any combination thereof.

[0297] The thickness of the adhesive layer can be in the nanometer or micrometer range, having an adhesive layer thickness of about 0.01 micrometer to about 0.1 micrometer, about 1.0 micrometer, about 5.0 micrometer, about 10.0 micrometer, about 20.0 micrometer, about 30.0 micrometer, about 50.0 micrometer, about 100.0 micrometer, about 200 micrometer, about 300 micrometer, about 400 micrometer, about 600 micrometer, about 750 micrometer, about 1000 micrometer, about 2000 micrometer, about 3000 micrometer or more, and can be uniformly or patterned on the barrier layer. The patterned configuration can cover approximately 1%, approximately 5%, approximately 10%, approximately 25%, approximately 33%, approximately 50%, approximately 66%, approximately 75%, or approximately 100% of the total adhesive area within the barrier layer, or any combination thereof, and the adhesive area of ​​the barrier layer can cover approximately 1%, approximately 5%, approximately 10%, approximately 25%, approximately 33%, approximately 50%, approximately 66%, approximately 75%, or approximately 100% of the entire barrier layer. The patterned configuration of the adhesive can be annular, having single or multiple annular layers with a thickness of approximately 0.1, approximately 0.25, approximately 0.5, or approximately 1.0 mm or more; or it can be dot-patterned, as square, rectangular, or circular dots, covering approximately 1%, approximately 5%, approximately 10%, approximately 25%, approximately 33%, approximately 50%, approximately 66%, approximately 75%, or approximately 100% of the total adhesive area within the barrier layer, or any combination thereof. The patterned configuration can also be striped, with the stripe layer thickness varying by about 0.1, about 0.25, about 0.5, or about 1.0 mm or more, and the stripe layer covers about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75%, or about 100% of the total adhesive area within the barrier layer, or any combination thereof. The shape, size, or position of the pattern, or any combination thereof, can be uniform, non-uniform, or random. The cross-section of the adhesive layer can be uniform, non-uniform, circular, spherical, elliptical, or ellipsoidal, such as... Figure 3 As shown. The adhesive layer may cover only the glans penis and expose highly sensitive areas of the penis, such as the frenulum, and may have a reservoir that allows semen to flow under the glans penis toward and around the base of the penis.

[0298] In another embodiment, adhesive patterning can promote adhesive crack propagation or shear-responsive pressure-sensitive adhesive delamination. For example, adhesive patterning can enable the barrier layer to have sufficient adhesion to the glans penis while allowing the barrier layer to be peeled off with minimal or user-acceptable pain. Such patterning includes, but is not limited to, continuous rings or repeating dotted rings at the base of the barrier layer, with a length ranging from 0.1 to 3000 micrometers, more preferably 1 to 2000 micrometers, even more preferably 20 to 2000 micrometers, and a thickness ranging from 0.1 to 3000 micrometers, more preferably 1 to 2000 micrometers, even more preferably 5 to 1000 micrometers, even more preferably 10 to 600 micrometers, the dotted pattern covering 10% to 100% of the usable adhesive area in the base ring region, more preferably 20% to 100% of the usable adhesive area in the base ring region, even more preferably 30% to 100% of the usable area in the base ring region. Additional dot patterns, chain configurations, stripes, or other adhesive configurations can be patterned along the interior of the barrier layer to facilitate delamination via peeling (pressure-sensitive adhesive behavior).

[0299] In one embodiment, the adhesive layer may be swollen by volumetric expansion of about 1%, 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, or may be made soluble in solvents to achieve delamination, including solvents (including water-based solvents) or chemical solutions applied by the wipe. In another embodiment, the wipe denatures proteins to achieve delamination, for example, by introducing a solvent containing ethanol or isopropanol to chemically denature water and PEG-doped (i.e., non-volatile plasticizer) albumin. In another embodiment, the wipe contains a volatile solvent that is blocked from diffusion by a diaphragm to achieve delamination through chemical reaction, dissolution, denaturation, or swelling of the adhesive layer. In yet another embodiment... In another embodiment, the wipe contains a volatile additive that cools the wipe upon evaporation to achieve temperature-based delamination.

[0300] In another embodiment, the adhesive is a medical adhesive. In one embodiment, the adhesive allows for closure, filling of spaces, covering of surfaces, promotion of healing (e.g., wound healing), promotion of tissue regeneration, filling of spaces, covering of surfaces, support of injured body parts, fixation of two structures, or fixation of a medical device to the body, in each case partially or completely.

[0301] In one embodiment, the adhesive is suitable for external medical use, internal medical use, or both. In some embodiments, the adhesive is formulated to form bandages, sealants, coverings, dressings, etc.

[0302] In one particular implementation, the adhesive is used for fixation to prevent the adhesion of damaged tissues or organs.

[0303] In one particular implementation, the adhesive is a dental adhesive.

[0304] In one particular implementation, the adhesive is transparent.

[0305] The adhesive composition may be provided, for example, as a diaphragm or membrane. The diaphragm or membrane may comprise a continuous adhesive layer having opposing first and second surfaces.

[0306] The thickness of the diaphragm or membrane can be in the nanometer or micrometer range, having an adhesive layer thickness range of about 0.01 micrometer to about 0.1 micrometer, about 1.0 micrometer, about 5.0 micrometer, about 10.0 micrometer, about 20.0 micrometer, about 30.0 micrometer, about 50.0 micrometer, about 100.0 micrometer, about 200 micrometer, about 300 micrometer, about 400 micrometer, about 600 micrometer, about 750 micrometer, about 1000 micrometer, about 2000 micrometer, about 3000 micrometer or greater, and can be uniformly or patterned on the barrier layer. The patterned configuration can cover about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75%, or about 100% of the total adhesive area within the barrier layer, or any combination thereof, and the adhesive area of ​​the barrier layer can cover about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75%, or about 100% of the entire layer. In cases where medical adhesives are used in three-dimensional geometry (such as adhesive contraceptive devices), the patterned configuration of the adhesive can be a ring with a single or multiple concentric ring patterns; or in cases where the geometry of a planar device is used (such as for securing intravenous (IV) needles or tubes, catheters, bandages, wound dressings, or other uses of medical adhesives), a combination of continuous lines and dots with a thickness varying from about 0.1, about 0.25, about 0.5, or about 1.0 mm or greater can be used, and can be dot-patterned as square, rectangular, or circular dots, covering about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75%, or about 100% of the total adhesive area within the covering membrane or diaphragm, or any combination thereof. The patterned configuration can also be striped, with the stripe layer thickness varying by about 0.1, about 0.25, about 0.5, or about 1.0 mm or greater, and the stripe layer covering about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75%, or about 100% of the total adhesive area within the membrane or diaphragm, or any combination thereof. The shape, size, or position of the pattern, or any combination thereof, can be uniform, non-uniform, or random. The cross-section of the adhesive layer can be uniform, non-uniform, circular, spherical, elliptical, or ellipsoidal.

[0307] In another implementation, adhesive patterning can facilitate adhesive crack propagation or shear-responsive pressure-sensitive adhesive delamination. For example, adhesive patterning can enable the barrier layer to adhere sufficiently to the target site while allowing it to be peeled off with minimal or acceptable pain to the user. Such patterning includes, but is not limited to, continuous rings or repeating dotted rings at the base annular portion or edge annular portion of the barrier, with a length ranging from 0.1 to 3000 micrometers, more preferably 1 to 2000 micrometers, more preferably 20 to 2000 micrometers, and a thickness ranging from 0.1 to 3000 micrometers, more preferably 1 to 2000 micrometers, more preferably 5 to 1000 micrometers, more preferably 10 to 600 micrometers. The dotted pattern covers 10% to 100% of the area of ​​available adhesive in the annular region, more preferably 20% to 100% of the area of ​​available adhesive in the annular region, and more preferably 30% to 100% of the area of ​​available adhesive in the base annular region (in the case of medical adhesives using three-dimensional geometry (such as adhesive contraceptive devices)); or in the case of planar device geometry (such as for fixing intravenous (IV) needles or tubes, catheters, bandages, wound dressings or other uses of medical adhesives), a combination of continuous lines and dots can be used. Additional dot patterns, chain configurations, stripes, or other adhesive configurations can be patterned along the interior of the diaphragm or membrane to facilitate delamination via peeling (pressure-sensitive adhesive behavior).

[0308] The size of the diaphragm or membrane can be customized for a specific intended use, or it can be supplied in sheet or roll form. In one embodiment, the adhesive composition is supplied as tape.

[0309] In one embodiment, the diaphragm or membrane is sized from about ¼ inch to about 2 or 3 inches or more, although the preferred width in the embodiment may be from about ½ to about 1 or 1½ inches, and the length may be from about ½ inch to about 4 or 5 inches or more, although the preferred length in the embodiment may be from about 1 to about 2 or 3 inches. In another embodiment, the diaphragm or membrane is sized from about 5 to about 8 inches or more.

[0310] The shape of the diaphragm or membrane can vary. In one embodiment, the geometry of the diaphragm or membrane is square, elliptical, spherical, rectangular, polygonal, or curved polygonal.

[0311] In one embodiment, the adhesive composition comprises a proximal adhesive layer that adheres to a target substrate (e.g., skin or mucous membrane). In another embodiment, the inner adhesive layer exhibits stimulus-responsive reversible or irreversible adhesive behavior, enabling the adhesive composition to selectively delaminate from the surface to which it adheres.

[0312] In another embodiment, the adhesive is not in contact with or provided with any final barrier, but is provided in solid, liquid or other form and is provided to promote adhesion between skin, mucous membrane tissue or other biomass and an additional barrier comprising polyurethane, poly(vinyl chloride), polymer, latex or other barrier.

[0313] In one particular implementation, the adhesive is applied as a solid film that is sticky on both sides, followed by the application of additional barriers.

[0314] In one particular embodiment, the inner adhesive layer may include two, three, or more adhesive regions that may exhibit different mechanical, chemical, and biological properties. These may include varying solubility parameters in a variety of solvents, including water or biological fluids. Reversible or irreversible adhesive behavior can be triggered by simultaneous or sequential exposure to temperature changes, chemical changes, light, ultrasound, changes in ionic strength, pH changes, magnetic, electrical, or mechanical forces, and other stimuli or any combination thereof.

[0315] In one embodiment, the adhesive layer may be swollen by volumetric expansion of about 1%, 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, or may be made soluble in solvents to achieve delamination, including solvents (including water-based solvents) or chemical solutions applied by the wipe. In another embodiment, the wipe denatures proteins to achieve delamination, for example, by introducing a solvent containing ethanol or isopropanol to chemically denature water and PEG-doped (i.e., non-volatile plasticizer) albumin. In another embodiment, the wipe contains a volatile solvent that is blocked from diffusion by a diaphragm to achieve delamination through chemical reaction, dissolution, denaturation, or swelling of the adhesive layer. In yet another embodiment... In another embodiment, the wipe contains a volatile additive that cools the wipe upon evaporation to achieve temperature-based delamination.

[0316] The adhesive layer may comprise one or more linear or crosslinked polymers, including, 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(isotridecyl 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(methacrylate), poly(acrylates of C20-C100 or more carbons, methacrylates and their acrylamides), poly(acrylate- 2-Hydroxyethyl acrylate), poly(butoxymethyl acrylate), poly(butoxyethyl acrylate), poly(butoxypropyl acrylate), poly(butoxybutyl acrylate), poly(phenyl acrylate), poly(octadecyl acrylate), poly(octadecyl methacrylate), poly(acrylic acid), and polyacrylates or polymethacrylates having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or up to 100 carbons in the side chain and having 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or up to 100 or more oxygens in the side chain, poly(methacrylate), poly(acrylamide) such as poly(N-isopropylacrylamide), poly(dimethacrylamide), poly(methacrylamide) versions of the above acrylates, amorphous or semi-crystalline polyurethanes, polyethers (including poly(ethylene glycol)(PEG) compounds and acrylated or polyurethane-containing PEG compounds), epoxy resins, silicones or other adhesives suitable for contact with human skin. In one embodiment, the adhesive may comprise a linear or crosslinked polymer having side chains that optionally undergo crystallization and / or melting in a region near body temperature and room temperature (in the range of 0°C to 50°C, more specifically in the range of 5°C to 45°C, more specifically in the range of 10°C to 40°C, more specifically in the range of 15°C to 35°C). For clarity, side chain crystallization is optional.In another embodiment, the adhesive may comprise a complex homogeneous or heterogeneous blend comprising: (1) a primary side chain optionally crystallizable side chain adhesive polymer, (2) optional secondary optional crystallizable side chains, (3) optional tackifiers or plasticizers, such as glycerol-based compounds, phthalates, polyethylene glycol derivatives with molecular weights ranging from 1 to 1000 or more repeating units, C10-C40 linear or branched wax or modified wax components (such as n-butyl stearate or ethyl decanoate), (4) optional additional amorphous polymer blend phase or heterogeneous phase, and (5) optional crosslinking agent, which is optionally uniformly incorporated into the polymer network and optionally aggregates and acts as high stress concentration network sites to promote adhesive failure when needed.

[0317] In some embodiments, the main side chain optionally contains a crystallizable polymer ranging from about 40% to about 100%, more specifically, from about 50% to 100%. In a particular embodiment, the range is 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 contained therein.

[0318] In some embodiments, the secondary side chain may optionally be a crystallizable polymer ranging from about 0 to about 50%, more specifically from 1% to about 49%, more specifically from about 2% to about 48%, more specifically from about 3% to 47%, more specifically from about 5% to about 45%, or any additional range or value contained herein.

[0319] In some implementations, the tackifier or plasticizer ranges from 0% to 60%, more specifically from 0.01% to 60%.

[0320] In some embodiments, the amorphous polymer blend ranges from 0 to 60%. In one embodiment, the crosslinking agent ranges from 0 to 30 wt%, more preferably from 0.001 to 29 wt%, more specifically from 0.005 to 28 wt%, more specifically from 0.0075 to 28 wt%, more specifically from 0.01 to 27 wt%, more specifically from 0.02 to 26 wt%, more specifically from 0.05 to 26 wt%, more specifically from 0.1 to 25 wt%, more specifically from 0.15 to 24 wt%, more preferably from 0.15 to 10 wt%, more preferably from 0.15 to 2 wt%, more preferably from 0.15 to 1.5 wt%, and includes the ranges therein. Statistically, crosslinking agents can exhibit functionality with more than n=1 reaction sites, for example, statistically averaging n = 2, 3, 4, 5, 6, 7, 8, 9, 10 or more reaction sites, and can promote branching, hyperbranching, interpenetrating networks, semi-interpenetrating networks, and networks that are substantially homogeneous or partially homogeneous and partially heterogeneous or substantially heterogeneous in relation to phase blending or crosslink density concentration. For example, advantageous disintegration or delamination of skin adhesion (including removal of residual adhesive after peeling off the adhesive) can be achieved by concentrating the disintegration sites within the network through a heterogeneous crosslinking distribution or by forming a “swollen network” through the polymerization of crosslinking agents and monomers with different reactivity ratios, such as a blend of lauryl methacrylate and trimethylolpropane triacrylate (TMPTA) containing 0.5 wt% TMPTA and 1.0 wt% DMPA photoinitiator. In one embodiment, TMPTA can form a swollen gel network infiltrated with lauryl methacrylate monomer, which is subsequently polymerized to form a complex swollen network or semi-interpenetrating network (Semi-IPN). This allows the polymer flow of the cured network to occur at different shear rates or frequencies or force modes, achieving adhesive behavior. This allows the adhesive barrier to be functionally adhered to the skin or other surfaces and removed using low shear rate or low frequency deformation or peeling. This allows the polymer flow to dissipate energy and does not cause pain upon removal.Representative crosslinking agents include poly(ethylene glycol) diacrylates with an internal repeating unit range of 1 to 1000 or more, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate or trimethacrylate with an internal repeating unit range of 1 to 1000 or more, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate or tetramethacrylate with an internal repeating unit range of 1 to 1000 or more, pentafunctional and hexafunctional acrylates or methacrylates, and ethoxylated versions as described above (including dipentaerythritol hexaacrylate and ethoxylated dipentaerythritol hexaacrylate (with a repeating unit range of 1 to 1000 or more)), di, tri, tetra, penta, hexa or higher functional epoxide monomers, polythiols, polyolefins (cured by ultraviolet light, visible light, gamma or electron beam radiation, heat or hydrosilaneization). In another embodiment, a linear or branched polymer having 1 to 1000 or more repeating units, wherein the repeating units may or may not contain acrylates, is cured by ultraviolet light, visible light, gamma or electron beam radiation, heat or hydrosilylation, metal coordination (including coordination of titanium with polymeric acid side chains). In one embodiment, the ultraviolet curing composition for adhesives of the present invention comprises 0.001 to 10 wt%, more specifically 0.01 to 5 wt%, more specifically 0.1 to 5 wt% of a photoinitiator. In another embodiment, the photoinitiator comprises 2,2-dimethoxy-2-phenylacetophenone (DMPA), Eosin Y, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), lithium phenyl-2,4,6-trimethylbenzoylphosphine oxide (LAP), or a biocompatible photoinitiator.

[0321] In another embodiment, the adhesive comprises a polymer component including linear, branched and crosslinked polymers, which includes (1) main chain chemistry, (2) side chain chemistry, (3) crosslinking, and (4) additives.

[0322] Main-chain chemistry includes polymers made from monomers, including acrylates, methacrylates, thiols-acrylates Michael addition, acrylate amines Michael addition, epoxy thiols, epoxy amines, polyethyleneimine (PEI), thiols-olefins, alternating copolymers made from C=C electron-deficient and C=C electron-rich monomers, urethanes, ureas, acrylamides, methacrylamides, polyesters, polycarbonates, polyamides, peptides, peptides, Diels-Alder, lactide, and lactams, as well as ring-opening metathesis polymerization or olefin metathesis reactions.

[0323] Side-chain chemistry includes linkages formed from monomers, including acrylates, methacrylates, thiols-acrylates Michael additions, acrylate-amine Michael additions, epoxy thiols, epoxy amines, polyethyleneimine (PEI), thiols-olefins, alternating copolymers of C=C electron-deficient and C=C electron-rich monomers, urethanes, ureas, acrylamides, methacrylamides, polyesters, polycarbonates, polyamides, peptides, peptides, Diels-Alder, lactide, and lactams, as well as ring-opening metathesis polymerization or olefin metathesis reactions. Side-chain chemistry includes C1-C100 side-chain linkages achieved through the synthetic routes disclosed herein.

[0324] Crosslinking chemistry includes linking bonds made from monomers, including acrylates, methacrylates, thiols-acrylates Michael addition, acrylate amines Michael addition, epoxy thiols, epoxy amines, polyethyleneimine (PEI), thiols-olefins, alternating copolymers made from C=C electron-deficient + C=C electron-rich monomers, urethanes, ureas, acrylamides, methacrylamides, polyesters, polycarbonates, polyamides, peptides, peptides, Diels-Alder, lactide, and lactams, as well as ring-opening metathesis polymerization or olefin metathesis reactions.

[0325] Acrylic monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, methoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, ethoxylated (2) hydroxyethyl acrylate, N-vinylpyrrolidone, 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) diacrylate, etc. Methacrylates, 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-dimethylacrylamide, Ethylene glycol diacrylate (EGDA), Triethylene glycol diacrylate (TEGDA), Propylene glycol diacrylate (PGDA), Butylene glycol diacrylate (BDD) A) Neopentyl glycol diacrylate (NPGDA), pentaerythritol tetraacrylate (PETA), 1,4-butanediol diacrylate (BDA), bis(trimethylolpropane)tetraacrylate (DTMPTA), bisphenol A ethoxylated 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 (HD) Trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate (TPGDA), pentaerythritol triacrylate (PETA), dipentaerythritol pentaacrylate (DPEPA), tri(2-hydroxyethyl) isocyanurate triacrylate (THEIC-TA), triethylene glycol dimethacrylate (TEGDMA), triallyl isocyanurate (TAIC), triethylene glycol diacrylate (TEGDA), ethoxylated trimethylolpropane triacrylate (ETMPTA), and triallyl cyanurate (TAC).

[0326] Vinyl ether monomers include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether (DVE-PEG), polypropylene glycol divinyl ether (DVE-PPG), poly(ethylene glycol) methyl ether divinyl ether (DVE-PEGME), poly(ethylene glycol) butyl ether divinyl ether (DVE), poly(ethylene glycol) phenyl ether divinyl ether (DVE-PEGPhE), glycerol divinyl ether (DVE-Gly), 1,4-cyclohexanediethanol divinyl ether (DVE-CHDM), and neopentyl glycol divinyl ether (DVE-NPG).

[0327] Allyl monomers include diallyl phthalate (DAP), diallyl maleate (DAM), diallyl succinate (DAS), diallyl fumarate (DAF), diallyl adipate (DAA), diallyl sebacic acid (DAS), diallyl terephthalate (DAT), diallyl isophthalate (DAI), diallyl itaconic acid (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), and triallyl cyanide (Triallyl). cyanide) (TACN), phenyl-1,2,4-tricarboxylic acid triallyl ester (TABTC), pyromellitic tricarboxylic acid triallyl ester (TATM), tris(2-hydroxyethyl) isocyanurate triallyl ether (THEIC-TAE).

[0328] Methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, stearyl methacrylate, lauryl methacrylate, isodecanyl 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) dipropylene glycol Acrylates, poly(ethylene glycol) dimethacrylate, poly(ethylene glycol) monoacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated trimethylolpropane triacrylate, hydroxypropyl methacrylate, methacrylic acid, acryloyloxyethyl trimethylammonium chloride, diethylaminoethyl methacrylate, butylaminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, methacryloyloxyethyl phthalate, N-vinylpyrrolidone, N-isopropylacrylamide, and cyclopropyl methacrylate.

[0329] Thiol monomers include 3-mercaptopropionic acid, mercaptoacetic acid, 3-mercapto-1-propanol, 2-mercaptoethanol, 2-(2-mercaptoethoxy)ethanol, 2-(2-mercaptopropionylamino)ethanol, ethyl acrylate-2-(2-mercaptosuccinoyl)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-trioxadecanthiol, 3-mercapto-1,2-propanediol, 2,2'-dithiodiethanol, and N-acetyl... L-cysteine, L-cysteine, 2-(2-mercaptoethyl)pyridine, 4-(2-mercaptoethyl)morpholine, 3-mercapto-1,2,4-triazole, thiophene, pentaerythritol tetra(3-mercaptopropionate) (PETMP), trimethylolpropane tri(3-mercaptopropionate) (TMPMP), triethanolamine tri(3-mercaptopropionate) (TEAMP), tri(2-hydroxyethyl) isocyanurate tri(3-mercaptopropionate) (THEICMP), bis(3-mercaptopropyl) sulfide (BMPS), 1,2-ethylenedithiol (EDT), 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and 1,8-octanedithiol.

[0330] Epoxy monomers include bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE), phenolic varnish diglycidyl ether (NGDE), phenolic varnish diglycidyl ether (PNGDE), alicyclic epoxy resins, fatty alcohol glycidyl ethers, aromatic alcohol glycidyl ethers, triglycidyl isocyanate (TGIC), 1,4-butanediol diglycidyl ether (BDDGE), neopentyl glycol diglycidyl ether (NPGDGE), propylene glycol diglycidyl ether (PGDGE), epoxidized soybean oil (ESO), epoxidized linseed oil (ELO), dicyclopentadienyl epoxy resins, tetrafunctional epoxy resins, and epoxy phenolic varnish resins.

[0331] 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, isophorone diamine, Jeffamine D-230, Jeffamine T-403, Jeffamine M-207, and Jeffamine EDR-148.

[0332] Electron-rich monomers include vinyl ethers (e.g., methyl vinyl ether, ethyl vinyl ether), vinyl acetate, allyl alcohol, allylamine, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxymethylallylamine, N-hydroxymethylvinylacetamide, 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, as well as N-vinylpyrrolidone, N-vinylformamide, N-vinylpyridine, styrene, and styrene derivatives.

[0333] Electron-deficient 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, α-methylstyrene, maleimide, N-phenylmaleimide and N-butylmaleimide, and maleic anhydride.

[0334] 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.

[0335] Lactam monomers include caprolactam, valproic acid lactam, heptanolactam, octyl lactam, laurolactam, propionolactam, 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.

[0336] Lactone monomers include β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, ω-pentadecanolactone, β-butyrolactone, δ-decylactolactone, ε-decylactolactone, γ-decylactolactone, δ-dodecylactolactone, γ-dodecylactolactone, α-methylene-γ-butyrolactone, β-methyl-γ-butyrolactone, β-methyl-γ-valerolactone, and γ-caprolactone.

[0337] Alcohol monomers include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, neopentanediol, diethylene glycol, triethylene glycol, tetraethylenediol, polyethylene glycol (PEG), polypropylene glycol (PPG), polycaprolactone diol, polyhydroxymethylpropane, HPHMB (hydroxyneoptiyl hydroxymethyl butyrate), and 1,4-cyclohexanediethanol.

[0338] 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 dodecanoic acid.

[0339] Isocyanate monomers include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HMDI), 4,4'-methylene bis(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.

[0340] Diels-Alder monomers include maleic anhydride, furan, cyclopentadiene, N-phenylmaleimide, anthracene, N-ethylmaleimide, N-phenylnorbornene, N,N-dimethylmaleimide, 2,5-dimethylfuran, tetracyanoethylene, and methyl vinyl ketone.

[0341] 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, and tricyclo[5.2.1.0(2,6)]dec-8-ene (TCD-diene).

[0342] Additives include plasticizers. Plasticizers include triacetin, glyceryl monooleate (GMO), glyceryl monostearate (GMS), glyceryl tristearate (tristearate), glyceryl tributyrin, glyceryl tripropionate (triproprionin), glyceryl trioleate (triolein), glyceryl dilaurate (GDL), glyceryl dimyristicate (GDM), glyceryl distearate (GDS), diethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), and other plasticizers. 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 any side of the ester.

[0343] 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, and aromatic resins.

[0344] Additives include fillers. Fillers include calcium carbonate, talc, silica, glass fiber, carbon black, barium sulfate, kaolin, mica, wollastonite, alumina, titanium dioxide, cellulose, wood flour, fly ash, and graphite.

[0345] In one embodiment, a Michael addition reaction under alkaline catalysis can be used to form a polymer, prepolymer, monomer, or curable mixture. In one embodiment, a thiol-acrylate or amine-acrylate reaction can be used. In one embodiment, these reactions can be catalyzed by any amine, tertiary amine, DABCO, dipropylamine, or triethylamine mentioned herein. In one embodiment, a thiol / epoxy reaction under similar catalytic conditions can be used to form a polymer, prepolymer, monomer, or curable mixture. In one embodiment, the mixture is prepared in a one-pot process.

[0346] In one embodiment, a compostable, bio-based, or biodegradable adhesive is prepared from the ingredients described herein. In one embodiment, the compostable adhesive is prepared from plasticized polycaprolactone or plasticized poly(lactic acid). In another embodiment, plasticization is performed to reduce glass transition or increase tackiness. In one embodiment, the adhesive is suitable for food-grade applications, such as fruit product labels.

[0347] In one embodiment, polymers having side chains or dangling chain ends between C6 and C30 carbons are preferred, wherein alkyl linkages are further preferred, C7, C8, C9 up to C18 linkages are preferred, and C12 to C18 linkages are further preferred. In one embodiment, polymers having more than 80 wt% side chains (with the same C linkage preference) are preferred. In another embodiment, polymers having C6 to C18 side chains or dangling chain ends are prepared from acrylates, methacrylates, alcohols, carboxylic acids, electron-rich olefins, electron-deficient olefins, epoxy resins, amines, ROMPs, Diels-Alders, lactones, lactams, peptides, peptide-like substances, acrylamides, methacrylamides, thiols, vinyl and allyl monomers. In another embodiment, a lightly crosslinked polymer, such as one provided by a dot concentration including but not limited to 0.4 wt%, 0.6 wt%, 0.75 wt%, or 0.95 wt% of trimethylolpropane triacrylate in poly(lauryl) or poly(stearyl methacrylate) polymers (including but not limited to 99.6 wt%, 99.4 wt%, 99.25 wt%, or 99.05 wt% of lauryl methacrylate or stearyl methacrylate), is preferred for providing a shear-rate responsive polymer that is tacky to human skin and can subsequently be removed from human skin with minimal pain, and for any residual adhesive left on human skin that can be removed with minimal pain by slight abrasion. In yet another embodiment, these long-side-chain / low-crosslink-density polymers can be prepared from any of the monomers, crosslinking agents, or other components described herein via any of the reaction processes described herein. For example, linear or branched poly(ethyleneimine) (PEI) can be modified at the side chains and chain ends via Michael addition under alkaline catalysis using lauryl acrylate or octadecyl acrylate, or via an isocyanate / amine reaction using lauryl isocyanate or octadecyl isocyanate. In another embodiment, mono-, di-, tri-, and tetrafunctional thiols and olefin monomers can be used in combination with a monofunctional component (such as lauryl mercaptopropionate or dodecyl vinyl ether) to prepare stoichiometric or deviated thiols-enes, such that the monofunctional component accounts for 0.1, 0.2, 0.3, 0.4, or 0.5 or more moles of the total thiols-ene composition. In another representative embodiment, a free radical alternating polymerization is used to prepare an alternating copolymer comprising maleimide or N-butylmaleimide and dodecyl vinyl ether, which can be lightly crosslinked with less than wt% dodecyl vinyl ether or polymethacrylate or acrylate to form a heterogeneous crosslinked network with low crosslink density and high wt% C12 side chains (60, 70, 80, 90 or more wt% C6 or larger alkyl side chains, preferably C12-C18). In another embodiment, octadecylamine is polymerized with a Michael addition comonomer (such as ethylene glycol diacrylate or hexanediol diacrylate) under alkaline catalytic conditions.In one embodiment, the resulting poly(β-amino ester) is prepared with a C=C:NH2 ratio of 1:25:1.0 (reaction with the bis(NH2) of acrylates), resulting in acrylate-terminated groups. The acrylate-terminated poly(β-amino ester) reaction product can be cured with UV light, and the crosslinking density can be reduced by adding monofunctional acrylates or methacrylates (such as stearyl methacrylate, lauryl methacrylate, stearyl acrylate, or lauryl acrylate) or by adding thiol chain transfer agents or capping agents (such as PETMP, IOMP, EGBMP, or 1,10-decanedithiol, or PETMP). In another embodiment, a similar Michael addition synthesis process can be used for thiol / acrylate Michael addition reaction products, preferably with an excess of acrylates.

[0348] In another embodiment, the adhesive is a semi-crystalline polyurethane elastomer that is linear or crosslinked, and has segments including polyether, polyester, polyurethane, polyurethane urea, poly(isoprene), poly(butadiene), or other crystalline segments, as described above or by other methods.

[0349] In another embodiment, the adhesive is cross-linked using the aforementioned cross-linking chemicals or other methods via a latent reaction after being processed onto the diaphragm. For example, residual epoxide and alcohol or amine chemicals may be used to achieve cross-linking after the adhesive is dip-coated onto the diaphragm barrier layer or applied by spraying or roll-to-roll coating methods.

[0350] In another embodiment, the adhesive is self-healing because it can be prepared separately from the barrier layer, applied to the barrier layer in an additional step, and optionally possess regenerative adhesiveness after removal from the skin or other application surface. An example of a transfer process that applies a separately prepared adhesive layer to the barrier layer is pad printing. Another example is that the adhesive can be prepared separately from the barrier layer and extruded and transferred to the barrier layer through an orifice or nozzle. Yet another example is that the adhesive can be prepared on a mold or die separate from the barrier layer, and the barrier layer is transferred to the adhesive as a solid layer, or in the form of a deposited liquid transferred by dip coating, spraying, brushing, painting, or roller coating.

[0351] In another embodiment, the adhesive is a linear or branched cross-linked polymer network, wherein the cross-linked polymer network contains 10 or more ester or thioester linkages, which hydrolyze in the presence of an added base or a thiol-containing compound or an amino-containing compound, wherein the hydrolysis causes the adhesive to dissolve and detach from the penile skin.

[0352] In another embodiment, the adhesive layer may be a linear or branched polymer comprising the product of a radical addition polymerization of mono-, di-, tri-, tetra-, penta-, and hexa-functional thiol-ene components (including triallyl isocyanurate, pentaerythritol tetra(3-mercaptopropionate), or any thiol-ene monomer component disclosed herein). In one embodiment, the thiol-ene adhesive may exhibit stimuli-responsive adhesive behavior when cooled below its glass transition temperature. In another embodiment, the thiol-ene adhesive layer may exhibit chemically responsive adhesive behavior, for example, thioether linkages may be oxidized by common oxidants such as hydrogen peroxide to form reversibly cleared disulfide linkages.

[0353] In another embodiment, the adhesive layer may contain additives that provide a physical pathway for delamination, such as water- or solvent-chemically swellable particulate additives, such as poly(sodium acrylate) with a molecular weight ranging from 1,000 to 5,000,000 Daltons, more specifically from 1,000 to 1,000,000 Daltons, more specifically from 1,000 to 1,000,000 Daltons, with a particle size ranging from 1 micrometer to 1,000 micrometers, more specifically from 20 micrometers to 800 micrometers, more specifically from 20 to 300 micrometers, and a concentration ranging from 0.01 to 95 wt%, more specifically from 0.1 to 75 wt%, more specifically from 1 to 60 wt%, more specifically from 2 to 55 wt%.

[0354] In another embodiment, the particulate additive can reduce the diffusion of water or other solvents into the adhesive layer and can be a hydrophobic component, such as stearic acid, hydrophobic fumed silica, or polyethylene wax, with a molecular weight ranging from 1 million to 5 million Daltons, more specifically from 1 million to 1 million Daltons, more specifically from 2 million to 1 million Daltons, a particle size ranging from 1 micrometer to 1,000 micrometers, more specifically from 20 micrometers to 800 micrometers, more specifically from 20 to 300 micrometers, and a concentration ranging from 0.01 to 95 wt%, more specifically from 0.1 to 75 wt%, more specifically from 1 to 60 wt%, more specifically from 2 to 55 wt%.

[0355] In another embodiment, the particulate additive can generate physical sites for increasing or decreasing skin adhesion and can be stimulus-responsive in nature. The component generating the physical sites for enhancing or decreasing skin adhesion can be a ceramic additive, such as fumed silica, zinc oxide, or titanium dioxide, or a polymer with a molecular weight ranging from 1,000 to 5,000,000 Daltons, more specifically 1,000,000 to 1,000,000 Daltons, more specifically 2,000,000 to 1,000,000 Daltons, with a particle size ranging from 1 micrometer to 1,000 micrometers, more specifically 20 to 300 micrometers, and a concentration ranging from 0.01 to 95 wt%, more specifically 0.1 to 75 wt%, more specifically 1 to 60 wt%, more specifically 2 to 55 wt%.

[0356] In another embodiment, the adhesive layer may comprise multiple adhesives, which are applied together or separately to the barrier layer. For example, the adhesive layer may comprise a hydrophobic, water-insoluble layer with a length of approximately 0.1 to 2 cm, more specifically 0.2 to 1 cm, and more specifically 0.25 to 1 cm, along its outer edge along the circumference of the diaphragm, and a hydrophilic, water-soluble layer above the hydrophobic adhesive layer, as shown in Figure 2. In one embodiment, the hydrophobic outer adhesive layer may be stimuli-responsive.

[0357] In another embodiment, the additive of the present invention can act as a nucleating agent to stimulate a change in the adhesive behavior of the responsive adhesive upon cooling and crystallization. Adding nucleating agents such as nanoscale fumed silica and polyethylene wax can be used to regulate the crystallization temperature of adhesives exhibiting a crystallization transition, such as poly(octadecyl methacrylate)). The nucleating additive comprises an additive with a particle size ranging from 1 nm to 1000 micrometers, more specifically from 10 nm to 500 micrometers, and more specifically from 10 nm to 250 micrometers. The nucleating additive can be blended with the adhesive in solution blending, high-shear blending, or other blending techniques, or can be generated in situ during adhesive preparation or contraceptive diaphragm formation by techniques including precipitation or phase separation. For example, stearic acid can be mixed with the adhesive solution under high-shear conditions to form a nanophase that remains dispersed in the adhesive blend (such as poly(stearyl methacrylate)).

[0358] In another embodiment, the additive can act as a crack propagation agent to facilitate adhesive failure during mechanical peeling removal.

[0359] The styrene-butadiene rubber (SBR) suitable for use in the present invention includes those used in the manufacture of pressure-sensitive tapes, including synthetic elastomers derived from styrene and butadiene. The SBRs suitable for use in the present invention, whether solvent-based or water-based, include SBRs having different percentages of bound styrene, average molecular weights and their distribution, and the presence of functional groups introduced during polymerization.

[0360] The adhesive layer may comprise linear or crosslinked polymers, including liquid crystal polymers with a thermal transition range of -10°C to 50°C, more specifically 0°C to 40°C, more specifically 5°C to 35°C, and more specifically 5°C to 20°C. The liquid crystal polymer compositions suitable for use in this invention include thiol-olefin and thiol-acrylate polymers prepared by base-catalyzed Michael addition or free radical polymerization processes, including those prepared from: thiol structural units such as 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanedithiol, 1,12-dodecanedithiol, hexanediol diacrylate, octanediol diacrylate, decanediol diacrylate, and diacrylates containing mesocrystalline materials 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]propyl acrylate).

[0361] Diacrylate mesocrystalline compounds include, but are not limited to, –M 257 - 4-(3-acryloyloxy-propoxy)benzoic acid 2-methyl-1,4-phenylene ester, and –RM 82 - 1,4-bis[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-toluene.

[0362] In one embodiment, radical polymerization can be used to crosslink acrylate-functionalized liquid crystal networks. Click chemistry reactions (such as Michael addition reactions) can also be used to introduce soft, flexible segments between mesocrystalline monomers to reduce Tg and achieve elastomeric behavior under ambient conditions. In one embodiment, dithiols can be used as flexible spacer groups, including but not limited to: ethylenedithiol, propylenedithiol or any other dithiol having a full carbon backbone, 2,2'-(ethylenedioxy)diethylenethiol or any other dithiol having a polyethylene glycol backbone, 1,4-phenylenediol, 4,4'-biphenyldithiol, ethylene bis(thioglycolate), and ethylene glycol dimercaptopropionate.

[0363] In another embodiment, amine-functionalized monomers, in addition to thiols, can also be used in a similar manner. For example, n-butylamine can be used as a flexible chain extender or spacer for mesocrystalline monomers. Acrylate-functionalized mesocrystalline oligomers can be produced by combining non-stoichiometric diacrylate mesocrystalline monomers with dithiol monomers or diacrylate mesocrystalline monomers with difunctional amines using Michael addition catalysts such as triethylamine or dipropylamine. In either case, an excess of acrylate functional groups is optionally preferred. These oligomers can then be photocrosslinked to form an LCE network.

[0364] In one embodiment, LCE can be synthesized in a one-pot process using a thiol or amine-functionalized crosslinking agent with a functionality of 2 or higher. Such a one-pot process can be used for both radical and Michael addition polymerization methods. Examples include, but are not limited to, pentaerythritol tetramercaptoacetate (PETMA), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), and dipentaerythritol tetra(3-mercaptopropionate).

[0365] The adhesives described herein contain a stimulus-responsive polymer, and optionally one or more additional polymers.

[0366] In some embodiments, the stimulus-responsive polymer has a glass transition temperature (Tg) ranging from 0°C to 50°C, 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, from 20°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.

[0367] In some embodiments, the stimulus-responsive polymer has a glass transition below ambient temperature, for example, 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.

[0368] In some embodiments, the stimulus-responsive polymer has a crystallization melt transition below ambient temperature, for example, 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.

[0369] In some embodiments, the stimulus-responsive polymer comprises a single copolymer. In some embodiments, the stimulus-responsive polymer comprises a blend of two or more homopolymers or copolymers, comprising a copolymer structure of two or more block, gradient, and random copolymers.

[0370] In some embodiments, one or more polymers are selected from, for example, polyacrylates, polymethacrylates, polyurethanes, polyolefins, polyethers, silicones, polyepoxys, synthetic rubbers, or other adhesives suitable for human skin, including their derivatives, copolymers, and mixtures.

[0371] In some implementations, the stimulus-responsive polymer comprises one or more polyacrylate or polymethacrylate polymers.

[0372] In some embodiments, the stimulus-responsive polymer comprises one or more polyacrylates or polymethacrylates having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or up to 100 carbons in its side chain and 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or up to 100 or more oxygens in its side chain.

[0373] 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(C15 acrylate), poly(C16 acrylate), poly(C17 acrylate), poly(C18 acrylate), poly(C19 acrylate), poly(acrylates, methacrylates and their acrylamides of C20-C100 or more carbons), poly(2-hydroxyethyl acrylate), poly(butoxymethyl acrylate), poly(butoxyethyl acrylate), poly(butoxypropyl acrylate), poly(butoxybutyl acrylate), poly(phenyl acrylate), poly(octadecyl acrylate), poly(octadecyl methacrylate), and poly(acrylic acid).

[0374] In some embodiments, the stimulus-responsive polymer comprises polymethacrylate, a polymethacrylate copolymer, or a blend thereof. The copolymer is derived from at least one methacrylate monomer and at least one polymerizable comonomer, including any monomer disclosed herein.

[0375] In some embodiments, the stimulus-responsive polymer comprises crosslinked polymethacrylate. The crosslinking agent may be multifunctional. In one embodiment, the stimulus-responsive polymer comprises polymethacrylate crosslinked with acrylate. In some embodiments, the polymethacrylate is poly(laurate methacrylate), and the acrylate crosslinking agent is TMPTA. The weight ratio of lauryl methacrylate to TMPTA may vary.

[0376] In some implementations, the weight ratio is 98:2, 98.5:1.5, or 99:1, or more specifically, 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 thereof.

[0377] In some implementations, the stimulus-responsive polymer does not contain polyacrylate or polymethacrylate.

[0378] In some implementations, the stimulus-responsive polymer comprises one or more amorphous or semi-crystalline polyurethanes.

[0379] In some embodiments, the stimulus-responsive polymer comprises a semi-crystalline polyurethane elastomer having segments including polyether, polyester, polyurethane, polyurethane urea, poly(isoprene), poly(butadiene), or other crystalline segments.

[0380] In some embodiments, the stimulus-responsive polymer comprises a semi-crystalline polyurethane elastomer that is linear or cross-linked and has segments including polyether, polyester, polyurethane, polyurethane urea, poly(isoprene), poly(butadiene), or other crystalline segments.

[0381] In some implementations, the stimulus-responsive polymer does not contain polyurethane.

[0382] In some embodiments, the stimulus-responsive polymer comprises a polyolefin. In some embodiments, the polyolefin is polyisoprene.

[0383] In some embodiments, the stimulus-responsive polymer comprises at least one polyether, such as a poly(ethylene glycol) (PEG) compound and an acrylated or polyurethane-containing PEG compound.

[0384] In some embodiments, the stimulus-responsive polymer comprises at least one polyepoxy. In some embodiments, the polyepoxy comprises one or more epoxy monomers disclosed herein. In some embodiments, the stimulus-responsive polymer does not comprise a polyepoxy. In some embodiments, the polyepoxy comprises one or more silicone monomers disclosed herein.

[0385] In some embodiments, the stimulus-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.

[0386] In some implementations, the stimulus-responsive polymer does not contain silicone polymers.

[0387] In some embodiments, the stimulus-responsive polymer comprises at least one synthetic rubber.

[0388] In some embodiments, the stimulus-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 suitable for use in this disclosure, whether solvent-based or aqueous, include SBRs with different percentages of bound styrene, average molecular weights and their distributions, and the presence of functional groups introduced during polymerization. The molecular weight range of SBRs is from 10 to 1,000,000 g / mol, more specifically from 25,000 to 750,000 g / mol, and more specifically from 50,000 to 500,000 g / mol. SBRs typically exhibit low water absorption, less than 1 wt% water, more specifically less than 0.5 wt% water, more specifically 0.1 wt% water, and more specifically less than 0.05 wt% water.

[0389] In some implementations, the stimulus-responsive polymer does not contain synthetic rubber.

[0390] In some embodiments, the stimulus-responsive polymer comprises a thiol monomer. Exemplary thiol monomers include, but are not limited to: 3-mercaptopropionic acid; mercaptoacetic acid; 3-mercapto-1-propanol; 2-mercaptoethanol; 2-(2-mercaptoethoxy)ethanol; 2-(2-mercaptopropionylamino)ethanol; ethyl acrylate-2-(2-mercaptosuccinoyl)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-trioxadecanthiol; 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; thiophene; pentaerythritol tetra(3-mercaptopropionate) (PETMP); trimethylolpropane tri(3-mercaptopropionate) (TMPMP); triethanolamine tri(3-mercaptopropionate) (TEAMP); tri(2-hydroxyethyl)isocyanurate tri(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.

[0391] In some embodiments, the stimulus-responsive polymer is a linear or branched cross-linked polymer network, wherein the cross-linked polymer network contains 10 or more ester or thioester linkages that hydrolyze in the presence of an added base or a thiol-containing compound or an amino-containing compound, wherein the hydrolysis causes the adhesive to dissolve and detach from the penile skin.

[0392] In another embodiment, the stimulus-responsive polymer can be a linear or branched polymer comprising the product of a radical addition polymerization of mono-, di-, tri-, tetra-, penta-, and hexa-functional thiol-ene components (including triallyl isocyanurate, pentaerythritol tetra(3-mercaptopropionate), or any thiol-ene monomer component disclosed herein). In some embodiments, the thiol-ene adhesive may exhibit stimulus-responsive adhesive behavior when cooled below its glass transition temperature. In some embodiments, the thiol-ene adhesive layer may exhibit chemically responsive adhesive behavior, for example, thioether linkages are oxidized by common oxidants such as hydrogen peroxide to form reversibly cleared disulfide linkages.

[0393] In some embodiments, the stimulus-responsive polymer includes linear or cross-linked polymers, including liquid crystal polymers with a thermal transition range of -10°C to 50°C, more specifically 0°C to 40°C, more specifically 5°C to 35°C, and more specifically 5°C to 20°C. Suitable liquid crystal polymer compositions include thiol-olefin and thiol-acrylate polymers prepared by base-catalyzed Michael addition or free radical polymerization processes, including those prepared from thiol structural units such as 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanedithiol, 1,12-dodecanedithiol, hexanediol diacrylate, octanediol diacrylate, decanediol diacrylate, and diacrylates containing mesocrystalline materials such as RM105 - 4-(6-acryloyloxyhexyloxy)benzoic acid (4-cyanophenyl ester), RM23 - 4-methoxyphenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate, CB3A - 3-[(3′-cyanobiphenyl-3-yl)oxy]propyl acrylate). Diacrylate mesocrystalline materials include, but are not limited to, RM 257 - 4-(3-acryloyloxy-propoxy)benzoic acid 2-methyl-1,4-phenylene ester and RM 82 - 1,4-bis[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-toluene.

[0394] In some embodiments, radical polymerization can be used to crosslink acrylate-functionalized liquid crystal networks. Click chemistry reactions (such as Michael addition reactions) can also be used to introduce soft, flexible segments between mesocrystalline monomers to reduce Tg and achieve elastomeric behavior under ambient conditions. In some embodiments, dithiols can be used as flexible spacer groups, including but not limited to: ethylenedithiol, propylenedithiol, or any other dithiol having a full carbon backbone, 2,2'-(ethylenedioxy)diethylenethiol, or any other dithiol having a polyethylene glycol backbone, 1,4-phenylenediol, 4,4'-biphenyldithiol, ethylene bis(thioglycolate), and ethylene glycol dimercaptopropionate.

[0395] In some embodiments, amine-functionalized monomers, in addition to thiols, can also be used in a similar manner. For example, n-butylamine can be used as a flexible chain extender or spacer for mesocrystalline monomers. Acrylate-functionalized mesocrystalline oligomers can be produced by combining non-stoichiometric diacrylate mesocrystalline monomers with dithiol monomers or diacrylate mesocrystalline monomers with difunctional amines using Michael addition catalysts such as triethylamine or dipropylamine. In either case, an excess of acrylate functional groups is optionally preferred. These oligomers can then be photocrosslinked to form an LCE network.

[0396] In some embodiments, LCEs can be synthesized in a one-pot process using thiols or amines with a functionality of 2 or higher. Such one-pot methods can be used for both radical and Michael addition polymerization methods. Examples include, but are not limited to, pentaerythritol tetramercaptoacetate (PETMA), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), and dipentaerythritol tetra(3-mercaptopropionate).

[0397] In some embodiments, the stimulus-responsive polymer comprises linear or crosslinked polymers, including silicone polymers, such as high molecular weight linear siloxane polymers and highly condensed silicate tackifying resins. Tackifying resins or tackifiers contain low molecular weight compounds with high glass transition temperatures used in formulating adhesives to increase tackiness, the stickiness of the adhesive surface. Tackifiers include resins (e.g., rosin and its derivatives, terpenes and modified terpenes, aliphatic, alicyclic, and aromatic resins (C5 aliphatic resins, C9 aromatic resins, and C5 / C9 aliphatic / aromatic resins), hydrogenated hydrocarbon resins and mixtures thereof, terpene-phenolic resins (TPR, often used with ethylene-vinyl acetate adhesives)), and phenolic varnishes. Suitable silicone rubber-based pressure-sensitive adhesives include special tackifiers based on “MQ” silicate resins, which consist of a monofunctional trimethylsilane (“M”) reacted with a tetrafunctional silicon tetrachloride (“Q”).

[0398] In some embodiments, the stimulus-responsive polymer exhibits one or more glass transition (Tg), crystallization temperature (Tc), melting temperature (Tm), or other thermal transitions 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 higher, as measured by differential scanning calorimetry (DSC) Tg, Tc, Tm peak inflection points or by dynamic mechanical analysis loss modulus or tan δ peak (at 1 Hz).

[0399] In some embodiments, the stimulus-responsive polymer may be a linear, brush-like, star-like, dendritic, or branched polymer with a weight-average molecular weight (Mw) of about 1 kDa, about 5 kDa, about 10 kDa, about 15 kDa, about 20 kDa, about 30 kDa, about 50 kDa, 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 higher.

[0400] In some implementations, the stimulus-responsive polymer is a cross-linked polymer that provides a semi-interpenetrating network or serves as an interpenetrating network.

[0401] In some implementations, the stimulus-responsive polymer is petroleum-based.

[0402] In some implementations, the stimulus-responsive polymer is partially or entirely bio-based.

[0403] In some embodiments, the stimulus-responsive polymer is a compostable, bio-based, or biodegradable polymer, such as that prepared from plasticized polycaprolactone or plasticized poly(lactic acid). In some embodiments, plasticization is performed to reduce glass transition or increase adhesion.

[0404] In some implementations, stimulus-responsive polymers are suitable for food-grade applications, such as for labeling agricultural products or fruits.

[0405] The amount of stimuli-responsive polymer present in the adhesive can vary. In some embodiments, the stimuli-responsive polymer constitutes at least 70 wt% of the adhesive, for example, at least about 80 wt%, at least 90 wt%, or at least 95 wt%.

[0406] In some embodiments, the stimulus-responsive polymer comprises at least 90 wt% of the adhesive, 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%.

[0407] In some embodiments, the linear and crosslinked polymer comprises (i) a main chain; (ii) at least one side chain; (iii) a crosslinker; and (iv) an additive. The main chain (i), the side chain (ii), and / or the crosslinker (iii) may comprise one or more monomers.

[0408] In some implementations, the monomers comprising (i), (ii) and (iii) may be the same monomer or different monomers.

[0409] The monomer can be any suitable monomer. In one embodiment, the monomer is selected from acrylate monomers, allyl monomers, thiol monomers, epoxy monomers, amine monomers, electron-rich monomers, electron-deficient monomers, lactam monomers, lactone monomers, alcohol monomers, carboxylic acid monomers, isocyanate monomers, Diels-Alder monomers, ring-opening metathesis monomers, etc.

[0410] In some implementations, the stimulus-responsive polymer does not contain acrylic-based adhesives containing unreacted polyol plasticizers.

[0411] In some embodiments, the stimulus-responsive polymer is not included in the hydrophobic polyoxyethylene-based adhesive derived from poly(ethylene glycol) prepared in the presence of a plasticizer.

[0412] In some embodiments, the stimulus-responsive polymer does not contain 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 contain an acrylic pressure-sensitive adhesive and (i) an elastomer with a tackifying resin or (b) a thermoplastic elastomer.

[0413] The adhesive described herein can be used as an adhesive layer in contraceptive devices disclosed herein (e.g., non-rigid partial condoms as described herein, such as rigid, non-curling partial condoms comprising a first adhesive layer (e.g., a stimulus-responsive polymer, as described herein) and a second layer comprising a barrier and a reservoir), wherein the condom does not contact the penile shaft or coronal sulcus; wherein the adhesive layer (a) is co-extended with the barrier layer; (b) is thicker than the barrier layer and / or (c) is the sole means of fixation. The adhesive can be, for example, a stimulus-responsive polymer comprising one or more methacrylate monomers and a trifunctional crosslinking agent (e.g., TMPTA), providing a low-density heterogeneous crosslinked polymer. The weight ratio of polymer to trifunctional crosslinking agent can be, for example, about 99.4:0.6. Non-rigid, partial condoms can exhibit one or more of the properties disclosed herein, such as painless removal, low peel strength at low peel rates, high peel strength at high peel rates, loss modulus, etc.

[0414] In some embodiments, the stimulus-responsive polymer, and optionally the adhesive, is formed from (i.e., comprising) monomers selected from: acrylate monomers, methacrylate monomers, vinyl ether monomers, allyl monomers, thiol monomers, epoxy monomers, amine monomers, electron-rich monomers, electron-deficient monomers, lactam monomers, lactone monomers, alcohol monomers, carboxylic acid monomers, isocyanate monomers, Diels-Alder monomers, ring-opening translocation monomers, or combinations thereof.

[0415] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising acrylate monomers. In some embodiments, the acrylate monomers are C6-C30 alkyl acrylate monomers, such as 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.

[0416] 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, heptadecanyl acrylate, octadecyl acrylate, nonadecanyl acrylate, eicosyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, isodecyl acrylate, isotridecyl acrylate, hexadecyl acrylate, heptadecanyl acrylate, octadecyl acrylate, nonadecanyl acrylate, triadecyl acrylate, and acrylic acid. 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 glyceryl 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), bis(trimethylolpropane)tetraacrylate (DTMPTA), bisphenol A ethoxylated diacrylate (BPAEDA), ethoxylated bisphenol A diacrylate (EBPA), decanediol diacrylate, polyethylene glycol diacrylate (PEGDA), trimethylolpropane... Propane 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), tri(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.

[0417] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising acrylate monomers selected from the following: octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecanyl acrylate, octadecyl acrylate, nonadecanyl acrylate, eicosyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecanyl acrylate, octadecyl acrylate, nonadecanyl acrylate, triadecyl acrylate, and combinations thereof.

[0418] In some implementations, the acrylate monomer is TMPTA.

[0419] In some embodiments, the stimulus-responsive polymer comprises at least 10 wt% of acrylate monomers, for example, at least 50 wt%, at least 75 wt%, or at least 90 wt%. In some embodiments, the stimulus-responsive polymer comprises at least 95 wt% of acrylate monomers, for example, at least 96 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt%.

[0420] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising methacrylate monomers. In some embodiments, the methacrylate monomers are C6-C30 alkyl methacrylate monomers, such as 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.

[0421] 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, heptadecanyl methacrylate, octadecyl methacrylate, nonadecanyl methacrylate, eicosyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecanyl methacrylate, octadecyl methacrylate, nonadecanyl methacrylate, triadecyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, and methacrylate. Isoborneol ester, stearyl methacrylate, lauryl methacrylate, isodecyl methacrylate, isotridecyl 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.

[0422] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising methacrylate monomers selected from the following: hexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecanyl methacrylate, octadecyl methacrylate, nonadecanyl methacrylate, eicosyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecanyl methacrylate, octadecyl methacrylate, nonadecanyl methacrylate, triadecyl methacrylate, and combinations thereof. In some embodiments, the stimulus-responsive polymer comprises undecyl methacrylate monomer, i.e., lauryl methacrylate monomer. In some embodiments, the stimulus-responsive polymer comprises octadecyl methacrylate monomer, i.e., stearyl methacrylate monomer.

[0423] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising at least 10 wt% of methacrylate monomers, for example, at least 50 wt%, at least 75 wt%, or at least 90 wt%. In some embodiments, the stimulus-responsive polymer contains at least 95 wt% of methacrylate monomers, for example, at least 96 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt%.

[0424] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising vinyl ether monomers. Exemplary vinyl ether monomers include, but are not limited to: ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether (DVE-PEG), polypropylene glycol divinyl ether (DVE-PPG), poly(ethylene glycol) methyl ether divinyl ether (DVE-PEGME), poly(ethylene glycol) butyl ether divinyl ether (DVE), poly(ethylene glycol) phenyl ether divinyl ether (DVE-PEGPhE), glycerol divinyl ether (DVE-Gly), 1,4-cyclohexanediethanol divinyl ether (DVE-CHDM), neopentyl glycol divinyl ether (DVE-NPG), and combinations thereof.

[0425] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising 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 itaconic acid (DAI), diallyl carbonate (DAC), diallyl diglycolate (DADG), and tris(2-hydroxyethyl)isocyanurate. diallyl ester (DATHEIC), triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), triallyl trimellitate (TATM), triallyl citrate (TAC), triallyl phosphate (TAP), triallylamine (TAA), triallyl cyanide (TACN), triallyl phenyl-1,2,4-tricarboxylate (TABTC), triallyl trimellitate (TATM), tris(2-hydroxyethyl) isocyanurate triallyl ether (THEIC-TAE), and combinations thereof.

[0426] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising thiol monomers. Exemplary thiol monomers include, but are not limited to: 3-mercaptopropionic acid; mercaptoacetic acid; 3-mercapto-1-propanol; 2-mercaptoethanol; 2-(2-mercaptoethoxy)ethanol; 2-(2-mercaptopropionylamino)ethanol; ethyl acrylate-2-(2-mercaptosuccinoyl)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-trioxadecanthiol; 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; thiophene; pentaerythritol tetra(3-mercaptopropionate) (PETMP); trimethylolpropane tri(3-mercaptopropionate) (TMPMP); triethanolamine tri(3-mercaptopropionate) (TEAMP); tri(2-hydroxyethyl)isocyanurate tri(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.

[0427] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising epoxy monomers. Exemplary epoxy monomers include, but are not limited to: bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE), phenolic varnish diglycidyl ether (NGDE), phenolic varnish diglycidyl ether (PNGDE), alicyclic epoxy resins, fatty alcohol glycidyl ethers, aromatic alcohol glycidyl ethers, triglycidyl isocyanate (TGIC), 1,4-butanediol diglycidyl ether (BDDGE), neopentyl glycol diglycidyl ether (NPGDGE), propylene glycol diglycidyl ether (PGDGE), epoxidized soybean oil (ESO), epoxidized linseed oil (ELO), dicyclopentadienyl epoxy resins, tetrafunctional epoxy resins, epoxy phenolic resins, and combinations thereof.

[0428] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising 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; isophorone diamine; Jeffamine D-230; Jeffamine T-403; Jeffamine M-207; Jeffamine EDR-148; and combinations thereof.

[0429] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising electron-rich monomers. Exemplary electron-rich monomers include, but are not limited to: vinyl ethers (e.g., methyl vinyl ether, ethyl vinyl ether), vinyl acetate, allyl alcohol, allylamine, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxymethylallylamine, N-hydroxymethylvinylacetamide, 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-vinylpyridine, styrene, styrene derivatives, and combinations thereof.

[0430] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising electron-deficient monomers. Exemplary electron-deficient 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, α-methylstyrene, maleimide, N-phenylmaleimide and N-butylmaleimide, maleic anhydride, and combinations thereof.

[0431] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising lactam monomers. Exemplary lactam monomers include, but are not limited to: caprolactam, valproic acid lactam, heptalactam, octyllactam, laurolactam, propionic acid lactam, butyrolactam, methionyllactam, methoxyethyllactam, methoxyethyl methionyllactam, dimethylaminoethyllactam, dimethylaminoethyl methionyllactam, dimethylaminoethyl acryloyllactam, dimethylaminoethyl methacryloyllactam, N-vinylpyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, and combinations thereof.

[0432] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising lactone monomers. Exemplary lactone monomers include, but are not limited to: β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, ω-pentadecanolactone, β-butyrolactone, δ-decanolactone, ε-decanolactone, γ-decanolactone, δ-dodecanolactone, γ-dodecanolactone, α-methylene-γ-butyrolactone, β-methyl-γ-butyrolactone, β-methyl-γ-valerolactone, γ-caprolactone, and combinations thereof.

[0433] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising 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; neopentanediol; diethylene glycol; triethylene glycol; tetraethylene glycol; polyethylene glycol (PEG); polypropylene glycol (PPG); polycaprolactone diol; polyhydroxymethylpropane; hydroxypentanoyl hydroxymethylbutyrate (HPHMB); 1,4-cyclohexanediol; and combinations thereof.

[0434] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising 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, dodecanoic acid, and combinations thereof.

[0435] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising 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.

[0436] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising 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-dimethylmaleimide, 2,5-dimethylfuran, tetracyanoethylene, methyl vinyl ketone, and combinations thereof.

[0437] In some embodiments, the stimulus-responsive polymer, or optionally the adhesive, contains one or more other polymers comprising ring-opening translocation monomers. Exemplary ring-opening translocation 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.

[0438] In some implementations, the stimulus-responsive polymer contains two or more side chains.

[0439] In some embodiments, the stimulus-responsive polymer comprises C6 to C30 side chains or C6 to C30 hanging chain ends. In some embodiments, the C6 to C30 side chains or C6 to C30 hanging chain ends are C6 to C30 alkyl side chains, preferably C12 to C18 alkyl side chains.

[0440] In some embodiments, the stimulus-responsive polymer contains at least 80 wt% of side chains, 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.

[0441] In some embodiments, the side chain comprises a linker made of monomers selected from: acrylates, methacrylates, thiols-acrylates Michael addition, acrylate-amines Michael addition, epoxy thiols, epoxy amines, polyethyleneimine (PEI), thiols-olefins, alternating copolymers made of C=C electron-deficient + C=C electron-rich monomers, urethanes, ureas, acrylamides, methacrylamides, polyesters, polycarbonates, polyamides, peptides, peptides, Diels-Alder, lactide, and lactams, as well as ring-opening metathesis polymerization or olefin metathesis reactions.

[0442] In some embodiments, the side-chain chemistry includes C1-C100 side-chain linkages achieved via the synthetic pathways disclosed herein.

[0443] In some embodiments, the stimulus-responsive polymer having C6 to C18 side chains or dangling chain ends is prepared from acrylates, methacrylates, alcohols, carboxylic acids, electron-rich olefins, electron-deficient olefins, epoxy resins, amines, ROMPs, Diels-Alders, lactones, lactams, peptides, peptide-like substances, acrylamides, methacrylamides, thiols, vinyl and allyl monomers.

[0444] In some embodiments, the stimulus-responsive polymer comprises a linear or cross-linked polymer having side chains that optionally undergo crystallization and / or melting in a region near body temperature and room temperature (in the range of 0°C to 50°C, more specifically in the range of 5°C to 45°C, more specifically in the range of 10°C to 40°C, more specifically in the range of 15°C to 35°C). For clarity, side chain crystallization is optional.

[0445] In some embodiments, the linear or crosslinked polymer ranges from about 40% to about 100%, more specifically, from about 50% to 100%. In some embodiments, the range is 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 contained therein.

[0446] In some embodiments, the secondary side chain may optionally be a crystallizable polymer ranging from about 0 to about 50%, more specifically from 1% to about 49%, more specifically from about 2% to about 48%, more specifically from about 3% to 47%, more specifically from about 5% to about 45%, or any additional range or value contained herein.

[0447] In some embodiments, the stimulus-responsive polymer, or one or more other polymers present in the optional adhesive, is a crosslinked polymer. The crosslinked polymer is prepared using one or more multifunctional crosslinking agents. Statistically, the crosslinking agent can exhibit functionality greater than n=1 reactive sites, for example, a statistical average of n=2, 3, 4, 5, 6, 7, 8, 9, 10 or more reactive sites, and can promote branching, hyperbranching, interpenetrating networks, semi-interpenetrating networks, and substantially homogeneous or partially homogeneous and partially heterogeneous or substantially heterogeneous networks with respect to phase blending or crosslink density concentration.

[0448] In some embodiments, the multifunctional crosslinker is selected from difunctional, trifunctional, or tetrafunctional crosslinkers. In some embodiments, the multifunctional crosslinker is a trifunctional crosslinker.

[0449] In some embodiments, the multifunctional crosslinker is a trifunctional crosslinker. In some embodiments, the trifunctional crosslinker is a trifunctional acrylate crosslinker.

[0450] In some embodiments, the multifunctional crosslinking agent is selected from poly(ethylene glycol) diacrylate, trimethylolpropane triacrylate (TMPTA); ethoxylated trimethylolpropane triacrylate; pentaerythritol tetraacrylate; ethoxylated pentaerythritol tetraacrylate; dipentaerythritol hexaacrylate; ethoxylated dipentaerythritol hexaacrylate; di, tri, tetra, penta, or hexacyclic oxides; polythiols; polyolefins; tris(2-acryloyloxyethyl) isocyanurate, ε-caprolactone-modified tris(2-acryloyloxyethyl) isocyanurate, ethoxylated glycerol triacrylate, pentaerythritol triacrylate, and combinations thereof.

[0451] In some embodiments, the multifunctional crosslinking agent is a poly(ethylene glycol) diacrylate with an internal repeating unit range of 1 to 1000 or more, trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate with an internal repeating unit range of 1 to 1000 or more, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate with an internal repeating unit range of 1 to 1000 or more, pentafunctional and hexafunctional acrylates and ethoxylated versions as described above (including dipentaerythritol hexaacrylate and ethoxylated dipentaerythritol hexaacrylate (with a repeating unit range of 1 to 1000 or more)), di, tri, tetra, penta, hexa or higher functional epoxide monomers, polythiols, polyolefins (cured by ultraviolet light, visible light, gamma or electron beam radiation, heat or hydrogen silanization).

[0452] In some embodiments, the multifunctional crosslinking agent 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 multifunctional crosslinking agent is trimethylolpropane triacrylate (TMPTA).

[0453] In some embodiments, the stimulus-responsive polymer is a cross-linked polymer with a homogeneous cross-linked network density. In some embodiments, the stimulus-responsive polymer is a cross-linked polymer with a heterogeneous cross-linked network. For example, advantageous adhesion disruption or delamination from the skin (including removal of residual adhesive after peeling off the adhesive) can be achieved by concentrating the disruption sites within the network through a heterogeneous cross-linked distribution or by forming a “swollen heterogeneous network” through polymerization of cross-linking agents and monomers with different reactive polymerization rates.

[0454] In some implementations, the stimulus-responsive polymer is characterized by low-density crosslinking.

[0455] In some implementations, the crosslinking agent is uniformly incorporated into the stimulus-responsive polymer network.

[0456] In some embodiments, the crosslinking agent aggregates within a stimulus-responsive polymer network. This embodiment creates high stress concentration network sites and / or drives rheological behavior and is able to dissipate energy (with high tan δ and high loss modulus compared to a more uniform network) to promote adhesive failure when needed.

[0457] The amount of crosslinking agent in the stimulus-responsive polymer or optionally one or more additional polymers can vary. In some embodiments, the polymer contains 0 to 30 wt% of crosslinking agent, for example, 0.001 to 29 wt%, more specifically 0.005 to 28 wt%, more specifically 0.0075 to 28 wt%, more specifically 0.01 to 27 wt%, more specifically 0.02 to 26 wt%, more specifically 0.05 to 26 wt%, more specifically 0.1 to 25 wt%, more specifically 0.15 to 24 wt%.

[0458] In some embodiments, the stimulus-responsive polymer comprises a crosslinking agent 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 relative to the weight of the polymer.

[0459] In one particular embodiment, the stimulus-responsive polymer contains about 0.1 wt% to about 1 wt%, about 0.2 wt% to about 0.8 wt%, about 0.3 wt% to about 0.7 wt%, or about 0.4 wt% to about 0.6 wt% of a crosslinking agent, in each case relative to the weight of the polymer.

[0460] In some embodiments, the stimulus-responsive polymer comprises 0.1 wt% to 2.5 wt% of a multifunctional crosslinking agent, for example, 0.1 wt% to 2 wt%, 0.1 to 1.5 wt%, 0.1 wt% to 1 wt%, 0.1 wt% to 0.9 wt%, 0.1 wt% to 0.8 wt%, 0.1 wt% to 0.7 wt%, 0.1 wt% to 0.6 wt%, 0.1 wt% to 0.5 wt%, 0.1 wt% to 0.4 wt%, 0.1 wt% to 0.3 wt%, 0.1 wt% to 0.2 wt%, 0.2 wt% to 1.5 wt%, 0.2 wt% to 1 wt%, 0.3 wt% to 1.5 wt%, 0.3 wt% to 1 wt%, 0.4 wt% to 1.5 wt%, 0.4 wt% to 1 wt%, and 0.5 wt% to 1.5 wt%. wt%, 0.5 wt% to 1 wt%, 0.6 wt% to 1.5 wt%, 0.6 wt% to 1 wt%, 0.7 wt% to 1.5 wt%, 0.7 wt% to 1 wt%, 0.8 wt% to 1.5 wt%, 0.8 wt% to 1 wt%, 0.9 wt% to 1.5 wt% or 0.9 wt% to 1 wt%.

[0461] In some embodiments, the stimulus-responsive polymer comprises 0.4 wt% to 0.8 wt% of a multifunctional crosslinker, for example, 0.4 wt% to 0.7 wt%, 0.4 wt% to 0.6 wt%, 0.4 wt% to 0.5 wt%, 0.5 wt% to 0.8 wt%, 0.5 wt% to 0.7 wt%, 0.5 wt% to 0.6 wt%, 0.6 wt% to 0.8 wt%, 0.6 wt% to 0.7 wt%, or 0.7 wt% to 0.8 wt%. In some embodiments, the multifunctional crosslinker is trimethylolpropane triacrylate (TMPTA).

[0462] In some embodiments, the weight ratio of one or more monomers to one or more multifunctional crosslinking agents 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.

[0463] In some embodiments, the weight ratio of one or more monomers to one or more multifunctional crosslinking agents is 98:2 to 99.9:0.1, for example, 98.5:1.5 to 99.9:0.1; 99:1 to 99.9:0.1, 99.1:0.9 to 99.9:0.1, 99.2:0.8 to 99.9:0.1; 99.3:0.7 to 99.9:0.1, 99.4:0.6 to 99.9:0.1, 99.5:0.5 to 99.9:0.1, 99.6:0.4 to 99.9:0.1, 99.7:0.3 to 99.9:0.1, or 99.8:0.2 to 99.9:0.1.

[0464] In some embodiments, the adhesive further comprises one or more additives. Exemplary additives include tackifiers, plasticizers, pigments, fillers, fluorescent agents, flow agents, wetting agents, surfactants, defoamers, rheology modifiers, colorants, penetration enhancers, stabilizers, antioxidants, and combinations thereof. In some embodiments, adhesive strength can be enhanced or reduced by adding additives.

[0465] Exemplary plasticizers include, but are not limited to, triacetin, glyceryl monooleate (GMO), glyceryl monostearate (GMS), glyceryl tristearate (tristearate), glyceryl tributyrin, glyceryl tripropionate (triproprionin), glyceryl trioleate (triolein), glyceryl dilaurate (GDL), glyceryl dimyristate (GDM), glyceryl distearate (GDS), diethylhexyl phthalate (DEHP), and 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 alkyl esters on either side of the ester.

[0466] In some implementations, plasticizers may be added to lower the glass transition temperature of the polymer to adjust the adhesive state. Suitable plasticizers include glycerol, 1-butanol, 1-octanol, stearic acid, n-butyl stearate, poly(ethylene glycol) with a Mw of 100 to 200, 400, 1000, 2000, 4000, 10000 Daltons or greater, water, various organic solvents, 1-decanoate, and 1-octanoate.

[0467] In some implementations, the additive is stimulus-responsive. For example, additives such as Mw 400 Dalton poly(ethylene glycol) or glycerol can be used in blends of 1 wt% to 90 wt% with adhesive layer components (such as poly(n-dimethylacylamide)) such that the additive plasticizes the adhesive layer above the additive's crystallization temperature, but no longer plasticizes the adhesive layer below the additive's crystallization temperature.

[0468] In some embodiments, the stimulus-responsive additive may exhibit crystallization, glass transition or other thermal transitions in the range of 0°C to 50°C, more specifically 5°C to 40°C, more specifically 10°C to 30°C, and even more specifically 12°C to 25°C.

[0469] The adhesive layer may comprise linear or crosslinked polymers, including silicone polymers, such as high molecular weight linear siloxane polymers and highly condensed silicate tackifying resins. Tackifying resins or tackifiers suitable for this invention comprise low molecular weight compounds with high glass transition temperatures used in formulating the adhesive to increase tackiness and the stickiness of the adhesive surface. Tackifiers suitable for this invention include resins (e.g., rosin and its derivatives, terpenes and modified terpenes, aliphatic, alicyclic, and aromatic resins (C5 aliphatic resins, C9 aromatic resins, and C5 / C9 aliphatic / aromatic resins), hydrogenated hydrocarbon resins and mixtures thereof, terpene-phenolic resins (TPR, often used with ethylene-vinyl acetate adhesives)), and phenolic varnishes. Silicone rubber-based pressure-sensitive adhesives suitable for this invention include special tackifiers based on “MQ” silicate resins, which consist of a monofunctional trimethylsilane (“M”) reacted with a tetrafunctional silicon tetrachloride (“Q”).

[0470] The adhesive layer may comprise blends of two or more homopolymers or copolymers, comprising a copolymer structure of block, gradient, and random copolymers containing two or more different repeating units. The adhesive layer may also comprise a single copolymer as described above. The adhesive layer may exhibit one or more glass transition (Tg), crystallization temperature (Tc), melting temperature (Tm), or other thermal transitions 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 higher, as measured by differential scanning calorimetry (DSC) Tg, Tc, Tm peak inflection points or by dynamic mechanical analysis loss modulus or tan δ peak.

[0471] The adhesive layer can be a linear, brush-like, star-like, dendritic, or branched polymer with a weight-average molecular weight (Mw) of about 1 kDa, about 5 kDa, about 10 kDa, about 15 kDa, about 20 kDa, about 30 kDa, about 50 kDa, 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 higher.

[0472] The adhesive layer may be a cross-linked blend of the above-mentioned linear polymers or a copolymer of the above-mentioned polymers, or it may be a semi-interpenetrating network or interpenetrating network of two or more polymers or copolymers.

[0473] The adhesive layer exhibits a heat-responsive stimulus behavior, enabling it to adhere to the penile skin at body temperature (approximately 37°C) and to reduce adhesion or delamination when cooled to below body temperature at approximately 25°C, 20°C, 15°C, 10°C, 5°C, 0°C, or lower. Cooling can be achieved, for example, by accelerating heat transfer, by rubbing a wet substrate (such as a soaked towel or tissue) on the diaphragm or at the interface of the adhered barrier layer (when adhered to the penis), or by running water from a source such as a shower, or by wiping with a cloth or tissue containing an agent that causes cooling (such as the evaporation or dissolution of ammonium nitrate in alcohol), thereby cooling the diaphragm through thermal transformation, making delamination easier compared to removing the diaphragm at body temperature.

[0474] The adhesive layer can exhibit chemically responsive behavior, be inherently water- or solvent-soluble, and can be removed by pulling back the edge and flowing water or solvent or rubbing a substrate impregnated with water or solvent until the diaphragm is removed due to weakening of the adhesive layer or dissolution by water or solvent. Chemical delamination can also be achieved in such a way as pH-triggered delamination, by flowing or wiping a substrate impregnated with a fluid of a pH suitable for skin contact (which also facilitates the delamination of the diaphragm from the skin). Alternatively, chemical delamination can also be achieved by dissolving the adhesive by flowing or wiping a substrate impregnated with a fluid that facilitates the delamination of the diaphragm from the skin.

[0475] Properties of adhesives and stimulus-responsive polymers

[0476] In some implementations, the stimulus is selected from temperature changes, physicochemical changes, light, ultrasound, changes in ionic strength, pH changes, magnetism, mechanical force, or mechanical action.

[0477] In some implementations, the stimulation is a mechanical action, such as shear rate. In some implementations, the shear rate is induced by peeling or pulling the contraceptive device at different rates or frequencies.

[0478] In some embodiments, the adhesive is shear rate responsive. In some embodiments, the stimulus-responsive polymer is shear rate responsive. In such embodiments, the adhesive maintains adhesion at higher shear rates and decreases tack at lower shear rates. Exemplary higher shear rates include forceful peeling or pulling. Exemplary lower shear rates include slight peeling or pulling. Higher and lower are relative to thresholds from which behavioral changes are observed. In this way, the adhesive layer and the contraceptive device can be easily removed from the penis or vagina after stimulation of the contraceptive device.

[0479] In some implementations, slight peeling corresponds to a peeling rate of 500 mm / min or lower, for example, 400 mm / min or lower, 300 mm / min or lower, 200 mm / min or lower, 100 mm / min or lower, or 50 mm / min or lower. In some embodiments, slight peeling corresponds to a peeling rate of 50 mm / min to 500 mm / min, 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.

[0480] In some implementations, slight peeling corresponds to a peeling rate of 25 mm / s or less, such as 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, slight peeling corresponds to peeling rates from 0.01 mm / s to 25 mm / s, 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 mm / s to 0.5 mm / s, from 0.01 mm / s to 0.3 mm / s, from 0.01 mm / s to 0.1 mm / s, 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 mm / s 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.

[0481] In some embodiments, the stimulus is a mechanical force. In some embodiments, the adhesive is force-responsive. In some embodiments, the stimulus-responsive polymer is force-responsive. In such embodiments, the adhesive maintains adhesion when a higher force is applied, while the tack decreases when a lower force is applied. Higher and lower are relative to thresholds from which a change in behavior is observed.

[0482] In some embodiments, the applied force causing delamination of the stimulus-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 to 1000 N. In some embodiments, the applied force causing delamination of the stimulus-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.

[0483] In some embodiments, the applied force causing adhesive delamination is, for example, 0.01 to 0.1 N, 0.1 to 1 N, 1 to 10 N, 10 to 100 N, or 100 to 1000 N. In some embodiments, the applied force causing adhesive delamination is, for example, 1 to 10 Pa, 10 to 100 Pa, 0.1 to 1 kPa, 1 to 10 kPa, 10 to 100 kPa, or 0.1 to 1 MPa.

[0484] In some embodiments, the stimulus-responsive polymer exhibits lower peel strength at lower peel rates and higher peel strength at higher peel rates. In some embodiments, the peel strength of the stimulus-responsive polymer at lower peel rates is at least 5% lower than that at higher peel rates, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100% lower.

[0485] In some embodiments, the peel strength of the stimuli-responsive polymer at a peel rate of 100 mm / min is lower than that at 200 mm / min. In some embodiments, the peel strength of the stimuli-responsive polymer at a peel rate of 100 mm / min is lower than that at 300 mm / min. In some embodiments, the peel strength of the stimuli-responsive polymer at a peel rate of 100 mm / min is lower than that at 400 mm / min. In some embodiments, the peel strength of the stimuli-responsive polymer at a peel rate of 100 mm / min is lower than that at 500 mm / min.

[0486] In some embodiments, the peel strength of the stimuli-responsive polymer at a peel rate of 1 mm / s is lower than that at 3 mm / s. In some embodiments, the peel strength of the stimuli-responsive polymer at a peel rate of 1 mm / s is lower than that at 5 mm / s. In some embodiments, the peel strength of the stimuli-responsive polymer at a peel rate of 1 mm / s is lower than that at 7 mm / s. In some embodiments, the peel strength of the stimuli-responsive polymer at a peel rate of 1 mm / s is lower than that at 10 mm / s.

[0487] In some embodiments, the peel strength of the stimulus-responsive polymer at a peel rate of 100 mm / min is at least 5% lower than that at a peel rate of 200 mm / min, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100%.

[0488] In some embodiments, the peel strength of the stimulus-responsive polymer at a peel rate of 100 mm / min is at least 5% lower than that at a peel rate of 300 mm / min, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100%.

[0489] In some embodiments, the peel strength of the stimulus-responsive polymer at a peel rate of 100 mm / min is at least 5% lower than that at a peel rate of 400 mm / min, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100%.

[0490] In some embodiments, the peel strength of the stimulus-responsive polymer at a peel rate of 100 mm / min is at least 5% lower than that at a peel rate of 500 mm / min, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100%.

[0491] In some embodiments, the peel strength of the stimulus-responsive polymer at a peel rate of 1 mm / s is at least 5% lower than that at a peel rate of 3 mm / s, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100%.

[0492] In some embodiments, the peel strength of the stimulus-responsive polymer at a peel rate of 1 mm / s is at least 5% lower than that at a peel rate of 5 mm / s, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100%.

[0493] In some embodiments, the peel strength of the stimulus-responsive polymer at a peel rate of 1 mm / s is at least 5% lower than that at a peel rate of 7 mm / s, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100%.

[0494] In some embodiments, the adhesive has lower peel strength at lower peel rates and higher peel strength at higher peel rates. In some embodiments, the adhesive has a peel strength at lower peel rates that is at least 5% lower than its peel strength at higher peel rates, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100% lower.

[0495] In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is lower than that at 200 mm / min. In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is lower than that at 300 mm / min. In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is lower than that at 400 mm / min. In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is lower than that at 500 mm / min.

[0496] In some embodiments, the peel strength of the adhesive at a peel rate of 1 mm / s is lower than that at 3 mm / s. In some embodiments, the peel strength of the adhesive at a peel rate of 1 mm / s is lower than that at 5 mm / s. In some embodiments, the peel strength of the adhesive at a peel rate of 1 mm / s is lower than that at 7 mm / s. In some embodiments, the peel strength of the adhesive at a peel rate of 1 mm / s is lower than that at 10 mm / s.

[0497] In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is at least 5% lower than that at a peel rate of 200 mm / min, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100%.

[0498] In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is at least 5% lower than that at a peel rate of 300 mm / min, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100%.

[0499] In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is at least 5% lower than that at a peel rate of 400 mm / min, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100%.

[0500] In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is at least 5% lower than that at a peel rate of 500 mm / min, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100%.

[0501] In some embodiments, the peel strength of the adhesive at a peel rate of 1 mm / s is at least 5% lower than that at a peel rate of 3 mm / s, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100%.

[0502] In some embodiments, the peel strength of the adhesive at a peel rate of 1 mm / s is at least 5% lower than that at a peel rate of 5 mm / s, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100%.

[0503] In some embodiments, the peel strength of the adhesive at a peel rate of 1 mm / s is at least 5% lower than that at a peel rate of 7 mm / s, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100%.

[0504] In some embodiments, the stimuli-responsive polymer exhibits a peel strength of 1 to 400 N / m at a peel rate of 100 mm / sec, for example, 1 to 300 N / m, 1 to 200 N / m, 1 to 100 N / m, or 1 to 50 N / m. Peel strength can be determined by a 180° peel test using a human skin-based substrate simulant, as described below.

[0505] In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / sec is 1 to 400 N / m, for example, 1 to 300 N / m, 1 to 200 N / m, 1 to 100 N / m, or 1 to 50 N / m. The peel strength can be determined by a 180° peel test using a human skin-based substrate simulant, as described below.

[0506] In some embodiments, the tack strength of the stimulus-responsive polymer at 25°C is at least 1 N, for example, 1 N to 5 N, 1 N to 4 N, 1 N to 3 N, or 1 N to 2 N. The tack strength can be measured as described below, for example, by compressing an aluminum-tipped rheometer containing the polymer onto an aluminum substrate for 60 seconds, withdrawing the rheometer at a rate of 100 micrometers per second, and measuring the axial force in N.

[0507] In some embodiments, the adhesive has an tack strength of at least 1 N at 25°C, for example, 1 N to 5 N, 1 N to 4 N, 1 N to 3 N, or 1 N to 2 N.

[0508] In some embodiments, the stimulus-responsive polymer has an adhesive strength of at least 20 N at 25°C. s， For example, at least 30 Ns, at least 40 Ns, at least 50 Ns, at least 60 Ns, at least 70 Ns, at least 80 Ns, at least 90 Ns, at least 100 Ns, at least 150 Ns, at least 200 Ns, at least 300 Ns, at least 400 Ns, or at least 500 Ns. Adhesive strength is calculated by integrating the area of ​​the sample under a measurement of axial force over time.

[0509] In some embodiments, the adhesive has an adhesive strength of at least 20 Ns at 25°C, for example, at least 30 Ns, at least 40 Ns, at least 50 Ns, at least 60 Ns, at least 70 Ns, at least 80 Ns, at least 90 Ns, at least 100 Ns, at least 150 Ns, at least 200 Ns, at least 300 Ns, at least 400 Ns, or at least 500 Ns.

[0510] In some embodiments, the stimulus-responsive polymer has a storage modulus of 0.01 MPa to 1 MPa, for example, 0.1 MPa to 1 MPa, 0.1 MPa to 0.8 MPa, or 0.1 MPa to 0.5 MPa.

[0511] In some embodiments, the adhesive has a storage modulus of 0.01 to 1 MPa, for example, 0.1 MPa to 1 MPa, 0.1 MPa to 0.8 MPa, or 0.1 MPa to 0.5 MPa.

[0512] In some embodiments, the stimulus-responsive polymer has a loss modulus of 0.1 MPa to 1 MPa, for example, 0.1 MPa to 0.8 MPa or 0.1 MPa to 0.5 MPa.

[0513] In some embodiments, the adhesive has a loss modulus of 0.1 MPa to 1 MPa, for example, 0.1 MPa to 0.8 MPa or 0.1 MPa to 0.5 MPa.

[0514] In some implementations, the stimulus-responsive polymer is at 25°C and 1 Hz (2 The tan(δ) (the ratio of storage modulus (G'') to loss modulus (G') at π radians / second is at least 0.1, 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 stimulus-responsive polymer has a tan(δ) of 0.1 to 5, for example, 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 some embodiments, the stimulus-responsive polymer has a tan(δ) of 0.2 to 2, for example, 0.1 to 1.5, 0.1 to 1, 0.1 to 0.5, 0.3 to 1, or 0.5 to 1.

[0515] In some implementations, the adhesive is used at 25°C and 1 Hz (2 The tan(δ) (the ratio of storage modulus (G'') to loss modulus (G') at π radians / second is at least 0.1, 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) of 0.1 to 5, for example, 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 some embodiments, the adhesive has a tan(δ) of 0.2 to 2, for example, 0.1 to 1.5, 0.1 to 1, 0.1 to 0.5, 0.3 to 1, or 0.5 to 1.

[0516] In some embodiments, the stimulus-responsive polymer exhibits lower tackiness when wet than when dry. In some embodiments, the adhesive exhibits lower tackiness when wet than when dry.

[0517] In some implementations, the stimulus-responsive polymer is a cross-linked polymer, a low-density cross-linked polymer, or a polymer with limited, heterogeneous cross-linking.

[0518] In some implementations, the stimulus-responsive polymer is lightly cross-linked as defined herein.

[0519] In some implementations, the stimulus-responsive polymer is a low molecular weight, lightly cross-linked polymer as defined herein.

[0520] In some embodiments, the adhesive comprises a lightly crosslinked polymer as defined herein.

[0521] In some embodiments, the adhesive comprises a low molecular weight, lightly crosslinked polymer as defined herein.

[0522] In some embodiments, when analyzed by sol-gel analysis, the stimulus-responsive polymer has a gel fraction consistent with a mildly cross-linked polymer network. In some embodiments, the gel fraction of the stimulus-responsive polymer is 0.0001 to 0.99, for example, 0.001 to 0.98, 0.01 to 0.95, 0.015 to 0.95, 0.02 to 0.96, 0.05 to 0.95, 0.1 to 0.95, 0.175 to 0.95, 0.2 to 0.95, 0.25 to 0.95, 0.3 to 0.95, 0.35 to 0.95, 0.4 to 0.95, 0.5 to 0.95, 0.6 to 0.95, 0.7 to 0.95, 0.8 to 0.95, 0.5 to 0.95, 0.6 to 0.93, 0.6 to 0.65 to 0.92, 0.7 to 0.9, or 0.7 to 0.89.

[0523] In some implementations, when analyzed by sol-gel analysis, the adhesive has a gel fraction consistent with a mildly cross-linked polymer network. In some embodiments, the gel fraction of the adhesive is 0.0001 to 0.99, for example, 0.001 to 0.98, 0.01 to 0.95, 0.015 to 0.95, 0.02 to 0.96, 0.05 to 0.95, 0.1 to 0.95, 0.175 to 0.95, 0.2 to 0.95, 0.25 to 0.95, 0.3 to 0.95, 0.35 to 0.95, 0.4 to 0.95, 0.5 to 0.95, 0.6 to 0.95, 0.7 to 0.95, 0.8 to 0.95, 0.5 to 0.95, 0.6 to 0.93, 0.6 to 0.65 to 0.92, 0.7 to 0.9, or 0.7 to 0.89.

[0524] In some embodiments, removal of the contraceptive device by gentle peeling after the adhesive layer has been adhered to the penis or vagina does not cause pain in the subject. In some embodiments, removal of the condom by gentle peeling after the adhesive layer has been adhered to the glans penis causes minimal or no pain in the subject. Any suitable method can be used to determine the presence of pain. Several validated instruments exist for measuring pain. These instruments can be one-dimensional, measuring only the intensity of pain, such as the Wong-Baker Qualitative Pain Assessment (WBQPA), the Numerical Rating Pain Scale (NRPS), the Visual Analogue Scale (VAS), and verbal rating scales. Multidimensional tools measure the intensity, characteristics, and impact of pain, such as the McGill Pain Questionnaire (MPQ) and the Brief Pain Inventory (BPI).

[0525] In some embodiments, pain is measured using the WBQPA on a scale from 0 (painless) to 10 (maximum pain). In some embodiments, when the adhesive layer is removed by gentle peeling, the pain on the WBQPA scale is less than 4, for example, less than 3, less than 2, less than 1, or 0. In some embodiments, the WBQPA score reported when the contraceptive device is removed by gentle peeling is 0. As described above, in some embodiments, gentle peeling corresponds to a user peeling rate of 25 mm / s or less for contraceptive devices (e.g., condoms), 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 peeling rate of 0.01 mm / s to 25 mm / s, for example, 0.01 mm / s to 10 mm / s, 0.01 mm / s to 5 mm / s, 0.01 mm / s to 1 mm / s, 0.01 mm / s to 0.5 mm / s, 0.01 mm / s to 0.3 mm / s, 0.01 mm / s to 0.1 mm / sec, 0.1 mm / s to 25 mm / s, 0.1 mm / s to 10 mm / s, 0.1 mm / s to 5 mm / s, 0.1 mm / s to 1 mm / s, 0.1 mm / s to 0.5 mm / s, 0.1 mm / s to 0.3 mm / s, 1 mm / s to 25 mm / s, 1 mm / s to 10 mm / s, or 1 mm / s to 5 mm / s.

[0526] In some implementations, light peel corresponds to a user peel rate of 500 mm / min or less for a contraceptive device (e.g., a condom), such as 400 mm / min or less, 300 mm / min or less, 200 mm / min or less, 100 mm / min or less, 50 mm / min or less, 25 mm / min or less, 10 mm / min or less, 5 mm / min or less, 1 mm / min or less, 0.5 mm / min or less, 0.3 mm / min or less, or 0.1 mm / min or less. In some embodiments, light peeling corresponds to a peeling rate of 50 mm / min to 500 mm / min, for example, 50 mm / min to 400 mm / min, 50 mm / min to 300 mm / min, 50 mm / min to 200 mm / min, 50 mm / min to 100 mm / min, 100 mm / min to 500 mm / min, 100 mm / min to 400 mm / min, 100 mm / min to 300 mm / min, 100 mm / min to 200 mm / min, 200 mm / min to 500 mm / min, 200 mm / min to 400 mm / min, 200 mm / min to 300 mm / min, 300 mm / min to 500 mm / min, 300 mm / min to 400 mm / min, or 400 mm / min to 500 mm / min.

[0527] In some embodiments, the adhesive is rate-responsive within a range relevant to human skin removal. For example, when the retraction rate of the rheometer adhesion test under the test conditions described in this invention changes from 1 micrometer per second to 8000 micrometers per second, the adhesive may exhibit a 30-fold change in adhesive work in J / m². The rate-responsive behavior may be characterized by a change in adhesive work of 1 to 1.5 times, more preferably 1 to 2 times, more preferably 1 to 3 times, more preferably 1 to 4 times, more preferably 1 to 5 times, more preferably 1 to 7 times, more preferably 1 to 10 times, more preferably 1 to 12 times, more preferably 1 to 13 times, more preferably 1 to 15 times, more preferably 1 to 16 times, more preferably 1 to 20 times, more preferably 1 to 23 times, more preferably 1 to 25 times, more preferably 1 to 27 times, more preferably 1 to 30 times or more.

[0528] In some embodiments, the stimulus-responsive polymer is rate-responsive within a range relevant to human skin removal. For example, when the retraction rate of the rheometer adhesion test under the test conditions described in this invention changes from 1 micrometer per second to 8000 micrometers per second, the adhesive can exhibit a 30-fold change in adhesive work in J / m². The rate-responsive behavior can manifest as a change in adhesive work of 1 to 1.5 times, more preferably 1 to 2 times, more preferably 1 to 3 times, more preferably 1 to 4 times, more preferably 1 to 5 times, more preferably 1 to 7 times, more preferably 1 to 10 times, more preferably 1 to 12 times, more preferably 1 to 13 times, more preferably 1 to 15 times, more preferably 1 to 16 times, more preferably 1 to 20 times, more preferably 1 to 23 times, more preferably 1 to 25 times, more preferably 1 to 27 times, more preferably 1 to 30 times or more, within a retraction rate of 1 to 8000 micrometers per second.

[0529] In some implementations, the resilience exhibited by the stimulus-responsive polymer, or tan δ multiplied by G The integral of the graph with respect to angular frequency is 2.5 [MPa (rad / s)] (in the angular frequency range of 0 to 50 rad / s). The stimulus-responsive polymer of this invention, in the angular frequency range of 0 to 50 rad / s, tan δ multiplied by G... The integral values ​​of the graph of the diagonal frequency can 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.

[0530] In some implementations, the adhesive exhibits resilience, or tan δ multiplied by G. The integral of the graph with respect to angular frequency is 2.5 [MPa (rad / s)] (in the angular frequency range of 0 to 50 rad / s). The adhesive containing the polymer of this invention has an angular frequency range of 0 to 50 rad / s. tan δ multiplied by G The integral values ​​of the graph of the diagonal frequency can 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.

[0531] In some implementations, when the contraceptive device is removed by gentle peeling after the adhesive layer has adhered to the penis or vagina, removal within less than 15 seconds (e.g., less than 10 seconds, less than 8 seconds, or less than 5 seconds) will cause minimal or no pain in the subject.

[0532] In some implementations, the adhesion site exhibits limited or no irritation after removal of the contraceptive device. In research settings, various methods for quantitatively assessing skin damage are known. Some of these models are based on measurements of baseline skin properties that change when the skin is subjected to stress. Measurable parameters such as skin hydration, transepidermal water loss (TEWL), and irritation will provide information distinguishing damaged skin from healthy skin. See, for example, Bernatchez, S. et al., ADVANCES IN WOUND CARE, Vol. 2, No. 4 (2022), which is incorporated herein by reference. Recombinant human epidermal models are also available, exhibiting reasonable similarity to native human tissue in morphology, lipid composition, and biochemical markers. See, for example, EpiSkin, SkinEthic, and EpiDerm. Animal models of skin damage are also known in the art, including pigs and rodents. See, for example, Summerfield, A. et al., Molecular Immunology, Vol. 66, No. 1, July 2015, pp. 14-21.

[0533] Methods for using the packaging or packaging adhesives disclosed herein are also disclosed.

[0534] In one embodiment, a method for packaging an adhesive is provided, comprising (i) providing a package disclosed herein; and (ii) introducing an adhesive (e.g., a condom, a medical adhesive) into the package.

[0535] 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 (iii) applying the adhesive to a target site. In some embodiments, the adhesive is a sensation-enhancing condom, for example, as disclosed herein. See Figure 2. In some embodiments, the adhesive is a medical adhesive, for example, as disclosed herein.

[0536] In another embodiment, a method of using the packaged adhesive disclosed herein is provided, comprising (i) opening the package; and (ii) inverting the package to align, adhere, and deposit the adhesive onto a target substrate. In some embodiments, the adhesive is a sensation-enhancing condom. In some embodiments, the adhesive is a medical adhesive, for example, for protecting or closing wounds.

[0537] In one implementation, the method requires the use of a single hand (or prosthetic assistance).

[0538] Methods for manufacturing the packaging and / or packaging adhesives disclosed herein are also disclosed.

[0539] In one embodiment, a method of manufacturing the packaging disclosed herein is provided, comprising (i) thermoforming a sheet of hot-melt thermoplastic or thermosetting material on a rigid molding die or an array of rigid molding dies; (ii) vacuuming to draw the stretchable plastic sheet into the shape of the rigid molding die or applying positive pressure to push the stretchable plastic sheet into the shape of the rigid molding die and allowing the stretchable plastic sheet to cool, thereby producing a container of the packaging; (iii) separating the container from excess plastic sheet by cutting or punching; (iv) optionally adding a thin layer of liquid to the container; (v) adding an adhesive to the container; and (vi) sealing the packaging by adhering a removable film cap to an opening in the container.

[0540] In some implementations, the thin layer of liquid in step (iv) is added at an elevated temperature or before the plastic packaging has fully cooled to ambient temperature after thermoforming, so that the liquid can more easily wet the inner surface of the packaging.

[0541] In one embodiment, the adhesive is a sensation-enhancing condom, such as those disclosed herein.

[0542] In one implementation, the adhesive is a medical adhesive, for example, used to protect or close a wound.

[0543] In one embodiment, the adhesive is sterilized before being added to the container in step (iv), for example, by electron beam or gamma irradiation.

[0544] In one embodiment, a feel-enhancing condom or other adhesive-containing substrate (e.g., medical skin adhesive) manufactured by roll-to-roll, thermoforming, or other planar processes can be deposited into the packaging by die-cutting or cutting the condom from a manufactured sheet and then depositing it by gravity dripping or by pick-and-place deposition using a suction or transfer liner (e.g., silicone paper or other suitable release liner). It is assumed that an optional liquid capillary membrane has been deposited in the packaging prior to condom insertion.

[0545] In another embodiment, a deformable transfer pad made of silicone or other (non)linear elastic material can be used to transfer the condom into the packaging.

[0546] In another embodiment, the condom can be made by reverse dip coating or conventional dip coating, allowing the condom to slide directly from the dip molding die into the packaging (if dip coating is done with the adhesive on the inside, i.e., reverse dip coating), or to flip upon removal from the dip molding die (conventional dip coating, where the adhesive is on the outside). The removal device can be a rigid or compliant arm, or an air jet.

[0547] In another embodiment of the packaging insertion process, the condom is placed in the packaging and may be vibrated or rotated about its axis to remove any trapped air bubbles and help it settle to a stable position within the packaging.

[0548] A method for manufacturing packaging without an adhesive-containing substrate is also disclosed, which may be added at a later time as disclosed herein.

[0549] One embodiment includes providing a method for manufacturing a package for subsequent manufacturers to encapsulate the adhesive-containing substrate disclosed herein, comprising (i) thermoforming a hot-melt thermoplastic sheet on a molding die or array of molding dies; (ii) vacuuming to draw the stretchable plastic sheet into the shape of a rigid molding die, thereby producing a container; (iii) separating the container from excess plastic sheet by cutting or punching; (iv) optionally adding a retaining element to the container; and (v) optionally partially or completely adhering a removable or resealable film cap to an opening in the container, thereby producing a package for containing an adhesive-containing substrate.

[0550] In some implementations, the thin layer of liquid in step (iv) is added at an elevated temperature or before the plastic packaging has fully cooled to ambient temperature after thermoforming, so that the liquid can more easily wet the inner surface of the packaging.

[0551] In some embodiments, the retaining element added in step (iv) may be covered with a suitable release liner, such as silicone-impregnated paper or other protective barrier, to prevent contamination of the retaining element before the substrate containing adhesive is added at a later time.

[0552] In some implementations, the retaining element added in step (iv) may be added in a later step after the packaging has been reopened and before the substrate containing the adhesive has been added to the container.

[0553] In one embodiment, the film cap may be attached to the opening of the container at a single point or on a small area of ​​the flange of the container, the area being less than 1% of the flange area, 1% to 10% of the flange area, 10% to 50% of the flange area, or 50% to 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 cap is adhered to the opening of the container.

[0554] In another embodiment, the membrane cover can be attached to the opening of the container with an adhesive that can be opened and resealed once or multiple times, so that the membrane cover can be removed at a later time, the substrate containing the adhesive can be placed in the container, and the cover can be reattached or resealed to the opening of the container.

[0555] In some implementations, the packaging may be sealed in a plastic bag or wrapping to prevent contamination of the packaging before the addition of a substrate containing adhesive at a later time.

[0556] Developable surface

[0557] Developable surfaces are a class of known surfaces in the field of differential geometry. Developable surfaces are smooth surfaces (without kinks, corners, or folds) with zero Gaussian curvature.

[0558] Developable surfaces have demonstrated value in shipbuilding, architectural structures, and automotive design. Developable surfaces can be constructed by bending and rolling an initially flat sheet of material into a desired three-dimensional shape without subjecting the material to localized stretching or compression. This is particularly advantageous when considering building materials that are not easily deformed (stretched or compressed). Common examples of such materials are paper and plywood, which can be easily bent, folded, or rolled. However, when these materials are subjected to tension exceeding a threshold load, they tend to tear or break rather than undergo large elastic or plastic deformation. And when they are subjected to compressive loads exceeding a threshold, they typically buckle.

[0559] In hull design, it's rare for a hull geometry to be formed entirely from a single deployable surface. Therefore, several deployable surfaces are typically joined together, where each "patch" can be considered a deployable surface. Together, they form the hull, which can be viewed as a "polysurface." Polysurfaces are usually watertight; however, the joints or boundaries between adjacent surfaces do not need to be continuous, smooth (e.g., corners or chines), or have the same or continuous properties. These joints are typically secured with glue / adhesives, fillers, welds, or other methods.

[0560] Materials with unfoldable surfaces have a 3D surface that can be "unfolded" into a flat surface without localized stretching or compression. Common examples include any ring or cone that can be made from a sheet of paper by rolling and bending it, and then gluing the ends together with tape / glue. This would constitute an unfoldable surface because the paper cannot be stretched or compressed; it would only tear. As another example, one could cover a hemisphere (such as a globe) by stretching a sheet of latex across it without causing the latex to wrinkle, fold, or tear. This cannot be done with a flat sheet of paper.

[0561] The implementation plan includes an enhanced sensation condom (ESC) designed to contain ejaculate fluid and, when used as a contraceptive, prevent the transfer of sperm to the receiving partner, thereby preventing pregnancy during vaginal intercourse. It can also be used to contain ejaculate fluid (i.e., semen, also understood to include pre-ejaculate fluid, particularly that which may contain sperm) and prevent its transfer to the receiving user during penetrating or non-penetrating vaginal, anal, or oral intercourse to mitigate the spread of sexually transmitted infections (STIs), prevent the receiving partner from unintentionally ingesting ejaculate fluid, or otherwise contain ejaculate fluid, such as in the hope of reducing cleanup or mess.

[0562] The ESC implementation includes a barrier (sometimes referred to as a "barrier layer") for containing ejaculate fluid, which is secured to the glans penis (hereinafter simply referred to as the "glans") by a second component, an adhesive layer that also serves to provide a seal between the barrier and the user's skin. The adhesive layer is designed to be secured to the glans; however, due to differences in human anatomy, some users may find that a portion of the adhesive area may wrap over the coronal sulcus, the frenulum, and may come into contact with a small portion of the surrounding penile skin. However, it should be understood that these are due to the significant differences naturally present in human anatomy and should not be interpreted as operating in a manner different from the exemplary pattern described in this disclosure. Furthermore, the geometry and mechanical properties of the barrier layer and adhesive layer have been selected to optimize performance without compromising the intended purpose of maintaining fixation to the male user during intercourse and containing ejaculate fluid. By being secured to the glans, the majority of the penile body remains exposed to natural naked contact for sexual stimulation, in contrast to the complete penile skin coverage provided by conventional condoms.

[0563] In one embodiment, the barrier comprises one, two, or more sheets of elastomeric or plastic material that conforms or hangs easily to the geometry of the user's glans penis and expands under the pressure of human ejaculation to contain the expelled fluid within a reservoir having a three-dimensional shape, and an adhesive layer connects to the reservoir at an angle that mitigates peeling of the adhesive layer from the glans penis skin by loading the adhesive layer primarily in a shear manner.

[0564] In one embodiment, the adhesive layer comprises an adhesive material exhibiting stimulus-responsive or dynamically changing material behavior. Such adhesives are adhesive when applied to the skin and remain fixed throughout sexual intercourse. When appropriate stimulation is applied to the adhesive, the stimulus-responsive adhesive exhibits lower peel force, making it easier and less painful to remove than when no specific stimulation is applied, particularly compared to medical and household adhesives known in the art (e.g., 3MTegaderm™). Several embodiments and compositions are disclosed herein, the most advantageous being shear rate-responsive adhesives, wherein the stimulation is a continuous change in the applied adhesive shear peel rate, and the measured peel force changes responsively and dynamically.

[0565] Embodiments of the adhesive compositions disclosed herein exhibit several properties novel to the art. Embodiments of the compositions are cross-linked or lightly cross-linked polymeric network materials that leave little or no residue on the skin after removal, including by peeling. Embodiments of the adhesives exhibit energy-dissipative viscoelastic behavior, with strain capacities consistent with or greater than those of human skin (particularly the glans penis), thus conforming to skin and body movements. The advantageous compositions disclosed herein exhibit very low to non-adhesiveness to naturally moist tissues or mucous membranes (e.g., tissues constituting the urethra, vaginal walls, rectum, and mouth). Such behavior mitigates problems associated with adhesives and adhesive condoms known in the art, where the adhesive can obstruct or seal the urethral opening or adhere to inner surfaces, causing significant pain upon removal. Furthermore, the adhesives disclosed herein mitigate the risks of adhesion to the vaginal wall or mouth, causing pain or discomfort to one or both users, or loss of the device within the receiving user's body. However, these compositions are hydrophobic, and once dry, their adhesive behavior is not diminished by exposure to water, nor is it dissolved or washed away by water from the substrate to which it is applied.

[0566] Exemplary adhesives include compositions of polymeric adhesives formed using roll-to-roll or sheet coating processes known in the art. However, manipulating cross-linked or lightly cross-linked adhesives from planar sheets or films into more complex surfaces presents a significant challenge. This document discloses novel deployable three-dimensional annular or enclosed adhesive layer geometries, and novel methods for manufacturing such three-dimensional adhesive rings containing adhesives, including cross-linked or lightly cross-linked adhesives. The combination of the deployable ring geometry and the manufacturing process enables machines to manipulate cross-linked adhesives attached to release liner (most typically siliconized paper or surface-treated thermosetting plastic films) to create ESCs. While not exhaustive, this method may be preferred when the barrier is composed of non-thermoplastic materials, such as natural rubber latex, condoms, and materials ubiquitous in the medical barrier field.

[0567] For implementation schemes addressing concerns about allergies to natural rubber latex, alternative manufacturing methods are disclosed for use with barrier bodies having thermoplastic alternative compositions, including thermoplastic polyurethanes, thermoplastic elastomers, polyisoprene, and nitrile rubber.

[0568] The implementation plan describes a solution to the unmet social need for pleasurable contraception solutions. The solution of an adhesive condom that adheres to the tip of the penis (glans) is an impactful innovation, embodying a novel adhesive strong and robust enough to remain adhered to the penis during intercourse, contain a certain amount of semen during ejaculation, and not damage penile skin tissue or otherwise cause pain, as also described in the background art above, including not damaging the mucous membrane tissue in the urethra by adhering to moist or aqueous tissue.

[0569] The implementation plan highlights the difference between a planar (flat) adhesive surface and a three-dimensional surface that can be unfolded (flattened) into a planar surface without deformation. It is important to note the distinction between "unfolding" a 3D surface into a planar (2D) surface (best expressed in colloquial terms as "flattening") and "projecting" a 3D surface onto a planar (2D) surface. Any surface can be projected onto any plane, but the ability of a given surface to unfold into its planar representation is a unique property of this particular family of 3D surfaces.

[0570] The geometry presented in this paper is referred to as a three-dimensional ring. The unfoldable three-dimensional ring used in this paper is a surface with infinitesimal or finite thickness and two edges (each edge can be traversed by an edge walk terminating at the starting position), and optionally may have corners, curves, or kinks. If these geometries exist in a plane, they are in the form of a generalized ring, where the region of interest spans the area between two planar polygons or curved polygons. See, for example, Figures 43 (cross-sectional view) and 49 (fabricated example).

[0571] The implementation plan provides a solution to the problem of implementing adhesive condoms in a manner that is robust in use (intercourse, fixation and / or sealing to body appendages such as the penis) and can be economically manufactured on a large scale.

[0572] In one implementation, for penises with significantly different geometries and anatomical structures among users (in terms of shape, size, and the position of the urethral opening on the glans), the condom is designed to fit snugly and withstand intercourse. This implementation addresses these issues through geometrical design innovation. The geometry described herein possesses a novel ability to fit different penile geometries and urethral opening positions, specifically in terms of three-dimensional geometry.

[0573] The implementation schemes differ from existing technologies in the field of adhesive or partial condoms in that, for example, they do not require the user to use their hands or fine dexterity, or both, to apply or remove the device, thereby enabling a wider user audience to use the device and improving the robustness of the device in any user's use to reduce the possibility of failure.

[0574] Various implementations feature geometries that conform to the smaller side of the penis's geometry, with minimal wrinkling or folding. Because the curvature of the adhesive layer geometry matches the smaller radius of curvature of the average penile geometry, the likelihood of wrinkling introduced during application is lower compared to an initially flat geometry that must be significantly bent by the user to match the smaller glans radius. Reduced wrinkling or folding lowers the risk of poor adhesion, thereby reducing the risk of delamination during intercourse, ejaculation, or when filled with semen. Reduced wrinkling or folding also reduces the likelihood of allowing semen or pre-ejaculate fluid to flow from the male user to the receiving user. The inventors suggest that the small user geometry is a limiting factor in the functional performance of ESCs or conventional condoms.

[0575] Furthermore, the novel geometry presented herein accommodates larger penises by simply “slipping higher” over the glans. In some non-limiting embodiments, the condom exhibits performance advantages over other partial condoms because it adheres substantially to the glans skin, which exhibits greater surface roughness and a larger adhesive surface area, as well as skin mechanical behavior and chemical properties, compared to the penile body skin adhered to by some partial condoms, enabling the adhesion to withstand intercourse. The glans geometry will also appear more gentle because the adhesive or device generally does not need to bend or wrinkle to an undesirable degree, as the penis size (particularly its principal curvature on the glans) is smaller compared to the condom size; i.e., the penis appears “flatter” to the adhesive. This relative “flatness” helps reduce unfavorable internal strain and bending moments that could lead to delamination or adverse (peeling) stress.

[0576] In cases of compressive "circumferential stress," this may be caused by the response of the adhesive condom to a larger penis, as the adhesive portion of the condom (along with the barrier layer in some embodiments) is stretched at the glans. In such cases, this compressive circumferential stress can provide an additional advantageous mechanism to help the condom seal and remain attached to the penis, enhancing the seal for containing semen in a manner similar to the compression seal of a conventional condom against the base of the penis (when the condom size is appropriate for the user).

[0577] One embodiment addresses challenges in the large-scale manufacturing of adhesives, including but not limited to adhesives that adhere to human skin. Some adhesives are prepared or formed by coating and / or drying / curing a liquid resin (neat or solvent-based) onto a substrate, tape, or release liner. In some embodiments, the adhesive is cured from monomers, prepolymers, or oligomers using thermal or UV curing techniques. In some embodiments, a UV-curable adhesive is coated onto a release liner, or between two release liners, and subsequently transferred or mated to a substrate in a later step. In some embodiments, a suitable release liner is a paper-based substrate (e.g., silicone paper). In other embodiments, suitable release liners include optically and UV-transparent films. In other embodiments, the optically or UV-transparent film is polyethylene terephthalate coated with a fluoropolymer or silicone.

[0578] One implementation addresses the difficulties associated with creating three-dimensional shapes using these adhesives. Processable, lightly crosslinked, branched, hyperbranched, or linear adhesives can be formed into layers and processed to adhere or mat to another shape, and coated onto deformable (e.g., compliant, plastically deformable, or highly elastic) release liner, after which they can be transferred or mated onto generally 3D geometric substrates (whether these substrates are rigid or compliant to any degree). However, if they are coated onto non-deformable release liner (e.g., silicone paper), the construction methods for achieving 3D geometry or transfer are limited to non-deformable operations. Adhesives can also be coated onto compliant barrier materials (i.e., latex, thermoplastic (elastomer), or thermoplastic polyurethane), which would allow the buildable to be configured into 3D geometry.

[0579] In some implementations, when attempting to achieve a smooth and continuous adhesive layer during transfer, manipulation, or otherwise transformation into a 3D shape, bending and “curling” into (generalized) cylinders, (generalized) cones, (generalized) helices, and tangential curves is the only option. These specific shapes allow the adhesive to remain fixed to the release liner, facilitating the manipulation and handling of the adhesive (and preventing contamination before it is ready for use). In one implementation, utilizing such geometry enables the performance required for the aforementioned problems and solutions to be achieved while also meeting the constraints of adhesive manufacturing. Note that these non-deformation requirements are typically driven by the release liner, but can also be driven by the adhesive.

[0580] In some implementations, it is desirable to add texture to the outer surface of the barrier layer, such as a texture to enhance the sensation for one or two users, or to add texture to the inner surface of the barrier layer to enhance the sensation for one or two users. Examples of such textures are raised areas, dots, ribs, diamonds, or random roughness. Additional reinforcements may also be added to enhance the use of the product, such as coloring, printed decorative or illustrative patterns and markings, fragrance additives, flavoring additives, irritating additives (e.g., additives that induce a cooling / icy or warming sensation), or lubricants.

[0581] In some implementations, these shapes may have internal stresses limited to internal bending moments. When integrated along the thickness (measured at any point on the surface), there are finite tensile or compressive stresses.

[0582] Enhanced Sensation Condoms - Single Body

[0583] In some embodiments, the ESC is a single unit comprising two components: a barrier body consisting of a single barrier layer and an adhesive layer. The barrier layer is a compliant diaphragm or membrane that acts as the body of the condom to contain ejaculate fluid. The barrier layer is secured to the glans penis by the adhesive layer. The adhesive layer of the condom has an annular (ring-shaped) region for attachment to the glans penis, more specifically a three-dimensional ring shape. In exemplary embodiments, the three-dimensional ring shape is a deployable surface.

[0584] In some embodiments, the non-rigid, non-curling partial condom can be removed with little or no pain, for example, measured using the Wong-Baker Qualitative Pain Assessment (WBQPA) on a scale of 0 (painless) to 10 (maximum pain). In some embodiments, the pain on the WBQPA scale is less than 4 when the adhesive layer is removed by gentle peeling, for example, less than 3, less than 2, less than 1, or 0. In some embodiments, the non-rigid, non-curling partial condom may have a loss modulus of 0.1 MPa to 0.5 MPa.

[0585] In some embodiments, the aforementioned non-rigid, non-curling partial condoms leave little or no residue on the skin after removal, for example, less than about 10%, less than about 5%, less than about 1%, or 0% residue.

[0586] In some implementations, when measured in subjects or groups of subjects, the failure rate of the contraceptive device (clinical or non-clinical) 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 lower. Clinical failure is defined as the contraceptive device (e.g., a condom) breaking, tearing, leaking, or completely slipping off after initial insertion and before final complete withdrawal. Non-clinical failure is defined as the contraceptive device (e.g., a condom) breaking, tearing, leaking, or partially slipping off.

[0587] In some implementations, the leakage rate of the condom is less than about 6%, for example, less than about 5%, less than about 4%, less than about 3%, less than about 2%, or less than about 1%.

[0588] Barrier layer

[0589] The barrier layer has an inner surface and an outer surface to contain semen between the inner surface and the surface of the user's penis. The barrier layer is between 5 and 250 micrometers, or between 25 and 100 micrometers in some embodiments, or between 25 and 75 micrometers in some embodiments.

[0590] In some embodiments, the barrier layer comprises a polymer diaphragm or membrane exhibiting elastomeric or flexible thermomechanical behavior. In some embodiments, the barrier layer is a diaphragm or membrane.

[0591] In some embodiments, the barrier layer comprises natural latex rubber, synthetic rubber, amorphous polyurethane, semi-crystalline polyurethane (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), elastomers or flexible materials, or blends thereof. In some embodiments, the barrier layer comprises natural latex rubber, synthetic rubber, or polyurethane.

[0592] In some implementations, the barrier layer is not polyurethane.

[0593] In some implementations, the barrier layer is not loosely fitted.

[0594] In some embodiments, the barrier layer exhibits stimulus-responsive behavior that enables selective permeability, controlled permeability, or controlled porosity. Exemplary stimuli for the stimulus-responsive barrier layer include temperature changes, physicochemical changes, light, ultrasound, changes in ionic strength, pH changes, magnetic fields, and mechanical forces. In some embodiments, the stimulus of the stimulus-responsive barrier layer differs from the stimulus of the stimulus-responsive polymer in the adhesive layer. In some embodiments, the stimulus of the stimulus-responsive barrier layer is the same as the stimulus of the stimulus-responsive polymer in the adhesive layer.

[0595] In some embodiments, the barrier layer further comprises one or more additives, for example, to enhance its performance. Exemplary additives include, but are not limited to, polymers, ceramics, metallic materials, or spherical, rod-shaped, disc-shaped, or other shaped structures. Additive materials include silica, metal oxides, iron oxides, metals, nitinol, ceramics, conductive polymers, etc. The additive materials may be uniformly or non-uniformly dispersed or cross-linked within the material.

[0596] In some embodiments, the thickness of the barrier layer is from 0.001 mm to 2 mm, for example, 0.001 mm to 1.5 mm, 0.001 mm to 1 mm, 0.001 mm to 0.5 mm, 0.001 mm to 0.1 mm, or 0.001 mm to 0.01 mm. In some embodiments, the thickness of the barrier layer is from 0.025 mm to 0.25 mm, for example, 0.025 mm to 0.2 mm, 0.025 mm to 0.15 mm, 0.025 mm to 0.1 mm, or 0.025 mm to 0.05 mm. In some embodiments, the thickness of the barrier layer is at least 0.01 mm, for example, 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.

[0597] In some implementations, the thickness of the barrier layer is less than about 200 micrometers, for example, about 40 to 100 micrometers, or about 40 micrometers, about 50 micrometers, about 60 micrometers, about 70 micrometers, about 80 micrometers, about 90 micrometers, or about 100 micrometers.

[0598] In some implementations, the thickness of the barrier layer is less than about 180 micrometers, for example, less than about 160 micrometers, less than about 140 micrometers, less than about 120 micrometers, less than about 100 micrometers, less than about 80 micrometers, less than about 60 micrometers, less than about 40 micrometers, or less than about 20 micrometers, but in each case it is greater than zero.

[0599] In some embodiments, the barrier layer has a planar or curved geometry selected from square, circular, elliptical, hemispherical, rectangular, polygonal, or curved polygonal shapes. In some embodiments, the barrier layer is not tubular.

[0600] In some embodiments, the barrier layer has a first geometry before being adhered to the penis and transforms into a second geometry upon application to the penis.

[0601] In some embodiments, the barrier layer has a circular geometry. In some embodiments, the radius of the circle is at least about 0.5 cm, for example, 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.

[0602] In some embodiments, the barrier layer has a rectangular geometry. In some embodiments, the rectangle has a length of 0.5 cm to 5 cm and a width of 0.5 cm to 5 cm. In some embodiments, the length of the rectangle is 0.5 cm to 4 cm, 0.5 cm to 3 cm, 0.5 cm to 2 cm, 0.5 cm to 1 cm, 1 cm to 5 cm, 1 cm to 4 cm, 1 cm to 3 cm, 1 cm to 2 cm, 2 cm to 5 cm, 2 cm to 4 cm, 2 cm to 3 cm, 3 cm to 5 cm, or 4 cm to 5 cm. In some embodiments, the width of the rectangle is 0.5 cm to 4 cm, 0.5 cm to 3 cm, 0.5 cm to 2 cm, 0.5 cm to 1 cm, 1 cm to 5 cm, 1 cm to 4 cm, 1 cm to 3 cm, 1 cm to 2 cm, 2 cm to 5 cm, 2 cm to 4 cm, 2 cm to 3 cm, 3 cm to 5 cm, or 4 cm to 5 cm.

[0603] In some embodiments, the barrier layer has an elliptical geometry. In some embodiments, the ellipse has a principal 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 individual secondary radii 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.

[0604] In some embodiments, in the case of a rectangular barrier layer, the main dimensions of the barrier layer are 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.

[0605] In some implementations, the barrier layer does not contain one or more protrusions. Instead, according to this implementation, the barrier layer is a conventional, simple geometry (e.g., rectangular, elliptical, or circular).

[0606] In some embodiments, the barrier layer does not contain one or more protrusions. Instead, according to this embodiment, the barrier layer is a conventional, simple geometry (e.g., rectangular, elliptical, or circular). This contrasts with the protruding wings disclosed, for example, in WO2014178661A1.

[0607] In some embodiments, the barrier layer contains a lubricant on its outer surface (e.g., the outer surface of a contraceptive device (condom or diaphragm)). In some embodiments, the lubricant is selected from water-based lubricants, silicone-based lubricants, and oil-based lubricants.

[0608] In some embodiments, the barrier layer contains a spermicide on its outer surface (i.e., the outer surface of the condom). In some embodiments, the spermicide is selected from nonoxynol-9, octoxynol-9, benzalkonium chloride, lactic acid, methylphenidate, and combinations thereof.

[0609] In some embodiments, the condom also includes a reservoir sized and shaped to collect semen ejaculated from the penis. In some embodiments, the reservoir is configured to be located distal to the urethral opening of the penis. In some embodiments, the reservoir is configured at the tip of the condom, along the side, or at the base, or below the base.

[0610] In some implementations, the reservoir and the barrier layer are continuous, that is, the reservoir and the barrier layer are part of the same structure / not separate structures, and are not adhered or otherwise connected by a connecting device.

[0611] In some implementations, the reservoir self-forms upon being subjected to pressure from penile ejaculation and does not have a predetermined geometry.

[0612] In some embodiments, the reservoir includes a polymer coating that swells or gels upon contact with semen. In some embodiments, such swelling or gelation retains sperm within the reservoir. Exemplary polymer coatings include, but are not limited to, chitosan, alginate, polyacrylic acid, cross-linked polyacrylic acid, sodium polyacrylate, cross-linked sodium polyacrylate, and combinations thereof.

[0613] In some embodiments, the reservoir is roughly spherical in nature and has 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, or about 5.0 mm or greater.

[0614] In some embodiments, the reservoir is roughly cylindrical in nature and has 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 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.

[0615] In some embodiments, the condom further includes an elastomeric ring attached to an outer portion of the inner surface of the barrier layer or to the edge of the barrier layer. In some embodiments, the elastomeric ring surrounds the base of the barrier layer and can be stretched to enclose the barrier layer and secure it to the base of the glans penis. Optionally, a contractile force can be applied to enhance the adhesion of the condom to the penis and prevent stress concentration or shear forces from removing the adhered barrier layer during mechanical disturbances such as those associated with sexual activity.

[0616] In some embodiments, the cross-sectional diameter of the elastomeric ring is at least 0.1 mm, for example, at least 0.5 mm, at least 1.0 mm, at least 2.0 mm, or at least 3.0 mm or greater. In some embodiments, the total diameter of the elastomeric ring is at least 0.25 times (0.25x) the diameter of the barrier layer, for example, 0.25x to 1x, or 0.25x, 0.50x, 0.75x, or 1.0x.

[0617] In some implementations, the elastomeric ring includes raised rings or bumps to enhance sexual sensation or pleasure.

[0618] In some embodiments, the condom further includes one or more protruding arms connected to the elastomeric ring or barrier layer. In some embodiments, the protruding arms can be stretched to expand to surround and secure the barrier layer to the base of the glans penis, and optionally apply a contractile force that enhances the adhesion of the condom to the penis and prevents stress concentration or shear forces from removing the adhered barrier layer during mechanical disturbances such as those associated with sexual activity.

[0619] In some embodiments, the projecting 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 projecting arms. In some embodiments, the projecting arms have 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 longer, 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 wider.

[0620] A portion of the inner surface of the barrier layer is covered by an adhesive layer that extends to the free edge (peripheral edge) of the inner surface of the barrier layer to prevent accidental peeling off the device during use. One embodiment addresses a significant problem associated with the free overhanging edge of the user's penis not adhering sufficiently, which can lead to partial or complete delamination of the device, thereby reducing and potentially impairing its ability to contain semen. The fraction of the barrier layer area covered by the adhesive layer can 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 a planar geometry, an unfoldable three-dimensional closed loop geometry, or a hyperbolic three-dimensional closed loop geometry that conforms to the geometry of the adhesive layer, with no wrinkles, folds, or gaps between the two layers.

[0621] The barrier layer is an impermeable elastic or plastic membrane with sufficient conformability to easily conform to the shape of the glans penis and surrounding anatomy. Suitable materials include natural latex rubber, thermoplastic elastomers, and thermoplastic polyurethanes, polyurethanes, polyethylene, polypropylene, and polyesters. Advantageous materials have a strain capacity (maximum strain before rupture or leakage failure) between 50% and 2000%, or between 100% and 800% in some embodiments, or between 125% and 700% in some embodiments. As a non-limiting rule of thumb, for hemispherical reservoirs, the strain capacity to accommodate a given increase in volume relative to the unstrained initial reservoir volume is approximately proportional to the 2 / 3 power of the ratio of the final volume to the initial void volume.

[0622] Both elastically deformable and plastically deformable 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 undergoes plastic deformation, the yield stress should be within the same limits. Non-limiting suitable materials may have Shore A hardness measurements between 30A and 100A.

[0623] The reservoir for containing semen includes a barrier layer area that does not adhere to the user's glans penis.

[0624] In one embodiment, the reservoir includes a pre-formed portion of a barrier layer with a void volume between 0.1 and 10 mL, or between 0.5 and 3.5 mL in some embodiments, or between 1.0 and 3.0 mL in some embodiments. In another embodiment, the reservoir is self-formed, such that the void volume is 0 mL.

[0625] In some embodiments, a portion of the inner surface area of ​​the adhesive layer near the center of the device (the surface that directly contacts the glans penis during use) is passivated so that it does not adhere to the skin, the barrier layer, or itself. The percentage of the adhesive layer surface area that is passivated can be as high as 60%, 50%, 40%, 30%, 20%, 10%, or 5% of the adhesive layer surface area. Exemplary methods of passivating the adhesive layer include covering the area with an elastomer or plastic film, such as natural latex rubber, polyurethane, polyisoprene, or thermoplastic elastomer.

[0626] The reservoir for containing semen comprises the volume defined by the glans penis and the area of ​​the barrier layer not covered by the adhesive layer, plus the area of ​​the passivated adhesive layer.

[0627] In some embodiments, the reservoir is pre-formed and has an absorbent material attached to a portion of its inner surface, such as a superabsorbent polymer contained within a thin, permeable polyethylene cover, which absorbs or gels ejaculate fluid to reduce the likelihood of leakage. The absorbent material can have a thickness between 50 and 150 micrometers. The portion of the reservoir covered by the absorbent material can be between 10% and 90%.

[0628] In some embodiments, the reservoir is self-forming and has an absorbent material attached to a portion of its inner surface, such as a superabsorbent polymer contained within a thin, permeable polyethylene covering, which absorbs or gels ejaculate fluid to reduce the likelihood of leakage. The absorbent material can have a thickness between 50 and 150 micrometers. The portion of the reservoir covered by the absorbent material can be between 10% and 90%.

[0629] Storage

[0630] In some embodiments, the reservoir is pre-formed before use and has a volume between 0.1 and 10 mL, or between 0.5 and 3.5 mL in some embodiments, between 1.0 and 3.0 mL in some embodiments, or between 1.5 and 2.5 mL in some embodiments.

[0631] In other implementations, the reservoir is self-formed and visually indistinguishable from the rest of the barrier layer before use.

[0632] In some other embodiments, the reservoir is self-formed and is distinguished from the barrier layer by the absence of adhesive on the inner surface of the barrier layer.

[0633] In some embodiments, the reservoir has an absorbable material, such as a superabsorbent polymer with a thin polyethylene cover, which is paired to the inner surface of a barrier layer covering the inner surface portion of the reservoir.

[0634] In some implementations, the surface containing the reservoir may be a hyperbolic surface.

[0635] Reinforcing ribs

[0636] In some embodiments, the reservoir has reinforcing ribs that assist in semen retention by forming a neck within the reservoir for the user to pinch during removal, and mitigate post-ejaculation creep delamination of the adhesive by constraining expansion of the reservoir at the point of contact with the adhesive layer, thereby maintaining a smaller angle and reducing the peeling effect that leads to undesirable adhesive delamination, which could result in partial or complete loss of semen retention. The reinforcing ribs comprise fine ribs made of a suitable material that has a hardening effect on the reservoir area. One such suitable material is natural latex rubber, polyisoprene, or polyurethane, in embodiments where the barrier layer comprises layers of natural latex rubber, polyisoprene, or polyurethane, and in such embodiments, the reinforcing ribs are molded into the barrier layer. Another suitable material is plastic filaments, such as nylon, wherein the filaments are adhered to the outer or inner surface of the barrier layer.

[0637] In some embodiments where the reinforcing rib is a filament, the filament is adhered to the outer surface of the barrier layer and one end is free, having sufficient length to be gripped between two fingers, and may have a knot or loop at the free end to aid gripping. In exemplary embodiments, the length of the free end is between 1 and 2 centimeters.

[0638] This article discloses a method using reinforcing ribs (e.g., threads or filaments bonded to the ribs) with free ends. After ejaculation, the free ends of the reinforcing ribs (e.g., filaments) can be grasped by the user (e.g., using fingers or suitable tools, such as tweezers, which may be provided in the packaging) and wrapped around the expanded semen-containing reservoir, or pulled to contract the outer edge of the reservoir, thereby helping to retain semen within the device when the adhesive portion is peeled from the skin during removal.

[0639] In some embodiments where the barrier layer or barrier-adhesive composite is formed by a thermoforming process, the reinforcing ribs or filaments may be positioned to the adhesive or barrier layer prior to the thermoforming step, as shown in the figure below. In other embodiments, if a thermoforming step is used, they are positioned and secured / fastened after the thermoforming step.

[0640] Figure 34A A condom comprising a barrier layer 1001 and a deployable adhesive layer 1002, which can be separated along a (approximately) vertical seam (as shown) and unfolded into a flat sheet without local stretching or compression (deformation). A reservoir 1003 is formed between the barrier layer and the glans penis; in this embodiment, no adhesive layer is present here. The reservoir area does not need to be deployable. In this embodiment, the condom is fully secured to the glans penis 1101, exposing the entire penile body 1100. As shown, a reinforcing rib 1004 is fixed to the barrier layer at a distance 1010 from the upper edge 1010 of the adhesive layer. In some embodiments, the distance 1010 is between 0 and 10 mm, or in some embodiments, between 0 and 4 mm.

[0641] Figure 34B The image shows a condom containing semen (volume 1011) discharged through the urethral opening (orifice) 1102 within a reservoir 1003. Fluid flow lines are for illustrative purposes only. The reservoir 1003 expands to accommodate the semen volume 1011, and reinforcing ribs 1004 constrain the barrier layer, thereby reducing the peeling force and peeling angle applied to the adhesive layer 1002 at its inner edge (described here as the upper edge of the adhesive layer).

[0642] Figure 35 : A schematic diagram of an embodiment of a manufacturing process using a thermoforming barrier layer 1001 on a rigid molding die, wherein a reinforcing ring 1004 and an annular adhesive layer 1002 are placed on the surface of the thermoformable barrier layer. Heat is first applied to the composite layer, as indicated by the arrow marked with a Q-dot. The bottom of the sketch depicts an airflow from a vacuum to draw heated material onto the molding die.

[0643] Adhesive layer

[0644] The adhesive layer comprises an adhesive containing a stimulus-responsive polymer and optionally one or more additional polymers, crosslinking agents, and / or additives, which substantially adheres to the surface of the user's glans penis and detaches from the user upon application of stimulation to the ESC. The adhesive layer may consist of one or more adhesive laminae. In some embodiments, the adhesive is preferably a shear rate-responsive adhesive, where the stimulus is mechanical, or a force-responsive polymer, where the stimulus is mechanical.

[0645] The total thickness of the adhesive layer is 10 to 1500 micrometers, or in some embodiments 25 to 750 micrometers, or in some embodiments between 50 and 500 micrometers, more specifically between 50 and 400 micrometers. In some embodiments, the adhesive layer comprises a composite of thinner adhesive flakes. For example, an adhesive layer with a total thickness of 200 micrometers may comprise two 100-micrometer-thick flakes, or comprise a 50-micrometer-thick flake and a 150-micrometer-thick flake. In some embodiments, the peripheral boundaries of the flakes are staggered to provide a stepped taper effect of adhesive thickness at the peripheral edges of the adhesive layer, allowing the peripheral edges of the device to transition more gently to the user's skin, thereby minimizing the peeling effect applied to the edges of the device during intercourse.

[0646] In some embodiments of a composite where the adhesive layer is a thin laminate, the seams between adjacent adhesive sheets of the same layer can be coincident or staggered. For example, if rectangular adhesive strips are joined together at the edges 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 ends of a single rectangular strip can be aligned between the inner and outer layers, or they can be staggered in some way.

[0647] In some other embodiments, the adhesive layer is patterned. In some 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%, or less than 0.1% of the width of the main adhesive layer. In some other embodiments, a secondary adhesive is used at the inner edge of the adhesive layer (the edge adjacent to the reservoir). The thickness of the secondary adhesive region may be the same as the main adhesive, or it may be 10% to 500% of the thickness of the main adhesive. For example, see Figure 2, which shows the main adhesive 0202 and the secondary adhesive 0203 at the peripheral and inner edges of the main adhesive.

[0648] Unfoldable geometry

[0649] The adhesive layer includes an annular contact area through which the adhesive secures the ESC to the glans and acts as a seal to contain ejaculate fluid. In one embodiment, the contact area is a three-dimensional ring before being applied to the glans. The barrier layer portion paired with the adhesive layer has a complementary geometry such that there are no wrinkles, voids, folds, or gaps in either the adhesive layer or the barrier layer.

[0650] In one embodiment, the adhesive layer geometry is a deployable surface satisfying the generalized cone equation: X(u,v) = P + v Y(u), where the uppercase sign represents a vector in 3D space, P is a fixed point, and lowercase (u,v) are scalar parameters. In one embodiment, the surface can be a cone having left-right symmetric planes passing through P. In various embodiments, the adhesive can be manufactured in planar form using roll-to-roll or sheet coating processes known in the art. Adhesive material is typically coated onto or covered by a release liner to facilitate manipulation of the adhesive in subsequent manufacturing processes. Common release liners are paper or plastic films surface-treated with silicone or fluoropolymers. Such exemplary release liners are non-deformable; they can be bent, rolled, and folded, but cannot be stretched or compressed into hyperbolic surfaces. The family of deployable shapes is those shapes that can be formed by rolling and bending an initially flat surface into a three-dimensional geometry.

[0651] In some embodiments, the three-dimensional adhesive ring is a deployable surface that is part of a cone. In some non-limiting embodiments, the three-dimensional adhesive ring is a deployable surface that is part of a cone, having an adhesive width between 0.1 and 25 mm, or between 5 and 20 mm, or between 10 and 15 mm, and a circumferential diameter between 2 and 6 cm, or between 3 and 5 cm, or between 4 and 5 cm.

[0652] In some embodiments, the three-dimensional adhesive ring is a deployable surface that is part of an elliptical cone. In some non-limiting embodiments, the three-dimensional adhesive ring is a deployable surface that is part of an elliptical cone, and its adhesive width is between 0.1 and 25 mm, or between 5 and 20 mm in some embodiments, or between 10 and 15 mm in some embodiments. The major axis of the peripheral edge is between 2 and 6 cm, or between 3 and 5 cm in some embodiments, or between 4 and 5 cm in some embodiments. The minor axis of the peripheral edge is between 2 and 6 cm, or between 2 and 5 cm in some embodiments, or between 2 and 4 cm in some embodiments.

[0653] In some specific embodiments, the three-dimensional adhesive ring is a deployable surface that is part of a cardioid, cockle, or heliocentric cone. In some non-limiting embodiments, the three-dimensional adhesive ring is a deployable surface that is part of a cardioid, cockle, or heliocentric cone, having an adhesive width 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 circumferential diameter between 2 and 6 cm, or in some embodiments between 3 and 5 cm, or in some embodiments between 4 and 5 cm.

[0654] The deployable three-dimensional ring surface adhesive layer must be formed by joining the free ends 3813 and 3814 of the unfolded (i.e., uncurled) planar adhesive together using a suitable reinforcing device as shown in Figure 38. One suitable device is an overlapping region where edges 3813 overlap adhesive layer regions bounded by 3814, and vice versa. Another such device is to bring edges 3813 into contact with edges 3814 so that they precisely align in the thickness direction to form a seam, and a barrier layer as a continuous material acts as the primary device for securing edges 3813 and 3814 in their abutted state. One device is to construct the adhesive layer from two or more adhesive sheets. In an exemplary preferred embodiment, the adhesive layer consists of two sheets. Figure 38B In this configuration, sheets 3821 and 3822 are folded / rolled in such a manner that edges 3813 and 3814 of the outer sheet 3821 are joined along 3812, and edges 3815 and 3816 of the inner sheet 3822 are joined along 3811. The sheets are then brought into contact such that the inner surface of the 3D ring formed by the sheet 3821 contacts the outer surface of the sheet 3822, and their inner and outer free edges are aligned, as shown. In this manner, sheet 3821 acts as a reinforcing device for the seam between edges 3815 and 3816 of sheet 3822, and sheet 3822 acts as a reinforcing device for the seam between edges 3813 and 3814 of sheet 3821. By staggering the seams, the possibility of openings between the edges forming channels and acting as the starting point for partial or complete delamination or as a leakage channel for ejaculate fluid is reduced. It should be understood that the shapes of edges 3813, 3814, 3815 and 3816, and the corresponding seams of the adhesive layers thus manufactured, are depicted as straight, but may also be wavy, creneled, serrated, curved or other edge shapes.

[0655] In one implementation, the adhesive layer is a deployable surface derived from a family of generalized cones, satisfying the equation: X(u,v) = P + v Y(u), where the uppercase sign represents a vector in 3D space, P is a fixed point, and lowercase (u,v) are scalar parameters. This constraint is introduced because most adhesives are manufactured in roll-to-roll or sheet coating applications, where the adhesive is formed on a release liner. Suitable release liners are typically silicone paper or surface-treated plastic films. Paper and plain plastic release liner films are non-deformable; the material can be bent and folded, but cannot be locally stretched or compressed into a hyperbolic surface. A family of deployable shapes is those that can be formed by rolling and bending an initially flat surface into a three-dimensional geometry. The adhesive is an open truncated body of these surfaces. The surface truncating the generalized cone does not need to be planar or parallel.

[0656] In one embodiment, the deployable surface is a cone. In some embodiments, the generalized cone is a cone with an adhesive width between 0.1 and 25 mm, or between 5 and 20 mm, or between 10 and 15 mm. In one embodiment, the deployable surface is an elliptical cone.

[0657] In one embodiment, the deployable surface is a cardioid cone. In another embodiment, the generalized cone is truncated by a parallel plane to form an open frustum.

[0658] In one implementation, the generalized cones are truncated by an oblique plane, i.e., they are not parallel and the angle between them is 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.

[0659] In one implementation, the generalized cone is truncated at its top edge by a left-right symmetrical curved surface and at its bottom edge by the same or different left-right symmetrical curved surfaces.

[0660] Figures 36A (top view), 36B (perspective view), 36C (rear view), and 36D (side view) show the 3D unfoldable adhesive surface.

[0661] Figures 36A (top view), 36B (perspective view), 36C (rear view), and 36D (side view) show a 3D unfoldable adhesive surface with a reservoir on top of the adhesive.

[0662] Figure 38A The image includes an exploded perspective view of two deployable adhesive layers that are bonded together and attached to a reservoir to form a fully assembled condom. Figure 38B It shows its exploded top view. Figure 38C Showing Figure 38AFront, side, and back views of a fully assembled condom.

[0663] Figure 38D A close-up of the barrier layer and adhesive layer assembly is shown. The figure shows a cross-section of a condom with a deployable adhesive ring geometry, consisting of a barrier layer and an adhesive layer covering a portion of the inner surface of the barrier layer. This adhesive layer extends to the periphery, exposing a portion of the barrier layer without adhesive, thus forming a reservoir. The adhesive layer comprises two adhesive laminates, each 100 micrometers thick in this rendering. The depicted barrier layer is also 100 micrometers thick.

[0664] Figure 32 The condom includes a two-part structure with an adhesive layer 1002. The main barrier layer 10011 is planar, and the reservoir barrier layer 10012 is joined at the engagement area 301 by a suitable means (e.g., adhesive or plastic welding). The two layers form a reservoir 1003. Optionally, in some embodiments, the area between the upper surface of 10011 (represented by 309) and the inner surface of 10012 may be filled with an absorbent material, such as a superabsorbent polymer pad, which swells, traps, or gels ejaculatory fluid. Although shown as a planar configuration, any of 10011, 10012, or 1002 may be curved. The barrier layers 10011 and 10012 do not need to be the same material, and in some embodiments, preferably 10011 comprises a thinner, more compliant layer to conform to the shape of the glans, while 10012 is more elastic to expand during ejaculation to accommodate fluid. In some embodiments, the adhesive ring width (the sum of distances 3101, 3102, and 3103) is approximately 10 mm. Optionally, an adhesive different from 1002 is patterned below the attachment region 301 to provide increased adhesion in the normal direction (not depicted) of the skin surface, thereby mitigating pull-up. Distances 3101, 3102, and 3103 should be selected for the specific barrier and adhesive materials chosen to provide sufficient resistance to peeling under fluid discharge or other mechanical forces. The attachment region 301 is located in a position that is embedded from the periphery (such as the leftmost edge of 1011 as depicted) to provide a more favorable orientation for the transfer of diaphragmatic stress to the adhesive and the underlying attachment surface (skin).

[0665] Manufacturing process

[0666] Well-Mandrel Method

[0667] The adhesive will be manufactured using an industrial roll-to-roll or sheet coating process, in which the adhesive is applied to a release liner or transfer release liner. In some embodiments, it can be sandwiched between two release liners.

[0668] In one embodiment, the adhesive is a deployable surface. The deployed form of the geometry (planar form) is cut from a planar adhesive sheet while still being secured to release liner on both sides. If the adhesive is applied only to a single release liner, it can be sandwiched between another release liner before or after cutting.

[0669] In one embodiment, this requires identifying and inserting seams for butt joints of single-laminated non-overlapping adhesive layers. In another embodiment, for single-laminated overlapping adhesive layers, this requires identifying the amount of overlap between one side and the other. In yet another embodiment, this requires identifying two seams, which can be coincident or staggered, where staggering is to provide redundant sealing capability at the seams, and in some embodiments located on opposite sides of the device (e.g., front centerline and rear centerline, or left centerline and right centerline) to con...

Claims

1. A system, comprising: A partial condom comprising a condom material comprising at least one of the following: rubber, latex, polyurethane, polyisoprene, thermoplastic elastomer, or a combination thereof; The packaging comprises a first packaging material, the first packaging material comprising at least one of the following: polyethylene, polyethylene terephthalate (PET), glycol-modified polyethylene terephthalate (PETG), polypropylene, acrylic resins, polyethylene, high-density polyethylene (HDPE), polycarbonate, poly(lactic acid), poly(hydroxyacrylate), thermoplastic polymers, or combinations thereof; The package includes: (a) a dome with a flange, and (b) a film that seals the dome closed and adheres to the flange; Wherein: (a) the membrane is arranged in a plane, (b) the axis is parallel to the plane and passes through the dome at the first dome position and the second dome position, (c) the axis passes through the condom at the first condom position and the second condom position, the condom position being located between the first dome position and the second dome position, and (d) the axis passes through the gap located between the first condom position and the second condom position; Wherein: (a) the condom is contained in the packaging, and (b) the condom material is directly adhered to the first packaging material.

2. The system according to claim 1, wherein the condom material is directly adhered to the first packaging material by adhesive adhesion.

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

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

5. The system according to any one of claims 1-4, wherein the condom material is substantially composed of rubber.

6. The system according to any one of claims 1-4, wherein the condom material is substantially composed of latex.

7. The system according to any one of claims 1-6, wherein the first packaging material comprises at least one of the following: PET, PETG, or a combination thereof.

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

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

10. The system according to any one of claims 1-6, wherein the first packaging material comprises polypropylene.

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

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

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

14. The system of claim 13, wherein the first packaging material comprises at least one of the following: PET, PETG, or a combination thereof.

15. The system according to any one of claims 1-14, wherein the condom is retained inside the packaging by resistance engagement.

16. The system of any one of claims 15, wherein the condom is resiliently biased outwardly away from the gap and toward the packaging.

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

18. The system of claim 17, wherein the packaging is in a compressed state and compresses the condom into the gap.

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

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

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

22. The system according to any one of claims 1-6, 10, wherein the first packaging material has a contact angle.

23. The system according to any one of claims 1-21, wherein the packaging comprises a plasma-treated inner surface that directly contacts the condom.

24. The system according to any one of claims 1-21, wherein the packaging comprises a corona-treated inner surface that directly contacts the condom.

25. The system according to any one of claims 20-23, wherein the voids in the package are dehumidified.

26. The system according to any one of claims 20-23, wherein: The voids in the packaging have a first humidity level; The atmosphere surrounding the packaging has a second humidity level, which is higher than the first humidity level.

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

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

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

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

31. The system according to any one of claims 1-30, wherein: The packaging includes a first opening and a second opening located at opposite ends of the packaging; The membrane covers the first opening but not the second opening.

32. The system of claim 31, wherein the condom includes a semen container directly adjacent to the second opening.

33. The system according to any one of claims 31-32, comprising an additional membrane covering the second opening.

34. The system according to any one of claims 1-33, wherein: The packaging includes a packaging wall that is in direct contact with the condom; The packaging wall has a thickness between 0.015 and 0.055 inches.

35. The system according to any one of claims 1-34, wherein the axis passes through the condom only at the first condom location and the second condom location, and does not pass through the condom at any additional condom location.

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

37. The system according to any one of claims 1-36, wherein: The condom includes an inner surface and an outer surface; No part of the inner surface of the condom comes into contact with any other part of the inner surface of the condom.

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

39. The system according to any one of claims 1-37, wherein: The condom is divided into a first third, a second third, and a third third; The second third is located between the first third and the third third; The first third is located between the membrane and the second third; No part of the first third was folded, wrinkled, or rolled up.

40. The system according to any one of claims 1-37, wherein: The condom is divided into a first third, a second third, and a third third; The second third is located between the first third and the third third; The first third is located between the membrane and the second third; No part of the second third was folded, wrinkled, or rolled up.

41. The system according to any one of claims 1-40, wherein: The first packaging material is contained in the first layer of the packaging; The packaging includes a second packaging material; The second packaging material is contained in the second layer of the packaging.

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

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

44. The system of claim 41, wherein the second layer is a thermoplastic film comprising the second packaging material.

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