Enhanced sensation condom

Abstract

This disclosure relates to a contraceptive device that provides an enhanced sensation to the user. The contraceptive device contains an adhesive containing a stimulus-responsive polymer that peels off easily and painlessly after the application of stimulation. This disclosure also relates to a partial condom that covers the glans of the penis. Methods for applying and removing the contraceptive device, as well as methods for manufacturing the contraceptive device, are also provided.

Description

Background Art

[0001] 1. Background A female pessary or cap is a device that functions as a barrier method of contraception. It fits inside the vagina and prevents sperm from passing through the cervix. The female pessary does not prevent the spread of sexually transmitted infections (STIs). From a pleasure perspective, the pessary provides the closest possible contact between the penis and the vagina.

[0002] Conventional male condoms are latex or polyurethane devices that attempt to prevent pregnancy and the spread of certain STIs by completely covering the penis and confining sperm within it. Since the condom substantially covers the head and shaft of the penis, it reduces the sensation of pleasure. This reduction in pleasure reduces the use of condoms during sex, leading to unwanted pregnancy or the spread of STIs, substantially changing human life in many situations, and increasing overall medical costs.

[0003] Partial male condoms, i.e., condoms with less coverage than conventional male condoms, are known in the art. GALACTIC CAP® is a commercially available partial condom marketed for pregnancy prevention (https: / / www.galacticcap.com / ). It is made of a polyurethane barrier layer with an adhesive backing and adheres to the head and shaft of the penis. However, it has several significant limitations. It can only be applied when aroused, and is applied to such an extent that it still covers a considerable portion of the shaft of the penis, thus limiting the user's sensation of pleasure accordingly. The condom is made from a material that cannot be used with oil lubricants, which are otherwise popular among users. The design is complex, making the condom difficult to apply and leading to the possibility of user error. Removal of the condom is also difficult (uncomfortable and painful). As indicated in the user's instructions, removal requires the use of baby oil, and the recommended (easiest) mode of removal requires the user to urinate into the condom to inflate it, and then peel it off. Aside from the discomfort this brings to the removal experience, it is also known to be painful. For example, see https: / / www.vice.com / en / article / znmmp4 / i-tried-the-latest-in-condom-technology-and-it-went-shockingly-well. Leaks have also been reported. The above restrictions significantly limit the impact of GALATIC CAP's appeal to consumers.

[0004] Other partial condoms have been reported in the art under similar limitations.

[0005] The Wondaleaf Cap® is a commercially available partial condom that includes an adhesive coating at the condom opening to adhere to the shaft of the penis and to itself in order to form the proximal portion of the condom and two lateral tabs. The loose-fit barrier layer is made of polyurethane. The user removes the condom by holding the tabs on the sides of the device and pulling the condom distally by applying counter-pressure against the skin of the penis. Similar to the GALATIC CAP®, this device can only be applied in an aroused state and is applied to such an extent that it still covers a significant portion of the shaft of the penis, thus limiting the user's sensation of pleasure accordingly. The design is also complex and creates the possibility of user error (https: / / www.wondaleaf.com / wondaleaf-cap / ).

[0006] International Publication No. 2014178661 describes a partial condom made of polyurethane and comprising a barrier layer having a discontinuous adhesive layer and a pre-formed semen reservoir that protrudes from the device before use (i.e., the condom is non-planar before use). The adhesive is said to be double-sided tape, e.g., 3M double-sided tape, or commonly referred to as a "medical adhesive layer" or pressure-sensitive adhesive.

[0007] U.S. Patent No. 11,234,858 describes a bodily fluid collection device comprising a mating component and a collection film applied to the penis via an adhesive layer. The collection film provides a pre-formed semen reservoir (i.e., the condom is non-planar before use). The mating component and the collection film are typically discontinuous, a structure said to more effectively prevent semen leakage. The component material of the adhesive layer may include, for example, a pressure-sensitive adhesive.

[0008] There is a need for a contraceptive device that prevents pregnancy, provides increased sensation compared to existing contraceptive devices, but is still easy to apply and remove. [Overview of the project]

[0009] 2. Overview In one embodiment, the Disclosure provides a condom suitable for preventing the passage of semen, comprising a barrier layer including an inner and outer surface, and an adhesive layer adhered to at least a portion of the inner surface of the barrier layer, wherein the condom is configured to adhere the adhesive layer to the glans of the penis of a human subject, and the condom is configured to provide partial coverage of the penis (e.g., a glans sheath), wherein the adhesive layer comprises an adhesive comprising a stimulus-responsive polymer formed from one or more monomers (e.g., acrylate or methacrylate) and optionally one or more polyfunctional crosslinkers (e.g., a trifunctional crosslinker), wherein when the condom is applied to the penis, the adhesive layer adheres to the glans of the penis, and the adhesive layer can be removed from the glans of the penis after application of stimulation to the condom (e.g., mechanical stimulation). In some embodiments, the partial condom is planar before use. In some embodiments, the barrier layer further comprises a self-forming semen reservoir. In some embodiments, the adhesive layer has the same extent as the barrier layer. In some embodiments, the adhesive layer is the sole means of securing the condom to the penis.

[0010] In some embodiments, partial coverage is limited to the tip of the penis. In some embodiments, partial coverage is limited to the head of the penis. In some embodiments, partial coverage does not include the shaft of the penis. In some embodiments, partial coverage includes the base of the penis or below the base of the penis.

[0011] In some embodiments, the condom allows for on-demand layer separation in response to stimulation, and the layer separation is substantially painless to the user and leaves substantially no residue or residue that is easily removed.

[0012] In another embodiment, the Disclosure provides a package including a condom as described herein.

[0013] In yet another embodiment, the Disclosure provides (a) a condom as described herein or a package containing a condom as described herein, and (b) a kit including instructions for use.

[0014] In yet another aspect, the Disclosure provides a method for applying a condom disclosed herein to the penis of a human subject, comprising: bringing the adhesive layer of the condom into contact with the glans of the penis; and applying sufficient pressure to the condom to adhere it to the glans of the penis.

[0015] In a further embodiment, the Disclosure provides a method for removing a condom disclosed herein from the penis of a human subject, comprising applying a stimulus to a condom whose adhesive layer is adhered to the glans of the penis, and removing the condom from the glans of the penis.

[0016] 3. Brief explanation of some of the figures in the drawing These and other features, aspects and advantages of this disclosure will be better understood in relation to the following description, the appended claims and drawings. [Brief explanation of the drawing]

[0017] [Figure 1]Figures 1A and 1B show perspective views of a composite curvature condom (A) and a flat condom (B). In panel A, the composite curvature condom (with non-zero Gaussian curvature) includes a continuous barrier layer (0101) and an adhesive layer (0102). An optional release liner (013) protects the adhesive layer before use to prevent adhesion to itself or unintended surfaces and facilitates user handling. Optionally, the portion of the barrier layer covering the urethral opening does not have adhesive (0104) to (a) mitigate unintended adhesion to the urethra and (b) provide space for ejaculate to flow into either a pre-formed or self-forming reservoir. In panel B, the flat condom, i.e., with zero Gaussian curvature, includes a continuous barrier layer (0101) and an adhesive layer (0102). An optional release liner (013) protects the adhesive layer before use to prevent adhesion to itself or unintended surfaces and facilitates user handling. Optionally, holes (0104) are present in the adhesive layer of the device portion covering the urethral opening (opening) to (a) reduce adhesion to the urethra and (b) provide space for ejaculate to flow into either a pre-formed or self-forming reservoir.

[0018] [Figure 2] Figure 2 shows a cross-sectional view of a condom comprising a barrier layer (0201) and two adhesive patterns consisting of a primary adhesive (0202) (for example, a water-soluble adhesive involved in the primary attachment of the device to the glans) and a gasket adhesive (0203) that enhances the sealing effect of the device or separates the water-soluble primary adhesive from aqueous vaginal fluid or (pre)ejaculatory fluid.

[0019] [Figure 3] Figures 3A and 3B show cross-sectional views of exemplary pessaries described herein, having (A) a constant thickness (0311) and (B) a non-constant thickness (0321).

[0020] [Figure 4] Figure 4 shows a plot of the adhesive strength of the adhesive according to Example 10.

[0021] [Figure 5] Figure 5 shows a graph of the tensile strain capacity of the adhesive according to Example 11.

[0022] [Figure 6] Figure 6 shows a graph of the tensile strain capacity of the adhesive according to Example 11.

[0023] [Figure 7] Figure 7 shows a graph of the tensile strain capacity of the adhesive according to Example 11.

[0024] [Figure 8] Figure 8 shows a graph of the peeling strength of the adhesive according to Example 12 in a 180-degree peeling test using a human skin substrate analog.

[0025] [Figure 9] Figure 9 shows a graph of the peeling strength of the adhesive according to Example 12 in a 180-degree peeling test using a glass substrate.

[0026] [Figure 10] Figure 10 shows a plot of tan(δ) of the adhesive according to Example 13.

[0027] [Figure 11] Figure 11 shows a plot of the storage modulus and loss modulus of the adhesive according to Example 13.

[0028] [Figure 12] Figure 12 shows an enlarged view of the loss modulus and storage modulus of the L6 adhesive, showing the crossover between the elastic regime and the viscous regime between 0.05 MPA and 8 rad / second.

[0029] [Figure 13] Figure 13 shows a plot of the change in tan(δ) of the adhesive according to Example 13 over the range of 0°C to 50°C.

[0030] [Figure 14]Figure 14 shows the DMA measurements of the storage modulus (G') and loss modulus (G") as a function of temperature for L6 adhesive.

[0031] [Figure 15] Figure 15 shows the DMA measurement of tan(δ), which is the ratio of the loss modulus to the storage modulus, for L6 adhesive.

[0032] [Figure 16] Figure 16 shows the DMA measurements of the storage modulus (G') and loss modulus (G") as a function of temperature for L6 adhesive.

[0033] [Figure 17] Figure 17 shows the DMA measurement of tan(δ), which is the ratio of the loss modulus to the storage modulus, for L6 adhesive.

[0034] [Figure 18] Figure 18 shows the DMA measurements of the storage modulus (G') and loss modulus (G") as functions of temperature for LMA and BA adhesives.

[0035] [Figure 19] Figure 19 shows the DMA measurement of tan(δ), which is the ratio of the loss modulus to the storage modulus, for LMA and BA adhesives.

[0036] [Figure 20] Figure 20 shows the angular strain of L6 adhesive at different temperatures.

[0037] [Figure 21] Figure 21 shows the shear rate of L6 adhesive at different temperatures.

[0038] [Figure 22] Figure 22 shows the angular strain of LMA and BA adhesives at different temperatures.

[0039] [Figure 23]Figure 23 shows the shear rates of LMA and BA adhesives at different temperatures.

[0040] [Figure 24] Figure 24 shows the tack strength of L6 adhesive at various different temperatures.

[0041] [Figure 25] Figure 25 shows the tack strength of LMA and BA adhesives at different temperatures.

[0042] [Figure 26] Figures 26A and 26B show perspective views of a condom. Panel B shows a cross-sectional side view of the embodiment shown in Panel A.

[0043] [Figure 27] Figure 27 shows a side view of a partial condom.

[0044] [Figure 28] Figure 28 shows a cross-sectional side view of a partial condom including a wrinkled barrier layer and a wrinkled adhesive layer.

[0045] [Figure 29] Figures 29A-B show cross-sectional perspective views of a partial condom having a horizontally folded semen receptacle.

[0046] [Figure 30] Figures 30A and 30B show flat condoms attached to the glans penis before ejaculation (A) and during ejaculation (B).

[0047] [Figure 31] Figure 31 shows a plot of mechanical features relating to the suitability of the embodiment for the expansion and containment of ejaculate.

[0048] [Figure 32] Figure 32 shows the gel fractions obtained from sol-gel analysis in 18 examples of various adhesives.

[0049] [Figure 33] Figure 33 shows the Wong-Baker qualitative pain assessment for removing various condoms in Example 19. [Modes for carrying out the invention]

[0050] 4. Detailed explanation 4.1.Definition When describing embodiments of this disclosure, the following terms, if present, have the following meanings unless otherwise indicated. Unless otherwise defined, the terms have their customary meanings in the relevant art.

[0051] In general, the terms used herein, and in particular in the appended claims (e.g., the body of the appended claims), will be understood by those skilled in the art to be generally intended as “open” terms (for example, “including” should be interpreted as “including but not limited to,” “having” as “having at least,” and “includes” as “includes but not limited to,” etc.). Where a particular number of introduced enumerations of claims is intended, such intent will be explicitly enumerated in the claims, and where there is no such enumeration, such intent will not be present, will be understood by those skilled in the art to be further understood. For example, for the sake of understanding, the following appended claims may contain the use of the introductory phrases “at least one” and “one or more” to introduce an enumeration of claims. However, the use of such phrases should not be interpreted as meaning that the introduction of a claim enumeration with the indefinite article "a" or "an" limits any particular claim containing such introduced claim enumeration to embodiments containing only one such enumeration, even if the same claim contains the introduction phrase "one or more" or "at least one" and an indefinite article such as "a" or "an" (for example, "a" and / or "an" should be interpreted as meaning "at least one" or "one or more"). The same applies to the use of the definite article used to introduce a claim enumeration. Furthermore, even if a particular number of introduced claim enumerations are explicitly listed, a person skilled in the art will recognize that such enumerations should be interpreted as meaning at least the number listed (for example, a bare enumeration of "two enumerations" without other modifiers means at least two enumerations or two or more enumerations).Furthermore, when a convention similar to "at least one of A, B, and C" is used, such configurations are generally intended in a way that a person skilled in the art would understand the convention (for example, "a system having at least one of A, B, and C" includes, but is not limited to, systems having only A, only B, only C, A and B together, A and C together, B and C together, and / or systems having A, B and C together). When a convention similar to "at least one of A, B, or C" is used, such configurations are generally intended in a way that a person skilled in the art would understand the convention (for example, "a system having at least one of A, B, or C" includes, but is not limited to, systems having only A, only B, only C, A and B together, A and C together, B and C together, and / or systems having A, B and C together). It will be further understood by those skilled in the art that substantially any disjunctive word and / or phrase presenting two or more alternative terms should be understood as construing the possibility of including one of the terms, either of the terms, or both of the terms, whether in the specification, claims, or drawings. For example, the phrase “A or B” is understood to include the possibilities of “A” or “B” or “A and B.”

[0052] Furthermore, if any feature or aspect of the present disclosure is described in relation to the Markush group, a person skilled in the art will recognize that the present disclosure also describes any individual member or subgroup of a member of the Markush group.

[0053] As will be understood by those skilled in the art, for any and all purposes, for providing, for example, written explanations, all scopes disclosed herein also encompass any and all possible subscopes and combinations thereof. Any scope listed can be readily recognized as sufficiently explainable and enabling the division of the same scope into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each scope described herein can be readily divided into a lower third, middle third, upper third, etc. Also, as will be understood by those skilled in the art, all language such as “up to,” “at least,” “greater than,” and “less than” includes the listed numbers and refers to scopes that can be later divided into subscopes as described above. Finally, as will be understood by those skilled in the art, a scope includes individual members. Thus, for example, a group having 1 to 3 articles refers to a group having 1, 2, or 3 articles. Similarly, a group having 1 to 5 articles refers to a group having 1, 2, 3, 4, or 5 articles, and so on.

[0054] As used herein, “adhesion” refers to the ability of a composition or material to adhere to or “stick” to a substrate (e.g., skin). Adhesion is measured as adhesive force in Newtons (N). The higher the adhesive force, the higher the number of Newtons required to peel one object from the other.

[0055] As used herein, “adhesive” refers to a composition or material that adheres to a substrate (e.g., skin or a barrier layer).

[0056] As used herein, "bio-based" refers to materials derived from natural sources.

[0057] As used herein, "biodegradable" means that, with respect to a composition, it can be decomposed by living microorganisms such as fungi or bacteria, or by living environmental conditions such as ambient moisture and air conditions, regardless of the specific time frame used herein.

[0058] As used herein, “compostable” refers to a composition or article that requires microorganisms, humidity, and heat to obtain a finished compost product (CO2, water, inorganic compounds, and biomass). Compostable is distinguished from biodegradable in that the compostable composition and article must decompose into natural elements within a specific time frame. In one embodiment, the compositions and articles disclosed herein are described by the US Composting Council, the Environmental Protection Agency, the American Society for Testing and Materials (ASTM International), or Tuv Austria.

[0059] As used herein, “controlled porosity” refers to pores that are normally closed, open when stimulated, and thereby allow the passage of fluids made possible by their rheological properties.

[0060] As used herein, “conventional condom” refers to a condom that, when in use, covers the head (i.e., the glans) and shaft of the penis, comprising a continuous elastic tubular wall with a closed distal end (tip) and an open proximal end, and is typically made of a thin, soft material such as latex or polyurethane. The length of a conventional condom in use is typically about 7 to 8 inches, but commercially available products range from a maximum of 9 inches to a minimum of about 6.3 inches. Numerous condom brands, 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, which are incorporated herein by reference, respectively.

[0061] As used herein, "crosslink density" refers to the average molecular weight between crosslinks. (https: / / www.pcimag.com / articles / 104955-calculation-of-crosslink-density-of-thermoset-polymers). Flory et al. presented a theory of crosslink density in the 1940s.

[0062] As used herein, "curing" refers to a chemical process that converts macromolecules into high molecular weight polymers through crosslinking reactions.

[0063] As used herein, "peeling" refers to peeling by different mechanisms, including, for example, phase change, chemical reaction, crosslinking, and volume expansion.

[0064] As used herein, “elastomer” or “elastomer behavior” refers to the generally linear elastic or combined linear elastic and plastic deformation stress / strain behavior of a material when strain occurs in a regime above a significant transition regime, such that stress / strain hysteresis is generally conserved.

[0065] As used herein, “flexibility” or “flexible behavior” refers to the behavior of a rigid, viscoelastic, or elastomer material that can be described as adaptable or deformable to meet the requirements of a particular engineering application.

[0066] As used herein, “partial coverage” means substantially less coverage of the penis than conventional condoms. In certain embodiments, the partial condoms disclosed herein do not contact or cover the shaft of the penis. In certain embodiments, the partial condoms do not contact or cover the coronal sulcus and frenulum.

[0067] As used herein, "room temperature" (used interchangeably with "ambient temperature") refers to a temperature of 20-25°C.

[0068] As used herein, “selectively permeable” refers to differential permeability. For example, a membrane contains channels or passages that allow certain molecules to pass through passively or actively, but not allow other molecules to pass through. Active transport through a membrane requires an energy input, which may come from a mechanical, acoustic, chemical, electrical, magnetic, pH change, ionic intensity, thermal, or optical source.

[0069] As used herein, "Tg" refers to the glass transition temperature of a polymer. At this temperature, the polymer transitions from a glassy state to a rubbery state. Tg is a key characteristic of polymer behavior. It represents a region of dramatic change in physical and mechanical properties. Below the polymer's Tg, the polymer is hard and brittle due to a lack of mobility. Above the polymer's Tg, the polymer becomes soft and flexible due to increased mobility.

[0070] As used herein, “stimulus responsiveness” refers to changes in the physical, environmental, physicochemical, thermomechanical, mechanical, thermal, energetic, or other properties of a composition or material resulting from exposure to stimuli, including, for example, temperature, pH, ionic strength, environmental conditions (including moisture, immersion, exposure, or humidity), solvent exposure, exposure to electromagnetic radiation (including gamma rays, X-rays, ultraviolet rays, visible light, infrared rays, radio waves, ultrasound, high humidity, magnetism, and electricity), and mechanical forces, such as changes in shear rate or peeling. In one embodiment, stimulus responsiveness does not include the application of liquids such as baby oil to the material to cause a change in the material's properties. In one embodiment, stimulus responsiveness refers to changes in the physical, environmental, physicochemical, thermomechanical, mechanical, thermal, energetic, or other properties of a composition or material previously applied to a substrate (e.g., skin) resulting from exposure to stimuli. Stimulus-responsive adhesives can be contrasted with mechanically passive adhesives.

[0071] "Mechanically passive adhesives" refer to adhesives designed to maintain their structural and mechanical properties after placement. Many pressure-sensitive adhesives are mechanically passive adhesives. In certain embodiments, the adhesive layer does not contain a mechanically passive adhesive or a pressure-sensitive adhesive.

[0072] As used herein, “shear rate” refers to the rate at which shear deformation occurs. Shear deformation is the deformation of parallel lamellae (layers) of a fluid, gel, or solid material as they slide against each other. These layers can be discrete (having a finite, measurable thickness) or continuous (infinitely thin or indistinguishable individually). The shear rate may be a constant function in time, a monotonic function in time, a non-periodic non-monotonic function, or a periodic function in time. Periodic is understood to mean a function that is truly periodic in time, or approximately periodic in time (e.g., a sinc function).

[0073] As used herein, “frequency response” refers to the behavior of a material or fluid that changes over time under the application of a periodic or nearly periodic force or displacement. This applied force or displacement may be called a “signal.” The applied signal has a defined amplitude and frequency, and optionally a phase, all of which may be constant or vary over time and / or space.

[0074] As used herein, "shear responsiveness" refers to the change in the behavior of a material (e.g., gel, solid, or liquid) under the application of different shear displacements or shear rates.

[0075] As used herein, "force responsiveness" refers to the change in the behavior of a material (e.g., gel, solid, or liquid) under the application of forces of different magnitudes.

[0076] As used herein, "nonlinear force" refers to a type of force in which the relationship between the force and its effect on the system is not proportional or does not follow a simple linear equation.

[0077] As used herein with respect to polymers, the term "network" refers to a macromolecular structure formed by crosslinked polymer chains. Crosslinking is a covalent bond or other strong interaction, such as entanglement, supramolecular interaction, or physical interaction, such as polymer chain interaction with a crystalline or glassy phase.

[0078] As used herein, “interpenetrating networks” (“IPN”) refer to a specific type of polymer material that contains two or more independent polymer networks that are physically intertwined but not covalently bonded to one another. Each network maintains its distinct identity, but the networks are intertwined at the molecular level, forming a composite material that possesses properties derived from the combination of the individual networks.

[0079] As used herein, “semi-interpenetrating network” (“semi-IPN”) refers to a crosslinked or branched polymer network and an entangled linear or branched additional polymer or series of polymers.

[0080] As used herein, "heterogeneous network" refers to a polymer network having a non-uniform crosslinking density distribution.

[0081] "Gel fraction" refers to the mass of polymer remaining after washing with a suitable solvent divided by the initial mass. Methods for determining the gel fraction are well known in the art.

[0082] "Sol fraction" refers to the mass of polymer lost after washing with a substantially suitable solvent, divided by the initial mass. Methods for determining the sol fraction are known in the art.

[0083] As used herein, "heterogeneous crosslinking" refers to crosslinks distributed in a heterogeneous polymer network or system.

[0084] As used herein, "monomer reactivity ratio" refers to a parameter used in polymer chemistry to describe the relative reactivity of two monomers in a copolymerization reaction. Copolymerization reactions involve the simultaneous polymerization of two different monomers, forming copolymers with various monomer compositions.

[0085] As used herein, "self-healing" refers to a class of high-performance materials that possess the ability to autonomously repair themselves when subjected to mechanical damage or microcracks. This self-healing process can occur without requiring external stimuli or intervention, thereby enhancing the durability, reliability, and lifespan of the material. Self-healing can occur through the flow of viscous or viscoelastic components.

[0086] As used herein, “enhanced sensation” or “enhanced pleasure” refers to increased exposure of sensory neurons and / or increased exposed penile surface area and / or increased sexual arousal and / or increased simulation of sensory neurons. Sensation or pleasure may be experienced by the user, their partner, or both (collectively, the “user”).

[0087] As used herein, “prevent” (to be used interchangeably with “prohibit”) means reducing, minimizing, or eliminating the release of semen outside the barrier layer in this disclosure compared to spontaneous release during ejaculation.

[0088] As used herein, “plasticizer” refers to an additive that, when added to a polymer, polymer blend, copolymer, copolymer blend, polymer network, or copolymer network, exhibits thermomechanical behavior consistent with what is understood to be associated with plasticization, namely, a decrease in glass transition temperature, a decrease in crystal melting temperature, a triggering of stress relaxation, or an increase or decrease in adhesive strength. Plasticizers may be added in amounts such as about 1% by weight, about 2% by weight, about 3% by weight, etc., increasing the polymer, copolymer, or network mixture or blend by up to about 30% by weight or about 50% by weight or more. Examples of plasticizers for 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 that are liquid at room temperature and have a molecular weight of repeating units ranging from 1 to 30 or more, vegetable oils, detergents, and other common plasticizers. Low molecular weight oligomers can also plasticize high molecular weight or crosslinked polymers of the same or similar chemical composition.

[0089] As used herein, “substantially less” means a reduction in the covered penile surface area compared to that covered by a conventional condom, resulting in enhanced sensation or pleasure. Substantially less could be, for example, about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% or less of the covered surface area.

[0090] As used herein, “elastomer behavior” refers to the generally linear elastic or combined linear elastic and plastic deformation stress / strain behavior of a material when strain occurs in a regime above a significant transition regime, such that stress / strain hysteresis is generally conserved.

[0091] As used herein, “flexible behavior” refers to the behavior of a rigid, viscoelastic, or elastomer material that can be described as adaptable or deformable to meet the requirements of a particular engineering application.

[0092] As used herein, “self-forming” refers to the natural expansion of the barrier layer in response to the application of the barrier layer to the penis and / or the forces resulting from ejaculation, such that the barrier layer expands but does not substantially release semen outside its boundaries.

[0093] As used herein, “reduce” or “amount reduced” refers to a decrease in a particular characteristic. A 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. A reduction may be measured by any suitable means, for example, by any suitable method known in the art. In the case of condom covering of an erect penis, a reduction may be, for example, a decrease in the surface area of ​​the erect penis of 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 condom coverage that primarily covers a portion of the head of the penis but exposes other parts of the head and shaft, the reduction may be, for example, a reduction of at least approximately 10%, at least approximately 20%, at least approximately 30%, at least approximately 40%, at least approximately 50%, at least approximately 60%, at least approximately 70%, at least approximately 80%, at least approximately 90%, or at least approximately 99% or more of the surface area of ​​the erect head of the penis. In all cases, the reduction of coverage of the erect penis may include the exposure of parts of the penis that have the presence of highly sensory / perceptual neurons, including the frenulum.

[0094] As used herein, “enhanced” refers to an increase in a particular characteristic. The enhancement 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 100% or more. The increase may be measured by any suitable means, for example, by any suitable method known in the art. In one embodiment, the condoms disclosed herein enhance sexual pleasure compared to other condoms known in the art, including but not limited to conventional condoms.

[0095] "Contraceptive device" (used interchangeably with "preventive device") refers, as used herein, to a mechanical barrier that prevents the transfer of fluids during sexual intercourse. A condom is a male contraceptive device. A diaphragm is a female contraceptive device.

[0096] As used herein, "membrane" refers to a layer or film of a solid continuous polymer material.

[0097] As used herein, “individual” means a person to whom a contraceptive device is applied or intended to be applied.

[0098] As used herein, “polymer” refers to a substance composed of macromolecules (very large molecules with molecular weights ranging from several thousand to several million grams / molecule) made up of simpler repeating units derived from lower molecular weight monomers. As used herein, polymer refers to both homopolymers and copolymers. A homopolymer is made from (i.e., contains) one type of monomer. A copolymer is made from (i.e., contains) two or more different types of monomers (e.g., styrene-butadiene copolymer). The adhesives described herein may contain one or more polymers, including but not limited to stimuli-responsive polymers.

[0099] As used herein, “pressure-sensitive adhesive” refers to an adhesive that obtains adhesive properties or tack through a polymer flow onto a surface to which it is pressed using force. In certain embodiments herein, the adhesive does not include a pressure-sensitive adhesive. As used in the art, the term “conventional pressure-sensitive adhesive” refers to any pressure-sensitive adhesive known in the art, and in some embodiments, refers to any commercially available pressure-sensitive adhesive mentioned herein or any pressure-sensitive adhesive used in the examples section herein.

[0100] 4.2. Contraceptive devices In one embodiment, the disclosure provides a contraceptive device comprising an adhesive comprising a stimulus-responsive polymer, optionally one or more other polymers, a crosslinking agent and / or additives, wherein the adhesive of the contraceptive device adheres to the genital surface of a human subject, and the adhesive delaminates from the genital surface when a stimulus is applied to the contraceptive device. In some embodiments, the contraceptive device is a condom, and the genital surface is the glans of the penis. In some embodiments, the contraceptive device is a pessary, and the genital surface is the vagina.

[0101] In some embodiments, the contraceptive device comprises a barrier layer, including an inner and outer surface, suitable for preventing the passage of bodily fluids during intercourse, and an adhesive layer adhered to at least a portion of the inner surface of the barrier layer; the adhesive layer comprises an adhesive comprising a stimulus-responsive polymer formed from one or more monomers and optionally one or more polyfunctional crosslinking agents, and when the contraceptive device is applied to the genital surface of a human subject, the adhesive layer adheres to the genital surface, and the adhesive layer can be removed from the genital surface after the application of stimulus to the contraceptive device. In some embodiments, the contraceptive device is a condom, and the genital surface is the glans of the penis. In some embodiments, the contraceptive device is a pessary, and the genital surface is the vagina.

[0102] In some embodiments, the human subject is male, and the contraceptive device is applied to and adheres to the penis. In some embodiments, the human subject is female, and the contraceptive device is applied to and adheres to the vagina.

[0103] In some embodiments, the contraceptive device is a partial condom. The partial condoms of this disclosure cover substantially less of the penis than conventional condoms, increasing the exposed penile surface area and providing a framework for enhancing user sensation. Like conventional condoms, the partial condoms described herein reduce the likelihood of pregnancy by preventing sperm from reaching the egg. Unlike conventional condoms, it does not cover the entire penis and, accordingly, may not prevent the spread of certain STIs.

[0104] In some embodiments, the partial condom is configured to adhere to the glans of the penis. In some embodiments, the partial condom is configured to adhere only to the glans of the penis. In some embodiments, the partial condom is sized and shaped such that when applied to the penis, the condom does not contact or cover the coronal sulcus of the penis. In some embodiments, the condom does not contact or cover the frenulum of the penis. In some embodiments, the partial condom is sized and shaped such that when applied to the penis, the condom does not contact the shaft of the penis.

[0105] In some embodiments, the partial condom has a planar geometric shape 1400. See, for example, Figure 26A (showing a perspective view of the condom 1400). The geometric shape of the device is planar and can be placed on a flat surface without significant stretching, wrinkles, folds, or creases. This embodiment includes a planar adhesive layer 1401 bonded to a planar barrier layer 1402. A backing layer 1403 can be bonded to the adhesive layer such that the adhesive layer is between the backing layer and the barrier layer. As shown in Figure 26B (which provides a side view of the embodiment in Figure 26A), such embodiments may include a specific portion of the device for a semen reservoir, but none of these reservoirs extend perpendicularly beyond the barrier layer (i.e., into region 1404). In other words, the thickness of the reservoir does not exceed the combined thickness of the adhesive layer and the barrier layer, and is therefore coplanar with the barrier layer (e.g., within region 1405), the adhesive layer, or a combination of the barrier layer and the adhesive layer.

[0106] In some embodiments, the geometric shape of the condom's barrier layer may have a constant or varying radius of curvature, but may have one principal curvature direction in which it may have zero curvature in any orthogonal direction. In other words, the Gaussian curvature of the adhesive layer is 0 or approximately 0. In the embodiment shown in Figure 27, the partial condom 1500 includes an outer barrier layer 1502 bonded to an inner adhesive layer 1501 (which bonds to a backing layer 1503). The barrier layer has a consistent radius of curvature 1512 over 50% of the barrier layer's width 1520. The adhesive layer is bonded to the barrier layer and "nested" beneath the barrier layer, thereby adopting the curvature of the barrier layer, although it has a slightly smaller radius of curvature 1511.

[0107] In some embodiments, the semen reservoir is a self-forming reservoir, i.e., it responds to the application of the condom to the penis and / or ejaculation during use. Upon removal of the package, there is not necessarily a reservoir protruding outward from the outer portion of the condom's barrier layer. See, for example, Figure 26B. In some embodiments, the reservoir is indistinguishable from the rest of the barrier and is, in a sense, non-existent while present within the condom package. However, the reservoir is formed during use by one or more of the following methods:

[0108] First, when the user ejaculates, the released fluid presses against the inner surface of the device covering the vicinity of the urethral opening, causing mechanical deformation of the barrier layer to accommodate the volume of ejaculated fluid. The resulting reservoir, which can be elastically or plastically deformed in the barrier layer and / or adhesive layer, is thereby said to be self-forming. For example, by adjusting the Young's modulus of the barrier layer, the mechanical deformation can be adjusted to accommodate the ejaculate.

[0109] In some embodiments, the condom may include a relatively thin barrier layer (e.g., less than 200 microns) (see thickness 1422) bonded to a relatively thick adhesive layer (e.g., greater than 300 microns) (see thickness 1421). The adhesive may not be present in region 1431 of the barrier layer (covering the urethral opening). The thickness of the adhesive 1421 creates a gap between the barrier layer and the glans, which is a void volume that can be filled with semen. For example, region 1431 may form a gap where no adhesive is present, and this gap is formed between the urethra, the adhesive layer portion, and the barrier layer.

[0110] In some embodiments, the adhesive may be present in region 1431 but may be perforated or thin (compared to the outer edge of the adhesive at location 1432) to better accommodate ejaculation or to provide flexibility to an otherwise thick adhesive layer. In some embodiments, the adhesive may be present in region 1431 but may include a thin film 1433 to shield the adhesive from the urethral opening. Embodiments in which the adhesive remains in region 1431 may facilitate manufacturing by reducing the need to precisely position the adhesive on the barrier layer.

[0111] Figure 28 shows an embodiment including a barrier layer bonded to an adhesive layer. When the condom is applied to the glans of the penis, the condom folds and wrinkles, but when the user presses the condom onto the skin of the glans, any folds or wrinkles are sealed due to the self-adhesive properties of the adhesive. See, for example, fold 1601. Such folds and wrinkles induce a void volume. The void volume may be further increased by pinching a portion of the barrier layer covering the urethral opening.

[0112] Figures 29A-B show embodiments including a barrier layer 1702 bonded to an adhesive layer 1701. The reservoir 1703 is pre-formed on the barrier layer using a process suitable for the material. For example, such processes include dipping coating of a natural rubber latex barrier layer or vacuum / thermoforming of a thermoplastic elastomer barrier layer. The reservoir 1703 is folded using concentric folding in the horizontal plane before ejaculation. During ejaculation, the reservoir is filled with fluid, causing it to unfold and stretch to contain the ejaculate. The horizontal concentric folding of the reservoir is manufacturable, reduces the thickness of the device to facilitate packaging and storage, and reduces the likelihood of the reservoir unfolding during removal from the package, during application to the glans, or before ejaculation during intercourse, compared to reservoirs with axial or vertical folding patterns.

[0113] The equilibrium pressure that should be contained by the device after a specific volume of ejaculation can be adjusted by selecting a combination of the Young's modulus, Poisson's ratio, thickness, and initial void volume of the barrier layer (or barrier and adhesive layer). The minimum limit of equilibrium pressure is the zero-gauge pressure measured across the reservoir wall, which occurs when the initial void volume is greater than or equal to the discharge volume. In one embodiment, a relatively smaller pre-formed semen reservoir simplifies manufacturing, reduces material costs, facilitates the user experience, and is more aesthetically pleasing to the user. If the initial void volume is less than the volume of ejaculate, the device may expand to accommodate the remainder of the ejaculate. At the limit where the initial void volume is zero or approximately zero (meaning less than 0.01 mL, less than 0.1 mL, less than 0.2 mL, less than 0.5 mL, or less than 1 mL), the reservoir is self-forming.

[0114] For example, Figure 30A shows a flat condom attached to the glans before ejaculation. Figure 30B shows a condom attached to the glans during ejaculation (showing the accumulation of semen and the stretching of the barrier layer to contain the fluid).

[0115] While not bound by any particular operating theory, embodiments having a "self-forming reservoir" exhibit the counterintuitive behavior of a thin-walled (hyper)elastic pressure vessel reservoir, which may or may not exhibit plastic deformation behavior, in that there exists a ratio of the reservoir volume divided by the initial (non-deformable) reservoir volume such that the equilibrium pressure contained in the reservoir is maximized. As the volume decreases or increases from this amount, the internal equilibrium pressure contained in the reservoir decreases. In some cases, as the volume increases, the pressure reaches an approximately constant asymptotic value. Therefore, from the viewpoint of the fluid sealing behavior of the device, it is advantageous to reduce the initial reservoir void volume to reduce the equilibrium pressure that is rapidly established after ejaculation. Furthermore, from a physiological viewpoint, it is advantageous to reduce the pressure exerted by semen on the urethra and reduce the risk of semen backflow.

[0116] Here, we address the equilibrium pressure of a spherical reservoir as a function of the volume of the expanded ejaculate. An exemplary spherical reservoir is considered under the assumption of a thin-walled pressure vessel, a linearly elastic material with a Poisson's ratio of 0.5, and spherical symmetry. The relationship between the pressure P and the radius r of the reservoir is derived.

[0117] P(r) = (2E(r-r_0)t_0 r_0) / r^3

[0118] In the above equation, E is Young's modulus, t_0 is the initial thickness of the reservoir wall, and r_0 is the initial radius of the reservoir. The volume of this reservoir is expressed as follows: V(r) = 4 / 3 πr^3

[0119] The functional shape of this curve is shown in Figure 31, and the peaks where the maximum pressure occurs are as follows: r(P_max)=3 / 2 r_0

[0120] A smaller reservoir also allows the device to fit into a smaller package, enabling users to store and transport the device more conveniently and frequently. Furthermore, in one embodiment, the device is planar without the need to open or unfold it, making it easier to operate and apply, especially for users with limited dexterity, mobility, or visual impairments (e.g., due to natural anatomical variations, injuries, or use in darkness).

[0121] In some embodiments, the condom is a partial condom, such as the condom in Figure 26B. The condom includes a barrier layer bonded to an adhesive layer. The barrier layer may have a thickness between 25 and 200 microns, and the adhesive layer may have a thickness between 25 and 750 microns. For example, the barrier layer (e.g., latex) may have a thickness between 30 and 150 microns, and the adhesive layer may be between 250 and 500 microns. While not bound by any particular operating theory, embodiments having an adhesive layer thicker than the barrier layer reduce or eliminate user pain during condom removal. Removal of the condom from the user is assisted by the cohesiveness of the crosslinked adhesive described herein. The thicker adhesive, due to the favorable combination of storage modulus and loss modulus with the thickness of the material, helps to painlessly remove the device from the glans, both of which dissipate energy and transmit the applied force during removal to the skin in a preferred manner to reduce the pain experienced. Furthermore, the thickness ratio between the adhesive layer and the barrier layer can also facilitate painless removal of the device from the user.

[0122] Furthermore, a thicker adhesive allows the adhesive to function as an adaptable gasket that deforms to conform to the movement of the user's skin during application, intercourse, ejaculation, and before removal, providing a strong seal that traps semen and pre-ejaculatory fluid. In contrast, thinner adhesives must rely on a barrier layer mechanism to provide all the adaptability and deformation necessary to contain fluid, especially when considering the dynamic deformation of the glans skin and structure under the act of intercourse and load.

[0123] In some embodiments, the contraceptive device has a shelf life of at least one month, for example, at least two months, at least three months, at least four months, at least five months, at least six months, at least seven months, at least eight months, at least nine months, at least ten months, at least eleven months, at least twelve months, or at least twenty-four months.

[0124] In some embodiments, the barrier performance of the contraceptive device is consistent with that demonstrated to be suitable for use in the relevant application field.

[0125] In some embodiments, the contraceptive device is compatible with personal lubricants. In some embodiments, the contraceptive device is compatible with oil-based lubricants.

[0126] In some embodiments, the contraceptive device does not include additional mechanical retention means, as in U.S. Patent No. 5,421,350.

[0127] In some embodiments, the adhesive layer does not adhere to itself, i.e., it is not self-adhesive.

[0128] In some embodiments, the condom is a non-rigid, unwound partial condom comprising a first adhesive layer (e.g., a stimuli-responsive polymer) and a second layer comprising a barrier and a reservoir, wherein the condom does not come into contact with the shaft or coronal sulcus of the penis; the adhesive layer (a) has the same extent as the barrier layer; (b) is thicker than the barrier layer; and / or (c) is the sole means of securing the partial condom to the penis. In some embodiments, the second layer is continuous, i.e., the barrier and reservoir are continuous. In some embodiments, the reservoir is self-forming. In some embodiments, the stimulation is mechanical, e.g., shearing velocity or peeling. In some embodiments, the partial condom consists of only two or three layers, the latter comprising a third backing layer. In some embodiments, the two or three layers include sub-layers. In some embodiments, the condom includes one or more additional means of mechanically securing the condom to the penis.

[0129] The first adhesive layer of the non-rigid, unwound partial condom described above may include any suitable irritation-responsive polymer, e.g., any irritation-responsive polymer described herein, and in some embodiments, an irritation-responsive polymer comprising an acrylate monomer or methacrylate monomer (e.g., lauryl methacrylate) and optionally a polyfunctional crosslinking agent (e.g., a trifunctional crosslinking agent such as TMPTA). The weight ratio of the polymer to the trifunctional crosslinking agent may be, for example, 99.1:0.9, more specifically 99.02:08, 99.04:06, or 99.04:06. In some embodiments, the adhesive is characterized by low-density heterogeneous crosslinking.

[0130] The non-rigid, unwound partial condoms described above may have one or more properties, including but not limited to, a disproportionate response to stimuli such as mechanical stimuli, such that the response can be achieved using lower intensity stimuli, as described herein. In some embodiments, the non-rigid, unwound partial condoms described above may exhibit lower peeling strength at lower peeling rates and higher peeling strength at higher peeling rates, for example, about 10 times, about 20 times, about 30 times, about 40 times, about 50 times, about 60 times, about 70 times, about 80 times, about 90 times, about 100 times, about 2 times, about 3 times, about 4 times, or about 5 times or less peeling strength at higher peeling rates.

[0131] In some embodiments, non-rigid, unwound partial condoms can be removed with little to no pain, as measured using the Wong-Baker Qualitative Pain Assessment (WBQPA) on a scale of 0 (no pain) to 10 (maximum pain). In some embodiments, pain is less than 4 on the WBQPA scale, e.g., less than 3, less than 2, less than 1, or 0, when the adhesive layer is removed by light peeling. In some embodiments, non-rigid, unwound partial condoms may have a loss modulus of elasticity of 0.1 MPa to 0.5 MPa.

[0132] In certain embodiments, the non-rigid, unwound partial condom leaves little to no residue on the skin after removal, for example, less than about 10%, less than about 5%, less than about 1%, or 0% residue.

[0133] In some embodiments, the rate of contraceptive device failure (clinical or nonclinical) when measured in a subject or control group is less than approximately 10%, less than approximately 8%, less than approximately 6%, less than approximately 4%, less than approximately 2%, less than approximately 1.5%, less than approximately 1%, less than approximately 0.9%, less than approximately 0.8%, less than approximately 0.7%, less than approximately 0.6%, less than approximately 0.5%, less than approximately 0.4%, less than approximately 0.3%, less than approximately 0.2%, or less than or equal to approximately 0.1%. Clinical failure refers to a contraceptive device, such as a condom, that breaks, tears, leaks, or slips completely after initial insertion but before being fully withdrawn. Nonclinical failure refers to a contraceptive device, such as a condom, that breaks, tears, leaks, or slips partially.

[0134] In some embodiments, the condom leakage rate 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%.

[0135] 4.2.1. Barrier Layer In some embodiments, the barrier layer includes an elastomer or a polymer film or membrane exhibiting flexible thermomechanical behavior. In some embodiments, the barrier layer is a film or membrane.

[0136] In some embodiments, the barrier layer includes natural latex rubber, synthetic rubber, amorphous polyurethane, various thermoplastic polyurethanes, semi-crystalline polyurethane including 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), elastomer or flexible material, or blends thereof. In some embodiments, the barrier layer includes natural latex rubber, synthetic rubber, or polyurethane.

[0137] In some embodiments, the barrier layer is not polyurethane.

[0138] In some embodiments, the barrier layer is not a loose fit.

[0139] In some embodiments, the barrier layer exhibits stimulus-responsive behavior that enables selective permeability, controlled permeability, or controlled porosity. Exemplary stimuli of a stimulus-responsive barrier layer include temperature changes, physicochemical changes, light, ultrasound, ionic intensity changes, pH changes, magnetic and mechanical forces. In some embodiments, the stimulus of the stimulus-responsive barrier layer differs from that of the stimulus-responsive polymer in the adhesive layer. In some embodiments, the stimulus of the stimulus-responsive barrier layer is the same as that of the stimulus-responsive polymer in the adhesive layer.

[0140] In some embodiments, the barrier layer further includes one or more additives, for example, to enhance its properties. Exemplary additives include, but are not limited to, polymers, ceramics, metallic materials, or structures of spherical, rod, disc, or other shapes. Additive materials include silicon dioxide, metal oxides, iron oxides, metals, nitinol, ceramics, conductive polymers, and the like. The additive materials may be uniformly or non-uniformly dispersed or crosslinked within the material.

[0141] In some embodiments, the barrier layer has a thickness of, for example, 0.001 mm to 2 mm, such as 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 barrier layer has a thickness of, for example, 0.025 mm to 0.25 mm, such as 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 barrier layer has a thickness of at least 0.01 mm, such as 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.

[0142] In some embodiments, the barrier layer has a thickness of less than about 200 microns, for example, about 40 to 100 microns, or about 40 microns, about 50 microns, about 60 microns, about 70 microns, about 80 microns, about 90 microns, or about 100 microns.

[0143] In some embodiments, the barrier layer has a thickness of less than approximately 180 microns, for example, less than approximately 160 microns, less than approximately 140 microns, less than approximately 120 microns, less than approximately 100 microns, less than approximately 80 microns, less than approximately 60 microns, less than approximately 40 microns, or less than approximately 20 microns, but in all cases it is greater than 0.

[0144] In some embodiments, the barrier layer has a planar or curved geometric shape selected from square, circular, oval, hemispherical, rectangular, polygonal, or curved polygonal. In some embodiments, the barrier layer is not tubular.

[0145] In some embodiments, the barrier layer has a first geometric shape before adhering to the penis and deforms into a second geometric shape upon application to the penis.

[0146] In some embodiments, the barrier layer has a circular geometric shape. In some preferred 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.

[0147] In some embodiments, the barrier layer has a rectangular geometric shape. 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 rectangle has a length of 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 rectangle has a width of 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.

[0148] In some embodiments, the barrier layer has an oval geometric shape. In some embodiments, the oval has a primary radius of about 0.5 cm, about 1.0 cm, about 2.0 cm, about 3.0 cm, about 5.0 cm, or about 10.0 cm, and a separate secondary radius of about 0.5 cm, about 1.0 cm, about 2.0 cm, about 3.0 cm, about 5.0 cm, or about 10.0 cm or greater.

[0149] In some embodiments, the barrier layer has primary dimensions of approximately 0.5 × 0.5 cm, approximately 1.0 × 1.0 cm, approximately 1.5 × 1.5 cm, approximately 2.5 × 2.5 cm, approximately 3.0 × 3.0 cm, or approximately 5.0 × 5.0 cm, or any combination thereof, in the case of a rectangular barrier layer.

[0150] In some embodiments, the barrier layer does not include one or more protrusions. Rather, according to this embodiment, the barrier layer is a conventionally simple geometric shape (e.g., rectangular, oval, or circular).

[0151] In some embodiments, the barrier layer does not include one or more protrusions. Rather, according to these embodiments, the barrier layer is a conventionally simple geometric shape (e.g., rectangular, oval, or circular). This is in contrast to the protruding wings disclosed, for example, in International Publication No. 2014178661.

[0152] In some embodiments, the barrier layer includes a lubricant on its outer surface, for example, 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.

[0153] In some embodiments, the barrier layer contains a spermicide on the outer surface of the barrier layer, i.e., the outer surface of the condom. In some embodiments, the spermicide is selected from nonoxynol-9, octoxynol-9, benzalkonium chloride, lactic acid, menfegol, and combinations thereof.

[0154] In some embodiments, the condom further comprises a reservoir of a size and shape suitable for collecting semen ejaculated from the penis. In some embodiments, the reservoir is configured distal to the urethral opening of the penis. In some embodiments, the reservoir is configured at the tip of the condom, along the side, at the base, or below the base.

[0155] In some embodiments, the reservoir is continuous with the barrier layer, i.e., the reservoir and barrier layer are part of the same structure / not separate structures and are not bonded or connected by connecting means.

[0156] In some embodiments, the reservoir self-forms upon receiving pressure from ejaculation by the penis and does not have a predetermined geometric shape.

[0157] In some embodiments, the reservoir includes a polymer coating that swells or gels upon contact with semen. In some embodiments, such swelling or gelling retains sperm within the reservoir. Exemplary polymer coatings include, but are not limited to, chitosan, arginate, polyacrylic acid, cross-linked polyacrylic acid, sodium polyacrylate, cross-linked sodium polyacrylate, and combinations thereof.

[0158] In some embodiments, the reservoir is essentially spherical 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.

[0159] In some embodiments, the reservoir is essentially cylindrical and has, for example, 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 more, and a length of about 1.0 mm, about 2.0 mm, about 5.0 mm, or about 10.0 mm or more.

[0160] In some embodiments, the condom further comprises an elastomer ring fixed to the outer portion of the inner surface of the barrier layer or to the edge of the barrier layer. In some embodiments, the elastomer ring surrounds the base of the barrier layer, is expandable by stretching, encloses the barrier layer and fixes to the base of the penile head, and can optionally exert a contractile force that enhances the adhesion of the condom to the penis and prevents the adhered barrier layer from being removed by stress concentration or shear force during mechanical perturbations such as those associated with sexual activity.

[0161] In some embodiments, the elastomer ring has a cross-sectional diameter of 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 elastomer ring has a total diameter of 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.

[0162] In some embodiments, the elastomer ring includes a raised ring or stud to enhance sexual sensation or pleasure.

[0163] In some embodiments, the condom further includes one or more protruding arms connected to an elastomer ring or barrier layer. In some embodiments, the more protruding arms are extendable by stretching, can enclose the barrier layer and secure it to the base of the penile head, and optionally exert a contracting force that enhances the adhesion of the condom to the penis and prevents the adhered barrier layer from being removed by stress concentration or shear forces during mechanical perturbations such as those associated with sexual activity.

[0164] In some embodiments, the protruding arms may have aspect ratios of approximately 1:1, 1:2, 1:5, 1:10, 1:20, or 1:100 or greater. In some embodiments, there may be 1, 2, 3, 4, 5, 6 or more protruding arms. In some embodiments, the protruding arms have lengths of approximately 0.5 cm, 1.0 cm, 2.0 cm, 3.0 cm, or 5.0 cm or greater, and widths of approximately 0.1 cm, 0.2 cm, 0.5 cm, 1.0 cm, or 2.0 cm or greater.

[0165] 4.2.2.Adhesive layer The contraceptive devices of this disclosure include an adhesive layer comprising an adhesive containing a stimuli-responsive polymer, optionally one or more additional polymers, crosslinking agents and / or additives. In some embodiments, the adhesive is stimuli-responsive in response to stimuli encountered in a bonded state after being previously applied to a surface (e.g., skin). In some embodiments, the stimuli-responsive polymer is a mechanical action or force-responsive polymer.

[0166] In some embodiments, the adhesive layer is bonded to at least a portion of the barrier layer. In some embodiments, the adhesive layer is bonded to a portion of the inner surface of the barrier layer. In some embodiments, the adhesive layer has the same extent as the inner surface of the barrier layer, i.e., it is bonded to the entire surface of the barrier layer. In some embodiments, the bonded area covers at least about 1% of the inner surface of the barrier layer, for example, at least about 5%, at least about 10%, at least about 25%, at least about 33%, at least about 50%, at least about 66%, at least about 75%, or about 100%.

[0167] In some embodiments, the adhesive layer has the same extent as the barrier layer. In some embodiments, the adhesive layer has the same extent as the barrier layer but is a limited area related to the self-formation of the reservoir. In some embodiments, the adhesive layer is located in front of the barrier layer. In some embodiments, the barrier layer and the reservoir are formed in a continuous manner, and (a) the adhesive layer is continuous with the barrier layer, or (b) the adhesive layer is located in front of the barrier layer.

[0168] In some embodiments, the adhesive layer extends to the elastomer ring and / or protruding arm of the condom. In some embodiments, the adhesive layer is the sole means of securing the condom to the penis.

[0169] In some embodiments, the adhesive layer includes a uniform, non-uniform, circular, spherical, elliptical, or ellipsoidal cross-section.

[0170] In some embodiments, the adhesive layer includes one or more patterned configurations. Patterning can facilitate adhesive crack propagation or shear-responsive layer delamination. For example, adhesive patterning can allow for sufficient adhesion of the barrier layer to the penis or vagina while simultaneously allowing for minimal or no pain peeling of the barrier layer. Such patterning includes, but is not limited to, a continuous ring or repeating dot ring layer at the base of the barrier layer, ranging in length from 0.1 to 3000 micrometers, more specifically 1 to 2000 micrometers, more specifically 20 to 2000 micrometers, and thickness from 0.1 to 3000 micrometers, more specifically 1 to 2000 micrometers, more specifically 5 to 1000 micrometers, more specifically 10 to 600 micrometers, where the dot pattern covers 10 to 100% of the available adhesive area in the base ring region, more specifically 20 to 100% of the available adhesive area in the base ring region, and more specifically 30 to 100% of the available area in the base ring region.

[0171] In certain embodiments, the patterning lengths are approximately 1 to 100 micrometers, approximately 100 to approximately 200 micrometers, approximately 200 to approximately 300 micrometers, approximately 300 to approximately 400 micrometers, approximately 400 to approximately 500 micrometers, approximately 500 to approximately 600 micrometers, approximately 600 to approximately 700 micrometers, approximately 700 to approximately 800 micrometers, approximately 800 to approximately 900 micrometers, and approximately 900 to approximately 1000 micrometers.

[0172] In certain embodiments, the patterning length is approximately 1000–1100 micrometers, approximately 1100–1200 micrometers, approximately 1200–1300 micrometers, approximately 1300–1400 micrometers, approximately 1400–1500 micrometers, approximately 1500–1600 micrometers, approximately 1600–1700 micrometers, approximately 1700–1800 micrometers, approximately 1800–1900 micrometers, or approximately 1900–200 micrometers.

[0173] In certain embodiments, the patterned thickness is approximately 0.1 to 500 micrometers, approximately 1 to 100 micrometers, approximately 100 to 200 micrometers, approximately 200 to 300 micrometers, approximately 300 to 400 micrometers, approximately 400 to 500 micrometers, approximately 500 to 600 micrometers, approximately 600 to 700 micrometers, approximately 700 to 800 micrometers, approximately 800 to 900 micrometers, and approximately 900 to 1000 micrometers.

[0174] In certain embodiments, the patterned thickness is approximately 1000-1100 micrometers, approximately 1100-1200 micrometers, approximately 1200-1300 micrometers, approximately 1300-1400 micrometers, approximately 1400-1500 micrometers, approximately 1500-1600 micrometers, approximately 1600-1700 micrometers, approximately 1700-1800 micrometers, approximately 1800-1900 micrometers, or approximately 1900-200 micrometers.

[0175] Exemplary pattern configurations include rings, stripes, dots, and combinations thereof. The patterning may be uniform, non-uniform, or random in shape, size, or location, or any combination thereof. In some embodiments, one or more patterned configurations may cover about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75%, or about 100% of the adhesive layer.

[0176] In some embodiments, the patterned configuration includes one or more rings or ring-shaped structures. The thickness of the rings can be, for example, about 0.1 mm, about 0.25 mm, about 0.5 mm, or about 1.0 mm or more. In some embodiments, the ring pattern covers at least about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75%, or about 100% of the adhesive layer.

[0177] In some embodiments, the patterned configuration includes dots (e.g., dots in the shape of squares, rectangles, or circles). In some embodiments, the dot pattern covers at least about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75%, or about 100% of the adhesive layer.

[0178] In some embodiments, the pattern configuration includes stripes. In some embodiments, the stripes may be of varying thicknesses, for example, about 0.1 mm, about 0.25 mm, about 0.5 mm, or about 1.0 mm or more. In some embodiments, the stripes 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.

[0179] In some embodiments, the adhesive layer has a thickness on the nanometer or micron scale. In some embodiments, the adhesive layer has a thickness such as 0.1 to 3,000 microns, for example, 0.1 to 2,000 microns, 0.1 to 1,000 microns, 0.1 to 750 microns, 0.1 to 500 microns, 0.1 to 250 microns, 1 to 2,000 microns, 1 to 1,000 microns, 1 to 750 microns, 1 to 500 microns, 1 to 250 microns, 25 to 2,000 microns, 25 to 1,000 microns, 25 to 750 microns, 25 to 500 microns, 25 to 250 microns, 100 to 2,000 microns, 100 to 1,000 microns, 100 to 750 microns, 100 to 500 microns, or 100 to 250 microns.

[0180] In some embodiments, the adhesive layer has a thickness of approximately 0.01 microns to approximately 0.1 microns, approximately 1.0 microns to approximately 5.0 microns, approximately 10.0 microns to approximately 20.0 microns, approximately 30.0 microns to approximately 50.0 microns, approximately 100.0 microns to approximately 200 microns, approximately 300 microns to approximately 400 microns, approximately 600 microns to approximately 750 microns, or approximately 1000 microns to approximately 2000 microns.

[0181] In some embodiments, the adhesive layer is 25 to 750 microns thick, for example, about 200 to about 500 microns, or about 400 microns thick.

[0182] In some embodiments, the adhesive layer has a thickness of approximately 25 microns, approximately 50 microns, approximately 100 microns, approximately 150 microns, approximately 200 microns, approximately 250 microns, approximately 300 microns, approximately 350 microns, approximately 400 microns, approximately 450 microns, approximately 500 microns, approximately 550 microns, approximately 600 microns, approximately 650 microns, approximately 700 microns, or approximately 750 microns.

[0183] In some embodiments, the adhesive layer has a thickness of about 100 microns to about 600 microns, for example, about 200 microns to about 500 microns, or about 300 to about 500 microns.

[0184] In some embodiments, the adhesive layer is thicker than the barrier layer. The adhesive layer may be, for example, about 1.5 times, about 2 times, about 2.5 times, about 3 times, about 3.5 times, about 4 times, about 4.5 times, about 5 times, about 5.5 times, about 6 times, about 6.5 times, about 7 times, about 7.5 times, about 8 times, 8.5 times, about 9 times, about 9.5 times, or at least about 10 times thicker than the barrier layer.

[0185] In some embodiments, the barrier layer is approximately 40 to 100 microns thick, and the adhesive layer is approximately 25 to 750 microns thick. In some embodiments, the barrier layer is approximately 200 microns thick, and the adhesive layer is approximately 400 microns thick.

[0186] In some embodiments, the adhesive layer is transparent.

[0187] In some embodiments, the adhesive layer comprises multiple adhesives that are blended together or applied separately to the barrier layer. For example, as shown in Figure 2, the adhesive layer may include a hydrophobic, water-insoluble layer along its outer edge along the circumference of the barrier layer, approximately 0.1–2 cm long, more specifically 0.2–1 cm long, and more specifically 0.25–1 cm long, and a hydrophilic, water-soluble layer on top of the hydrophobic adhesive layer. In some embodiments, the hydrophobic outer adhesive layer may be stimulus-responsive.

[0188] In some embodiments, the adhesive comprises (1) optionally crystallizable primary side-chain adhesive polymers, (2) optionally additives, (3) optionally additional polymers, and optionally amorphous polymer blend phases or different phases, and (4) optionally crosslinking agents, which are optionally uniformly incorporated into the polymer network, optionally aggregate, and act as high-stress concentration network sites to promote poor adhesion or a desired tack profile, if desired. In some embodiments, the adhesive comprises a blend or copolymer of crystallizable amorphous polymers.

[0189] In some embodiments, the adhesive layer of the contraceptive device described herein comprises an adhesive comprising a stimulus-responsive polymer formed from one or more monomers and optionally one or more polyfunctional crosslinking agents. In some embodiments, the adhesive consists of a stimulus-responsive polymer. In some embodiments, the adhesive is essentially composed of a stimulus-responsive polymer. As used herein with respect to adhesives, "consists essentially of" refers to additional components that do not substantially affect the basic characteristics of the adhesive, such as additives that do not possess adhesive properties themselves.

[0190] In some embodiments, the adhesive does not contain additional components, such as additives, adhesive polymers, and / or other polymers.

[0191] In some embodiments, the adhesive layer comprises a single layer. In some embodiments, the adhesive layer comprises multiple layers, for example, two, three, four, or five or more layers. The layers may be the same or different.

[0192] In some embodiments, the adhesive layer comprises two, three, or more adhesive regions that may exhibit different mechanical, chemical, and biological properties. These may include different solubility parameters in various solvents, including water, vaginal fluid, or ejaculatory fluid. Reversible or irreversible adhesive behavior may be triggered simultaneously or sequentially by exposure to temperature changes, physicochemical changes, light, ultrasound, ionic intensity changes, pH changes, magnetic, electrical, or mechanical forces, and other stimuli or any combination thereof.

[0193] 4.2.2.1 Adhesive properties In some embodiments, when the condom is applied to the penis, the adhesive layer adheres to the penis. In some embodiments, when the condom is applied to the glans of the penis, the adhesive layer adheres to the glans of the penis. In some embodiments, when the pessary is applied to the vagina, the adhesive layer adheres to the vagina.

[0194] When a stimuli are applied to a contraceptive device, the adhesive layer becomes less tacky or delaminates from the skin (e.g., the penis or vagina), thereby enabling selective delamination (i.e., on-demand delamination). Reversible or irreversible adhesive behavior can be triggered by exposure to temperature changes (e.g., temperature decrease), physicochemical changes (e.g., dissolution), light, ultrasound, ionic intensity changes, pH changes, magnetic, electrical, or mechanical actions or forces, and other stimuli or any combination thereof.

[0195] The properties of stimulus-responsive polymers listed below may also apply to adhesives, which may optionally include additional components, such as additives and / or polymers (e.g., adhesive polymers or non-adhesive polymers).

[0196] In some embodiments, the stimulus-responsive polymer loses its adhesion or delaminates from the vagina or penis (e.g., the glans of the penis) in response to stimulation by the contraceptive device for 0.1 to 60 seconds, for example, 1 to 60 seconds, 1 to 30 seconds, 1 to 15 seconds, 1 to 10 seconds, 1 to 5 seconds, 2 to 30 seconds, or 1 to 15 seconds.

[0197] In some embodiments, the adhesive loses its adhesiveness or delaminates from the vagina or penis (e.g., the glans of the penis) in response to stimulation by the contraceptive device for 0.1 to 60 seconds, for example, 1 to 60 seconds, 1 to 30 seconds, 1 to 15 seconds, 1 to 10 seconds, 1 to 5 seconds, 2 to 30 seconds, or 1 to 15 seconds.

[0198] In some embodiments, the stimulus-responsive polymer delaminates from the vagina or penis faster than a non-stimulus-responsive polymer, such as a conventional pressure-sensitive adhesive polymer. In some embodiments, the stimulus-responsive polymer delaminates at least twice as fast as a non-stimulus-responsive polymer, such as a conventional pressure-sensitive adhesive polymer, for example, at least three times faster, at least four times faster, at least five times faster, at least six times faster, at least seven times faster, at least eight times faster, at least nine times faster, or at least ten times faster than a non-stimulus-responsive polymer, such as a conventional pressure-sensitive adhesive polymer.

[0199] In some embodiments, adhesives containing irritation-responsive polymers delaminate from the vagina or penis faster than adhesives containing non-irritation-responsive polymers, such as conventional pressure-sensitive adhesive polymers. In some embodiments, adhesives containing irritation-responsive polymers delaminate at least twice as fast, for example, at least three times faster, at least four times faster, at least five times faster, at least six times faster, at least seven times faster, at least eight times faster, at least nine times faster, or at least ten times faster than adhesives containing non-irritation-responsive polymers, such as conventional pressure-sensitive adhesive polymers.

[0200] In some embodiments, the stimulus is selected from temperature changes, physicochemical changes, light, ultrasound, ionic intensity changes, pH changes, magnetism, mechanical force, or mechanical action.

[0201] In some embodiments, the stimulus is a mechanical action, such as shearing velocity. In some embodiments, the shearing velocity is induced by peeling or pulling the contraceptive device at different speeds or frequencies.

[0202] 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 remains adhered when a higher shear rate is applied and exhibits reduced adhesion at lower shear rates. Exemplary higher shear rates include strong peeling or strong pulling. Exemplary lower shear rates include light peeling or light pulling. Higher and lower are taken relative to the threshold at which a change in behavior is observed. In this way, the adhesive layer and the contraceptive device can be easily removed from the penis or vagina after the application of stimulus to the contraceptive device.

[0203] In some embodiments, light peeling corresponds to peeling speeds of 500 mm / min or less, for example, 400 mm / min or less, 300 mm / min or less, 200 mm / min or less, 100 mm / min or less, or 50 mm / min or less. In some embodiments, light peeling corresponds to peeling speeds 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.

[0204] In some embodiments, light peeling corresponds to peeling speeds of 25 mm / s or less, 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 peeling speeds such as 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 mms to 0.5 mm / s, 0.01 mm / s to 0.3 mm / s, 0.01 mm / s to 0.1 mm / s, 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 mms 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.

[0205] 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 remains adhered when a higher force is applied and becomes less adherent when a lower force is applied. Higher and lower are taken relative to the threshold at which a change in behavior is observed.

[0206] In some embodiments, the applied force that causes delamination of the stimulus-responsive polymer is, for example, 0.01-0.1N, 0.1-1N, 1-10N, 10-100N, or 100-1000N. In some embodiments, the applied force that causes delamination of the stimulus-responsive polymer is, for example, 1-10Pa, 10-100Pa, 0.1-1kPa, 1-10kPa, 10-100kPa, or 0.1-1MPa.

[0207] In some embodiments, the applied force that causes delamination of the adhesive layer is, for example, 0.01-0.1N, 0.1-1N, 1-10N, 10-100N, or 100-1000N. In some embodiments, the applied force that causes delamination of the adhesive layer is, for example, 1-10Pa, 10-100Pa, 0.1-1kPa, 1-10kPa, 10-100kPa, or 0.1-1MPa.

[0208] In some embodiments, the irritation-responsive polymer has a lower peeling strength at lower peeling rates and a higher peeling strength at higher peeling rates. In some embodiments, the irritation-responsive polymer has a peeling strength at lower peeling rates that is at least 5% lower, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower compared to the peeling strength at higher peeling rates.

[0209] In some embodiments, the irritation-responsive polymer has a lower peeling intensity at a peeling rate of 100 mm / min than at 200 mm / min. In some embodiments, the irritation-responsive polymer has a lower peeling intensity at a peeling rate of 100 mm / min than at 300 mm / min. In some embodiments, the irritation-responsive polymer has a lower peeling intensity at a peeling rate of 100 mm / min than at 400 mm / min. In some embodiments, the irritation-responsive polymer has a lower peeling intensity at a peeling rate of 100 mm / min than at 500 mm / min.

[0210] In some embodiments, the irritation-responsive polymer has a lower peeling strength at a peeling speed of 1 mm / s than at 3 mm / s. In some embodiments, the irritation-responsive polymer has a lower peeling strength at a peeling speed of 1 mm / s than at 5 mm / s. In some embodiments, the irritation-responsive polymer has a lower peeling strength at a peeling speed of 1 mm / s than at 7 mm / s. In some embodiments, the irritation-responsive polymer has a lower peeling strength at a peeling speed of 1 mm / s than at 10 mm / s.

[0211] In some embodiments, the irritation-responsive polymer has a peeling strength that is at least 5% lower at a peeling speed of 100 mm / min than 200 mm / min, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0212] In some embodiments, the irritation-responsive polymer has a peeling strength that is at least 5% lower at a peeling speed of 100 mm / min than 300 mm / min, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0213] In some embodiments, the irritation-responsive polymer has a peeling strength that is at least 5% lower at a peeling speed of 100 mm / min than 400 mm / min, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0214] In some embodiments, the irritation-responsive polymer has a peeling strength that is at least 5% lower at a peeling speed of 100 mm / min than 500 mm / min, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0215] In some embodiments, the irritation-responsive polymer has a peeling strength that is at least 5% lower than 3 mm / s at a peeling speed of 1 mm / s, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0216] In some embodiments, the irritation-responsive polymer has a peeling strength that is at least 5% lower than 5 mm / s at a peeling speed of 1 mm / s, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0217] In some embodiments, the irritation-responsive polymer has a peeling strength that is at least 5% lower than 7 mm / s at a peeling speed of 1 mm / s, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0218] In some embodiments, the adhesive has a lower peeling strength at a lower peeling rate and a higher peeling strength at a higher peeling rate. In some embodiments, the adhesive has a peeling strength at a lower peeling rate that is at least 5% lower, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower compared to the peeling strength at a higher peeling rate.

[0219] In some embodiments, the adhesive has a lower peeling strength at a peeling speed of 100 mm / min than at 200 mm / min. In some embodiments, the adhesive has a lower peeling strength at a peeling speed of 100 mm / min than at 300 mm / min. In some embodiments, the adhesive has a lower peeling strength at a peeling speed of 100 mm / min than at 400 mm / min. In some embodiments, the adhesive has a lower peeling strength at a peeling speed of 100 mm / min than at 500 mm / min.

[0220] In some embodiments, the adhesive has a lower peeling strength at a peeling speed of 1 mm / s than at 3 mm / s. In some embodiments, the adhesive has a lower peeling strength at a peeling speed of 1 mm / s than at 5 mm / s. In some embodiments, the adhesive has a lower peeling strength at a peeling speed of 1 mm / s than at 7 mm / s. In some embodiments, the adhesive has a lower peeling strength at a peeling speed of 1 mm / s than at 10 mm / s.

[0221] In some embodiments, the adhesive has a peeling strength that is at least 5% lower at a peeling speed of 100 mm / min than 200 mm / min, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0222] In some embodiments, the adhesive has a peeling strength that is at least 5% lower at a peeling speed of 100 mm / min than 300 mm / min, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0223] In some embodiments, the adhesive has a peeling strength that is at least 5% lower than 400 mm / min at a peeling speed of 100 mm / min, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0224] In some embodiments, the adhesive has a peeling strength that is at least 5% lower than 500 mm / min at a peeling speed of 100 mm / min, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0225] In some embodiments, the adhesive has a peeling strength that is at least 5% lower than 3 mm / s at a peeling speed of 1 mm / s, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0226] In some embodiments, the adhesive has a peeling strength that is at least 5% lower than 5 mm / s at a peeling speed of 1 mm / s, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0227] In some embodiments, the adhesive has a peeling strength that is at least 5% lower than 7 mm / s at a peeling speed of 1 mm / s, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0228] In some embodiments, the irritation-responsive polymer has a peeling strength of 1 to 400 N / m, e.g., 1 to 300 N / m, 1 to 200 N / m, 1 to 100 N / m, or 1 to 50 N / m at a peeling rate of 100 mm / second. The peeling strength can be determined by a 180° peeling test using a human skin substrate analog as described below.

[0229] In some embodiments, the adhesive has a peeling strength of 1 to 400 N / m, e.g., 1 to 300 N / m, 1 to 200 N / m, 1 to 100 N / m, or 1 to 50 N / m at a peeling speed of 100 mm / second. The peeling strength can be determined by a 180° peeling test using a human skin substrate analog as described below.

[0230] In some embodiments, the stimulus-responsive polymer has a 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. The tack strength can be measured, for example, by compressing an aluminum tip rheometer containing the polymer onto an aluminum base plate for 60 seconds, withdrawing the rheometer at 100 micrometers per second, and measuring the axial force in N, as described below.

[0231] In some embodiments, the adhesive has a tack strength of at least 1N at 25°C, for example, 1N to 5N, 1N to 4N, 1N to 3N, or 1N to 2N.

[0232] In some embodiments, the stimulus-responsive polymer has an adhesive strength of at least 20 N*s at 25°C, for example, at least 30 N*s, at least 40 N*s, at least 50 N*s, at least 60 N*s, at least 70 N*s, at least 80 N*s, at least 90 N*s, at least 100 N*s, at least 150 N*s, at least 200 N*s, at least 300 N*s, at least 400 N*s, or at least 500 N*s. The adhesive strength is calculated by integrating the area under the axial force versus time measurement of the sample.

[0233] In some embodiments, the adhesive has an adhesive strength of at least 20 N*s at 25°C, for example, at least 30 N*s, at least 40 N*s, at least 50 N*s, at least 60 N*s, at least 70 N*s, at least 80 N*s, at least 90 N*s, at least 100 N*s, at least 150 N*s, at least 200 N*s, at least 300 N*s, at least 400 N*s, or at least 500 N*s.

[0234] 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.

[0235] In some embodiments, the adhesive has a storage modulus of 0.01 to 1 MPa, for example, 0.1 to 1 MPa, 0.1 to 0.8 MPa, or 0.1 to 0.5 MPa.

[0236] In some embodiments, the stimulus-responsive polymer has a loss modulus of elasticity of 0.1 MPa to 1 MPa, for example, 0.1 MPa to 0.8 MPa or 0.1 MPa to 0.5 MPa.

[0237] In some embodiments, the adhesive has a loss modulus of elasticity of 0.1 MPa to 1 MPa, for example, 0.1 MPa to 0.8 MPa or 0.1 MPa to 0.5 MPa.

[0238] In some embodiments, the stimulus-responsive polymer has a tan of 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 at 25°C and 1 Hz (2*π radians / second). The stimulus-responsive polymer has a tan(δ) such as 0.1 to 5, e.g., 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 a particular embodiment, the stimulus-responsive polymer has a tan(δ) such as 0.2 to 2, e.g., 0.1 to 1.5, 0.1 to 1, 0.1 to 0.5, 0.3 to 1, or 0.5 to 1.

[0239] In some embodiments, the adhesive has a coefficient of at least 0.1 at 25°C and 1 Hz (2*π radians / second), 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, etc. The adhesive has tan(δ) (the ratio of the storage modulus (G") to the loss modulus (G'). In some embodiments, the adhesive has tan(δ) such as 0.1 to 5, e.g., 0.1 to 4, 0.1 to 3, 0.1 to 2, 0.1 to 1, 0.5 to 5, 0.5 to 4, 0.5 to 3, 0.5 to 3, 0.5 to 2, 0.5 to 1, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 5, 2 to 4, 2 to 3, 3 to 5, 3 to 4, or 4 to 5. In certain embodiments, the adhesive has tan(δ) such as 0.2 to 2, e.g., 0.1 to 1.5, 0.1 to 1, 0.1 to 0.5, 0.3 to 1, or 0.5 to 1.

[0240] In some embodiments, the stimulus-responsive polymer has lower tack when wet compared to when dry. In some embodiments, the adhesive has lower tack when wet compared to when dry.

[0241] In some embodiments, the stimulus-responsive polymer is a crosslinked polymer that is a low-density crosslinked polymer or a polymer having limited heterogeneous crosslinking.

[0242] In some embodiments, the stimulus-responsive polymer has a gel fraction that matches the gel fraction of a lightly crosslinked polymer network when analyzed by sol-gel analysis. In some embodiments, the stimulus-responsive polymer has a gel fraction of 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.

[0243] In some embodiments, the adhesive has a gel fraction that matches the gel fraction of a lightly crosslinked polymer network when analyzed by sol-gel analysis. In some embodiments, the adhesive has a gel fraction of 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.

[0244] In some embodiments, removal of the contraceptive device by light peeling after the adhesive layer has been applied to the penis or vagina does not cause pain in the subject. In some embodiments, removal of the condom by light peeling after the adhesive layer has been applied to the glans of the penis causes minimal or no pain in the subject. Any suitable method can be used to determine the presence or absence of pain. There are several validated instruments for measuring pain. The instruments may be one-dimensional and measure only the intensity of pain, and may be, for example, the Wong-Baker Qualitative Pain Assessment (WBQPA), the Numerical Pain Assessment Scale (NRPS), the Visual Analog Scale (VAS), and the Oral Assessment Scale. Multidimensional instruments measure the intensity, characteristics, and impact of pain, for example, the McGill Pain Questionnaire (MPQ) and the Brief Pain Inventory (BPI).

[0245] In some embodiments, pain is measured using WBQPA on a scale of 0 (no pain) to 10 (maximum pain). In some embodiments, pain is less than 4 on the WBQPA scale, e.g., less than 3, less than 2, less than 1, or 0, when the adhesive layer is removed by light peeling. In some embodiments, a WBQPA score of 0 is reported when the contraceptive device is removed by light peeling. As described above, in some embodiments, light peeling corresponds to a user peeling speed of the contraceptive device (e.g., condom) of 25 mm / s or less, e.g., less than 10 mm / s, less than 5 mm / s, less than 1 mm / s, less than 0.5 mm / s, less than 0.3 mm / s, or less than 0.1 mm / s. In some embodiments, light peeling corresponds to peeling speeds such as 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 mms to 0.5 mm / s, 0.01 mm / s to 0.3 mm / s, 0.01 mm / s to 0.1 mm / s, 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 mms 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.

[0246] In some embodiments, light peeling corresponds to user peeling speeds of contraceptive devices (e.g., condoms) of 500 mm / min or less, for example, 400 mm / min or less, 300 mm / min or less, 200 mm / min or less, 100 mm / min or less, or 50 mm / min or less, or 25 mm / min or less, or 10 mm / min or less, or 5 mm / min or less, or 1 mm / min or less, or 0.5 mm / min or less, or 0.3 mm / min or less, or 0.1 mm / min or less. In some embodiments, light peeling corresponds to peeling speeds 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.

[0247] In some embodiments, removal of the contraceptive device by light peeling after adhesion of the adhesive layer to the penis or vagina causes minimal or no pain in the subject if removed in less than 15 seconds, for example, less than 10 seconds, less than 8 seconds, or less than 5 seconds.

[0248] In some embodiments, the adhesion site exhibits limited hypersensitivity or no hypersensitivity upon removal of the contraceptive device. Various methods for quantitatively assessing skin injury are known in the field. Some of these models are based on the measurement of baseline skin properties that change when the skin is stressed. Measurable parameters such as skin hydration, transepidermal water content (TEWL), and hypersensitivity, in particular, provide information to distinguish injured skin from healthy skin. See, for example, Bernatchez, S. et al, ADVANCES IN WOUND CARE, Vol.2, No.4 (2022), incorporated herein by reference. Reconstructed human epidermal models that demonstrate reasonable similarity to natural human tissue with respect to morphology, lipid composition, and biochemical markers are also available. See, for example, EpiSkin, SkinEthic, and EpiDerm. Animal models of skin injury, including those in pigs and rodents, are also known in the art. For example, see Summerfield, A. et al., Molecular Immunology, Vol. 66, Issue 1, July 2015, pp. 14-21.

[0249] In some embodiments, the stimulus is a temperature change. In some embodiments, the adhesive layer adheres to the penis or vagina at a temperature of 37°C and has poor adhesion or peels off from the penis or vagina at temperatures below 25°C. In some embodiments, the adhesive layer adheres to the glans of the penis at a temperature of 37°C and has poor adhesion or peels off from the glans of the penis at temperatures below 25°C.

[0250] In some embodiments, the adhesive layer may exhibit thermally responsive, stimulus-responsive behavior that allows adhesion to the penile skin at body temperature (approximately 37°C) and allows for a decrease in adhesion or delamination when cooled to temperatures below body temperature, such as approximately 25°C, 20°C, 15°C, 10°C, 5°C, 0°C, or lower. Cooling can be achieved, for example, by rubbing a damp substrate, such as a water-impregnated towel or paper towel, onto the condom or the interface of the barrier layer while adhering it to the penis, or by flowing water from a source such as a shower or cloth or tissue wipe containing a cooling reagent (e.g., evaporation of alcohol or dissolution of ammonium nitrate) to cool the condom by thermal transition, thereby achieving delamination more easily than when removing the condom at body temperature.

[0251] In some embodiments, the stimulus is a physicochemical change. An exemplary physicochemical change is dissolution. In some embodiments, the stimulus is a change in the dissolution of the adhesive layer upon contact with a solvent. In some embodiments, the composition adheres to the penis or vagina in the absence of a solvent, and exhibits low adhesion or delamination from the penis or vagina upon contact with a solvent. In some embodiments, the composition adheres to the glans of the penis in the absence of a solvent, and exhibits low adhesion or delamination from the glans of the penis upon contact with a solvent.

[0252] In some embodiments, the adhesive layer may exhibit chemically responsive behavior and be essentially soluble in water or a solvent, and may be removed by pulling back the edges and running water or solvent over it, or by rubbing a water or solvent-impregnated substrate, until the condom is removed by weakening of the adhesive layer or dissolution by water or a solvent. Chemical delamination can also be achieved by pH-triggered delamination by flowing or wiping a substrate impregnated with a fluid having a pH suitable for skin contact, which also achieves delamination of the condom from the skin. Alternatively, chemical delamination can also be achieved by dissolving the adhesive by flowing or wiping a substrate impregnated with a fluid, which also achieves delamination of the condom from the skin.

[0253] 4.2.2.2 Polymers The adhesives described herein comprise a stimulus-responsive polymer and optionally one or more additional polymers.

[0254] In some embodiments, the stimulus-responsive polymer has a glass transition temperature (Tg) of 0°C to 50°C, for example, 0°C to 40°C, 0°C to 30°C, 0°C to 20°C, 0°C to 10°C, 5°C to 50°C, 5°C to 40°C, 5°C to 30°C, 5°C to 20°C, 5°C to 10°C, 10°C to 50°C, 10°C to 40°C, 10°C to 30°C, 10°C to 20°C, 20°C to 50°C, 20°C to 40°C, 20°C to 30°C, 30°C to 50°C, 30°C to 40°C, or 40°C to 50°C.

[0255] In some embodiments, the stimulus-responsive polymer has a glass transition below ambient temperature, for example, -90°C to 20°C, -90°C to -80°C, -80°C to -70°C, -70°C to -60°C, -60°C to -50°C, -50°C to -40°C, -40°C to -30°C, -30°C to -20°C, -20°C to -10°C, -10°C to 0°C, 0°C to 10°C, or 20°C to 20°C.

[0256] In some embodiments, the stimulus-responsive polymer has a crystalline melt transition below ambient temperature, such as -90°C to 20°C, -90°C to -80°C, -80°C to -70°C, -70°C to -60°C, -60°C to -50°C, -50°C to -40°C, -40°C to -30°C, -30°C to -20°C, -20°C to -10°C, -10°C to 0°C, 0°C to 10°C, or 20°C to 20°C.

[0257] 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, which include copolymer structures of two or more block copolymers, gradient copolymers, and random copolymers.

[0258] In some embodiments, one or more polymers are selected from other adhesives suitable for use on human skin, including, for example, polyacrylates, polymethacrylates, polyurethanes, polyolefins, polyethers, silicones, polyepoxys, synthetic rubbers, or their derivatives, copolymers, and mixtures.

[0259] In some embodiments, the stimulus-responsive polymer comprises one or more polyacrylate polymers or polymethacrylate polymers.

[0260] 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 carbon atoms in their side chains and 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or up to 100 or more oxygen atoms in their side chains.

[0261] Typical 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( Examples include C18 acrylate, poly(C19 acrylate), poly(C20-C100 or higher acrylates, methacrylates and their acrylamides), poly(2-hydroxyethyl acrylate), poly(butoxymethyl acrylate), poly(butoxyethyl acrylate), poly(butoxypropyl acrylate), poly(butoxybutyl acrylate), poly(finding-nemo-acrylate), poly(octadecyl acrylate), poly(octadecyl methacrylate), and poly(acrylic acid).

[0262] In some embodiments, the stimulus-responsive polymer comprises a polymethacrylate, a polymethacrylate copolymer, or a blend thereof. The copolymer is derived from at least one methacrylate monomer and at least one polymerizable comonomer, comprising any monomer disclosed herein.

[0263] In some embodiments, the stimulus-responsive polymer comprises a crosslinked polymethacrylate. The crosslinking agent may be polyfunctional. In one embodiment, the stimulus-responsive polymer comprises a polymethacrylate crosslinked with acrylate. In some embodiments, the polymethacrylate is poly(lauryl)methacrylate, and the acrylate crosslinking agent is TMPTA. The weight ratio of lauryl methacrylate to TMPTA can vary.

[0264] In some embodiments, the weight ratio is 98:2, 98.5:1.5, or 99:1, 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 within these.

[0265] In some embodiments, the stimulus-responsive polymer does not contain polyacrylate or polymethacrylate.

[0266] In some embodiments, the stimulus-responsive polymer comprises one or more amorphous or semi-crystalline polyurethanes.

[0267] In some embodiments, the stimulus-responsive polymer includes a semicrystalline polyurethane elastomer having segments containing polyether, polyester, polyurethane, polyurethane urea, poly(isoprene), poly(butadiene), or other crystalline segments.

[0268] In some embodiments, the stimulus-responsive polymer comprises a linear or crosslinked semi-crystalline polyurethane elastomer having segments including polyethers, polyesters, polyurethanes, polyurethane ureas, poly(isoprene), poly(butadiene), or other crystalline segments.

[0269] In some embodiments, the stimulus-responsive polymer does not include polyurethane.

[0270] In some embodiments, the stimulus-responsive polymer includes a polyolefin. In some embodiments, the polyolefin is polyisoprene.

[0271] In some embodiments, the stimulus-responsive polymer includes at least one polyether, such as poly(ethylene glycol) (PEG) compounds and acrylated or polyurethane-containing PEG compounds.

[0272] In some embodiments, the stimulus-responsive polymer includes at least one polyepoxy. In some embodiments, the polyepoxy includes one or more epoxy monomers disclosed herein. In some embodiments, the stimulus-responsive polymer does not include polyepoxy. In some embodiments, the polyepoxy includes one or more silicone monomers disclosed herein.

[0273] In some embodiments, the stimulus-responsive polymer includes at least one silicone polymer. In some embodiments, the silicone polymer is a high molecular weight linear siloxane polymer and a highly condensed silicate tackifier resin.

[0274] In some embodiments, the stimulus-responsive polymer does not include a silicone polymer.

[0275] In some embodiments, the stimulus-responsive polymer includes at least one synthetic rubber.

[0276] In some embodiments, the stimulus-responsive polymer includes styrene-butadiene rubber (SBR). Examples of SBR include synthetic elastomers derived from styrene and butadiene, used in the manufacture of pressure-sensitive tapes. SBR includes SBR having various percentages of bound styrene, average molecular weight and its distribution, and the presence of functional groups introduced during polymerization, whether in a solvent system suitable for use in this disclosure or an aqueous system. The molecular weight of SBR ranges from 10 to 1,000,000 g / mol, more specifically 25,000 to 750,000 g / mol, and more specifically 50,000 to 500,000 g / mol. SBR generally exhibits low water absorption, with a water content of less than 1% by weight, more specifically less than 0.5% by weight, more specifically 0.1% by weight, and more specifically less than 0.05% by weight.

[0277] In some embodiments, the stimulus-responsive polymer does not contain synthetic rubber.

[0278] In some embodiments, the stimulus-responsive polymer comprises a thiol monomer. Exemplary thiol monomers include, but are not limited to, 3-mercaptopropionic acid; thioglycolic acid; 3-mercapto-1-propanol; 2-mercaptoethanol; 2-(2-mercaptoethoxy)ethanol; 2-(2-mercaptopropionylamino)ethanol; 2-(2-mercaptosuccinyl)ethyl acrylate; 3-(2-mercaptopropionylamino)propionic acid; 3-(mercaptopropyl)trimethoxysilane; 2,2'-(ethylenebis(thio))diethanol; 3-mercaptopropyltrimethoxysilane; 3-mercaptopropylmethyldimethoxysilane; 3-(2,2-dithiobis(ethylthio)propionylamino)propionic acid; 3,6,9-trioxadecanethiol; 3-mercapto-1,2-propanediol; 2,2'-dithiodiethanol; N-acetyl- Examples include L-cysteine; L-cysteine; 2-(2-mercaptoethyl)pyridine; 4-(2-mercaptoethyl)morpholine; 3-mercapto-1,2,4-triazole; thiophenol; pentaerythritol tetrakis(3-mercaptopropionate) (PETMP); trimethylolpropane tris(3-mercaptopropionate) (TMPMP); triethanolamine tris(3-mercaptopropionate) (TEAMP); tris(2-hydroxyethyl)isocyanurate tris(3-mercaptopropionate) (THEICMP); bis(3-mercaptopropyl) sulfide (BMPS); 1,2-ethanedithiol (EDT); 1,3-propanedithiol; 1,4-butanedithiol; 1,6-hexanedithiol; 1,8-octanedithiol and combinations thereof.

[0279] In some embodiments, the stimulus-responsive polymer is a linear or branched crosslinked polymer network, the crosslinked polymer network containing 10 or more ester-thiol ester bonds that are hydrolyzed in the presence of an added base or thiol-containing compound, or an amino-containing compound, the hydrolysis resulting in the dissolution of the adhesive and the peeling of the layer from the penile skin.

[0280] In another embodiment, the stimulus-responsive polymer may be a linear or branched polymer comprising reaction products obtained by free radical addition polymerization of monofunctional, difunctional, trifunctional, tetrafunctional, pentafunctional, and hexafunctional thiol-ene components, which include triallyl isocyanurate pentaerythritol tetrakis (3-mercaptopropionate) or any of the thiol-ene monomer components 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, such as oxidation of thioether bonds by common oxidizing agents such as hydrogen peroxide, and may form reversibly cleavable disulfide bonds.

[0281] In some embodiments, the stimulus-responsive polymer includes linear or crosslinked polymers containing liquid crystal polymers having a thermal transition in the 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 crystalline polymer compositions include thiol-ene and thiol-acrylate polymers prepared by base-catalyzed Michael addition or free radical polymerization processes, which include those prepared from thiol building blocks, such as 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decandithiol, 1,12-dodecandithiol, hexanediol diacrylate, octanediol diacrylate, decanediol diacrylate, and mesogen-containing diacrylate species, such as RM105-4-(6-acryloyloxyhexyloxy)-benzoic acid (4-cyanophenyl ester), RM23-4-methoxyphenyl 4-((6-(acryloyloxy)hexyl)oxy)benzoate, and CB3A-3-[(3'-cyanobiphenyl-3-yl)oxy]propyl acrylate. Examples of diacrylate mesogens, though not limited to them, include RM257-4-(3-acryloyloxypropyloxy)benzoate 2-methyl-1,4-phenylene ester and RM82-1,4-bis[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene.

[0282] In some embodiments, free radical polymerization can be used to crosslink the acrylate-functionalized liquid crystal network. Click chemistry reactions, such as Michael addition reactions, may be used to reduce the Tg and incorporate soft, flexible segments between mesogenic monomers to enable elastomeric behavior under ambient conditions. In some embodiments, dithiols can be used as flexible spacers and include, but are not limited to, ethanedithiol, propanedithiol, or any other dithiol having a full carbon skeleton, 2,2'-(ethylenedioxy)diethanethiol, or any other dithiol having a polyethylene glycol skeleton, 1,4-benzenedithiol, 4,4'-biphenyldithiol, ethylenebis(thioglycolate), glycol dimercaptopropionate.

[0283] In some embodiments, amine-functionalized monomers may be used in a similar manner in addition to thiols. For example, n-butylamine can be used as a flexible chain extender or spacer for mesogenic monomers. Acrylate-functionalized mesogenic oligomers can be created by combining a diacrylate mesogen with a dithiol monomer or a diacrylate mesogen with a difunctional amine in a non-stoichiometric ratio using a Michael addition catalyst such as triethylamine or dipropylamine. In any case, an excess of acrylate functional groups is optionally preferred. These oligomers can then be photocrosslinked to form an LCE network.

[0284] In some embodiments, LCE can be synthesized in a one-pot manner by utilizing thiol or amine-functionalized crosslinking agents having a functional value of 2 or more. This one-pot method can be used in both free radical polymerization and Michael addition polymerization. Examples include, but are not limited to, pentaerythritol tetramercaptoacetate (PETMA), trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), and di-pentaerythritol tetra(3-mercaptopropionate).

[0285] In some embodiments, the stimulus-responsive polymer includes silicone polymers, such as linear or crosslinked polymers including high molecular weight linear siloxane polymers and high condensation silicate tackifiers. The tackifier or tackifier includes low molecular weight compounds with high glass transition temperatures used when formulating adhesives to increase tack (adhesion of the adhesive surface). Examples of 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-phenol resins (TPR, often used with ethylene vinyl acetate adhesives)), and novolacs. Suitable silicone rubber pressure-sensitive adhesives for use include special tackifiers based on "MQ" silicate resins consisting of monofunctional trimethylsilane ("M") reacted with tetrafunctional silicon tetrachloride ("Q").

[0286] In some embodiments, the stimulus-responsive polymer exhibits one or more glass transitions (Tg), crystallization temperature (Tc), melting temperature (Tm), or other thermal transitions in the range of -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 above, as measured by differential scanning calorimetry (DSC) Tg, Tc, Tm peak inflection points or dynamic mechanical analysis loss modulus or tan delta peak at 1 Hz.

[0287] In some embodiments, the stimulus-responsive polymer may be a linear, brushed, star-shaped, dendritic, or branched polymer having a weight-average molecular weight (Mw) of approximately 1 kDa, about 5 kDa, about 10 kDa, about 15 kDa, about 20 kDa, about 30 kDa, about 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 more.

[0288] In some embodiments, the stimulus-responsive polymer is either a crosslinked polymer providing a semi-interpenetrating network or a fully interpenetrating network.

[0289] In some embodiments, the stimulus-responsive polymer is petroleum-based.

[0290] In some embodiments, the stimulus-responsive polymer is entirely or partially bio-based.

[0291] In some embodiments, the stimulus-responsive polymer is a compostable, biodegradable, or biodegradable polymer prepared, for example, from plasticized polycaprolactone or plasticized poly(lactic acid). In some embodiments, plasticization is performed to reduce glass transition or increase tack.

[0292] In some embodiments, the stimulus-responsive polymer is suitable for food-grade applications such as stickers used on agricultural products or fruits.

[0293] The amount of the stimulus-responsive polymer present in the adhesive can vary. In some embodiments, the stimulus-responsive polymer comprises at least 70% by weight of the adhesive, such as at least about 80% by weight, at least 90% by weight, or at least 95% by weight.

[0294] In some embodiments, the stimulus-responsive polymer comprises at least 90% by weight of the adhesive, such as at least 91% by weight, at least 92% by weight, at least 93% by weight, at least 94% by weight, at least 95% by weight, at least 96% by weight, at least 97% by weight, at least 98% by weight, or at least 99% by weight.

[0295] In some embodiments, the linear and crosslinked polymers comprise (i) a main chain; (ii) at least one side chain; (iii) crosslinking; and (iv) additives. The main chain (i), side chain (ii), and / or crosslinking agent (iii) can include one or more monomers.

[0296] In some embodiments, the monomers comprising (i), (ii), and (iii) can be the same monomer or different monomers.

[0297] 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-poor monomers, lactam monomers, lactone monomers, alcohol monomers, carboxylic acid monomers, isocyanate monomers, Diels-Alder monomers, ring-opening metathesis monomers, and the like.

[0298] In some embodiments, the stimulus-responsive polymer does not include an acrylic adhesive containing an unreacted polyol plasticizer.

[0299] In some embodiments, the stimulus-responsive polymer does not contain a hydrophobic polyoxyalkylene adhesive derived from poly(ethylene glycol) prepared in the presence of a plasticizer.

[0300] In some embodiments, the stimulus-responsive polymer does not include an acrylic pressure-sensitive adhesive and (i) an elastomer having a tackifying resin or (b) a thermoplastic elastomer. In some embodiments, the adhesive does not include an acrylic pressure-sensitive adhesive and (i) an elastomer having a tackifying resin or (b) a thermoplastic elastomer.

[0301] The adhesives described herein may be used as the adhesive layer in a contraceptive device disclosed herein, e.g., a non-rigid partial condom, e.g., a rigid non-roll partial condom comprising a first adhesive layer (e.g., a stimuli-responsive polymer, e.g., a stimuli-responsive polymer described herein) and a second layer comprising a barrier and a reservoir, such that the condom does not come into contact with the shaft or coronal sulcus of the penis; the adhesive layer (a) has the same extent as the barrier layer; (b) is thicker than the barrier layer; and / or (c) is the sole means of fastening. The adhesive may be a stimuli-responsive polymer comprising, for example, one or more methacrylate monomers and a trifunctional crosslinking agent (e.g., TMPTA) that provide a low-density heterogeneous crosslinked polymer. The weight ratio of the polymer to the trifunctional crosslinking agent may be, for example, about 99.4:06. The non-rigid partial condom may exhibit one or more of the properties disclosed herein, e.g., painless removal, low peeling strength at low peeling rates, high peeling strength at high peeling rates, loss modulus, etc.

[0302] 4.2.2.2.1 Monomer In some embodiments, the stimulus-responsive polymer, and optionally one or more other polymers present in the adhesive, are formed from (i.e., include) monomers selected from acrylate monomers, methacrylate monomers, vinyl ether monomers, allyl monomers, thiol monomers, epoxy monomers, amine monomers, electron-rich monomers, electron-poor monomers, lactam monomers, lactone monomers, alcohol monomers, carboxylic acid monomers, isocyanate monomers, Diels-Alder monomers, ring-opening metathesis monomers, or combinations thereof.

[0303] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises an acrylate monomer. In some embodiments, the acrylate monomer is a C6-C30 alkyl acrylate monomer, such as a C8-C30 alkyl acrylate monomer, a C8-C20 alkyl acrylate monomer, a C8-C16 alkyl acrylate monomer, a C8-C12 alkyl acrylate monomer, a C12-C30 alkyl acrylate monomer, a C12-C20 alkyl acrylate monomer, or a C12-C16 alkyl acrylate monomer.

[0304] Exemplary acrylate monomers include, but are not limited to, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate, nonadecyl acrylate, eicosyl acrylate, heneicosyl acrylate, docosyl acrylate, tricosyl acrylate, tetracosyl acrylate, penta Cosyl acrylate, hexacosyl acrylate, heptacosyl acrylate, octacosyl acrylate, nonacosyl acrylate, triacontyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, methoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, ethoxylated hydroxyethyl acrylate, glycidyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate 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, etoxy Silylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, stearyl acrylate, lauryl acrylate, isodecyl acrylate, acrylic acid, ethylene glycol diacrylate (EGDA), triethylene glycol diacrylate (TEGDA), propylene glycol diacrylate (PGDA), butanediol diacrylate (BDDA), neopentyl glycol diacrylate (NPGDA), pentaerythritol tetraacrylate (PETA), 1,4-Butanediol diacrylate (BDA), di(trimethylolpropane)tetraacrylate (DTMPTA), bisphenol A ethoxylate diacrylate (BPAEDA), ethoxylated bisphenol A diacrylate (EBPA), decanediol diacrylate, polyethylene glycol diacrylate (PEGDA), trimethylolpropane triacrylate (TMPTA), diethylene glycol diacrylate (DEGDA), 1,6-Hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), trip Examples include propyl glycol diacrylate (TPGDA), pentaerythritol triacrylate (PETA), dipentaerythritol pentaacrylate (DPEPA), tris(2-hydroxyethyl) isocyanurate triacrylate (THEIC-TA), triethylene glycol dimethacrylate (TEGDMA), triallyl isocyanurate (TAIC), triethylene glycol diacrylate (TEGDA), ethoxylated trimethylolpropane triacrylate (ETMPTA), triallyl cyanurate (TAC), and combinations thereof.

[0305] In certain embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, includes acrylate monomers selected from octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate, nonadecyl acrylate, eicosyl acrylate, heneicosyl acrylate, docosyl acrylate, tricosyl acrylate, tetracosyl acrylate, pentacosyl acrylate, hexacosyl acrylate, heptacosyl acrylate, octacosyl acrylate, nonacosyl acrylate, triacontyl acrylate, and combinations thereof.

[0306] In some embodiments, the acrylate monomer is TMPTA.

[0307] In some embodiments, the stimulus-responsive polymer contains at least 10% by weight of an acrylate monomer, for example, at least 50% by weight, at least 75% by weight, or at least 90% by weight. In some embodiments, the stimulus-responsive polymer contains at least 95% by weight of an acrylate monomer, for example, at least 96% by weight, at least 97% by weight, at least 98% by weight, or at least 99% by weight.

[0308] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises a methacrylate monomer. In some embodiments, the methacrylate monomer is a C6-C30 alkyl methacrylate monomer, such as a C8-C30 alkyl methacrylate monomer, a C8-C20 alkyl methacrylate monomer, a C8-C16 alkyl methacrylate monomer, a C8-C12 alkyl methacrylate monomer, a C12-C30 alkyl methacrylate monomer, a C12-C20 alkyl methacrylate monomer, or a C12-C16 alkyl methacrylate monomer.

[0309] Examples of analogous methacrylate monomers include, but are not limited to, hexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, eicosyl methacrylate, heneicosyl methacrylate, and docosyl methacrylate. Methacrylate, tricosyl methacrylate, tetracosyl methacrylate, pentacosyl methacrylate, hexacosyl methacrylate, heptacosyl methacrylate, octacosyl methacrylate, nonacosyl methacrylate, triacontyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, stearyl methacrylate, lauryl methacrylate, isodecyl methacrylate, tetrahydrofluor Examples include furyl 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.

[0310] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, includes methacrylate monomers selected from hexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, eicosyl methacrylate, heneicosyl methacrylate, docosyl methacrylate, tricosyl methacrylate, tetracosyl methacrylate, pentacosyl methacrylate, hexacosyl methacrylate, heptacosyl methacrylate, octacosyl methacrylate, nonacosyl methacrylate, triacontyl methacrylate, and combinations thereof. In some embodiments, the stimulus-responsive polymer comprises an undecyl methacrylate monomer, i.e., a lauryl methacrylate monomer. In some embodiments, the stimulus-responsive polymer comprises an octadecyl methacrylate monomer, i.e., a stearyl methacrylate monomer.

[0311] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, contains at least 10% by weight, for example, at least 50% by weight, at least 75% by weight, or at least 90% by weight, of a methacrylate monomer. In some embodiments, the stimulus-responsive polymer contains at least 95% by weight, for example, at least 96% by weight, at least 97% by weight, at least 98% by weight, or at least 99% by weight, of a methacrylate monomer.

[0312] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises vinyl ether monomers. Exemplary vinyl ether monomers include, but are not limited to, divinyl ether of ethylene glycol, divinyl ether of diethylene glycol, divinyl ether of triethylene glycol, divinyl ether of polyethylene glycol (DVE-PEG), divinyl ether of polypropylene glycol (DVE-PPG), divinyl ether of poly(ethylene glycol) methyl ether (DVE-PEGME), divinyl ether of poly(ethylene glycol) butyl ether (DVE), divinyl ether of poly(ethylene glycol) phenyl ether (DVE-PEGPhE), divinyl ether of glycerol (DVE-Gly), divinyl ether of 1,4-cyclohexanedimethanol (DVE-CHDM), divinyl ether of neopentyl glycol (DVE-NPG), and combinations thereof.

[0313] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises allyl monomers. Exemplary allyl monomers include diallyl phthalate (DAP), diallyl maleate (DAM), diallyl succinate (DAS), diallyl fumarate (DAF), diallyl adipate (DAA), diallyl sebacate (DAS), diallyl terephthalate (DAT), diallyl isophthalate (DAI), diallyl itaconate (DAI), diallyl carbonate (DAC), diallyl diglycolate (DADG), diallyl tris(2-hydroxyethyl) isocyanurate (DATHEIC), and triallyl cyanurate. Examples include, but are not limited to, tris(2-hydroxyethyl) isocyanurate (TAC), triallyl isocyanurate (TAIC), triallyl trimelitate (TATM), triallyl citrate (TAC), triallyl phosphate (TAP), triallylamine (TAA), triallyl cyanide (TACN), triallylbenzene-1,2,4-tricarboxylate (TABTC), triallyl trimesate (TATM), tris(2-hydroxyethyl) isocyanurate trialyl ether (THEIC-TAE), and combinations thereof.

[0314] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises a thiol monomer. Exemplary thiol monomers include, but are not limited to, 3-mercaptopropionic acid; thioglycolic acid; 3-mercapto-1-propanol; 2-mercaptoethanol; 2-(2-mercaptoethoxy)ethanol; 2-(2-mercaptopropionylamino)ethanol; 2-(2-mercaptosuccinyl)ethyl acrylate; 3-(2-mercaptopropionylamino)propionic acid; 3-(mercaptopropyl)trimethoxysilane; 2,2'-(ethylenebis(thio))diethanol; 3-mercaptopropyltrimethoxysilane; 3-mercaptopropylmethyldimethoxysilane; 3-(2,2-dithiobis(ethylthio)propionylamino)propionic acid; 3,6,9-trioxadecanethiol; 3-mercapto-1,2-propanediol; 2,2'-dithiodiethanol; N-acetyl- Examples include L-cysteine; L-cysteine; 2-(2-mercaptoethyl)pyridine; 4-(2-mercaptoethyl)morpholine; 3-mercapto-1,2,4-triazole; thiophenol; pentaerythritol tetrakis(3-mercaptopropionate) (PETMP); trimethylolpropane tris(3-mercaptopropionate) (TMPMP); triethanolamine tris(3-mercaptopropionate) (TEAMP); tris(2-hydroxyethyl)isocyanurate tris(3-mercaptopropionate) (THEICMP); bis(3-mercaptopropyl) sulfide (BMPS); 1,2-ethanedithiol (EDT); 1,3-propanedithiol; 1,4-butanedithiol; 1,6-hexanedithiol; 1,8-octanedithiol and combinations thereof.

[0315] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises epoxy monomers. Exemplary epoxy monomers include, but are not limited to, bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE), novolac diglycidyl ether (NGDE), phenol novolac diglycidyl ether (PNGDE), alicyclic epoxy resins, glycidyl ethers of aliphatic alcohols, glycidyl ethers of aromatic alcohols, triglycidyl isocyanurate (TGIC), diglycidyl ether of 1,4-butanediol (BDDGE), diglycidyl ether of neopentyl glycol (NPGDGE), diglycidyl ether of propylene glycol (PGDGE), epoxidized soybean oil (ESO), epoxidized linseed oil (ELO), dicyclopentadiene-based epoxy resins, tetrafunctional epoxy resins, epoxyphenol novolac resins, and combinations thereof.

[0316] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises amine monomers. Exemplary amine monomers include, but are not limited to, ethylenediamine; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; polyethyleneimine; diaminopropane; diaminobutane; diaminopentane; diethylenetriaminepentaacetic acid (DTPA); tris(2-aminoethyl)amine; N-(2-aminoethyl)piperazine; N-(3-aminopropyl)morpholine; N,N-dimethylaminopropylamine; N,N-dimethylethylenediamine; 1,3-diaminopropane; isophoronediamine; Jeffamine D-230; Jeffamine T-403; Jeffamine M-207; Jeffamine EDR-148; and combinations thereof.

[0317] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises electron-rich monomers. Exemplary electron-rich monomers include, but are not limited to, vinyl ethers (e.g., vinyl methyl ether, vinyl ethyl ether), vinyl acetate, allyl alcohol, allylamine, N-methylolacrylamide, N-methylolmethacrylamide, N-methylolallylamine, N-methylolvinylacetamide, acrolein diethyl acetal, acrolein diethyl ketal, diacetone acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycidyl methacrylate, glycidyl acrylate, tetrahydrofurfuryl methacrylate, and N-vinylpyrrolidone, n-vinylformamide, n-vinylpyridine, styrene, styrene derivatives, and combinations thereof.

[0318] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises an electron-poor monomer. Exemplary electron-poor monomers include, but are not limited to, acrylonitrile, methacrylonitrile, methyl methacrylate, acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide, methacrylamide, N-vinylcarbazole, vinylidene chloride, vinyl chloride, vinyl sulfonic acid, vinyl acetate, styrene, α-methylstyrene, maleimide, N-phenylmaleimide, and N-butylmaleimide, maleic anhydride, and combinations thereof.

[0319] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises lactam monomers. Exemplary lactam monomers include, but are not limited to, caprolactam, valerolactam, enantractam, caprylactam, laurinlactam, prolactam, butyrolactam, methionyllactam, methoxyethyllactam, methoxyethylmethionyllactam, dimethylaminoethyllactam, dimethylaminoethylmethionyllactam, dimethylaminoethylacryloyllactam, dimethylaminoethylmethacryloyllactam, N-vinylpyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, and combinations thereof.

[0320] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises lactone monomers. Exemplary lactone monomers include, but are not limited to, β-propiolactone, γ-butyrolactone, 8-valerolactone, ε-caprolactone, ω-pentadecalactone, β-butyrolactone, 8-decalactone, ε-decalactone, γ-decalactone, 8-dodecalactone, γ-dodecalactone, α-methylene-γ-butyrolactone, β-methyl-γ-butyrolactone, β-methyl-γ-valerolactone, γ-hexalactone, and combinations thereof.

[0321] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises an alcohol monomer. Exemplary alcohol monomers include, but are not limited to, ethylene glycol; propylene glycol; 1,3-butanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 1,10-decanediol; neopentyl glycol; diethylene glycol; triethylene glycol; tetraethylene glycol; polyethylene glycol (PEG); polypropylene glycol (PPG); polycaprolactone diol; polymethylolpropane; hydroxypivalyl hydroxymethyl butyrate (HPHMB); 1,4-cyclohexanedimethanol; and combinations thereof.

[0322] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises a carboxylic acid monomer. Exemplary carboxylic acid monomers include, but are not limited to, adipic acid, succinic acid, glutaric acid, sebacic acid, malonic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, itaconic acid, citric acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, dodecanedioic acid, and combinations thereof.

[0323] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises an isocyanate monomer. Examples of 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.

[0324] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises a Diels-Alder monomer. 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.

[0325] In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, comprises a ring-opening metathesis monomer. Exemplary ring-opening metathesis monomers include, but are not limited to, norbornene, dicyclopentadiene (DCPD), cyclooctene, tetracyclododecene (TCD), cyclopentene, cycloheptene, cyclohexene, bicyclo[2.2.1]hepta-2-ene, bicyclo[2.2.2]octa-5-ene, tricyclo[5.2.1.0(2,6)]deca-8-ene (TCD-diene), and combinations thereof.

[0326] 4.2.2.2.2 Side chains In some embodiments, the stimulus-responsive polymer includes two or more side chains.

[0327] In some embodiments, the stimulus-responsive polymer includes C6-C30 side chains or C6-C30 dangling chain ends. In some embodiments, the C6-C30 side chains or C6-C30 dangling chain ends are C6-C30 alkyl side chains, preferably C12-C18 alkyl side chains.

[0328] In some embodiments, the stimulus-responsive polymer contains at least 80% by weight of side chains, for example, at least 85% by weight, at least 90% by weight, or at least 95% by weight. In some embodiments, the side chains are the same. In some embodiments, the side chains are different.

[0329] In some embodiments, the side chains include bonds made from monomers selected from acrylates, methacrylates, thiol-acrylate Michael additions, acrylateamine Michael additions, epoxythiols, epoxyamines, polyethyleneimines (PEI), thiol-enes, alternating copolymers made from C=C electron-poor + C=C electron-rich monomers, urethanes, ureas, acrylamides, methacrylamides, polyesters, polycarbonates, polyamides, peptoids, peptides, Diels-alders, lactides and lactams, ring-opening metathesis polymerization, or olefin metathesis reactions.

[0330] In some embodiments, the side-chain chemistry includes C1-C100 side-chain linking achieved by the synthetic routes disclosed herein.

[0331] In some embodiments, stimulus-responsive polymers having C6-C18 side chains or dangling chain ends are prepared from acrylates, methacrylates, alcohols, carboxylic acids, electron-rich alkenes, electron-poor alkenes, epoxys, amines, ROMPs, Diels-Alders, lactones, lactams, peptides, peptoids, acrylamides, methacrylamides, thiols, vinyls, and allyl monomers.

[0332] In some embodiments, the stimulus-responsive polymer comprises a linear or crosslinked polymer having side chains that optionally undergo crystallization and / or melting in the range of 0°C to 50°C, more specifically 5°C to 45°C, more specifically 10°C to 40°C, and more specifically 15°C to 35°C, in the range of body and room temperature. For clarity, side chain crystallization is optional.

[0333] In some embodiments, the range of linear or crosslinked polymers is about 40 to about 100%, more specifically 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 included therein.

[0334] In some embodiments, the range of optionally crystallizable secondary side-chain polymers is about 0 to about 50%, more specifically 1 to about 49%, more specifically about 2 to about 48%, more specifically about 3 to about 47%, more specifically about 5 to about 45%, or any additional range or value included therein.

[0335] 4.2.2.2.3 Polyfunctional Crosslinking Agents In some embodiments, the stimulus-responsive polymer, or optionally one or more other polymers present in the adhesive, is a crosslinked polymer. The crosslinked polymer is prepared using one or more polyfunctional crosslinking agents. The crosslinking agents may exhibit functionality statistically exceeding n=1 reactive site, e.g., a statistical average of n=2, 3, 4, 5, 6, 7, 8, 9, 10 or more reactive sites, and may promote branched, hyperbranched, interpenetrating networks, semi-interpenetrating networks, and generally homogeneous or partially homogeneous and partially heterogeneous or generally heterogeneous networks with respect to the phase blend or concentration of crosslinking density.

[0336] In some embodiments, the polyfunctional crosslinking agent is selected from a bifunctional crosslinking agent, a trifunctional crosslinking agent, or a tetrafunctional crosslinking agent. In some embodiments, the polyfunctional crosslinking agent is a trifunctional crosslinking agent.

[0337] In some embodiments, the polyfunctional crosslinking agent is a trifunctional crosslinking agent. In some embodiments, the trifunctional crosslinking agent is a trifunctional acrylate crosslinking agent.

[0338] In some embodiments, the polyfunctional 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 hexa-epoxides; polythiols; polyalkenes; tris(2-acryloxyethyl) isocyanurate, ε-caprolactone-modified tris(2-acryloxyethyl) isocyanurate, ethoxylated glycerin triacrylate, pentaerythritol triacrylate, and combinations thereof.

[0339] In some embodiments, the polyfunctional crosslinking agent is a penta- and hexa-functional acrylate as described above, including poly(ethylene glycol) diacrylate, trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and ethoxylated dipentaerythritol hexaacrylate, all having internal repeating units in the range of 1 to 1000 or more.

[0340] In some embodiments, the polyfunctional 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 polyfunctional crosslinking agent is trimethylolpropane triacrylate (TMPTA).

[0341] In some embodiments, the stimulus-responsive polymer is a crosslinked polymer having a homogeneous crosslinked network density. In some embodiments, the stimulus-responsive polymer is a crosslinked polymer having a heterogeneous crosslinked network. For example, desirable adhesion failure or delamination from the skin, including the removal of residual adhesive after peeling of the adhesive, can be achieved by concentrating the defect sites within the network through a heterogeneous crosslinking distribution, or by a "swollen heterogeneous network" formed by polymerization at different reaction ratios of crosslinking agents and monomers.

[0342] In some embodiments, the stimulus-responsive polymer is characterized by low-density crosslinking.

[0343] In some embodiments, the crosslinking agent is uniformly incorporated into the stimulus-responsive polymer network.

[0344] In some embodiments, the crosslinking agent aggregates within a stimulus-responsive polymer network. This embodiment generates high-stress concentration network regions and / or drives rheological behavior, enabling energy dissipation (higher tan delta and higher loss modulus compared to a more uniform network) and, if desired, promoting poor adhesion.

[0345] 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 a crosslinking agent in an amount of 0 to 30% by weight, for example, 0.001 to 29% by weight, more specifically 0.005 to 28% by weight, more specifically 0.0075 to 28% by weight, more specifically 0.01 to 27% by weight, more specifically 0.02 to 26% by weight, more specifically 0.05 to 26% by weight, more specifically 0.1 to 25% by weight, more specifically 0.15 to 24% by weight.

[0346] In some embodiments, the stimulus-responsive polymer contains, in each case, an amount of crosslinking agent selected from about 0.1% by weight, about 0.2% by weight, about 0.3% by weight, about 0.4% by weight, about 0.5% by weight, about 0.6% by weight, about 0.7% by weight, about 7.5% by weight, about 0.8% by weight, about 0.9% by weight, about 9.5% by weight, or about 1.0% by weight or more, relative to the weight of the polymer.

[0347] In certain embodiments, the stimulus-responsive polymer contains, in each case, an amount of crosslinking agent relative to the weight of the polymer, in the amounts of about 0.1% to about 1% by weight, about 0.2% to about 0.8% by weight, about 0.3% to about 0.7% by weight, or about 0.4% to about 0.6% by weight.

[0348] In some embodiments, the stimulus-responsive polymer is present in amounts of 0.1% to 2.5% by weight, for example, 0.1% to 2% by weight, 0.1% to 1.5% by weight, 0.1% to 1% by weight, 0.1% to 0.9% by weight, 0.1% to 0.8% by weight, 0.1% to 0.7% by weight, 0.1% to 0.6% by weight, 0.1% to 0.5% by weight, 0.1% to 0.4% by weight, and 0.1% to 0.3% by weight. The product contains a polyfunctional crosslinking agent in amounts of 0.1% to 0.2% by weight, 0.2% to 1.5% by weight, 0.2% to 1% by weight, 0.3% to 1.5% by weight, 0.3% to 1% by weight, 0.4% to 1.5% by weight, 0.4% to 1% by weight, 0.5% to 1.5% by weight, 0.5% to 1% by weight, 0.6% to 1.5% by weight, 0.6% to 1% by weight, 0.7% to 1.5% by weight, 0.7% to 1% by weight, 0.8% to 1.5% by weight, 0.8% to 1% by weight, 0.9% to 1.5% by weight, or 0.9% to 1% by weight.

[0349] In some embodiments, the stimulus-responsive polymer contains a polyfunctional crosslinking agent in an amount of 0.4% to 0.8% by weight, for example, 0.4% to 0.7% by weight, 0.4% to 0.6% by weight, 0.4% to 0.5% by weight, 0.5% to 0.8% by weight, 0.5% to 0.7% by weight, 0.5% to 0.6% by weight, 0.6% to 0.8% by weight, 0.6% to 0.7% by weight, or 0.7% to 0.8% by weight. In some embodiments, the polyfunctional crosslinking agent is trimethylolpropane triacrylate (TMPTA).

[0350] In some embodiments, the weight ratio of one or more monomers to one or more polyfunctional 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, 77:2 3, 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.

[0351] In some embodiments, the weight ratio of one or more monomers to one or more polyfunctional 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.

[0352] 4.2.2.2.4 Embodiments In some embodiments, the stimulus-responsive polymer comprises one or more methacrylate monomers and one or more acrylate monomer crosslinkers. In some embodiments, the weight ratio of one or more methacrylate monomers to one or more acrylate monomer crosslinkers can vary. In some embodiments, the weight ratios are 99:1, 98:2, 97:3, 96:4, 95.3, 94:6, 93.7:92:8, 91:9, 90:10, 89:11, 88:12 m 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.

[0353] In some embodiments, the stimulus-responsive polymer comprises one or more C6-C30 alkyl methacrylate monomers and one or more C6-C30 alkyl acrylate monomers. The weight ratio of one or more C6-C30 alkyl methacrylate monomers to one or more C6-C30 alkyl acrylate monomers can vary. In some embodiments, the weight ratios are 99:1, 98:2, 97:3, 96:4, 95.3, 94:6, 93.7:92:8, 91:9, 90:10, 89:11, 88:12 m 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.

[0354] In some embodiments, the stimulus-responsive polymer comprises both C6-C30 alkyl acrylate monomers and C6-C30 alkyl methacrylate monomers. The molar ratios of the components in this embodiment may vary in accordance with stoichiometric calculations from mass equivalents.

[0355] In some embodiments, the stimulus-responsive polymer comprises poly(lauryl methacrylate), i.e., poly(dodecyl methacrylate), crosslinked with one or more polyfunctional crosslinking agents. In some embodiments, the weight ratio of lauryl methacrylate to one or more polyfunctional 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, or 99.7:0.3 to 99.9:0.1, 99.8:0.2 to 99.9:0.1.

[0356] In some embodiments, the stimulus-responsive polymer comprises poly(lauryl methacrylate) crosslinked with one or more trifunctional crosslinking agents. In some embodiments, the weight ratio of lauryl methacrylate to one or more trifunctional 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, or 99.7:0.3 to 99.9:0.1, or 99.8:0.2 to 99.9:0.1.

[0357] In some embodiments, the stimulus-responsive polymer comprises poly(lauryl methacrylate) crosslinked with an acrylate crosslinking agent. In some embodiments, the weight ratio of lauryl methacrylate to one or more acrylate 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, or 99.7:0.3 to 99.9:0.1, or 99.8:0.2 to 99.9:0.1.

[0358] In some embodiments, the stimulus-responsive polymer comprises poly(lauryl methacrylate) crosslinked with a trifunctional acrylate crosslinking agent. In some embodiments, the weight ratio of lauryl methacrylate to one or more trifunctional acrylate 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, or 99.7:0.3 to 99.9:0.1, or 99.8:0.2 to 99.9:0.1.

[0359] In some embodiments, the stimulus-responsive polymer includes poly(ethylene glycol) diacrylate, trimethylolpropane triacrylate; ethoxylated trimethylolpropane triacrylate; pentaerythritol tetraacrylate; ethoxylated pentaerythritol tetraacrylate; dipentaerythritol hexaacrylate; ethoxylated dipentaerythritol hexaacrylate; di-, tri-, tetra-, penta- or hexa-epoxides; polythiols; polyalkenes; and poly(lauryl methacrylate) crosslinked with one or more polyfunctional crosslinking agents selected from tris(2-acryloxyethyl) isocyanurate, ε-caprolactone-modified tris(2-acryloxyethyl) isocyanurate, ethoxylated glycerin triacrylate, ethoxylated glycerin triacrylate, and pentaerythritol triacrylate. In some embodiments, the weight ratio of lauryl methacrylate to one or more polyfunctional 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, or 99.7:0.3 to 99.9:0.1, or 99.8:0.2 to 99.9:0.1.

[0360] In some embodiments, the stimulus-responsive polymer includes poly(lauryl methacrylate) crosslinked with one or more polyfunctional crosslinking agents selected from trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, hexanediol diacrylate, and combinations thereof. In some embodiments, the weight ratio of lauryl methacrylate to one or more polyfunctional 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, or 99.7:0.3 to 99.9:0.1, or 99.8:0.2 to 99.9:0.1.

[0361] In some embodiments, the stimulus-responsive polymer includes poly(lauryl methacrylate) crosslinked with trimethylolpropane triacrylate. In some embodiments, the weight ratio of lauryl methacrylate to trimethylolpropane triacrylate 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, or 99.7:0.3 to 99.9:0.1, or 99.8:0.2 to 99.9:0.1.

[0362] In some embodiments, the adhesive comprises poly(lauryl methacrylate) and TMPTA, where TMPTA crosslinks the lauryl methacrylate. The weight ratios of the components according to this embodiment can vary. In some embodiments, the weight ratio is 99:1, or more specifically, about 99.4:0.6, about 99.6:0.4, or about 99.8:0.2.

[0363] Any of the above-mentioned irritation-responsive polymers may optionally form an adhesive layer containing other additives or components of the non-rigid, unwound partial condom described herein, which comprises a first adhesive layer (e.g., an irritation-responsive polymer, e.g., an irritation-responsive polymer as described herein) and a second layer comprising a barrier and a reservoir, and which does not come into contact with the shaft or coronal sulcus of the penis; the adhesive layer (a) has the same extent as the barrier layer; (b) is thicker than the barrier layer; and / or (c) is the sole means of fastening. Optionally, the second layer is continuous, i.e., the barrier and reservoir are formed together, i.e., integrally. Optionally, the reservoir is self-forming. Optionally, the partial condom consists of only three layers, including a backing layer. Optionally, the condom includes one or more additional means of fastening the condom to the penis. The condom may exhibit one or more of the properties disclosed herein, such as painless removal, low peeling strength at a low peeling rate, high peeling strength at a high peeling rate, loss modulus of elasticity, etc.

[0364] 4.2.3 Additives In some embodiments, the adhesive further comprises one or more additives. Exemplary additives include tackifiers, plasticizers, pigments, fillers, fluorescent agents, flowing agents, wetting agents, surfactants, defoamers, rheology modifiers, colorants, penetration enhancers, stabilizers, antioxidants, and combinations thereof. In some embodiments, adhesion may be enhanced or reduced by the addition of additives.

[0365] Examples of plasticizers include, but are not limited to, glyceryl triacetate (triacetin), glyceryl monooleate (GMO), glyceryl monostearate (GMS), glyceryl tristearate (tristearin), glyceryl tripylate (tributylin), glyceryl trippropionate (triplonine), glyceryl trioleate (triolein), glyceryl dilaurate (GDL), glyceryl dimyristart (GDM), glyceryl distearate (GDS), diethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), and dibutyl phthalate (DB). Examples include P), diisodecylphthalate (DIDP), butylbenzylphthalate (BBP), dimethylphthalate (DMP), di-n-octylphthalate (DnOP), diisobutylphthalate (DIBP), diethylphthalate (DEP), dicyclophthalate (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 both sides of esters.

[0366] In some embodiments, plasticizers may be added to polymers with lower glass transitions to adjust the adhesive regime. Suitable plasticizers for use include glycerol, 1,-butanol, 1-octanol, stearic acid, n-butyl stearate, poly(ethylene glycol), water, various organic solvents, 1-decanoate, and 1-octanoate, with Mw varying from 100 to 200 to 400 to 1000 to 2000 to 4000 to over 10000 daltons.

[0367] In some embodiments, the additive is stimulus-responsive. For example, an additive such as poly(ethylene glycol) Mw 400 Dalton or glycerol can be used in a blend ratio of 1% to 90% by weight with an adhesive layer component such as poly(n-dimethylacylamide) such that the additive plasticizes the adhesive layer at a temperature higher than the additive's crystallization temperature, but no longer plasticizes the adhesive layer at a temperature lower than the additive's crystallization temperature.

[0368] In some embodiments, the stimulus-responsive additive may exhibit crystallization, glass transition, or other thermal transition within 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.

[0369] Examples of tackifiers include, but are not limited to, rosin esters, hydrocarbon resins, terpene resins, styrene resins, polyterpene resins, coumarone-indene resins, phenolic resins, tall oil rosin, aliphatic resins, and aromatic resins.

[0370] Exemplary tackifying resins or tackifiers include low molecular weight compounds with high glass transition temperatures used when formulating adhesives to increase tack (adhesion of the adhesive surface). In some embodiments, 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-phenol resins (TPR, often used with ethylene vinyl acetate adhesives)), and novolacs. Silicone rubber pressure-sensitive adhesives suitable for use in this disclosure include special tackifiers based on "MQ" silicate resins consisting of monofunctional trimethylsilane ("M") reacted with tetrafunctional silicon tetrachloride ("Q").

[0371] In some embodiments, the tackifier or plasticizer is selected from glyceryl, phthalate, polyethylene glycol derivatives having a molecular weight in the range of 1 to 1000 or more repeating units, and C10-C40 linear or branched wax or modified wax components, such as n-butyl stearate or ethyl decanoate.

[0372] Exemplary fillers include, but are not limited to, calcium carbonate, talc, silica, glass fiber, carbon black, barium sulfate, kaolin, mica, wollastonite, alumina, titanium dioxide, cellulose, wood flour, fly ash, and graphite.

[0373] Examples of water- or solvent-chemically swellable particulate additives include, but are not limited to, poly(sodium acrylate) molecular weights in the range of 1 million to 5 million daltons, more specifically 1 million to 1 million daltons, and more specifically 10 million to 1 million daltons; particle sizes in the range of 1 micron to 1000 microns, more specifically 20 microns to 800 microns, and more specifically 20 to 300 microns; and concentrations in the range of 0.01 to 95% by weight, more specifically 0.1 to 75% by weight, more specifically 1 to 60% by weight, and more specifically 2 to 55% by weight.

[0374] In some embodiments, the particulate additive can reduce the diffusion of water or other solvents into the adhesive layer and may be a hydrophobic component, such as a stereoic acid, hydrophobic fumed silica, or polyethylene wax, with a molecular weight in the range of 1 million to 5 million daltons, more specifically 1 million to 1 million daltons, or more specifically 2 million to 1 million daltons, with a particle size in the range of 1 micron to 1,000 microns, more specifically 20 microns to 800 microns, or more specifically 20 to 300 microns, with a concentration in the range of 0.01 to 95% by weight, more specifically 0.1 to 75% by weight, more specifically 1 to 60% by weight, or more specifically 2 to 55% by weight.

[0375] In some embodiments, particulate additives can create physical sites for increasing or decreasing adhesion to the skin and may be inherently irritation-responsive. The component that creates physical sites for enhancing or decreasing adhesion to the skin may be a ceramic additive such as fumed silica, zinc oxide, or titanium dioxide, or a polymer having a molecular weight in the range of 1 to 5 million daltons, more specifically 1 to 1 million daltons, or more specifically 2 to 1 million daltons, with a particle size in the range of 1 to 1000 microns, more specifically 20 to 800 microns, or more specifically 20 to 300 microns, and a concentration in the range of 0.01 to 95% by weight, more specifically 0.1 to 75% by weight, more specifically 1 to 60% by weight, or more specifically 2 to 55% by weight.

[0376] The additives used herein may include nucleating agents that cause stimulus-responsive adhesives to undergo changes in adhesive behavior upon crystallization by cooling. The addition of nucleating agents such as nanoscale fumed silica and polyethylene wax can be used to adjust the crystallization temperature of adhesives exhibiting crystal transitions, such as poly(octadecyl methacrylate). Nucleation-inducing additives include those with particle sizes ranging from 1 nm to 1000 microns, more specifically from 10 nm to 500 microns, and more specifically from 10 nm to 250 microns. Nucleation-inducing additives may be blended with the adhesive by solution blending, high-shear mixing, or other blending techniques, or they may be generated in situ during adhesive preparation or pessary 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.

[0377] In some embodiments, the additive may function as a crack propagator that promotes poor adhesion during removal by mechanical peeling.

[0378] In some embodiments, the additive is present in the adhesive in amounts of 0 to 60% by weight, more specifically 0.1% to 50% by weight, 0.1% to 40% by weight, 0.1% to 30% by weight, 0.1% to 20% by weight, 0.1% to 10% by weight, 0.1% to 5% by weight, 0.1% to 2.5% by weight, and 0.1% to 1% by weight.

[0379] In some embodiments, one or more additives are present in the adhesive in an amount of about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, or about 15% by weight or more.

[0380] In some embodiments, one or more additives are present in an amount of about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, about 50% by weight, about 55% by weight, or about 60% by weight of the adhesive.

[0381] In some embodiments, one or more additives are present in amounts of about 0.1% by weight, about 0.2% by weight, about 0.3% by weight, about 0.4% by weight, about 0.5% by weight, about 0.6% by weight, about 0.7% by weight, about 0.8% by weight, or about 0.9% by weight or more of the adhesive.

[0382] In some embodiments, one or more additives are present in amounts of about 0.01% by weight, about 0.02% by weight, about 0.03% by weight, about 0.04% by weight, about 0.05% by weight, about 0.06% by weight, about 0.07% by weight, about 0.08% by weight, or about 0.09% by weight or more of the adhesive.

[0383] 4.2.4. Method for preparing stimulus-responsive polymers In some embodiments, the stimulus-responsive polymer is prepared by curing one or more monomers and one or more polyfunctional crosslinking agents in a first amount to form a prepolymer, and then post-curing the prepolymer to provide the stimulus-responsive polymer.

[0384] In some embodiments, the weight ratio of one or more monomers to one or more polyfunctional 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; 99.8:0.2 to 99.9:0.1.

[0385] In some embodiments, curing is photopolymerization utilizing a photoinitiator. Exemplary photoinitiators include, but are not limited to, 2,2-dimethoxy-2-phenylacetophenone (DMPA), eosin y, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), lithium phenyl-2,4,6-trimethylbenzoylphosphineate (LAP), and biocompatible photoinitiators.

[0386] In some embodiments, curing is carried out neatly, i.e., in the absence of a solvent.

[0387] In some embodiments, post-curing involves subjecting the prepolymer to a high temperature for curing, for example, at least 50°C, at least 100°C, at least 150°C, or at least 200°C.

[0388] In some embodiments, the method further includes pausing the curing before completion, adding a second amount of one or more polyfunctional crosslinking agents, and then resuming the curing.

[0389] In some embodiments, polymers having C6-C18 side chains or dangling chain ends are prepared from acrylates, methacrylates, alcohols, carboxylic acids, electron-rich alkenes, electron-poor alkenes, epoxys, amines, ROMPs, Diels-Alders, lactones, lactams, peptides, peptoids, acrylamides, methacrylamides, thiols, vinyls, and allyl monomers. In some embodiments, light crosslinking, such as net point concentrations obtained by a range including but not limited to 0.4 wt%, 0.6 wt%, 0.75 wt%, and 0.95 wt% trimethylolpropane triacrylate in poly(lauryl) or poly(stearyl methacrylate polymer (including, but not limited to, 99.6 wt%, 99.4 wt%, 99.25 wt%, and 99.05 wt%) lauryl or stearyl methacrylate), provides a shear rate-responsive polymer that is tacky to human skin and can then be removed from human skin with minimal pain, and any residual adhesive remaining on human skin can be removed with minimal pain by light rubbing.

[0390] In some embodiments, these long side-chain / low crosslink density polymers can be prepared by any reaction process described herein using any monomer, crosslinking agent or other component described herein. For example, linear or branched poly(ethyleneimine, PEI) can have its side chains and chain ends modified using lauryl or octadecyl acrylate under base-catalyzed conditions by Michael addition, or using lauryl or octadecyl isocyanate by isocyanate / amine reaction. In another embodiment, off- or on-stoichiometric thiolenes can be prepared using combinations of monofunctional, difunctional, trifunctional and tetrafunctional thiols and alkene monomers with monofunctional components such as lauryl mercaptopropionate or dodecyl vinyl ether, such that the monofunctional component accounts for 0.1, 0.2, 0.3, 0.4 or 0.5 mol% or more of the total thiolene component. In another representative embodiment, an alternating copolymer comprising maleimide or n-butylmaleimide and dodecyl vinyl ether can be prepared using radical alternating polymerization and lightly crosslinked with less than wt% dodecyl vinyl ether or polymethacrylate or acrylate to form a heterogeneous crosslinked network having a low crosslink density and high wt% C12 side chains (preferably 60, 70, 80, 90 or more wt% alkyl side chains C6 or higher, C12-C18). In another embodiment, octadecylamine polymerizes red with Michael addition comonomers such as ethylene glycol diacrylate or hexanediol diacrylate under base-catalyzed conditions. In one embodiment, the obtained poly(beta-aminoester) is prepared by a 1:25:1.0 C=C:NH2 (double NH2 reaction with acrylate) reaction, generating acrylate-terminated sealing groups. The acrylate-terminated poly(beta-aminoester) reaction product can be photocured using UV light. The crosslink density can be reduced by adding monofunctional acrylates or methacrylates such as stearyl or lauryl methacrylate or acrylate, or by adding thiol chain transfer or chelating agents such as PETMP, IOMP, EGBMP, 1,10-decandiothiol, or PETMP.In another embodiment, a similar Michael addition synthesis process can be used for the thiol / acrylate-Michael addition reaction product, with excess acrylate being preferred.

[0391] In another embodiment, the adhesive is a linear or branched crosslinked polymer network, the crosslinked polymer network containing 10 or more ester-thiol ester bonds that are hydrolyzed in the presence of an added base or thiol-containing compound, or an amino-containing compound, the hydrolysis resulting in the dissolution of the adhesive and the peeling of the layer from the penile skin.

[0392] In another embodiment, the adhesive layer may be a linear or branched polymer comprising reaction products obtained by free radical addition polymerization of monofunctional, difunctional, trifunctional, tetrafunctional, pentafunctional, and hexafunctional thiol-ene components, which include triallyl isocyanurate pentaerythritol tetrakis (3-mercaptopropionate) or any of the thiol-ene monomer components disclosed herein. In one embodiment, the thiol-ene adhesive may exhibit stimulus-responsive adhesive behavior when cooled below its glass transition temperature. In another embodiment, the thiol-ene adhesive layer may exhibit chemically responsive adhesive behavior, such as oxidation of thioether bonds by common oxidizing agents such as hydrogen peroxide, and may form reversibly cleavable disulfide bonds.

[0393] 4.3 Package In one embodiment, the present disclosure provides a package including a contraceptive device described herein.

[0394] In some embodiments, the package includes the condom described herein. In some embodiments, the package includes the pessary described herein.

[0395] In some embodiments, the package may be rigid, semi-rigid, flexible, or a combination thereof, and may or may not have additional uses other than storage as described herein, in which the contraceptive device is placed until use. In some embodiments, the package may be 0.005 mm or less, 0.005 mm or more, 0.01 mm or more, 0.02 mm or more, 0.03 mm or more, 0.04 mm or more, or 0.05 mm or more. The package may be approximately rectangular, circular, elliptical polygonal, or curved polygonal in shape.

[0396] In some embodiments, the package includes a flexible packaging body comprising foil, plastic, plastic-lined paper, foil-lined paper, or a combination thereof.

[0397] In some embodiments, the package is a blister pack design. In some embodiments, the blister pack design package includes semi-rigid plastic or paper or cardboard that is sufficiently covered with a thin metal, paper or plastic film that can be punctured by pressing the bottom of a rigid well. Semi-rigid is defined as the material and thickness that maintains its designed geometric shape, but can be deformed by applying forces of 1 to 5 N (Newtons), or 5 to 10 N, or 10 to 20 N, or 20 to 100 N, or 100 to 150 N, or 150 to 200 N, or 200 to 300 N. The deformation can be elastic bending deformation, or buckling deformation or crease deformation. The well may be cylindrical, conical, spherical, revolutionary, polyhedron, irregular or asymmetrical in shape. The well may have a circular, rectangular, elliptical, polygonal or curved polygonal cross-section.

[0398] In some embodiments, the package is well-designed. In some embodiments, the well-designed package includes a rigid plastic, paper, or cardboard structure. In some embodiments, one or more sides of the container are sealed via a removable plastic film or metal foil film. In some embodiments, the tabs may protrude from the film and can be peeled off by the strength of a finger or by another means of grasping the tabs. In some embodiments, the sealing film may be punctured to expose the contraceptive device inside.

[0399] In some embodiments, the package is used to contain and dispose of the contraceptive device after use. In some embodiments, the package contains any ejaculate, which may be deposited inside or on the condom.

[0400] In some embodiments, the package further includes a delamination composition suitable for inducing delamination of the adhesive layer from the penis or vagina when the adhesive layer is adhered to the penis or vagina. In some embodiments, the package further includes a delamination composition suitable for inducing delamination of the adhesive layer from the glans of the penis when the adhesive layer is adhered to the glans of the penis.

[0401] In some embodiments, the delamination composition is a wipe. In some embodiments, the wipe contains a solvent that dissolves, modifies, or swells a stimuli-responsive polymer, thereby inducing delamination of the adhesive layer from the penis or vagina when the adhesive layer is adhered to the penis or vagina and the wipe is subsequently applied to a contraceptive device. In some embodiments, the wipe contains a solvent that dissolves, modifies, or swells a stimuli-responsive polymer, thereby inducing delamination of the adhesive layer from the glans of the penis when the adhesive layer is adhered to the glans of the penis and the wipe is subsequently applied to a condom.

[0402] In some embodiments, the wipe contains a volatile additive that cools the wipe upon evaporation, thereby inducing delamination of the adhesive layer from the penis or vagina when the adhesive layer adheres to the penis or vagina and the wipe is subsequently applied to a contraceptive device. In some embodiments, the wipe contains a volatile additive that cools the wipe upon evaporation, thereby inducing delamination of the adhesive layer from the glans of the penis when the adhesive layer adheres to the glans of the penis and the wipe is subsequently applied to a condom.

[0403] In some embodiments, the package may further include a lubricant, a spermicide, or both.

[0404] 4.4. Kit In one embodiment, the present disclosure provides a kit comprising a contraceptive device and instructions for use as described herein.

[0405] In some embodiments, the kit includes condoms and instructions for use as described herein. In some embodiments, the kit includes packaged condoms and instructions for use as described herein.

[0406] In some embodiments, the kit includes the partial condom and instructions for use as described herein. In some embodiments, the kit includes the packaged partial condom and instructions for use as described herein.

[0407] In some embodiments, the kit includes a pessary and instructions for use as described herein. In some embodiments, the kit includes a packaged pessary and instructions for use as described herein.

[0408] In some embodiments, the kit may include a lubricant, a spermicide, or both.

[0409] 4.5.How to use In one embodiment, the Disclosure provides a method for applying a condom described herein to the penis of a human subject, comprising: bringing the adhesive layer of the condom described herein into contact with the penis; and applying sufficient pressure to the condom to adhere it to the penis. In some embodiments, the pressure is applied by one or more fingers or hands of the subject.

[0410] In some embodiments, the method of applying the partial condom described herein to the penis of a human subject includes bringing the adhesive layer of the condom into contact with the glans of the penis; and applying sufficient pressure to the condom to adhere it to the glans of the penis. In some embodiments, the pressure is applied by one or more fingers or hands of the subject.

[0411] In some embodiments, the condoms or partial condoms disclosed herein are applied before sexual arousal or before complete sexual arousal.

[0412] In some embodiments, a method for applying the pessary described herein to the vagina of a human subject includes bringing the adhesive layer of the pessary into contact with the vagina; and applying sufficient pressure to the pessary to adhere it to the vagina. In some embodiments, the pressure is applied by one or more fingers or hands of the subject.

[0413] In some embodiments, adhesion to the skin may be achieved by a hot-melt process by oral fusion, or by other external heat such as that provided by a hairdryer, or by compression by human hands for about 0 to about 20 seconds, and the adhesive exhibits increased adhesion when heated to about 30°C, about 35°C, about 37°C, about 40°C, about 45°C, about 55°C, about 60°C or about 65°C or higher.

[0414] In some embodiments, the application of the partial condoms disclosed herein to the penis of a human subject is easier than the application of partial condoms known in the art, including, but not limited to, GALATIC CAP®.

[0415] In some embodiments, the application of the partial condoms disclosed herein is easier than the application of partial condoms known in the art, such as GALATIC CAP®.

[0416] In some embodiments, the application of the partial condoms disclosed herein is easier by about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, or about 100% or more than the application of partial condoms known in the Art (e.g., GALATIC CAP®), as measured by any suitable method in non-clinical or clinical situations (e.g., user self-reporting in a sexual intercourse log).

[0417] In certain embodiments, less than 30% of users find condom application difficult or very difficult, more specifically, less than 25%, less than 20%, less than 15%, less than 10%, or less than 5%.

[0418] In some embodiments, the partial condoms disclosed herein remain adhered to the penis of a human subject in a manner superior to other partial condoms known in the art, including, but not limited to, the condoms disclosed in International Publication No. 2014178661 and U.S. Patent No. 11,234,858. Adhesion can be measured by any suitable method in non-clinical or clinical settings (e.g., user self-reporting in a sexual intercourse log).

[0419] In some embodiments, the use of the condoms disclosed herein enhances adhesion by about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, or about 100% or more compared to other partial condoms known in the art.

[0420] In some embodiments, the use of the condoms disclosed herein enhances the sexual pleasure of the user and / or partner by about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, or about 100% or more, as measured by any appropriate method in non-clinical or clinical situations (e.g., user self-report in a sexual intercourse log by the user, partner, or both). Comparisons may be with respect to conventional condoms or partial condoms.

[0421] In some embodiments, the condoms disclosed herein enhance user and / or partner sexual pleasure by approximately 2, 3, 4, 5, 6, 7, 8, 9, or 10 times or more, as measured by individual self-reports (e.g., using sexual logs) or more formal studies including comparative population studies.

[0422] Sexual pleasure can be measured by any appropriate method. See, for example, Siegler AJ, et al. Arch Sex Behav. 2018 Aug;47(6):1745-1754 (which is incorporated herein by reference). In one embodiment, sexual pleasure is measured by an event-level male sexual pleasure scale such as EMSEXpleasure. In another embodiment, sexual pleasure is measured using the Quality of Sexual Experience (QSE) scale (S. Sanders, et al., J Sex Med. 2013 Oct;10(10):2409-17, which is incorporated herein by reference). Both are reliable event-level measures of the quality of sexual experience, the latter being for both men and women.

[0423] In other embodiments, sexual pleasure may be assessed using the Sexual Pleasure Scale (SPS) (Patricia M Pascoal et al. (2016) The Journal of Sexual Medicine, 13(9), 1408-1413), the Body, Emotions, Sensations, Touch / Trust (BEST) scale (Beckmeyer et al. (2021) Journal of American College Health, 1-12), or the Pleasuremeter (Castellanos-Usigli and Braeken-van Schaik (2019). Sexual and reproductive health matters, 27(1), 313-315).

[0424] In some embodiments, the use of the condoms disclosed herein enhances the sexual sensation of the user and / or partner by about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, or about 100% or more, as measured by any suitable method in non-clinical or clinical settings. In one embodiment, the enhancement of sexual pleasure is measured by any suitable method in non-clinical settings, for example, by individual self-reporting (e.g., via a sexual intercourse log) or in clinical settings. Comparisons may be between conventional condoms and partial condoms.

[0425] In some embodiments, the condoms disclosed herein enhance the sexual sensation of the user and / or partner by approximately 2, 3, 4, 5, 6, 7, 8, 9, or 10 times or more, as measured by any suitable method (e.g., user self-report in a sexual intercourse log) in non-clinical settings, for example, through individual self-reporting (e.g., via a sexual intercourse log) or in clinical settings. Comparisons may be with respect to conventional condoms or partial condoms.

[0426] In some embodiments, the use of condoms disclosed herein is preferred over conventional condoms by at least a majority of user groups (either actual users or their partners), where the majority constitutes about 80%, 85%, 90%, or 95% or more of the group. Users may be a non-clinical or clinical group of users.

[0427] In some embodiments, the use of condoms disclosed herein is preferred over conventional condoms by approximately 85% to 100% of users.

[0428] In one embodiment, at least 175 out of 200 users in a group prefer the condoms disclosed herein to conventional condoms.

[0429] In some embodiments, the use of condoms disclosed herein results in increased condom use among user populations in non-clinical or clinical situations.

[0430] In one embodiment, the population is a group of human subjects in a clinical trial.

[0431] In another aspect, the present disclosure provides a method for removing a condom described herein from the penis of a human subject, comprising applying a stimulus to a condom with an adhesive layer attached to the penis, and removing the condom from the penis.

[0432] In some embodiments, a method for removing a partial condom described herein from the glans of a human subject's penis includes applying stimulation to a condom whose adhesive layer is adhered to the glans of the penis, and removing the condom from the glans of the penis.

[0433] In some embodiments, a method for removing a pessary described herein from the vagina of a human subject includes applying stimulation to a pessary to which an adhesive layer is adhered to the vagina, and removing the pessary from the vagina.

[0434] In some embodiments, the condoms disclosed herein are easier to remove than partial condoms known in the art.

[0435] In some embodiments, the ease of removal is improved by approximately 5%, approximately 10%, approximately 15%, approximately 20%, approximately 25%, approximately 30%, approximately 35%, approximately 40%, approximately 45%, approximately 50%, approximately 55%, approximately 60%, approximately 65%, approximately 70%, approximately 75%, approximately 80%, approximately 85%, approximately 90%, approximately 95%, or approximately 100% or more, as measured by any appropriate method in non-clinical or clinical settings (e.g., individual self-reports in sexual intercourse logs).

[0436] In some embodiments, less than 30% of users found condom removal difficult or very difficult, more specifically, less than 25%, less than 20%, less than 15%, less than 10%, or less than 5%.

[0437] In some embodiments, the removal of the contraceptive device is injury-free.

[0438] In some embodiments, removal of the contraceptive device is measured by WBQPA to cause minimal or no pain in the subject, for example, a WBQPA score of less than 4, less than 3, less than 2, less than 1, or 0.

[0439] In some embodiments, removal of the contraceptive device does not cause significant hypersensitivity, inflammation, or redness in the user.

[0440] In some embodiments, when the contraceptive device is removed from the penis or vagina, an amount of adhesive less than 50% by weight remains on the penis or vagina, such as 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, or 5% by weight or less. In some embodiments, even if adhesive remains on the penis or vagina after removal, the adhesive is such that it can be easily removed by light rubbing or rolling.

[0441] In some embodiments, the stimulus is a mechanical action or force. In some embodiments, the mechanical action is a shear rate. In some embodiments, the shear rate is induced by peeling, pulling, or rubbing at various speeds.

[0442] In some embodiments, the peeling is a light peeling as described above. In some embodiments, light peeling corresponds to a peeling speed of 25 mm / s or less, 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 peeling speeds such as 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 mms to 0.5 mm / s, 0.01 mm / s to 0.3 mm / s, 0.01 mm / s to 0.1 mm / s, 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 mms 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. In some embodiments, light peeling corresponds to peeling speeds of 500 mm / min or less, for example, 400 mm / min or less, 300 mm / min or less, 200 mm / min or less, 100 mm / min or less, or 50 mm / min or less. In some embodiments, light peeling corresponds to peeling speeds 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.

[0443] In some embodiments, the stimulus is a temperature change, and the application of the stimulus includes cooling the temperature of the contraceptive device to 25°C or below. In some embodiments, the stimulus is a temperature change, and the application of the stimulus includes cooling the temperature of the condom to 25°C or below.

[0444] In some embodiments, the stimulation is a physicochemical change, and the application of the stimulation involves applying a wipe to a contraceptive device, the wipe containing a solvent that dissolves, denatures or swells the stimulation-responsive polymer, thereby inducing the delamination of the adhesive layer from the penis or vagina. In some embodiments, the stimulation is a physicochemical change, and the application of the stimulation involves applying a wipe to a condom, the wipe containing a solvent that dissolves, denatures or swells the stimulation-responsive polymer, thereby inducing the delamination of the adhesive layer from the glans of the penis.

[0445] In some embodiments, the condoms disclosed herein are removed without the application of a liquid such as baby oil.

[0446] In some embodiments of this specification, the condom is removed without leaving the site of intercourse.

[0447] In some embodiments, the condom is removed without the user needing to urinate.

[0448] 4.6. Manufacturing method In one embodiment, the present disclosure provides a method for preparing a contraceptive device described herein, comprising adhering an adhesive layer to a barrier layer, wherein the adhesive layer comprises an adhesive comprising a stimulus-responsive polymer formed from one or more monomers and optionally one or more polyfunctional crosslinking agents.

[0449] In some embodiments, a method for preparing a condom includes adhering an adhesive layer to a barrier layer, wherein the adhesive layer comprises an adhesive comprising a stimulus-responsive polymer formed from one or more monomers and optionally one or more polyfunctional crosslinking agents.

[0450] In some embodiments, a method for preparing a pessary includes adhering an adhesive layer to a barrier layer, wherein the adhesive layer comprises an adhesive comprising a stimulus-responsive polymer formed from one or more monomers and optionally one or more polyfunctional crosslinking agents.

[0451] In some embodiments, a method is provided for manufacturing the contraceptive device disclosed herein, comprising (i) providing the adhesive composition described herein, and (ii) applying the adhesive to a substrate using one of the following methods: screen printing, pad printing, roll-to-roll coating, dipping coating, thermoforming, extrusion, injection molding, or other scaled film manufacturing methods, thereby providing the contraceptive device disclosed herein. In some embodiments, the substrate is a release liner. In some embodiments, the substrate is a barrier layer.

[0452] In some embodiments, the contraceptive device includes an adhesive layer that is cured using photopolymerization. In some embodiments, the adhesive is applied as a coating on a barrier substrate and then cured using UV or visible light. In some embodiments, the adhesive is fully or partially cured with UV or visible light and then applied to the substrate.

[0453] In some embodiments, the adhesive is crosslinked after processing onto the release liner or barrier layer by a latent reaction using the crosslinking chemistry described above. For example, residual epoxides and alcohol or amine chemistry can be used to achieve crosslinking after the adhesive has been dipped into a coating on the release liner or barrier layer, or after it has been applied via spray or roll-to-roll coating.

[0454] In some embodiments, the adhesive is self-healing in that it can be prepared separately from the barrier layer, applied to the barrier layer in an additional step, and optionally undergoes regenerative adhesive properties after removal from skin or other application surfaces. One example of a transfer process for applying 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 through an orifice or nozzle to be transferred to the barrier layer. Yet another example is that the adhesive can be prepared separately on a foam or mold from the barrier, and the barrier can transfer a solid or liquid layer deposited by dipping coating, spraying, brushing, painting, or roll transfer to the adhesive.

[0455] In some embodiments, the contraceptive device is subjected to one or more quality testing steps. In some embodiments, the contraceptive device is subjected to a leak test or an electrical test (e.g., a dry electrical test).

[0456] In some embodiments, the contraceptive device is subjected to one or more tests of its physical properties, including but not limited to tensile strength, tensile or overlapping shear strength, peeling adhesion strength, and / or impact strength, to provide satisfactory results.

[0457] In some embodiments, the contraceptive device is subjected to one or more tests selected from the following: ASTM F2255-05 Standard Test Method for Strength Properties of Tissue Adhesives in Lap-Shear by Tension Loading; ASTM F2256-05 Standard Test Method for Strength Properties of Tissue Adhesives in T-Peel by Tension Loading; and ASTM F2258-05 Standard Test Method for Strength Properties of Tissue Adhesives in Tension, to satisfy the factory results. [Examples]

[0458] 4.7. Example The following are examples of specific embodiments for carrying out this disclosure. These examples are provided for illustrative purposes only and are not intended to limit the scope of this disclosure. While efforts have been made to ensure accuracy with respect to the numbers used (e.g., quantity, temperature, etc.), some experimental errors and deviations should naturally be tolerated. 4.7.1. Example 1 Poly(ethyl acrylate), with an average Mw of approximately 95 kDa according to GPC, was purchased from Sigma Aldrich as a solid 18-22 wt% toluene solution and cast onto a polyethylene plastic substrate to a thickness of approximately 0.1 mm, as measured by calipers. The toluene solvent was evaporated in a ventilated hood for approximately 72 hours. After solvent evaporation, a polymer film approximately 50-500 microns thick remained on the polyethylene substrate, with the polymer film portions measuring approximately 200 and 400 microns, respectively, as measured by calipers. This polymer film was sandwiched between a second 0.3 mm layer of polyethylene and stored for 6 months at approximately 20°C and approximately 45-60% relative humidity. After 6 months, the poly(ethyl acrylate) film remained readily adhered to the 0.3 mm thick polyethylene film on which it was cast. To demonstrate thermally responsive layer delamination from human skin, a polyethylene / poly(ethyl acrylate) substrate was pressed against a bare human arm, and the adhesion behavior was demonstrated and recorded via video, showing that it was strong enough to substantially limit the easy removal of the polyethylene / poly(ethyl acrylate) substrate from the human arm.

[0459] An adhesive polyethylene / poly(ethyl acrylate) substrate attached to a human arm was rinsed under room temperature water (approximately 20°C) from a kitchen sink for approximately 5-10 seconds, while simultaneously being subjected to light pulling / peeling force from the hand. After 5-10 seconds, layer delamination was achieved without pain or substantially any applied force from the hand, and no observable adhesive residue was found on the arm.

[0460] 4.7.2. Example 2 A poly(ethyl acrylate), with an average Mw of approximately 95 kDa according to GPC, solid 18-22 wt% toluene solution was purchased from Sigma Aldrich and cast onto commercially available 6-inch x 6-inch dental dam latex and polyurethane substrates with a thickness of approximately 0.2 mm. The dental dam was measured to approximately 0.20 mm using calipers. The toluene solvent was evaporated in ambient air at approximately 45-60% relative humidity for 72 hours. After solvent evaporation, a polymer film approximately 50-500 microns thick remained on the dental dam substrate, with the polymer film portions measuring approximately 200 and 400 microns, respectively, using calipers.

[0461] Unlike the poly(ethyl acrylate) film stored for 6 months reported in Example 1, the poly(ethyl acrylate) film in Example 2 exhibited limited tack at room temperature (approximately 19°C) when qualitatively evaluated for skin adhesion 72 hours after casting to latex and polyurethane dental dams.

[0462] To demonstrate heat-responsive layer delamination from human skin, a latex dental dam / poly(ethyl acrylate) substrate having a circular adhesive layer approximately 50–500 microns thick (cross-sections measured by calipers were approximately 200 and 400 microns thick, respectively) and approximately 4 cm in diameter (measured by calipers) was pressed against an erect human penis and heated for approximately 5 seconds using a hairdryer on a warm setting while pressed against the penile head. The adhesive behavior was observed immediately after the 5-second hairdryer exposure (oral fusion is an alternative technique to a hairdryer in one embodiment of this disclosure, which heats a partially tacky adhesive in a hot-melt process to a more ideal thermomechanical regime to achieve adhesion). A rubber band was placed around the base of the tip of the penis to secure the non-adherent portion of the dental dam substrate, preventing shear removal / stress concentration from forming at the non-adherent site, and the erect penis was subjected to forces corresponding to those observed during intercourse using a masturbation technique. During ejaculation, even after removing the rubber band placed below the head of the penis, no semen was observed to leak from the condom that had been adhered to the head of the penis. The adhered latex dental dam was then gently removed by exposing it to cold water (approximately 10-20°C) in a regular shower and peeling along its edges. While cold water was flowing along the adhered dental dam / water interface for approximately 10-20 seconds, minimal or no pain was observed in the penile skin, and no adhesive residue was observed on the penile skin or in the urethra. Urination was easily achieved immediately after removal of the adhered dental dam.

[0463] The same results were observed when Example 2 was repeated. When the method in Example 2 was repeated, a paper towel was run across the base of the head of the penis, but no semen was observed on the paper towel. In Example 2, when a flaccid penis with a condom attached was immersed in ice water, the condom was easily removed, and no adhesive residue was observed on the penis.

[0464] 4.7.3. Example 3 Approximately 10 mL of poly(ethyl acrylate), with an average Mw of approximately 95 kDa according to GPC and 18-22 wt% solid toluene solution, was added to a stainless steel mixing vessel. Approximately 1 mL of poly(butyl acrylate), with an average Mw of 99 kDa according to GPC and 25-30 wt solid, was added to the same stainless steel mixing vessel and stirred for approximately 20 seconds using a polyethylene pipette. After stirring for approximately 20 seconds, this poly(ethyl acrylate) / poly(butyl acrylate) mixture appeared homogeneous and optically clear, with no visible signs of phase separation or precipitation. Both the poly(ethyl acrylate) and poly(butyl acrylate) solutions were Sigma The product was purchased from Aldrich and used as received. After mixing, approximately 3 mL of the blended poly(ethyl acrylate) / poly(butyl acrylate) solution was drawn into a 3 mL polyethylene pipette and dropped in three strips onto a 6-inch x 6-inch latex dental dam. The dental dam was measured to be approximately 200 microns thick using calipers. The dental dam / adhesive solution was evaporated for approximately 72 hours under ambient air conditions at a temperature in the range of 15°C to 25°C and a relative humidity of approximately 40% to 60%. After solvent evaporation, a polymer blend film approximately 50 to 500 microns thick remained on the latex dental dam substrate, and the adhesive / latex substrate portions were measured to have adhesive layers approximately 200 and 400 microns thick, respectively. Measurements were taken using calipers. To demonstrate thermally responsive layer delamination from human skin, a latex / poly(ethyl acrylate) / poly(butyl acrylate) substrate was pressed against a bare human arm, and the adhesive behavior was demonstrated to be strong enough to substantially limit the easy removal of the polyethylene / poly(ethyl acrylate) / poly(butyl acrylate) substrate from the human arm. The adhesive polyethylene / poly(ethyl acrylate) / poly(butyl acrylate) substrate attached to the human arm was rinsed under cold water (approximately 5-10°C) from a bottle cooled in a refrigerator, while simultaneously being subjected to light pulling / peeling force from the hand. After 2-5 seconds, layer delamination was achieved with no pain or substantially no applied force from the hand, and no observable adhesive residue was found on the arm, nor was any pain observed during removal.

[0465] 4.7.4. Example 4 Circular / oval substrates were cut using ordinary scissors from one of a triple latex dental dam / poly(ethyl acrylate) / poly(butyl acrylate) sample prepared using the method of Example 3, so as to obtain an adhesive elastomer substrate that covered approximately 100% of the latex surface after cutting. The resulting circular / oval substrates, measured with calipers, had a large diameter of approximately 5.5 cm and a small diameter of approximately 5 cm. The resulting adhesive / latex substrates were then placed almost symmetrically on the head of an erect human penis, with the urethra at the center of the adhesive substrate ("adhesive condom") and the edge of the adhesive condom covering approximately 50% to 75% of the surface area of ​​the erect penis head, noting that the urethra was completely covered and the base of the frenulum was exposed. When the adhesive condom was placed on the head of an erect penis, a natural fold occurred and it functioned as a semen reservoir.

[0466] After applying the adhesive condom to the erect penis, the condom appeared to be firmly secured to the head of the penis. The erect penis, with its head partially covered by the adhesive condom as described above, was inserted into the vagina of a woman after applying a small amount of general sexual lubricant to the vagina, and intercourse proceeded. The erect penis with the adhesive condom applied was removed from the vagina and examined approximately every 15 seconds for several minutes, and the adhesive condom appeared to remain in place without any peeling of the layers from the head of the erect penis. After several minutes of intercourse, ejaculation occurred, which began while the adhesive condom covering the erect penis was inside the vagina and ended outside the vagina, thereby allowing us to evaluate the ability of the adhesive condom to prevent semen from flowing out during ejaculation. No semen was observed during or immediately after ejaculation. To remove the semen-containing adhesive condom, the surface and edges of the condom were exposed to cold water (approximately 10°C to 15°C) discharged from a standard showerhead. The condom was then slowly removed piece by piece by hand, with minimal or no pain, by pulling back the edges of the condom for approximately 15 to 45 seconds in the presence of the cold water. For the man with the penis described in Example 4, ejaculation was easily achieved, and the sexual experience was significantly different from that with conventional condoms covering the head, frenulum, and shaft of the penis. For comparison, repeated intercourse using a lubricated latex condom did not result in ejaculation in the same sexual position as with the adhesive condom until the conventional latex condom was removed.

[0467] 4.7.5. Example 5 Poly(n-dimethylacrylamide) ("pDMAA"), Mw approximately 150,000 Da, was purchased from Scientific Polymer Products, Inc. Glycerol (>99%) was purchased from Sigma Aldrich, Inc. A 50 / 50 pDMAA / glycerol blend by weight was prepared by dissolving 4.17 g of pDMAA and 4.17 g of glycerol in a solution mixture of (4.17 g of acetone (technical grade) and 2.50 g of 190 proof ethanol, purchased from a local hardware store). The pDMAA / glycerol / acetone / ethanol solution was mixed in a sealed glass vial for 10 minutes, heated to approximately 50°C, and the mixture was repeatedly vortexed (heat, vortex, repeat) until a homogeneous and generally clear solution was observed. Next, the pDMAA / glycerol solution was cast onto a 6-inch x 6-inch latex dental dam and evaporated for approximately 48–96 hours at ambient temperature inside a chemical ventilation hood. After evaporation of acetone, ethanol, and any water impurities present in the acetone / ethanol blend, the resulting pDMAA / glycerol film was approximately 400 microns thick, generally tacky to contact at 20°C, and significantly more tacky / adhesive at 37°C. A 5-inch x 5-inch 50 / 50 pDMAA / glycerol adhesive dental dam was applied to a human forearm and demonstrated significant adhesion on video. The adhesive was observed to be completely soluble in tap water and could be painlessly peeled off a human forearm while running room-temperature tap water over the arm.

[0468] 4.7.6. Example 6 Poly(octadecyl methacrylate) ("pODMA"), Mw approximately 96,000 Da, was purchased from Scientific Polymer Products, Inc. in a toluene solution (approximately 20 wt%). The pODMA solution was cast onto a 6-inch x 6-inch latex dental dam and evaporated for approximately 48–96 hours at ambient temperature in a chemically ventilated hood. After evaporation of toluene, the resulting p(ODMA) film was approximately 300 microns thick and was non-tacky to contact at 20°C (essentially waxy) and significantly tacky / adhesive at 37°C. A 5-inch x 5-inch p(ODMA) adhesive dental dam was applied to a human forearm and demonstrated significant adhesion on video. This ODMA-containing substrate can be removed from a human arm using ice water at approximately 0°C, and any residual ODMA remaining on the human arm can be removed using olive oil or molten candle wax.

[0469] 4.7.7. Example 7 A polymer blend containing 1.0 part poly(n-butyl acrylate), 6.50 parts poly(n-ethyl acrylate), and 3.0 parts poly(octadecyl methacrylate) was prepared on a latex dental dam by repeating the method of Example 7. Solutions of poly(n-butyl acrylate), Mw approximately 99,000 and poly(ethyl acrylate), Mw approximately 95,000 in toluene were purchased from Sigma Aldrich, and pODMA was purchased from Scientific Polymer Products as described in Example 6. Compared to the 100% pODMA-coated adhesive dental dam reported in Example 6, the three-component dental dam of Example 7 showed significantly less migration of residual poly(ODMA) to human skin during layer delamination at 0°C.

[0470] 4.7.8. Example 8 Poly(ethylene) glycol (Mw 400 da) (PEG-400) and poly(n-dimethylacrylamide) ("pDMAA"), with a Mw of approximately 150,000 Da, were purchased from Scientific Polymer Products, Inc. A 50 / 50 wt blend of PEG-400 and pDMAA was prepared in a 50 wt total solution of acetone and ethanol (the solution was prepared using 4 g of PEG-400, 4 g of pDMAA, 4 g of acetone (crude, from a hardware store, with any water present), and 4 g of 190 proof ethanol). A latex dental dam substrate, taped to the lid of a polypropylene Tupperware dish, was placed in a vacuum oven at ambient pressure and 65°C with a constant airflow in a ventilation hood and equilibrated at 65°C. The PEG-400 / pDMAA 50 / 50 wt solution was cast onto this 65°C substrate in a vacuum oven under constant airflow and ambient pressure for 24 hours. The resulting film showed strong adhesive behavior in the range of 45-65°C (above the crystallization temperature of PEG-400) and no tack / adhesion was observed at ambient temperature (below the crystallization temperature of PEG-400).

[0471] 4.7.9. Example 9 A series of adhesives and barrier substrates were prepared by polymerization of monomer species. Monomers including n-butyl acrylate, n-ethyl acrylate, n-octyl acrylate, n-hexyl acrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, cetyl methacrylate, octadecyl methacrylate, lauryl methacrylate, acrylamide, n-isopropyl acrylamide, poly(ethylene glycol) diacrylate, Mn approximately 750, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate and diurethane dimethacrylate, triethylene glycol divinyl ether, n-vinyl dodecyl ether (dodecyl vinyl ether), isooctyl 3-mercaptopropionate, and triallyl isocyanurate were purchased from Sigma Aldrich and / or Scientific Polymer.

[0472] Using an analytical balance, a large quantity of monomer was extracted, and 1.0 wt% of DMPA photoinitiator was added until a homogeneous solution was formed. These solutions were then injected between 1.0 mm thick glass slides coated with Rain-X, separated by 1.0 mm thick spacers, and UV-cured in UVP CL-1000 crosslinking agent at 365 nm for 15 minutes. The samples were then post-cured at 90°C for approximately 10 hours under ambient conditions. After post-curing at 90°C, the optically clear samples were cooled to room temperature and appeared optically clear to the naked eye. They were then placed in a -20°C freezer for 5 minutes, after which the samples appeared cloudy or opaque to varying degrees. The samples could be removed from the glass slides and handled. Initially, the cloudy room-temperature samples behaved as non-sticky waxy solids. Upon heating to body temperature, the samples became very sticky to skin, more sticky to polyurethane dental dams, and less sticky to latex dental dams. Samples that appeared optically clear and did not become cloudy after cooling behaved as gels with limited tack or adhesion to polyurethane or latex dental dams.

[0473] In specific cases, samples with varying degrees of turbidity exhibited the following characteristics: (A) waxy solid at room temperature; (B) good adhesion to human skin after melting and good simultaneous adhesion to latex and polyurethane condoms or dental dams when applied to human skin; (C) frequency-responsive and / or shear-responsive adhesive behavior, such that the molten wax adhesive maintains adhesion to polyurethane and latex condom and dental dam barriers to human skin while being "pulled" or "suddenly pulled" with higher forces, frequencies, or shear rates expected to remove the adhesive barrier from human skin, while also exhibiting the ability to be removed from human skin with minimal or no pain by low frequency or low force or very soft or slow peeling; (D) in selected samples, residual adhesive remaining on human skin after removal was melted and very difficult to remove, whereas in other cases, the adhesive could be very easily scraped off with minimal or no pain in a very natural human manner. Videos of the observed behavior were taken. Optically opaque samples that demonstrated melting into human skin, including human forearm, biceps, shoulder, and penile head skin, and virtually painless removal at various frequencies, shears, or shear rates, include UV-curable poly(stearyl methacrylate samples) with various crosslinkers, including poly(ethylene glycol) diacrylate, Mn 750, trimethylolpropane triacrylate, pentaerythrital tetraacrylate, and ethoxylated trimethylolpropane triacrylate, in a crosslinker range containing 0%, 0.2%, 0.4%, 0.6%, 0.75%, 0.85%, 0.95%, 1.0%, 2.0%, 3.0%, 5.0%, 7.5%, 10.0%, 15.0%, 20%, 25%, and 30% crosslinkers, prepared using 1.0% by weight of DMPA photoinitiator.

[0474] Optically clear samples that demonstrated strong adhesion to human skin, including the skin of the human forearm, biceps, shoulder, and penile head, and virtually painless removal at various frequencies, shearing, or shearing rates, include UV-curable poly(stearyl methacrylate samples) with various crosslinking agents, including poly(ethylene glycol) diacrylate, Mn 750, trimethylolpropane triacrylate, pentaerythrital tetraacrylate, and ethoxylated trimethylolpropane triacrylate, in a crosslinking agent range containing 0%, 0.2%, 0.4%, 0.6%, 0.75%, 0.85%, 0.95%, 1.0%, 2.0%, 3.0%, 5.0%, 7.5%, 10.0%, 15.0%, 20%, 25%, and 30% crosslinking agents, prepared using 1.0% by weight of DMPA photoinitiator.

[0475] Compositions that did not show strong adhesion to human skin, including the skin of the human forearm, biceps muscle, shoulder, and penile head, included poly(butyl acrylate) and poly(hexyl acrylate) crosslinked with crosslinking agents of 0.2, 0.4, 0.6, 1.0, and 2.0% by weight or more, including poly(ethylene glycol) diacrylate, Mn 750, trimethylolpropane triacrylate, pentaerythrital tetraacrylate, and ethoxylated trimethylolpropane triacrylate.

[0476] Compositions that showed strong adhesion to human skin, including the skin of the human forearm, biceps, shoulder, and penile head, included poly(lauryl methacrylate) and poly(octadecyl methacrylate) crosslinked with 0.4, 0.5, 0.6, and 0.7% by weight of trimethylolpropane triacrylate crosslinking agent and 1.0% by weight of DMPA, which were photopolymerized and post-cured at 90C for more than 10 hours. Higher concentrations of crosslinking agents, such as 1.0 and 2.0% by weight of TMPTA, gave skin adhesion samples with lower adhesion strength.

[0477] 4.7.10. Example 10 Adhesive samples were prepared by photopolymerization of monomer solutions of 98.43 wt% lauryl methacrylate (LMA) and 0.59 wt% trimethylolpropane triacrylate (TMPTA) with 0.98 wt% 2,2-dimethoxy-2-phenylacetophenone (DMPA) photoinitiator. A large volume of monomer was extracted using an analytical balance and mixed using a FlackTek SpeedMixer (DAC 330-100 PRO) until a homogeneous solution was formed. Approximately 3 mL of the solution was pipettered onto a 25 mm disposable aluminum rheometer baseplate (TA Instruments) and cured under an inert nitrogen atmosphere and a 365 nm UV lamp (UVP CL-1000 UV crosslinker) for 1 hour. The sample was then post-cured at 120°C for 1 hour at atmospheric pressure. Finally, the sample was cooled to ambient temperature.

[0478] A set of comparative samples was prepared using n-butyl acrylate (BA), TMPTA, and DMPA. The comparative monomer solutions had the following compositions: (a) 98.37 wt% BA, 0.55 wt% TMPTA, 1.08 wt% DMPA; (b) 98.27 wt% BA, 0.75 wt% TMPTA, 0.98 wt% DMPA; (c) 97.87 wt% BA, 1.16 wt% TMPTA, 0.98 wt% DMPA. Solutions (a-c) were injected between two 1.0 mm thick Rain-X coated glass slides separated by a 1.0 mm glass spacer. The samples were cured for 15 minutes under a 365 nm UV light source (UVP CL-1000 UV crosslinker), post-cured for 12 hours at 90°C and atmospheric pressure, and then cooled to ambient temperature. The sample was removed from the glass slide and placed on the surface of the base plate of a 25mm rheometer.

[0479] Manual inspection revealed that both the adhesive and comparison samples were optically transparent to the naked eye. All samples exhibited viscoelastic behavior without flow (soft solid). The adhesive samples showed strong tack against human skin (inner fingertips and wrists), nitrile, and glass, while the comparison samples exhibited elastomer properties with little to no tack against human skin (inner fingertips or wrists) and nitrile.

[0480] Tack strength was quantitatively measured using a TA Instruments Discovery HR-2 rheometer equipped with an 8.00 mm aluminum tip and a Peltier cooled aluminum baseplate, with measurements performed at a sample temperature of 25°C. The sample was compressed in contact for 60 seconds, and then the rheometer tip was withdrawn at a speed of 100 micrometers / second to measure the axial force. The maximum axial tack force measured was 6 N for the adhesive sample. The same process was repeated for the comparison samples, yielding peak tack forces of 5 N, 6 N, and 4 N for samples (a), (b), and (c) against aluminum, respectively. The adhesive strength, measured in Newton-seconds (Ns), was calculated by integrating the area under the force-time measurements for each sample, yielding 88.4 Ns for the adhesive and 9.6 Ns, 5.9 Ns, and 3.8 Ns for comparison samples (a), (b), and (c) (Figure 4). The tack energy of the adhesive was also calculated by multiplying the integral of the adhesive strength by a constant pull-out rate of 100 micrometers / second, yielding a tack energy of 8.84 × 10⁻³ joules (J) for the adhesive, and 0.96 × 10⁻³ J, 0.59 × 10⁻³ J, and 0.38 × 10⁻³ J for comparative samples (a), (b), and (c), respectively.

[0481] 4.7.11. Example 11 A series of adhesive samples were prepared by photopolymerization of monomer solutions with the following composition: 98.43 wt% LMA, 0.59 wt% TMPTA, and 0.98 wt% 2DMPA photoinitiator. Large quantities of monomer were extracted using an analytical balance and mixed using a FlackTek SpeedMixer (DAC 330-100 PRO) until a homogeneous solution was formed.

[0482] The prepolymer solutions were formed by partially curing 90 g of monomer solution for 14 minutes in a “pre-curing” step under a continuous flow inert nitrogen atmosphere with a 365 nm UV light source (UVP CL-1000 UV crosslinking agent). This was repeated four times individually. After pre-curing, an additional mass of TMPTA was added to each of the four samples: (1) 0.00 wt% TMPTA ("L6"), (2) 0.06 wt% TMPTA ("L6 10% TMPTA"), (3) 0.12 wt% TMPTA, and (4) 0.18 wt% TMPTA. The solutions were mixed again using a SpeedMixer until homogeneous.

[0483] Next, a 5 mL volume of the prepolymer solution was pipetteed onto silicone-impregnated paper fixed to a 1.0 mm thick glass slide, and cured for a further 41 minutes under UV light in an inert nitrogen atmosphere. After removal from the crosslinking agent, each sample was individually sandwiched between separate pieces of silicone-impregnated paper fixed to a 1.0 mm thick glass slide, compressed to a thickness of 600-700 micrometers using a spring clamp, and post-cured at 120°C and atmospheric pressure for 1 hour before cooling to ambient temperature. The samples were observed to be optically clear to the naked eye.

[0484] Tensile strain capacity was evaluated using a universal testing machine (Instron 5944). The sample was measured to a thickness of 600 micrometers, cut into a 2 cm wide rectangular strip, and clamped in an Instron fixture with a starting clamp spacing of 5 cm. The sample was pulled at a speed of 300 mm / min until it broke and strained (Figure 5). Sample (1) broke at a stress of 0.15 MPa and 182% strain. Sample (2) broke at a stress of 0.12 MPa and 217% strain. Sample (4) broke at a stress of 0.067 MPa and 120% strain.

[0485] An additional non-adhesion comparison sample was prepared from a monomer solution containing 98.27 wt% BA, 0.75 wt% TMPTA, and 0.98 wt% DMPA. This was injected between two 1.0 mm thick Rain-X coated glass slides separated by a 1.0 mm glass spacer. The sample was cured for 15 minutes under a 365 nm UV light source (UVP CL-1000 UV crosslinking agent), post-cured for 12 hours at 90°C and atmospheric pressure, and then cooled to ambient temperature. This sample fractured at a stress of 0.22 MPa and a strain of 152%.

[0486] Additional strain capacity measurements were performed on L6 10% TMPTA, BA, and LA samples. The thickness of the samples was measured, cut into 1.6 cm wide rectangular strips, and clamped in Instron fixtures with a starting clamp spacing of 3 cm. The samples were pulled and strained at a speed of 300 mm / min until they failed (Figures 6 and 7). L6 10% TMPTA had a significantly higher strain capacity than the LA elastomer. Young's modulus was calculated from the slope of the stress-strain curve between 0% strain and 5% strain, and was found to be 1.33 ± 0.47 kPa for L6 10% TMPTA, 1.33 ± 0.40 kPA for LA, and 3.15 ± 1.13 kPA for BA.

[0487] Alien tape, a commercially available thick elastomer nanotexture tape, was also tested in the same manner. It did not fail before reaching the maximum range of the Instron.

[0488] 4.7.12. Example 12 Adhesive samples were prepared by photopolymerizing monomer solutions of 98.43 wt% lauryl methacrylate (LMA) and 0.59 wt% trimethylolpropane triacrylate (TMPTA) with 0.98 wt% 2,2-dimethoxy-2-phenylacetophenone (DMPA) photoinitiator. A large volume of monomer was extracted using an analytical balance and mixed using a FlackTek SpeedMixer (DAC 330-100 PRO) until a homogeneous solution was formed. Approximately 1.5 mL of the solution was pipetteed onto a 1.0 mm thick 75 × 50 mm glass slide and cured for 1 hour under an inert nitrogen atmosphere with a 365 nm UV lamp (UVP CL-1000 UV crosslinker). The sample was removed from the crosslinker, sandwiched between separate pieces of silicone paper fixed to a 1.0 mm thick glass slide, and compressed using a spring clip to obtain a gap thickness of approximately 100 microns. Next, the sample was post-cured at 120°C for 1 hour under atmospheric pressure, and then cooled to ambient temperature.

[0489] A 180-degree peeling test was performed using a universal testing machine (Instron 5944) and Vitro-Skin (Florida Suncare Testing Inc, IMS Division) as a human skin substrate analog (Figure 8). A rectangular strip of Vitro-Skin with a width of 5 cm was pressed into the adhesive with moderate pressure and left to stand for 1 minute before the test. The glass slide was fixed in place to the lower Instron fixture. Vitro-Skin was fixed to the upper fixture in a standard 180-degree peeling test configuration. Vitro-Skin was peeled from the adhesive at 100 mm / min and this was repeated for three samples. The average peeling strength (force per unit width) was measured to be approximately 300 N / m. Repeating this procedure at a peeling speed of 300 mm / min yielded an average of approximately 700 N / m, demonstrating the shear rate response behavior of the adhesive, where the peeling force is low at very low peeling speeds and the adhesive strength remains high at high peeling speeds.

[0490] A comparative analysis was conducted on 3M Tegaderm, a commercially available medical adhesive. Before the test, a rectangular strip of Tegaderm, 26 mm wide, was pressed onto a clean 500-gram glass slide for 1 minute. The glass slide was fixed in place using a lower Instron fixture. Tegaderm was fixed to the upper fixture using a standard 180-degree peeling test configuration. The adhesive was then peeled from the glass slide again at 100 mm / min and 300 mm / min, with 10 repetitions for each peeling speed. The average peeling forces were approximately 98 N / m and 94 N / m, respectively, indicating no significant shear rate dependence of the adhesive.

[0491] Additional comparisons were made with several other commercially available adhesives (Figure 9). With conventional pressure-sensitive adhesives, the observed variation in the peeling force required for removal is mainly influenced by the pressure used to apply the adhesive to the target surface and optionally the contact time with the target surface (e.g., peeling strength), compared to the rate at which the adhesive is removed or peeled, which has little or no effect on the delamination behavior.

[0492] In contrast, the stimulus-responsive adhesives described herein exhibit different behaviors (peeling intensity or perceived pain) during delamination at different peeling rates, which are primarily influenced by the peeling or shearing rate of the adhesive when removed (or another stimulus applied to the adhesive immediately before delamination). The delamination behavior is independent of, or weakly dependent on, the pressure used to apply the adhesive to the target surface and, optionally, the time of contact with the target surface. (These descriptions assume that the target surface, environmental conditions, temperature, and humidity are all controlled to be equivalent).

[0493] 4.7.13. Example 13 Adhesive samples were prepared by photopolymerization of monomer solutions of 98.43 wt% lauryl methacrylate and 0.59 wt% trimethylolpropane triacrylate (TMPTA) with 0.98 wt% 2,2-dimethoxy-2-phenylacetophenone (DMPA) photoinitiator. A large volume of monomer was extracted using an analytical balance and mixed using a FlackTek SpeedMixer (DAC 330-100 PRO) until a homogeneous solution was formed. Approximately 3 mL of the solution was pipetteed onto a 25 mm disposable aluminum rheometer baseplate (TA Instruments) and cured under an inert nitrogen atmosphere and a 365 nm UV lamp (UVP CL-1000 UV crosslinking agent) for 1 hour. The sample was then post-cured at 120°C for 1 hour at atmospheric pressure. The sample was then cooled to ambient temperature.

[0494] A set of comparative samples was prepared using n-butyl acrylate (BA), TMPTA, and DMPA. The comparative monomer solutions had the following compositions: (a) 98.37 wt% BA, 0.55 wt% TMPTA, 1.08 wt% DMPA; (b) 98.27 wt% BA, 0.75 wt% TMPTA, 0.98 wt% DMPA; (c) 97.87 wt% BA, 1.16 wt% TMPTA, 0.98 wt% DMPA. Solutions (a-c) were injected between two 1.0 mm thick Rain-X coated glass slides separated by a 1.0 mm glass spacer. The samples were cured for 15 minutes under a 365 nm UV light source (UVP CL-1000 UV crosslinker), post-cured for 12 hours at 90°C and atmospheric pressure, and then cooled to ambient temperature. The sample was removed from the glass slide and placed on the surface of the base plate of a 25mm rheometer.

[0495] Vibrational temperature sweeps were performed using a TA Instruments Discovery HR-2 rheometer. Strain vibrational amplitude sweeps were performed on adhesive samples at 25°C to determine the nominal vibrational strain amplitude. The storage modulus curve and loss modulus curve were found to be constant, and 1% strain was selected (Figures 11 and 12). Logarithmic sweeps were performed at angular frequencies from 1.0 to 100.0 rad / s in 5 points / decade, in 5°C steps over temperature sweeps from 0°C to 50°C (Figures 10 and 13). The high loss modulus of L6 was observed by high tan(delta) values ​​between 0.5 at low frequencies and 0.9 at high frequencies. In contrast, the comparative samples (represented as "butyl acrylate (2-droplet TMPTA)" (b), "butyl acrylate (3-droplet TMPTA)" (c), and "butyl acrylate (4-droplet TMPTA)" (d)) had significantly lower loss moduli, close to approximately 0.1, across the entire frequency range.

[0496] 4.7.14. Example 14 Adhesive samples were prepared by photopolymerization of a monomer solution consisting of the following composition: 98.43 wt% LMA, 0.59 wt% TMPTA, and 0.98 wt% 2DMPA photoinitiator. Large quantities of monomer were extracted using an analytical balance and mixed using a FlackTek SpeedMixer (DAC 330-100 PRO) until a homogeneous solution was formed.

[0497] The prepolymer solution was formed by partially curing 90 g of monomer solution for 14 minutes in a "pre-curing" step under a continuous flow inert nitrogen atmosphere with a 365 nm UV light source (UVP CL-1000 UV crosslinking agent). Subsequently, 5 mL of the prepolymer solution was pipetteed onto silicone-impregnated paper fixed to a 1.0 mm thick glass slide and cured for a further 41 minutes under UV light in an inert nitrogen atmosphere. After removal from the crosslinking agent, the sample was sandwiched between another piece of silicone-impregnated paper fixed to a 1.0 mm thick glass slide, compressed to a thickness of 600-700 micrometers using a spring clamp, and post-cured for 1 hour at 120°C and atmospheric pressure before cooling to ambient temperature. The sample was observed to be optically clear to the naked eye.

[0498] Dynamic mechanical analysis (DMA) was performed using a Mettler Toledo DMA1-Star instrument. The sample was carefully cut into a disc with a thickness of approximately 0.80 mm and a diameter of 4.75 mm. The shear deformation mode was selected with a displacement limit of 1.0 micrometer. A temperature sweep was performed from -50°C to 100°C at a stepwise heating rate of 3°C / min. Furthermore, the deformation frequency was set to 2 Hz. The storage modulus and loss modulus were measured (Figure 14), and tan(δ) was measured (Figure 15).

[0499] 4.7.15. Example 15 LMA, TMPTA, and 1.0 wt% DMPA photoinitiator were mixed until a homogeneous solution was formed. This mixture was then UV-cured in a polypropylene box (samples approximately 0.1–1.0 mm thick) under nitrogen at 365 nm in UVP CL-1000 crosslinking agent for 45 minutes. The samples were then post-cured at 120°C for approximately 1 hour under ambient conditions. After post-curing at 120°C, the optically clear samples were cooled to room temperature and appeared optically clear to the naked eye. The samples exhibited excellent tackiness against human skin and could be removed with minimal or no pain.

[0500] Samples were also prepared separately using a photoreactor. A magnetic stirring plate was placed under the UVP CL-1000L crosslinking agent, and approximately 100 mL of homogeneous LMA, TMPTA, and 1.0 wt% DMPA photoinitiator were irradiated at 365 nm for approximately 15–20 minutes while stirring at approximately 180 RPM using a magnetic stirrer, after which viscosity increased and all more uniform adhesive film coatings were prepared. Optionally, additional TMPA (10%, 20%, or 30% increase from the original TMPTA composition) was added after the first 15–20 minutes of irradiation and mixed at 800 rpm for 15 minutes using a FlackTek SpeedMixer (DAC 330-100 PRO) to ensure homogeneous mixing. Additional TMPTA was added considering the conversion of TMPTA used to build molecular weight and increase viscosity which might not be incorporated into the network. Adhesive coatings ranging in thickness from 0.025 mm to 1.75 mm, made from an increased viscosity prepolymer, were prepared from an increased viscosity LMA / TMPTA / DMPA mixture on silicone release liner paper under nitrogen and UVP CL-1000L crosslinking agent at 365 nm for 45 minutes and post-curing at 120°C for 1 hour. The release liner / adhesive coating layer can be sandwiched between additional silicone release liner paper and stored for further use, and the demonstrated process is consistent with its suitability for use in roll-to-roll UV coating of adhesives on release liners.

[0501] Rolls or sheets of adhesive can be manufactured into condom devices by a suitable transfer process for mating the adhesive to a latex, elastomer, or other polymer barrier layer. Furthermore, multiple layers of adhesive may be laminated together using a suitable roll-to-roll or sheet lamination process to form a composite adhesive layer of greater thickness as needed.

[0502] 4.7.16. Example 16 Monomer species and DMPA photoinitiator samples were prepared to form linear polymers. Using an analytical balance, three compositions were prepared: (a) 99.0% by weight of lauryl methacrylate (LMA) and 1.0% by weight of DMPA, (b) 99.0% by weight of lauryl acrylate (LA) and 1.0% by weight of DMPA, and (c) 99.0% by weight of butyl acrylate (BA) and 1.0% by weight of DMPA. Each solution was mixed at 400 rpm using a FlackTek SpeedMixer (DAC 330-100 PRO) until a homogeneous solution was obtained. Approximately 6 mL of the solution was pipetteed into 1-inch x 3-inch compartments in a polypropylene tray, for a total of 12 compartments per solution. The solutions were UV-cured for 1 hour under a nitrogen-inert atmosphere (UVP CL-1000 crosslinking agent), and then post-cured at 120°C for 1 hour. After post-curing, the sample cooled to ambient temperature was observed to be optically transparent.

[0503] Samples of each cured polymer in a 2 mg / mL solution were prepared in HPLC-grade THF. The solutions were filtered through a 0.22 micron PTFE filter, and 0.5 microliters were injected into a GPC along with THF and a polystyrene standard as the eluent. A flow rate of 1 mL / min and a light scattering detector were used. The BA sample was found to have an average molecular weight of 1,381,218 g / mol and a polydispersity index (PDI) of 1.2. The LMA sample was found to have an average molecular weight of 27,040 g / mol and a PDI of 2.4. The LA sample was found to have an average molecular weight of 759,767 g / mol and a PDI of 3.2.

[0504] 4.7.17. Example 17 A crosslinked adhesive sample was prepared by photopolymerizing a monomer solution of 98.43 wt% lauryl methacrylate and 0.59 wt% trimethylolpropane triacrylate (TMPTA) with 0.98 wt% 2,2-dimethoxy-2-phenylacetophenone (DMPA) photoinitiator (L6). A large volume of monomer was extracted using an analytical balance and mixed using a FlackTek SpeedMixer (DAC 330-100 PRO) until a homogeneous solution was formed. Approximately 3 mL of the solution was pipettered onto a 25 mm disposable aluminum rheometer baseplate (TA Instruments) and cured under an inert nitrogen atmosphere and a 365 nm UV lamp (UVP CL-1000 UV crosslinker) for 1 hour. The sample was then post-cured at 120°C for 1 hour at atmospheric pressure. The sample was then cooled to ambient temperature.

[0505] Comparative samples consisting of linear polymers were prepared by photopolymerization of monomer solutions of (a) 99.0 wt% lauryl methacrylate (LMA) and 1.0 wt% DMPA, and (b) 99.0 wt% butyl acrylate (BA) and 1.0 wt% DMPA, using an analytical balance. Each solution was mixed at 400 rpm using a FlackTek SpeedMixer (DAC 330-100 PRO) until a homogeneous solution was obtained. Approximately 6 mL of the solution was pipetteed into 1-inch x 3-inch compartments in a polypropylene tray, for a total of 12 compartments per solution. The solutions were UV-cured for 1 hour under a nitrogen-inert atmosphere (UVP CL-1000 crosslinking agent), and then post-cured at 120°C for 1 hour. After post-curing, the samples were cooled to ambient temperature and observed to be optically clear. Approximately 0.5 mL of polymer sample was scooped onto a 25 mm disposable aluminum rheometer base plate and allowed to stand for 30 minutes.

[0506] Frequency sweeps were performed using a TA Instruments Discovery HR-2 rheometer to measure the loss modulus and storage modulus. Strain vibration amplitude sweeps were performed on adhesive samples at 25°C to determine the nominal vibration-strain amplitude. The storage modulus curve and loss modulus curve were found to be constant, and 1% strain was selected. Logarithmic sweeps were performed at angular frequencies from 0.2 to 20.0 rad / s at 25°C, 50°C, 80°C, and 100°C. The ratio of the loss modulus to the storage modulus, tan(delta), has been reported, indicating high loss behavior (Figures 16-19).

[0507] Next, a constant torque of 500 micronewton meters was applied to the sample at 25°C, 50°C, 80°C, and 100°C, and the resulting shear rate and strain were measured over time for 180 seconds at 25°C and 50°C, and for 600 seconds at 80°C and 100°C (Figures 20-23).

[0508] Finally, tack strength was measured at 25°C, 50°C, 80°C, and 100°C (Figures 24 and 25). The sample was compressed by contacting it for 60 seconds, and then the rheometer tip was withdrawn at a speed of 100 micrometers / second to measure the axial force. The peak tack force of L6 was found to be 3.8 N at 25°C, 2.0 N at 50°C, 1.3 N at 80°C, and 0.9 N at 100°C. The LMA comparison sample was found to have a peak tack force of 6.0 N at 25°C and 3.7 N at 80°C. The BA comparison sample was found to have a peak tack force of 4.1 N at 80°C.

[0509] The same process was repeated for the comparison samples, yielding peak tack forces of 5 N, 6 N, and 4 N for samples (a), (b), and (c) against aluminum. The adhesive strength, measured in Newton-seconds (Ns), was calculated by integrating the area under the force-time measurements for each sample, yielding 88.4 Ns for the adhesive and 9.6 Ns, 5.9 Ns, and 3.8 Ns for the comparison samples (a), (b), and (c). The tack energy of the adhesive was also calculated by multiplying the adhesive strength integral by a constant pull-out rate of 100 micrometers / second, yielding 8.84 × 10⁻¹⁶ for the adhesive. -3 For Joules (J), comparative samples (a), (b), and (c), the values ​​are 0.96 × 10⁻⁶ each. -3 J, 0.59 × 10 -3 J and 0.38 × 10 -3 I gained J's attack energy.

[0510] 4.7.18. Example 18 Sol-gel analysis was performed on UV-cured samples in dichloromethane (DCM) according to known methods. Cured polymer samples in masses ranging from approximately 0.2 g to 0.6 g were mass-measured in tare-filled glass vials and then placed in approximately 40 mL of DCM in sealed glass vials. The vials were mixed in a RapidVap vortex apparatus at 35 RPM at approximately 25°C for 24 hours, followed by decanting with DCM to obtain a consistent gel. This gel was then highly swollen in DCM and dried in a commercially available chemical ventilation hood at ambient temperature and pressure for 24 hours, followed by further drying at 60°C for 3 hours and then at 120°C for 2 hours. The final mass of the remaining sample / vial was taken, and the gel fraction was calculated by dividing the final polymer mass by the initial polymer mass. Representative data are shown in Table 1 and Figure 32. [Table 1]

[0511] Despite high weight and molar ratios (within 2 × crosslinking density), the adhesives exhibited similar gel fractions in the range of 0.70–0.90.

[0512] 4.7.19. Example 19 A series of condoms were manufactured using lauryl acrylate (LA) and styrene-based adhesives containing L6, L6+10 wt% increased TMPTA, L6+20 wt% increased TMPTA, L6+30 wt% increased TMPTA, and 0.6 wt% TMPTA. Condoms in approximately 1 inch x 2 inch rectangular or 1 inch circular shapes were prepared by transferring an approximately 3 inch x 3 inch square of adhesive onto a latex dental dam with a diameter of approximately 0.20 mm. The thickness of the adhesive ranged from 200 microns to 800 microns.

[0513] The manufactured condoms were placed on the erect and flaccid penises of several individuals. In some cases, vaginal intercourse followed, while in others, manual stimulation was performed. Subsequently, the adhesive was removed from the penises, and pain was self-reported using a standard Wong-Baker type pictogram numerical pain scale ranging from 0 (no pain) to 10 (worst pain imaginable).

[0514] Furthermore, commercially available adhesive tapes, including Galactic Cap, FLEXcon medical adhesive, 3M Scotch brand clear packing tape, 3M Scotch brand Blue Painters tape, and 3M Post-it notes, were tested. The results are shown in Figure 33, and the number of samples per unit for each type of adhesive is reported in Table 2. [Table 2]

[0515] L6 and L6 variant samples were observed to typically take 3–15 seconds to remove, averaging 5–8 seconds. Galactic Cap samples took over 5 minutes to remove per case and required the use of coconut oil or hydrating lotion. Packing tape, FLEXcon medical adhesive, and Blue Painter's Tape all typically took 10–30 seconds to remove, depending on the surface area of ​​the sample. Post-it notes were relatively painless and quick to remove (1–5 seconds), but had relatively low adhesive strength.

[0516] 5. Incorporation by equivalents and references While the provided disclosure is specifically illustrated and described with reference to preferred embodiments and various alternative embodiments, those skilled in the art will understand that various modifications in form and detail can be made herein without departing from the spirit and scope of the provided disclosure.

[0517] All references, published patents, and patent applications cited herein are incorporated herein by reference in their entirety for all purposes. In particular, U.S. Provisional Patent Applications 63 / 381,071 (filed October 26, 2022); 63 / 381,653 (filed October 31, 2022); 63 / 493,761 (April 2, 2023); 63 / 501,237 (filed May 10, 2023); 63 / 493,762 (filed April 2, 2023); and 63 / 501,238 (filed May 10, 2023) are incorporated herein by reference in their entirety. Furthermore, the following PCT patent applications filed concurrently with this application are also incorporated herein by reference in their entirety. • An application titled "STIMULUS-RESPONSIVE, REVERSIBLE ADHESIVE MEDICAL COMPOSITIONS, ARTICLES AND METHODS" was filed on October 26, 2023, under agent reference number 41822-57382 (002WO).

Claims

1. It is a condom, A barrier layer, including an inner and outer surface, suitable for preventing the passage of semen, The barrier layer comprises an adhesive layer bonded to at least a portion of its inner surface, The condom is configured to adhere the adhesive layer to the glans of the penis of a human subject. The condom is configured to provide partial coverage of the penis, The adhesive layer comprises an adhesive containing a stimulus-responsive polymer formed from one or more monomers and optionally one or more polyfunctional crosslinking agents. When the condom is applied to the penis, the adhesive layer adheres to the glans of the penis. The adhesive layer of the condom can be removed from the glans of the penis after the application of stimulation to the condom.

2. The condom according to claim 1, wherein the condom is sized and shaped such that when applied to the penis, the condom does not come into contact with the coronal sulcus of the penis.

3. The condom according to claim 1 or 2, wherein the condom is sized and shaped such that when applied to the penis, the condom does not come into contact with the shaft of the penis.

4. The condom according to any one of claims 1 to 3, wherein the barrier layer includes a membrane or film.

5. The condom according to any one of claims 1 to 4, wherein the barrier layer comprises natural latex rubber, synthetic rubber, amorphous polyurethane, semicrystalline polyurethane (including various thermoplastic polyurethanes, polyethylene, polypropylene, polydimethylsiloxane and other silicone rubbers), polyethylene terephthalate, poly(vinyl chloride), polyisoprene, vulcanized polyisoprene or other vulcanized or crosslinked rubber, ethylene vinyl acetate, poly(vinyl acetate), elastomer or flexible material, or a combination thereof.

6. The condom according to claim 5, wherein the barrier layer comprises natural latex rubber, synthetic rubber, or polyurethane.

7. The condom according to any one of claims 1 to 6, wherein the barrier layer exhibits stimulus-responsive behavior that enables selective permeability, controlled permeability, or controlled porosity.

8. The condom according to claim 7, wherein the stimulus of the stimulus-responsive barrier layer is selected from temperature changes, physicochemical changes, light, ultrasound, ionic intensity changes, pH changes, magnetic fields, mechanical actions, or mechanical forces.

9. The condom according to claim 7 or 8, wherein the irritation of the irritation-responsive barrier layer is different from the irritation of the irritation-responsive polymer in the adhesive layer.

10. The condom according to claim 7 or 8, wherein the irritation of the irritation-responsive barrier layer is the same as the irritation of the irritation-responsive polymer in the adhesive layer.

11. The condom according to any one of claims 1 to 10, wherein the barrier layer has a thickness of 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, 0.001 mm to 0.01 mm, 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.

12. The condom according to any one of claims 1 to 11, wherein the barrier layer further comprises a reservoir of a size and shape suitable for collecting semen ejaculated from the penis.

13. The condom according to claim 12, wherein the reservoir is configured distal to the urethral opening of the penis.

14. The condom according to claim 11 or 12, wherein the reservoir is spherical or cylindrical.

15. The condom according to any one of claims 12 to 14, wherein the reservoir self-forms when subjected to pressure from ejaculation by the penis.

16. The condom according to any one of claims 12 to 15, wherein the reservoir includes a polymer coating that swells or gels upon contact with the semen.

17. The condom according to claim 16, wherein the polymer coating comprises chitosan, arginate, polyacrylic acid, crosslinked polyacrylic acid, sodium polyacrylate, crosslinked sodium polyacrylate, or a combination thereof.

18. The condom according to any one of claims 1 to 17, wherein the condom or the barrier layer has a planar or curved geometric shape selected from a square, circle, oval, hemisphere, rectangle, polygon, or curved polygon.

19. The condom according to claim 18, wherein the barrier layer has a circular geometric shape.

20. The condom according to claim 19, wherein 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.

21. The condom according to any one of claims 1 to 18, wherein the barrier layer has a rectangular geometric shape.

22. The condom according to claim 21, wherein the rectangle has a length of 0.5 cm to 5 cm and a width of 0.5 cm to 5 cm.

23. The condom according to any one of claims 18 to 22, wherein the condom or the barrier layer is planar.

24. The condom according to any one of claims 1 to 23, further comprising a lubricant on the outer surface of the barrier layer.

25. The condom according to claim 24, wherein the lubricant is selected from a water-based lubricant, a silicone-based lubricant, a polysaccharide-based lubricant, a natural lubricant, and an oil-based lubricant.

26. The condom according to any one of claims 1 to 25, further comprising a spermicide on the outer surface of the barrier layer in the form of a solution or gel.

27. The condom according to claim 26, wherein the spermicide is selected from nonoxynol-9, octoxynol-9, benzalkonium chloride, lactic acid, menfegol, and combinations thereof.

28. The condom according to any one of claims 1 to 27, further comprising an elastomer ring fixed to the outer portion of the inner surface of the barrier layer or to the edge of the barrier layer.

29. The condom according to claim 28, further comprising one or more protruding arms connected to the elastomer ring.

30. The condom according to any one of claims 1 to 29, wherein the adhesive layer is bonded only to a portion of the inner surface of the barrier layer.

31. The condom according to claim 30, wherein the adhesive is bonded to the outer portion of the inner surface of the barrier layer.

32. The condom according to any one of claims 1 to 29, wherein the adhesive layer has the same extent as the inner surface of the barrier layer.

33. The condom according to any one of claims 1 to 32, wherein the adhesive layer has a patterned configuration.

34. The condom according to any one of claims 1 to 33, wherein the adhesive layer has a thickness of 0.1 microns to 3,000 microns, for example, 1 micron to 2,000 microns, 25 microns to 1,000 microns, 25 microns to 750 microns, or 25 microns to 500 microns.

35. The condom according to any one of claims 1 to 34, wherein the stimulus-responsive polymer becomes less adhesive or peels off from the glans of the penis in response to the stimulus within 0.1 to 60 seconds, preferably 2 to 30 seconds, more preferably 1 to 15 seconds.

36. The condom according to claim 35, wherein the stimulus is selected from temperature changes, physicochemical changes, light, ultrasound, ionic intensity changes, pH changes, magnetism, or mechanical action or mechanical force.

37. The condom according to claim 36, wherein the stimulus is a mechanical action.

38. The condom according to claim 37, wherein the mechanical action is the shear rate.

39. The condom according to claim 38, wherein the shear rate is induced by pulling, peeling, or rubbing at various speeds.

40. The condom according to any one of claims 1 to 39, wherein the irritation-responsive polymer has lower peeling strength at a lower peeling rate and higher peeling strength at a higher peeling rate.

41. The condom according to any one of claims 1 to 40, wherein the irritation-responsive polymer has a peeling strength at a lower peeling speed that is at least 5% lower, for example, at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower, compared to the peeling strength at a higher peeling speed.

42. The condom according to any one of claims 1 to 41, wherein the irritation-responsive polymer has a lower peeling strength at a peeling speed of 100 mm / min than at 200 mm / min.

43. The condom according to any one of claims 1 to 41, wherein the irritation-responsive polymer has a lower peeling strength at a peeling speed of 100 mm / min than at 300 mm / min.

44. The condom according to any one of claims 1 to 43, wherein the irritation-responsive polymer has a peeling strength of 1 to 400 N / m, preferably 1 to 300 N / m, more preferably 1 to 200 N / m, and even more preferably 1 to 100 N / m at a peeling rate of 100 mm / min, and the peeling strength is determined by a 180° peeling test using a human skin substrate analog.

45. The condom according to any one of claims 1 to 44, wherein the stimulus-responsive polymer has (a) a tack strength of at least 1 N, for example 1 N to 5 N, at 25°C, or (b) an adhesive strength of at least 20 N*s, for example at least 50 N*s, or at least 100 N*s, at 25°C.

46. The condom according to any one of claims 1 to 45, wherein 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, 0.1 MPa to 0.5 MPa, or 0.1 to 0.3 MPa.

47. The condom according to any one of claims 1 to 46, wherein the stimulus-responsive polymer has a loss modulus of elasticity of 0.1 MPa to 1 MPa, preferably 0.1 MPa to 0.8 MPa, and more preferably 0.1 MPa to 0.5 MPa.

48. The condom according to any one of claims 1 to 47, wherein the stimulus-responsive polymer has a tan(δ) (ratio of storage modulus (G'') to loss modulus (G'')) of 0.1 to 2 at 25°C and 1 Hz, for example, 0.1 to 1.5, 0.1 to 1, 0.1 to 0.5, 0.3 to 1, 0.5 to 1, or 0.5 to 2.

49. The condom according to any one of claims 1 to 48, wherein the stimulus-responsive polymer has less tack when wet compared to when dry.

50. The condom according to any one of claims 1 to 49, wherein, after the adhesive layer is adhered to the glans of the penis, removal of the condom from the glans of the penis by light peeling induces minimal or no pain as measured by the WBQPA, for example, a WBQPA score of less than 4, less than 3, less than 2, less than 1, or 0.

51. The condom according to claim 36, wherein the stimulus is a change in temperature.

52. The condom according to claim 51, wherein the adhesive layer adheres to the glans of the penis at a temperature of 37°C, and has low adhesion or peels off from the glans of the penis at a temperature of 25°C or lower.

53. The condom according to claim 36, wherein the stimulus is a physicochemical change, and the physicochemical change is the dissolution of the composition when it comes into contact with a solvent.

54. The condom according to claim 53, wherein the adhesive layer adheres to the glans of the penis in the absence of the solvent, and when it comes into contact with the solvent, it exhibits low adhesion or peels off from the glans of the penis.

55. The condom according to any one of claims 1 to 54, wherein the stimulus-responsive polymer has a glass transition temperature (Tg) of 0°C to 50°C, preferably 0°C to 40°C, more preferably 5°C to 40°C.

56. The condom according to any one of claims 1 to 55, wherein the stimulus-responsive polymer is a crosslinked polymer.

57. The condom according to claim 56, wherein the crosslinked polymer has a heterogeneous crosslinking density.

58. The condom according to claim 56 or 57, wherein the crosslinked polymer comprises one or more C6-C30 side chains or one or more C6-C30 dangling chain ends.

59. The condom according to claim 58, wherein the C6-C30 side chain or C6-C30 dangling chain end is a C6-C30 alkyl side chain, preferably a C12-C18 alkyl side chain.

60. The condom according to any one of claims 56 to 59, wherein the crosslinked polymer is a semi-interpenetrating network, or the crosslinked copolymer is an interpenetrating network.

61. The condom according to any one of claims 1 to 60, wherein the stimulus-responsive polymer comprises monomers selected from acrylate monomers, methacrylate monomers, vinyl ether monomers, allyl monomers, thiol monomers, epoxy monomers, amine monomers, electron-rich monomers, electron-poor monomers, lactam monomers, lactone monomers, alcohol monomers, carboxylic acid monomers, isocyanate monomers, Diels-Alder monomers, ring-opening metathesis monomers, or combinations thereof.

62. The condom according to claim 61, wherein the stimulus-responsive polymer comprises an acrylate monomer.

63. The condom according to claim 62, wherein the acrylate monomer is a C6-C30 alkyl acrylate monomer, preferably a C8-C20 alkyl acrylate monomer, preferably a C8-C20 alkyl acrylate monomer, and more preferably a C8-C16 alkyl acrylate monomer.

64. The condom according to claim 63, wherein the C8-C30 alkyl acrylate monomer is selected from octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate, nonadecyl acrylate, eicosyl acrylate, heneicosyl acrylate, docosyl acrylate, tricosyl acrylate, tetracosyl acrylate, pentacosyl acrylate, hexacosyl acrylate, heptacosyl acrylate, octacosyl acrylate, nonacosyl acrylate, triacontyl acrylate, and combinations thereof.

65. The acrylate monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, methoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, ethoxylated (2) 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, and ethoxylated trimethylolpropane triacrylate. Acrylate, propoxylated glycerol triacrylate, stearyl acrylate, lauryl acrylate, isodecyl acrylate, acrylic acid, ethylene glycol diacrylate (EGDA), triethylene glycol diacrylate (TEGDA), propylene glycol diacrylate (PGDA), butanediol diacrylate (BDDA), neopentyl glycol diacrylate (NPGDA), pentaerythritol tetraacrylate (PET A) 1,4-butanediol diacrylate (BDA), di(trimethylolpropane)tetraacrylate (DTMPTA), bisphenol A ethoxylate diacrylate (BPAEDA), ethoxylated bisphenol A diacrylate (EBPA), decanediol diacrylate, polyethylene glycol diacrylate (PEGDA), trimethylolpropane triacrylate (TMPTA), diethylene glycol diacrylate (DEGDA), 1,The condom according to claim 62, selected from 6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate (TPGDA), pentaerythritol triacrylate (PETA), dipentaerythritol pentaacrylate (DPEPA), tris(2-hydroxyethyl) isocyanurate triacrylate (THEIC-TA), triethylene glycol dimethacrylate (TEGDMA), triallyl isocyanurate (TAIC), triethylene glycol diacrylate (TEGDA), ethoxylated trimethylolpropane triacrylate (ETMPTA), triallyl cyanurate (TAC), and combinations thereof.

66. The condom according to any one of claims 62 to 65, wherein the stimulus-responsive polymer comprises at least 10% by weight, for example, at least 50% by weight, at least 65% by weight, at least 95% by weight, at least 96% by weight, at least 97% by weight, at least 98% by weight, or at least 99% by weight of an acrylate monomer.

67. The condom according to claim 61, wherein the stimulus-responsive polymer comprises a methacrylate monomer.

68. The condom according to claim 67, wherein the methacrylate monomer is a C6-C30 alkyl methacrylate monomer, preferably a C8-C30 alkyl methacrylate monomer, more preferably a C8-C20 alkyl methacrylate monomer, and more preferably a C8-C16 alkyl methacrylate monomer.

69. The condom according to claim 68, wherein the C8-C30 alkyl methacrylate monomer is selected from octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, eicosyl methacrylate, heneicosyl methacrylate, docosyl methacrylate, tricosyl methacrylate, tetracosyl methacrylate, pentacosyl methacrylate, hexacosyl methacrylate, heptacosyl methacrylate, octacosyl methacrylate, nonacosyl methacrylate, triacontyl methacrylate, and combinations thereof.

70. The methacrylate monomers mentioned above include ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, stearyl methacrylate, lauryl methacrylate, isodecyl methacrylate, tetrahydrofurfuryl methacrylate, glyceryl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetramethacrylate, poly(ethylene glycol) monomethyl ether methacrylate, poly(ethylene glycol) monomethyl ether acrylate, and poly(ethylene glycol) The condom according to claim 67, selected from 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.

71. The condom according to any one of claims 67 to 70, wherein the stimulant-responsive polymer comprises poly(lauryl methacrylate).

72. The condom according to any one of claims 67 to 71, wherein the irritation-responsive polymer comprises poly(lauryl methacrylate) and one or more other polymethacrylates.

73. The condom according to any one of claims 67 to 71, wherein the irritation-responsive polymer adhesive comprises poly(lauryl methacrylate) and one or more polyacrylates.

74. The condom according to any one of claims 67 to 73, wherein the stimulus-responsive polymer comprises at least 10% by weight, for example, at least 50% by weight, at least 65% by weight, at least 95% by weight, at least 96% by weight, at least 97% by weight, at least 98% by weight, or at least 99% by weight of a methacrylate monomer.

75. The condom according to claim 61, wherein the stimulus-responsive polymer comprises vinyl ether monomers selected from 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-cyclohexanedimethanol divinyl ether (DVE-CHDM), neopentyl glycol divinyl ether (DVE-NPG), and combinations thereof.

76. The condom according to claim 75, wherein the stimulus-responsive polymer further comprises acrylate monomer, methacrylate monomer, allyl monomer, thiol monomer, epoxy monomer, amine monomer, electron-rich monomer, electron-poor monomer, lactam monomer, lactone monomer, alcohol monomer, carboxylic acid monomer, isocyanate monomer, Diels-Alder monomer, ring-opening metathesis monomer, or a combination thereof.

77. The aforementioned stimulus-responsive polymers include diallyl phthalate (DAP), diallyl maleate (DAM), diallyl succinate (DAS), diallyl fumaraate (DAF), diallyl adipate (DAA), diallyl sebacate (DAS), diallyl terephthalate (DAT), diallyl isophthalate (DAI), diallyl taconate (DAI), diallyl carbonate (DAC), diallyl diglycolate (DADG), diallyl tris(2-hydroxyethyl) isocyanurate (DATHEIC), and triallyl cyanurate (TAC). The condom according to claim 61, comprising an allyl monomer selected from trialyl isocyanurate (TAIC), trialyl trimelitate (TATM), trialyl citrate (TAC), trialyl phosphate (TAP), trialylamine (TAA), trialyl cyanide (TACN), trialylbenzene-1,2,4-tricarboxylate (TABTC), trialyl trimesate (TATM), tris(2-hydroxyethyl) isocyanurate trialyl ether (THEIC-TAE), and combinations thereof.

78. The condom according to claim 77, wherein the stimulus-responsive polymer further comprises acrylate monomer, methacrylate monomer, vinyl ether monomer, thiol monomer, epoxy monomer, amine monomer, electron-rich monomer, electron-poor monomer, lactam monomer, lactone monomer, alcohol monomer, carboxylic acid monomer, isocyanate monomer, Diels-Alder monomer, ring-opening metathesis monomer, or a combination thereof.

79. The aforementioned stimulus-responsive polymers include: 3-mercaptopropionic acid; thioglycolic acid; 3-mercapto-1-propanol; 2-mercaptoethanol; 2-(2-mercaptoethoxy)ethanol; 2-(2-mercaptopropionylamino)ethanol; 2-(2-mercaptosuccinyl)ethyl acrylate; 3-(2-mercaptopropionylamino)propionic acid; 3-(mercaptopropyl)trimethoxysilane; 2,2'-(ethylenebis(thio))diethanol; 3-mercaptopropyltrimethoxysilane; 3-mercaptopropylmethyldimethoxysilane; 3-(2,2-dithiobis(ethylthio)propionylamino)propionic acid; 3,6,9-trioxadecanethiol; 3-mercapto-1,2-propanediol; 2,2'-dithiodiethanol; N-acetyl-L-cysteine; L-cysteine; 2-( The condom according to claim 61, comprising thiol monomers selected from 2-mercaptoethyl)pyridine; 4-(2-mercaptoethyl)morpholine; 3-mercapto-1,2,4-triazole; thiophenol; pentaerythritol tetrakis(3-mercaptopropionate) (PETMP); trimethylolpropane tris(3-mercaptopropionate) (TMPMP); triethanolamine tris(3-mercaptopropionate) (TEAMP); tris(2-hydroxyethyl)isocyanurate tris(3-mercaptopropionate) (THEIMP); bis(3-mercaptopropyl) sulfide (BMPS); 1,2-ethanedithiol (EDT); 1,3-propanedithiol; 1,4-butanedithiol; 1,6-hexanedithiol; 1,8-octanedithiol and combinations thereof.

80. The condom according to claim 79, wherein the stimulus-responsive polymer further comprises acrylate monomer, methacrylate monomer, vinyl ether monomer, allyl monomer, epoxy monomer, amine monomer, electron-rich monomer, electron-poor monomer, lactam monomer, lactone monomer, alcohol monomer, carboxylic acid monomer, isocyanate monomer, Diels-Alder monomer, ring-opening metathesis monomer, or a combination thereof.

81. The condom according to claim 61, wherein the stimulus-responsive polymer comprises epoxy monomers selected from bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE), novolac diglycidyl ether (NGDE), phenol novolac diglycidyl ether (PNGDE), alicyclic epoxy resins, glycidyl ethers of aliphatic alcohols, glycidyl ethers of aromatic alcohols, triglycidyl isocyanurate (TGIC), diglycidyl ether of 1,4-butanediol (BDDGE), diglycidyl ether of neopentyl glycol (NPGDGE), diglycidyl ether of propylene glycol (PGDGE), epoxidized soybean oil (ESO), epoxidized linseed oil (ELO), dicyclopentadiene-based epoxy resins, tetrafunctional epoxy resins, epoxyphenol novolac resins, and combinations thereof.

82. The condom according to claim 81, further comprising acrylate monomer, methacrylate monomer, vinyl ether monomer, allyl monomer, thiol monomer, amine monomer, electron-rich monomer, electron-poor monomer, lactam monomer, lactone monomer, alcohol monomer, carboxylic acid monomer, isocyanate monomer, Diels-Alder monomer, ring-opening metathesis monomer, or a combination thereof.

83. The condom according to claim 61, wherein the stimulus-responsive polymer comprises an amine monomer selected from ethylenediamine; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; polyethyleneimine; diaminopropane; diaminobutane; diaminopentane; diethylenetriaminepentaacetic acid (DTPA); tris(2-aminoethyl)amine; N-(2-aminoethyl)piperazine; N-(3-aminopropyl)morpholine; N,N-dimethylaminopropylamine; N,N-dimethylethylenediamine; 1,3-diaminopropane; isophoronediamine; Jeffamine D-230; Jeffamine T-403; Jeffamine M-207; Jeffamine EDR-148; and combinations thereof.

84. The condom according to claim 83, wherein the stimulus-responsive polymer further comprises acrylate monomer, methacrylate monomer, vinyl ether monomer, allyl monomer, thiol monomer, epoxy monomer, electron-rich monomer, electron-poor monomer, lactam monomer, lactone monomer, alcohol monomer, carboxylic acid monomer, isocyanate monomer, Diels-Alder monomer, ring-opening metathesis monomer, or a combination thereof.

85. The condom according to claim 61, wherein the stimulus-responsive polymer comprises an electron-rich monomer selected from vinyl ethers (e.g., vinyl methyl ether, vinyl ethyl ether), vinyl acetate, allyl alcohol, allylamine, N-methylolacrylamide, N-methylolmethacrylamide, N-methylolallylamine, N-methylolvinylacetamide, acrolein diethyl acetal, acrolein diethyl ketal, diacetone acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycidyl methacrylate, glycidyl acrylate, tetrahydrofurfuryl methacrylate, and N-vinylpyrrolidone, n-vinylformamide, n-vinylpyridine, styrene, styrene derivatives, and combinations thereof.

86. The condom according to claim 85, wherein the stimulus-responsive polymer further comprises acrylate monomer, methacrylate monomer, vinyl ether monomer, allyl monomer, thiol monomer, epoxy monomer, amine monomer, electron-poor monomer, lactam monomer, lactone monomer, alcohol monomer, carboxylic acid monomer, isocyanate monomer, Diels-Alder monomer, ring-opening metathesis monomer, or a combination thereof.

87. The condom according to claim 61, wherein the stimulus-responsive polymer comprises an electron-poor monomer selected from 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.

88. The condom according to claim 87, wherein the stimulus-responsive polymer further comprises acrylate monomer, methacrylate monomer, vinyl ether monomer, allyl monomer, thiol monomer, epoxy monomer, amine monomer, electron-rich monomer, lactam monomer, lactone monomer, alcohol monomer, carboxylic acid monomer, isocyanate monomer, Diels-Alder monomer, ring-opening metathesis monomer, or a combination thereof.

89. The condom according to claim 61, wherein the stimulant-responsive polymer comprises a lactam monomer selected from caprolactam, valerolactam, enantractam, caprylactam, laurin lactam, prolactam, butyrolactam, methionyl lactam, methoxyethyl lactam, methoxyethylmethionyl lactam, dimethylaminoethyl lactam, dimethylaminoethylmethionyl lactam, dimethylaminoethyl acryloyl lactam, dimethylaminoethyl methacryloyl lactam, N-vinylpyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, and combinations thereof.

90. The condom according to claim 89, wherein the stimulus-responsive polymer comprises an acrylate monomer, a methacrylate monomer, a vinyl ether monomer, an allyl monomer, a thiol monomer, an epoxy monomer, an amine monomer, an electron-rich monomer, an electron-poor monomer, a lactone monomer, an alcohol monomer, a carboxylic acid monomer, an isocyanate monomer, a Diels-Alder monomer, a ring-opening metathesis monomer, or a combination thereof.

91. The condom according to claim 61, wherein the stimulus-responsive polymer comprises a lactone monomer selected from β-propiolactone, γ-butyrolactone, 8-valerolactone, ε-caprolactone, ω-pentadecalactone, β-butyrolactone, 8-decalactone, ε-decalactone, γ-decalactone, 8-dodecalactone, γ-dodecalactone, α-methylene-γ-butyrolactone, β-methyl-y-butyrolactone, β-methyl-γ-valerolactone, γ-hexalactone, and combinations thereof.

92. The condom according to claim 91, wherein the stimulus-responsive polymer further comprises acrylate monomer, methacrylate monomer, vinyl ether monomer, allyl monomer, thiol monomer, epoxy monomer, amine monomer, electron-rich monomer, electron-poor monomer, lactam monomer, alcohol monomer, carboxylic acid monomer, isocyanate monomer, Diels-Alder monomer, ring-opening metathesis monomer, or a combination thereof.

93. The condom according to claim 61, wherein the stimulus-responsive polymer comprises an alcohol monomer selected from ethylene glycol; propylene glycol; 1,3-butanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 1,10-decanediol; neopentyl glycol; diethylene glycol; triethylene glycol; tetraethylene glycol; polyethylene glycol (PEG); polypropylene glycol (PPG); polycaprolactone diol; polymethylolpropane; hydroxypivalyl hydroxymethyl butyrate (HPHMB); 1,4-cyclohexanedimethanol; and combinations thereof.

94. The condom according to claim 93, wherein the stimulus-responsive polymer further comprises acrylate monomer, methacrylate monomer, vinyl ether monomer, allyl monomer, thiol monomer, epoxy monomer, amine monomer, electron-rich monomer, electron-poor monomer, lactam monomer, lactone monomer, carboxylic acid monomer, isocyanate monomer, Diels-Alder monomer, ring-opening metathesis monomer, or a combination thereof.

95. The condom according to claim 61, wherein the stimulus-responsive polymer comprises a carboxylic acid monomer selected from adipic acid, succinic acid, glutaric acid, sebacic acid, malonic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, itaconic acid, citric acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, dodecanedioic acid, and combinations thereof.

96. The condom according to claim 95, wherein the stimulus-responsive polymer further comprises acrylate monomer, methacrylate monomer, vinyl ether monomer, allyl monomer, thiol monomer, epoxy monomer, amine monomer, electron-rich monomer, electron-poor monomer, lactam monomer, lactone monomer, alcohol monomer, isocyanate monomer, Diels-Alder monomer, ring-opening metathesis monomer, or a combination thereof.

97. The aforementioned stimulus-responsive polymers include 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, and Desmodur The condom according to claim 61, comprising isocyanate monomers selected from Z and combinations thereof.

98. The condom according to claim 97, wherein the stimulus-responsive polymer further comprises acrylate monomer, methacrylate monomer, vinyl ether monomer, allyl monomer, thiol monomer, epoxy monomer, amine monomer, electron-rich monomer, electron-poor monomer, lactam monomer, lactone monomer, alcohol monomer, carboxylic acid monomer, Diels-Alder monomer, ring-opening metathesis monomer, or a combination thereof.

99. The condom according to claim 61, wherein the stimulus-responsive polymer comprises a Diels-Alder monomer selected from maleic anhydride, furan, cyclopentadiene, N-phenylmaleimide, anthracene, N-ethylmaleimide, N-phenylnorbornene, N,N-dimethylmaleimide, 2,5-dimethylfuran, tetracyanoethylene, methyl vinyl ketone, and combinations thereof.

100. The condom according to claim 99, wherein the stimulus-responsive polymer further comprises acrylate monomer, methacrylate monomer, vinyl ether monomer, allyl monomer, thiol monomer, epoxy monomer, amine monomer, electron-rich monomer, electron-poor monomer, lactam monomer, lactone monomer, alcohol monomer, carboxylic acid monomer, isocyanate monomer, ring-opening metathesis monomer, or a combination thereof.

101. The condom according to claim 61, wherein the stimulus-responsive polymer comprises norbornene, dicyclopentadiene (DCPD), cyclooctene, tetracyclododecene (TCD), cyclopentene, cycloheptene, cyclohexene, bicyclo[2.2.1]hepta-2-ene, bicyclo[2.2.2]octa-5-ene, tricyclo[5.2.1.0(2,6)]deca-8-ene (TCD-diene), and ring-opening metathesis monomers selected from combinations thereof.

102. The condom according to claim 101, wherein the stimulus-responsive polymer further comprises acrylate monomer, methacrylate monomer, vinyl ether monomer, allyl monomer, thiol monomer, epoxy monomer, amine monomer, electron-rich monomer, electron-poor monomer, lactam monomer, lactone monomer, alcohol monomer, carboxylic acid monomer, isocyanate monomer, Diels-Alder monomer, or a combination thereof.

103. The condom according to any one of claims 1 to 102, wherein the stimulus-responsive polymer further comprises a polyfunctional crosslinking agent.

104. The condom according to claim 103, wherein the polyfunctional crosslinking agent is selected from a bifunctional crosslinking agent, a trifunctional crosslinking agent, or a tetrafunctional crosslinking agent.

105. The condom according to claim 103 or 104, wherein the polyfunctional crosslinking agent is a trifunctional crosslinking agent.

106. The condom according to claim 105, wherein the trifunctional crosslinking agent is an acrylate crosslinking agent.

107. The condom according to claim 103, wherein the polyfunctional crosslinking agent is selected from poly(ethylene glycol) diacrylate, trimethylolpropane triacrylate; ethoxylated trimethylolpropane triacrylate; pentaerythritol tetraacrylate; ethoxylated pentaerythritol tetraacrylate; dipentaerythritol hexaacrylate; ethoxylated dipentaerythritol hexaacrylate; di, tri, tetra, penta, or hexa epoxide; polythiol; polyalkene; tris(2-acryloxyethyl) isocyanurate, ε-caprolactone-modified tris(2-acryloxyethyl) isocyanurate, ethoxylated glycerin triacrylate, ethoxylated glycerin triacrylate, pentaerythritol triacrylate, and combinations thereof.

108. The condom according to any one of claims 1 to 107, wherein the stimulus-responsive polymer comprises 0.1% to 1.5% by weight, preferably 0.2% to 1% by weight, and more preferably 0.4% to 0.8% by weight of a polyfunctional crosslinking agent.

109. The condom according to any one of claims 103 to 108, wherein the weight ratio of the one or more monomers to the one or more polyfunctional 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.

110. The condom according to claim 1, wherein the stimulus-responsive polymer comprises a poly(lauryl methacrylate) polymer crosslinked with one or more polyfunctional crosslinking agents.

111. The condom according to claim 110, wherein the polyfunctional crosslinking agent is selected from a bifunctional crosslinking agent, a trifunctional crosslinking agent, or a tetrafunctional crosslinking agent.

112. The condom according to claim 110 or 111, wherein the polyfunctional crosslinking agent is a trifunctional crosslinking agent.

113. The condom according to claim 112, wherein the trifunctional crosslinking agent is an acrylate crosslinking agent.

114. The condom according to claim 110, wherein the polyfunctional crosslinking agent is selected from poly(ethylene glycol) diacrylate, trimethylolpropane triacrylate; ethoxylated trimethylolpropane triacrylate; pentaerythritol tetraacrylate; ethoxylated pentaerythritol tetraacrylate; dipentaerythritol hexaacrylate; ethoxylated dipentaerythritol hexaacrylate; di, tri, tetra, penta, or hexa epoxide; polythiol; polyalkene; tris(2-acryloxyethyl) isocyanurate, ε-caprolactone-modified tris(2-acryloxyethyl) isocyanurate, ethoxylated glycerin triacrylate, ethoxylated glycerin triacrylate, pentaerythritol triacrylate, and combinations thereof.

115. The condom according to any one of claims 110 to 114, wherein the weight ratio of the lauryl methacrylate to the one or more polyfunctional 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.

116. The condom according to any one of claims 1 to 115, wherein the adhesive layer further comprises additives selected from tackifiers, plasticizers, pigments, fillers, fluorescent agents, flowing agents, wetting agents, surfactants, defoaming agents, rheology modifiers, colorants, penetration enhancers, stabilizers, antioxidants, and combinations thereof.

117. The condom according to any one of claims 1 to 116, wherein the adhesive layer is transparent.

118. A package comprising a condom according to any one of claims 1 to 117.

119. The package according to claim 118, wherein the package includes a flexible packaging body comprising foil, plastic, plastic-lined paper, foil-lined paper, or a combination thereof.

120. The package according to claim 118 or 119, selected from a blister pack design and a well design.

121. The package according to any one of claims 118 to 120, further comprising a delamination composition suitable for inducing delamination of the adhesive layer from the glans of the penis when the adhesive layer is adhered to the glans of the penis.

122. The package according to claim 121, wherein the layer release composition is a wipe.

123. The package according to claim 122, wherein the wipe contains a solvent that dissolves, modifies, or swells the stimulus-responsive polymer, thereby causing the adhesive layer to adhere to the glans of the penis, and subsequently, when the wipe is applied to the condom, it induces the peeling of the adhesive layer from the glans of the penis.

124. The package according to claim 122, wherein the wipe contains a volatile additive that cools the wipe when evaporated, thereby inducing the peeling of the adhesive layer from the glans of the penis when the adhesive layer adheres to the glans of the penis and the wipe is subsequently applied to the condom.

125. The package according to any one of claims 118 to 124, further comprising a lubricant, a spermicide, or a combination thereof.

126. (a) a condom according to any one of claims 1 to 117 or a package according to any one of claims 118 to 125, and (b) a kit comprising instructions for use.

127. A method for applying a condom according to any one of claims 1 to 117 to the penis of a human subject, To bring the adhesive layer of the condom into contact with the glans of the penis; and A method comprising applying sufficient pressure to the condom to adhere it to the glans of the penis.

128. The method according to claim 127, wherein the pressure is applied to one or more fingers or hands of the object.

129. A method for removing a condom according to any one of claims 1 to 117 from the penis of a human subject, Applying stimulation to the condom, which has an adhesive layer attached to the glans of the penis, and A method comprising removing the condom from the glans of the penis.

130. The method according to claim 129, wherein the stimulus is a mechanical action.

131. The method according to claim 130, wherein the mechanical action is the shear rate.

132. The method according to claim 131, wherein the shear rate is induced by pulling, peeling, or rubbing at various speeds.

133. The method according to claim 129, wherein the stimulus is a temperature change, and the application of the stimulus includes cooling the temperature of the condom to 25°C or below.

134. The method according to claim 129, wherein the stimulus is a physicochemical change, and the application of the stimulus comprises applying a wipe to the condom, the wipe comprising a solvent that dissolves, modifies or swells the stimulus-responsive polymer, thereby inducing the delamination of the adhesive layer from the glans of the penis.

135. The package according to claim 134, wherein the wipe contains a volatile additive that cools the wipe when it evaporates, thereby inducing the peeling of the adhesive layer from the glans of the penis when the wipe is applied to the condom.

136. The method according to any one of claims 129 to 135, wherein the condom is removed from the penis of the subject with minimal or no pain as measured by the WBQPA, for example, with a WBQPA score of less than 4, less than 3, less than 2, less than 1, or 0.

137. The method according to any one of claims 129 to 136, wherein when the condom is removed from the penis, less than 50% by weight of the adhesive, for example less than 40% by weight, less than 30% by weight, less than 20% by weight, or less than 10% by weight remains on the penis.

138. A method for preparing a condom according to any one of claims 1 to 117, A method for preparing a condom, comprising adhering an adhesive layer to a barrier layer, wherein the adhesive layer comprises an adhesive containing a stimulus-responsive polymer formed from one or more monomers and optionally one or more polyfunctional crosslinking agents.

139. The method according to claim 138, wherein the barrier layer includes a film or membrane.

140. The method according to claim 138 or 139, wherein the barrier layer comprises natural latex rubber, synthetic rubber, amorphous polyurethane, semicrystalline polyurethane (including various thermoplastic polyurethanes, polyethylene, polypropylene, polydimethylsiloxane and other silicone rubbers), polyethylene terephthalate, poly(vinyl chloride), polyisoprene, vulcanized polyisoprene or other vulcanized or crosslinked rubber, ethylene vinyl acetate, poly(vinyl acetate), elastomer or flexible material, or a combination thereof.

141. The method according to claim 140, wherein the barrier layer comprises natural latex rubber, synthetic rubber, or polyurethane.

142. The method according to any one of claims 138 to 141, wherein the stimulus-responsive polymer comprises poly(lauryl methacrylate).

143. The method according to any one of claims 138 to 142, wherein the stimulus-responsive polymer further comprises a polyfunctional crosslinking agent.

144. The method according to any one of claims 138 to 143, wherein the weight ratio of the one or more monomers to the one or more polyfunctional 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.

145. The method according to any one of claims 138 to 144, wherein the polyfunctional crosslinking agent is selected from poly(ethylene glycol) diacrylate, trimethylolpropane triacrylate; ethoxylated trimethylolpropane triacrylate; pentaerythritol tetraacrylate; ethoxylated pentaerythritol tetraacrylate; dipentaerythritol hexaacrylate; ethoxylated dipentaerythritol hexaacrylate; di, tri, tetra, penta, or hexa epoxide; polythiol; polyalkene; tris(2-acryloxyethyl) isocyanurate, ε-caprolactone-modified tris(2-acryloxyethyl) isocyanurate, ethoxylated glycerin triacrylate, ethoxylated glycerin triacrylate, pentaerythritol triacrylate, and combinations thereof.

146. The method according to claims 138 to 145, wherein the adhesive is first prepared and then applied to the barrier layer in a subsequent step to obtain the condom.

147. The method according to claims 138 to 145, wherein the adhesive is prepared directly on the barrier layer to obtain the condom.

148. For example, the method according to any one of claims 138 to 145, further comprising sterilizing the condom with gamma rays, an electron beam, ethylene oxide gas, moist heat, dry heat, or vaporized hydrogen peroxide.

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