Condom capable of enhancing feeling

Abstract

The present disclosure relates to contraceptive devices that provide enhanced sensation to a user. The contraceptive device comprises an adhesive comprising a stimuli-responsive polymer that is readily delaminated without pain upon application of a stimuli. The invention further discloses a partial condom covering the penis and the glans penis. Methods of applying and removing contraceptive devices, as well as methods of making contraceptive devices, are also provided.

Description

[0001] 1. Background

[0002] A female diaphragm or cervical cap is a device that acts as a contraceptive barrier method. It is inserted into the vagina and prevents sperm from passing through the cervix. Female diaphragms do not prevent the transmission of sexually transmitted infections (STIs). From a pleasure perspective, diaphragms provide near-optimal contact between the penis and vagina.

[0003] Conventional male condoms are latex or polyurethane devices that completely cover the penis and attempt to trap sperm within to prevent pregnancy and the transmission of certain STIs. Since condoms essentially cover the glans penis and the shaft of the penis, they reduce pleasure. This reduction in pleasure decreases condom use during sexual intercourse and leads to unwanted pregnancies or STI transmission, which in many cases significantly alters human lives and increases overall healthcare costs.

[0004] Partial male condoms (i.e., condoms with less coverage than conventional male condoms) are known in the art. GALACTIC CAP TM is a commercially available partial condom used to prevent pregnancy ( https: / / www.galacticcap.com / ). It is made of a polyurethane barrier layer with an adhesive backing that attaches to the glans penis and the shaft of the penis. However, it suffers from some important limitations. It can only be applied in an aroused state, and to some extent it still covers most of the shaft of the penis, and the user's pleasure is correspondingly limited. The condom is made of a material that cannot be used with oil-based lubricants, which are popular among users. This complex design makes the condom difficult to apply and increases the likelihood of user error. The condom is also difficult (embarrassing, painful) to remove. As shown in the instructions, removal requires the use of baby oil, and the recommended (simplest) removal method requires the user to urinate into the condom, inflate it, and then peel it off. This is not only embarrassing but 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 . Leakage has also been reported. The above limitations significantly limit the appeal of GALATIC CAP TM to consumers.

[0005] Other partial condoms have been reported in the prior art, which suffer from similar limitations.

[0006] Wondaleaf is a commercially available partial condom that includes an adhesive coating at the condom opening to adhere to the penile shaft and to itself to form the proximal portion of the condom and two side tabs. The loose barrier layer is made of polyurethane. The user removes the condom by grasping the tabs on the side of the device and pulling the condom distally while applying counterpressure to the penile skin. Similar to the GALATIC CAP TM , this device can only be used in an aroused state and still covers a large portion of the penile shaft to some extent, and the user's pleasure is correspondingly limited. The design is also complex and there is a risk of user error( https: / / www.wondaleaf.com / wondaleaf-cap / ).

[0007] WO2014178661A describes a partial condom that has a barrier layer made of polyurethane and has a discontinuous adhesive layer and a preformed semen reservoir that protrudes from the device before use (i.e., the condom is non-planar before use). The adhesive is said to be a double-sided tape, such as 3M double-sided tape, or generally a "medical adhesive layer" or a pressure-sensitive adhesive.

[0008] US11,234,858 describes a body fluid collection device that includes a fitting assembly and a collection membrane that is applied to the penis through an adhesive layer. The collection membrane provides a preformed semen container (i.e., the condom is non-planar before use). The fitting assembly and the collection membrane are generally discontinuous, and its structure is said to more effectively prevent semen leakage. The constituent material of the adhesive layer can include, for example, a pressure-sensitive adhesive.

[0009] A contraceptive device that is needed to prevent pregnancy and that provides enhanced sensation compared to existing contraceptive devices and is easy to apply and remove. 2. Summary of the Invention

[0010] On the one hand, the present disclosure provides a condom that includes a barrier layer adapted to prevent semen passage (the barrier layer includes an inner surface and an 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 penis of a human subject, the condom is configured to provide partial coverage of the penis (e.g., a sheath for the glans), and the adhesive layer contains an adhesive that includes a stimulus-responsive polymer formed from one or more monomers (e.g., acrylate or methacrylate monomers) and optionally one or more polyfunctional crosslinking agents (e.g., trifunctional crosslinking agents), wherein when the condom is applied to the penis, the adhesive layer adheres to the glans penis, and after applying a stimulus (e.g., mechanical stimulus) to the condom, the adhesive layer can be removed from the glans penis. In some embodiments, the partial condom is planar before use. In some embodiments, the barrier layer further includes a self-forming semen reservoir. In some embodiments, the adhesive layer coextends with the barrier layer. In some embodiments, the adhesive layer is the only means of securing the condom to the penis.

[0011] In some embodiments, the partial coverage is limited to the tip of the penis. In some embodiments, the partial coverage is limited to the glans penis. In some embodiments, the partial coverage does not include the penile shaft. In some embodiments, the partial coverage includes the base of the penis or below the base of the penis.

[0012] In some embodiments, the condom allows for on-demand delamination in response to a stimulus, wherein the delamination causes substantially no pain to the user and leaves substantially no residue, or the residue can be removed in an easy manner.

[0013] On the other hand, the present disclosure provides a package that includes the condom described herein.

[0014] Yet another aspect, the present disclosure provides a kit that includes (a) the condom described herein or a package containing the condom described herein, and (b) instructions for use.

[0015] In yet another aspect, the present disclosure provides a method of applying the condom disclosed herein to the penis of a human subject, including contacting the adhesive layer of the condom with the glans penis and applying sufficient pressure to the condom to adhere the condom to the glans penis.

[0016] In a further aspect, the present disclosure provides a method of removing the condom described herein from the penis of a human subject, including applying a stimulus to the condom whose adhesive layer is adhered to the glans penis and removing the condom from the glans penis.

[0017] 3. Brief Description of the Several Views of the Drawings

[0018] These and other features, aspects, and advantages of the present disclosure can be better understood in light of the following description and the accompanying drawings, where:

[0019] Figure 1 A - B shows perspective views of a condom with complex curvature (A) and a flat condom (B). In Picture A, the condom with complex curvature (a condom having a 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 an undesired surface and facilitates user handling. Optionally, the portion of the barrier layer covering the urethral opening (orifice) does not have adhesive (0104) to (a) reduce undesired adhesion to the urethra and (b) provide space for ejaculatory fluid to flow into a pre - formed or self - formed reservoir. In Picture B, the flat condom or a condom having a 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 an undesired surface and facilitates user handling. Optionally, there are holes (0104) in the adhesive layer in the device portion covering the urethral opening (orifice) such that (a) reduce adhesion to the urethra and (b) provide space for ejaculatory fluid to flow into a pre - formed or self - formed reservoir.

[0020] Figure 2 Shows a cross - section of a condom consisting of a barrier layer (0201) and a dual - adhesive pattern, the dual - adhesive pattern consisting of a primary adhesive (0202) and a gasket adhesive (0203). The primary adhesive (0202), such as a water - soluble adhesive, is responsible for attaching the device mainly to the glans penis, and the gasket adhesive (0203) can enhance the sealing effect of the device or separate the water - soluble primary adhesive from vaginal fluid or (pre) - ejaculatory fluid.

[0021] Figure 3 A - B shows cross - sections of an exemplary contraceptive diaphragm described herein, having (A) a constant thickness (0311) and (B) a non - constant thickness (0321).

[0022] Figure 4 Shows an adhesion strength graph of the adhesive according to Example 10.

[0023] Figure 5 Shows a graph of the tensile strain capacity of the adhesive according to Example 11.

[0024] Figure 6 Shows a graph of the tensile strain capacity of the adhesive according to Example 11.

[0025] Figure 7A graph showing the tensile strain capacity of the adhesive according to Example 11.

[0026] Figure 8 A graph showing the peel strength of the adhesive according to Example 12 in a 180-degree peel test using a human skin substrate analogue.

[0027] Figure 9 A graph showing the peel strength of the adhesive according to Example 12 in a 180-degree peel test using a glass substrate.

[0028] Figure 10 A graph showing the tan(δ) of the adhesive according to Example 13.

[0029] Figure 11 A graph showing the storage modulus and loss modulus of the adhesive according to Example 13.

[0030] Figure 12 An enlarged view of the loss modulus and storage modulus of the L6 adhesive, illustrating the crossover between the elastic and viscous states between 0.05 MPA and 8 rad / sec.

[0031] Figure 13 A graph showing the change in tan(δ) of the adhesive according to Example 13 in the temperature range of 0°C to 50°C.

[0032] Figure 14 DMA measurements showing the storage modulus (G’) and loss modulus (G”) of the L6 adhesive as a function of temperature.

[0033] Figure 15 DMA measurements showing the tan(δ) (ratio of loss modulus to storage modulus) of the L6 adhesive.

[0034] Figure 16 DMA measurements showing the storage modulus (G’) and loss modulus (G”) of the L6 adhesive as a function of temperature.

[0035] Figure 17 DMA measurements showing the tan(δ) (ratio of loss modulus to storage modulus) of the L6 adhesive.

[0036] Figure 18 DMA measurements showing the storage modulus (G’) and loss modulus (G”) of the LMA and BA adhesives as a function of temperature.

[0037] Figure 19 DMA measurements showing the tan(δ) (ratio of loss modulus to storage modulus) of the LMA and BA adhesives.

[0038] Figure 20Shows the angular strain of L6 adhesive at different temperatures.

[0039] Figure 21 Shows the shear rate of L6 adhesive at different temperatures.

[0040] Figure 22 Shows the angular strain of LMA and BA adhesives at different temperatures.

[0041] Figure 23 Shows the shear rate of LMA and BA adhesives at different temperatures.

[0042] Figure 24 Shows the adhesion strength of L6 adhesive at different temperatures.

[0043] Figure 25 Shows the adhesion strength of LMA and BA adhesives at different temperatures.

[0044] Figure 26 A - B shows a perspective view of a condom. Picture B shows a cross - sectional side view of an embodiment of Picture A.

[0045] Figure 27 Shows a side view of a partial condom.

[0046] Figure 28 Shows a cross - sectional side view of a partial condom including a pleated barrier layer and a pleated adhesive layer.

[0047] Figure 29 A - B shows a cross - sectional perspective view of a partial condom with a horizontally folded semen container.

[0048] Figure 30 A - B shows a flat condom adhered to the glans penis before ejaculation (A) and during ejaculation (B).

[0049] Figure 31 Shows a diagram of the mechanical properties related to the applicability of the expansion and regulation of ejaculation in an embodiment.

[0050] Figure 32 Shows the gel fraction of the sol - gel analysis of various adhesives in Example 18.

[0051] Figure 33 Shows the Wong - Baker qualitative pain assessment for removing various condoms according to Example 19.

[0052] 4. Detailed Description

[0053] 4.1. Definitions

[0054] When describing embodiments of the present disclosure, unless otherwise specified, the following terms (if any) have the following meanings. If not otherwise defined, the terms have their customary meanings in the relevant art.

[0055] Those skilled in the art will understand that, generally speaking, the terms used herein, especially the terms used in the appended claims (e.g., the subject matter of the appended claims), are generally intended to be "open" terms (e.g., the term "comprising" should be interpreted as "comprising but not limited to", the term "having" should be interpreted as "having at least", the term "including" should be interpreted as "including but not limited to", etc.). Those skilled in the art will further understand that if an intention to introduce a specific number of claim recitations is present, such intention will be explicitly recited in the claims, and if there is no such recitation, there is no such intention. For example, for the sake of understanding, the following appended claims may include the use of introductory phrases "at least one / kind" and "one / kind or more than one / kind" to introduce claim recitations. However, the use of such phrases should not be construed as implying that a claim recitation introduced by the indefinite article "a" or "an" limits any particular claim including such introduced claim recitation to only those embodiments that include only one / kind of such recitation, even when the same claim includes an introductory phrase "one / kind or more than one / kind" or "at least one / kind" and the indefinite article such as "a" or "an" (e.g., "a" and / or "an" should be interpreted as meaning "at least one / kind" or "one / kind or more than one / kind"); the same applies to the use of the definite article for introducing claim recitations. In addition, even when the specific number of introduced claim recitations is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted as meaning at least the recited number (e.g., a simple recitation of "two / kinds of recitations" without any other modifiers means at least two / kinds of recitations, or two / kinds or more than two / kinds of recitations). Further, in those cases where there is a convention similar to "at least one / kind of A, B, and C, etc.", generally speaking, such a structure is intended to enable those skilled in the art to understand the convention (e.g., "a system having at least one / kind of A, B, and C" will include but not be limited to systems having A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). In cases where there is a convention similar to "at least one / kind of A, B, or C, etc.", generally speaking, such a structure is intended to enable those skilled in the art to understand the convention (e.g., "a system having at least one / kind of A, B, or C" will include but not be limited to systems having A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). Those skilled in the art will further understand that, whether in the specification, claims, or drawings, almost any disjunctive word and / or phrase representing two or more alternative terms should be understood as contemplating the possibility of including one term, either term, or both terms. For example, the phrase "A or B" will be understood as including the possibilities of "A" or "B" or "A and B".

[0056] In addition, when describing the features or aspects of the present disclosure in terms of a Markush group, those skilled in the art will recognize that the present disclosure is thus also described in terms of any individual member or subgroup of members of the Markush group.

[0057] As will be understood by those skilled in the art, for any and all purposes, such as for providing a written description, all ranges disclosed herein also cover any and all possible subranges and combinations of their subranges. Any listed range can be readily considered to be fully described and capable of dividing the same range into at least equal halves, thirds, fourths, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third, upper third, etc. Those skilled in the art will also understand that all languages, such as "at most", "at least", "greater than", "less than", etc., include the recited numbers and refer to ranges that can subsequently be broken down into subranges as described above. Finally, as will be understood by those skilled in the art, a range includes each individual member. Thus, for example, a group having 1 - 3 articles refers to a group having 1, 2, or 3 articles. Similarly, a group having 1 - 5 articles refers to a group having 1, 2, 3, 4, or 5 articles, and so on.

[0058] As used herein, "adhesion" refers to the ability of a composition or material to adhere or "stick" to a substrate (e.g., skin). Adhesion is measured as the adhesive force in Newtons (N). The greater the adhesive force, the greater the number of Newtons required to peel one object from another.

[0059] As used herein, an "adhesive" refers to a composition or material that adheres to a substrate (e.g., skin or a barrier layer).

[0060] As used herein, "bio-based" refers to materials derived from natural sources.

[0061] As used herein, "biodegradable" means that the compositions used herein or the compositions can be degraded by living microorganisms such as fungi or bacteria, regardless of a specific time range, or can be degraded by environmental conditions suitable for life such as environmental humidity and atmospheric conditions.

[0062] As used herein, "compostable" refers to a composition or article that requires microorganisms, humidity, and heat to obtain a final compost product (CO2, water, inorganic compounds, and biomass). The difference between compostable and biodegradable is that compostable compositions and articles must decompose into natural elements within a specific time range. In one embodiment, the compositions and articles disclosed herein comply with the regulations of the US Composting Council, the Environmental Protection Agency, ASTM International, or Tuv Austria.

[0063] As used herein, "controlled porosity" means that pores that are normally closed are stimulated to open, thus allowing fluid passage as permitted by their rheological properties.

[0064] As used herein, "conventional condom" means a condom that includes a continuous elastic tubular wall having a closed distal end (tip) and an open proximal end, typically made of a thin flexible material such as latex or polyurethane, and providing coverage of the glans penis (i.e., the head of the penis) and the shaft of the penis during use. The length of a conventional condom in use is typically between about 7 inches and about 8 inches, but commercially available products can be up to 9 inches in length and as short as about 6.3 inches. Many condom brand manufacturers and products are known in the art. See, for example, https: / / www.trojanbrands.com / en / products / condoms and https: / / www.durexusa.com / collections / condoms, each of which is hereby incorporated by reference.

[0065] As used herein, "crosslink density" means the average molecular weight between crosslink points. (https: / / www.pcimag.com / articles / 104955-calculation-of-crosslink-den sity-of-thermoset-polymers). The theory of crosslink density was proposed by Flory et al. in the 1940s.

[0066] As used herein, "curing" means a chemical process of converting macromolecules into higher molecular weight polymers through crosslinking reactions.

[0067] As used herein, "debonding" means that the mechanism of debonding can vary and includes, for example, phase change, chemical reaction, crosslinking, and volume expansion.

[0068] As used herein, "elastomeric" or "elastomeric behavior" means that when a material is strained in a state in a region above a critical transition region, the material exhibits approximately linear elasticity or a combined linear elastic and plastic deformation stress / strain behavior such that the stress / strain hysteresis remains approximately constant.

[0069] As used herein, "flexible" or "flexible behavior" means the behavior of a rigid, viscoelastic, or elastomeric material that can be described as compliant or deformable to meet the requirements of a particular engineering application.

[0070] As used herein, "partial coverage" means far less penile coverage than a conventional condom. In certain embodiments, the partial condoms disclosed herein do not contact or cover the shaft of the penis. In certain embodiments, the partial condom does not contact or cover the corona and frenulum.

[0071] As used herein, "room temperature" (which may be used interchangeably with "ambient temperature") refers to a temperature of 20 - 25 °C.

[0072] As used herein, "selective permeability" refers to different permeation rates. For example, a membrane contains channels or pathways that allow specific molecules to pass through passively or actively, while not allowing other molecules to pass through. Active transport through the membrane requires an energy input, which can come from mechanical, acoustic, chemical, electrical, magnetic, pH changes, ionic strength, heat, or light sources.

[0073] As used herein, "Tg" refers to the glass transition temperature of a polymer. At this temperature, the polymer undergoes a transition from a glassy state to a rubbery state. Tg is an important characteristic of polymer behavior. It marks the region where significant changes in physical and mechanical properties occur. When below the Tg of the polymer, due to the lack of mobility, the polymer becomes hard and brittle. When above the Tg of the polymer, due to increased mobility, the polymer becomes soft and elastic.

[0074] As used herein, "stimulus response" refers to a change in the physical, environmental, physicochemical, thermomechanical, mechanical, thermal, energy, or other properties of a composition or material due to exposure to a stimulus, where the stimulus includes, for example, temperature, pH, ionic strength, environmental conditions (including moisture, water immersion, exposure, or humidity), solvent exposure, exposure to electromagnetic radiation (including gamma rays, x-rays, ultraviolet light, visible light, infrared waves, radio waves), ultrasound, high humidity, magnetism, electricity, and mechanical forces (such as shear rate or peel). In one embodiment, the stimulus response does not include applying a liquid (such as baby oil) to the material to effect a change in the material properties. In one embodiment, the stimulus response refers to a change in the physical, environmental, physicochemical, thermomechanical, mechanical, thermal, energy, or other properties of a composition or material previously applied to a substrate (such as skin) due to exposure to a stimulus. A stimulus-responsive adhesive can be contrasted with a mechanically passive adhesive.

[0075] A "mechanically passive adhesive" refers to an adhesive designed to maintain its structure and mechanical properties after placement. Many pressure-sensitive adhesives are mechanically passive adhesives. In certain embodiments, the adhesive layer does not include a mechanically passive adhesive or a pressure-sensitive adhesive.

[0076] As used herein, "shear rate" refers to the rate at which shear deformation occurs. Shear deformation is a deformation in which parallel sheets (layers) of a fluid, gel, or solid material pass by one another in a sliding manner. These layers can be discrete (having a finite measurable thickness) or continuous (extremely thin or not individually distinguishable). Shear rate can be a function of a time constant, a monotonic function of time, a non-periodic non-monotonic function of time, or a periodic function of time. Periodicity is understood to refer to a function that is truly periodic in time, or a function that is approximately periodic in time (e.g., a sinc function).

[0077] As used herein, "frequency response" refers to the change in behavior of a material or fluid when a periodic or approximately periodic force or displacement is applied. This applied quantity can be referred to as a "signal". The applied signal has a defined amplitude and frequency, and optionally a phase, all of which can be constant or vary with time and / or space.

[0078] As used herein, "shear response" refers to the change in behavior of a material (e.g., a gel, solid, or liquid) when different shear displacements or shear rates are applied.

[0079] As used herein, "force response" refers to the change in behavior of a material (e.g., a gel, solid, or liquid) when different magnitudes of force are applied.

[0080] As used herein, "nonlinear force" refers to a type of force in which the relationship between the force and its effect on a system is not proportional or does not follow a simple linear equation.

[0081] As used herein, "network" when referring to a polymer 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 the interaction of polymer chains with a crystalline or glassy phase.

[0082] As used herein, "interpenetrating network" ("IPN") refers to a unique type of polymer material that contains two or more independent polymer networks that are physically entangled with each other but not covalently bonded. Each network retains its unique properties, but these networks are intertwined at the molecular level to form a composite material whose properties are derived from the combination of the individual networks.

[0083] As used herein, "semi-interpenetrating network" ("Semi-IPN") refers to a crosslinked or branched polymer network and an additional polymer or polymer series of entangled linear or branched chains.

[0084] As used herein, "heterogeneous network" refers to a polymer network having a non-uniform distribution of crosslinking density.

[0085] "Gel fraction" refers to the mass of the polymer remaining after washing with a suitable solvent divided by the initial mass. The method for determining the gel fraction is known in the art.

[0086] "Sol fraction" refers to the mass of the polymer lost after washing with a substantially suitable solvent divided by the initial mass. The method for determining the sol fraction is known in the art.

[0087] As used herein, "heterogeneous crosslinking" refers to crosslinking distributed in an inhomogeneous polymer network or system.

[0088] As used herein, "monomer reactivity ratio" is a parameter used in polymer chemistry to describe the relative reactivity of two monomers in a copolymerization reaction. Copolymerization involves the simultaneous polymerization of two different monomers to form a copolymer with a different monomer composition.

[0089] As used herein, "self-healing" refers to a type of smart material that has the ability to autonomously repair itself when subjected to mechanical damage or microcracks. This self-repair process can occur without external stimuli or intervention, thus enhancing the durability, reliability, and lifespan of the material. The flow of viscous or viscoelastic components enables self-healing to occur.

[0090] As used herein, "enhanced sensation" or "enhanced pleasure" refers to increasing sensory neuron exposure and / or increasing penile exposed surface area and / or increasing sexual arousal and / or increasing sensory neuron stimulation. The sensation or pleasure can be of the user, the partner, or both (collectively referred to as the "user").

[0091] As used herein, "prevent" (which can be used interchangeably with "prohibit") refers to reducing, minimizing, or eliminating the release of semen outside the barrier layer in the present disclosure compared to the natural release during ejaculation.

[0092] As used herein, a "plasticizer" refers to an additive that, when added to a polymer, polymer blend, copolymer, copolymer blend, polymer network, or copolymer network, results in a thermomechanical behavior understood to be associated with plasticization, namely, lowering the glass transition temperature, lowering the crystalline melting temperature, initiating stress relaxation, or causing an increase or decrease in adhesion strength. The plasticizer can be added to the polymer, copolymer, or network mixture or blend in amounts of approximately 1 wt%, approximately 2 wt%, approximately 3 wt%, etc., up to about 30 wt% or about 50 wt% 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 with a molecular weight of 1 - 30 or more repeat units that are liquid at room temperature, 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.

[0093] As used herein, "substantially less" means a reduction in the surface area of the penis covered compared to the surface area of the penis covered by a traditional condom, thus resulting in enhanced sensation or pleasure. Substantially less can be, for example, a surface area that is about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, or about 90% or less.

[0094] As used herein, "elastomeric behavior" means the substantially linear elastic or combined linear elastic and plastic deformation stress / strain behavior of a material when the material is strained in a region above the critical transition region, such that the stress / strain hysteresis remains substantially constant.

[0095] As used herein, "flexible behavior" means the behavior of a rigid, viscoelastic, or elastomeric material that can be described as compliant or deformable to conform to the requirements of a particular engineering application.

[0096] As used herein, "self-forming" means that the barrier layer in the present disclosure naturally expands under the action of the forces generated during application to the penis and / or ejaculation, such that the barrier layer expands but substantially does not release semen beyond its boundaries.

[0097] As used herein, "reduce" or "decrease" means a reduction in a particular property. The reduction can be, for example, at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, or at least about 99% or more. The decrease can be measured by any suitable means, for example, by any suitable method known in the art. In the case of a condom covering an erect penis, the reduction can be, for example, a reduction 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 where the condom mainly covers a part of the glans penis but exposes other parts of the glans penis and the penile shaft, the surface area of the erect glans penis can be reduced, for example, by at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, or at least about 99% or more. In all cases, the reduction in the coverage of the erect penis can include exposing parts of the penis where there is a high presence of sensory / sensory neurons, including the frenulum.

[0098] As used herein, "enhanced" refers to an increase in a particular property. The enhancement can 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 higher. This increase can be measured by any suitable means, for example, by any suitable method known in the art. In one embodiment, the condom disclosed herein improves sexual pleasure as compared to other condoms known in the art (including but not limited to conventional condoms). In one embodiment, the condom disclosed herein enhances sexual pleasure as compared to other condoms known in the art (including but not limited to conventional condoms).

[0099] "Contraceptive device" (which may be used interchangeably with "preventive device"), as used herein, refers to a mechanical barrier that prevents the transmission of fluids during sexual intercourse. A condom is a male contraceptive device. A diaphragm is a female contraceptive device.

[0100] As used herein, "film" refers to a layer or membrane of a solid continuous polymeric material.

[0101] As used herein, "subject" refers to a person to whom a contraceptive device is applied or is intended to be applied.

[0102] As used herein, "polymer" refers to a substance composed of macromolecules, very large molecules with molecular weights ranging from several thousand to up to several million grams per mole, the macromolecules being made of simpler repeating units and derived from monomers of lower molecular weight. The polymers used herein refer to both homopolymers and copolymers. Homopolymers are made of one type of monomer (i.e., they contain one type of monomer). Copolymers are made of two or more different types of monomers (i.e., they contain 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 stimulus-responsive polymers.

[0103] As used herein, "pressure-sensitive adhesive" refers to an adhesive that obtains adhesion properties or tack by the flow of a polymer onto a surface, and adhesion is achieved by pressing the adhesive onto the surface with force. In certain embodiments herein, the adhesive does not include a pressure-sensitive adhesive. The term "conventional pressure-sensitive adhesive" as used in the art 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.

[0104] 4.2. Contraceptive device

[0105] On the one hand, the present disclosure provides a contraceptive device comprising an adhesive, the adhesive comprising a stimulus-responsive polymer, and optionally one or more other polymers, crosslinking agents, and / or additives, wherein when the adhesive of the contraceptive device adheres to the genital surface of a human subject, the adhesive delaminates from the genital surface upon application of a stimulus to the contraceptive device. In some embodiments, the contraceptive device is a condom and the genital surface is the glans penis. In some embodiments, the contraceptive device is a contraceptive diaphragm and the genital surface is the vagina.

[0106] In some embodiments, the contraceptive device comprises a barrier layer adapted to prevent the passage of body fluids during sexual intercourse, including an inner surface and an outer surface, and an adhesive layer comprising an adhesive adhered to at least a portion of the inner surface of the 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, wherein when the contraceptive device is applied to the genital surface of a human subject, the adhesive layer adheres to the genital surface, and after application of a stimulus to the contraceptive device, the adhesive layer can be removed from the genital surface. In some embodiments, the contraceptive device is a condom and the genital surface is the glans penis. In some embodiments, the contraceptive device is a contraceptive diaphragm and the genital surface is the vagina.

[0107] In some embodiments, the human subject is male and the contraceptive device is applied to and adhered to the penis. In some embodiments, the human subject is female and the contraceptive device is applied to and adhered to the vagina.

[0108] In some embodiments, the contraceptive device is a partial condom. The partial condom of the present disclosure covers a significantly smaller portion of the penis than a conventional condom, thus increasing the exposed penile surface area and providing a framework for increased user sensation. Like a conventional condom, the partial condom described herein reduces the chance of pregnancy by preventing sperm from reaching the egg. Unlike a conventional condom, it does not cover the entire penis and thus may not prevent the transmission of certain STIs.

[0109] In some embodiments, the partial condom is configured to adhere to the glans penis. In some embodiments, the partial condom is configured to adhere only to the glans of the penis. In some embodiments, the size and shape of the partial condom are designed such that when applied to the penis, the condom does not contact or cover the penile corona. In some embodiments, the condom does not contact or cover the frenulum. In some embodiments, the size and shape of the partial condom are designed such that when applied to the penis, the condom does not contact the penile shaft.

[0110] In some embodiments, the partial condom has a planar geometry 1400. See, for example Figure 26A (which presents a perspective view of condom 1400). The geometry of the device is planar such that it can be placed on a flat surface without significant stretching, wrinkling, folding, or creasing. The embodiment includes a planar adhesive layer 1401 bonded to a planar barrier layer 1402. A backing layer 1403 may be bonded to the adhesive layer such that the adhesive layer is between the backing layer and the barrier layer. As Figure 26 shown in B (which provides a side view of the embodiment of Figure 26 A), such an embodiment may include a device-specific portion for a semen reservoir, however, no such reservoir extends vertically 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 thus is coplanar with the barrier layer (e.g., within region 1405), the adhesive layer, or the combination of the barrier layer and the adhesive layer.

[0111] In some embodiments, the geometry of the condom barrier layer may have a principal curvature direction, which may have a constant or varying radius of curvature, but the curvature in any orthogonal direction is zero. In other words, the Gaussian curvature of the adhesive layer is zero or approximately zero. In the embodiment as Figure 27 shown, the partial condom 1500 includes an outer barrier layer 1502 bonded to an inner adhesive layer 1501 (which is bonded to a backing layer 1503). The barrier layer includes a consistent radius of curvature 1512 over 50% of the barrier layer width 1520. The adhesive layer is bonded to the barrier layer and "nests" under the barrier layer and thus takes on the curvature of the barrier layer, although the radius of curvature 1511 is slightly smaller.

[0112] In some embodiments, the semen reservoir is a self-forming semen reservoir, i.e., in response to the application of the condom on the penis and / or ejaculation during use. When the packaging is removed, there need not be a reservoir that protrudes outwardly from the exterior of the condom barrier layer. For example, see Figure 26 B. In some embodiments, the reservoir is indistinguishable from the other parts of the barrier and, in a sense, does not exist in the condom packaging. However, the reservoir is formed during use by one or more of the following methods.

[0113] First, when the user ejaculates, the expelled fluid will squeeze against the inner surface of the device near the urethral opening (orifice), causing mechanical deformation of the barrier layer to accommodate the ejaculate fluid volume. Thus, the resulting reservoir that can elastically or plastically deform the barrier layer and / or the adhesive layer is 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 ejaculation.

[0114] In some embodiments, a condom may include a relatively thin barrier layer (e.g., less than 200 microns) (see thickness 1422) combined with a relatively thick adhesive layer (e.g., greater than 300 microns) (see thickness 1421). The adhesive may not be present in region 1431 (covering the urethral opening) of the barrier layer. The thickness of the adhesive 1421 creates a gap between the barrier layer and the glans, and this gap is a void volume that can be filled with semen. For example, region 1431 may form a gap without adhesive, and this gap is formed between the urethra, the adhesive layer portion, and the barrier layer.

[0115] In some embodiments, the adhesive may be present in region 1431, but may be perforated or thinned (compared to the outer edge of the adhesive at location 1432) to provide flexibility in the otherwise thick adhesive layer, and thus better accommodate ejaculation. In some embodiments, the adhesive may be present in region 1431, but may include a thin film 1433 to isolate the adhesive from the urethral opening. Embodiments where the adhesive remains in region 1431 can contribute to ease of manufacture by reducing the need to precisely place the adhesive on the barrier layer.

[0116] Figure 28 Embodiments are shown that include a barrier layer bonded to an adhesive layer. When the condom is applied to the penile glans, it wrinkles and folds, and the user squeezes the condom against the skin of the glans, thus closing any folds or wrinkles due to the self - adhesion of the adhesive. See, for example, fold 1601. Such folds and wrinkles result in a void volume. The void volume can be further increased by pinching the portion of the barrier layer that covers the urethral opening.

[0117] Figure 29 A - B shows an embodiment that includes a barrier layer 1702 bonded to an adhesive layer 1701. A reservoir 1703 is pre - formed into the barrier layer using a process compatible with the material. For example, such a process includes dip - coating for a natural rubber latex barrier layer or vacuum / thermo - forming for a thermoplastic elastomer barrier layer. Before ejaculation, the reservoir 1703 is folded in a horizontal plane using concentric folds. At ejaculation, the reservoir fills with fluid, causing it to unfold and extend to accommodate ejaculation. Compared to a reservoir with an axial or vertical fold pattern, the horizontal concentric fold of this reservoir contributes to both manufacturability and reduces the thickness of the device for ease of packaging and storage, and reduces the likelihood of the reservoir unfolding when removed from the package, during application to the glans, or during sexual intercourse prior to ejaculation.

[0118] By selecting a combination of the Young's modulus, Poisson's ratio, thickness, and initial void volume of the barrier layer (or the barrier layer and the adhesive layer), the equilibrium pressure that a post-ejaculation device of a specific volume must contain can be adjusted. The minimum limit of the equilibrium pressure is the zero gauge pressure measured on the reservoir wall, which occurs when the initial void volume is equal to or greater than the ejaculate volume. In embodiments, a preformed semen reservoir of relatively small size simplifies manufacturing, reduces material costs, facilitates the user experience, and is more aesthetically pleasing to the user. When the initial void volume is less than the ejaculate volume, the device can stretch to accommodate the remaining ejaculatory fluid. Within the limit that the initial void volume is zero or approximately zero (meaning less than 0.01 mL or less than 0.1 mL or less than 0.2 mL or less than 0.5 mL or less than 1 mL), the reservoir is self-forming.

[0119] For example, Figure 30 A shows a flat condom attached to the glans penis before ejaculation. Figure 30 B shows a condom attached to the glans penis during ejaculation (showing the accumulation and stretching of the ejaculate and the barrier layer to accommodate the fluid).

[0120] Without being bound by any specific operating theory, embodiments with a "self-forming reservoir" illustrate the counterintuitive behavior of a thin-walled (ultra) elastic pressure vessel reservoir, which may or may not exhibit plastic deformation behavior because there is a ratio of the reservoir volume to the initial (undeformed) reservoir volume such that the equilibrium pressure value contained in the reservoir is maximized. If the volume starts to decrease or increase from this amount, the internal equilibrium pressure contained in the reservoir will decrease. In some cases, as the volume increases, the pressure reaches an approximately constant asymptotic value. Similarly, from the perspective of the fluid sealing behavior of the device, it is beneficial to reduce the initial reservoir void volume to reduce the equilibrium pressure that will be quickly established after ejaculation. In addition, from a physiological perspective, it is beneficial to reduce the pressure exerted by the semen on the urethra to reduce the risk of semen reflux.

[0121] The equilibrium pressure of a spherical reservoir is now presented as a function of the expanded ejaculate volume. Considering an exemplary spherical reservoir under the assumptions of a thin-walled pressure vessel, a linear elastic material with a Poisson's ratio of 0.5, and spherical symmetry, the relationship between the pressure P and the reservoir radius r is derived.

[0122] P(r) = (2E(r - r_0)t_0r_0) / r^3

[0123] In the above expression, E is the 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 the reservoir is expressed as:

[0124] V(r) = 4 / 3πr^3

[0125] The functional shape of this curve is as Figure 31As shown, the peak of the maximum pressure is:

[0126] r(P_max) = 3 / 2r_0

[0127] Smaller reservoirs can also enable the device to match smaller packaging, making it more convenient and frequent for users to store and carry the device. Additionally, since the implementation is planar and there is no need to spread out or unfold the device, it is convenient for operation and application, especially for those with limitations in the flexibility, mobility, or vision of using the product (e.g., due to natural anatomical variations, injuries, or use in the dark).

[0128] In some embodiments, the condom is a partial condom, such as Figure 26 the condom shown in B. The condom includes a barrier layer combined with an adhesive layer. The barrier layer can have a thickness 1422 between 25 and 200 microns, and the adhesive layer can have a thickness 1421 between 25 and 750 microns. For example, the thickness of the barrier layer (such as latex) can be between 30 and 150 microns, while the thickness of the adhesive layer is between 250 and 500 microns. Although not bound by any particular theory of operation, embodiments with an adhesive layer thicker than the barrier layer reduce or eliminate the pain experienced by the user during condom removal. The adhesive properties of the crosslinked adhesives described herein contribute to the removal of the condom from the user. Through a favorable combination of storage and loss moduli and material thickness, the thick adhesive helps to painlessly remove the device from the glans penis, which both dissipates energy and transfers the applied force to the skin in a favorable manner during removal to reduce the pain experienced. Additionally, the thickness ratio between the adhesive layer and the barrier layer also contributes to the painless removal of the device from the user.

[0129] Furthermore, the thick adhesive can enable the adhesive to act as a conforming pad that can deform and adapt to the skin movement of the user during application, intercourse, ejaculation, and pre-removal processes to provide a secure seal to intercept semen and pre-ejaculatory fluids. In contrast, a thinner adhesive must rely on the mechanics of the barrier layer to provide all the compliance and deformation required to contain fluids, especially when considering the dynamic deformation of the glans penis skin and structure under the actions and loads of intercourse.

[0130] In some embodiments, the shelf life of the contraceptive device is at least 1 month, such as at least 2 months, at least 3 months, at least 4 months, at least 5 months, at least 6 months, at least 7 months, at least 8 months, at least 9 months, at least 10 months, at least 11 months, at least 12 months, or at least 24 months.

[0131] In certain embodiments, the barrier performance of the contraceptive device is consistent with the performance proven applicable to the relevant field of use.

[0132] In certain embodiments, the contraceptive device is compatible with a personal lubricant. In some embodiments, the contraceptive device is compatible with an oil-based lubricant.

[0133] In certain embodiments, the contraceptive device does not include additional mechanical securing means, such as those described in U.S. Patent No. 5,421,350.

[0134] In some embodiments, the adhesive layer does not adhere to itself, i.e., is not self-adhesive.

[0135] In some embodiments, the condom is a non-rigid, non-rolled, partial condom that includes a first adhesive layer (e.g., a stimulus-responsive polymer) and a second adhesive layer that includes a barrier and a reservoir, where the condom does not contact the penile shaft or the corona of the penis; where the adhesive layer (a) coextends with the barrier layer; (b) is thicker than the barrier layer; and / or (c) is the only means of securing the partial condom to the penis. In some embodiments, the second layer is continuous, i.e., the barrier and the reservoir are continuous. In some embodiments, the reservoir is self-forming. In some embodiments, the stimulus is mechanical, such as shear rate or peel. In some embodiments, the partial condom consists of only two or three layers, the latter including a third backing layer. In some embodiments, the two or three layers include sublayers. In some embodiments, the condom includes one or more additional means of mechanically securing the condom to the penis.

[0136] The first adhesive layer of the non-rigid, non-rolled, partial condom described above may comprise any suitable stimulus-responsive polymer, e.g., any of the stimulus-responsive polymers described herein. In some embodiments, the stimulus-responsive polymer comprises acrylate or methacrylate monomers (e.g., lauryl methacrylate) and an optional polyfunctional crosslinker (e.g., a trifunctional crosslinker such as TMPTA). The weight ratio of the polymer to the trifunctional crosslinker can be, for example, 99.1:0.9, more particularly 99.02:0.8, 99.04:0.6, or 99.06:0.4. In some embodiments, the adhesive is characterized by low density, heterogeneous crosslinking.

[0137] The above non-rigid, non-rolled partial condom may have one or more characteristics as described herein, including but not limited to a disproportionate response to stimulation (such as mechanical stimulation), such that a lower intensity of stimulation can be used to achieve a response. In some embodiments, the above non-rigid, non-rolled partial condom may exhibit a lower peel strength at a lower peel rate and a higher peel strength at a higher peel rate. For example, the peel strength is about 1 / 10, about 1 / 20, about 1 / 30, about 1 / 40, about 1 / 50, about 1 / 60, about 1 / 70, about 1 / 80, about 1 / 90, about 1 / 100, about 1 / 2, about 1 / 3, about 1 / 4, about 1 / 5 or lower of the peel strength at the higher peel rate.

[0138] In some embodiments, the non-rigid, non-rolled partial condom can be removed with little or no pain, for example, measured using the Wong-Baker Qualitative Pain Assessment (WBQPA) in the range of 0 (no pain) to 10 (maximum pain). In some embodiments, when the adhesive layer is removed by gentle peeling, the pain is less than 4 on the WBQPA scale, such as less than 3, less than 2, less than 1 or 0. In some embodiments, the non-rigid, non-rolled partial condom may have a loss modulus of 0.1 MPa to 0.5 MPa.

[0139] In certain embodiments, the above non-rigid, non-rolled partial condom leaves little or no residue on the skin after removal, for example, less than about 10%, less than about 5%, less than about 1% or no residue.

[0140] In some embodiments, when measured on a subject or a group of subjects, the failure rate (clinical or non-clinical) of the contraceptive device is less than about 10%, less than about 8%, less than about 6%, less than about 4%, less than about 2%, less than about 1.5%, less than about 1%, less than about 0.9%, less than about 0.8%, less than about 0.7%, less than about 0.6%, less than about 0.5%, less than about 0.4%, less than about 0.3%, less than about 0.2% or about 0.1% or less. Clinical failure means that the contraceptive device (such as a condom) ruptures, tears, leaks or completely slips off after initial insertion and before final complete removal. Non-clinical failure means that the contraceptive device (such as a condom) ruptures, tears, leaks or partially slips off.

[0141] In some embodiments, the leakage rate of the condom is less than about 6%, for example, less than about 5%, less than about 4%, less than about 3%, less than about 2%, or less than about 1%.

[0142] 4.2.1. Barrier layer

[0143] In some embodiments, the barrier layer comprises a polymeric film or membrane that exhibits elastic or flexible thermomechanical behavior. In some embodiments, the barrier layer is a thin film or membrane.

[0144] In some embodiments, the barrier layer comprises natural latex rubber, synthetic rubber, amorphous polyurethane, semi-crystalline polyurethane, including various thermoplastic polyurethanes, polyethylene, polypropylene, polydimethylsiloxane and other silicone rubbers, polyethylene terephthalate, poly(vinyl chloride), polyisoprene, vulcanized polyisoprene and other vulcanized or crosslinked rubbers, ethylene vinyl acetate, poly(vinyl acetate), an elastomeric or flexible material, or blends thereof. In some embodiments, the barrier layer comprises natural latex rubber, synthetic rubber or polyurethane.

[0145] In some embodiments, the barrier layer is not polyurethane.

[0146] In some embodiments, the barrier layer is not loose fitting.

[0147] In some embodiments, the barrier layer exhibits stimulus-responsive behavior enabling selective permeability, controlled permeability or controlled porosity. Exemplary stimuli for the stimulus-responsive barrier layer include temperature change, physicochemical change, light, ultrasound, change in ionic strength, pH change, magnetic force and mechanical force. In some embodiments, the stimulus of the stimulus-responsive barrier layer is different from the stimulus of the stimulus-responsive polymer of the adhesive layer. In some embodiments, the stimulus of the stimulus-responsive barrier layer is the same as the stimulus of the stimulus-responsive polymer of the adhesive layer.

[0148] In some embodiments, the barrier layer further comprises one or more additives, for example, to enhance its properties. Exemplary additives include, but are not limited to, polymers, ceramics, metallic materials or structures in the shape of spheres, rods, disks or other shapes. Additive materials include silica, metal oxides, iron oxides, metals, nitinol, ceramics, conductive polymers, etc. The additive materials may be dispersed or crosslinked in the material uniformly or non-uniformly.

[0149] In some embodiments, the thickness of the barrier layer is from 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, 0.001 mm to 0.01 mm. In some embodiments, the thickness of the barrier layer is from 0.025 mm to 0.25 mm, 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 thickness of the barrier layer is 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.

[0150] In some embodiments, the thickness of the barrier layer is 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.

[0151] In some embodiments, the thickness of the barrier layer is less than about 180 microns, such as less than about 160 microns, less than about 140 microns, less than about 120 microns, less than about 100 microns, less than about 80 microns, less than about 60 microns, less than about 40 microns, or less than about 20 microns, but greater than zero in each case.

[0152] In some embodiments, the barrier layer has a planar or curved geometric shape selected from square, circular, oval, hemispherical, rectangular, polygonal, or curvilinear polygonal. In some embodiments, the barrier layer is not tubular.

[0153] In some embodiments, the barrier layer has a first geometric shape before adhering to the penis and transforms into a second geometric shape when applied to the penis.

[0154] In some embodiments, the barrier layer has a circular geometric shape. In some embodiments, the radius of the circle is at least about 0.5 cm, such as 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.

[0155] In some embodiments, the barrier layer has a rectangular geometry. In some embodiments, the length of the rectangle is from 0.5 cm to 5 cm and the width is from 0.5 cm to 5 cm. In some embodiments, the length of the rectangle is from 0.5 cm to 4 cm, 0.5 cm to 3 cm, 0.5 cm to 2 cm, 0.5 cm to 1 cm, 1 cm to 5 cm, 1 cm to 4 cm, 1 cm to 3 cm, 1 cm to 2 cm, 2 cm to 5 cm, 2 cm to 4 cm, 2 cm to 3 cm, 3 cm to 5 cm, or 4 cm to 5 cm. In some embodiments, the width of the rectangle is from 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.

[0156] In some embodiments, the barrier layer has an oval geometry. In some embodiments, the major radius of the oval 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, and the minor radius 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.

[0157] In some embodiments, in the case of a rectangular barrier layer, the major dimensions of the barrier layer are about 0.5 x 0.5 cm, about 1.0 x 1.0 cm, about 1.5 x 1.5 cm, about 2.5 x 2.5 cm, about 3.0 x 3.0 cm, or about 5.0 x 5.0 cm or any combination thereof.

[0158] In some embodiments, the barrier layer does not include one or more protrusions. Instead, according to this embodiment, the barrier layer is a conventional simple geometry (e.g., rectangular, oval, or circular).

[0159] In some embodiments, the barrier layer does not include one or more protrusions. Instead, according to this embodiment, the barrier layer is a conventional simple geometry (e.g., rectangular, oval, or circular). This is contrary to the protruding wings disclosed in, for example, WO2014178661A1.

[0160] In some embodiments, the barrier layer contains a lubricant on its outer surface (e.g., the outer surface of a contraceptive device (condom or contraceptive diaphragm)). In some embodiments, the lubricant is selected from water-based lubricants, silicone-based lubricants, and oil-based lubricants.

[0161] In some embodiments, the barrier layer includes 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.

[0162] In some embodiments, the condom further includes a reservoir sized and shaped to collect semen ejaculated from the penis. In some embodiments, the reservoir is configured to be away from the urethral orifice of the penis. In some embodiments, the reservoir is configured at the tip of the condom, along the sides, or at the base, or below the base.

[0163] In some embodiments, the reservoir is continuous with the barrier layer, i.e., the reservoir and the barrier layer are part of the same structure / non-separated structure and are not adhered or otherwise connected by a joining means.

[0164] In some embodiments, when subjected to the pressure generated by penile ejaculation, the reservoir forms spontaneously and does not have a pre-defined geometry.

[0165] In some embodiments, the reservoir includes a polymer coating that swells or gels when contacted with semen. In some embodiments, this swelling or gelling retains sperm within the reservoir. Exemplary polymer coatings include, but are not limited to, chitosan, alginate, polyacrylic acid, cross-linked polyacrylic acid, sodium polyacrylate, cross-linked sodium polyacrylate, and combinations thereof.

[0166] In some embodiments, the reservoir is substantially spherical in nature, having 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.

[0167] In some embodiments, the reservoir is substantially cylindrical in nature, having a radius of, for example, about 0.1 mm, about 0.25 mm, about 0.5 mm, about 0.75 mm, about 1.0 mm, or about 2.0 mm or greater, and a length of about 1.0 mm, about 2.0 mm, about 5.0 mm, or about 10.0 mm or greater.

[0168] In some embodiments, the condom further includes an elastomeric ring fixed outside the inner surface of the barrier layer or at the edge of the barrier layer. In some embodiments, the elastomeric ring surrounds the base of the barrier layer and can be expanded by stretching to surround the barrier layer and secure it to the base of the glans penis, and can optionally impart a constricting force that enhances the adhesion of the condom to the penis and prevents stress concentration or shear forces from removing the adhered barrier layer during mechanical perturbations (such as those associated with sexual activity).

[0169] In some embodiments, the cross-sectional diameter of the elastomeric ring is at least 0.1 mm, such as at least 0.5 mm, at least 1.0 mm, at least 2.0 mm, or at least 3.0 mm or greater. In some embodiments, the total diameter of the elastomeric ring is at least 0.25 times (0.25x) the diameter of the barrier layer, such as 0.25x to 1x, or 0.25x, 0.50x, 0.75x, or 1.0x.

[0170] In some embodiments, the elastomeric ring includes raised rings or studs to enhance sexual sensation or pleasure.

[0171] In some embodiments, the condom further includes one or more projecting arms connected to the elastomeric ring or the barrier layer. In some embodiments, the plurality of arms can be inflated by stretching to surround the barrier layer and secure it to the base of the glans penis, and can optionally impart a constricting force that enhances the adhesion of the condom to the penis and prevents stress concentration or shear forces from removing the adhered barrier layer during mechanical perturbations (such as those associated with sexual activity).

[0172] In some embodiments, the aspect ratio of the projecting arms can be about 1:1, about 1:2, about 1:5, about 1:10, about 1:20, or about 1:100 or greater. In some embodiments, there can be 1, 2, 3, 4, 5, 6 or more projecting arms. In some embodiments, the length of the projecting arms is about 0.5 cm, about 1.0 cm, about 2.0 cm, about 3.0 cm, or about 5.0 cm or longer, and the width is about 0.1 cm, about 0.2 cm, about 0.5 cm, about 1.0 cm, or about 2.0 cm or longer.

[0173] 4.2.2. Adhesive layer

[0174] The contraceptive device of the present disclosure includes an adhesive layer that includes an adhesive, which includes a stimulus-responsive polymer and optionally one or more additional polymers, cross-linking agents, and / or additives. In some embodiments, the adhesive has been pre-applied to a surface (e.g., the skin) and is stimulus-responsive, responding to a stimulus encountered in the bound state. In some embodiments, the stimulus-responsive polymer is a mechanically-acting or force-responsive polymer.

[0175] In some embodiments, the adhesive layer adheres to at least a portion of the barrier layer. In some embodiments, the adhesive layer adheres to a portion of the inner surface of the barrier layer. In some embodiments, the adhesive layer coextends with the inner surface of the barrier layer, i.e., adheres to the entire surface of the barrier layer. In some embodiments, the adhesive area covers at least about 1%, such as 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% of the inner surface of the barrier layer.

[0176] In some embodiments, the adhesive layer coextends with the barrier layer. In some embodiments, the adhesive layer coextends with the barrier layer except in limited areas associated with the self-formation of the reservoir. In some embodiments, the adhesive layer is positioned in front of the barrier layer. In some embodiments, the barrier layer and the reservoir are formed continuously and (a) the adhesive layer is continuous with the barrier layer or (b) the adhesive layer is positioned in front of the barrier layer.

[0177] In some embodiments, the adhesive layer extends to the elastomeric ring and / or the protruding arm(s) of the condom. In some embodiments, the adhesive layer is the only means of securing the condom to the penis.

[0178] In some embodiments, the adhesive layer includes a uniform, non-uniform, circular, spherical, oval, or ellipsoidal cross-section.

[0179] In some embodiments, the adhesive layer includes one or more patterned configurations. The patterning can facilitate adhesive crack propagation or shear-responsive delamination. For example, the adhesive patterning can allow the barrier layer to adhere sufficiently to the penis or vagina while also minimizing or eliminating pain upon peeling of the barrier layer. Such patterning includes, but is not limited to, a continuous ring or a repeating ring of dots at the base of the barrier layer, having a length ranging from 0.1 to 3000 microns, more specifically a length of 1 to 2000 microns, more specifically a length of 20 to 2000 microns, a thickness ranging from 0.1 to 3000 microns, more specifically a thickness of 1 to 2000 microns, more specifically a thickness of 5 to 1000 microns, more specifically a thickness of 10 to 600 microns, wherein the dot pattern covers between 10% and 100% of the available adhesive area in the base ring region, more specifically, between 20% and 100% of the available adhesive area in the base ring region, more specifically, between 30% and 100% of the available area in the base ring region.

[0180] In certain embodiments, the length of the patterning is about 1 to 100 microns, about 100 to about 200 microns, about 200 to about 300 microns, about 300 to about 400 microns, about 400 to about 500 microns, about 500 to about 600 microns, about 600 to about 700 microns, about 700 to about 800 microns, about 800 to about 900 microns, about 900 to about 1000 microns (by length).

[0181] In certain embodiments, the patterned length is between about 1000 and 1100 microns, between about 1100 and about 1200 microns, between about 1200 and about 1300 microns, between about 1300 and about 1400 microns, between about 1400 and about 1500 microns, between about 1500 and about 1600 microns, between about 1600 and about 1700 microns, between about 1700 and about 1800 microns, between about 1800 microns and about 1900 microns, or between about 1900 and about 200 microns (by length).

[0182] In certain embodiments, the patterned thickness is between 0.1 and about 500 microns, between about 1 and about 100 microns, between about 100 and about 200 microns, between about 200 and about 300 microns, between about 300 and about 400 microns, between about 400 and about 500 microns, between about 500 and about 600 microns, between about 600 and about 700 microns, between about 700 and about 800 microns, between about 800 and about 900 microns, between about 900 and about 1000 microns (by thickness).

[0183] In certain embodiments, the patterned thickness is between about 1000 and 1100 microns, between about 1100 and about 1200 microns, between about 1200 and about 1300 microns, between about 1300 and about 1400 microns, between about 1400 and about 1500 microns, between about 1500 and about 1600 microns, between about 1600 and about 1700 microns, between about 1700 and about 1800 microns, between about 1800 microns and about 1900 microns, or between about 1900 and about 200 microns (by thickness).

[0184] Exemplary patterned configurations include rings, stripes, dots, and combinations thereof. The patterning can be uniform, non-uniform, or random in shape, size, or position, or any combination thereof. In some embodiments, one or more patterned configurations can cover about 1%, about 5%, about 10%, about 25%, about 33%, about 50%, about 66%, about 75%, or about 100% of the adhesive layer.

[0185] In some embodiments, the patterned configuration includes one or more rings or annular structures. The thickness of the ring can be, for example, about 0.1 mm, about 0.25 mm, about 0.5 mm, or about 1.0 mm or greater. In some embodiments, the ring patterning 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.

[0186] In some embodiments, the patterned structure includes dots (e.g., square, rectangular, or circular dots). In some embodiments, the dot patterning 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.

[0187] In some embodiments, the patterned structure includes stripes. In some embodiments, the stripes can have different thicknesses, such as about 0.1 mm, about 0.25 mm, about 0.5 mm, or about 1.0 mm or greater. 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.

[0188] In some embodiments, the thickness of the adhesive layer is on the nanometer or micrometer scale. In some embodiments, the thickness of the adhesive layer is from 0.1 micrometers to 3,000 micrometers, such as 0.1 micrometers to 2,000 micrometers, 0.1 micrometers to 1,000 micrometers, 0.1 micrometers to 750 micrometers, 0.1 micrometers to 500 micrometers, 0.1 micrometers to 250 micrometers, 1 micrometers to 2,000 micrometers, 1 micrometers to 1,000 micrometers, 1 micrometers to 750 micrometers, 1 micrometers to 500 micrometers, 1 micrometers to 250 micrometers, 25 micrometers to 2,000 micrometers, 25 micrometers to 1,000 micrometers, 25 micrometers to 750 micrometers, 25 micrometers to 500 micrometers, 25 micrometers to 250 micrometers, 100 micrometers to 2,000 micrometers, 100 micrometers to 1,000 micrometers, 100 micrometers to 750 micrometers, 100 micrometers to 500 micrometers, or 100 micrometers to 250 micrometers.

[0189] In some embodiments, the thickness of the adhesive layer is from about 0.01 micrometers to about 0.1 micrometers, about 1.0 micrometers to about 5.0 micrometers, about 10.0 micrometers to about 20.0 micrometers, about 30.0 micrometers to about 50.0 micrometers, about 100.0 micrometers to about 200 micrometers, about 300 micrometers to about 400 micrometers, about 600 micrometers to about 750 micrometers, or about 1000 micrometers to about 2000 micrometers.

[0190] In some embodiments, the thickness of the adhesive layer is from 25 to 750 micrometers, for example, from about 200 to about 500 micrometers, or about 400 micrometers thick.

[0191] In some embodiments, the thickness of the adhesive layer is about 25 micrometers, about 50 micrometers, about 100 micrometers, about 150 micrometers, about 200 micrometers, about 250 micrometers, about 300 micrometers, about 350 micrometers, about 400 micrometers, about 450 micrometers, about 500 micrometers, about 550 micrometers, about 600 micrometers, about 650 micrometers, about 700 micrometers, or about 750 micrometers.

[0192] In some embodiments, the thickness of the adhesive layer is from about 100 microns to about 600 microns, such as from about 200 microns to about 500 microns, or from about 300 to about 500 microns.

[0193] In some embodiments, the adhesive layer is thicker than the barrier layer. The adhesive layer can be, for example, about 1.5X, about 2X, about 2.5X, about 3X, about 3.5X, about 4X, about 4.5X, about 5X, about 5.5X, about 6X, about 6.5X, about 7X, about 7.5X, about 8X, 8.5X, about 9X, about 9.5X, or at least about 10X as thick as the barrier layer.

[0194] In some embodiments, the barrier layer is from about 40 to about 100 microns thick and the adhesive layer is from about 25 to about 750 microns thick. In some embodiments, the barrier layer is about 200 microns thick and the adhesive layer is about 400 microns thick.

[0195] In some embodiments, the adhesive layer is transparent.

[0196] In some embodiments, the adhesive layer comprises a plurality of adhesives, blended together or applied separately to the barrier layer. For example, as Figure 2 shown, the adhesive layer may include a hydrophobic, water-insoluble layer having a length of about 0.1 to 2 cm, more particularly a length of 0.2 to 1 cm, more particularly a length of 0.25 to 1 cm, along the outer edge of its circumference around the barrier layer, and a hydrophilic, water-soluble layer on the hydrophobic adhesive layer. In some embodiments, the hydrophobic outer adhesive layer can be stimulus-responsive.

[0197] In some embodiments, the adhesive comprises (1) a main side-chain optionally crystallizable side-chain adhesive polymer, (2) optionally an additive, (3) optionally an additional polymer, and an optionally amorphous polymer blend or multiphase, and (4) optionally a crosslinker, which is optionally uniformly incorporated into the polymer network and optionally aggregated to act as high stress concentration network sites to promote adhesive failure or to promote a desired adhesion distribution when needed. In some embodiments, the adhesive comprises a blend or copolymer of a crystallizable amorphous polymer.

[0198] In some embodiments, the adhesive layer of the contraceptive device described herein comprises an adhesive that comprises a stimulus-responsive polymer formed from one or more monomers and optionally one or more polyfunctional crosslinkers. In some embodiments, the adhesive consists of a stimulus-responsive polymer. In some embodiments, the adhesive consists essentially of a stimulus-responsive polymer. As used herein, "consisting essentially of" with respect to the adhesive means additional components that do not significantly affect the basic properties of the adhesive, such as additives that do not have adhesive properties themselves.

[0199] In some embodiments, the adhesive does not include additional components such as additives, adhesive polymers, and / or other polymers.

[0200] In some embodiments, the adhesive layer comprises a single layer. In some embodiments, the adhesive layer comprises multiple layers, such as 2, 3, 4, or 5 layers or more. These layers can be the same or different.

[0201] In some embodiments, the adhesive layer comprises two or three or more adhesive regions that can exhibit different mechanical, chemical, and biological properties. These can include different solubility parameters in various solvents including water or vaginal fluid or ejaculatory fluid. Reversible or irreversible adhesion behavior can be triggered by simultaneous or sequential exposure to temperature changes, physicochemical changes, light, ultrasound, changes in ionic strength, pH changes, magnetic, electrical, or mechanical forces, and other stimuli or any combination thereof.

[0202] 4.2.2.1 Adhesive Properties

[0203] 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 penis, the adhesive layer adheres to the glans penis. In some embodiments, when the contraceptive diaphragm is applied to the vagina, the adhesive layer adheres to the vagina.

[0204] Applying a stimulus to the contraceptive device results in lower adhesion of the adhesive layer or peeling from the skin (such as the penis or vagina), thus achieving selective delamination (i.e., delamination on demand). Reversible or irreversible adhesion behavior can be triggered by exposure to temperature changes (e.g., temperature decrease), physicochemical changes (e.g., dissolution), light, ultrasound, changes in ionic strength, pH changes, magnetic, electrical, or mechanical actions or forces, and other stimuli or any combination thereof.

[0205] The properties of the stimulus-responsive polymers described below can also be applied to the adhesive, which can optionally contain additional components such as additives and / or polymers (e.g., adhesive polymers or non-adhesive polymers).

[0206] In some embodiments, in response to a stimulus of the contraceptive device, the stimulus-responsive polymer becomes less adhesive or delaminates from the vagina or penis (e.g., glans penis) within 0.1 s to 60 s, such as 1 s to 60 s, 1 s to 30 s, 1 s to 15 s, 1 s to 10 s, 1 s to 5 s, 2 s to 30 s, or 1 s to 15 s.

[0207] In some embodiments, in response to stimulation of the contraceptive device, the adhesive becomes less adhesive or delaminates from the vagina or penis (e.g., the glans penis) within 0.1 s to 60 s, such as 1 s to 60 s, 1 s to 30 s, 1 s to 15 s, 1 s to 10 s, 1 s to 5 s, 2 s to 30 s, or 1 s to 15 s.

[0208] 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 rate at which the stimulus-responsive polymer delaminates is at least 2X that of the non-stimulus-responsive polymer (e.g., a conventional pressure-sensitive adhesive polymer), such as at least 3X, at least 4X, at least 5X, at least 6X, at least 7X, at least 8X, at least 9X, or at least 10X.

[0209] In some embodiments, an adhesive comprising a stimulus-responsive polymer delaminates from the vagina or penis faster than an adhesive comprising a non-stimulus-responsive polymer (e.g., a conventional pressure-sensitive adhesive polymer). In some embodiments, the rate at which the adhesive comprising a stimulus-responsive polymer delaminates is at least 2X that of the adhesive comprising a non-stimulus-responsive polymer (e.g., a conventional pressure-sensitive adhesive polymer), such as at least 3X, at least 4X, at least 5X, at least 6X, at least 7X, at least 8X, at least 9X, or at least 10X.

[0210] In some embodiments, the stimulus is selected from temperature change, physicochemical change, light, ultrasound, change in ionic strength, pH change, magnetism, mechanical force, or mechanical action.

[0211] In some embodiments, the stimulus is mechanical action, such as shear rate. In some embodiments, the shear rate is induced by peeling or pulling the contraceptive device at different rates or frequencies.

[0212] 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 adhesive when a higher shear rate is applied and becomes less adhesive at a lower shear rate. Exemplary higher shear rates include hard peeling or hard pulling. Exemplary lower shear rates include mild peeling or mild pulling. Higher and lower values are taken relative to a threshold at which a behavioral change is observed. In this way, after applying a stimulus to the contraceptive device, the adhesive layer and the contraceptive device can be easily removed from the penis or vagina.

[0213] In some embodiments, mild delamination corresponds to a delamination rate of 500 mm / min or less, e.g., 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, mild delamination corresponds to a delamination rate of 50 mm / min to 500 mm / min, e.g., 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.

[0214] In some embodiments, mild delamination corresponds to a delamination rate of 25 mm / s or less, e.g., 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, mild delamination corresponds to a delamination rate of 0.01 mm / s to 25 mm / s, e.g., 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 / sec, 0.1 mm / s to 25 mm / s, 0.1 mm / s to 10 mm / s, 0.1 mm / s to 5 mm / s, 0.1 mm / s to 1 mm / s, 0.1 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.

[0215] 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 adhered when a lower force is applied. Higher and lower values are taken relative to a threshold at which a change in behavior is observed.

[0216] In some embodiments, the applied force that causes delamination of the stimulus-responsive polymer is, for example, 0.01 to 0.1 N, 0.1 to 1 N, 1 to 10 N, 10 to 100 N, or 100 to 1000 N. In some embodiments, the applied force that causes delamination of the stimulus-responsive polymer is, for example, 1 to 10 Pa, 10 to 100 Pa, 0.1 to 1 kPa, 1 to 10 kPa, 10 to 100 kPa, or 0.1 to 1 Mpa.

[0217] In some embodiments, the applied force that causes delamination of the adhesive is, for example, 0.01 to 0.1 N, 0.1 to 1 N, 1 to 10 N, 10 to 100 N, or 100 to 1000 N. In some embodiments, the applied force that causes delamination of the adhesive is, for example, 1 to 10 Pa, 10 to 100 Pa, 0.1 to 1 kPa, 1 to 10 kPa, 10 to 100 kPa, or 0.1 to 1 MPa.

[0218] In some embodiments, the stimulus-responsive polymer has a lower peel strength at a lower peel rate and a higher peel strength at a higher peel rate. In some embodiments, compared to the peel strength at a higher peel rate, the peel strength of the stimulus-responsive polymer at a lower peel rate is at least 5% lower, such as 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.

[0219] In some embodiments, the stimulus-responsive polymer has a lower peel strength at a peel rate of 100 mm / min than at a peel rate of 200 mm / min. In some embodiments, the stimulus-responsive polymer has a lower peel strength at a peel rate of 100 mm / min than at a peel rate of 300 mm / min. In some embodiments, the stimulus-responsive polymer has a lower peel strength at a peel rate of 100 mm / min than at a peel rate of 400 mm / min. In some embodiments, the stimulus-responsive polymer has a lower peel strength at a peel rate of 100 mm / min than at a peel rate of 500 mm / min.

[0220] In some embodiments, the stimulus-responsive polymer has a lower peel strength at a peel rate of 1 mm / s than at a peel rate of 3 mm / s. In some embodiments, the stimulus-responsive polymer has a lower peel strength at a peel rate of 1 mm / s than at a peel rate of 5 mm / s. In some embodiments, the stimulus-responsive polymer has a lower peel strength at a peel rate of 1 mm / s than at a peel rate of 7 mm / s. In some embodiments, the stimulus-responsive polymer has a lower peel strength at a peel rate of 1 mm / s than at a peel rate of 10 mm / s.

[0221] In some embodiments, the peel strength of the stimulus-responsive polymer at a peel rate of 100 mm / min is at least 5% lower, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower than the peel strength at a peel rate of 200 mm / min.

[0222] In some embodiments, the peel strength of the stimulus-responsive polymer at a peel rate of 100 mm / min is at least 5% lower, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower than the peel strength at a peel rate of 300 mm / min.

[0223] In some embodiments, the peel strength of the stimulus-responsive polymer at a peel rate of 100 mm / min is at least 5% lower, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower than the peel strength at a peel rate of 400 mm / min.

[0224] In some embodiments, the peel strength of the stimulus-responsive polymer at a peel rate of 100 mm / min is at least 5% lower, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower than the peel strength at a peel rate of 500 mm / min.

[0225] In some embodiments, the peel strength of the stimulus-responsive polymer at a peel rate of 1 mm / s is at least 5% lower than the peel strength at a peel rate of 3 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 peel strength of the stimulus-responsive polymer at a peel rate of 1 mm / s is at least 5% lower than the peel strength at a peel rate of 5 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 peel strength of the stimulus-responsive polymer at a peel rate of 1 mm / s is at least 5% lower than the peel strength at a peel rate of 7 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 adhesive has a lower peel strength at a lower peel rate and a higher peel strength at a higher peel rate. In some embodiments, the peel strength of the adhesive at a lower peel rate is at least 5% lower than the peel strength at a higher peel rate, for example, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 100% lower.

[0229] In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is lower than the peel strength at a peel rate of 200 mm / min. In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is lower than the peel strength at a peel rate of 300 mm / min. In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is lower than the peel strength at a peel rate of 400 mm / min. In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is lower than the peel strength at a peel rate of 500 mm / min.

[0230] In some embodiments, the adhesive has a lower peel strength at a peel rate of 1 mm / s than at a peel rate of 3 mm / s. In some embodiments, the adhesive has a lower peel strength at a peel rate of 1 mm / s than at a peel rate of 5 mm / s. In some embodiments, the adhesive has a lower peel strength at a peel rate of 1 mm / s than at a peel rate of 7 mm / s. In some embodiments, the stimulus-responsive polymer has a lower peel strength at a peel rate of 1 mm / s than at a peel rate of 10 mm / s.

[0231] In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is at least 5% lower than the peel strength at a peel rate of 200 mm / min, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0232] In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is at least 5% lower than the peel strength at a peel rate of 300 mm / min, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0233] In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is at least 5% lower than the peel strength at a peel rate of 400 mm / min, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0234] In some embodiments, the peel strength of the adhesive at a peel rate of 100 mm / min is at least 5% lower than the peel strength at a peel rate of 500 mm / min, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower, or at least 100% lower.

[0235] In some embodiments, the peel strength of the adhesive at a peel rate of 1 mm / s is at least 5% lower than the peel strength at a peel rate of 3 mm / s, e.g., at least 10% lower, at least 20% lower, at least 30% lower, at least 40% lower, at least 50% lower, at least 60% lower, at least 70% lower, at least 80% lower, at least 90% lower or at least 100% lower.

[0236] In some embodiments, the peel strength of the adhesive at a peel rate of 1 mm / s is at least 5% lower than the peel strength at a peel rate of 5 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.

[0237] In some embodiments, the peel strength of the adhesive at a peel rate of 1 mm / s is at least 5% lower than the peel strength at a peel rate of 7 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.

[0238] In some embodiments, the stimulus-responsive polymer has a peel strength of 1 to 400 N / m, for example, 1 to 300 N / m, 1 to 200 N / m, 1 to 100 N / m, or 1 to 50 N / m at a peel rate of 100 mm / second. The peel strength can be determined by a 180° peel test using a human skin substrate analogue as described below.

[0239] In some embodiments, the adhesive has a peel strength of 1 to 400 N / m, for example, 1 to 300 N / m, 1 to 200 N / m, 1 to 100 N / m, or 1 to 50 N / m at a peel rate of 100 mm / second. The peel strength can be determined by a 180° peel test using a human skin substrate analogue as described below.

[0240] In some embodiments, the stimulus-responsive polymer has an adhesion strength of at least 1 N, for example, 1 N to 5 N, 1 N to 4 N, 1 N to 3 N, or 1 N to 2 N at 25 °C. The adhesion strength can be measured as described below, for example, by extruding an aluminum tip rheometer containing the polymer onto an aluminum substrate for 60 s, withdrawing the rheometer at a speed of 100 micrometers per second, and measuring the axial force in N.

[0241] In some embodiments, the adhesive has an adhesion strength of at least 1 N, for example, 1 N to 5 N, 1 N to 4 N, 1 N to 3 N, or 1 N to 2 N at 25 °C.

[0242] In some embodiments, the stimulus-responsive polymer has an adhesion 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 adhesion strength is calculated by integrating the area under the axial force on the sample over the measurement time.

[0243] In some embodiments, the adhesive has an adhesion 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.

[0244] In some embodiments, the storage modulus of the stimulus-responsive polymer is from 0.01 MPa to 1 MPa, such as from 0.1 MPa to 1 MPa, from 0.1 MPa to 0.8 MPa, or from 0.1 MPa to 0.5 MPa.

[0245] In some embodiments, the storage modulus of the adhesive is from 0.01 to 1 MPa, such as from 0.1 MPa to 1 MPa, from 0.1 MPa to 0.8 MPa, or from 0.1 MPa to 0.5 MPa.

[0246] In some embodiments, the loss modulus of the stimulus-responsive polymer is from 0.1 MPa to 1 MPa, such as from 0.1 MPa to 0.8 MPa, or from 0.1 MPa to 0.5 MPa.

[0247] In some embodiments, the loss modulus of the adhesive is from 0.1 MPa to 1 MPa, such as from 0.1 MPa to 0.8 MPa, or from 0.1 MPa to 0.5 MPa.

[0248] In some embodiments, the tan(δ) (ratio of storage modulus (G”) to loss modulus (G’)) of the stimulus-responsive polymer at 25 °C and 1 Hz (2*π radians / s) is at least 0.1, such as at least 0.2, at least 0.3, at least 0.4, at least 0.5, at least 0.6, at least 0.7, at least 0.8, at least 0.9, at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9, at least 2.0, at least 3.0, at least 4.0, or at least 5.0. In some embodiments, the tan(δ) of the stimulus-responsive polymer is from 0.1 to 5, such as from 0.1 to 4, from 0.1 to 3, from 0.1 to 2, from 0.1 to 1, from 0.5 to 5, from 0.5 to 4, from 0.5 to 3, from 0.5 to 3, from 0.5 to 2, from 0.5 to 1, from 1 to 5, from 1 to 4, from 1 to 3, from 1 to 2, from 2 to 5, from 2 to 4, from 2 to 3, from 3 to 5, from 3 to 4, or from 4 to 5. In certain embodiments, the tan(δ) of the stimulus-responsive polymer is from 0.2 to 2, such as from 0.1 to 1.5, from 0.1 to 1, from 0.1 to 0.5, from 0.3 to 1, or from 0.5 to 1.

[0249] In some embodiments, the tan(δ) (ratio of storage modulus (G”) to loss modulus (G’)) of the adhesive at 25 °C and 1 Hz (2*π radians / s) is at least 0.1, such as at least 0.2, at least 0.3, at least 0.4, at least 0.5, at least 0.6, at least 0.7, at least 0.8, at least 0.9, at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9, at least 2.0, at least 3.0, at least 4.0, or at least 5.0. In some embodiments, the tan(δ) of the adhesive is from 0.1 to 5, such as from 0.1 to 4, from 0.1 to 3, from 0.1 to 2, from 0.1 to 1, from 0.5 to 5, from 0.5 to 4, from 0.5 to 3, from 0.5 to 3, from 0.5 to 2, from 0.5 to 1, from 1 to 5, from 1 to 4, from 1 to 3, from 1 to 2, from 2 to 5, from 2 to 4, from 2 to 3, from 3 to 5, from 3 to 4, or from 4 to 5. In certain embodiments, the tan(δ) of the adhesive is from 0.2 to 2, such as from 0.1 to 1.5, from 0.1 to 1, from 0.1 to 0.5, from 0.3 to 1, or from 0.5 to 1.

[0250] In some embodiments, the stimulus-responsive polymer has less tack when wet than when dry. In some embodiments, the adhesive has less tack when wet than when dry.

[0251] In some embodiments, the stimulus-responsive polymer is a crosslinked polymer, a low-density crosslinked polymer, or a polymer having limited heterogeneous crosslinking.

[0252] In some embodiments, when analyzed by sol-gel analysis, the gel fraction of the stimulus-responsive polymer is consistent with the gel fraction of a lightly crosslinked polymer network. In some embodiments, the gel fraction of the stimulus-responsive polymer is from 0.0001 to 0.99, such as from 0.001 to 0.98, from 0.01 to 0.95, from 0.015 to 0.95, from 0.02 to 0.96, from 0.05 to 0.95, from 0.1 to 0.95, from 0.175 to 0.95, from 0.2 to 0.95, from 0.25 to 0.95, from 0.3 to 0.95, from 0.35 to 0.95, from 0.4 to 0.95, from 0.5 to 0.95, from 0.6 to 0.95, from 0.7 to 0.95, from 0.8 to 0.95, from 0.5 to 0.95, from 0.6 to 0.93, from 0.6 to 0.65 to 0.92, from 0.7 to 0.9, or from 0.7 to 0.89.

[0253] In some embodiments, when analyzed by sol-gel analysis, the gel fraction of the adhesive is consistent with the gel fraction of a lightly crosslinked polymer network. In some embodiments, the gel fraction of the adhesive is from 0.0001 to 0.99, such as from 0.001 to 0.98, from 0.01 to 0.95, from 0.015 to 0.95, from 0.02 to 0.96, from 0.05 to 0.95, from 0.1 to 0.95, from 0.175 to 0.95, from 0.2 to 0.95, from 0.25 to 0.95, from 0.3 to 0.95, from 0.35 to 0.95, from 0.4 to 0.95, from 0.5 to 0.95, from 0.6 to 0.95, from 0.7 to 0.95, from 0.8 to 0.95, from 0.5 to 0.95, from 0.6 to 0.93, from 0.6 to 0.65 to 0.92, from 0.7 to 0.9, or from 0.7 to 0.89.

[0254] In some embodiments, after the adhesive layer is adhered to the penis or vagina, the contraceptive device can be removed by gentle peeling without causing pain to the subject. In some embodiments, after the adhesive layer is adhered to the glans penis, removal of the condom by gentle peeling causes minimal or no pain to the subject. Any suitable method can be used to determine the presence or absence of pain. There are several validated instruments for measuring pain. These instruments can be one-dimensional and measure only the intensity of pain, such as the Wong-Baker Qualitative Pain Assessment (WBQPA), the Numerical Rating Pain Scale (NRPS), the Visual Analog Scale (VAS), and the Verbal Rating Scale. Multidimensional tools measure the intensity, characteristics, and impact of pain, such as the McGill Pain Questionnaire (MPQ) and the Brief Pain Inventory (BPI).

[0255] In some embodiments, WBQPA is used to measure pain on a scale of 0 (no pain) to 10 (maximum pain). In some embodiments, when the adhesive layer is removed by gentle peeling, the pain is less than 4 on the WBQPA scale, such as less than 3, less than 2, less than 1, or 0. In some embodiments, after the contraceptive device is removed by gentle peeling, the WBQPA score is 0. As described above, in some embodiments, gentle peeling corresponds to a user peeling rate of the contraceptive device (such as a condom) of 25 mm / s or less, such as 10 mm / s or less, 5 mm / s or less, 1 mm / s or less, 0.5 mm / s or less, 0.3 mm / s or less, or 0.1 mm / s or less. In some embodiments, gentle peeling corresponds to a peeling rate of 0.01 mm / s to 25 mm / s, such as, 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 / second, 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.

[0256] In some embodiments, mild peeling corresponds to a user peeling rate of a contraceptive device (such as a condom) 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, mild peeling corresponds to a peeling rate of 50 mm / min to 500 mm / min, for example, 50 mm / min to 400 mm / min, 50 mm / min to 300 mm / min, 50 mm / min to 200 mm / min, 50 mm / min to 100 mm / min, 100 mm / min to 500 mm / min, 100 mm / min to 400 mm / min, 100 mm / min to 300 mm / min, 100 mm / min to 200 mm / min, 200 mm / min to 500 mm / min, 200 mm / min to 400 mm / min, 200 mm / min to 300 mm / min, 300 mm / min to 500 mm / min, 300 mm / min to 400 mm / min, or 400 mm / min to 500 mm / min.

[0257] In some embodiments, after the adhesive layer is adhered to the penis or vagina, the contraceptive device is removed by mild peeling, and the subject experiences minimal or no pain when it is removed in less than 15 seconds (for example, less than 10 seconds, less than 8 seconds, or less than 5 seconds).

[0258] In some embodiments, after removal of the contraceptive device, the adhesion site exhibits limited or no irritation. Various methods are known in the research environment for quantitatively evaluating skin damage. 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, trans-epidermal water loss (TEWL), and irritation will provide information to distinguish damaged skin from healthy skin. See, for example, Bernatchez, S. et al., ADVANCES IN WOUND CARE, Vol. 2, No. 4 (2022), which is incorporated herein by reference. Reconstructed human epidermal models are also available, which exhibit reasonable similarity to native human tissue in terms of morphology, lipid composition, and biochemical markers. For example, see EpiSkin, SkinEthic, and EpiDerm. Animal models of skin damage are also known in the art, including pigs and rodents. See, for example, Summerfield, A. et al., Molecular Immunology, Vol. 66, Issue 1, July 2015, p. 14-21.

[0259] 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 adheres less or delaminates from the penis or vagina at a temperature of 25°C or lower. In some embodiments, the adhesive layer adheres to the glans penis at a temperature of 37°C, and adheres less or delaminates from the glans penis at a temperature of 25°C or lower.

[0260] In some embodiments, the adhesive layer can exhibit thermoresponsive stimulus-responsive behavior, capable of adhering to the penile skin at body temperature (about 37°C), and when cooled to below body temperature by about 25°C, about 20°C, about 15°C, about 10°C, about 5°C, about 0°C or lower, capable of reducing the adhesion force or delaminating. For example, cooling can be achieved as follows: by rubbing a wet substrate (such as a towel or tissue paper soaked in water) on the condom or at the interface of the adhesion barrier layer (when adhered to the penis) to accelerate heat transfer, or by flushing with water from a source (such as a shower), or by including a reagent cloth or tissue paper that causes cooling (such as ethanol evaporation or ammonium nitrate dissolution) to cool the condom through a thermal transition, thus making it easier to delaminate the condom than at body temperature.

[0261] In some embodiments, the stimulus is a physicochemical change. An exemplary physicochemical change is dissolution. In some embodiments, the stimulus is a change in which the adhesive layer dissolves upon contact with a solvent. In some embodiments, the composition adheres to the penis or vagina in the absence of a solvent and adheres less or delaminates from the penis or vagina when contacted with a solvent. In some embodiments, in the absence of a solvent, the composition adheres to the glans penis and adheres less or delaminates from the glans penis when contacted with a solvent.

[0262] In some embodiments, the adhesive layer exhibits chemically responsive behavior inherently, is soluble in water or a solvent, and can be removed by pulling on the edge and flowing water or solvent, or by rubbing the substrate impregnated with water or solvent until the condom is removed by subsequent adhesive weakening or water or solvent dissolution. Chemical delamination can also be achieved in this way by pH-triggered delamination, which is achieved by flowing or wiping the substrate to impregnate it 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 in this way by flowing or wiping the substrate impregnated with a fluid to dissolve the adhesive, which also achieves delamination of the condom from the skin.

[0263] 4.2.2.2 Polymer

[0264] The adhesives described herein comprise a stimulus-responsive polymer and optionally one or more additional polymers.

[0265] In some embodiments, the glass transition temperature (Tg) of the stimulus-responsive polymer is from 0 °C to 50 °C, such as 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.

[0266] In some embodiments, the stimulus-responsive polymer has a glass transition below ambient temperature, for example, a glass transition of -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.

[0267] In some embodiments, the stimulus-responsive polymer has a crystalline melting transition below ambient temperature, e.g., from -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.

[0268] 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, the copolymers comprising copolymer structures of two or more of block, gradient, and random copolymers.

[0269] In some embodiments, one or more polymers are selected from, e.g., polyacrylates, polymethacrylates, polyurethanes, polyolefins, polyethers, silicones, polyepoxides, synthetic rubbers, or other adhesives suitable for human skin, including derivatives, copolymers, and mixtures thereof.

[0270] In some embodiments, the stimulus-responsive polymer comprises one or more polyacrylate or polymethacrylate polymers.

[0271] In some embodiments, the stimulus-responsive polymer comprises one or more polyacrylates or polymethacrylates having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or up to 100 carbons in the side chain and 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or up to 100 or more oxygens in the side chain.

[0272] Representative non-limiting polymers include poly(2-ethylhexyl acrylate), poly(butyl acrylate), poly(propyl acrylate), poly(ethyl acrylate), poly(methyl acrylate), poly(octyl acrylate), poly(nonyl acrylate), poly(decyl acrylate), poly(undecyl acrylate), poly(dodecyl acrylate), poly(tridecyl acrylate), poly(C14 acrylate), poly(C15 acrylate), poly(C16 acrylate), poly(C17 acrylate), poly(C18 acrylate), poly(C19 acrylate), poly(C20-C100 or more acrylates, methacrylates, and acrylamides), poly(2-hydroxyethyl acrylate), poly(butoxymethyl acrylate), poly(butoxyethyl acrylate), poly(butoxypropyl acrylate), poly(butoxybutyl acrylate), poly(fin(ding)-nemo-acrylate), poly(octadecyl acrylate), poly(octadecyl methacrylate), and poly(acrylic acid).

[0273] 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, including any of the monomers disclosed herein.

[0274] In some embodiments, the stimulus-responsive polymer comprises a crosslinked polymethacrylate. The crosslinking agent can be multifunctional. In one embodiment, the stimulus-responsive polymer comprises a polymethacrylate crosslinked by an 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.

[0275] In some embodiments, the weight ratio is 98:2, 98.5:1.5, or 99:1, or more particularly, 99.1:0.9, 99.2:0.8, 99.3:0.7, 99.4:0.6, 99.6:0.4, or 99.8:0.2, 99.0:0.1 or any range therebetween.

[0276] In some embodiments, the stimulus-responsive polymer does not comprise a polyacrylate or a polymethacrylate.

[0277] In some embodiments, the stimulus-responsive polymer comprises one or more amorphous or semi-crystalline polyurethanes.

[0278] In some embodiments, the stimulus-responsive polymer comprises a semi-crystalline polyurethane elastomer having segments including polyethers, polyesters, polyurethanes, polyurethane ureas, poly(isoprene), poly(butadiene), or other crystalline segments.

[0279] In some embodiments, the stimulus-responsive polymer comprises a linear or crosslinked semi-crystalline polyurethane elastomer with segments including polyethers, polyesters, polyurethanes, polyurethane ureas, poly(isoprene), poly(butadiene), or other crystalline segments.

[0280] In some embodiments, the stimulus-responsive polymer does not comprise a polyurethane.

[0281] In some embodiments, the stimulus-responsive polymer comprises a polyolefin. In some embodiments, the polyolefin is polyisoprene.

[0282] In some embodiments, the stimulus-responsive polymer comprises at least one polyether, e.g., a poly(ethylene glycol) (PEG) compound and an acrylated or polyurethane-containing PEG compound.

[0283] In some embodiments, the stimulus-responsive polymer comprises at least one polyepoxide. In some embodiments, the polyepoxide comprises one or more of the epoxy monomers disclosed herein. In some embodiments, the stimulus-responsive polymer does not comprise a polyepoxide. In some embodiments, the polyepoxide comprises one or more of the silicone monomers disclosed herein.

[0284] In some embodiments, the stimulus-responsive polymer comprises at least one silicone polymer. In some embodiments, the silicone polymer is a high molecular weight linear siloxane polymer and a highly concentrated silicate tackifying resin.

[0285] In some embodiments, the stimulus-responsive polymer does not comprise a silicone polymer.

[0286] In some embodiments, the stimulus-responsive polymer comprises at least one synthetic rubber.

[0287] In some embodiments, the stimulus-responsive polymer comprises styrene-butadiene rubber (SBR). Examples of SBR include those used in the manufacture of pressure-sensitive tapes, including synthetic elastomers derived from styrene and butadiene. SBRs suitable for the present disclosure, whether solvent-based or aqueous, include SBRs having different percentages of bound styrene, average molecular weights and their distributions, and functional groups introduced during the polymerization process. The molecular weight of the SBR ranges from 10 to 1,000,000 g / mol, more specifically from 25,000 to 750,000 g / mol, more specifically from 50,000 to 500,000 g / mol. SBR generally exhibits low water absorption, less than 1 wt% water, more specifically less than 0.5 wt% water, more specifically 0.1 wt% water, more specifically less than 0.05 wt% water.

[0288] In some embodiments, the stimulus-responsive polymer does not comprise a synthetic rubber.

[0289] In some embodiments, the stimulus-responsive polymer comprises a thiol monomer. Exemplary thiol monomers include, but are not limited to, 3-mercaptopropionic acid; mercaptoacetic acid; 3-mercapto-1-propanol; 2-mercaptoethanol; 2-(2-mercaptoethoxy)ethanol; 2-(2-mercaptopropionylamino)ethanol; 2-(2-mercaptosuccinyl)ethyl acrylate; 3-(2-mercaptopropionylamino)propionic acid; 3-(mercaptopropyl)trimethoxysilane; 2,2'-(ethylenebis(thio))diethanol; 3-(mercaptopropyl)trimethoxysilane; 3-(mercaptopropyl)methyldimethoxysilane; 3-(2,2-dithiobis(ethylthio)propionylamino)propionic acid; 3,6,9-trioxadecane thiol; 3-mercapto-1,2-propanediol; 2,2'-dithiobisethanol; N-acetyl-L-cysteine; L-cysteine; 2-(2-mercaptoethyl)pyridine; 4-(2-mercaptoethyl)morpholine; 3-mercapto-1,2,4-triazole; benzenethiol; pentaerythritol tetra(3-mercaptopropionate) (PETMP); trimethylolpropane tri(3-mercaptopropionate) (TMPMP); triethanolamine tri(3-mercaptopropionate) (TEAMP); tris(2-hydroxyethyl)isocyanurate tri(3-mercaptopropionate) (THEICMP); bis(3-mercaptopropyl) sulfide (BMPS); 1,2-ethanedithiol (EDT); 1,3-propanedithiol; 1,4-butanedithiol; 1,6-hexanedithiol; 1,8-octanedithiol; and combinations thereof.

[0290] In some embodiments, the stimulus-responsive polymer is a linear or branched crosslinked polymer network, wherein the crosslinked polymer network contains 10 or more ester to thiol ester linkers that hydrolyze in the presence of an added base or a thiol-containing compound or an amino-containing compound, wherein the hydrolysis causes the adhesive to dissolve and delaminate from the penile skin.

[0291] In another embodiment, the stimulus-responsive polymer can be a linear or branched polymer that comprises the reaction product of a free radical addition polymerization of mono-, di-, tri-, tetra-, penta-, and hexa-functional thiol-ene components, the thiol-ene components including triallyl isocyanurate pentaerythritol tetra(3-mercaptopropionate) or any of the thiol-ene monomer components disclosed herein. In some embodiments, the thiol-ene adhesive can exhibit stimulus-responsive adhesion behavior when cooled below its glass transition. In some embodiments, the thiol-ene adhesive layer can exhibit chemically responsive adhesive behavior, e.g., the thioether linkers are oxidized by a common oxidant such as hydrogen peroxide to form reversibly cleavable disulfide linkers.

[0292] In some embodiments, the stimulus-responsive polymer comprises a linear or crosslinked polymer that includes a liquid crystal polymer having a thermal transition range of from -10 °C to 50 °C, more particularly from 0 °C to 40 °C, more particularly from 5 °C to 35 °C, more particularly from 5 °C to 20 °C. Suitable liquid crystal polymer compositions include thiol-ene and thiol-acrylate polymers prepared by base-catalyzed Michael addition or free radical polymerization methods, including those prepared from thiol building units such as 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanedithiol, 1,12-dodecanedithiol, hexanediol diacrylate, octanediol diacrylate, decanediol diacrylate, and mesogenic-containing diacrylate materials such as RM105 - 4-(6-acryloyloxyhexyloxy)-benzoic acid (4-cyanophenyl ester), RM 23 - 4-((6-(acryloyloxy)hexyl)oxy)benzoic acid 4-methoxyphenyl ester, CB3A - 3-[(3'-cyanobiphenyl-3-yl)oxy]propyl acrylate. Di-acrylate mesogens include, but are not limited to, RM 257 - 4-(3-acryloyloxy-propyloxy)benzoic acid 2-methyl-1,4-phenylene ester, RM 82 - 1,4-bis[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene.

[0293] In some embodiments, free radical polymerization can be used to crosslink acrylate-functionalized liquid crystal networks. Click chemistry reactions such as Michael addition reactions can also be used to introduce soft flexible segments between mesogenic monomers to lower the Tg and achieve elastomeric behavior under ambient conditions. In some embodiments, dithiols can be used as flexible spacers, including but not limited to: ethanedithiol, propanedithiol, or any other dithiol having an all-carbon backbone, 2,2'-(ethylenedioxy)diethanethiol or any other dithiol having a polyethylene glycol backbone, 1,4-benzenedithiol, 4,4’-diphenyldithiol, ethylene bis(thioglycolate), ethylene bis(mercapto propionate).

[0294] In some embodiments, in addition to thiols, amine-functionalized monomers can also be used in a similar manner. For example, n-butylamine can be used as a flexible chain extender or spacer for mesogenic monomers. Using a Michael addition catalyst such as triethylamine or dipropylamine, acrylate-functionalized mesogenic oligomers can be produced by combining a non-stoichiometric ratio of diacrylate mesogens with dithiol monomers or diacrylate mesogens with bifunctional amines. In either case, an excess of acrylate functional groups is optionally preferred. These oligomers can then be photocrosslinked to form an LCE network.

[0295] In some embodiments, LCE can be synthesized in a one-pot manner by utilizing a thiol or amine functionalized crosslinker with a functionality of 2 or greater. This one-pot method can be used for free radical and Michael addition polymerization methods. Examples include, but are not limited to, pentaerythritol tetrakis(thioglycolate) (PETMA), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), di-pentaerythritol tetrakis(3-mercaptopropionate).

[0296] In some embodiments, the stimulus-responsive polymer includes a linear or crosslinked polymer that comprises a silicone polymer, e.g., a high molecular weight linear siloxane polymer and a highly concentrated silicate tackifying resin. The tackifying resin or tackifier includes low molecular weight compounds having a high glass transition temperature, which are used to formulate adhesives to increase adhesion, the tackiness of the adhesive surface. Tackifiers include resins (e.g., rosin and its derivatives, terpenes and modified terpenes, aliphatic, alicyclic, and aromatic resins (C5 aliphatic resin, C9 aromatic resin, and C5 / C9 aliphatic / aromatic resin), hydrogenated hydrocarbon resins and mixtures thereof, terpene-phenolic resins (TPR, typically used with ethylene-vinyl acetate adhesives)), novolacs. Suitable silicone rubber-based pressure-sensitive adhesives include special tackifiers based on "MQ" silicate resins, which are composed of monofunctional trimethylsilane ("M") reacted with tetrafunctional silicon tetrachloride ("Q").

[0297] In some embodiments, the stimulus-responsive polymer exhibits one or more glass transition (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 higher, as measured by differential scanning calorimetry (DSC) Tg, Tc, Tm peak inflection points or dynamic mechanical analysis loss modulus or tanδ peak (at 1 Hz).

[0298] In some embodiments, the stimulus-responsive polymer can be a linear, brush-like, star-shaped, or dendritic or branched polymer having a weight average molecular weight (Mw) of about 1 kDa, about 5 kDa, about 10 kDa, about 15 kDa, about 20 kDa, about 30 kDa, about 50 kDa, about 75 kDa, about 90 kDa, about 100 kDa, about 110 kDa, about 200 kDa, about 300 kDa, about 400 kDa, about 500 kDa, or about 1000 kDa or higher.

[0299] In some embodiments, the stimulus-responsive polymer is a crosslinked polymer that provides a semi-interpenetrating network or an interpenetrating network.

[0300] In some embodiments, the stimulus-responsive polymer is petroleum-based.

[0301] In some embodiments, the stimulus-responsive polymer is wholly or partially bio-based.

[0302] In some embodiments, the stimulus-responsive polymer is prepared from compostable, bio-based or biodegradable polymers, such as those prepared from plasticized polycaprolactone or plasticized poly(lactic acid). In some embodiments, plasticization is carried out to lower the glass transition or increase tack.

[0303] In some embodiments, the stimulus-responsive polymer is suitable for food-grade applications, such as stickers for agricultural products or fruits.

[0304] 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.

[0305] 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.

[0306] In some embodiments, 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 crosslinker (iii) may comprise one or more monomers.

[0307] In some embodiments, the monomers comprising (i), (ii) and (iii) may be the same monomers or different monomers.

[0308] The monomers can be any suitable monomers. In one embodiment, the monomers are selected from acrylate monomers, allyl monomers, thiol monomers, epoxy monomers, amine monomers, electron-rich monomers, electron-deficient monomers, lactam monomers, lactone monomers, alcohol monomers, carboxyl monomers, isocyanate monomers, Diels Alder monomers, ring-opening metathesis monomers, etc.

[0309] In some embodiments, the stimulus-responsive polymer does not comprise an acrylic-based adhesive containing unreacted polyol plasticizer.

[0310] In some embodiments, the stimulus-responsive polymer does not comprise a hydrophobic polyoxyalkylene-based adhesive derived from poly(ethylene glycol) prepared in the presence of a plasticizer.

[0311] In some embodiments, the stimulus-responsive polymer does not comprise 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 comprise an acrylic pressure-sensitive adhesive and (i) an elastomer having a tackifying resin or (b) a thermoplastic elastomer.

[0312] The adhesives described herein can be used as an adhesive layer in the contraceptive devices disclosed herein, such as the non-rigid partial condoms described herein, e.g., a rigid non-rolled partial condom, which comprises a first adhesive layer (e.g., a stimulus-responsive polymer such as the stimulus-responsive polymers described herein) and a second layer, the second layer comprising a barrier and a reservoir, wherein the condom does not contact the penile shaft or the corona of the penis; wherein the adhesive layer (a) coextends with the barrier layer; (b) is thicker than the barrier layer and / or (c) is the sole means of attachment. The adhesive can be, for example, a stimulus-responsive polymer that comprises one or more methacrylate monomers and a trifunctional crosslinker (e.g., TMPTA), providing a low-density heterophasic crosslinked polymer. The weight ratio of the polymer to the trifunctional crosslinker can be, for example, about 99.4:0.6. The non-rigid partial condom can exhibit one or more of the properties disclosed herein, such as painless removal, low peel strength at low peel rates, high peel strength at high peel rates, loss modulus, etc.

[0313] 4.2.2.2.1 Monomers

[0314] In some embodiments, the stimulus-responsive polymer present in the adhesive and optionally one or more other polymers are formed from (i.e., comprise) monomers selected from: acrylate monomers, methacrylate monomers, vinyl ether monomers, allyl monomers, thiol monomers, epoxy monomers, amine monomers, electron-rich monomers, electron-deficient monomers, lactam monomers, lactone monomers, alcohol monomers, carboxylic acid monomers, isocyanate monomers, Diels-Alder monomers, ring-opening metathesis monomers, or combinations thereof.

[0315] In some embodiments, the stimulus-responsive polymer present in the adhesive, or optionally, one or more other polymers comprise acrylate monomers. In some embodiments, the acrylate monomer is an acrylic C6-C30 alkyl ester monomer, such as an acrylic C8-C30 alkyl ester monomer, an acrylic C8-C20 alkyl ester monomer, an acrylic C8-C16 alkyl ester monomer, an acrylic C8-C12 alkyl ester monomer, an acrylic C12-C30 alkyl ester monomer, an acrylic C12-C20 alkyl ester monomer, or an acrylic C12-C16 alkyl ester monomer.

[0316] Exemplary acrylate monomers include, but are not limited to, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate, nonadecyl acrylate, eicosyl acrylate, heneicosyl acrylate, docosyl acrylate, tricosyl acrylate, tetracosyl acrylate, pentacosyl acrylate, hexacosyl acrylate, heptacosyl acrylate, octacosyl acrylate, nonacosyl acrylate, triacontyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-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, ethoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, stearyl acrylate, lauryl acrylate, isodecyl acrylate, acrylic acid, ethylene glycol diacrylate (EGDA), triethylene glycol diacrylate (TEGDA), propylene glycol diacrylate (PGDA), butylene glycol diacrylate (BDDA), neopentyl glycol diacrylate (NPGDA), pentaerythritol tetraacrylate (PETA), 1,4-butanediol diacrylate (BDA), bis(trimethylolpropane) tetraacrylate (DTMPTA), bisphenol A ethoxylated diacrylate (BPAEDA), ethoxylated bisphenol A diacrylate (EBPA), decanediol diacrylate, polyethylene glycol diacrylate (PEGDA), trimethylolpropane triacrylate (TMPTA), diethylene glycol diacrylate (DEGDA), and 1,6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate (TPGDA), pentaerythritol triacrylate (PETA), dipentaerythritol pentaacrylate (DPEPA), tris(2-hydroxyethyl) isocyanurate triacrylate (THEIC-TA), triethylene glycol dimethacrylate (TEGDMA), triallyl isocyanurate (TAIC), triethylene glycol diacrylate (TEGDA), ethoxylated trimethylolpropane triacrylate (ETMPTA), triallyl cyanurate (TAC), and combinations thereof.

[0317] In certain embodiments, the stimuli-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprises acrylate monomers selected from: octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate, nonadecyl acrylate, eicosyl acrylate, henicosyl acrylate, docosyl acrylate, tricosyl acrylate, tetracosyl acrylate, pentacosyl acrylate, hexacosyl acrylate, heptacosyl acrylate, octacosyl acrylate, nonacosyl acrylate, triacontyl acrylate, and combinations thereof.

[0318] In some embodiments, the acrylate monomer is TMPTA.

[0319] In some embodiments, the stimuli-responsive polymer comprises at least 10 wt% acrylate monomer, such as at least 50 wt%, at least 75 wt%, or at least 90 wt%. In some embodiments, the stimuli-responsive polymer comprises at least 95 wt% acrylate monomer, such as at least 96 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt%.

[0320] In some embodiments, the stimuli-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprises methacrylate monomers. 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.

[0321] Exemplary methacrylate monomers include, but are not limited to: hexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, eicosyl methacrylate, henicosyl methacrylate, docosyl methacrylate, tricosyl methacrylate, tetracosyl methacrylate, pentacosyl methacrylate, hexacosyl methacrylate, heptacosyl methacrylate, octacosyl methacrylate, nonacosyl methacrylate, triacontyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, stearyl methacrylate, lauryl methacrylate, isodecyl methacrylate, tetrahydrofurfuryl methacrylate, glycerol 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, acryloyloxyethyl trimethylammonium chloride, diethylaminoethyl methacrylate, butylaminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, methacryloyloxyethyl phthalate, cyclopropyl methacrylate, and combinations thereof.

[0322] In some embodiments, the stimuli-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprises methacrylate monomers selected from: hexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, eicosyl methacrylate, henicosyl methacrylate, docosyl methacrylate, tricosyl methacrylate, tetracosyl methacrylate, pentacosyl methacrylate, hexacosyl methacrylate, heptacosyl methacrylate, octacosyl methacrylate, nonacosyl methacrylate, triacontyl methacrylate, and combinations thereof. In some embodiments, the stimuli-responsive polymer comprises undecyl methacrylate monomer, i.e., lauryl methacrylate monomer. In some embodiments, the stimuli-responsive polymer comprises octadecyl methacrylate monomer, i.e., stearyl methacrylate monomer.

[0323] In some embodiments, the stimuli-responsive polymer present in the adhesive or optionally one or more other polymers comprises at least 10 wt% methacrylate monomers, such as at least 50 wt%, at least 75 wt%, or at least 90 wt%. In some embodiments, the stimuli-responsive polymer comprises at least 95 wt% methacrylate monomers, such as at least 96 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt%.

[0324] In some embodiments, the stimuli-responsive polymer present in the adhesive, or optionally, one or more other polymers, 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.

[0325] In some embodiments, the stimuli-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprises an allyl monomer. Exemplary allyl monomers include, but are not limited to: diallyl phthalate (DAP), diallyl maleate (DAM), diallyl succinate (DAS), diallyl fumarate (DAF), diallyl adipate (DAA), diallyl sebacate (DAS), diallyl terephthalate (DAT), diallyl isophthalate (DAI), diallyl itaconate (DAI), diallyl carbonate (DAC), diallyl diglycolate (DADG), diallyl tris(2-hydroxyethyl) isocyanurate (DATHEIC), triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), triallyl trimellitate (TATM), triallyl citrate (TAC), triallyl phosphate (TAP), triallyl amine (TAA), triallyl cyanide (TACN), triallyl 1,2,4-benzenetricarboxylate (TABTC), triallyl mellitate (TATM), triallyl tris(2-hydroxyethyl) isocyanurate ether (THEIC-TAE), and combinations thereof.

[0326] In some embodiments, the stimuli-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprise thiol monomers. Exemplary thiol monomers include, but are not limited to, 3-mercaptopropionic acid; mercaptoacetic acid; 3-mercapto-1-propanol; 2-mercaptoethanol; 2-(2-mercaptoethoxy)ethanol; 2-(2-mercaptopropionylamino)ethanol; 2-(2-mercaptosuccinyl)ethyl acrylate; 3-(2-mercaptopropionylamino)propionic acid; 3-(mercaptopropyl)trimethoxysilane; 2,2'-(ethylenedi(thio))diethanol; 3-(mercaptopropyl)trimethoxysilane; 3-(mercaptopropyl)methyldimethoxysilane; 3-(2,2-dithiobis(ethylthio)propionylamino)propionic acid; 3,6,9-trioxadecane thiol; 3-mercapto-1,2-propanediol; 2,2'-dithiodyethanol; N-acetyl-L-cysteine; L-cysteine; 2-(2-mercaptoethyl)pyridine; 4-(2-mercaptoethyl)morpholine; 3-mercapto-1,2,4-triazole; benzenethiol; pentaerythritol tetra(3-mercaptopropionate) (PETMP); trimethylolpropane tri(3-mercaptopropionate) (TMPMP); triethanolamine tri(3-mercaptopropionate) (TEAMP); tris(2-hydroxyethyl)isocyanurate tri(3-mercaptopropionate) (THEICMP); bis(3-mercaptopropyl) sulfide (BMPS); 1,2-ethanedithiol (EDT); 1,3-propanedithiol; 1,4-butanedithiol; 1,6-hexanedithiol; 1,8-octanedithiol; and combinations thereof.

[0327] In some embodiments, the stimuli-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprise epoxy monomers. Exemplary epoxy monomers include, but are not limited to: bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE), novolac diglycidyl ether (NGDE), phenol novolac diglycidyl ether (PNGDE), cycloaliphatic epoxy resins, glycidyl ethers of aliphatic alcohols, glycidyl ethers of aromatic alcohols, triglycidyl isocyanurate (TGIC), 1,4-butanediol diglycidyl ether (BDDGE), neopentyl glycol diglycidyl ether (NPGDGE), propylene glycol diglycidyl ether (PGDGE), epoxidized soybean oil (ESO), epoxidized linseed oil (ELO), dicyclopentadienyl epoxy resin, tetrafunctional epoxy resin, epoxy novolac resin, and combinations thereof.

[0328] In some embodiments, the stimuli-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprises amine monomers. Exemplary amine monomers include, but are not limited to: ethylenediamine; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; polyethyleneimine; diaminopropane; diaminobutane; diamino-pentane; 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.

[0329] In some embodiments, the stimuli-responsive polymer present in the adhesive, or optionally, one or more other polymers, 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-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxymethylallylamine, N-hydroxymethylvinylacetamide, acrolein diethyl acetal, acrolein diethyl ketal, diacetoneacrylamide, 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.

[0330] In some embodiments, the stimuli-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprises electron-deficient monomers. Exemplary electron-deficient monomers include, but are not limited to: acrylonitrile, methacrylonitrile, methyl methacrylate, acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide, methacrylamide, N-vinylcarbazole, vinylidene chloride, vinyl chloride, vinylsulfonic acid, vinyl acetate, styrene, α-methylstyrene, maleimide, N-phenylmaleimide, and N-butylmaleimide, maleic anhydride; and combinations thereof.

[0331] In some embodiments, the stimulus-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprises lactam monomers. Exemplary lactam monomers include, but are not limited to: caprolactam, valerolactam, heptanolactam, octanolactam, laurolactam, proline lactam, butyrolactam, methionyl lactam, methoxyethyl lactam, methoxyethyl methionyl lactam, dimethylaminoethyl lactam, dimethylaminoethyl methionyl lactam, dimethylaminoethyl acryloyl lactam, dimethylaminoethyl methacryloyl lactam, N-vinylpyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, and combinations thereof.

[0332] In some embodiments, the stimulus-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprises lactone monomers. Exemplary lactone monomers include, but are not limited to: β-propiolactone, γ-butyrolactone, 8-valerolactone, ε-caprolactone, ω-pentadecanolide, 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-caprolactone, and combinations thereof.

[0333] In some embodiments, the stimulus-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprises alcohol monomers. Exemplary alcohol monomers include, but are not limited to: ethylene glycol; propylene glycol; 1,3-butanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 1,10-decanediol; neopentyl glycol; diethylene glycol; triethylene glycol; tetraethylene glycol; polyethylene glycol (PEG); polypropylene glycol (PPG); polycaprolactone diol; polyhydroxymethyl propane; hydroxypivaloyl hydroxymethyl butyrate (HPHMB); 1,4-cyclohexanedimethanol, and combinations thereof.

[0334] In some embodiments, the stimulus-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprises carboxylic acid monomers. Exemplary carboxylic acid monomers include, but are not limited to: adipic acid, succinic acid, glutaric acid, sebacic acid, malonic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, itaconic acid, citric acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, dodecanedioic acid, and combinations thereof.

[0335] In some embodiments, the stimulus-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprises isocyanate monomers. Exemplary isocyanate monomers include, but are not limited to: toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HMDI), 4,4'-methylenebis(cyclohexyl isocyanate) (H12MDI), naphthalene diisocyanate (NDI), 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), polymethylene polyphenyl isocyanate (PAPI), Desmodur N-100, Desmodur L-75, Desmodur HL, Desmodur H, Desmodur VP, Desmodur Z, and combinations thereof

[0336] In some embodiments, the stimulus-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprises Diels-Alder monomers. Exemplary Diels-Alder monomers include, but are not limited to, maleic anhydride, furan, cyclopentadiene, N-phenylmaleimide, anthracene, N-ethylmaleimide, N-phenylnorbornene, N,N-dimethylmaleimide, 2,5-dimethylfuran, tetracyanoethylene, methyl vinyl ketone, and combinations thereof.

[0337] In some embodiments, the stimulus-responsive polymer present in the adhesive, or optionally, one or more other polymers, comprises ring-opening metathesis monomers. Exemplary ring-opening metathesis monomers include, but are not limited to: norbornene, dicyclopentadiene (DCPD), cyclooctene, tetracyclododecene (TCD), cyclopentene, cycloheptene, cyclohexene, bicyclo[2.2.1]hept-2-ene, bicyclo[2.2.2]oct-5-ene, tricyclo[5.2.1.0(2,6)]dec-8-ene (TCD-diene), and combinations thereof.

[0338] 4.2.2.2.2 Side Chains

[0339] In some embodiments, the stimulus-responsive polymer comprises two or more side chains.

[0340] In some embodiments, the stimulus-responsive polymer comprises C6 to C30 side chains or C6 to C30 pendant chain ends. In some embodiments, the C6 to C30 side chains or C6 to C30 pendant chain ends are C6 to C30 alkyl side chains, preferably C12 to C18 alkyl side chains.

[0341] In some embodiments, the stimulus-responsive polymer comprises at least 80 wt% side chains, such as at least 85 wt%, at least 90 wt%, or at least 95 wt%. In some embodiments, the side chains are the same. In some embodiments, the side chains are different.

[0342] In some embodiments, the side chain comprises a linking group made from monomers selected from: acrylate, methacrylate, thiol-acrylate Michael adduct, acrylate-amine Michael adduct, epoxy-thiol, epoxy-amine, polyethyleneimine (PEI), thiol-ene, alternating copolymers made from C═C electron-deficient monomers + C═C electron-rich monomers, urethane, urea, acrylamide, methacrylamide, polyester, polycarbonate, polyamide, peptoid, peptide, Diels-alder, lactide, and lactam, and ring-opening metathesis polymers or olefin metathesis.

[0343] In some embodiments, the side chain chemistry comprises C1-C100 side chain linking groups obtained by the synthetic routes disclosed herein.

[0344] In some embodiments, the stimulus-responsive polymer having C6 to C18 side chains or pendant chain ends is made from: acrylate, methacrylate, alcohol, carboxylic acid, electron-rich olefins, electron-deficient olefins, epoxy groups, amines, ROMP, Diels-Alder, lactones, lactams, peptides, peptoids, acrylamides, methacrylamides, thiols, vinyls, and allyl monomers.

[0345] In some embodiments, the stimulus-responsive polymer comprises a linear or crosslinked polymer having side chains that optionally crystallize and / or melt in the range of 0 °C to 50 °C, more specifically in the range of 5 °C to 45 °C, more specifically in the range of 10 °C to 40 °C, more specifically in the range of 15 °C to 35 °C, in the region near body temperature and room temperature. For clarity, side chain crystallization is optional.

[0346] In some embodiments, the linear or crosslinked polymer ranges from about 40 to about 100%, more particularly, 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 subsumed therein.

[0347] In some embodiments, the optionally crystallizable secondary side chain polymer ranges from about 0 to about 50%, more particularly 1 to about 49%, more particularly about 2 to about 48%, more particularly about 3 to 47%, more particularly about 5 to about 45% or any additional range or value subsumed therein.

[0348] 4.2.2.2.3 Multifunctional crosslinking agents

[0349] In some embodiments, the stimulus-responsive polymer present in the adhesive, or optionally, one or more other polymers are crosslinked polymers. The crosslinked polymers are prepared using one or more polyfunctional crosslinking agents. The crosslinking agent can exhibit a functionality statistically greater than n = 1 reactive sites, e.g., a statistical average of n = 2, 3, 4, 5, 6, 7, 8, 9, 10 or more reactive sites, and can promote branching, hyperbranching, interpenetrating networks, semi-interpenetrating networks and networks that are generally uniform or partially uniform and partially non-uniform or generally non-uniform in terms of the phase blend or crosslink density concentration.

[0350] In some embodiments, the polyfunctional crosslinking agent is selected from difunctional crosslinking agents, trifunctional crosslinking agents or tetrafunctional crosslinking agents. In some embodiments, the polyfunctional crosslinking agent is a trifunctional crosslinking agent.

[0351] 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.

[0352] 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 hexaepoxides; polythiols; polyolefins; tris(2-acryloyloxyethyl) isocyanurate, ε-caprolactone-modified tris(2-acryloyloxyethyl) isocyanurate, ethoxylated glycerol triacrylate, pentaerythritol triacrylate, and combinations thereof.

[0353] In some embodiments, the polyfunctional crosslinking agent is poly(ethylene glycol) diacrylate with internal repeating units in the range of 1 to 1000 or more, trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate with repeating units in the range of 1 to 1000 or more, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate with repeating units in the range of 1 to 1000 or more, pentafunctional and hexafunctional acrylates and ethoxylated versions as described above (including dipentaerythritol hexaacrylate and ethoxylated dipentaerythritol hexaacrylate) (with repeating units in the range of 1 to 1000 or more), di-, tri-, tetra-, penta-, hexa-, more epoxide monomers, polythiols, polyolefins (cured by ultraviolet light, visible light, γ or electron beam radiation, heating or hydrosilylation).

[0354] In some embodiments, the multifunctional crosslinker is selected from trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, hexanediol diacrylate, and combinations thereof. In some embodiments, the multifunctional crosslinker is trimethylolpropane triacrylate (TMPTA).

[0355] In some embodiments, the stimulus-responsive polymer is a crosslinked polymer having a uniform crosslink network density. In some embodiments, the stimulus-responsive polymer is a crosslinked polymer having a heterogeneous crosslink network. For example, advantageous adhesive failure or delamination from the skin, including removal of residual adhesive after peeling the adhesive, can be achieved by a heterogeneous crosslink distribution to concentrate the failure sites within the network or "swollen multiphase network" (formed by polymerization of a crosslinker and monomers having different reactivity ratios).

[0356] In some embodiments, the stimulus-responsive polymer is characterized by a low density of crosslinks.

[0357] In some embodiments, the crosslinker is uniformly incorporated into the stimulus-responsive polymer network.

[0358] In some embodiments, the crosslinker aggregates within the stimulus-responsive polymer network. This embodiment produces high stress concentration network sites and / or drives rheological behavior and is capable of dissipating energy (having a high tanδ and high loss modulus compared to a more uniform network) to facilitate adhesive failure when needed.

[0359] The amount of crosslinker in the stimulus-responsive polymer or optionally one or more additional polymers can vary. In some embodiments, the polymer comprises from 0 to 30 wt%, such as from 0.001 to 29 wt%, more particularly from 0.005 to 28 wt%, more particularly from 0.0075 to 28 wt%, more particularly from 0.01 to 27 wt%, more particularly from 0.02 to 26 wt%, more particularly from 0.05 to 26 wt%, more particularly from 0.1 to 25 wt%, more particularly from 0.15 to 24 wt% of the crosslinker.

[0360] In some embodiments, the stimulus-responsive polymer comprises an amount of crosslinker selected from: about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 7.5 wt%, about 0.8 wt%, about 0.9 wt%, about 9.5 wt% or about 1.0 wt% or more, in each case relative to the weight of the polymer.

[0361] In a specific embodiment, the stimulus-responsive polymer comprises a crosslinking agent, and the amount of the crosslinking agent is 0.1 wt% to about 1 wt%, about 0.2 wt% to about 0.8 wt%, about 0.3 wt% to about 0.7 wt%, or about 0.4 wt% to about 0.6 wt%, in each case relative to the weight of the polymer.

[0362] In some embodiments, the stimulus-responsive polymer comprises 0.1 wt% to 2.5 wt%, such as 0.1 wt% to 2 wt%, 0.1 to 1.5 wt%, 0.1 wt% to 1 wt%, 0.1 wt% to 0.9 wt, 0.1 wt% to 0.8 wt%, 0.1 wt% to 0.7 wt%, 0.1 wt% to 0.6 wt%, 0.1 wt% to 0.5 wt%, 0.1 wt% to 0.4 wt%, 0.1 wt% to 0.3 wt%, 0.1 wt% to 0.2 wt%, 0.2 wt% to 1.5 wt%, 0.2 wt% to 1 wt%, 0.3 wt% to 1.5 wt%, 0.3 wt% to 1 wt%, 0.4 wt% to 1.5 wt%, 0.4 wt% to 1 wt%, 0.5 wt% to 1.5 wt%, 0.5 wt% to 1 wt%, 0.6 wt% to 1.5 wt%, 0.6 wt% to 1 wt%, 0.7 wt% to 1.5 wt%, 0.7 wt% to 1 wt%, 0.8 wt% to 1.5 wt%, 0.8 wt% to 1 wt%, 0.9 wt% to 1.5 wt%, or 0.9 wt% to 1 wt% of a multifunctional crosslinking agent.

[0363] In some embodiments, the stimulus-responsive polymer comprises 0.4 wt% to 0.8 wt%, such as, 0.4 wt% to 0.7 wt%, 0.4 wt% to 0.6 wt%, 0.4 wt% to 0.5 wt%, 0.5 wt% to 0.8 wt%, 0.5 wt% to 0.7 wt%, 0.5 wt% to 0.6 wt%, 0.6 wt% to 0.8 wt%, 0.6 wt% to 0.7 wt%, or 0.7 wt% to 0.8 wt% of a multifunctional crosslinking agent. In some embodiments, the multifunctional crosslinking agent is trimethylolpropane triacrylate (TMPTA).

[0364] 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, 77:23, 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.

[0365] In some embodiments, the weight ratio of one or more monomers to one or more polyfunctional crosslinking agents is from 98:2 to 99.9:0.1, such as from 98.5:1.5 to 99.9:0.1; from 99:1 to 99.9:0.1, from 99.1:0.9 to 99.9:0.1, from 99.2:0.8 to 99.9:0.1; from 99.3:0.7 to 99.9:0.1, from 99.4:0.6 to 99.9:0.1, from 99.5:0.5 to 99.9:0.1, from 99.6:0.4 to 99.9:0.1, from 99.7:0.3 to 99.9:0.1, or from 99.8:0.2 to 99.9:0.1.

[0366] 4.2.2.2.4 Embodiment

[0367] 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 ratio is 99:1, 98:2, 97:3, 96:4, 95:3, 94:6, 93:7, 92:8, 91:9, 90:10, 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34, 65:35, 64:36, 63:37, 62:38, 61:39, 60:40, 59:41, 58:42, 57:43, 56:44, 55:45, 54:46, 53:47, 52:48, 51:49 or 50:50.

[0368] 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 ratio is 99:1, 98:2, 97:3, 96:4, 95:3, 94:6, 93:7, 92:8, 91:9, 90:10, 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34, 65:35, 64:36, 63:37, 62:38, 61:39, 60:40, 59:41, 58:42, 57:43, 56:44, 55:45, 54:46, 53:47, 52:48, 51:49 or 50:50.

[0369] In some embodiments, the stimulus-responsive polymer comprises both C6-C30 alkyl acrylate monomers and C6-C30 alkyl methacrylate monomers. According to this embodiment, the molar ratio of the components can vary consistently according to the stoichiometry of the mass ratio equivalents.

[0370] In some embodiments, the stimulus-responsive polymer comprises poly(lauyl methacrylate), i.e., poly(dodecyl methacrylate) crosslinked with one or more polyfunctional crosslinkers. In some embodiments, the weight ratio of lauryl methacrylate to one or more polyfunctional crosslinkers is from 98:2 to 99.9:0.1, for example, from 98.5:1.5 to 99.9:0.1; from 99:1 to 99.9:0.1, from 99.1:0.9 to 99.9:0.1, from 99.2:0.8 to 99.9:0.1; from 99.3:0.7 to 99.9:0.1, from 99.4:0.6 to 99.9:0.1, from 99.5:0.5 to 99.9:0.1, from 99.6:0.4 to 99.9:0.1, or from 99.7:0.3 to 99.9:0.1, from 99.8:0.2 to 99.9:0.1.

[0371] In some embodiments, the stimulus-responsive polymer comprises poly(lauyl methacrylate) crosslinked with one or more trifunctional crosslinkers. In some embodiments, the weight ratio of lauryl methacrylate to one or more trifunctional crosslinkers is from 98:2 to 99.9:0.1, for example, from 98.5:1.5 to 99.9:0.1; from 99:1 to 99.9:0.1, from 99.1:0.9 to 99.9:0.1, from 99.2:0.8 to 99.9:0.1; from 99.3:0.7 to 99.9:0.1, from 99.4:0.6 to 99.9:0.1, from 99.5:0.5 to 99.9:0.1, from 99.6:0.4 to 99.9:0.1, or from 99.7:0.3 to 99.9:0.1, or from 99.8:0.2 to 99.9:0.1.

[0372] In some embodiments, the stimulus-responsive polymer comprises poly(lauyl methacrylate) crosslinked with an acrylate crosslinker. In some embodiments, the weight ratio of lauryl methacrylate to one or more acrylate crosslinkers is from 98:2 to 99.9:0.1, for example, from 98.5:1.5 to 99.9:0.1; from 99:1 to 99.9:0.1, from 99.1:0.9 to 99.9:0.1, from 99.2:0.8 to 99.9:0.1; from 99.3:0.7 to 99.9:0.1, from 99.4:0.6 to 99.9:0.1, from 99.5:0.5 to 99.9:0.1, from 99.6:0.4 to 99.9:0.1, or from 99.7:0.3 to 99.9:0.1, or from 99.8:0.2 to 99.9:0.1.

[0373] In some embodiments, the stimulus-responsive polymer comprises poly(lauroly methacrylate) crosslinked with a trifunctional acrylate crosslinker. In some embodiments, the weight ratio of lauroly methacrylate to one or more trifunctional acrylate crosslinkers is from 98:2 to 99.9:0.1, for example, from 98.5:1.5 to 99.9:0.1; from 99:1 to 99.9:0.1, from 99.1:0.9 to 99.9:0.1, from 99.2:0.8 to 99.9:0.1; from 99.3:0.7 to 99.9:0.1, from 99.4:0.6 to 99.9:0.1, from 99.5:0.5 to 99.9:0.1, from 99.6:0.4 to 99.9:0.1, or from 99.7:0.3 to 99.9:0.1, or from 99.8:0.2 to 99.9:0.1.

[0374] In some embodiments, the stimulus-responsive polymer comprises poly(lauroly methacrylate) crosslinked with one or more polyfunctional crosslinkers selected from the following: 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; polyolefins; tris(2-acryloyloxyethyl) isocyanurate; ε-caprolactone-modified tris(2-acryloyloxyethyl) isocyanurate; ethoxylated glycerol triacrylate; ethoxylated glycerol triacrylate and pentaerythritol triacrylate. In some embodiments, the weight ratio of lauroly methacrylate to one or more polyfunctional crosslinkers is from 98:2 to 99.9:0.1, for example, from 98.5:1.5 to 99.9:0.1; from 99:1 to 99.9:0.1, from 99.1:0.9 to 99.9:0.1, from 99.2:0.8 to 99.9:0.1; from 99.3:0.7 to 99.9:0.1, from 99.4:0.6 to 99.9:0.1, from 99.5:0.5 to 99.9:0.1, from 99.6:0.4 to 99.9:0.1, or from 99.7:0.3 to 99.9:0.1, or from 99.8:0.2 to 99.9:0.1.

[0375] In some embodiments, the stimulus-responsive polymer comprises poly(lauroly methacrylate) crosslinked with one or more multifunctional crosslinking agents selected from the following: 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 lauroly methacrylate to one or more multifunctional crosslinking agents is from 98:2 to 99.9:0.1, such as, from 98.5:1.5 to 99.9:0.1; from 99:1 to 99.9:0.1, from 99.1:0.9 to 99.9:0.1, from 99.2:0.8 to 99.9:0.1; from 99.3:0.7 to 99.9:0.1, from 99.4:0.6 to 99.9:0.1, from 99.5:0.5 to 99.9:0.1, from 99.6:0.4 to 99.9:0.1, or from 99.7:0.3 to 99.9:0.1, or from 99.8:0.2 to 99.9:0.1.

[0376] In some embodiments, the stimulus-responsive polymer comprises poly(lauroly methacrylate) crosslinked with trimethylolpropane triacrylate. In some embodiments, the weight ratio of lauroly methacrylate to trimethylolpropane triacrylate is from 98:2 to 99.9:0.1, such as, from 98.5:1.5 to 99.9:0.1; from 99:1 to 99.9:0.1, from 99.1:0.9 to 99.9:0.1, from 99.2:0.8 to 99.9:0.1; from 99.3:0.7 to 99.9:0.1, from 99.4:0.6 to 99.9:0.1, from 99.5:0.5 to 99.9:0.1, from 99.6:0.4 to 99.9:0.1, or from 99.7:0.3 to 99.9:0.1, or from 99.8:0.2 to 99.9:0.1.

[0377] In some embodiments, the adhesive comprises poly(lauroly methacrylate) and TMPTA, where TMPTA crosslinks the lauroly methacrylate. According to this embodiment, the weight ratio of the components can vary. In some embodiments, the weight ratio is 99:1, or more particularly, about 99.4:0.6, about 99.6:0.4 or about 99.8:0.2.

[0378] Any of the above stimulus-responsive polymers can form the adhesive layer of the condom described herein, optionally in combination with other additives or components. More particularly, the non-rigid, non-rolled, partial condom described herein includes a first adhesive layer (e.g., a stimulus-responsive polymer such as the stimulus-responsive polymers described herein) and a second layer, the second adhesive layer including a barrier and a reservoir, wherein the condom does not contact the penile shaft or the glans penis; wherein the adhesive layer (a) coextends with the barrier layer; (b) is thicker than the barrier layer and / or (c) is the sole means of attachment. Optionally, the second layer is continuous, i.e., the barrier and the reservoir are formed together, i.e., are integral. 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 securing the condom to the penis. The condom may exhibit one or more of the properties disclosed herein, such as painless removal, low peel strength at low peel rates, high peel strength at high peel rates, loss modulus, etc.

[0379] 4.2.3. Additives

[0380] In some embodiments, the adhesive further comprises one or more additives. Exemplary additives include tackifiers, plasticizers, pigments, fillers, fluorescent agents, flow agents, wetting agents, surfactants, defoamers, rheology modifiers, colorants, penetration enhancers, stabilizers, antioxidants, and combinations thereof. In some embodiments, the adhesion can be enhanced or reduced by adding additives.

[0381] Exemplary plasticizers include, but are not limited to: glyceryl triacetate (triacetin), glyceryl monooleate (GMO), glyceryl monostearate (GMS), glyceryl tristearate (tristearin), glyceryl tributyrate (tributyrin), glyceryl tripropionate (tripropionin), glyceryl trioleate (triolein), glyceryl dilaurate (GDL), glyceryl dimyristate (GDM), glyceryl distearate (GDS), di(2-ethylhexyl) phthalate (DEHP), diisononyl phthalate (DINP), dibutyl phthalate (DBP), diisodecyl phthalate (DIDP), benzyl butyl phthalate (BBP), dimethyl phthalate (DMP), di-n-octyl phthalate (DnOP), diisobutyl phthalate (DIBP), diethyl phthalate (DEP), dicyclohexyl phthalate (DCHP), methyl caprate, ethyl caprate, propyl caprate, isopropyl caprate, butyl caprate, isobutyl caprate, pentyl caprate, hexyl caprate, heptyl caprate, octyl caprate, decyl caprate, and C1-C20 alkanoates on both sides of the ester.

[0382] In some embodiments, a plasticizer may be added to lower the glass transition temperature of the polymer to adjust the adhesion state. Suitable plasticizers include glycerol, 1-butanol, 1-octanol, stearic acid, n-butyl stearate, poly(ethylene glycol) with Mw of 100 to 200 to 400 to 1000 to 2000 to 4000 to 10000 daltons or higher, water, various organic solvents, 1-decanoate, and 1-octanoate.

[0383] In some embodiments, the additive is stimulus-responsive. For example, an additive such as poly(ethylene glycol) with Mw of 400 daltons or glycerol can be used at a blend ratio of 1 wt% to 90 wt% with a binder layer component such as poly(n-dimethyl acrylamide), such that the additive plasticizes the binder layer above the crystallization temperature of the additive and no longer plasticizes the binder layer below the crystallization temperature of the additive.

[0384] In some embodiments, the stimulus-responsive additive can exhibit crystallization, glass transition, or other thermal transitions in the range of 0 °C to 50 °C, more particularly in the range of 5 °C to 40 °C, more particularly in the range of 10 °C to 30 °C, and even more particularly in the range of 12 °C to 25 °C.

[0385] Exemplary tackifiers include, but are not limited to, rosin esters, hydrocarbon resins, terpene resins, styrene resins, polyterpene resins, coumarone-indene resins, phenolic resins, tall oil rosins, aliphatic resins, and aromatic resins.

[0386] Exemplary tackifying resins or tackifiers include low molecular weight compounds having a high glass transition temperature, used to formulate adhesives to increase tack, the stickiness of the adhesive surface. In some embodiments, the tackifier includes 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 their mixtures, terpene-phenolic resins (TPR, typically used with ethylene-vinyl acetate adhesives)), novolacs. Silicone rubber-based pressure-sensitive adhesives suitable for the present invention include special tackifiers based on "MQ" silicate resins (composed of monofunctional trimethylsilane ("M") reacting with tetrafunctional silicon tetrachloride ("Q")).

[0387] In some embodiments, the tackifier or plasticizer is selected from glycerol-based, phthalate, polyethylene glycol derivatives with a molecular weight of 1 to 1000 or more repeating units, and C10-C40 straight-chain or branched wax or modified wax components, such as n-butyl stearate or ethyl caproate.

[0388] 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.

[0389] Exemplary water- or solvent-chemically swellable particulate additives include, but are not limited to, poly(sodium acrylate) having a molecular weight in the range of 100 to 5 million Daltons, more particularly 100 to 1 million Daltons, more particularly 1000 to 1 million Daltons, a particle size in the range of 1 micron to 1000 microns, more particularly 20 microns to 800 microns, more particularly 20 to 300 microns, and a concentration in the range of 0.01 to 95 wt%, more particularly 0.1 to 75 wt%, more particularly 1 to 60 wt%, more particularly 2 to 55 wt%.

[0390] In some embodiments, the particulate additive can reduce the diffusion of water or other solvents into the adhesive layer and can be a hydrophobic component, such as stearic acid, hydrophobic fumed silica, or polyethylene wax, having a molecular weight in the range of 100 to 5 million Daltons, more particularly 100 to 1 million Daltons, more particularly 200 to 1 million Daltons, a particle size in the range of 1 micron to 1000 microns, more particularly 20 microns to 800 microns, more particularly 20 to 300 microns, and a concentration in the range of 0.01 to 95 wt%, more particularly 0.1 to 75 wt%, more particularly 1 to 60 wt%, more particularly 2 to 55 wt%.

[0391] In some embodiments, the particulate additive can create physical sites that increase or decrease skin adhesion and can be stimulus-responsive. The component that creates physical sites that enhance or reduce skin adhesion can be a ceramic additive, such as fumed silica, zinc oxide, or titanium dioxide, or can be a polymer having a molecular weight in the range of 100 to 5 million Daltons, more particularly 100 to 1 million Daltons, more particularly 200 to 1 million Daltons, a particle size in the range of 1 micron to 1000 microns, more particularly 20 microns to 800 microns, more particularly 20 to 300 microns, and a concentration in the range of 0.01 to 95 wt%, more particularly 0.1 to 75 wt%, more particularly 1 to 60 wt%, more particularly 2 to 55 wt%.

[0392] The additives used herein may include nucleating agents for stimuli-responsive adhesives, which undergo changes in adhesion behavior upon cooling crystallization. The addition of nucleating agents, such as nanoscale fumed silica and polyethylene wax, can be used to adjust the crystallization temperature of adhesives (such as poly(octadecyl methacrylate)) that exhibit a crystallization transition. Nucleation-inducing additives include additives having a particle size in the range of 1 nm to 1000 microns, more particularly 10 nm to 500 microns, and more particularly 10 nm to 250 microns. The nucleation-inducing additives can be blended with the adhesive in solution blending, high-shear mixing, or other blending techniques, or can be generated in situ during adhesive preparation or contraceptive diaphragm formation by techniques including precipitation or phase separation. For example, stearic acid can be mixed with the adhesive solution under high-shear conditions to form a nanophase that remains dispersed in an adhesive blend such as poly(stearyl methacrylate).

[0393] In some embodiments, the additive can be used as a crack propagator to facilitate adhesive failure upon removal by mechanical peeling.

[0394] In some embodiments, the amount of additive present in the adhesive is from 0 to 60 wt%, more particularly 0.1 wt% to 50 wt%, 0.1 wt% to 40 wt%, 0.1 wt% to 30 wt%, 0.1 wt% to 20 wt%, 0.1 wt% to 10 wt%, 0.1 wt% to 5 wt%, 0.1 wt% to 2.5 wt%, 0.1 wt% to 1 wt%.

[0395] 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 wt% or more.

[0396] In some embodiments, one or more additives are present in the adhesive in an amount of about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, or about 60 wt%.

[0397] In some embodiments, one or more additives are present in the adhesive in an amount of about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, or about 0.9 wt% or more.

[0398] In some embodiments, one or more additives are present in an amount of about 0.01 wt%, about 0.02 wt%, about 0.03 wt%, about 0.04 wt%, about 0.05 wt%, about 0.06 wt%, about 0.07 wt%, about 0.08 wt%, or about 0.09 wt% or more of the binder.

[0399] 4.2.4. Method for preparing a stimulus-responsive polymer

[0400] In some embodiments, the stimulus-responsive polymer is prepared by curing one or more monomers and a first amount of one or more polyfunctional crosslinkers to form a prepolymer, and then post-curing the prepolymer; thereby providing the stimulus-responsive polymer.

[0401] In some embodiments, the weight ratio of one or more monomers to one or more polyfunctional crosslinkers is from 98:2 to 99.9:0.1, for example, from 98.5:1.5 to 99.9:0.1; from 99:1 to 99.9:0.1, from 99.1:0.9 to 99.9:0.1, from 99.2:0.8 to 99.9:0.1; from 99.3:0.7 to 99.9:0.1, from 99.4:0.6 to 99.9:0.1, from 99.5:0.5 to 99.9:0.1, from 99.6:0.4 to 99.9:0.1, from 99.7:0.3 to 99.9:0.1, from 99.8:0.2 to 99.9:0.1.

[0402] In some embodiments, the curing is photopolymerization using 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-trimethylbenzoylphosphinate (LAP), and biocompatible photoinitiators.

[0403] In some embodiments, the curing is done neat, i.e., solvent-free.

[0404] In some embodiments, the post-curing includes subjecting the prepolymer to an elevated temperature relative to the curing, such as at least 50 °C, at least 100 °C, at least 150 °C, or at least 200 °C.

[0405] In some embodiments, the method further includes pausing the curing before completion, adding a second amount of one or more polyfunctional crosslinkers, and restarting the curing.

[0406] In some embodiments, polymers having C6 to C18 side chains or pendant chain termini are prepared from: acrylates, methacrylates, alcohols, carboxylic acids, electron-rich alkenes, electron-deficient alkenes, epoxies, amines, ROMP, Diels-Alder, lactones, lactams, peptides, peptoids, acrylamides, methacrylamides, thiols, vinyl, and allyl monomers. In some embodiments, a low level of crosslinking, such as the dot concentration provided by a range of 0.4 wt%, 0.6 wt%, 0.75 wt%, 0.95 wt% of trimethylolpropane triacrylate in a polymer including but not limited to poly(lauroyl methacrylate) or poly(stearoyl methacrylate) (including but not limited to 99.6 wt%, 99.4 wt%, 99.25 wt%, 99.05 wt% lauroyl methacrylate or stearoyl methacrylate), provides a shear rate-responsive polymer that adheres to human skin and can subsequently be removed from human skin with minimal pain, and the residual adhesive remaining on the human skin can be removed with minimal pain by gentle rubbing.

[0407] In some embodiments, these long side-chain / low crosslink density polymers can be prepared from any of the monomers, crosslinkers, or other ingredients described herein by any of the reaction methods described herein. For example, linear or branched poly(ethyleneimine, PEI) can be modified at the side chains and chain ends using lauryl acrylate or stearyl acrylate via Michael addition under base-catalyzed conditions or using isocyanate / amine reactions using lauryl isocyanate or stearyl isocyanate. In another embodiment, non-stoichiometric or stoichiometric thiol-ene can be prepared using a combination of mono-, di-, tri-, and tetra-functional thiols and olefin monomers with a monofunctional component such as lauryl mercaptopropionate or dodecyl vinyl ether such that the monofunctional component comprises 0.1, 0.2, 0.3, 0.4, or 0.5 mol% or more of the total thiol-ene composition. In another representative embodiment, an alternating copolymer comprising maleimide or n-butyl maleimide and dodecyl vinyl ether is prepared using radical alternating polymerization and can be lightly crosslinked by dodecyl vinyl ether with less than wt% or polymethacrylate or acrylate to form a heterogeneous crosslinked network with low crosslink density and high C12 side-chain wt% (60, 70, 80, 90, or higher wt% alkyl side-chain C6 or higher, preferably C12-C18). In another embodiment, octadecylamine is polymerized with a Michael addition comonomer such as ethylene glycol diacrylate or hexanediol diacrylate under base-catalyzed conditions. In one embodiment, the resulting poly(β-amino ester) is prepared by reacting 1:25:1.0 C═C:NH2 (reacting with the double NH2 of the acrylate) such that acrylate-capped groups are produced, and the acrylate-capped poly(β-amino ester) reaction product can be photocured using UV light and the crosslink density can be reduced by adding a monofunctional acrylate or methacrylate such as stearyl methacrylate or lauryl methacrylate or stearyl acrylate or lauryl acrylate or by adding a thiol chain transfer agent or capping agent such as PETMP or IOMP or EGBMP or 1,10-decanedithiol or PETMP. In another embodiment, a similar Michael addition synthesis method can be used for the thiol / acrylate Michael addition reaction product, preferably with an excess of acrylate.

[0408] In another embodiment, the adhesive is a linear or branched crosslinked polymer network, wherein the crosslinked polymer network comprises 10 or more ester to thioester linkages that are hydrolyzed in the presence of an added base or a thiol-containing compound or an amino-containing compound, wherein the hydrolysis causes the adhesive to dissolve and delaminate from the penile skin.

[0409] In another embodiment, the adhesive layer can be a linear or branched polymer comprising the reaction product of a free radical addition polymerization of mono-, di-, tri-, tetra-, penta- and hexa-functional thiol-ene components, the thiol-ene components comprising triallyl isocyanurate, pentaerythritol tetra(3-mercaptopropionate) or any of the thiol-ene monomer components disclosed herein. In one embodiment, the thiol-ene adhesive can exhibit stimulus-responsive adhesion behavior when cooled below its glass transition. In another embodiment, the thiol-ene adhesive layer can exhibit chemically-responsive adhesion behavior, e.g., the thioether linkages are oxidized by common oxidants such as hydrogen peroxide to form reversibly removable disulfide linkages.

[0410] 4.3. Packaging

[0411] In one aspect, the present disclosure provides a package comprising a contraceptive device described herein.

[0412] In some embodiments, the package includes a condom described herein. In some embodiments, the package includes a contraceptive diaphragm described herein.

[0413] In some embodiments, the package can be rigid, semi-rigid, flexible, or a combination thereof, in which the contraceptive device is placed prior to use, and the package can have or not have an additional use in addition to storage described herein. In some embodiments, the package can be 0.005 mm or thinner, 0.005 mm or thicker, 0.01 mm or thicker, 0.02 mm or thicker, 0.03 mm or thicker, 0.04 mm or thicker, or 0.05 mm or thicker. The package can be approximately rectangular, circular, elliptical, polygonal, or curvilinear in shape.

[0414] In some embodiments, the package includes a flexible packaging material comprising foil, plastic, plastic-lined paper, foil-lined paper, or a combination thereof.

[0415] 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 recesses covered by a thin metal, paper, or plastic film, which can be pierced by pressing on the bottom of the rigid recess. Semi-rigid is defined as a material and thickness that retains its designed geometry but can be deformed by applying a force between 1 and 5 N (Newtons) or between 5 and 10 N or between 10 and 20 N, or between 20 and 100 N, or between 100 and 150 N, or between 150 and 200 N, or between 200 and 300 N. The deformation can be elastic bending deformation, buckling deformation, or crease deformation. The recesses can be cylindrical, conical, spherical, of revolution, polyhedral, irregular, or asymmetric in shape. The recesses can have a circular, rectangular, elliptical, polygonal, or curvilinear cross-section.

[0416] In some embodiments, the package is a recessed design. In some embodiments, the recessed design package comprises a rigid plastic, paper, or cardboard structure. In some embodiments, one or more faces of the container are sealed by a removable plastic film or metal foil film. In some embodiments, a tab may project from the film such that it can be peeled off by finger strength or another means of grasping the tab. In some embodiments, the sealing film can be pierced to expose the contraceptive device therein.

[0417] In some embodiments, the package is for containing and discarding the contraceptive device after use. In some embodiments, the package contains any ejaculate that may have been deposited inside or on the condom.

[0418] In some embodiments, the package further comprises a delaminating composition adapted to induce delamination of the adhesive layer from the penis or vagina when the adhesive layer has adhered to the penis or vagina. In some embodiments, the package further includes a delaminating composition adapted to induce delamination of the adhesive layer from the glans penis when the adhesive layer has adhered to the glans penis.

[0419] In some embodiments, the delaminating composition is a wipe. In some embodiments, the wipe comprises a solvent that dissolves, denatures, or swells a stimulus-responsive polymer such that when the adhesive layer has adhered to the penis or vagina and the wipe is subsequently applied to the contraceptive device, it induces delamination of the adhesive layer from the penis or vagina. In some embodiments, the wipe comprises a solvent that dissolves, denatures, or swells a stimulus-responsive polymer such that when the adhesive layer has adhered to the glans penis and the wipe is subsequently applied to the condom, it induces delamination of the adhesive layer from the glans penis.

[0420] In some embodiments, the wipe contains a volatile additive that cools the wipe upon evaporation such that when the adhesive layer has adhered to the penis or vagina and the wipe is subsequently applied to the condom, it induces delamination of the adhesive layer from the penis or vagina. In some embodiments, the wipe includes a volatile additive that cools the wipe upon evaporation such that when the adhesive layer has adhered to the glans penis and the wipe is subsequently applied to the condom, it induces delamination of the adhesive layer from the glans penis.

[0421] In some embodiments, the package may further comprise a lubricant, a spermicide, or both.

[0422] 4.4. Kits

[0423] In one aspect, the present disclosure provides a kit comprising the contraceptive device described herein and instructions for use.

[0424] In some embodiments, the kit includes a condom as described herein and instructions for use. In some embodiments, the kit includes a packaged condom as described herein and instructions for use.

[0425] In some embodiments, the kit includes a sectional condom as described herein and instructions for use. In some embodiments, the kit includes a packaged sectional condom as described herein and instructions for use.

[0426] In some embodiments, the kit includes a contraceptive diaphragm as described herein and instructions for use. In some embodiments, the kit includes a packaged contraceptive diaphragm as described herein and instructions for use.

[0427] In some embodiments, the kit may contain a lubricant, a spermicide, or both.

[0428] 4.5. Method of Use

[0429] On the one hand, the present disclosure provides a method of applying a condom as described herein to the penis of a human subject, including contacting the adhesive layer of the condom as described herein with the penis and applying sufficient pressure to the condom to adhere the condom to the penis. In some embodiments, the pressure is applied with one or more fingers or hands of the subject.

[0430] In some embodiments, the method of applying a sectional condom as described herein to the penis of a human subject includes contacting the adhesive layer of the condom with the glans penis and applying sufficient pressure to the condom to adhere the condom to the glans penis. In some embodiments, the pressure is applied with one or more fingers or hands of the subject.

[0431] In some embodiments, the condom or sectional condom disclosed herein is applied before sexual arousal or before full sexual arousal.

[0432] In some embodiments, the method of applying a contraceptive diaphragm as described herein to the vagina of a human subject includes contacting the adhesive layer of the contraceptive diaphragm with the vagina and applying sufficient pressure to the contraceptive diaphragm to adhere the contraceptive diaphragm to the vagina. In some embodiments, the pressure is applied with one or more fingers or hands of the subject.

[0433] In some embodiments, adhesion to the skin can be achieved by a hot melt method, which is achieved by oral fusion or by other external heating, such as a hot melt process provided by a hair dryer or by squeezing in a human hand for about 0 to about 20 seconds, wherein the adhesive exhibits enhanced 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.

[0434] In some embodiments, applying the partial condom disclosed herein to the penis of a human subject is easier than applying partial condoms known in the art (including but not limited to GALATIC CAP TM ).

[0435] In some embodiments, applying the partial condom disclosed herein is easier than applying partial condoms known in the art (such as GALATIC CAP TM ).

[0436] In some embodiments, applying the partial condom disclosed herein is 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 easier than applying partial condoms known in the art (such as GALATIC CAP TM ), as measured by any suitable method (e.g., user self-report in a sexual intercourse log) in a non-clinical or clinical setting.

[0437] In certain embodiments, less than 30% of users find it difficult or very difficult to apply the condom, and more specifically, less than 25%, less than 20%, less than 15%, less than 10%, or less than 5%.

[0438] In some embodiments, the partial condom disclosed herein adheres 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 WO2014178661A and US 11,234,858). The adhesion can be measured by any suitable method (e.g., user self-report in a sexual intercourse log) in a non-clinical or clinical setting.

[0439] In some embodiments, the use of the condom disclosed herein enhances the 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.

[0440] In some embodiments, use of the condoms disclosed herein can increase 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 suitable method (e.g., self-reporting by the user, partner, or both in a sexual intercourse log) in a non-clinical or clinical setting. Comparison can be made to conventional condoms or partial condoms.

[0441] In some embodiments, the condoms disclosed herein enhance the sexual pleasure of the user and / or partner to about 2X, about 3X, about 4X, about 5X, about 6X, about 7X, about 8X, about 9X, or about 10X or more, as measured by self-reporting by the individual(s) (e.g., using a sexual intercourse log) or more formal studies (including comparative group studies).

[0442] Sexual pleasure can be measured by any suitable method. For example, see Siegler AJ et al., Arch Sex Behav. August 2018; 47(6):1745–1754, which is hereby incorporated by reference in its entirety. 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. October 2013; 10(10):2409-17), which is hereby incorporated by reference. Both are reliable event-level measures of the quality of sexual experience, and the latter is applicable to both men and women.

[0443] In other embodiments, sexual pleasure can be evaluated by the Sexual Pleasure Scale (SPS) (Patrícia M Pascoal et al. (2016) The Journal of Sexual Medicine, 13(9), 1408-1413), the Body, Emotion, Sensation, Touch / Trust (B.E.S.T.) scale (Beckmeyer et al. (2021) Journal of American College Health, 1-12), or the Pleasure Meter (Castellanos-Usigli and Braeken-van Schaik (2019). Sexual and reproductive health matters, 27(1), 313-315).

[0444] In some embodiments, the use of the condoms disclosed herein can enhance the sexual sensations 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, measured by any suitable method in a non-clinical or clinical setting. In one embodiment, the enhanced sexual pleasure is measured by any suitable method in a non-clinical setting (e.g., by individual self-report (e.g., via a sexual intercourse log)) or in a clinical setting. Comparison can be made to conventional condoms or partial condoms.

[0445] In some embodiments, the condoms disclosed herein can enhance the sexual sensations of the user and / or partner to about 2X, about 3X, about 4X, about 5X, about 6X, about 7X, about 8X, about 9X, or about 10X or more, which can be measured by any suitable method in a non-clinical setting (e.g., user self-report in a sexual intercourse log) or in a clinical setting (e.g., by individual self-report (e.g., via a sexual intercourse log)). The comparison can be made with respect to conventional condoms or partial condoms.

[0446] In some embodiments, at least a majority of the user population (actual users and / or partners) prefer to use the condoms disclosed herein over conventional condoms, where the majority represents about 80%, about 85%, about 90%, or about 95% or more of the population. The users can be a non-clinical or clinical user population.

[0447] In some embodiments, about 85% to 100% of users prefer to use the condoms disclosed herein rather than conventional condoms.

[0448] In an embodiment, at least 175 out of 200 users in a population prefer the condoms disclosed herein over conventional condoms.

[0449] In some embodiments, using the condoms disclosed herein results in an increase in the condom usage rate among the user population in a non-clinical or clinical setting.

[0450] In one embodiment, the group is a group of human subjects in a clinical trial.

[0451] On the other hand, the present disclosure provides a method for removing the condoms described herein from a human subject's penis, comprising applying a stimulus to the condom whose adhesive layer is adhered to the penis and removing the condom from the penis.

[0452] In some embodiments, a method of removing a partial condom as described herein from the glans penis of a human subject includes applying a stimulus to the condom whose adhesive layer is adhered to the glans penis and removing the condom from the glans penis.

[0453] In some embodiments, a method of removing a contraceptive diaphragm as described herein from the vagina of a human subject includes applying a stimulus to the contraceptive diaphragm whose adhesive layer is adhered to the vagina and removing the contraceptive diaphragm from the vagina.

[0454] In some embodiments, the condoms disclosed herein are easier to remove than partial condoms known in the prior art.

[0455] In some embodiments, the ease of removal is improved 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 (e.g., personal self - reporting in a sexual intercourse log) in a non - clinical or clinical setting.

[0456] In some embodiments, less than 30% of users find it difficult or very difficult to remove the condom, more specifically, less than 25%, less than 20%, less than 15%, less than 10%, or less than 5%.

[0457] In certain embodiments, removing the contraceptive device does not cause damage.

[0458] In some embodiments, the pain caused by removing the contraceptive device to the subject is minimal or painless (as measured by WBQPA), such as a WBQPA score less than 4, less than 3, less than 2, less than 1, or 0.

[0459] In some embodiments, removing the contraceptive device does not cause significant irritation, inflammation, or redness to the user.

[0460] In some embodiments, when removing the contraceptive device from the penis or vagina, 50 wt% or less, e.g., 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, or 5 wt% or less of the adhesive remains on the penis or vagina. In some embodiments, even if the adhesive remains on the penis or vagina after removal, the nature of the adhesive is such that it is easy to remove by mild friction or rolling.

[0461] 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 different rates.

[0462] In some embodiments, the peeling is the mild peeling as described above. In some embodiments, the mild peeling corresponds to a peeling rate of 25 mm / s or less, such as 10 mm / s or less, 5 mm / s or less, 1 mm / s or less, 0.5 mm / s or less, 0.3 mm / s or less, or 0.1 mm / s or less. In some embodiments, the mild peeling corresponds to a peeling rate of 0.01 mm / second to 25 mm / second, such as, 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 / sec, 0.1 mm / s to 25 mm / s, 0.1 mm / s to 10 mm / s, 0.1 mm / s to 5 mm / s, 0.1 mm / s to 1 mm / s, 0.1 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, the mild peeling corresponds to a peeling rate of 500 mm / min or less, 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, the mild peeling corresponds to a peeling rate of 50 mm / min to 500 mm / min, such as, 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.

[0463] 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 lower. 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 lower.

[0464] In some embodiments, the stimulus is a physicochemical change, and the application of the stimulus includes applying a wipe to the contraceptive device, where the wipe contains a solvent that can dissolve, denature, or swell the stimulus-responsive polymer, thereby inducing delamination of the adhesive layer from the penis or vagina. In some embodiments, the stimulus is a physicochemical change, and the application of the stimulus includes applying a wipe to a condom, where the wipe includes a solvent that dissolves, denatures, or swells the stimulus-responsive polymer, thereby inducing delamination of the adhesive layer from the glans penis.

[0465] In some embodiments, the condoms disclosed herein can be removed without applying a liquid such as baby oil.

[0466] In some embodiments herein, the condom is removed without leaving the location of sexual intercourse.

[0467] In certain embodiments, the user can remove the condom without urinating.

[0468] 4.6. Manufacturing Method

[0469] In one aspect, the present disclosure provides a method for preparing the contraceptive device described herein, including adhering an adhesive layer to a barrier layer, where the adhesive layer contains an adhesive that includes a stimulus-responsive polymer formed from one or more monomers and optionally one or more polyfunctional crosslinking agents.

[0470] In some embodiments, the method for preparing a condom includes adhering an adhesive layer to a barrier layer, where the adhesive layer contains an adhesive that includes a stimulus-responsive polymer formed from one or more monomers and optionally one or more polyfunctional crosslinking agents.

[0471] In some embodiments, the method for preparing a contraceptive diaphragm includes adhering an adhesive layer to a barrier layer, where the adhesive layer contains an adhesive that includes a stimulus-responsive polymer formed from one or more monomers and optionally one or more polyfunctional crosslinking agents.

[0472] In some embodiments, a method for manufacturing the contraceptive device described herein is provided, including (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, dip coating, thermoforming, extrusion, injection molding, or other large-scale film manufacturing methods, thereby providing the contraceptive device described herein. In some embodiments, the substrate is a release liner. In some embodiments, the substrate is a barrier layer.

[0473] In some embodiments, the contraceptive device comprises an adhesive layer cured using photopolymerization. In some embodiments, after being applied as a coating to a barrier substrate, the adhesive is 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.

[0474] In some embodiments, using the foregoing crosslinking chemicals or other substances, the adhesive is crosslinked through a latent reaction after being processed onto a release liner or barrier layer. For example, after dip-coating the adhesive onto a release liner or barrier layer or applying it by spraying or in a roll-to-roll coating method, crosslinking can be achieved using residual epoxide and alcohol or amine chemicals.

[0475] 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 made to have the ability to re-bond after being removed from the skin or other application surface. An example of a transfer method of applying a separately prepared adhesive layer to a barrier layer is pad printing. Another example is that the adhesive can be prepared separately from the barrier layer and extruded through holes or nozzles and then transferred onto the barrier layer. Another example is that the adhesive can be prepared on a template or mold separate from the barrier, and the barrier is deposited and transferred onto the adhesive in a solid layer form or in a liquid form by dip-coating, spraying, brushing, painting, or roll-coating transfer methods.

[0476] In some embodiments, one or more quality testing steps are performed on the contraceptive device. In some embodiments, the contraceptive device undergoes a leak test or an electrical test (e.g., a dry electrical test).

[0477] In some embodiments, one or more of its physical property tests are performed on the contraceptive device, including but not limited to tensile strength, tensile or overlap shear strength, peel adhesion strength, and / or impact strength, and satisfactory results are provided.

[0478] In some embodiments, one or more tests are performed on the contraceptive device, which are selected from: ASTM F2255-05 Standard Test Method for Tensile Loading of Lap Shear Strength Properties of Tissue Adhesives; ASTM F2256-05 Standard Test Method for Tensile Loading of T-Peel Strength Properties of Tissue Adhesives; and ASTM F2258-05 Standard Test Method for Tensile Strength Properties of Tissue Adhesives, and satisfactory factory results are provided.

[0479] 4.7. Examples

[0480] The following are examples of specific implementation schemes for implementing the present disclosure. These examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure in any way. Efforts have been made to ensure the accuracy of the numbers used (e.g., quantity, temperature, etc.), but of course some experimental errors and deviations should be taken into account.

[0481] 4.7.1. Example 1

[0482] A toluene solution of poly(ethyl acrylate) (average Mw ∼ 95 kDa measured by GPC) with 18 - 22 wt% solids was purchased from Sigma Aldrich and cast onto a polyethylene plastic substrate with a thickness of about 0.1 mm, measured by caliper. The toluene solvent was allowed to evaporate in a fume hood for about 72 hours. After solvent evaporation, a polymer film with a thickness of about 50 - 500 microns remained on the polyethylene substrate, and the cross-sectional thicknesses of the polymer film measured by caliper were about 200 and 400 microns respectively. This polymer film was sandwiched with a second 0.3 mm polyethylene layer and stored at about 20 °C and a relative humidity of about 45% - 60% for 6 months. After 6 months, the poly(ethyl acrylate) film was easily maintained adhered to the 0.3 mm thick polyethylene film on which it was cast. To demonstrate the thermoresponsive delamination from human skin, the polyethylene / poly(ethyl acrylate) substrate was pressed onto a bare human arm, and the adhesion behavior was confirmed and recorded by video, showing that it was strong enough to substantially restrict the easy removal of the polyethylene / poly(ethyl acrylate) substrate from the human arm.

[0483] The adhered polyethylene / poly(ethyl acrylate) substrate attached to the human arm was rinsed with tap water (about 20 °C) from a kitchen sink for about 5 - 10 seconds while also being subjected to a gentle pulling / stripping hand force. After 5 - 10 seconds, painless or delamination without significant hand force was achieved, and no adhesive residue was observed on the arm.

[0484] 4.7.2. Example 2

[0485] A toluene solution of poly(ethyl acrylate) (average Mw ∼ 95 kDa measured by GPC) with 18 - 22 wt% solids was purchased from Sigma Aldrich and cast onto a commercially available 6”×6” dental dam latex and polyurethane substrate with a thickness of about 0.2 mm. The dental dam was about 0.20 mm as measured by caliper. The toluene solvent was allowed to evaporate in ambient air with a relative humidity of about 45% - 60% for 72 hours. After solvent evaporation, a polymer film with a thickness of about 50 to 500 microns remained on the dental dam substrate, and the cross-sectional thicknesses of the polymer film measured by caliper were about 200 and 400 microns respectively.

[0486] Unlike the poly(ethyl acrylate) film reported in Example 1 stored for 6 months, when qualitatively evaluating skin adhesion 72 hours after casting onto latex and polyurethane dental dams, the poly(ethyl acrylate) film in Example 2 exhibited limited tack at room temperature (about 19 °C).

[0487] To demonstrate thermoresponsive delamination from human skin, a latex dental dam / poly(ethyl acrylate) substrate with a circular adhesive layer approximately 50 to 500 microns thick (cross-sections measured with calipers were approximately 200 and 400 microns thick respectively) and a diameter of approximately 4 cm was pressed onto an erect human penis. While pressing on the glans penis, it was heated with a hair dryer at a warm setting for approximately 5 seconds, and the adhesion behavior was observed immediately after 5 seconds of exposure to the hair dryer (in one embodiment of the present disclosure, oral fusion is an alternative technique to the hair dryer for heating a partially tacky adhesive to a more desirable thermomechanical state for adhesion during a hot melt process). A rubber band was wrapped around the base of the glans penis to secure the non-adhesive portion of the dental dam substrate and prevent any shear removal / stress concentration from forming at non-adhesive sites, and the erect penis was subjected to forces consistent with those observed during sexual intercourse using masturbation techniques. At ejaculation, even after removing the rubber band placed under the glans penis, no semen was observed to leave the condom adhered to the glans penis. Then, the adhered latex dental dam was subjected to cold water (about 10 - 20 °C) in a normal shower and gently removed by peeling along the edges. Within approximately 10 - 20 seconds, as the cold water rinsed along the adhered dental dam / water interface, penile skin delamination was observed with minimal or no pain, and no adhesive residue was observed on the penile skin or within the urethra. After removing the adhered dental dam, immediate urination was easily achieved.

[0488] Example 2 was repeated and similar results were observed. When repeating the method of Example 2, after wiping the base of the glans penis with a tissue, no semen was observed on the tissue. In Example 2, a flaccid penis with an adhered condom was immersed in ice water, and the condom was easily removed with no adhesive residue observed on the penis.

[0489] 4.7.3. Example 3

[0490] Add a toluene solution containing approximately 10 mL of poly(ethyl acrylate) (average Mw ~ 95 kDa measured by GPC) with a solids content of 18 - 22 wt% to a stainless-steel mixing container. Add approximately 1 mL of poly(butyl acrylate) (average molecular weight of 99 kDa measured by GPC, solids content of 25 - 30 wt%) to the same stainless-steel mixing container and stir for approximately 20 seconds using a polyethylene pipette. This poly(ethyl acrylate) / poly(butyl acrylate) mixture appears homogeneous and optically transparent after stirring for approximately 20 seconds, with no visible signs of phase separation or precipitation. Both the poly(ethyl acrylate) and poly(butyl acrylate) solutions were purchased from Sigma Aldrich and used as received. After mixing, aspirate approximately 3 mL of the blended poly(ethyl acrylate) / poly(butyl acrylate) solution into a 3 mL polyethylene pipette and drip it onto 6” x 6” latex oral dental dams (in triplicate). The dental dams have a thickness of approximately 200 microns as measured by calipers. Under ambient air conditions with a relative humidity of approximately 40% - 60%, in the temperature range of 15 °C to 25 °C, allow the dental dam / adhesive solution to evaporate for approximately 72 hours. After solvent evaporation, a polymer blend film with a thickness of approximately 50 to 500 microns remains on the latex oral dental dam substrate, and the cross-section of the adhesive / latex substrate is measured using calipers such that the adhesive layer is measured to be approximately 200 and 400 microns thick, respectively. To demonstrate thermoresponsive delamination from human skin, press the latex / poly(ethyl acrylate) / poly(butyl acrylate) substrate onto a bare human arm and demonstrate that the adhesion behavior is strong enough to substantially restrict the easy removal of the polyethylene / poly(ethyl acrylate) / poly(butyl acrylate) substrate from the human arm. Rinse the adhered polyethylene / poly(ethyl acrylate) / poly(butyl acrylate) substrate attached to the human arm with cold water (approximately 5 - 10 °C) from a refrigerated bottle while also subjecting it to a mild pulling / stripping hand force, and painless or force-free delamination is achieved after 2 - 5 seconds, no adhesive residue is observed on the arm, and no pain is observed upon removal.

[0491] 4.7.4. Example 4

[0492] Using ordinary scissors, a circular / oval substrate was cut from one of three latex dental dams / poly(ethyl acrylate) / poly(butyl acrylate) samples prepared by the method of Example 3, such that after cutting, an adhesive elastomeric substrate covering approximately 100% of the latex surface was produced. The resulting circular / oval substrate had a major diameter of approximately 5.5 cm and a minor diameter of approximately 5 cm as measured with calipers. The resulting adhesive / latex substrate was then placed approximately symmetrically on the erect human glans penis such that the urethra was centered within the adhesive substrate ("adhesive condom"), and the edge of the adhesive condom extended to approximately 50% to 75% of the surface area of the erect glans penis, taking care that the urethra was fully covered and the base of the frenulum was exposed. When the adhesive condom was placed on the erect glans penis, natural folding resulted in the formation of a semen reservoir.

[0493] After application of the adhesive condom to the erect penis, the condom was observed to be firmly fixed to the glans. After application of a small amount of ordinary sexual lubricant to the vagina, the erect penis with the glans partially covered by the adhesive condom as described above was inserted into the human vagina and sexual intercourse was performed. After a few minutes, approximately every 15 seconds, the erect penis with the adhesive condom applied was removed from the vagina and inspected, and the adhesive condom was observed to remain in place without delaminating from the head of the erect penis. After sexual intercourse for a few minutes, ejaculation occurred, starting while the adhesive condom covering the erect penis was within the vagina and ending outside the vagina, such that the ability of the adhesive condom to prevent semen outflow during ejaculation could be evaluated. No semen was observed during or immediately after ejaculation. To remove the semen-containing adhesive condom, the surface and edge of the condom were exposed to cold water at approximately 10°C to 15°C flowing from an ordinary shower head, and the edge of the condom was pulled backward by hand in the presence of cold water for approximately 15 - 45 seconds to slowly remove the condom in parts with minimal pain or no pain. For the individual with a penis in Example 4, ejaculation was easily achieved, and the sexual experience was significantly different from that using a traditional condom covering the glans, frenulum, and shaft of the penis. For comparison, sexual intercourse was repeated using a lubricated latex condom, and ejaculation could not be achieved in the same sexual position as when using the adhesive condom until after the traditional latex condom was removed.

[0494] 4.7.5. Example 5

[0495] Poly(n-dimethylacrylamide) (“pDMAA”) (Mw ~150,000 Da) was purchased from Scientific Polymer Products, Inc. Glycerol (>99%) was purchased from Sigma Aldrich, Inc. A 50 / 50 pDMAA / glycerol blend was prepared by dissolving 4.17 g of pDMAA and 4.17 g of glycerol in a solution mixture of (4.17 g of technical grade acetone purchased from a local hardware store and 2.50 g of 190 proof ethanol). The pDMAA / glycerol / acetone / ethanol solution was mixed in a sealed glass vial and heated to approximately 50 °C for 10 minutes, and the mixture was vortexed repeatedly (heat, vortex, repeat) until a clear solution was observed, observing a homogeneous, substantially clear solution. The pDMAA / glycerol solution was then cast onto a 6” x 6” latex dental dam and allowed to evaporate in a chemical fume hood at ambient temperature for approximately 48 to 96 hours. After any water impurities present in the acetone, ethanol, and acetone / ethanol blend had evaporated, the resulting pDMAA / glycerol film was approximately 400 microns thick and was substantially tacky to the touch at 20 °C and significantly more tacky / adhesive at 37 °C. A 5” x 5” 50 / 50 pDMAA / glycerol adhesive dental dam was applied to a human forearm and video showed significant adhesion. When rinsed with tap water on a human arm at room temperature, this adhesive could be painlessly peeled off the human forearm and was observed to completely dissolve in tap water.

[0496] 4.7.6. Example 6

[0497] Poly(octadecyl methacrylate) (“pODMA”) (Mw ~96,000 Da) was purchased from Scientific Polymer Products, Inc. as a toluene solution (approx. 20 wt%). The pODMA solution was cast onto a 6” x 6” latex dental dam and allowed to evaporate in a chemical fume hood at ambient temperature for approximately 48 to 96 hours. After the toluene had evaporated, the resulting p(ODMA) film was approximately 300 microns thick and was non-tacky to the touch at 20 °C (waxy in nature) and significantly more tacky / adhesive at 37 °C. A 5” x 5” p(ODMA) adhesive dental dam was applied to a human forearm and video showed significant adhesion. This ODMA-containing substrate could be removed from the human arm with ice water at approximately 0 °C, and any residual ODMA remaining on the human arm could be removed with olive oil or melted candle wax.

[0498] 4.7.7. Example 7

[0499] The method of Example 7 was repeated to prepare a polymer blend on a latex dental dam containing 1.0 part of poly(n-butyl acrylate), 6.50 parts of poly(ethyl acrylate), and 3.0 parts of poly(octadecyl methacrylate). As described in Example 6, toluene solutions of poly(n-butyl acrylate) with Mw ~99,000 and poly(ethyl acrylate) with Mw ~95,000 were purchased from Sigma Aldrich, and pODMA was purchased from Scientific Polymer Products. Compared to the 100% pODMA-coated adhesive dental dam reported in Example 6, the three-component dental dam of Example 7 transferred significantly less residual poly(ODMA) to human skin during delamination at 0 °C.

[0500] 4.7.8. Example 8

[0501] Poly(ethylene) glycol (Mw 400 da) (PEG-400) and poly(n-dimethylacrylamide) (“pDMAA”) (Mw ~150,000 Da) were purchased from Scientific Polymer Products, Inc. A 50 / 50% weight blend of PEG-400 and pDMAA was prepared in a 50% total weight solution of acetone and ethanol (the solution was prepared using 4 g of PEG-400, 4 g of pDMAA, 4 g of acetone (crude acetone, from a hardware store, may contain water), and 4 g of 190 proof ethanol). A latex dental dam substrate taped to the lid of a polypropylene Tupperware container was placed in a vacuum oven at ambient pressure and 65 °C with a constant airflow into a fume hood and allowed to equilibrate to 65 °C. Under constant airflow conditions and ambient pressure, the PEG-400 / pDMAA 50 / 50 weight % solution was cast onto the 65 °C substrate in the vacuum oven for 24 hours. The resulting film was observed to exhibit strong adhesion behavior in the range of 45 - 65 °C (above the crystallization temperature of PEG-400) and no tack / adhesion at ambient temperature (below the crystallization temperature of PEG-400).

[0502] 4.7.9. Example 9

[0503] A series of adhesives and barrier substrates are prepared by polymerization of monomeric substances. The monomers include: n-butyl acrylate, n-ethyl acrylate, n-octyl acrylate, n-hexyl acrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, cetyl methacrylate, stearyl methacrylate, lauryl methacrylate, acrylamide, n-isopropylacrylamide, poly(ethylene glycol) diacrylate, Mn~750, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate and dimethylcarbamate dimethacrylate, triethylene glycol divinyl ether, n-vinyl dodecyl ether (dodecyl vinyl ether), isooctyl 3-mercaptopropionate, triallyl isocyanurate, purchased from Sigma Aldrich and / or Scientific Polymer.

[0504] The monomers are weighed using an analytical balance and 1.0 wt% of DMPA photoinitiator is added until a homogeneous solution is formed. These solutions are then injected between Rain-X coated 1.0 mm thick glass slides separated by a 1.0 mm thick spacer and UV cured at 365 nm for 15 minutes in a UVP CL-1000 crosslinker, after which the samples are post-cured at 90 °C for about 10 hours under ambient conditions. Samples that are optically transparent after post-curing at 90 °C are then cooled to room temperature, are optically transparent to the naked eye at room temperature, and then placed in a -20 °C refrigerator for 5 minutes, after which the samples exhibit varying degrees of turbidity or become opaque. The samples can be removed from the glass slides and processed. Initially, the room temperature samples with turbidity appear as non-sticky waxy solids. When heated to body temperature, the samples become very adhesive to the skin, more adhesive to a polyurethane dental dam, and less adhesive to a latex dental dam. Samples that are optically transparent and do not become turbid after cooling appear as gels and have limited adhesion or stickiness to a polyurethane dental dam or a latex dental dam.

[0505] In some cases, samples with varying degrees of turbidity exhibit the following properties: (A) a waxy solid at room temperature, (B) upon melting when applied to human skin, they adhere to human skin and simultaneously adhere well to latex and polyurethane condoms or dental dams, (C) a frequency response and / or shear response adhesion behavior such that the melted wax adhesive maintains the barrier adhesion of polyurethane and latex condoms and dental dams to human skin while "pulling" or "snapping" the barrier at higher forces or frequencies or shear rates, such as those expected to remove the adhesive barrier from human skin, while also exhibiting the ability to be removed from human skin with minimal pain or no pain by low frequency or low force or very gentle or slow peeling. (D) For selected samples, the residual adhesive left on the human skin after removal is melted and very difficult to remove, while in other cases, the adhesive can be very easily wiped off in a very natural human way with only minimal pain or no pain. The observed behaviors were video recorded. Optically opaque samples that exhibit melting and near-painless removal at varying degrees of frequency, shear, or shear rate on human skin (including human forearm, biceps, shoulder, and glans penis skin) include UV-cured poly(stearyl methacrylate) samples with different crosslinkers, the crosslinkers including poly(ethylene glycol) diacrylate, Mn 750, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and ethoxylated trimethylolpropane triacrylate, with crosslinker ranges including 0 wt%, 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.75 wt%, 0.85 wt%, 0.95 wt%, 1.0 wt%, 2.0 wt%, 3.0 wt%, 5.0 wt%, 7.5 wt%, 10.0 wt%, 15.0 wt%, 20 wt%, 25 wt%, and 30 wt% of crosslinker, prepared using 1.0 wt% DMPA photoinitiator.

[0506] Optically transparent samples that show strong adhesion to human skin (including human forearm, biceps, shoulder, and glans penis skin) and near-painless removal at varying degrees of frequency, shear, or shear rate include UV-cured poly(stearyl methacrylate) samples with different crosslinkers, the crosslinkers including poly(ethylene glycol) diacrylate, Mn 750, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and ethoxylated trimethylolpropane triacrylate, with crosslinker ranges including 0 wt%, 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.75 wt%, 0.85 wt%, 0.95 wt%, 1.0 wt%, 2.0 wt%, 3.0 wt%, 5.0 wt%, 7.5 wt%, 10.0 wt%, 15.0 wt%, 20 wt%, 25 wt%, and 30 wt% of crosslinker, prepared using 1.0 wt% DMPA photoinitiator.

[0507] Compositions that do not show strong adhesion to human skin (including human forearm, biceps, shoulder, and glans penis skin) include poly(butyl acrylate) and poly(hexyl acrylate) crosslinked with 0.2, 0.4, 0.6, 1.0, and 2.0 or higher weight % crosslinking agents, said crosslinking agents including poly(ethylene glycol) diacrylate, Mn 750, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and ethoxylated trimethylolpropane triacrylate.

[0508] Compositions that show strong adhesion to human skin (including human forearm, biceps, shoulder, and glans penis skin) include poly(lauryl methacrylate) and poly(octadecyl methacrylate) crosslinked with 0.4, 0.5, 0.6, 0.7 weight % trimethylolpropane triacrylate crosslinking agent and 1.0 weight % DMPA, which are photopolymerized and post-cured at 90 °C for 10 hours or longer. Higher concentrations of crosslinking agent, such as 1.0 and 2.0 weight % TMPTA, provide skin adhesion samples with less adhesion.

[0509] 4.7.10. Example 10

[0510] Adhesive samples were prepared by photopolymerizing a monomer solution of 98.43 weight % lauryl methacrylate (LMA) and 0.59 weight % trimethylolpropane triacrylate (TMPTA) with 0.98 weight % 2,2-dimethoxy-2-phenylacetophenone (DMPA) photoinitiator. Monomers were weighed using an analytical balance and mixed using a FlackTek high-speed mixer (DAC 330-100PRO) until a homogeneous solution was formed. Approximately 3 mL of the solution was pipetted onto a 25 mm disposable aluminum rheometer substrate (TA Instruments) and cured under an inert nitrogen atmosphere for 1 hour under a 365 nm UV lamp (UVP CL-1000UV crosslinker). The sample was then post-cured at 120 °C for 1 hour at atmospheric pressure. The sample was then cooled to ambient temperature.

[0511] Comparative sample groups were prepared using 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 Rain - X coated 1.0 mm thick 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 the samples were cooled to ambient temperature. The samples were removed from the glass slides and placed on the surface of a 25 mm rheometer substrate.

[0512] By visual inspection, it was observed that the adhesive samples and the comparative samples were optically transparent to the naked eye. All samples exhibited viscoelastic behavior without flow (soft solids). It was observed that the adhesive samples showed strong adhesion to human skin (fingertips and inner wrist), nitrile, and glass, while the comparative samples exhibited elastomeric properties and showed little adhesion to human skin (fingertips or inner wrist) and nitrile.

[0513] The adhesion strength was quantitatively measured using a TA Instruments Discovery HR - 2 rheometer with an 8.00 mm aluminum tip and a Peltier - cooled aluminum substrate. The measurement was carried out at a sample temperature of 25 °C. The sample was contacted and squeezed for 60 seconds, after which the rheometer tip was withdrawn at a rate of 100 microns / second, and the axial force was measured. For the adhesive samples, the maximum measured axial adhesive force was 6 N. The same procedure was repeated for the comparative samples, and samples (a), (b), and (c) produced peak adhesive forces of 5 N, 6 N, and 4 N on aluminum, respectively. The adhesion strength measured in Newton - seconds (Ns) was calculated by integrating the area under the force - versus - time measurement for each sample, resulting in 88.4 Ns for the adhesive and 9.6 Ns, 5.9 Ns, and 3.8 Ns for comparative samples (a), (b), and (c) Figure 4 ). The adhesion energy of the adhesive was also calculated by multiplying the integrated adhesion strength by a constant stretching rate of 100 microns / second, resulting in an adhesion energy of 8.84×10−3 joules (J) for the adhesive, and adhesion energies of 0.96×10−3 J, 0.59×10−3 J, and 0.38×10−3 J for comparative samples (a), (b), and (c), respectively.

[0514] 4.7.11. Example 11

[0515] A series of adhesive samples was prepared by photopolymerizing a monomer solution having the following composition with 0.98 wt% 2DMPA photoinitiator: 98.43 wt% LMA and 0.59 wt% TMPTA. The monomers were weighed using an analytical balance and mixed using a FlackTek high-speed mixer (DAC330-100PRO) until a homogeneous solution was formed.

[0516] In the "pre-curing" step, a prepolymer solution was formed by partially curing 90 g of the monomer solution for 14 minutes under a continuous flow of inert nitrogen atmosphere using a 365 nm UV light source (UVPCL-1000 UV crosslinker). This process was repeated four times separately. 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 high-speed mixer until homogeneous.

[0517] Subsequently, 5 mL of the prepolymer solution was pipetted onto silicone-impregnated paper fixed on a 1.0 mm thick glass slide and further cured under UVV light in an inert nitrogen atmosphere for 41 minutes. After removal from the crosslinker, each sample was individually clamped between another piece of silicone-impregnated paper fixed on a 1.0 mm thick glass slide, compressed with a spring clamp to a thickness of 600 - 700 microns, post-cured at 120 °C and atmospheric pressure for 1 hour, and then cooled to ambient temperature. The samples were observed to be optically transparent to the naked eye.

[0518] Tensile strain capacity evaluation was performed using a universal testing machine (Instron 5944). The samples were measured to be 600 microns thick using a micrometer and cut into rectangular strips 2 cm wide, which were clamped in the Instron fixtures with an initial fixture spacing of 5 cm. The samples were strained in tension at a rate of 300 mm / min until failure ( Figure 5 ). Sample (1) failed at a stress of 0.15 MPa and a strain of 182%. Sample (2) failed at a stress of 0.12 MPa and a strain of 217%. Sample (4) failed at a stress of 0.067 MPa and a strain of 120%.

[0519] An additional non-adhesive comparative sample was prepared from a monomer solution containing: 98.27 wt% BA, 0.75 wt% TMPTA, 0.98 wt% DMPA; which was injected between two Rain-X coated 1.0 mm thick 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 crosslinker), post-cured for 12 hours at 90 °C and atmospheric pressure, and then cooled to ambient temperature. The sample failed at 0.22 MPa stress and 152% strain.

[0520] Additional strain capacity measurements were performed on the L6 10% TMPTA sample, the BA sample, and the LA sample. The sample thickness was measured, cut into 1.6 cm wide rectangular strips, and clamped in an Instron fixture with an initial fixture spacing of 3 cm. The sample was stretched at a rate of 300 mm / min until failure ( Figure 6 and Figure 7 ). The strain capacity of L6 10% TMPTA was significantly higher than that of the LA elastomer. The Young's modulus was calculated from the slope of the stress-strain curve between 0% and 5% strain and found to be 1.33 ± 0.47 kPa for L6 10% TPMTA, 1.33 ± 0.40 kPa for LA, and 3.15 ± 1.13 kPa for BA.

[0521] Alien tape (a commercially available thick elastomeric nanotextured tape) was also tested in the same manner. It did not fail before reaching the maximum range of the Instron.

[0522] 4.7.12. Example 12

[0523] The adhesive sample was prepared by photopolymerizing a monomer solution 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. The monomers were weighed using an analytical balance and mixed using a FlackTek high-speed mixer (DAC 330-100PRO) until a homogeneous solution was formed. Approximately 1.5 mL of the solution was pipetted onto a 75 × 50 mm 1.0 mm thick glass slide and cured for 1 hour under a 365 nm UV lamp (UVP CL-1000 UV crosslinker) in an inert nitrogen atmosphere. The sample was removed from the crosslinker, clamped between another piece of silicone paper fixed to a 1.0 mm thick glass slide, and squeezed with a spring clip to create a gap of approximately 100 microns thick. The sample was then post-cured for 1 hour at 120 °C under atmospheric pressure and then cooled to ambient temperature.

[0524] An Instron 5944 universal testing machine and Vitro-Skin (Florida sun care Testing Inc, IMS Division) were used to conduct a 180-degree peel test as a human skin substrate analog ( Figure 8 ). A 5-cm-wide rectangular strip of Vitro-Skin was pressed onto the adhesive with moderate finger pressure and allowed to sit for 1 minute before testing. A glass slide was fixed in the stationary position of the lower Instron fixture. The Vitro-Skin was fixed to the upper fixture in the standard 180-degree peel test configuration. The Vitro-Skin was peeled from the adhesive at a rate of 100 mm / min and repeated for three samples. The average peel strength (force per unit width) was measured to be approximately 300 N / m. The process was repeated for a peel rate of 300 mm / min, yielding an average of approximately 700 N / m, demonstrating the shear rate response behavior of the adhesive, i.e., at very low peel rates, the peel force is low, while at high peel rates, the adhesive force remains high.

[0525] A comparative analysis was performed on 3M Tegaderm (a commercially available medical adhesive). Before testing, a 26-mm-wide rectangular strip of Tegaderm was pressed onto a clean glass slide with a mass of 500 grams for 1 minute. The glass slide was fixed in the stationary position of the lower Instron fixture. The Tegaderm was fixed to the upper fixture in the standard 180-degree peel test configuration. The adhesive was again peeled from the glass slide at rates of 100 mm / min and 300 mm / min, with each peel rate repeated 10 times. The average peel forces were approximately 98 N / m and 94 N / m, respectively, indicating that the adhesive has no significant shear rate dependence.

[0526] Additional comparisons were made with several other commercially available adhesives ( Figure 9 ). For conventional pressure-sensitive adhesives, the change in the peel force required for removal is mainly affected by the pressure used to apply the adhesive to the target surface and optionally the contact time with the target surface, compared to the speed or peel rate at which the adhesive is removed, and the speed or peel rate has no or a weak effect on the delamination behavior (e.g., peel strength).

[0527] In contrast, the stimulus-responsive adhesives described herein exhibit different behaviors (peel strength or perceived pain) during delamination at different peel rates, which are mainly affected by the peel rate or shear rate at which the adhesive is 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 contact time with the target surface. (These statements assume that the target surface, environmental variables, temperature, and humidity are controlled to be equivalent.)

[0528] 4.7.13. Example 13

[0529] The 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. The monomers were weighed using an analytical balance and mixed using a FlackTek high-speed mixer (DAC 330-100PRO) until a homogeneous solution was formed. Approximately 3 mL of the solution was pipetted onto a 25 mm disposable aluminum rheometer substrate (TA Instruments) and cured for 1 hour in an inert nitrogen atmosphere under a 365 nm UV lamp (UVP CL-1000 UV crosslinker). The sample was then post-cured at 120 °C for 1 hour at atmospheric pressure. The sample was then cooled to ambient temperature.

[0530] A control sample set 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 Rain-X coated 1.0 mm thick 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 at 90 °C and atmospheric pressure for 12 hours, and then cooled to ambient temperature. The samples were removed from the glass slides and placed on the surface of a 25 mm rheometer substrate.

[0531] Oscillatory temperature scans were performed on a TA Instruments Discovery HR-2 rheometer. A strain oscillatory amplitude scan was performed on the adhesive sample at 25 °C to determine the nominal oscillatory strain amplitude. The storage modulus and loss modulus curves were found to be constant, and a strain of 1% ( Figure 11 and Figure 12 ) was selected. A logarithmic scan of the angular frequency from 1.0 to 100.0 rad / sec was performed at 5 points per decade, and the scan temperature was from 0 °C to 50 °C in 5 °C steps ( Figure 10 and Figure 13)。The high loss modulus of L6 was observed through high tan(δ) values between 0.5 at low frequencies and 0.9 at high frequencies. In contrast, the comparative samples (denoted by "butyl acrylate (2 drops of TMPTA)" (b), "butyl acrylate (3 drops of TMPTA)" (c), and "butyl acrylate (4 drops of TMPTA) (d)) had significantly lower loss moduli, approaching 0.1 across the entire frequency range.

[0532] 4.7.14. Example 14

[0533] The adhesive samples were prepared by photopolymerizing a monomer solution having the following composition with 0.98 wt% of 2DMPA photoinitiator: 98.43 wt% of LMA and 0.59 wt% of TMPTA. The monomers were weighed using an analytical balance and mixed using a FlackTek high-speed mixer (DAC 330-100PRO) until a homogeneous solution was formed.

[0534] In the "pre-curing" step, under a continuous flowing inert nitrogen atmosphere, a prepolymer solution was formed by partially curing 90 g of the monomer solution for 14 minutes under a 365 nm UV light source (UVPCL-1000 UV crosslinker). Subsequently, 5 mL of the prepolymer solution was pipetted onto silicone-impregnated paper fixed on a 1.0 mm thick glass slide and re-cured for 41 minutes under ultraviolet light in an inert nitrogen atmosphere. After removal from the crosslinker, the sample was sandwiched between another piece of silicone-impregnated paper fixed on a 1.0 mm thick glass slide, compressed to a thickness of 600 - 700 microns using a spring clip, post-cured at 120 °C and atmospheric pressure for 1 hour, and then cooled to ambient temperature. The sample was observed to be optically transparent to the naked eye.

[0535] Dynamic mechanical analysis (DMA) was performed using a Mettler Toledo DMA1-Star instrument. Samples were prepared by carefully cutting the samples into discs with a thickness of approximately 0.80 mm and a diameter of approximately 4.75 mm. The shear deformation mode was selected with a displacement limit of 1.0 micron. A temperature scan was performed from -50 °C to 100 °C with a gradual heating rate of 3 °C per minute. Additionally, the frequency of deformation was set to 2 Hz. The storage modulus and loss modulus ( Figure 14 ), as well as tan(δ) ( Figure 15 ) were measured.

[0536] 4.7.15. Example 15

[0537] Mix LMA, TMPTA, and 1.0 wt% DMPA photoinitiator until a homogeneous solution is formed, then in a UVP CL-1000 crosslinker, under nitrogen, in a polypropylene box (sample about 0.1 - 1.0 mm thick), cure under UV at 365 nm for 45 minutes, and then post-cure the sample at 120 °C for about 1 hour under ambient conditions. The optically transparent sample after post-curing at 120 °C is then cooled to room temperature and appears optically transparent to the naked eye at room temperature. The sample exhibits excellent adhesion to human skin and can be removed in a manner with minimal pain or no pain.

[0538] Samples were also prepared separately using a photoreactor. Place a magnetic stirring plate under the UVP CL-1000L crosslinker and stir about 100 mL of a homogeneous mixture of LMA, TMPTA, and 1.0 wt% DMPA photoinitiator with a magnetic stir bar at about 180 RPM while irradiating at 365 nm for about 15 - 20 minutes, after which the viscosity increases to form a more homogeneous adhesive film coating for all to be prepared. Optionally, after the initial 15 to 20 minutes of irradiation, additional TMPA (10%, 20%, or 30% increase relative to the original TMPTA composition) is added and mixed for 15 minutes at 800 rpm using a FlackTek high-speed mixer (DAC 330 - 100PRO) to ensure homogeneous mixing. The addition of additional TMPTA is to compensate for the converted TMPTA, which is used to increase the molecular weight and increase the viscosity, and which may not have been incorporated into the network. Under nitrogen, irradiate in a UVP CL-1000L crosslinker at 365 nm for 45 minutes and thermally post-cure at 120 °C for 1 hour to prepare an adhesive coating with a thickness of 0.025 mm to 1.75 mm from the pre-polymer with increased viscosity from the LMA / TMPTA / DMPA mixture with increased viscosity on a silicone release liner. The release liner / adhesive coating can be sandwiched between additional silicone release liner papers and stored for further use, and the method demonstrated is consistent with the roll-to-roll UV coating method applicable to adhesives on release liners.

[0539] The adhesive roll or sheet can be made into a condom device by a suitable transfer method to match the adhesive with a latex, elastomer, or other polymer barrier layer. Additionally, if desired, a suitable roll-to-roll or sheet lamination manufacturing method can be used to laminate multiple adhesive layers together to form a composite adhesive layer with a greater thickness.

[0540] 4.7.16. Example 16

[0541] Samples were prepared from monomeric substances and DMPA photoinitiator to form linear polymers. Three compositions were prepared using an analytical balance: (a) 99.0 wt% lauryl methacrylate (LMA) and 1.0 wt% DMPA, (b) 99.0 wt% lauryl acrylate (LA) and 1.0 wt% DMPA, and (c) 99.0 wt% butyl acrylate (BA) and 1.0 wt% DMPA. Each solution was mixed using a FlackTek high-speed mixer (DAC 330-100PRO) at 400 rpm until a homogeneous solution was obtained. Approximately 6 mL of solution was pipetted into compartments 1 inch by 3 inches in a polypropylene tray, with a total of 12 compartments for each solution. The solutions were UV cured (UVP CL-1000 crosslinker) for 1 hour under a nitrogen inert atmosphere, after which they were post-cured thermally at 120 °C for 1 hour. After post-curing, the samples were cooled to ambient temperature and were observed to be optically transparent.

[0542] Samples of 2 mg / mL solutions of each cured polymer were prepared in HPLC grade THF. The solutions were filtered through a 0.22 micron PTFE filter and 0.5 microliters were injected onto a GPC using THF as the eluent and polystyrene standards. A flow rate of 1 mL / min and a light scattering detector were used. The average molecular weight of the BA sample was found to be 1381218 g / mol and the polydispersity index (PDI) was 1.2. The average molecular weight of the LMA sample was found to be 27040 g / mol and the PDI was 2.4. The average molecular weight of the LA sample was found to be 759767 g / mol and the PDI was 3.2.

[0543] 4.7.17. Example 17

[0544] Crosslinked adhesive samples were 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). The monomers were weighed using an analytical balance and mixed using a FlackTek high-speed mixer (DAC330-100PRO) until a homogeneous solution was formed. Approximately 3 mL of solution was pipetted onto a 25 mm disposable aluminum rheometer substrate (TA Instruments) and cured for 1 hour under an inert nitrogen atmosphere using a 365 nm UV lamp (UVP CL-1000 UV crosslinker). The samples were then post-cured at 120 °C under atmospheric pressure for 1 hour. The samples were then cooled to ambient temperature.

[0545] A comparative sample containing a linear polymer was prepared by photopolymerizing (a) a monomer solution of 99.0 wt% lauryl methacrylate (LMA) and 1.0 wt% DMPA, and (b) a monomer solution of 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 high-speed mixer (DAC 330-100PRO) until a homogeneous solution was obtained. Approximately 6 mL of the solution was pipetted into a 1 in. × 3 in. compartment in a polypropylene tray, with a total of 12 compartments for each solution. The solution was UV cured (UVP CL-1000 crosslinker) for 1 h under a nitrogen inert atmosphere and then post-cured thermally at 120 °C for 1 h. After post-curing, the sample was cooled to ambient temperature and was observed to be optically transparent. Approximately 0.5 mL of the polymer sample was scooped onto a 25 mm disposable aluminum rheometer substrate and left to stand for 30 min.

[0546] Frequency sweeps were performed on a TA Instruments Discovery HR-2 rheometer to measure the loss modulus and storage modulus. A strain oscillation amplitude sweep was performed on the adhesive sample at 25 °C to determine the nominal oscillation strain amplitude. The storage modulus and loss modulus curves were found to be constant, and a strain of 1% was selected. Logarithmic frequency sweeps from 0.2 to 20.0 rad / sec were performed at 25 °C, 50 °C, 80 °C, and 100 °C. The ratio of the loss modulus to the storage modulus, tan(δ), was reported, showing high loss behavior ( Figures 16 - 19 ).

[0547] Then a constant torque of 500 μN·m was applied to the samples at 25 °C, 50 °C, 80 °C, and 100 °C, and the resulting shear rate and strain were measured over time, for 180 s at 25 °C and 50 °C and for 600 s at 80 °C and 100 °C ( Figures 20 - 23 ).

[0548] Finally, the adhesion strength was measured at 25 °C, 50 °C, 80 °C, and 100 °C ( Figure 24 and Figure 25 ). The sample was contacted and squeezed for 60 s, after which the rheometer tip was withdrawn at a speed of 100 μm per second, and the axial force was measured. The peak adhesion 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 peak adhesion force of the LMA comparative sample was found to be 6.0 N at 25 °C and 3.7 N at 80 °C. The peak adhesion force of the BA comparative sample was found to be 4.1 N at 80 °C.

[0549] Repeat the same process for the comparative samples, where samples (a), (b), and (c) produce peak adhesion forces of 5 N, 6 N, and 4 N to aluminum, respectively. The adhesion strength, measured in Newton-seconds (Ns), is calculated by integrating the area under the force-versus-time measurement for each sample, resulting in 88.4 Ns for the adhesive and 9.6 Ns, 5.9 Ns, and 3.8 Ns for comparative samples (a), (b), and (c), respectively. The adhesion energy of the adhesive is also calculated by multiplying the integrated adhesion strength by a constant tensile rate of 100 micrometers per second, resulting in an adhesion energy of 8.84×10 -3 Joules (J), and the adhesion energies of comparative samples (a), (b), and (c) are 0.96×10 -3 J, 0.59×10 -3 J, and 0.38×10 -3 J, respectively.

[0550] 4.7.18. Example 18

[0551] Perform sol-gel analysis on the UV-cured samples in dichloromethane (DCM) according to known methods. Weigh cured polymer samples in the mass range of approximately 0.2 g to 0.6 g into a tared glass vial and subject them to approximately 40 mL of DCM in a sealed glass vial. Mix the vial in a RapidVap vortexer at 35 RPM at approximately 25 °C for 24 hours, then decant the DCM to obtain a consistent gel highly swollen in DCM and allow it to dry in a commercial chemical fume hood at ambient temperature and pressure for 24 hours, then further dry it at 60 °C for 3 hours, and subsequently at 120 °C for 2 hours. Take the final mass of the remaining sample / vial and calculate the gel fraction as the final mass divided by the initial mass. Representative data are shown in Table 1 and Figure 32 as follows.

[0552] Table 1.

[0553]

[0554] Despite the high weight and molar ratios (within 2x crosslink density), the adhesives show similar gel fractions in the range of 0.70 to 0.90.

[0555] 4.7.19. Example 19

[0556] A series of condoms were manufactured using L6, TMPTA with a 10 wt% increase, TMPTA with a 20 wt% increase, TMPTA with a 30 wt% increase, lauryl acrylate (LA) with 0.6 wt% TMPTA, and a styrene adhesive. Rectangular condoms shaped approximately 1 inch by 2 inches or circular condoms with a diameter of 1 inch were prepared by transferring a square adhesive of approximately 3 inches by 3 inches onto a latex dental dam with a diameter of approximately 0.20 mm. The adhesive thickness ranged from 200 microns to 800 microns thick.

[0557] The manufactured condoms were placed on the combined erect and flaccid penises of several individuals. In some cases, vaginal intercourse was subsequently performed, and in other cases, manual stimulation was carried out. Subsequently, the adhesive was removed from the penis, and pain was self-reported using a standard Wong-Baker type pictorial-numeric pain scale (ranging from 0 (no pain) to 10 (the most severe pain imaginable)).

[0558] In addition, commercially available tapes were tested, which included Galactic Cap, FLEXcon medical adhesive, 3M Scotch-brand clear packaging tape, 3M Scotch-brand blue painters tape, and 3M Post-it notes. The results are as Figure 33 shown, and the number of samples of each adhesive for each individual is recorded in Table 2.

[0559] Table 2

[0560]

[0561] It was observed that L6 and L6 variant samples generally took 3 to 15 seconds to remove, with an average of 5 to 8 seconds. Each removal of a Galactic Cap sample took more than 5 minutes and required the use of coconut oil or moisturizing lotion. Packaging tape, FLEXcon medical adhesive, and blue painters tape generally took 10 to 30 seconds to remove, depending on the surface area of the sample. Post-it notes, although relatively painless and removed quickly (between 1 and 5 seconds), had a relatively low adhesive force.

[0562] 5. Equivalents and Incorporation by Reference

[0563] Although the provided disclosure has been specifically shown and described with reference to preferred embodiments and various alternative embodiments, those skilled in the relevant art should understand that various changes in form and detail may be made without departing from the spirit and scope of the provided disclosure.

[0564] All references, issued patents, and patent applications cited in the body of this specification are hereby incorporated by reference in their entirety for all purposes. In particular, U.S. Provisional Patent Application Nos. 63 / 381,071 (filed Oct. 26, 2022); 63 / 381,653 (filed Oct. 31, 2022); 63 / 493,761 (Apr. 2, 2023); 63 / 501,237 (filed May 10, 2023); 63 / 493,762 (filed Apr. 2, 2023); and 63 / 501,238 (filed May 10, 2023) are hereby incorporated by reference in their entirety. Additionally, the following PCT patent applications, filed concurrently with this application, are hereby incorporated by reference in their entirety

[0565] An application entitled “STIMULUS-RESPONSIVE, REVERSIBLE ADHESIVE MEDICAL COMPOSITIONS, ARTICLES AND METHODS,” filed Oct. 26, 2023, with Attorney Docket No. 41822-57382 (002WO).

Claims

1. A condom, comprising: A barrier layer adapted to prevent semen passage and including an inner surface and an 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 penis of a human subject, The condom is configured to provide partial coverage of the penis, and The adhesive layer contains an adhesive, the adhesive containing a stimulus-responsive polymer formed from one or more monomers and optionally one or more polyfunctional crosslinking agents, wherein When the condom is applied to the penis, the adhesive layer adheres to the glans penis, and After applying a stimulus to the condom, the adhesive layer can be removed from the glans penis.

2. The condom according to claim 1, wherein the size and shape of the condom are designed such that when applied to the penis, the condom does not contact the corona of the penis.

3. The condom according to claim 1 or 2, wherein the size and shape of the condom are designed such that when applied to the penis, the condom does not contact the shaft of the penis.

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

5. The condom according to any one of claims 1-4, wherein the barrier layer comprises: Natural latex rubber, synthetic rubber, amorphous polyurethane, semi-crystalline polyurethane (including various thermoplastic polyurethanes, polyethylene, polypropylene, polydimethylsiloxane and other silicone rubbers), polyethylene terephthalate, poly(vinyl chloride), polyisoprene, vulcanized polyisoprene or other vulcanized or crosslinked rubbers, ethylene vinyl acetate, poly(vinyl acetate), elastomeric or flexible materials, or combinations 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 1-6, 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 for the stimulus-responsive barrier layer is selected from temperature change, physicochemical change, light, ultrasound, ionic strength change, pH change, magnetic force, mechanical action, or mechanical force.

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

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

11. The condom according to any one of claims 1-10, wherein the thickness of the barrier layer is from 0.001 mm to 2 mm, for example, from 0.001 mm to 1.5 mm, from 0.001 mm to 1 mm, from 0.001 mm to 0.5 mm, from 0.001 mm to 0.1 mm, from 0.001 mm to 0.01 mm, from 0.025 mm to 0.25 mm, for example from 0.025 mm to 0.2 mm, from 0.025 mm to 0.15 mm, from 0.025 mm to 0.1 mm, or from 0.025 mm to 0.05 mm.

12. The condom according to any one of claims 1-11, wherein the barrier layer further comprises a reservoir sized and shaped to be adapted to collect semen ejaculated from the penis.

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

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 12-14, wherein the reservoir is self-formed when subjected to the pressure from ejaculation through the penis.

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

17. The condom according to claim 16, wherein the polymer coating comprises chitosan, alginate, polyacrylic acid, cross-linked polyacrylic acid, sodium polyacrylate, cross-linked sodium polyacrylate, or a combination thereof.

18. The condom according to any one of claims 1-17, wherein the condom or the barrier layer has a planar or curved surface geometry selected from square, circular, oval, hemispherical, rectangular, polygonal, or curvilinear polygonal.

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

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 1-18, wherein the barrier layer has a rectangular geometry.

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 18-22, wherein the condom or the barrier layer is planar.

24. The condom according to any one of claims 1-23, 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 water-based lubricants, silicone-based lubricants, polysaccharide-based lubricants, natural lubricants, and oil-based lubricants.

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

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 1-27, further comprising an elastomeric ring fixed to the inner surface of the barrier layer or the edge of the barrier layer.

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

30. The condom according to any one of claims 1-29, wherein the adhesive layer adheres only to a part of the inner surface of the barrier layer.

31. The condom according to claim 30, wherein the adhesive adheres to the outside of the inner surface of the barrier layer.

32. The condom according to any one of claims 1-29, wherein the adhesive layer extends coextensively with the inner surface of the barrier layer.

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

34. The condom according to any one of claims 1-33, wherein the thickness of the adhesive layer is from 0.1 micrometers to 3,000 micrometers, such as from 1 micrometer to 2,000 micrometers, from 25 micrometers to 1,000 micrometers, from 25 micrometers to 750 micrometers, or from 25 micrometers to 500 micrometers.

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

36. The condom according to claim 35, wherein the stimulus is selected from temperature change, physicochemical change, light, ultrasound, change in ionic strength, pH change, magnetic force, or mechanical action or mechanical force.

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

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

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

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

41. The condom according to any one of claims 1-40, wherein the peel strength of the stimulus-responsive polymer at a lower peel rate is at least 5% lower than the peel strength at a higher peel rate, such as 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.

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

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

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

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

46. The condom according to any one of claims 1 - 45, wherein the stimulus-responsive polymer has a storage modulus of 0.01 MPa to 1 MPa, such as, 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 - 46, wherein the stimulus-responsive polymer has a loss modulus of 0.1 MPa to 1 MPa, preferably 0.1 MPa to 0.8 MPa, more preferably 0.1 MPa to 0.5 MPa.

48. The condom according to any one of claims 1 - 47, wherein the tan(δ) (the ratio of the storage modulus (G”) to the loss modulus (G’)) of the stimulus-responsive polymer at 25 °C and 1 Hz is 0.1 to 2, such as 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 - 48, wherein the stimulus-responsive polymer has less adhesiveness when wet than when dry.

50. The condom according to any one of claims 1 to 49, wherein, After adhering the adhesive layer to the glans penis, removing the condom from the glans penis by gentle peeling induces minimal pain or no pain as measured by WBQPA, such as, a WBQPA score 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 temperature change.

52. The condom according to claim 51, wherein the adhesive layer adheres to the glans penis at a temperature of 37 °C and adheres poorly or delaminates from the glans 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 dissolution of the composition when in contact with a solvent.

54. The condom according to claim 53, wherein the adhesive layer adheres to the glans penis in the absence of the solvent and adheres poorly or delaminates from the glans penis when in contact with the solvent.

55. The condom according to any one of claims 1 - 54, wherein the glass transition temperature (Tg) of the stimulus-responsive polymer is 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 - 55, wherein the stimulus-responsive polymer is a crosslinked polymer.

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

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

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

60. The condom according to any one of claims 56-59, 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 1-60, wherein the stimulus-responsive polymer comprises monomers selected from the group consisting of: acrylate monomers, methacrylate monomers, vinyl ether monomers, allyl monomers, thiol monomers, epoxy monomers, amine monomers, electron-rich monomers, electron-deficient monomers, lactam monomers, lactone monomers, alcohol monomers, carboxylic acid monomers, isocyanate monomers, Diels-Alder monomers, ring-opening metathesis monomers, or combinations thereof.

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

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, 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 the group consisting of 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 condom according to claim 62, wherein the acrylate monomer is selected from the following: methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, methoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-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, ethoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, stearyl acrylate, lauryl acrylate, isodecyl acrylate, acrylic acid, ethylene glycol diacrylate (EGDA), triethylene glycol diacrylate (TEGDA), propylene glycol diacrylate (PGDA), butanediol diacrylate (BDDA), neopentyl glycol diacrylate (NPGDA), pentaerythritol tetraacrylate (PETA), 1,4-butanediol diacrylate (BDA), bis(trimethylolpropane) tetraacrylate (DTMPTA), bisphenol A ethoxylated diacrylate (BPAEDA), ethoxylated bisphenol A diacrylate (EBPA), decanediol diacrylate, polyethylene glycol diacrylate (PEGDA), trimethylolpropane triacrylate (TMPTA), diethylene glycol diacrylate (DEGDA), and 1,6-hexanediol diacrylate (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 62-65, wherein the stimulus-responsive polymer comprises at least 10 wt%, such as at least 50 wt%, at least 65 wt%, at least 95 wt%, at least 96 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt% of 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 even 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, henicosyl methacrylate, docosyl methacrylate, tricosyl methacrylate, tetracosyl methacrylate, pentacosyl methacrylate, hexacosyl methacrylate, heptacosyl methacrylate, octacosyl methacrylate, nonacosyl methacrylate, triacontyl methacrylate, and combinations thereof.

70. The condom according to claim 67, wherein the methacrylate monomer is selected from: ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, stearyl methacrylate, lauryl methacrylate, isodecyl methacrylate, tetrahydrofurfuryl methacrylate, glycerol 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, acryloyloxyethyl trimethylammonium 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 67-70, wherein the stimulus-responsive polymer comprises poly(lauryl methacrylate).

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

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

74. The condom according to any one of claims 67 - 73, wherein the stimulus-responsive polymer comprises at least 10 wt%, such as at least 50 wt%, at least 65 wt%, at least 95 wt%, at least 96 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt% of methacrylate monomers.

75. The condom according to claim 61, wherein the stimulus-responsive polymer comprises a vinyl ether monomer selected from: 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.

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

77. The condom according to claim 61, wherein the stimulus-responsive polymer comprises an allyl monomer selected from: diallyl phthalate (DAP), diallyl maleate (DAM), diallyl succinate (DAS), diallyl fumarate (DAF), diallyl adipate (DAA), diallyl sebacate (DAS), diallyl terephthalate (DAT), diallyl isophthalate (DAI), diallyl itaconate (DAI), diallyl carbonate (DAC), diallyl diglycolate (DADG), diallyl tris(2-hydroxyethyl) isocyanurate (DATHEIC), triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), triallyl trimellitate (TATM), triallyl citrate (TAC), triallyl phosphate (TAP), triallyl amine (TAA), triallyl cyanide (TACN), triallyl 1,2,4-benzenetricarboxylate (TABTC), triallyl mellitate (TATM), triallyl ether of tris(2-hydroxyethyl) isocyanurate (THEIC-TAE), and combinations thereof.

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

79. The condom according to claim 61, wherein the stimulus-responsive polymer comprises a thiol monomer selected from the following: 3-mercaptopropionic acid; mercaptoacetic 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-(mercaptopropyl)trimethoxysilane; 3-(mercaptopropyl)methyldimethoxysilane; 3-(2,2-dithiobis(ethylthio)propionylamino)propionic acid; 3,6,9-trioxadecane thiol; 3-mercapto-1,2-propanediol; 2,2'-dithiobisethanol; N-acetyl-L-cysteine; L-cysteine; 2-(2-mercaptoethyl)pyridine; 4-(2-mercaptoethyl)morpholine; 3-mercapto-1,2,4-triazole; benzenethiol; pentaerythritol tetra(3-mercaptopropionate) (PETMP); trimethylolpropane tri(3-mercaptopropionate) (TMPMP); triethanolamine tri(3-mercaptopropionate) (TEAMP); tris(2-hydroxyethyl)isocyanurate tri(3-mercaptopropionate) (THEICMP); bis(3-mercaptopropyl) sulfide (BMPS); 1,2-ethanedithiol (EDT); 1,3-propanedithiol; 1,4-butanedithiol; 1,6-hexanedithiol; 1,8-octanedithiol; and combinations thereof.

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

81. The condom according to claim 61, wherein the stimulus-responsive polymer comprises an epoxy monomer selected from the following: bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE), novolac diglycidyl ether (NGDE), phenol novolac diglycidyl ether (PNGDE), cycloaliphatic epoxy resin, glycidyl ether of aliphatic alcohol, glycidyl ether of aromatic alcohol, triglycidyl isocyanurate (TGIC), 1,4-butanediol diglycidyl ether (BDDGE), neopentyl glycol diglycidyl ether (NPGDGE), propylene glycol diglycidyl ether (PGDGE), epoxidized soybean oil (ESO), epoxidized linseed oil (ELO), dicyclopentadienyl epoxy resin, tetrafunctional epoxy resin, epoxy novolac resin, and combinations thereof.

82. The condom according to claim 81, further comprising an acrylate monomer, a methacrylate monomer, a vinyl ether monomer, an allyl monomer, a thiol monomer, an amine monomer, an electron-rich monomer, an electron-deficient monomer, a lactam 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.

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

84. The condom according to claim 83, wherein the stimulus-responsive polymer further comprises an acrylate monomer, a methacrylate monomer, a vinyl ether monomer, an allyl monomer, a thiol monomer, an epoxy monomer, an electron-rich monomer, an electron-deficient monomer, a lactam 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.

85. The condom according to claim 61, wherein the stimulus-responsive polymer comprises an electron-rich monomer selected from the following: vinyl ethers (such as vinyl methyl ether, vinyl ethyl ether), vinyl acetate, allyl alcohol, allyl amine, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxymethylallylamine, N-hydroxymethylethylacetamide, 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 an acrylate monomer, a methacrylate monomer, a vinyl ether monomer, an allyl monomer, a thiol monomer, an epoxy monomer, an amine monomer, an electron-deficient monomer, a lactam 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.

87. The condom according to claim 61, wherein the stimulus-responsive polymer comprises an electron-deficient monomer selected from the following: 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 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, a lactam 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.

89. The condom according to claim 61, wherein the stimulus-responsive polymer comprises a lactam monomer selected from the following: caprolactam, valerolactam, heptalactam, octalactam, laurolactam, proline lactam, butyrolactam, methionine lactam, methoxyethyl lactam, methoxyethyl methionine lactam, dimethylaminoethyl lactam, dimethylaminoethyl methionine 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 acrylate monomers, methacrylate monomers, vinyl ether monomers, allyl monomers, thiol monomers, epoxy monomers, amine monomers, electron-rich monomers, electron-deficient monomers, lactone monomers, alcohol monomers, carboxylic acid monomers, isocyanate monomers, Diels-Alder monomers, ring-opening metathesis monomers, or combinations thereof.

91. The condom according to claim 61, wherein the stimulus-responsive polymer comprises lactone monomers selected from the group consisting of β-propiolactone, γ-butyrolactone, 8-valerolactone, ε-caprolactone, ω-pentadecanolide, 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-caprolactone, and combinations thereof.

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

93. The condom according to claim 61, wherein the stimulus-responsive polymer comprises alcohol monomers selected from the group consisting of 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; polyhydroxymethyl propane; hydroxypivaloyl hydroxymethyl butyrate (HPHMB); 1,4-cyclohexanedimethanol; and combinations thereof.

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

95. The condom according to claim 61, wherein the stimulus-responsive polymer comprises carboxylic acid monomers selected from the group consisting of 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 monomers, methacrylate monomers, vinyl ether monomers, allyl monomers, thiol monomers, epoxy monomers, amine monomers, electron-rich monomers, electron-deficient monomers, lactam monomers, lactone monomers, alcohol monomers, isocyanate monomers, Diels-Alder monomers, ring-opening metathesis monomers, or combinations thereof.

97. The condom according to claim 61, wherein the stimulus-responsive polymer comprises an isocyanate monomer selected from the group consisting of 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.

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

99. The condom according to claim 61, wherein the stimulus-responsive polymer comprises a Diels-Alder monomer selected from the group consisting of 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 monomers, methacrylate monomers, vinyl ether monomers, allyl monomers, thiol monomers, epoxy monomers, amine monomers, electron-rich monomers, electron-deficient monomers, lactam monomers, lactone monomers, alcohol monomers, carboxylic acid monomers, isocyanate monomers, ring-opening metathesis monomers, or combinations thereof.

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

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

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

104. The condom according to claim 103, wherein the multifunctional crosslinker is selected from difunctional crosslinkers, trifunctional crosslinkers, or tetrafunctional crosslinkers.

105. The condom according to claim 103 or 104, wherein the multifunctional crosslinker is a trifunctional crosslinker.

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

107. The condom according to claim 103, wherein the multifunctional crosslinker 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-epoxides; polythiols; polyolefins; tris(2-acryloyloxyethyl) isocyanurate, ε-caprolactone-modified tris(2-acryloyloxyethyl) isocyanurate, ethoxylated glycerol triacrylate, ethoxylated glycerol triacrylate, pentaerythritol triacrylate, and combinations thereof.

108. The condom according to any one of claims 1-107, wherein the stimulus-responsive polymer comprises 0.1 wt% to 1.5 wt%, preferably 0.2 wt% to 1 wt%, more preferably 0.4 wt% to 0.8 wt% of the multifunctional crosslinker.

109. The condom according to any one of claims 103-108, wherein the weight ratio of one or more monomers to one or more multifunctional crosslinkers is from 98:2 to 99.9:0.1, for example, from 98.5:1.5 to 99.9:0.1; from 99:1 to 99.9:0.1, from 99.1:0.9 to 99.9:0.1, from 99.2:0.8 to 99.9:0.1; from 99.3:0.7 to 99.9:0.1, from 99.4:0.6 to 99.9:0.1, from 99.5:0.5 to 99.9:0.1, from 99.6:0.4 to 99.9:0.1, from 99.7:0.3 to 99.9:0.1, or from 99.8:0.2 to 99.9:0.

1.

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

111. The condom according to claim 110, wherein the multifunctional crosslinker is selected from difunctional crosslinkers, trifunctional crosslinkers, or tetrafunctional crosslinkers.

112. The condom according to claim 110 or 111, wherein the multifunctional 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 multifunctional 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-epoxides; polythiols; polyolefins; tris(2-acryloyloxyethyl) isocyanurate, ε-caprolactone-modified tris(2-acryloyloxyethyl) isocyanurate, ethoxylated glycerol triacrylate, ethoxylated glycerol triacrylate, pentaerythritol triacrylate, and combinations thereof.

115. The condom according to any one of claims 110-114, wherein the weight ratio of lauryl methacrylate to the one or more multifunctional crosslinking agents is from 98:2 to 99.9:0.1, for example, from 98.5:1.5 to 99.9:0.1; from 99:1 to 99.9:0.1, from 99.1:0.9 to 99.9:0.1, from 99.2:0.8 to 99.9:0.1; from 99.3:0.7 to 99.9:0.1, from 99.4:0.6 to 99.9:0.1, from 99.5:0.5 to 99.9:0.1, from 99.6:0.4 to 99.9:0.1, from 99.7:0.3 to 99.9:0.1, or from 99.8:0.2 to 99.9:0.

1.

116. The condom according to any one of claims 1-115, wherein the adhesive layer further comprises an additive selected from: tackifier, plasticizer, pigment, filler, fluorescent agent, flow agent, wetting agent, surfactant, defoamer, rheology modifier, colorant, penetration enhancer, stabilizer, antioxidant, and combinations thereof.

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

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

119. The package according to claim 118, wherein the package comprises a flexible packaging material, the packaging material comprising foil, plastic, plastic-lined paper, foil-lined paper, or combinations thereof.

120. The package according to claim 118 or 119, wherein the package is selected from blister packaging designs and recessed designs.

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

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

123. The package according to claim 122, wherein the wipe comprises a solvent that dissolves, denatures, or swells the stimulus-responsive polymer, such that when the adhesive layer has adhered to the glans penis and the wipe is subsequently applied to the condom, the adhesive layer is induced to delaminate from the glans penis.

124. The package according to claim 122, wherein the wipe contains a volatile additive that cools the wipe upon evaporation, such that when the adhesive layer has adhered to the glans penis and the wipe is subsequently applied to the condom, the adhesive layer is induced to delaminate from the glans penis.

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

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

127. A method of applying a condom according to any one of claims 1 - 117 to the penis of a human subject, comprising: contacting the adhesive layer of the condom with the glans penis; and applying sufficient pressure to the condom to cause the condom to adhere to the glans penis.

128. The method according to claim 127, wherein the pressure is applied with one or more fingers or the hand of the subject.

129. A method of removing a condom according to any one of claims 1 - 117 from the penis of a human subject, comprising: applying a stimulus to the condom whose adhesive layer is adhered to the glans penis, and removing the condom from the glans 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 a shear rate.

132. The method according to claim 131, wherein the shear rate is induced by stretching, peeling, or rubbing at different rates.

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

134. The method according to claim 129, wherein the stimulus is a physicochemical change, and applying the stimulus comprises applying a wipe to the condom, wherein the wipe comprises a solvent that dissolves, denatures, or swells the stimulus-responsive polymer, such that the adhesive layer is induced to delaminate from the glans penis.

135. The package according to claim 134, wherein the wipe contains a volatile additive that cools the wipe upon evaporation, such that when the wipe is applied to the condom, the adhesive layer is induced to delaminate from the glans penis.

136. The method according to any one of claims 129 - 135, wherein the condom is removed from the penis of the subject with minimal or no pain as measured by WBQPA, e.g., 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 - 136, wherein when the condom is removed from the penis, less than 50% by weight, e.g., less than 40% by weight, less than 30% by weight, less than 20% by weight, or less than 10% by weight of the adhesive remains on the penis.

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

139. The method according to claim 138, wherein the barrier layer comprises 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, semi - crystalline polyurethane (including various thermoplastic polyurethanes, polyethylene, polypropylene, polydimethylsiloxane, and other silicone rubbers), polyethylene terephthalate, poly(vinyl chloride), polyisoprene, vulcanized polyisoprene, or other vulcanized or cross - linked rubbers, ethylene vinyl acetate, poly(vinyl acetate), an 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 - 141, wherein the stimulus - responsive polymer comprises poly(lauryl methacrylate).

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

144. The method according to any one of claims 138 - 143, wherein the weight ratio of the one or more monomers to the one or more polyfunctional cross - linkers is from 98:2 to 99.9:0.1, e.g., from 98.5:1.5 to 99.9:0.1; from 99:1 to 99.9:0.1, from 99.1:0.9 to 99.9:0.1, from 99.2:0.8 to 99.9:0.1; from 99.3:0.7 to 99.9:0.1, from 99.4:0.6 to 99.9:0.1, from 99.5:0.5 to 99.9:0.1, from 99.6:0.4 to 99.9:0.1, from 99.7:0.3 to 99.9:0.1, or from 99.8:0.2 to 99.9:0.

1.

145. The method according to any one of claims 138 - 144, wherein the multifunctional 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-epoxides; polythiols; polyolefins; tris(2-acryloyloxyethyl) isocyanurate, ε-caprolactone-modified tris(2-acryloyloxyethyl) isocyanurate, ethoxylated glycerol triacrylate, ethoxylated glycerol triacrylate, pentaerythritol triacrylate, and combinations thereof.

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

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

148. The method according to any one of claims 138 - 145, further comprising sterilizing the condom, for example, by gamma radiation, electron beam, ethylene oxide gas, moist heat, dry heat, or vaporized hydrogen peroxide.

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