Elastomeric article with surface texture

Abstract

The present disclosure provides a hydrogel-latex composition that may include a natural or synthetic rubber latex, a water-soluble polymer, a bulking agent, and a rheological stabilizer. A solids content of the hydrogel-latex composition is about 30% to about 50%. The water-soluble polymer may include a mixture of a first water-soluble polymer and a second water-soluble polymer. A molecular weight of the first water-soluble polymer is about 500,000 g / mol to about 700,000 g / mol, and a molecular weight of the second water-soluble polymer is about 1,000,000 g / mol to about 5,000,000 g / mol. The present disclosure further provides elastomeric products and articles that include the hydrogel-latex composition on at least a portion of a surface of the elastomeric product or article to form a texture or pattern.

Description

AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT ELASTOMERIC ARTICLE WITH SURFACE TEXTURE Field of the Disclosure

[0001] The present disclosure relates to elastomeric articles that may be coated with a hydrogel-latex composition that is configured as a texture or pattern on a surface of the elastomeric articles. The elastomeric articles may particularly include condoms. Background

[0002] Many types of elastomeric articles, such as condoms and gloves, are typically formed of natural or synthetic latex polymer and are formed to be very thin in order to provide an acceptable level of tactile stimulation to the consumer while also being elastically fitted.

[0003] As an example of an elastomeric article, condoms are generally produced by dipping a shaped mandrel made of glass, porcelain, or metal into a latex bath, and subsequently coagulating and curing the thin film of latex, which adheres to the mandrel. Thicker films are obtained by repeating the dipping, coagulating, and curing operations as desired. The films are stripped from the mandrels and may optionally be further cured at elevated temperatures.

[0004] Textured condoms have been previously developed and can provide additional stimulation to the consumer by increasing sensation to nerve endings during use. The textures may have various forms such as “ribs”, and such features or protrusions are typically made by dipping a mandrel with an etched surface into a latex bath. Latex deposits on the surface of the dipped mandrel to form the basic condom shape, while the latex that deposits in the etchings leaves behind a ribbed feature on the finished condom exterior.

[0005] For a condom having a typical mid-point thickness of 0.075 mm, the maximum height that can be accomplished by the above-mentioned technique is only about 0.1 mm or less. Such height usually does not provide much sensation to the condom user or partner. Attempting to make protrusions with a greater height, through deeper etching of the condom mandrel, results in the formation of unacceptable weak spots on the condom. Broader (or wider) raised patterns are also problematic at least because latex tends to form a uniform coating in a broadly etched section of the mandrel rather than filling the void. This results in the pattern being lost once the condom is removed from the mandrel.AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT

[0006] By using a grooved mandrel on which condoms are manufactured by a dip molding process, it is possible to produce condoms with ribs that are claimed to heighten stimulation during use. However, the ribs on such condoms produced by the known method are not effectively positioned or lack sufficient structural rigidity to produce effective clitoral and labial stimulation, and the production of pronounced ribbing by shaping of the mandrel weakens the structural integrity of the condom which is plainly unacceptable. Previous attempts have been made to address these issues such as by modifying the solids content of the latex composition, or by using a hydrogel composition as described in the following documents. Nevertheless, there remains a need to provide a composition and method of patterning the surface of a condom, where the pattern has raised features that stimulate the users during use, and provide additional lubrication. Summary of the Disclosure

[0007] In one or more embodiments, the present disclosure can relate to a hydrogel-latex composition. The composition may include a natural or synthetic rubber latex and at least one water-soluble polymer. The composition further may include one or both of a metal oxide bulking agent and a rheological stabilizer. The hydrogel-latex composition may be dispensed directly onto a condom that has either been prefabricated or created inline during the dipping process to form features or protrusions on an outer surface of the condom. Once dried on the surface, the hydrogel-latex composition creates a broader and more raised feature than is presently commercially available. The present disclosure thus further can provide elastomeric articles comprising the hydrogel-latex composition, and particularly can provide condoms including the hydrogel- latex composition.

[0008] Condoms prepared with hydrogel-latex features can have a lower solids content and different sensory feel than those made using thickened pre-vulcanized latex features dispensed in the same manner onto a condom. The lower solids content and nature of the hydrogel-latex feature allows the absorption of fluid, which swells the structure further and creates a spongy-feel with a textured surface on the condom. Additionally, once the feature is hydrated, it becomes lubricated to provide a changing sensory experience when moving between hydrogel-latex feature and latex base layer of the condom. Condoms prepared with hydrogel-latex functionalized features may be both visually pleasing and physically stimulating to a consumer.

[0009] In some embodiments, the combination of the latex, a water-soluble polymer, a bulking agent, and a rheological stabilizer provide a unique viscoelastic property that traps air within an open cell structure duringAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT the evaporation process, creating a porous outer surface. Air may also become trapped in the film based on the initial mixing process used to manufacture the thickened hydrogel-latex. This already entrapped air and evaporation may add to the spongy, porous nature of the film. The water-soluble polymer within the composition provides lubricity once the article is hydrated and promotes moisture absorption into the open cell structure. The hydrogel-latex features may visibly swell and provide a unique skin like sensory when touched.

[0010] In one or more embodiments, the present disclosure may relate to hydrogel-latex compositions. Such compositions can include a natural or synthetic rubber latex, a water-soluble polymer, a bulking agent, and a rheological stabilizer. Preferably, a solids content of the hydrogel-latex composition may be about 30% to about 50%. In further embodiments, the hydrogel-latex compositions may be defined in relation to one or more of the following statements, which may be combined in any number and order.

[0011] The water-soluble polymer can include a mixture of a first water-soluble polymer and a second water- soluble polymer.

[0012] A molecular weight of the first water-soluble polymer may be about 500,000 g / mol to about 700,000 g / mol.

[0013] A molecular weight of the second water-soluble polymer may be about 1,000,000 g / mol to about 5,000,000 g / mol.

[0014] A ratio of the first water-soluble polymer to the second water-soluble polymer may be about 4:1 to about 19:1.

[0015] A viscosity of the hydrogel-latex composition may be about 300,000 cP or less.

[0016] The hydrogel-latex composition may be configured to have an open cell structure.

[0017] The hydrogel-latex composition may have a water absorption percentage of about 15 wt% to about 20 wt%.

[0018] The water-soluble polymer may include at least one polyethylene oxide.

[0019] In some embodiments, the present disclosure may provide products or articles of manufacture. Such products / articles can include at least one layer of an elastomeric latex defining a surface of the product, where at least a portion of the surface has at least one protrusion extending outwardly therefrom, the at least one protrusion comprising the hydrogel-latex composition as otherwise described herein. In further embodiments,AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT such articles may be further defined in relation to one or more of the following statements, which can be combined in any number and order.

[0020] The at least one protrusion may have a height of about 0.3 mm or greater and a width of about 3 mm or greater, the height being measured from the surface of the at least one layer of the elastomeric latex to a terminal edge of the at least one protrusion, and the width being measured from a first lateral surface to a second, opposing lateral surface of the at least one protrusion.

[0021] The at least one protrusion may be configured as a rib, a dot, a stripe, or a series of concentric circles.

[0022] The product may be a condom.

[0023] The at least one layer of an elastomeric latex of the product may include a polymer selected from the group consisting of polyisoprene, poly(styrene-isoprene-styrene), poly(styrene ethylene butylene styrene), water-based polyurethane, nitrile rubber, natural rubber, and combinations thereof.

[0024] In some embodiments, the present disclosure may provide a moisture-absorptive condom prepared by a process including the steps of forming a condom including at least one layer of a polymer latex, the condom defining an outer surface; applying to the outer surface of the condom a hydrogel-latex composition comprising a natural or synthetic rubber latex, a water-soluble polymer, a bulking agent, and a rheological stabilizer, wherein a solids content of the hydrogel-latex composition is about 30% to about 50%; and curing the hydrogel latex composition. The hydrogel-latex composition is applied to the condom to define at least one protrusion extending outwardly from the outer surface of the condom, and the hydrogel-latex composition is configured so that, after said curing, the at least one protrusion is configured to be moisture absorptive.

[0025] In some embodiments, the present disclosure may provide a condom that includes at least one layer of a natural or synthetic rubber latex having an outer surface; and a pattern on the outer surface including a hydrogel-latex composition. The pattern comprises at least one protrusion extending outwardly from the outer surface. The hydrogel-latex composition may include a natural or synthetic rubber latex, a water-soluble polymer, a bulking agent, and a rheological stabilizer. A solids content of the hydrogel-latex composition may be about 30% to about 50%. In further embodiments, such condoms may be further defined in relation to one or more of the following statements, which can be combined in any number and order.

[0026] The at least one protrusion may be configured as a rib, a dot, a stripe, or a series of concentric circles.AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT

[0027] The at least one protrusion may have a height of about 0.3 mm or greater and a width of about 3 mm or greater, the height being measured from the surface of the at least one layer of the natural or synthetic rubber latex to a terminal edge of the at least one protrusion, and the width being measured from a first lateral surface to a second, opposing lateral surface of the at least one protrusion.

[0028] The pattern may be moisture-absorptive.

[0029] The pattern may include an open cell structure.

[0030] Aspects and advantages of these exemplary embodiments and other embodiments, are discussed in detail herein. Moreover, it is to be understood that both the foregoing information and the following detailed description provide merely illustrative examples of various aspects and embodiments, and are intended to provide an overview or framework for understanding the nature and character of the claimed aspects and embodiments. Accordingly, these and other objects, along with advantages and features of the present disclosure, will become apparent through reference to the following description and the accompanying drawings. Furthermore, it is to be understood that the features of the various embodiments described herein are not mutually exclusive and may exist in various combinations and permutations. Brief Description of the Drawings

[0031] The accompanying drawings, which are included to provide a further understanding of the embodiments of the present disclosure, are incorporated in and constitute a part of this specification, illustrate embodiments of the present disclosure, and together with the detailed description, serve to explain principles of the embodiments discussed herein. No attempt is made to show structural details of this disclosure in more detail than may be necessary for a fundamental understanding of the embodiments discussed herein and the various ways in which they may be practiced. According to common practice, the various features of the drawings discussed below are not necessarily drawn to scale. Dimensions of various features and elements in the drawings may be expanded or reduced to more clearly illustrate embodiments of the disclosure.

[0032] FIGS.1A to 1E illustrate condoms with patterns formed of hydrogel-latex compositions according to example embodiments of the present disclosure, the condoms having different patterns or shapes of protrusions on a surface thereof, and the protrusions have a height and a width.AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT

[0033] FIG. 2 is an image at 50x magnification illustrating an open cell structure of a feature formed of a hydrogel-latex composition according to an example embodiment of the present disclosure.

[0034] FIG.3 is an image of the open cell structure pore size measurement of a feature formed of a hydrogel- latex composition according to an example embodiment of the present disclosure.

[0035] FIG. 4A and FIG. 4B are images comparing condoms fabricated with features using the hydrogel- latex composition of the present disclosure and a comparative hydrogel-latex blend, wherein features or protrusions prepared using a hydrogel-latex composition according to an example embodiment of the present disclosure (FIG.4B) is compared to features formed using a comparative hydrogel-latex blend (FIG.4A).

[0036] FIG.5A, FIG.5B, and FIG.5C provide images of features formed from hydrogel-latex compositions according to example embodiments of the present disclosure illustrating differences arising from the use of different molecular weight poly(ethylene oxide) polymers.

[0037] FIG. 6 is an image showing a comparison of features formed using a hydrogel-latex composition according to an example embodiment of the present disclosure, and features formed using thickened PV latex (PV latex) as a control, wherein the features were made to mimic a condom rib by dispensing approximately 2.0g of thickened latex into a scoopula and drying at 50°C until fully dry before removal.

[0038] FIG.7A is an image of the cross section of the hydrogel-latex composition of the present disclosure that shows the open cell structure, while FIG.7B shows the lack of an open cell structure in the cross section of the PV latex, and each image is at 50x magnification.

[0039] FIG.8 is a graph showing a water absorption analysis for a hydrogel-latex composition according to an example embodiment of the present disclosure compared with a PV latex composition.

[0040] FIG. 9A and FIG.9B show a comparison between condoms having textured features or protrusions on the surface using the hydrogel-latex composition of the present disclosure (FIG. 9A) versus using a PV latex composition (FIG.9B).

[0041] FIG.10A and FIG. 10B show a comparison between wet and dry condoms having textured features or protrusions on the surface using the hydrogel-latex composition of the present disclosure (FIG.10A) versus using a PV latex composition (FIG.10B).

[0042] FIG. 11 is a graph showing the dynamic yield value for a hydrogel-latex formulation according to embodiments of the present disclosure as provided in Example 11 of Table 9.AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT

[0043] FIG. 12 is a graph showing the dynamic yield value for a hydrogel-latex formulation according to embodiments of the present disclosure as provided in Example 12 of Table 9.

[0044] FIG.12A and FIG.12B show images of the hydrogel-latex formula according to embodiments of the present disclosure as provided in Example 11, Table 9 applied to a condom surface using an 18-gauge nozzle.

[0045] FIG. 13 shows an image of the hydrogel-latex formula according to embodiments of the present disclosure as provided in Example 11, Table 9 applied to a condom surface using a 16-gauge nozzle.

[0046] FIG. 14A and FIG. 14B show images of hydrogel-latex formula according to embodiments of the present disclosure as provided in Example 12, Table 9 applied to a condom surface using an 18-gauge nozzle.

[0047] FIG. 15 shows an image of the hydrogel-latex formula according to embodiments of the present disclosure as provided in Example 12, Table 9 applied to a condom surface using a 16-gauge nozzle.

[0048] FIG.16A, FIG.16B, and FIG.16C are each images of the hydrogel-latex compositions according to embodiments of the present disclosure prepared for testing the rib tension of the hydrogel-latex.

[0049] FIG.17A and FIG.17B are each images of a small arm dipping apparatus for testing the rib tension of the hydrogel-latex compositions according to embodiments of the present disclosure.

[0050] FIG. 18 is a graph of the rib tension testing data of the hydrogel-latex compositions according to embodiments of the present disclosure. Detailed Description of the Disclosure

[0051] The invention now will be described more fully herein after through reference to various embodiments. These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Indeed, the invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. As used in the specification, and in the appended claims, the singular forms “a”, “an”, “the”, include plural referents unless the context clearly dictates otherwise.

[0052] The description may use the phrases “in certain embodiments,” “in various embodiments,” “in an embodiment,” or “in embodiments,” which may each refer to one or more of the same or different embodiments. Furthermore, the terms “comprising,” “including,” “having,” and the like, as used with respectAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT to embodiments of the present disclosure, are synonymous. The term “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%. The terms “removing,” “removed,” “reducing,” “reduced,” or any variation thereof, when used in the claims and / or the specification includes any measurable decrease of one or more components in a mixture to achieve a desired result. The use of the words “a” or “an” when used in conjunction with any of the terms “comprising,” “including,” “containing,” or “having,” in the claims or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” The term “plurality” as used herein refers to two or more items or components. The terms “wt.%”, “vol.%”, or “mol.%” refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt.% of component.

[0053] The present disclosure relates to elastomeric articles, such as condoms, that may include features or protrusions composed of a hydrogel-latex composition that may include a film former, bulking agent, water- soluble polymer, and rheological stabilizer to provide a unique viscoelastic property trapping air within the hydrogel-latex composition structure formed during the drying or evaporation process to yield an open cell architecture and a porous outer surface. The composition creates a prominent feature, or protrusion, that can be seen visually and provides a pleasant tactile sensation when deposited onto the surface of an elastomeric article such as a condom. The amount of solids that may be present in the hydrogel-latex composition to create the raised feature or protrusion is significantly lower than would be expected. The hydrogel polymer within the composition provides lubricity to the features or protrusions once the article is hydrated, and promotes moisture absorption into the open cell architecture, which may be redistributed during use of the elastomeric article. In some embodiments, the hydrogel-latex protrusions visibly swell, providing a unique and skin-like feel when touched.

[0054] Some embodiments use a thickened hydrogel-latex that can include a metal oxide bulking agent, water-soluble polymer, natural or synthetic rubber latex and a rheological stabilizer. The hydrogel-latex composition can be dispended directly onto a condom that has been prefabricated or can be created inline while a condom is being formed, such as during the dipping process. Once dried, the hydrogel-latex creates aAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT broader and more raised feature, or protrusion than commercially available. The heights of each individual protrusion in some embodiments may be greater than 0.82 mm and widths may be greater than 3 mm. The features or protrusions that are formed using the present hydrogel-latex compositions can have a lower solids content and different sensory-feel similar features made using thickened latex compositions dispensed in the same manner onto an elastomeric article. The lower solids content and nature of the hydrogel-latex composition allows for the absorption of fluid, which swells the protrusion further, creating a spongy feel with a textured surface on the protrusion. Additionally, once the hydrogel forming polymer in the structure is hydrated, the protrusion becomes lubricious or slippery and provides a changing sensory experience in skin moving across a surface of an article between a hydrogel-latex protrusion and a latex base layer in between protrusions. Condoms prepared with hydrogel-latex functionalized protrusions may be both visually pleasing and physically stimulating to a consumer.

[0055] The presently disclosed hydrogel-latex compositions beneficially can provide improved sensory properties to a variety of underlying articles, include elastomeric latex articles, such as condoms. Moreover, such added characteristics have substantially no deleterious effect on further properties of the articles. For example, elastomeric latex articles are desired to exhibit high strength (e.g., high tensile modulus) and good stretch properties. It has been shown through testing that the application of a hydrogel-latex coating does not negatively affect the desired physical characteristics of the underlying article. Likewise, the formed coating layers have been found to remain substantially undisturbed (e.g., exhibiting little flaking and substantially no delamination) even under repeated cycles of extension (e.g., up to 500% elongation) of elastomeric articles with the hydrogel-polymer composition applied thereto. The hydrogel-polymer compositions thus beneficially form a coating layer on the underlying articles that can be dried or otherwise cured to form a substantially powdery feeling layer on the article, the layer being effective for re-hydration upon contact with aqueous fluids (e.g., water and bodily fluids) as well as synthetic lubricants to thus achieve a hydrated, slippery coating layer that is effective for imparting good lubricity to the article.

[0056] In one or more embodiments, the present disclosure can relate to articles that include a hydrogel or a hydrogel component or a hydrogel region or a hydrogel feature. A hydrogel is understood as including a network of crosslinked polymer chains. These polymers can be either natural or synthetic. Due to their hydrophilic nature, hydrogels can absorb large quantities of water. When hydrated, hydrogels may swell andAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT retain water within their structure. The presently described compositions and articles include hydrogel forming components that are water-based. The hydrogel forming components in some embodiments can be applied to a wide variety of substrates to provide a coating layer thereon and impart desired properties. The hydrogel- forming components utilized in the present compositions can comprise any suitable, water-soluble polymer that, when applied (by itself or in combination with other components) as a coating layer on a substrate, is adapted to or configured to form a hydrogel. In some embodiments, the water-soluble polymer can be a material that is adapted to or configured to form an interpenetrating polymer network.

[0057] In one or more embodiments, the present disclosure can provide polymer compositions that minimally include both of a hydrogel-forming component and a latex polymer component. As such, the polymer compositions may be characterized as a hydrogel-latex composition in that the hydrogel-forming component and the latex polymer component are blended and can provide a substantially uniform polymer composition of the two base components. Further components may be utilized in the polymer composition as desired to provide specific properties to the overall material and / or to provide specific properties to coatings of the polymer composition as applied to a substrate (e.g., a specific article of manufacture, such as a glove or condom).

[0058] In some embodiments, a latex component useful in the present polymer composition can be any latex material that is combinable with the water-soluble polymer (e.g., will form a stable mixture and thus will not separate into discrete partitions). In one or more embodiments, one or both of a natural rubber latex (“NRL”) and a synthetic rubber latex polymer may be utilized. Non-limiting examples of synthetic rubber latex polymers that may be used include synthetic polyisoprene, synthetic poly(styrene-isoprene-styrene) (“SIS”), intermediate modulus (“IM”) styrene ethylene butylene styrene (“SEBS”), high modulus (“HM”) SEBS, water-based polyurethane, nitrile rubber (e.g., acrylonitrile butadiene rubber, or “NBR”), styrene-co- butadiene, styrene-co-isoprene, triblock copolymers, such as styrene-block-butadiene and block styrene (SBS), and similar, synthetic latex polymers in the form of homopolymers and / or co-polymers. In some embodiments, NRL can be particularly useful for combination with the water-soluble polymer component. Further, in some embodiments, a synthetic rubber latex polymer may be expressly excluded from the present compositions. Likewise, if desired (e.g., as an option to minimize or eliminate any reaction by individuals exhibiting an allergy to NRL), a natural rubber latex may be expressly excluded from the present compositions.AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT The latex component can be particularly useful for providing elastomeric properties to the polymer composition and / or for improving bonding between the polymer composition and any substrate, product, article, or the like to which the polymer composition may be applied as a coating, as further described herein. In some embodiments, the latex component utilized in the present compositions may be at least partially pre- vulcanized. As such, the latex particles may be characterized as including intra-particle crosslinks. Likewise, some level of inter-particle crosslinking may be present.

[0059] The latex component of the present compositions may be utilized in a substantially unmodified state (i.e., comprising substantially only the latex polymer itself and any water used to form the aqueous dispersion of the latex polymer). In other embodiments, however, it can be useful to utilize a latex component in a compounded form (i.e., combined with one or more further materials), which may be indicative of the latex being at least partially pre-vulcanized and / or post-vulcanized, as noted above. For example, the aqueous dispersion of the latex polymer may include one or both of a crosslinking agent and a cure accelerator. In some embodiments, it may be preferred for any accelerator utilized in the latex component to be substantially or completely free of zinc. For example, sodium N-dialkyl dithiocarbamates and dithiocarbamate blends may be utilized as accelerators. Suitable vulcanizing agents that may be utilized in some embodiments can include diisopropyl xanthogen polysulfide, sulfur (e.g., free sulfur, such as being present in a configuration), and sulfur donors. Suitable accelerating agents (i.e., accelerators) that may be utilized can include dithiocarbomates, thiaxoles, and xanthates, with particular, non-limiting examples including TMTD, TETD, ZDEC, and ZDBC. Suitable sulfur donors can include one or more thiurams, such as dipentamethylenethiuram hexasulfide (DPTTH), dipentamethylenethiuram tetrasulfide (DPTT), tetramethylthiuram mono sulfide (TMTM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and tetrabenzylthiuram disulfide (TBzTD). Additionally, or alternatively, other types of sulfur donors may also be utilized. For example, 4,4’- dithiodimorpholine (DTDM), thiocarbamyl sulfonamide, and N-oxydiethylene thiocarbamyl-N- oxydiethylene sulfenamide (OTOS) may be utilized in some embodiments. Suitable antioxidants that may be utilized in some embodiments can include amine derivatives or phenolic derivatives (e.g., diphenyl-p- phenylenediamine, 1,2-dihydro-2,2,4-trimethylquinoline, poly(dicyclopentadiene-co-p-cresol). Suitable surfactants that may be utilized in some embodiments can include anionic surfactants, cationic surfactants, or amphoteric surfactants (e.g., sodium lauryl sulfate, sodium polynaphthalene sulfonate, sodiumAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT polymethacrylate, and potassium laurate). Suitable fillers that may be used in some embodiments can include one or both of inorganic and organic fillers (e.g., fumed silica and zinc oxide). Further, in some embodiments, a cure activator, such as zinc oxide, may be used.

[0060] In some embodiments, the latex component can be present in the polymer composition in an amount that can be substantially equal to or less than the amount of the water-soluble polymer that is present. For example, the latex component (e.g., one or both of a natural or synthetic rubber latex) can be present in total amount (e.g., all of any one or more latex components that are present) of less than 30% by weight based on the total weight of the hydrogel-latex composition. In some embodiments, the latex component can be present in a minimum amount of at least 5%, at least 10%, or at least 15% by weight (e.g., up to a maximum of 45% by weight in embodiments wherein the water-soluble polymer is the predominant component of the composition), based on the total weight of the composition. More particularly, the latex component can be present in an amount of about 5% to about 50%, about 10% to about 45% by weight, about 15% to about 40%, or about 20% to about 30% by weight, based on the total weight of the composition. The latex component can be utilized in the polymer composition as an aqueous dispersion, and the foregoing ranges can relate to the amount of the aqueous dispersion that is included in the polymer composition. The aqueous dispersion can have a solids content of about 30% to about 50%, about 35% to about 45%, about 30% to about 40%, or about 32% to about 36%. In any case, the amount of the aqueous dispersion of the latex component can be adjusted within the ranges noted above so that the total solids content of the hydrogel-latex composition is within the ranges otherwise noted herein.

[0061] It is understood that the compositions described herein comprising a water-soluble polymer and a latex component can be used for application to a surface of an elastomeric article, such as a condom. The elastomeric article itself may comprise a latex component, and it is understood that any latex component present in the elastomeric article is independent of the latex component utilized in the present polymer compositions that comprise a water-soluble polymer and a latex component. The latex in the elastomeric article may be the same latex material or a different latex material relative to the latex component used in forming the present polymer composition that is a combination of a water-soluble polymer and a latex component. The latex used in the elastomeric article itself may include any of the latex materials otherwise described herein.AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT

[0062] In some embodiments, a water-soluble polymer useful in the present compositions can be a polymer that is adapted to or configured to form an interpenetrating polymer network with the latex component of the polymer composition. For example, in some embodiments, the water-soluble polymer may be adapted to or configured to form a gel due a least in part to hydrogen bonding between long, linear chains of the polymer and other associations between the polymer chains.

[0063] Further, one or both polymer materials may become entrapped within the interpenetrating network of the other component and form linkages therebetween. As such, in some embodiments, it can be particularly useful for the water-soluble polymer to include long linear chains that are configured for arranging into interpenetrating polymer networks that can readily form hydrogels via hydrogen bonding. In further embodiments, the water-soluble polymer particularly may be a homopolymer. Moreover, it can be useful in some embodiments for the water-soluble polymer to include a low incidence of crosslinks between the groups on the polymer that participate in crosslinking. For example, in some embodiments, less than 10%, less than 5%, less than 2%, or less than 1% of the crosslinkable groups of the water-soluble polymer will be crosslinked. In further embodiments, the water-soluble polymer may be substantially non-crosslinked, indicating that only an insignificant of the crosslinkable groups of the water-soluble polymer are actually crosslinked, such insignificant content being 5% or less, 2% or less, 1% or less, 0.5% or less, or 0.1% or less.

[0064] In some embodiments, polyethylene oxides (PEO) can be particularly useful as a water-soluble polymer according to the present disclosure. Polyethylene oxides may be available in a wide range of materials exhibiting a scale of useful properties. In some embodiments, it can be beneficial to utilize a PEO having, for example, a molecular weight within a defined range. In some embodiments, a first water-soluble polymer and a second water-soluble may be present in the hydrogel-latex composition. The first water-soluble polymer may have a molecular weight of about 500,000 g / mol to about 700,000 g / mol, about 550,000 g / mol to about 650,000 g / mol, about 575,000 g / mol to about 625,000 g / mol, or about 600,000 g / mol. The second water- soluble polymer may have a molecular weight of about 1,000,000 g / mol to about 5,000,000 g / mol, about 1,500,000 g / mol to about 4,500,000 g / mol, about 2,000,000 g / mol to about 4,000,000 g / mol, or about 4,000,000 g / mol.

[0065] Molecular weight can be expressed as a weight average molecular weight (Mw) or a number average molecular weight (Mn). Both expressions are based upon the characterization of macromolecularAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT solute containing solution as having an average number of molecules (ni) and a molar mass for each molecule (Mi). Accordingly, number average molecular weight is defined by Equation 1 below.

[0066] Mn= ^ni Mi[Equation 1]^ n i

[0067] Weight average molecularas molecular weight average) is directly measurable using light scattering methods and is defined by Equation 2 below.

[0068] Mw= ^n 2i Mi[Equation 2]M i

[0069] Molecular weight can also beaverage molar weight (Mz), wherein the calculation places greater emphasis on molecules with large molar weights. Z-average molar weight is defined by Equation 3 below. 70] Mz=ni M3 [00 ^ i[Equation 3]^n M 2

[0071] Unless otherwise noted,is expressed herein as weight average molecular weight.

[0072] Although PEO polymers may be particularly useful as a water-soluble polymer according to the present disclosure, other types of water-soluble polymers may also be utilized, particularly when further components of the present hydrogel-latex composition are included to provide a stabilizing effect, as further described below. In particular, any water-soluble polymer that is adapted to or configured to form a hydrogel and is also stable in combination with the latex polymer may be utilized. PEO, for example, is a non-ionic polymer, and similar non-ionic polymers may likewise be utilized. As non-limiting examples, in some embodiments, one or more of the following water-soluble polymers may also be utilized: hyaluronic acids and salt forms thereof (e.g., sodium hyaluronate); cellulosic polymers; derivatives of cellulosic polymers (e.g., carboxymethylcellulose, hydroxyethylcellulose, hydroxy methylcellulose, and similar derivatives); polysaccharides, such as alginic acids and derivatives thereof (e.g., alginates). In further embodiments, water- based polyurethanes and / or crosslinked polyacrylic acid polymers may be utilized. For example, an anionic (polyurethane / acrylate) copolymer blend may be used. Anionic polymers in particular (e.g., alginates, cellulose derivatives, such as carboxymethylcellulose, and hyaluronates) may be utilized. While anionicAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT polymers can be preferred, in some embodiments, polymers including cationic groups may likewise be utilized if the system includes sufficient negatively charged moieties to reduce the charge density of an otherwise cationic polymer. For example, polyampholytes may be utilized in some embodiments. Polyampholytes are understood to reference polymeric systems including monomeric components of varying charge. Suitable polyampholytes may include polymer systems wherein at least 10%, at least 25%, or at least 50% by weight of the monomer units forming the polymer are anionic (e.g., about 10% to about 95%, about 25% to about 90%, or about 50% to about 90% anionic monomers), said percentages being wt / wt, based on the total weight of the polymer. Although the above examples are listed individually, it is understood that a blend of water- soluble polymers likewise may be used. Such blends may be utilized in a variety of ratios. For example, a first water-soluble polymer and a second-water soluble polymer (e.g., any two polymers listed above) may be used in a ratio of 1:20 to 20:1, 1:19 to 19:1, 1:10 to 10:1, 1:5 to 5:1, 10:1 to 19:1, 4.8:1 to about 19:1, or about a 1:1 ratio (wt / wt). In some embodiments, certain types of water-soluble polymers may be excluded. For example, cationic polymers may be excluded as such polymers have been found to lead to phase separation when compounded with rubber latex materials. In particular embodiments, when useful, any specific polymer listed herein may be expressly excluded.

[0073] The water-soluble polymer(s) used to prepare the polymer compositions described herein preferably can be utilized as an aqueous solution. As such, the actual polymer(s) will particularly be prepared as an aqueous solution such that the aqueous solution comprises the polymer material solubilized in water at a concentration such that the aqueous solution has a suitable viscosity for further processing as described herein and / or at a concentration that is below the solubility limit for the particular polymer used. In example embodiments, water soluble polymers for use herein can solubilized at a concentration of about 0.1% to about 5%, about 0.25% to about 4%, about 0.5% to about 3%, or about 1% to about 3% by weight of the polymer based on the total weight of the aqueous solution. The solubilized polymer may be referenced as a hydrogel. This hydrogel thus may be modified through addition of one or more further components as further discussed below. The modified hydrogel combined with the latex component discussed herein may then be referenced as the hydrogel-latex composition.

[0074] In some embodiments, the present polymer compositions can include a bulking agent, and the bulking agent may also be referred to as a thickener. The bulking agent may include, for example, inorganic salts,AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT alkoxylated alcohols, organic acids, low polarity diesters, polar and low polarity polyols, metal oxides or fumed metal oxides. The bulking agent enables good processability, tensile strength, and elongation of a mixture or composition. The inorganic salts as bulking agents may be used to control rheology and examples include neutral salts, acidic salts, and basic salts, such as sodium chloride, ammonium chloride, sodium pyrophosphate, and sodium acid pyrophosphate. The low polarity diesters or polar and low polarity polyols may also control the rheology of the composition, and examples include diisopropyl adipate, glycerin and hexylene glycol. These increase the viscosity and aid in reorganizing interactions in the system to control the rheology. In addition, using organic acids in low concentration along with alkoxylated alcohols controls the rheology of the formulation along with some bulking of the formulation viscosity. For example, acetic acid and PPG-5-Ceteth-20 may be used as components to control rheology.

[0075] In some embodiments, it can be particularly useful to include one or more rheological stabilizers in the polymer composition. Such components may be beneficial to impart stability to the polymer blend by, for example, reducing or prevent phase separation in the completed composition, particularly when the composition is present as a coating layer on an article. Likewise, the presence of one or more rheological stabilizers can be effective to improve pick-up of the hydrogel-polymer composition on the surface of the article to which it is applied. Improved "pick-up" can mean imparting greater uniformity of the ultimate coating layer, thus avoiding thin spots or even voids in the coating layer. Preferably, polymer compositions according to the present disclosure, either being stable in the express exclusion of any rheological stabilizer, or being stable when a rheological stabilizer is expressly included, exhibit a stability such that the polymer composition alone or the polymer composition when present as a coating layer on an article does not separate into visibly identifiable, separate layers for at least a defined time. In some embodiments, sufficient stability may be characterized in relation to a minimum degree of visibly identifiable phase separation. For example, a stable composition or layer thereof may be defined in relation to exhibiting less than 10%, less than 5%, less than 2%, less than 1%, or exhibiting 0% phase separation for a time of at least one week, at least two weeks, at least one month, at least 2 months, or at least six months when stored at ambient conditions.

[0076] A rheological stabilizer can be a component that may be adapted to or configured to provide or increase thixotropy of the polymer composition. The polymer composition thus can be thixotropic in nature and may exhibit improved coating uniformity when applied to a substrate. The separate water-soluble,AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT hydrogel-forming component and the latex component can separately exhibit properties that provide a desirable, combined material. For example, the water soluble, hydrogel-forming component can be adapted to or configured to be shear thinning between 0.3 rpm to 3 rpm. At 3 rpm about 78% of the original viscosity is lost under shear, at 1.5 rpm about 64% of the original viscosity is lost under shear, at 0.6 rpm about 33% of the original viscosity is lost, as measured on a Brookfield viscometer LV. The dynamic yield may be measured using a standard bench top viscometer. The operator performs an up / down speed ramp and records the torque values at each speed using a “controlled rate” method. Using excel and plotting the torque versus rpm, a ‘best fit’ line, can be used to interpolate what the torque yield value would be at zero rpms, which is the “dynamic yield”. Each rpm used in the controlled ramp is held for 1 minute to record in succession for each rpm explored. There is no wait time between the next rpm used in the ramp up / down other than the 1 minute recordation time. The overall polymer composition may be adapted to or configured to exhibit a dynamic yield in the range of about 290 dyne-cm to 300 dyne-cm, about 292 dyne-cm to about 299 dyne-cm, or about 293 dyne- cm to about 298 dyne-cm. The ability to provide the hydrogel-polymer composition in a liquid form that is shear thinning form and with a yield value as noted above may be beneficial in that it improves the ability to coat the hydrogel-polymer composition onto a surface of a latex article such that the hydrogel-polymer composition will be maintained on the surface of the article during curing, without dripping or other loss of the hydrogel-polymer composition.

[0077] In one or more embodiments, useful rheological stabilizers can be any additive, particularly a polymer additive, that is adapted to or configured to improve film uniformity and / or stability without significantly adversely affecting other film properties. Particularly useful rheological stabilizers can include one or more materials categorized as a hydrophobically modified alkali swellable emulsion ("HASE") polymer. Known HASE materials that may be utilized according to the present disclosure include materials which preferably include structural units of a) an acrylate, for example ethyl acrylate, butyl acrylate, or ethylhexyl acrylate, preferably ethyl acrylate; b) an acid, preferably acrylic acid, methacrylic acid, itaconic acid, or phosphoethyl methacrylate, preferably acrylic acid or methacrylic acid; and c) an alkylated ethoxylate monomer, preferably an alkylated ethoxylate acrylate or methacrylate. In some embodiments, useful HASE polymers include materials comprising ethyl acrylate, methacrylic acid, and hydrophobically modified (e.g., with C22 behenyl pendant groups) methacrylate with 25 moles of ethoxylation. In a non-limiting exampleAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT embodiment, a suitable HASE material is available under the name NovethixTML-10 and is an acrylates / beheneth-25 methacrylate copolymer. In one or more embodiments, a single HASE material or a total HASE material content in a polymer composition according to the present disclosure can be in an amount of less than 1% by weight based on the total weight of the composition. In further embodiments, the rheological stabilizer can be present in an amount of at least 0.01%, at least 0.05%, or at least 0.1% by weight based on the total weight of the polymer composition. More particularly, the rheological stabilizer can be present in an amount of about 0.01% to about 3% by weight, about 0.01% to about 1% by weight, about 0.05% to about 0.8% by weight, about 0.1% to about 0.6% by weight, about 0.15% to about 0.5%, or about 0.2% to about 0.4% by weight, based on the total weight of the polymer composition.

[0078] In some embodiments, the hydrogel-latex composition may be present as a component of an elastomeric article. The hydrogel-latex composition particularly may be present as a coating or a partial coating on a surface of the elastomeric article, specifically an outer surface. The hydrogel-latex composition further may be present as a feature that is present in discrete parts, areas, or sections of the elastomeric article. More particularly, the hydrogel-latex composition may be present on a surface of the elastomeric article in an arrangement that defines one or more patterns. The hydrogel-latex composition may define a single feature or a plurality of features on the elastomeric article. A plurality of features may be arranged in a series or a specific pattern or may be randomly positioned. A feature or features present on an elastomeric article and formed from a hydrogel-latex composition as described herein may be visually identifiable and may provide a specific, identifying arrangement so as to be indicative of a specific shape, pattern, symbol, graphic, trademark, text, or the like. A plurality of features likewise may define a plurality of different shapes, patterns, symbols, graphics, trademarks, text, or the like. Moreover, individual features may be provided with different sizes and shapes relative to other features on the elastomeric article. In addition to, or in the alternative to a visual arrangement, a feature or features present on an elastomeric article and formed from a hydrogel-latex composition as described herein may be configured to provide tactile sensations when moved along a surface of human tissue, such as skin or a body part of a user. A plurality of features may be shaped and / or sized and / or arranged on the elastomeric article to provide a plurality of different tactile sensations. For example, features at one location on the article may be shaped / sized to provide lighter or softer sensations while features at another location on the article may be shaped / sized to provide stronger or rougher sensations. As such,AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT features on the article can be shaped, sized, and arranged as desired to provide any specific effects or sensations for a user to experience.

[0079] Individual features formed from the hydrogel-latex composition can be characterized as protrusions that extend outward from a surface of the elastomeric article as shown in FIGS. 1A to 1E. One or more protrusions may be present, in some embodiments, on an outer surface of the elastomeric article. One or more protrusions may be present, in some embodiments, on an inner surface of the elastomeric article. One or more protrusions may be present on both an outer surface and an inner surface of the elastomeric article. As shown in FIG. 1A, a feature or protrusion individually can have a height that is measured from a surface of the elastomeric article (c) to a terminal edge of the feature or protrusion (b), the terminal edge being a surface that is furthest away from the surface of the elastomeric article (a) that defines the starting point of the measurement. For example, a feature or protrusion on an outer surface of an article would be measured from the outer surface and not the inner surface of the article so that the thickness of the article itself is not included in the measurement. An individual protrusion may have a height of about 0.3 mm or greater, about 0.4 mm or greater, about 0.5 mm or greater, about 0.6 mm or greater, about 0.7 mm or greater, about 0.8 mm or greater, about 0.9 mm or greater, about 1.0 mm or greater, about 1.1 mm or greater, about 1.2 mm or greater, or about 1.3 mm or greater. The height may range from about 0.3 mm to about 1.0 mm, about 0.3 mm to about 0.7 mm, about 0.3 mm to about 0.5 mm, about 0.3 mm to about 0.470 mm, about 0.5 mm to about 1.3 mm, about 0.6 mm to about 1.2 mm, 0.7 mm to about 1.1 mm, about 0.8 mm to about 1.25 mm, about 0.82 mm to about 1.2 mm, about 0.83 mm to about 1.1 mm, about 0.84 mm to about 1.0 mm.

[0080] The at least one protrusion has a width measured from a first lateral surface of the protrusion (d) to a second, opposing lateral surface of the protrusion (e). A lateral surface may be a surface of the feature or protrusion that extends between the surface of the elastomeric article and the terminal edge of the feature or protrusion. A lateral surface may be substantially straight so that a thickness of the feature or protrusion is substantially uniform along the thickness of the feature or protrusion, such as being substantially uniform along at least 50%, at least 65%, or at least 80% of the thickness of the feature or protrusion. In some embodiments, a lateral surface may be substantially curved or non-linear. A width of a feature or protrusion thus may be measured between opposing lateral surfaces defining the widest part of the feature or protrusion. In some embodiments, a width may be defined at a specific distance from the surface of the elastomeric articleAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT from which the feature or protrusion extends or at a specific point along the height of the feature or protrusion. For example, a width may be defined at a point that, starting from the surface of the elastomeric article, is 1% of the total height of the feature or protrusion, is 99% of the total height of the feature or protrusion, or is any percentage between 1% and 99% of the total height of the feature or protrusion, such as, without limitation, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% of the total height of the feature or protrusion. The width of the at least one protrusion may range from about 2.5 mm or greater, about 3 mm or greater, about 3.5 mm or greater, about 4 mm or greater, about 4.5 mm or greater, or about 5 mm or greater. The width may range from about 2.5 mm to about 5 mm, about 2.7 mm to about 4.7 mm, about 3 mm to about 4.5 mm, about 3.3 mm to about 3.8 mm, or about 3.5 mm to about 4.0 mm.

[0081] The polymer composition, in one or more embodiments, may be provided with a specific total solids content. This may be adjusted accordingly, such as by reducing or increasing the specific weight percentage of total polymer components present in the composition. More particularly, this may be controlled through increasing or reducing the water content of the polymer composition. In particular, the water-soluble polymer and the latex polymer component can be present in a sufficient amount such that the polymer composition has a total solids content of about 30% to about 50%, about 31% to about 49%, about 32% to about 48%, about 33% to about 47%, about 34% to about 46%, about 35% to about 45%, about 36% to about 44%, about 37% to about 43%, about 38% to about 42%, or about 39% to about 41%.

[0082] Water may be provided in the polymer composition in a sufficient content to provide the proper dilution and total solids content. Preferably, water is included in an amount sufficient to achieve a 100% composition total after accounting for the polymer components, any rheological stabilizer, and any further components that may be included in the polymer composition.

[0083] In some embodiments, the polymer composition in its final form (e.g., as the hydrogel-latex composition), ready for coating onto an article, may be adapted to or configured to exhibit a defined viscosity, which may be inclusive or exclusive of any rheological stabilizer component. For example, the polymer composition prior to being applied to a substrate may exhibit a viscosity of about 300,000 cP or less, 250,000 cP or less, 200,000 cP or less, 150,000 cP or less, 100,000 cP or less, 50,000 cP or less, 25,000 cP or less, 15,000 or less, 10,000 or less. For example, the polymer composition prior to being applied to a substrate mayAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT exhibit a viscosity of about 4,000 cP to about 300,000 cP, about 5,000 cP to about 250,000 cP, about 10,000 cP to about 200,000 cP, about 15,00 cP to about 150,000 cP, about 25,000 cP to about 100,000 cP, or about 50,000 cP to about 75,000 cP.

[0084] The hydrogel-latex composition may form or be configured to form an open cell structure when dried or cured. As such, the one or more features or protrusions that can be formed using the hydrogel-latex composition may exhibit the open cell structure. Likewise, an elastomeric article with one or more features or protrusions comprising the hydrogel-latex composition may exhibit the open cell structure. The open cell structure forms in the finished hydrogel-latex composition after it has been dried or cured so as to reach its final form for the finished product. The open cell structure arises at least because the hydrogel-latex composition traps air throughout the structure (FIG.2) during the evaporation process. This open cell structure may lead to increased height, create a spongy tactile sensation when the feature is pressed, and a pleasant tactile sensation on the surface of the feature. The water-soluble polymer within the hydrogel-latex composition provides lubricity once a protrusion is hydrated and promotes moisture absorption into the open cell structure. The hydrogel-latex features may visibly swell and provide a unique skin like feel when touched.

[0085] The open cell structure may be partially porous or contain pores. The pores may have a pore size ranging from about 40 µm to about 80 µm, from about 45 µm to about 75 µm, from about 50 µm to about 70 µm, and from 55 µm to about 65 µm. The pores may have an average pore size of about 60 µm. FIG.3 shows a measurement of the pore sizes obtained in an exemplary condom. The open cell structure may also be referred to as an open cell architecture, open cell microarchitecture, open cell framework, or open cell matrix. The open cell structure allows for the hydrogel-latex composition to be moisture-absorptive by allowing access for moisture into the interior of the feature formed from the hydrogel-latex composition and facilitating distribution of moisture throughout the feature.

[0086] The presence of the hydrogel-latex composition of the present disclosure on at least a portion of a surface of an elastomeric article (e.g., a natural or synthetic rubber latex article) can be beneficial to impart a variety of desirable properties to the underlying article, such as a condom. As already discussed above, the hydrogel-latex composition may be disposed on a surface of the elastomeric article in the form of one or more features that may be defined by one or more protrusions and may define a specific pattern on the surface of the elastomeric article. In some embodiments, a feature or protrusion or a plurality of features or protrusionsAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT may be shaped as, for example, a rib, a dot, a stripe, a concentric circle, a zigzag, a series of any of the foregoing, or the like. A rib does not connect around the base layer and forms a “C” shape around the base layer having a gap between the end points of the rib. A concentric circle would form a shape that encircles the base layer and closes having an “O” shape. Any shapes may be aligned to be substantially parallel with a longitudinal axis of the elastomeric article, to be substantially perpendicular to the longitudinal axis of the elastomeric article or may be aligned at any angle up to 180 degrees relative to the longitudinal axis of the elastomeric article. FIG. 1A illustrates a raised stripe pattern, FIG. 1B illustrates a rib pattern, FIG. 1C illustrates dot pattern, FIG.1D illustrates a concentric circle pattern, and FIG.1E illustrates a concentric dot pattern.

[0087] The polymer composition may be added to a substrate, such as a latex article, via a variety of suitable mechanisms. For example, the polymer composition may be substantially adhered to the underlying article. In embodiments wherein the polymer composition is layered onto a latex article, the inclusion of the latex component in the polymer composition may be effective to enhance adhesion of the water-soluble polymer to the underlying latex surface through at least chemical bonding. While not wishing to be bound by theory, in some embodiments, the water-soluble, hydrogel-forming polymer may be at least partially entrapped within at least a portion of the latex component during coalescence and cohesion of the individual latex particles. Additionally, the water-soluble polymer component may be further locked into the polymer matrix due to polymer chain interdiffusion during the process. In some embodiments, the combination of the hydrogel- polymer composition layer with the latex article can be particularly defined in relation to the express absence of any independent adhesives, glues, or similar chemical compounds or compositions that may be available for adhering together of relatively thin layers. Examples

[0088] The present disclosure is more fully illustrated by the following examples, which are set forth to illustrate certain embodiments of the present disclosure and are not to be construed as limiting thereof.

[0089] Example 1: Preparation of Hydrogel-Latex Compositions

[0090] Several hydrogel-latex compositions were prepared for evaluation and testing. First, the water-soluble polymer weight was investigated. The polymer blend composition that was used is listed in Table 1 and includes of a mixture of high molecular weight poly(ethylene oxide) polymer (Dow Corning FoamysenseTMAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT 301) and a low molecular weight poly(ethylene oxide) polymer (Dow Corning FoamysenseTM205). The ratio of high molecular weight to low molecular weight poly(ethylene oxide) may be adjusted for ease of processing, feature height, feature width as well as sensory feel associated with the feature.

[0091] The hydrogel-latex composition and total solids level of the hydrogel-latex composition may be adjusted depending on final product characteristics desired. The below example of the hydrogel-latex composition in Table 2 (approximately 33% total solids concentration) was used to create textured features with prominent height that are able to absorb moisture, swell, and become self-lubricated. The swollen lubricated feature may provide a sensory benefit and provide a comfortable feel during use to mimic skin feel.

[0092] Table 1: Polymer Composition of Example 1: FoamysenseTM301 solution – Blend 3 Polymer Composition FoamysenseTM301 polyox solution- Blend 3 Wet Dry Ingredient Function %Active Weight Solids 5 505

[0093] Table 2: Thickened Hydrogel-Latex of Example 1: FoamysenseTM301 solution – Blend 3 Wet DrysAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT Wet DryIngredient Function %Active Weight Solids

[0094]

[0095] The ability of the presently described hydrogel-latex composition to produce thickened features was compared to three comparative examples of hydrogel-latex compositions that used only a high molecular weight water-soluble polymer (FoamysenseTM301). Three formulations were made in comparison to the thickened hydrogel-latex composition blend as described in Table 3. The viscosities achieved using the comparative hydrogel-latex compositions were lower, despite increasing both the total percentage solids and level of rheological stabilizer. The maximum viscosity attainable for the comparative hydrogel-latex compositions was approximately 9,200 cp (as shown in Comparative Example 3 in Table 3). In Table 3, the column indicating “wet” corresponds to the amount of material weight “as is,” which includes a water content. The column indicating “dry” corresponds to the actual solids content of the material without any water, which can aid in understanding the total solids of the formulation or activity.

[0096] Condoms were fabricated with features of dispensed latex of Comparative Example 3 and Example 1 (Thickened Hydrogel-Latex: FoamysenseTM301 solution – Blend 3) described below in Table 3. The features or protrusions produced using the Example 1 according to the present disclosure (FIG. 4B) provided more defined features or protrusions with a prominent height, narrower feature width, and pleasant sensory feel when touched compared to features possible with comparative hydrogel-latex composition according to Comparative Example 3 (FIG. 4A). The higher percentage solids and viscosity associated with Example 1 may be an indication of a more structured format for the thickened hydrogel-latex composition.AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT

[0097] Table 3: Hydrogel-Latex Composition and Viscosity Comparisons Comparative Example

[0098] Table 3 continued Example 1 (Thickened Hydrogel-Latex:AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT FoamysenseTMhydrogel 205 Polyox formation solutionxamp e : a er-so u e poymer en

[0100] The use of polymers having different molecular weights of poly(ethylene oxide) polymers were prepared to determine the impact on viscosity, feature appearance, dimensions and sensory experience. The following poly(ethylene oxide) polymers were tested within the 6 formulations (referred to as Formulas 1-6 of Example 2) described in Table 4 (FoamysenseTM205 (low molecular weight), FoamysenseTM60k (medium molecular weight), and FoamysenseTM301 (high molecular weight)). The FoamysenseTM301 and FoamysenseTM60k were prepared at lower solids solutions of 1.55% and 3%, respectively, to facilitate processing. When using higher solids levels for the high and medium molecular weight poly(ethylene oxide), there was an increase in the viscoelastic nature of the polymer solutions and hydrogel-latex blends, which were found to be very stringy and difficult to manipulate.

[0101] Films of each of FoamysenseTM301, FoamysenseTM60k, and FoamysenseTM205 were drawn down of 7 mL (approximately 70 microns) onto a glass plate using a professional film applicator, then dried in a lab dispatch oven at 104°C until dried. Features were then dispensed on top of the dried PV latex films using a 10 mL syringe and again fully dried at 104°C to simulate a textured condom. The ribbed films were compared visually (FIG. 5A, FIG. 5B, and FIG. 5C) and the dimensions measured using a micrometer and ruler to determine the height and width.

[0102] Although ribbed features or protrusions are described, dots were also created, and other designs can be made per desire. The ribbed features made using FoamysenseTM205 had the narrowest width, approximately 3 mm to 4 mm in range coupled with the heights feature heights approximately 0.540 mm toAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT 0.820 mm Table 4. The sensory noted between all ribs were found to be similar in the dry stage with a rubbery tactile feel similar to latex. When an index finger was wet and rubbed on top of the hydrogel-latex features there was a noticeable lubrication in contrast to the drag felt on the PV latex base layer. The hydrated hydrogel- latex ribs created a “slip” over the surface of the feature, which may be pleasant for the consumer. The higher molecular weight poly(ethylene oxide) polymers were found to have a sensory experience that felt longer lasting than the lower molecular weight poly(ethylene oxide) (FoamysenseTM205).

[0103] Table 4: Thickened Hydrogel-Latex Compositions and Solids Comparisons Formula 1 2 3 4 5 6Ingredients Function %Active wt (g) wt (g) wt (g) wt (g) wt (g) wt (g) 0 0 2 1 43800 6

[0104] Example 3: Blends of different molecular weight poly(ethylene oxide) polymers with the lower molecular weight FoamysenseTM205.AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT

[0105] Further investigations were conducted to blend different molecular weight poly(ethylene oxide) polymers with the lower molecular weight FoamysenseTM205. Example 3 includes tests of 10 different formulas as shown in Tables 5 and 6 below (Formulas 1-10). The desire was to enhance the sensory experience for the consumer and provide more control over the feature or protrusions definition coupled with a prominent height of the protrusions. The polymer solution level remained 5% to limit viscoelastic behavior and to facilitate processing. The polymer solution blends used to study the effect on the thickened hydrogel-latex features are described in Table 5. The 5% FoamysenseTM205 (“205 solution Non-blended”) was used to compare with the other 5% polymer solutions that were made by blending in portions of the FoamysenseTM301 and FoamysenseTM60k poly(ethylene oxide) polymers. The 10 formula combinations reported in Table 5 are examples tested, and could be mixed in other proportions for performance and function. Blending in higher molecular weight poly(ethylene oxide) polymers into the lower molecular weight FoamysenseTM205 was found to increase the viscosity and change the flow properties from medium flow to long flow, and impacted the visual and sensory characteristics.

[0106] The polymer solution blends and non-blended FoamysenseTM205 (approximately 2.6% polymer solids) were tested within thickened hydrogel-latex formulations (approximately 2.5% polymer solids) and a total solids level at approximately 33% total solids as shown in Table 6. The concentrations and solids levels are examples of the formulations tested and can be adjusted depending on desired properties. The molecular weight blending of poly(ethylene oxide) and use of lower percentage polymer solids were found to have an unexpected benefit on the feature height compared with using non-blended FoamysenseTM205 at a higher percentage polymer solids level. The achievable feature height was increased when using 2.5% polymer blends, while the feature width remained narrow. Heights were recorded between approximately 0.820 mm to 1.21 mm while maintaining a feature width 3 mm to 4 mm as shown in Table 6.

[0107] Changes in visual viscoelastic properties were also noted as an increase in “stringiness” within the blends of higher molecular weights and their ability to readily entrap more air bubbles. Despite the changes in observed viscoelastic properties, the protrusion definition and control during dispensing remained. The incorporation of small air bubbles into the structure was an unexpected benefit in that this appeared to impact the ability to achieve increased feature height and improved texture after curing. The hydrogel-latex composition of the present disclosure was found to have the best sensory characteristics with more lubricationAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT and a longer lasting sensation of lubrication compared with other blends tested. The hydrogel-latex composition of the present disclosure was used for continued study based on the sensory benefit coupled with a feature height of approximately 1.01 mm and narrow width of approximately 4 mm.

[0108] Table 5: Polymer Solution Molecular Weight Blends for use in Thickened Hydrogel-Latex 205 Formula solution N n 1 2 3 4 )AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT 205 Formula solution Non- 1 2 3 4 ) 00y

[0109] Table 5 continued 205 F l solution 7 )AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT 205 Formula solution Non- 5 6 7 8 ) 00yAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT

[0110] Table 5 continued Formula205 solution9 10 Non-blendedAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT Formula205 solution9 10 Non-blended nga e ce e y oge- ae o pos o s us g e e oye ye e o e oecuar Weights Formula 205 Non- blended 1 2 3 4 5 ) 0AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT Formula 205 Non- blended 1 2 3 4 5 I di t %Ati t ( ) t ( ) t ( ) t ( ) t ( ) t ( ) 1 0 y, f s, o w,AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT

[0112] Table 6 continued Formula 205 Non- blended 6 7 8 9 10 i i )AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT Formula 205 Non- blended 6 7 8 9 10 I di t %A ti t ( ) t ( ) t ( ) t ( ) t ( ) t ( ) 0 , s, o ,

[0113] The structure of the FoamysenseTM301 polyox solution-Blend 3 ribbed beads were examined to understand contributions to the tactile sensation. Larger scale ribs of the FoamysenseTM301 polyox solution- Blend 3 and thickened PV latex (PV latex) without hydrogel and NovethixTML-10 were prepared as a control. The ribs were made, mimicking the smaller scale condom ribs by dispensing approximately 2.0g of thickened latex into a scoopula (FIG.6) and drying at 50°C until fully dry before removal (FIG.6). The hydrogel-latex rib had a noticeably more pliable nature and spongy tactile feel as well as a more textured porous surface which was also noted during draw down film studies. The ribs were cut open to observe the cross-sectional structure (FIG. 7A and FIG. 7B) for comparison. It is believed that the hydrogel-latex blend traps air throughout the structure creating an open cell structure (FIGS.2 and 3) during the evaporation process. This open cell structure appears to increase aspects of height, create a spongy tactile sensation when the feature is pressed and a pleasant tactile sensation on the surface of the feature.

[0114] The hydrogel-latex feature was tested to determine the interaction with aqueous fluids for absorption and visual change. Four of the large rib beads were used to study water absorption. The ribs were cut into approximately 1 inch pieces and weighed before and after fully soaking, separately, for 15 minutes in a petriAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT dish filled with 20g of deionized water. The increase in weight was compared graphically and by One way Analysis of Variance (FIG.8), respectively. The hydrogel-latex feature was found to absorb significantly more water compared with the PV latex feature with an approximate 17% increase in weight versus 4% respectively as shown in Table 7. The reason for the significant difference in water absorption may be due to the porous nature, inner open cell structure of the hydrogel-latex feature and the hydrophilic nature the poly(ethylene oxide) polymers in the composition.

[0115] Table 7: Water Absorption Initial Soaked Change in Hydrogel Weight Weight weight

[0116] Preparation of Textured Condoms

[0117] Condoms were fabricated to determine the tactile sensory difference and visual difference between hydrogel-latex and thickened PV latex features. Condoms were prepared using PV latex and dipping on the diptech lab scale dipping machine for 2 dip and 2 dry cycles, with drying at 212°F (100°C) for 240 seconds (4 min) between dips. The features of either hydrogel-latex or PV latex features were then dispensed by hand using a 10mL syringe onto the PV latex base layer and dried in lab dispatch oven at 95°C until the features were fully dry. The condoms were then dry removed using corn starch; and excess powder was brushed offAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT the condoms by hand. The initial appearance of the textured features or protrusions on the condom were compared for feature definition, prominence, and dry texture as shown in FIG.9A and FIG.9B. The features produced using the hydrogel-latex using FoamysenseTM301 polyox solution-Blend 3 (FIG. 9A) had better definition with a more prominent height and narrower width of the individual protrusions than the PV latex (FIG. 9B). The features made using the hydrogel-latex composition had a more textured surface when compared with the thickened latex and a more pliable spongy feel when pressed. The condoms were foiled in a blank foil after lubricating with 0.55g of an ASTROGLIDETMwater-based lubricant and aged 1 week at room temperature (approximately 25°C) undisturbed. The condoms that were lubricated were compared to a dry standard of the same design as shown in FIG.10A and FIG.10B.

[0118] Measurement of the Pore Size of the Open Cell Structure

[0119] The pore size of the open cell structure was measured using the following method. The condom was cut open and splayed to place on a slide under 12x magnification to observed the ribbed features. One drop of deionized water was placed on the ribbed feature in the area under the microscope to form a film. The film was allowed to rest for approximately 1 minute to allow moisture to soak into the film. Excess water around the rib was removed with gentle blotting using an absorbent material. The image in FIG.3 was captured using an Olympus Microscope model SZX-ILLD100 equipped with DP27 Microscope Digital Camera. Five measurements were take of random pores identified in the film as shown in Table 8 below.

[0120] Table 8: Pore size Pore Size Measurement (µm) 5 4AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT

[0121] Properties of Textured Condoms

[0122] The lubricated hydrogel-latex condom features were significantly different visually compared with a dry hydrogel-latex control and against dry and lubricated condoms with thickened PV latex features. The porous surface, inner open cell structure and hydrophilic nature of the hydrogel-latex blend may have enabled the feature to absorb lubricant and swell over time. This property may be beneficial to a consumer due to the potential to have a soft raised surface and possibly dispense lubricant during use. The tactile sensory nature of the hydrogel-latex condom was also investigated. The hydrogel-latex condom was found to have a pleasant spongy lubricated feel and textured surface, which mimicked a skin-like sensation. The hydrogel-latex feature may enhance the consumer experience due to its prominence and add a more natural feel based on the tactile and lubricated feature. The attributes may be adjusted depending on polymer combination used and design dispensed.

[0123] Rheological Properties

[0124] Each of the hydrogel-latex compositions of Examples 11 and 12 shown in Table 9 were prepared to test the rheology of the hydrogel-latex compositions for manufacturing. Example 11 performed well during manufacturing tests with adjustments for apparent viscosity and dynamic yield.

[0125] Each of the hydrogel-latex compositions in Table 9 were prepared as follows. The PV latex (filtered through a 200 µm filter) was added to beaker and mixed with a high shear 45 degree pitched axial blade adjust speed to create a vortex as the Cab-O-Sil® was slowly added. The mixture was mixed for about 10 minutes to 15 minutes to disperse. Once the mixture was observed to be particle-free, the anchor blade was changed for low shear mixing / sweeps, and the amount of the FoamysenseTM301 polyox soln-Blend 3 was slowly added and mixed until uniform. Once a uniform mixture was obtained, the NovethixTML-10 was slowly added and mixed until uniform.

[0126] Next a pre-mixed amount of sodium pyrophosphate and sodium acid pyrophospahte (dibasic) was prepared, and then added slowly using the sweep blade at approximately 25 rpm or the lowest setting. This was mixed until the mixture was uniform and free of lumps.

[0127] Next, a pre-mixed amount of the solvents that included deionized water and acetic acid were added while mixing until the mixture was uniform.AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT

[0128] Each hydrogel-latex formula was obtained was filtered. The appearance, pH, viscosity and percentage of total solids (after filtering) were measured and / or observed.

[0129] Table 9: Hydrogel-latex Formulations for Rheological Tests Ex. 11 Ex. 12Ingredient %Activewt (g) wt (g)2357 1 28009

[0130] The dynamic yield of each of Examples 11 and 12 in Table 9 were measured and obtained in FIGS. 11 and 12. The data of the dynamic yield tests are shown below in Table 10 and Table 11.

[0131] For Example 11, the dynamic yield value extrapolated (% maximum torque) was 22.77% with a maximum spring torque of 673.7 dyne-cm. The dynamic yield value was 153.8 dyne-cm. For Example 12, the dynamic yield value extrapolated (% maximum torque) was 13.73% with a maximum spring torque of 673.7 dyne-cm. The dynamic yield value was 92.51 dyne-cm.AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT

[0132] Table 10 Example 1 Dynamic yield measurements R m %Tor ueExample 2 Dynamic Yield measurementthe hydrogel-latex compositions on a surface of a condom, a nozzle set-up was used. Different nozzle orifice diameters were tested for the effect on feature formation and dispensation based on the rheology of the hydrogel-latex compositions. Two different nozzle sizes were tested: an 18-gauge luer lock nozzle having an inner diameter of 0.035 inches; and a 16-gauge luer lock nozzle having an inner diameter of 0.048 inches. The hydrogel-latex composition was loaded and dispersed on a condom surface using each nozzle to form both full ring patterns and c-ring patterns. The results of testing the hydrogel-latex compositions on condoms are shown in FIGS.12A, 12B, 13, 14A, 14B, and 15. There was found to be more control with the feature formation with the hydrogel-latex formula of Example 11 due to a combination of a higher dynamic yield value and moderate apparent viscosity.

[0135] Rib tension testing

[0136] The thickened hydrogel-latex functionalized features with full ring concentric circle designs (Examples 11 and 12 of Table 9) were dispensed onto a condom surface using the 18-gauge nozzle with average rib height within the typical range for thickened latex (approximately 300 µm to 600 µm, i.e., 0.3 mm to 0.6 mm). This was tested against the C-ring design feature using a thickened latex rib that does not containAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT a hydrogel component. This serves as a control to understand the additional benefits of the open cell structure provided by the thickened hydrogel-latex composition of the present disclosure. In addition, a commercially available, non-textured condom was used as a control to understand the restriction imposed on the film by a raised feature. The objective was to assess the additional benefits of the open cell structure provided by the thickened hydrogel-latex feature.

[0137] The testing was performed using a small arm dipping apparatus as shown in FIG.17A and Fig.17B, and was adjusted to use a tension test mode at a speed of 10.00 mm / sec, trigger distance of 20 mm and time of 60 sec. The test samples were prepared as shown in FIG.16A, FIG.16B, and FIG.16C. The test samples each had a width of approximately 1 mm.

[0138] Tension was applied to each sample at a speed of 10mm / sec to a distance of 20mm where it was then held for 60 seconds. Three runs were performed for each sample, and 10 time (sec) points were selected from each run and the force (in kg) was averaged as shown in Table 12. The average of each sample was used to analyze and compare the data as shown in FIG.18. Statistics were generated using a one-way ANOVA with a Fisher comparison.

[0139] Table 12 Commercially available Example 11, Example 12,

[0140] Due to the higher solids and solid composition of the thickened hydrogel-latex, the rib tension increases necessitating a C-ring pattern for user comfort. The open cell structure of the thickened hydrogel- latex compositions creates a more flexible feature that can stretch, reducing restriction and potentiallyAttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT enhancing user comfort by providing a less restrictive condom with rib tension that is as comfortable as the commercially available, non-textured condom.

[0141] Other objects, features and advantages of the disclosure will become apparent from the foregoing figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the disclosure, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the disclosure will become apparent to those skilled in the art from the detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.

Claims

AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT Claims 1. A hydrogel-latex composition, comprising: a natural or synthetic rubber latex; a water-soluble polymer; a bulking agent; and a rheological stabilizer, wherein a solids content of the hydrogel-latex composition is about 30% to about 50%.

2. The hydrogel-latex composition of claim 1, wherein the water-soluble polymer comprises a mixture of a first water-soluble polymer and a second water-soluble polymer.

3. The hydrogel-latex composition of claim 2, wherein a molecular weight of the first water-soluble polymer is about 500,000 g / mol to about 700,000 g / mol.

4. The hydrogel-latex composition of claim 2, wherein a molecular weight of the second water-soluble polymer is about 1,000,000 g / mol to about 5,000,000 g / mol.

5. The hydrogel-latex composition of claim 2, wherein a ratio of the first water-soluble polymer to the second water-soluble polymer is about 4:1 to about 19:

1.

6. The hydrogel-latex composition of claim 1, wherein a viscosity of the hydrogel-latex composition is about 300,000 cP or less.

7. The hydrogel-latex composition of claim 1, wherein the hydrogel-latex composition is configured to have an open cell structure.

8. The hydrogel-latex composition of claim 1, wherein the hydrogel-latex composition has a water absorption percentage of about 15 wt% to about 20 wt%.

9. The hydrogel-latex composition of claim 1, wherein the water-soluble polymer comprises at least one polyethylene oxide.

10. A product, comprising at least one layer of an elastomeric latex defining a surface of the product, wherein at least a portion of the surface has at least one protrusion extending outwardly therefrom, the at least one protrusion comprising the hydrogel-latex composition of any one of claims 1 to 9.AttyDktNo. C63806-10590WO C&D Docket No.: 99539PCT 11. The product of claim 10, wherein the at least one protrusion has a height of about 0.3 mm or greater and a width of about 3 mm or greater, the height being measured from the surface of the at least one layer of the elastomeric latex to a terminal edge of the at least one protrusion, and the width being measured from a first lateral surface to a second, opposing lateral surface of the at least one protrusion.

12. The product of claim 10, wherein the at least one protrusion is configured as a rib, a dot, a stripe, or a series of concentric circles.

13. The product of claim 10, wherein the product is a condom.

14. The product of claim 10, wherein the at least one layer of an elastomeric latex comprises a polymer selected from the group consisting of polyisoprene, poly(styrene-isoprene-styrene), poly(styrene ethylene butylene styrene), water-based polyurethane, nitrile rubber, natural rubber, and combinations thereof.

15. A moisture-absorptive condom prepared by a process comprising: forming a condom comprising at least one layer of a polymer latex, the condom defining an outer surface; applying to the outer surface of the condom a hydrogel-latex composition comprising a natural or synthetic rubber latex, a water-soluble polymer, a bulking agent, and a rheological stabilizer, wherein a solids content of the hydrogel-latex composition is about 30% to about 50%; and curing the hydrogel latex composition, wherein the hydrogel-latex composition is applied to the condom to define at least one protrusion extending outwardly from the outer surface of the condom, and wherein the hydrogel-latex composition is configured so that, after said curing, the at least one protrusion is configured to be moisture absorptive.

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