Molded Polyurethane Hydrogel

Abstract

The present technology relates to a method for forming a molded polyurethane hydrogel, e.g., a condom, the method including forming a solution of at least one polyurethane having a molecular weight between about 40,000 and about 500,000 in a water:organic polar solvent containing less than about 40% (v / v) water; applying a layer of the solution to a mold; drying the first solution layer to form a polyurethane film on the mold; and contacting the polyurethane film with a swelling agent under conditions such that the film forms a polyurethane hydrogel having a swelling agent content between about 1% and about 95%.

Description

[Technical Field]

[0001] The present technology relates to polyether- and polyester-based polyurethane hydrogels and their use in condoms.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to Australian Provisional Patent Application No. 2019902307, which is incorporated by cross-reference in its entirety. [Background technology]

[0003] Although condoms are often viewed as contraceptive devices, their action as a physical barrier also serves a valuable hygienic function by reducing or preventing sexually transmitted diseases such as herpes, chlamydia, syphilis, gonorrhea, hepatitis, human papillomavirus (HPV), trichomoniasis, and acquired immune deficiency syndrome (AIDS) caused by the human immunodeficiency virus (HIV).

[0004] Condoms are commonly made from latex, although other materials, such as nitrile, nitrile rubber, polyurethane, AT-10 resin (polyethylene resin), and polyisoprene, are also used. Disadvantages of latex condoms and gloves include the inherent allergic reactions to the material and latex rubber's sensitivity to oil-based lubricants, which can cause discomfort and disease transmission. Furthermore, like other commonly used materials, latex has a high coefficient of friction, resulting in reports of loss of sensation during use. This contributes to reduced condom use and increases the likelihood of disease transmission. Polyurethane has several advantages over latex in that it can be used with oil-based lubricants, is less allergenic than latex, and has no odor. However, polyurethane condoms are less elastic than latex and are more prone to slipping or tearing, losing their shape, or bunching up.

[0005] Protective gloves are typically made from latex rubber, nitrile or nitrile rubber (a synthetic copolymer of acrylonitrile and butadiene), polyvinyl alcohol, and polychloroprene. These materials offer a range of protection against materials such as organic solvents, inorganic compounds, and other harmful materials, but offer limited thermal and physical protection. Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors have developed a method for producing molded polyurethane hydrogels that are substantially impermeable to biological agents and have sufficient strength and durability to be useful in the manufacture of barrier devices, such as condoms and gloves. [Means for solving the problem]

[0007] In a first embodiment, there is provided a method of making a molded polyurethane hydrogel, comprising: forming a first solution of at least one polyurethane having a molecular weight between about 40,000 and about 500,000 in an aqueous:organic polar solvent containing less than about 40% (v / v) water; applying a layer of said first solution to a mold; drying the layer of the first solution to form a polyurethane film on the mold; and contacting the polyurethane film with a swelling agent under conditions whereby the film forms a polyurethane hydrogel having a swelling agent content of between about 1% and about 95%. A method is provided that includes:

[0008] In an embodiment, the molecular weight of the polyurethane is about 40,000 to about 50,000, or 50,000 to about 75,000, or 75,000 to about 100,000, or 100,000 to about 125,000, about 125,000 to about 150,000, about 150,000 to about 175,000, about 175,000 to about 200,000, about 200,000 to about 225,000, about 225,000 to about 250,000, or about 2 50,000 to about 275,000, about 275,000 to about 300,000, about 300,000 to about 3,250,000, about 325,000 to about 350,000, about 350,000 to about 375,000, about 375,000 to about 400,000, about 400,000 to about 425,000, about 4,250,000 to about 450,000, about 450,000 to about 475,000, or about 475,000 to about 500,000.

[0009] In a preferred embodiment, the molecular weight of the polyurethane is about 150,000 to about 350,000.

[0010] In embodiments, the polyurethane is derived from the polymerization of 4,4'-dicyclohexylmethane diisocyanate.

[0011] In embodiments, the polyurethane is a polyether-based or polyester-based polyurethane.

[0012] In embodiments, the polyether-based polyurethane is derived from the polymerization of 4,4'-dicyclohexylmethane diisocyanate and a polyether.

[0013] In embodiments, the polyether comprises 1 to 35 ethyl ether groups.

[0014] In embodiments, the polyester-based polyurethane is derived from the polymerization of 4,4'-dicyclohexylmethane diisocyanate and a polyester.

[0015] In embodiments, the polyester comprises 1 to 35 ethyl ester groups.

[0016] In embodiments, the polyurethane may have methyl and / or hydroxyl end groups.

[0017] In embodiments, the organic polar solvent is selected from the group consisting of ethanol, methanol, isopropanol, butanol, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, acetone, acetonitrile, and any combination thereof.

[0018] In an embodiment, the organic polar solvent is ethanol.

[0019] In embodiments, the ratio of water to organic polar solvent is selected from about 5:95, about 10:90, about 15:85, about 20:80, about 25:75, about 30:70, about 35:65, or about 40:60.

[0020] In embodiments, the ratio of water to organic polar solvent is about 10:90.

[0021] In embodiments, the swelling agent is selected from at least one of water, a glycol solution, a hydroxyethylcellulose solution, a paraben-based solution, a glycol-based solution, a glycerin-based solution, an oil-based solution, or a silicone-based solution.

[0022] In embodiments, the bulking agent comprises one or more of a spermicide, a lubricant, an antiviral agent, an antifungal agent, an antibacterial agent, a prebiotic, a probiotic, a microbiome enhancer, a flavor compound, an aroma compound, a sensory enhancer, a sterilant, or a disinfectant.

[0023] In embodiments, the polyurethane film is contacted with the swelling agent for about 1 to about 30 seconds. In some embodiments, the polyurethane film is contacted with the swelling agent for up to 24 hours, e.g., about 15 minutes, about 30 minutes, about 45 minutes, about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 11 hours, about 12 hours, about 13 hours, about 14 hours, about 15 hours, about 16 hours, about 17 hours, about 18 hours, about 19 hours, about 20 hours, about 21 hours, about 22 hours, about 23 hours, or about 24 hours.

[0024] In embodiments, the temperature of the expansion solution is from about 20°C (293.15K) to about 90°C (363.15K). For example, the temperature may be about 20°C (293.15K), about 25°C (298.15K), about 30°C (303.15K), about 35°C (308.15K), about 40°C (313.15K), about 45°C (318.15K), about 50°C (323.15K), about 55°C (328.15K), about 60°C (333.15K), about 65°C (338.15K), about 70°C (343.15K), about 75°C (348.15K), about 80°C (353.15K), about 85°C (358.15K), or about 90°C (363.15K).

[0025] In embodiments, the method comprises: Water containing less than about 40% (v / v) water: about 40,000 to about 50,000, or 50,000 to about 75,000, or 75,000 to about 100,000, or 100,000 to about 125,000, about 125,000 to about 150,000, about 150,000 to about 175,000, about 175,000 to about 200,000, about 200,000 to about 225,000, about 225,000 to about 250,000, about 250,000 to about 27 forming a second solution of polyurethane having a molecular weight between about 5,000, about 275,000 and about 300,000, about 300,000 and about 3,250,000, about 325,000 and about 350,000, about 350,000 and about 375,000, about 375,000 and about 400,000, about 400,000 and about 425,000, about 4,250,000 and about 450,000, about 450,000 and about 475,000, or about 475,000 and about 500,000; applying a layer of the second solution to the polyurethane film on the mold; drying the layers of the second solution, which layers form a polyurethane film on the mold; and contacting the polyurethane film with a swelling agent under conditions such that the film forms a polyurethane hydrogel having a swelling agent content of between about 1% and about 95%; Further includes:

[0026] In one embodiment, the polyurethane is -CH2-(CH2-O-CH2) n -CH2-[O-OCHN(CH 10 )CH2(C6H 10 )NHCO-O-(CH2CH2-O-CH2CH2)-O-OCHN(C6H 10 )CH2(C6H 10 )NHCO-NH-(CH 10 )CH2(C6H 10 )NHCO-O-CH2CH2-O-CH2CH2-O-OCHN(C6H 10 )CH2(C6H 10 )NHCO-O] m -CH2-(CH2-O-CH2) n -CH2, n is an average independently selected from any number from 1 to 35; m is an average independently selected from any number between 15 and 500.

[0027] In some embodiments, the relationship between n and m may be a ratio.

[0028] In some embodiments, the ratio of n:m may be from about 1:0.1 to about 1:75.

[0029] In some embodiments, the at least one polyurethane in the second solution may not be the same as the at least one polyurethane in the first solution.

[0030] In embodiments, the method further comprises applying a subsequent layer of the first or second solution to the polyurethane film on the mold to increase the thickness of or create particular characteristics of the polyurethane film.

[0031] In embodiments, the method further includes applying a subsequent layer of the first or second solution to a portion of the polyurethane film on the mold to increase the thickness of or create particular characteristics in the portion of the polyurethane film.

[0032] The particular feature formed from a subsequent layer may have a different modulus, tensile strength, and / or linear expansion range than the hydrogel formed from the layer to which the subsequent layer is applied.

[0033] In embodiments, either or both of the molecular weight and n:m ratio of the at least one polyurethane in the first solution is different from the molecular weight and / or n:m ratio of the at least one polyurethane in the second solution.

[0034] In embodiments, additional subsequent layers are applied to increase the thickness to a predetermined value.

[0035] In embodiments, the molded polyurethane hydrogel has a linear expansion range of about 1% to about 100%.

[0036] In embodiments, the molded polyurethane hydrogel has a tensile strength of about 1 MPa to about 20 MPa, about 20 MPa to 40 MPa, about 40 MPa to about 60 MPa, or about 80 MPa to about 100 MPa.

[0037] In preferred embodiments, the molded polyurethane hydrogel has a tensile strength of about 20 MPa to 40 MPa, for example, 20 MPa, 22 MPa, 24 MPa, 26 MPa, 28 MPa, 30 MPa, 32 MPa, 34 MPa, 36 MPa, 38 MPa, or about 40 MPa.

[0038] In embodiments, the molded polyurethane hydrogel has an elongation at break range of about 200% to about 2000%.

[0039] In embodiments, the molded polyurethane hydrogel has a shear modulus of 50% modulus from about 80 kPa to about 15 MPa, a 100% modulus from about 200 kPa to about 15 MPa, and a 300% modulus from about 700 kPa to about 15 MPa.

[0040] In a second aspect, there is provided a molded polyurethane hydrogel condom produced according to the first aspect.

[0041] In a third aspect, there is provided a molded polyurethane hydrogel condom, wherein the polyurethane hydrogel comprises one or more polyurethanes having a molecular weight of between about 40,000 and about 500,000 and a swelling agent content of between about 1% and about 95%.

[0042] In an embodiment, the molecular weight of the polyurethane is about 40,000 to about 50,000, or 50,000 to about 75,000, or 75,000 to about 100,000, or 100,000 to about 125,000, about 125,000 to about 150,000, about 150,000 to about 175,000, about 175,000 to about 200,000, about 200,000 to about 225,000, about 225,000 to about 250,000, or about 2 50,000 to about 275,000, about 275,000 to about 300,000, about 300,000 to about 3,250,000, about 325,000 to about 350,000, about 350,000 to about 375,000, about 375,000 to about 400,000, about 400,000 to about 425,000, about 4,250,000 to about 450,000, about 450,000 to about 475,000, or about 475,000 to about 500,000.

[0043] In embodiments, the polyurethane is derived from the polymerization of 4,4'-dicyclohexylmethane diisocyanate.

[0044] In embodiments, the polyurethane is a polyether-based or polyester-based polyurethane.

[0045] In embodiments, the polyether-based polyurethane is derived from the polymerization of 4,4'-dicyclohexylmethane diisocyanate and a polyether.

[0046] In embodiments, the polyether comprises 1 to 35 ethyl ether groups.

[0047] In embodiments, the polyester-based polyurethane is derived from the polymerization of 4,4'-dicyclohexylmethane diisocyanate and a polyester.

[0048] In embodiments, the polyester comprises 1 to 35 ethyl ester groups.

[0049] In embodiments, the molded polyurethane hydrogel condom has one or more of a linear expansion range of about 1% to about 100%, a tensile strength of about 1 MPa to about 100 MPa, an elongation at break range of about 200% to about 2000%, and at least one of a 50% modulus of about 80 kPa to about 15 MPa, a 100% modulus of about 200 kPa to about 15 MPa, and a 300% modulus of about 700 kPa to about 15 MPa.

[0050] In an embodiment, the condom is substantially impermeable to biological agents having an average diameter of 30 nm or greater.

[0051] In embodiments, the condom is substantially impermeable to biological agents having an average diameter of 30 nm or greater under a simulated use pressure of up to about 10 kilopascals applied to the condom, which may be, for example, up to about 1 kPa, up to about 2 kPa, up to about 3 kPa, up to about 4 kPa, up to about 5 kPa, up to about 6 kPa, up to about 7 kPa, up to about 8 kPa, up to about 9 kPa, or up to about 10 kPa.

[0052] In an embodiment, the condom has an air burst volume of about 5L to about 50L.

[0053] In embodiments, the condom has a burst pressure of from about 1 kPa to about 5 kPa, for example, from 1.3 kPa to about 3.6 kPa.

[0054] definition Throughout this specification, unless the context clearly requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

[0055] Throughout this specification the term "consisting of" means consisting solely of.

[0056] Any discussion of documents, acts, materials, devices, articles or the like which has been included in this specification is solely for the purpose of providing a context for the present technology and should not be taken as an admission that any or all of such matter formed part of the prior art or was common general knowledge in the art relevant to the present technology as it existed prior to the priority date of each claim herein.

[0057] Unless the context otherwise requires or specifically states to the contrary, integers, steps, or elements of the technology recited herein as singular integers, steps, or elements explicitly encompass both the singular and plural forms of the recited integer, step, or element.

[0058] In the context of this specification, the terms "a" and "an" are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, a reference to "an element" means one element or more than one element.

[0059] In the context of this specification, the term "about" means that reference to a number or value should not be taken as an absolute number or value, but includes a margin of variation above or below that number or value consistent with what one of ordinary skill in the art would understand in accordance with the art, including within a typical margin of error or instrumental limitations. In other words, the use of the term "about" is understood to refer to a range or approximation that one of ordinary skill in the art would consider equivalent to the recited value in the context of achieving the same function or result.

[0060] Those skilled in the art will appreciate that the technology described herein is susceptible to variations and modifications other than those specifically described. The technology is to be understood to include all such variations and modifications. For the avoidance of doubt, the technology also includes all of the steps, features, and compounds, individually or collectively, referenced or shown herein, and any and all combinations of any two or more of such steps, features, and compounds.

[0061] In order that the present technology may be more clearly understood, preferred embodiments will now be described with reference to the following figures and examples. [Brief explanation of the drawings]

[0062] [Figure 1] Figure 1 shows an example of a load vs. elongation curve for a hydrogel made with a polymer containing Polymer A. The condom has a double-wall thickness of 0.125 mm, a width of 58 mm, and a sample ring width of 20 mm. [Figure 2] Figure 2 shows an example of a load vs. elongation curve for a hydrogel made with a polymer containing Polymer B. The condom has a double-wall thickness of 0.148 mm, a width of 53 mm, and a sample ring width of 20 mm. DETAILED DESCRIPTION OF THE INVENTION

[0063] The present invention is based on a method for producing molded polyurethane hydrogels (either polyether- or polyester-based). The hydrogels produced by this method possess a number of properties, such as linear expansion, tensile strength, elongation range at break, modulus, and impermeability to biological agents, which, individually or in combination, make them suitable for use in barrier devices such as condoms and gloves.

[0064] The methods disclosed herein involve forming a solution of polyurethane in a water:organic polar solvent. A layer of the solution is then applied to a mold, for example, by dipping the mold into the solution. Once applied, the layer is allowed to dry, forming a polyurethane film on the mold. Additional layer(s) of the solution, or a different solution (e.g., using a different polyurethane), can then be applied. Once the layer is dry, the film can then be contacted with a swelling agent, e.g., an aqueous solution that may contain buffers, salts, and / or preservatives. The swelling agent permeates the film to form a polyurethane hydrogel, which typically has a swelling agent content of between about 1% and about 95%, with water-based swelling agents typically closer to 30-90%. With oil- or silicone-based swelling agents, the hydrogel typically has a swelling agent content of between about 0.1% and about 30%, e.g., between about 0.1% and about 10% after 24 hours of contact with the swelling agent.

[0065] Polyurethane As used herein, the term "polyurethane" refers to a polymer obtained from the reaction of an isocyanate and an alcohol, where the isocyanate contains two or more isocyanate functional groups.

[0066] Numerous polyurethanes are useful in the methods described herein. Suitable polyurethanes include those derived from the polymerization of: 4,4'-dicyclohexylmethane diisocyanate; 4,4'-dicyclohexylmethane diisocyanate and polyethers; 4,4'-dicyclohexylmethane diisocyanate and polyesters, or any combination thereof.

[0067] In embodiments, the polyurethane is a hydrophilic polyurethane block copolymer, such as a hydrophilic polyurethane block copolymer comprising 4,4'-dicyclohexylmethane diisocyanate. The hydrophilic polyurethane block copolymer may comprise repeating ethyl ether groups, for example, the hydrophilic polyurethane block copolymer comprises at least 1 to 50 repeating ethyl ether groups.

[0068] In another embodiment, the hydrophilic polyurethane block copolymer is a polyether-based polyurethane. For example, the hydrophilic polyurethane block copolymer includes 4,4'-dicyclohexylmethane diisocyanate and an ethyl ether. The hydrophilic polyurethane block copolymer may include 4,4'-dicyclohexylmethane diisocyanate and repeating ethyl ether groups, for example, at least four repeating ethyl ether groups. In another embodiment, the hydrophilic polyurethane block copolymer includes 4,4'-dicyclohexylmethane diisocyanate and 1 to 35 repeating ethyl ether groups.

[0069] The hydrophilic polyurethane block copolymer may include repeating ethyl ester groups, for example, the hydrophilic polyurethane block copolymer may include at least 1 to 35 repeating ethyl ester groups.

[0070] In another embodiment, the hydrophilic polyurethane block copolymer is a polyester-based polyurethane. For example, the hydrophilic polyurethane block copolymer includes 4,4'-dicyclohexylmethane diisocyanate and an ethyl ester. The hydrophilic polyurethane block copolymer may include 4,4'-dicyclohexylmethane diisocyanate and repeating ethyl ester groups, for example, at least four repeating ethyl ester groups. In another embodiment, the hydrophilic polyurethane block copolymer includes 4,4'-dicyclohexylmethane diisocyanate and 1 to 35 repeating ethyl ester groups.

[0071] In embodiments, the polyurethane has a molecular weight of between about 40,000 and about 500,000, for example, a molecular weight of between about 40,000 and about 50,000, or 50,000 and about 75,000, or 75,000 and about 100,000, or 100,000 and about 125,000, about 125,000 and about 150,000, about 150,000 and about 175,000, about 175,000 and about 200,000, about 200,000 and about 225,000, or about 225,000. 000 to about 250,000, about 250,000 to about 275,000, about 275,000 to about 300,000, about 300,000 to about 3,250,000, about 325,000 to about 350,000, about 350,000 to about 375,000, about 375,000 to about 400,000, about 400,000 to about 425,000, about 4,250,000 to about 450,000, about 450,000 to about 475,000, or about 475,000 to about 500,000.

[0072] In an embodiment, the hydrophilic polyurethane block copolymer has a molecular weight of about 40,000 to about 50,000, or 50,000 to about 75,000, or 75,000 to about 100,000, or 100,000 to about 125,000, about 125,000 to about 150,000, about 150,000 to about 175,000, about 175,000 to about 200,000, about 200,000 to about 225,000, about 225,000 to about 250,000, The molecular weight is about 250,000 to about 275,000, about 275,000 to about 300,000, about 300,000 to about 3,250,000, about 325,000 to about 350,000, about 350,000 to about 375,000, about 375,000 to about 400,000, about 400,000 to about 425,000, about 4,250,000 to about 450,000, about 450,000 to about 475,000, or about 475,000 to about 500,000.

[0073] In an embodiment, the polyester polyurethane has a molecular weight of about 40,000 to about 50,000, or 50,000 to about 75,000, or 75,000 to about 100,000, or 100,000 to about 125,000, about 125,000 to about 150,000, about 150,000 to about 175,000, about 175,000 to about 200,000, about 200,000 to about 225,000, about 225,000 to about 250,000, or about 25 The molecular weight is about 0,000 to about 275,000, about 275,000 to about 300,000, about 300,000 to about 3,250,000, about 325,000 to about 350,000, about 350,000 to about 375,000, about 375,000 to about 400,000, about 400,000 to about 425,000, about 4,250,000 to about 450,000, about 450,000 to about 475,000, or about 475,000 to about 500,000.

[0074] In an embodiment, the polyether polyurethane has a molecular weight of about 40,000 to about 50,000, or 50,000 to about 75,000, or 75,000 to about 100,000, or 100,000 to about 125,000, about 125,000 to about 150,000, about 150,000 to about 175,000, about 175,000 to about 200,000, about 200,000 to about 225,000, about 225,000 to about 250,000, or about 25 The molecular weight is about 0,000 to about 275,000, about 275,000 to about 300,000, about 300,000 to about 3,250,000, about 325,000 to about 350,000, about 350,000 to about 375,000, about 375,000 to about 400,000, about 400,000 to about 425,000, about 4,250,000 to about 450,000, about 450,000 to about 475,000, or about 475,000 to about 500,000.

[0075] In an embodiment, the polyurethane is: CH2-(CH2-O-CH2) n -CH2-[O-OCHN(CH 10 )CH2(C6H 10 )NHCO-O-(CH2CH2-O-CH2CH2)-O-OCHN(C6H 10 )CH2(C6H 10 )NHCO-NH-(CH 10 )CH2(C6H 10 )NHCO-O-CH2CH2-O-CH2CH2-O-OCHN(C6H 10 )CH2(C6H 10 )NHCO-O] m -CH2-(CH2-O-CH2) n and m is independently selected from any number from 15 to 500, e.g., 15, 25, 75, 100, 125, 150, 175, 200, 225, 25, 275, 300, 325, 350, 375, 400, 425, 450, 475, or 500.

[0076] In some embodiments, either or both of n and m are averages.

[0077] In one embodiment, n is an average of 1.5 and m is 10 to 20, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In one embodiment, m is 15.

[0078] In one embodiment, n is an average of 4, and m is an average of 100 to 120, for example, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, or 120. In one embodiment, m is 108.

[0079] In one embodiment, n is an average of 5, and m is an average of 10 to 130, e.g., 10, 10, 10, 10, 10, 10, 11, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, or 130. In one embodiment, m is 110.

[0080] In one embodiment, n is an average of 34, and m is an average of 75 to 85, for example, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, or 85. In one embodiment, m is 80.

[0081] In one embodiment, n is an average of 4 and m is an average of 180 to 220, for example, 180, 182, 184, 186, 190, 192, 194, 196, 198, 200, 202, 204, 206, 208, 210, 212, 214, 216, 218, or 220.

[0082] In one embodiment, n is an average of 30.5 and m is an average of 140 to 160, for example, 140, 142, 148, 150, 152, 154, 156, 158, or 160.

[0083] In one embodiment, n is an average of 7 and m is an average of 200 to 240, for example, 200, 202, 204, 206, 208, 210, 212, 214, 216, 218, 220, 222, 224, 226, 228, 230, 232, 234, 236, 238, or 240.

[0084] In one embodiment, the end groups of the polyurethane are independently selected from methyl and hydroxyl.

[0085] Water:organic polar solvent (water-organic polar solvent) The methods disclosed herein involve the formation of a water:organic polar solvent solution of polyurethane. The polyurethane can be solubilized in the solvent prior to the addition of water, or the polyurethane can be solubilized in the water:organic polar solvent.

[0086] The polar solvent may be protic or aprotic. The solvent may be any lower aliphatic alcohol or chlorinated solvent. For example, the solvent may be selected from the group including ethanol, methanol, isopropanol, butanol, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, acetone, acetonitrile, and any combination thereof.

[0087] The ratio of water:organic solvent may be about 5:95, about 10:90, about 15:85, about 20:80, about 25:75, about 30:70, about 35:65, or about 40:60.

[0088] The water:organic solvent used to prepare the polyurethane solution may be at room temperature or at an elevated temperature, for example, between about 25°C (298.15K) and about 60°C (333.15K); for example, the water:organic solvent solution may be heated to about 25°C (298.15K), about 30°C (303.15K), about 35°C (308.15K), about 40°C (313.15K), about 45°C (318.15K), about 50°C (323.15K), about 55°C (328.15K), or about 60°C (333.15K).

[0089] The concentration of polyurethane in the water:organic polar solvent is between about 1% and about 20% (w / v), e.g., about 1% (w / v), about 2% (w / v), about 3% (w / v), about 4% (w / v), about 5% (w / v), about 6% (w / v), about 7% (w / v), about 8% (w / v), about 9% (w / v), about 10% (w / v), about 11% (w / v), about 12% (w / v), about 13% (w / v), about 14% (w / v), about 15% (w / v), about 16% (w / v), about 17% (w / v), about 18% (w / v), about 19% (w / v), or about 20% (w / v). In one embodiment, the polyurethane has a concentration of about 6% (w / v).

[0090] Type The methods disclosed herein require the application of a polyurethane solution to a mold. Any mold shape may be used to create articles such as condoms, gloves, films, or other molds and devices. In some embodiments, an existing device (e.g., a condom) may be used as a mold.

[0091] For example, the mold may be a mandrel, a mold, a plate, or a sheet. In embodiments in which condoms are manufactured, the mold may be cylindrical or penile.

[0092] In some embodiments, the mold is glass, ceramic (eg, TiN), plastic, metal, or a combination of materials or coatings.

[0093] In embodiments, the mold is heated. For example, the mold may be heated to any temperature up to about 90° C. (363.15 K) using convection, infrared, electromagnetic induction, or conduction.

[0094] The polyurethane solution is applied to the mold to form a layer of the solution over at least a portion of the mold, which may be accomplished, for example, by immersing the mold in the solution, or by spraying, pouring, injecting, brushing, or rolling the solution onto or into the mold, or any combination of these methods.

[0095] The polyurethane solution may be applied to the mold at room temperature or may be heated before application to the mold, for example, the polyurethane solution may be heated (with or without stirring) to a temperature of about 37°C (310.15K) before application to the mold.

[0096] In some embodiments, the mold is stationary when the solution is applied, while in other embodiments, the mold is in motion when the polyurethane solution is applied.

[0097] In embodiments, the mold is immersed in the polyurethane solution at a speed of about 1 mm / s to about 1000 mm / s. For example, the immersion speed can be about 1 mm / s, about 50 mm / s, about 100 mm / s, about 200 mm / s, about 300 mm / s, about 400 mm / s, about 500 mm / s, about 600 mm / s, about 700 mm / s, about 800 mm / s, about 900 mm / s, or about 1000 mm / s.

[0098] In embodiments, the mold is withdrawn from the polyurethane solution at a speed of 1 mm / s to about 1000 mm / s. For example, the withdrawal speed can be about 1 mm / s, about 50 mm / s, about 100 mm / s, about 200 mm / s, about 300 mm / s, about 400 mm / s, about 500 mm / s, about 600 mm / s, about 700 mm / s, about 800 mm / s, about 900 mm / s, or about 1000 mm / s.

[0099] Variation of the dipping and / or withdrawal speed can be used to control the thickness of the polyurethane film.

[0100] After the layer of polyurethane solution is applied to the mold, the solution is dried to form a film on the mold. Drying may be accomplished by evaporation in an open atmosphere or in an oven or evaporator.

[0101] In some embodiments, drying may occur while the mold is stationary. In other embodiments, drying may occur while the mold is moving.

[0102] In some embodiments, the mold is heated to facilitate drying. For example, the mold may be heated to any temperature up to about 90° C. (363.15 K) using convection, infrared radiation, electromagnetic induction, or conduction.

[0103] The polyurethane solution may be dried at room temperature or at an elevated temperature, for example, from about 25°C (298.15K) to about 90°C (363.15K). The elevated temperature may be about 25°C (298.15K), about 30°C (303.15K), about 35°C (308.15K), about 37°C (310.15K), about 40°C (313.15K), about 45°C (318.15K), about 55°C (328.15K), about 60°C (333.15K), about 65°C (338.15K), about 70°C (343.15K), about 75°C (348.15K), about 80°C (353.15K), about 85°C (358.15K), or about 90°C (363.15K).

[0104] Once a film is formed on the mold, further applications of polyurethane solution may be made. In some embodiments, multiple polyurethane solutions may be utilized. For example, a first polyurethane solution (e.g., using a polyurethane having a molecular weight of between about 40,000 and about 500,000) may be applied. A second application may be made using either the same solution or a different solution (e.g., using a polyurethane having a molecular weight of between about 40,000 and about 500,000). Further applications of polyurethane solution may be made. For example, two, three, four, five, six, or more cycles of applying polyurethane solution and drying the solution may be used. In this manner, any number of the disclosed polyurethane solutions may be used to prepare a multilayer polyurethane film on a mold.

[0105] In some embodiments, the polyurethane solution may be applied to all or a portion of the mold. For example, the polyurethane solution may be applied to a portion of the mold or to a portion of the polyurethane film on the mold to increase the thickness of the film over a portion of the mold or to create a particular feature, such as a rib pattern, in the portion of the mold or in the polyurethane film on the mold.

[0106] Each layer of the multilayer polyurethane film may have different physical properties. For example, a polyurethane solution that is too weak by itself to be used to make a condom, but that has desirable properties such as a skin-like feel, can be used in combination with one or more other polyurethane solutions to prepare a multilayer polyurethane film on a mold. One or more layers can provide at least one of tensile strength, linear expansion, and modulus, while other layers can provide, for example, a skin-like feel or a moist skin-like feel.

[0107] In one embodiment, the condom is formed from at least two different polyurethane solutions, for example, to form inner and outer layers of different polyurethanes. In this embodiment, each layer has properties that impart a different feel to either side of the condom. For example, the different polyurethanes may have different moduli, tensile strengths, linear expansion ranges, and / or elongations at break.

[0108] In some embodiments, the use of different polymer solutions may require adhesion between the layers. This adhesion can be achieved by applying a polyurethane solution to the dried film so that a portion of the dried film becomes solubilized or the applied solution diffuses into the dried film. Alternatively, an adhesive may be applied to the film prior to the application of additional polyurethane solutions.

[0109] In some embodiments, the polymer solution can be cast into non-hydrogel materials as layers for structure and / or features. For example, the polymer solution can be cast into latex, polyisoprene, non-hydrating polyurethane, and other typical or atypical materials for devices, including condoms.

[0110] The polymer solution may be applied to the interior or exterior of a non-hydrogel material, for example, to all or a portion of the interior, inner, or outer surface of a device, such as a condom.

[0111] The initial polymer film or multilayer film may be dried before the application of a subsequent amount of polyurethane solution. Alternatively, the application of a subsequent amount of polyurethane solution may be done without drying the previous application.

[0112] In some embodiments, repeated applications of polyurethane solution can be used to produce a polyurethane film of a predetermined thickness, for example, from about 50 to about 200 microns. The predetermined thickness can be about 10 microns, about 20 microns, about 30 microns, about 40 microns, about 50 microns, about 60 microns, about 70 microns, about 80 microns, about 90 microns, about 100 microns, about 110 microns, about 120 microns, about 130 microns, about 140 microns, about 150 microns, about 160 microns, about 170 microns, about 180 microns, about 190 microns, or about 200 microns. In some embodiments, the predetermined thickness is about 70 microns to about 80 microns.

[0113] leavening agent The methods disclosed herein involve contacting a polyurethane film or multi-layer polyurethane film with a swelling agent under conditions such that the film forms a polyurethane hydrogel.

[0114] The swelling agent may comprise or consist of water. In other embodiments, the swelling agent is one or more of an aqueous solution, a hydroxyethyl cellulose solution, a paraben-based solution, a glycol-based solution, a glycerin-based solution, an oil-based solution, or a silicone-based solution. In some embodiments, the swelling agent may be one or more of the solutions.

[0115] In one embodiment, the swelling agent is water.

[0116] The bulking agent may comprise a spermicide, a lubricant, an antiviral, an antifungal, an antibacterial, a prebiotic, a probiotic, a microbiome enhancer, a flavor compound, an aroma compound, a sensory enhancer, a sterilant, or a disinfectant.

[0117] The polymer film may be immersed in the swelling agent and immediately withdrawn. Alternatively, the polymer film or material may be immersed in the swelling agent and allowed to remain in contact with the swelling agent for a period of time before being withdrawn. The polymer film or material may remain on the mold while in contact with the agent, or alternatively, the polymer film may be removed from the mold prior to contact with the swelling agent.

[0118] In some embodiments, the polyurethane film is contacted with the swelling agent for about 1 to about 60 seconds, which may be followed by further contact with the swelling agent either immediately or at a later time.

[0119] In other embodiments, the polyurethane film is contacted with the swelling agent overnight for up to about 24 hours. For example, the polyurethane film is contacted with the swelling agent for about 15 minutes, about 30 minutes, about 45 minutes, about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 11 hours, about 12 hours, about 13 hours, about 14 hours, about 15 hours, about 16 hours, about 17 hours, about 18 hours, about 19 hours, about 20 hours, about 21 hours, about 22 hours, about 23 hours, or about 24 hours.

[0120] In some embodiments, the polyurethane film is contacted with the swelling agent until maximum swelling of the polyurethane hydrogel is achieved, which in some cases may take more than 24 hours.

[0121] In embodiments, the temperature of the swelling agent is room temperature, or from about 20° C. (293.15 K) to about 90° C. (363.15 K). Increasing the temperature of the swelling agent can decrease the time required to expand the polyurethane film into a polyurethane hydrogel. Thus, the temperature of the expansion agent may be about 20°C (293.15K), about 25°C (298.15K), about 30°C (303.15K), about 35°C (308.15K), about 40°C (313.15K), about 45°C (318.15K), about 50°C (323.15K), about 55°C (328.15K), about 60°C (333.15K), about 65°C (338.15K), about 70°C (343.15K), about 75°C (348.15K), about 80°C (353.15K), about 85°C (358.15K), or about 90°C (363.15K).

[0122] Polyurethane Hydrogel The polyurethane hydrogel formed by contacting the polyurethane film with a swelling agent can have a swelling agent content of between about 1% and about 95%, e.g., about 1%, 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%, or about 95%. In some embodiments, the swelling agent content is about 45%, about 50%, or about 55%, e.g., about 54%. In some embodiments, the hydrogel has a swelling agent content that approximates or is the same as the moisture content of skin. The moisture content of skin is roughly around 64%, and therefore, in some embodiments, the swelling agent content of the polyurethane hydrogel is about 60% to about 70%, e.g., about 64%.

[0123] In some embodiments, the swelling agent is oil- or silicone-based. In these embodiments, the polyurethane hydrogel formed by contacting the polyurethane film with the silicone- or oil-based swelling agent preferably has a swelling agent content of about 0.1% to about 30%, e.g., about 1%, about 2%, about 4%, about 8%, about 10%, about 12%, about 14%, about 16%, about 18%, about 20%, about 22%, about 24%, about 26%, about 28%, or about 30%. For example, after 24 hours of contact with the swelling agent, the polyurethane hydrogel may have a silicone or oil-based swelling agent content of about 0.1% to about 10%, e.g., about 0.1%, about 0.5%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, or about 10%.

[0124] In some embodiments, the swelling agent is a mixture or hybrid of two or more base swelling agents, for example, in some embodiments, the swelling agent is a water:silicone hybrid.

[0125] The polyurethane hydrogel formed by the methods disclosed herein has many properties that make it suitable for use in applications such as condoms, including favorable linear expansion properties, tensile strength, modulus, and the ability to stretch substantially before breaking while still being impermeable to biological agents and permeable to small molecules.

[0126] These properties can be adjusted by selecting one or more of the following for each polymer: polymer type, polymer molecular weight range, average molecular weight, n:m range, or by blending two or more polymers. In some embodiments, higher molecular weight polymers produce stronger, but stiffer, less flexible hydrogels, while lower molecular weight polymers produce weaker, but softer, more flexible hydrogels. Thus, by blending polymers and selecting polymers with particular average molecular weights, molecular weight profiles, and n:m ratios, hydrogels can be produced by the methods described herein with a desired range of properties (linear expansion, tensile strength, modulus, elongation, impermeability) appropriate for a particular application, e.g., condoms. These properties, along with the amount and type of swelling agent in the hydrogel, contribute to how the user experiences the hydrogel, i.e., contribute to the "feel" of the hydrogel.

[0127] In one embodiment, properties can be adjusted by using polymers with different values ​​for n and m, or specific n:m ratios. For example, the n:m ratio affects the amount of swelling of the hydrogel, which in turn affects the modulus, which in turn is related to the feel of the hydrogel. While modulus is an important contributor to the feel of a hydrogel, it should be noted that other properties and factors, such as swelling agent content and type, also contribute to feel.

[0128] In some embodiments, the n:m ratio is 1:0.1 to 1:75. For example, suitable n:m ratios include 1:21 to 1:26 (corresponding to A in Example 1), 1:25 to 1:30 (corresponding to B in Example 1), 1:6.67 to 13.33 (corresponding to C in Example 1), 1:2.2 to 1:2.5 (corresponding to D in Example 1), 1:4.59 to 1:5.25 (corresponding to E in Example 1), and 1:28.57 to 1:34.30 (corresponding to F in Example 1). Considering that n and m are averages in some embodiments, the n:m ratio also represents the ratio of average n to average m.

[0129] In some embodiments, the n:m ratio is any number between about 1:0.1 and 1:75, such as 1:0.1, about 1:0.5, about 1:1, about 1:5, about 1:10, about 1:15, about 1:20, about 1:25, about 1:30, about 1:35, about 1:40, about 1:45, about 1:50, about 1:55, about 1:60, about 1:65, about 1:70, or about 1:75.

[0130] "Linear expansion" refers to the ratio of the change in length of a material to its initial length. In embodiments, the polyurethane hydrogel film or material has a linear expansion of between about 1% and 100%, e.g., about 10%, 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%.

[0131] The term "tensile strength" refers to the maximum force absorbed by a sample before sample failure. Tensile strength is the ratio of the maximum force to the initial cross-sectional area of ​​the sample. In embodiments, the hydrogel material has a tensile strength of between about 1 MPa and about 100 MPa, e.g., about 3 MPa, about 4 MPa, about 5 MPa, about 6 MPa, about 7 MPa, about 8 MPa, about 9 MPa, about 10 MPa, about 11 MPa, about 12 MPa, about 13 MPa, about 14 MPa, about 15 MPa, about 16 MPa, about 17 MPa, about 18 MPa, about 20 MPa, about 25 MPa, about 30 MPa, about 35 MPa, about 40 MPa, about 45 MPa, about 50 MPa, about 55 MPa, about 60 MPa, about 65 MPa, about 70 MPa, about 75 MPa, about 80 MPa, about 85 MPa, about 90 MPa, about 95 MPa, or about 100 MPa.

[0132] The term "modulus," as used herein, refers to the force at a particular elongation value and relates to the hardness of a material. In embodiments, the hydrogel material has a 50% modulus of about 80 kPa to about 15 MPa, a 100% modulus of about 200 kPa to about 15 MPa, and a 300% modulus of about 700 kPa to about 15 MPa.

[0133] In one embodiment, the 50% modulus is from about 80 kPa to about 15 MPa, for example, 80 kPa, 100 kPa, 500 kPa, 750 kPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, 12 MPa, 13 MPa, 14 MPa, or 15 MPa.

[0134] In one embodiment, the 100% modulus is from about 200 kPa to about 156 MPa, for example, 200 kPa, 250 kPa, 500 kPa, 750 kPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, 12 MPa, 13 MPa, 14 MPa, or 15 MPa.

[0135] In one embodiment, the 300% modulus is about 700 kPa to 15 MPa, for example, 700 kPa, 750 kPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, 12 MPa, 13 MPa, 14 MPa, or 15 MPa.

[0136] The term "elongation at break" refers to the maximum linear elongation of a material before sample failure. Elongation at break is defined as the percentage (%) increase in the material over its initial length.

[0137] With reference to Figures 1 and 2, the elongation at break can be calculated using a load versus elongation curve. In each of Figures 1 and 2, a 20 mm sample ring of hydrogel condom (containing either Polymer A or B) produced by the methods described herein was tested as described in the Examples. The condom in Figure 1 had a double wall thickness of 0.125 mm and a width of 58 mm, and in Figure 2, the condom had a double wall thickness of 0.148 mm and a width of 53 mm.

[0138] In embodiments, the hydrogel material has an elongation to break of about 200%, about 300%, about 400%, about 500%, about 600%, about 700%, about 800%, about 900%, about 1000%, about 1100%, about 1200%, about 1300%, about 1400%, about 1500%, about 1600%, about 1700%, about 1800%, about 1900%, or about 2000%.

[0139] In embodiments, the hydrogel is substantially impermeable to biological agents, such as viruses or virus models (e.g., phiX174) or bacteria (e.g., E. coli). phiX174 has an average diameter of approximately 30 nm, and therefore the hydrogel is substantially impermeable to biological agents having an average diameter of 30 nm or greater. In embodiments, the hydrogel is substantially impermeable to biological agents 30 nm or greater when a pressure of up to about 10 kPa is applied to the hydrogel. The pressure may be up to about 1 kPa, up to about 2 kPa, up to about 3 kPa, up to about 4 kPa, up to about 5 kPa, up to about 6 kPa, up to about 7 kPa, up to about 8 kPa, up to about 9 kPa, or up to about 10 kPa.

[0140] In another embodiment, the hydrogel is permeable to small molecules, e.g., water-soluble small molecules. The inventors have demonstrated that polyurethane hydrogels are permeable to sodium fluorescein (molecular weight 376.275 g / mol) and rhodamine B (molecular weight 479.02 g / mol). Thus, the hydrogel is permeable to water-soluble small molecules having a molecular weight of about 500 g / mol or less.

[0141] One advantage of the polyurethane hydrogels described herein, for example, when used in condoms, is that they are visually transparent, in contrast to conventional latex or polyisoprene condoms.

[0142] In one embodiment, a condom formed from the polyurethane hydrogel has a linear expansion of about 40%, a swelling agent content of about 60%, a tensile strength of about 15.2 MPa, an elongation at break of about 747%, and a 50% modulus of about 2.8 MPa, a 100% modulus of about 3.6 MPa, and a 300% modulus of about 6.7 MPa.

[0143] In another embodiment, a condom formed from the polyurethane hydrogel has a linear expansion of about 30%, a swelling agent content of about 50%, a tensile strength of about 26.3 MPa, an elongation at break of about 591%, and a 50% modulus of about 2.5 MPa, a 100% modulus of about 3.3 MPa, and a 300% modulus of about 6.6 MPa.

[0144] Testing a condom may involve inflating the condom with air to test the volume of air that can be contained within the condom before bursting. The volume of air contained within the condom at the time of bursting is known as the air burst volume. In preferred embodiments, the hydrogel condoms described herein have an air burst volume of about 5 L to 40 L. For example, the air burst volume can be about 5 L, about 10 L, about 15 L, about 20 L, about 25 L, about 30 L, about 35 L, about 40 L, about 45 L, or about 50 L.

[0145] Additionally, filling a condom with air also increases the pressure, and the maximum air pressure at which it bursts is known as the burst pressure. In preferred embodiments, the hydrogel condoms described herein have a burst pressure of about 0.75 kPa to about 4 kPa. For example, the burst pressure may be about 0.75 kPa, about 1 kPa, about 1.25 kPa, about 1.5 kPa, about 1.75 kPa, about 2 kPa, about 2.25 kPa, about 2.5 kPa, about 2.75 kPa, about 3 kPa, about 3.25 kPa, about 3.5 kPa, about 3.75 kPa, about 4 kPa, about 4.25 kPa, about 4.5 kPa, about 4.75 kPa, or about 5 kPa. In some embodiments, the burst pressure may be about 1.3 kPa to about 3.6 kPa.

[0146] Polyurethane hydrogels have additional favorable attributes, including users reporting that the polyurethane hydrogel material feels like skin, feels moist, feels soft, feels like the user is numb (i.e., feels empty), or a combination thereof. In some embodiments, the polyurethane hydrogel is visually transparent, so that visual appeal or visual stimulation is not compromised.

[0147] In some embodiments, the polyurethane hydrogel component conducts heat more efficiently than other condom materials, resulting in less impairment of body heat transfer.

[0148] The polyurethane hydrogel can be made to have no adverse effects on odor or taste.

[0149] In some embodiments, the polyurethane hydrogel is hypoallergenic, i.e., does not induce an allergic reaction.

[0150] In some embodiments, polyurethane hydrogels are fabricated to have multiple regions with different physical properties (e.g., modulus, linear expansion, elongation at break, burst pressure, etc.). This is achieved by using different polymers for each of these multiple regions. For example, a condom may be fabricated with a higher modulus hydrogel on the inner surface, which may feel firmer, and a lower modulus hydrogel on the outer surface, which may feel softer, or vice versa. Alternatively, or in addition, there may be areas of different modulus; for example, a condom may have a tip region with a different modulus than the shaft portion, a shaft portion with multiple regions, or a loop with a different modulus or other property. By using polymers with varying values ​​of molecular weight, n:m ratio, or both, devices may be fabricated using the methods described herein to have distinctly different feels at different aspects of the finished device upon use; for example, a condom with varying feels along the device will evoke different sensations for each partner. In particular, the hydrogel may be skin-like.

[0151] As set forth in Table 1, the properties of the polyurethane hydrogel condoms described herein compare favorably with those of conventional condoms.

[0152] [Table 1] [Example]

[0153] Example 1: Polyurethane solution preparation solvent: The ethanol:water ratio can range from 60:40 to 95:5 depending on the polyurethane. 90:10 ethanol:water was chosen as the ratio in which the following polymers (including each of A-F below) are readily soluble: A: -CH2-(CH2-O-CH2) n -CH2-[O-OCHN(CH 10 )CH2(C6H 10)NHCO - O - (CH2CH2 - O - CH2CH2) - O - OCHN(C6H 10 )CH2(C6H 10 )NHCO - NH - (C6H 10 )CH2(C6H 10 )NHCO - O - CH2CH2 - O - CH2CH2 - O - OCHN(C6H 10 )CH2(C6H 10 )NHCO - O] m -CH2 - (CH2 - O - CH2) n -CH 2, -, n has an average = 5, and m is about 105 - 130; or B: -CH2 - (CH2 - O - CH2) n -CH2 - [O - OCHN(C6H 10 )CH2(C6H 10 )NHCO - O - (CH2CH2 - O - CH2CH2) - O - OCHN(C6H 10 )CH2(C6H 10 )NHCO - NH - (C6H 10 )CH2(C6H 10 )NHCO - O - CH2CH2 - O - CH2CH2 - O - OCHN(C6H 10 )CH2(C6H 10 )NHCO - O] m -CH2 - (CH2 - O - CH2) n -CH2 -, n has an average = 4, and m is about 100 - 120; C: -CH2 - (CH2 - O - CH2) n -CH2 - [O - OCHN(C6H 10 )CH2(C6H 10 )NHCO - O - (CH2CH2 - O - CH2CH2) - O - OCHN(C6H 10 )CH2(C6H 10 )NHCO - NH - (C6H 10 )CH2(C6H 10 )NHCO - O - CH2CH2 - O - CH2CH2 - O - OCHN(C6H 10 )CH2(C6H 10 )NHCO - O] m -CH2 - (CH2 - O - CH2) n-CH2-, n is on average 1.5, and m is about 10-20; D: -CH2-(CH2-O-CH2) n -CH2-[O-OCHN(CH 10 )CH2(C6H 10 )NHCO-O-(CH2CH2-O-CH2CH2)-O-OCHN(C6H 10 )CH2(C6H 10 )NHCO-NH-(CH 10 )CH2(C6H 10 )NHCO-O-CH2CH2-O-CH2CH2-O-OCHN(C6H 10 )CH2(C6H 10 )NHCO-O] m -CH2-(CH2-O-CH2) n -CH2-, n is on average 34, and m is approximately 75-85 E: -CH2-(CH2-O-CH2) n -CH2-[O-OCHN(CH 10 )CH2(C6H 10 )NHCO-O-(CH2CH2-O-CH2CH 2) -O-OCHN(C6H 10 )CH2(C6H 10 )NHCO-NH-(CH 10 )CH2(C6H 10 )NHCO-O-CH2CH2-O-CH2CH2-O-OCHN(C6H 10 )CH2(C6H 10 )NHCO-O] m -CH2-(CH2-O-CH2) n -CH2-, n is on average 30.5, and m is about 140-160. F: -CH2-(CH2-O-CH2) n -CH2-[O-OCHN(CH 10 )CH2(C6H 10 )NHCO-O-(CH2CH2-O-CH2CH 2) -O-OCHN(C6H 10 )CH2(C6H 10 )NHCO-NH-(CH 10 )CH2(C6H 10)NHCO-O-CH2CH2-O-CH2CH2-O-OCHN(C6H 10 )CH2(C6H 10 )NHCO-O] m -CH2-(CH2-O-CH2) n -CH2-, n is 7 on average, and m is about 200 to 240.

[0154] Polymer solution: The polymers are dissolved separately in a solvent (EtOH:W 90:10 v / v). The polymer concentration can range from 1% w / v up to 10% w / v to form a film. A concentration of 6% w / v was selected to fabricate all films (see Table 2). However, in a dip-coating process, the concentration can be further optimized to control the film quality and the number of dips required to reach the desired thickness.

[0155] The mixture is stirred overnight to solubilize the polymer, and heating to 70° C. (343.15 K) increases the rate of solubilization.

[0156] The stress of the hydrogels prepared in the above examples was measured as a function of elongation using "dog-bone" shaped hydrogel samples stretched at a rate of 500 mm / min. The stress was calculated by finding the ratio of the force to the initial cross-sectional area of ​​the dog-bone sample. The elongation was defined as the ratio of the stretched length to the initial length. The modulus was calculated by applying the stress at 50%, 100%, and 300% sample elongation.

[0157] [Table 2]

[0158] Example 2: Bulking Agent Compatibility To investigate one measure of polymer swelling agent compatibility, a series of personal care products were investigated. Polymer sheets were cast by adding 5 mL of a 6% (w / v) polymer solution to a mold. The dried sheets were cut to shape and measured for length. The polymers were then immersed in various swelling compounds, which are commercially available sexually relevant products. The polymers were left in the swelling agents for 24 hours and remeasured to determine instantaneous swelling compared to a control dry material.

[0159] A variety of polymers and lubricant types were investigated, including water-based, silicone-based, and oil-based formulations, as listed in Table 3.

[0160] Measurements of the linear expansion of swollen hydrogels using various personal care products were investigated. Table 3 shows examples from Polymer A and Polymer B. Tensile strength was analyzed for each base type, and the results showed that the lubricant-based swelling agent did not reduce tensile strength. The results indicate that hydrogel condoms are more compatible with lubricant options than traditional latex or polyisoprene condoms, which cannot be used with oil-based lubricants because the oil degrades the material. Furthermore, the hydrogels are compatible with silicone lubricants, which are not recommended for use with silicone toys.

[0161] [Table 3]

[0162] Example 3: Condom prototype production: Condom prototypes were made using a dip-coating process in which a cylindrical mold was dipped into a heated polymer solution. The mold is preferably made of glass or metal. The inventors found that plastic molds were not ideal because the polyurethane solution tended to coat the mold unevenly after dipping.

[0163] In one experiment, a mold rig is assembled from multiple glass or metal molds to produce multiple prototype condoms.

[0164] The polymer solution is placed in a large container that is wide enough to accommodate the rig and tall enough to account for all of the liquid displacement. The container is placed under the rig.

[0165] The polymer solution in the vessel was heated to 25°C (298.15K) with constant stirring. The mold was immersed in the polymer solution and withdrawn at a speed between 20 and 200 mm / s. After removal of the mold, the polymer solution was covered to minimize solvent evaporation.

[0166] The molds, with the polymer solution applied to them, are held at room temperature for at least 5-10 minutes until the solvent evaporates from the coating and a polyurethane film is formed on the molds, which time can be significantly shortened when drying is performed at elevated temperatures, for example in an oven or dehydrator.

[0167] Repeated dipping and drying processes increase the thickness of the polyurethane film that forms the condom. The polymer is typically dipped 1 to 6 times to create the condom.

[0168] In some cases, condoms were created by a series of dipping with a polymer of one molecular weight and a dip or series of dipping with a polymer of another molecular weight.

[0169] In one example, a condom was prepared having a first layer of hydrogel comprising polymer A and a second layer of hydrogel comprising polymer B. In another case, a condom was prepared having a first layer of hydrogel comprising polymer B and a second layer of hydrogel comprising polymer A.

[0170] Once the solvent has completely evaporated from the coated former, the former can be immersed in a container filled with excess swelling agent or (hydrating solution) to expand the dried film and form a hydrogel.

[0171] Example 4: ISO Standard Condom Test: The following data are results from standard conventional international testing on condoms. The tests are from ISO 23409:2011 Male condoms - Requirements and test methods for condoms made from synthetic materials and ISO 4074:2015 Natural rubber latex male condoms - Requirements and test methods required for batch test qualification of condoms. Tensile testing is not currently found in ISO or ASTM protocols, but is a useful guide in the development of alternative condom materials.

[0172] Condoms were manufactured using a selection of Polymers A and B (described above). Testing was performed by Enersol and by independent quality assurance testing equipment and services accredited to meet the requirements of ISO 17025:2017 and ISO 9001:2015 and tested for dimensional, tensile, air burst and leak tests.

[0173] To measure length, the condom is stretched slightly (5 percent to 10 percent) to smooth out any wrinkles caused by rolling and suspended over a graduated mandrel. Width is measured perpendicular to the condom's length when unfolded and flat without any creases. Typically, three thickness measurements are taken from each sample condom and averaged. Table 4 provides measurements from condoms designated as Condom Type A and Condom Type B; in each case, the condom type was defined as if the condom's primary component was the corresponding polymer type from Table 2.

[0174] [Table 4]

[0175] The tensile strength of the condoms was evaluated using 20 mm wide samples cut from the center of the condom. The test involves applying equal pressure to the entire condom using a constant speed circular motion to stretch this cross-sectional piece (ring) of material until it breaks. The test measures the force required to break the material (breaking force in Newtons); the length of the material piece at break (percent elongation, the percent increase in circumference from the initial to final circumference); and the tensile breaking strength (megapascals), which is calculated using the material thickness and the Newtons of breaking force. Table 5 provides tensile strength measurements from condoms containing polymer A or polymer B.

[0176] [Table 5]

[0177] Burst pressure and volume were evaluated by expanding the condom like a balloon and measuring the volume and pressure of air required to burst it. The condom was unfolded and secured to a stem, allowing it to expand to approximately 150 mm. The test device expands the condom with clean, oil-free / moisture-free air at a specified rate. Table 6 gives the burst pressure from condoms containing Polymer A or Polymer B.

[0178] [Table 6]

[0179] The leakage test was performed using the hanging method. In this method, condoms are filled with water, usually while hanging vertically, and checked by an observer for leakage. In addition, the end of the water-filled condom is tied and then rolled across absorbent paper, and water is found on the paper. The test was performed on samples from various condom batches that passed the no-hole (leak) test.

[0180] Additional condoms were made by adding layers of various polymers. In one example, a condom made from polymer A was laminated with polymer B, and vice versa. In these examples, the condoms had different properties as shown in Table 1. The condoms were tested for mechanical properties and met or exceeded ISO standards and were within the parameters found in the mechanical test results above.

[0181] Example 5: Bacteriophage barrier testing Polymers A and B were tested for biological barrier properties, preventing the spread of a small bacterial virus (bacteriophage Φ-X174) when used as a challenge particle. The use of Φ-X174 is known as a viral penetration test and is typically performed to check the barrier properties of condoms (based on ISO 23409:2011). In these tests, a sample condom is restrained and filled with a suspension of the surrogate virus bacteriophage Φ-X174. By submerging the sample in a collection fluid, leakage of viral particles through the sample can be detected by analyzing the fluid for the presence of viral particles.

[0182] Hydrogel materials A and B were immobilized between the donor and receiver chambers of a Franz cell. The receptor compartment was filled with phosphate-buffered saline (PBS), and the donor chamber was loaded with Φ-X174 bacteriophage in PBS. Samples were withdrawn from the receptor compartment and analyzed, and the phage was quantified by plaque formation assay. As a positive control, materials were wounded by puncturing with a 25G needle. Test materials showed that they were not permeable to Φ-X174.

[0183] Tests were also performed on constrained and compressed condoms made from Polymer A and Polymer B. The condoms passed the viral penetration test.

[0184] Additionally, hydrogels A and B were exposed to Escherichia coli, a bacterium that causes urinary tract infections. Hydrogel materials A and B were immobilized between the donor and receiver chambers of a Franz cell. The receptor compartment was filled with phosphate-buffered saline (PBS), and the donor chamber was loaded with E. coli in PBS. Samples were withdrawn from the receptor compartment and analyzed by growth on LB agar plates. No E. coli growth was observed in samples taken from the receptor compartment. As a positive control, hydrogel materials were injured by puncturing them with a 25G needle. Test materials demonstrated that they were not permeable to E. coli.

[0185] It will be appreciated by those skilled in the art that numerous variations and / or modifications may be made to the invention shown in the specific embodiments without departing from the spirit or scope of the invention as broadly described, and the present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. Some embodiments of the present invention are described in the following items [1]-

[37] . [1] 1. A method for making a molded polyurethane hydrogel comprising: forming a first solution of at least one polyurethane having a molecular weight between about 40,000 and about 500,000 in an aqueous:organic polar solvent containing less than about 40% (v / v) water; applying a layer of said first solution to a mold; drying the layer of the first solution to form a polyurethane film on the mold; and contacting the polyurethane film with a swelling agent under conditions whereby the film forms a polyurethane hydrogel having a swelling agent content of between about 1% and about 95%. A method comprising: [2] Item 2. The method according to item 1, wherein the molecular weight of the polyurethane is about 40,000 to about 200,000, about 150,000 to about 350,000, or about 300,000 to about 500,000. [3] 3. The method according to claim 1 or 2, wherein the polyurethane is derived from the polymerization of 4,4'-dicyclohexylmethane diisocyanate. [4] 3. The method according to item 1 or 2, wherein the polyurethane is a polyether-based or polyester-based polyurethane. [5] 5. The method according to claim 4, wherein the polyether-based polyurethane is derived from the polymerization of 4,4'-dicyclohexylmethane diisocyanate and a polyether. [6] Item 6. The method according to item 5, wherein the polyether contains 1 to 35 ethyl ether groups. [7] 7. The method of claim 6, wherein the polyester-based polyurethane is derived from the polymerization of 4,4'-dicyclohexylmethane diisocyanate and a polyester. [8] 8. The method of claim 7, wherein the polyester contains 1 to 35 ethyl ester groups. [9] 9. The method according to any one of items 1 to 8, wherein the organic polar solvent is selected from the group consisting of ethanol, methanol, isopropanol, butanol, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, acetone, acetonitrile, and any combination thereof.

[10] Item 10. The method according to item 9, wherein the organic polar solvent is ethanol.

[11] 11. The method of any one of items 1 to 10, wherein the ratio of water:organic polar solvent is selected from about 5:95, about 10:90, about 15:85, about 20:80, about 25:75, about 30:70, about 35:65, or about 40:60.

[12] Item 12. The method of item 11, wherein the ratio of water to organic polar solvent is about 10:90.

[13] 13. The method according to any one of items 1 to 12, wherein the swelling agent is selected from at least one of water, a glycol solution, a hydroxyethyl cellulose solution, a paraben-based solution, a glycol-based solution, a glycerin-based solution, an oil-based solution, or a silicone-based solution.

[14] Item 14. The method of item 13, wherein the bulking agent comprises one or more of a spermicide, a lubricant, an antiviral agent, an antifungal agent, an antibacterial agent, a prebiotic, a probiotic, a microbiome enhancer, a flavor compound, an aroma compound, a sensory enhancer, a sterilant, or a disinfectant.

[15] 15. The method according to any one of items 1 to 14, wherein the polyurethane film is contacted with the swelling agent for at least 1 second at ambient temperature.

[16] forming a second solution of at least one polyurethane having a molecular weight of about 40,000 to about 200,000, about 150,000 to about 350,000, or about 300,000 to about 500,000 in an aqueous:organic polar solvent containing less than about 40% (v / v) water; applying a layer of the second solution to the polyurethane film on the mold; drying the layers of the second solution to form a polyurethane film on the mold; and contacting the polyurethane film with a swelling agent under conditions whereby the film forms a polyurethane hydrogel having a swelling agent content of between about 1% and about 95%. 16. The method according to any one of items 1 to 15, further comprising:

[17] The polyurethane is -CH 2 -(CH 2 -O-CH 2 ) n -CH 2 -[O-OCHN(C 6 H 10 )CH 2 (C 6 H 10 )NHCO-O-(CH 2 CH 2 -O-CH 2 CH 2 )-O-OCHN(C 6 H 10 )CH 2 (C 6 H 10 )NHCO-NH-(C 6 H 10 )CH 2 (C 6 H10 )NHCO-O-CH 2 CH 2 -O-CH 2 CH 2 -O-OCHN(C 6 H 10 )CH 2 (C 6 H 10 )NHCO-O] m -CH 2 -(CH 2 -O-CH 2 ) n -CH 2 Includes n is an average independently selected from any number from 1 to 35; m is a mean independently selected from any number from 15 to 500; 17. The method according to any one of items 1 to 16.

[18] Item 18. The method according to item 17, wherein the ratio of n:m is about 1:0.1 to about 1:75.

[19] 19. The method according to any one of items 16 to 18, wherein the at least one polyurethane in the second solution is not the same as the at least one polyurethane in the first solution.

[20] 20. The method of any one of items 1 to 19, further comprising applying a subsequent layer of the first or second solution to the polyurethane film on the mold to increase the thickness of or create particular characteristics of the polyurethane film.

[21] 21. The method of any one of items 1 to 20, further comprising applying a subsequent layer of the first or second solution to a portion of the polyurethane film on the mold to increase the thickness of the portion of the polyurethane film or to create a particular feature in the portion of the polyurethane film.

[22] 22. The method of claim 21, wherein the specific feature formed from the subsequent layer has a different modulus, tensile strength, and / or linear expansion range than the hydrogel formed from the layer to which the subsequent layer is applied.

[23] 23. The method according to any one of items 16 to 22, wherein one or both of a molecular weight and an n:m ratio of the at least one polyurethane in the first solution is different from a molecular weight and an n:m ratio of the at least one polyurethane in the second solution.

[24] 24. The method according to any one of items 16 to 23, wherein further subsequent layers are applied to increase the thickness to a predetermined value.

[25] 25. The method of any one of items 1 to 24, wherein the molded polyurethane hydrogel has a linear expansion range of about 1% to about 100%.

[26] 26. The method according to any one of items 1 to 25, wherein the molded polyurethane hydrogel has a tensile strength of about 1 MPa to about 100 MPa; about 1 MPa to about 20 MPa, about 20 MPa to about 60 MPa, about 60 MPa to about 80 MPa, or about 60 MPa to about 80 MPa.

[27] 27. The method of any one of items 1 to 26, wherein the molded polyurethane hydrogel has an elongation at break range of about 200% to about 2000%.

[28] 28. The method of any one of items 1 to 27, wherein the molded polyurethane hydrogel has at least one of a 50% modulus of about 80 kPa to about 15 MPa, a 100% modulus of about 200 kPa to about 15 MPa, and a 300% modulus of about 700 kPa to about 15 MPa.

[29] 29. A molded polyurethane hydrogel condom produced by the method according to any one of items 1 to 28.

[30] 1. A molded polyurethane hydrogel condom, wherein the polyurethane hydrogel comprises a polyurethane having a molecular weight of between about 40,000 and about 500,000, and a swelling agent content of between about 40% and about 70%.

[31] Item 31. The molded polyurethane hydrogel condom according to item 30, having one or more of a linear expansion range of about 1% to about 100%, a tensile strength of about 1 MPa to about 40 MPa, and an elongation at break range of about 200% to about 750%, and at least one of a 50% modulus of about 80 kPa to about 15 MPa, a 100% modulus of about 200 kPa to about 15 MPa, and a 300% modulus of about 700 kPa to about 15 MPa.

[32] 32. The condom according to any one of items 30 to 31, which is substantially impermeable to biological agents having an average diameter of 30 nm or more.

[33] 33. The condom according to any one of items 30 to 32, which is substantially impermeable to biological agents having an average diameter of 30 nm or more under a simulated use pressure of from atmospheric pressure to about 5 kilopascals.

[34] 34. The molded polyurethane hydrogel condom of any one of items 30 to 33, having an air burst volume of about 5 L to about 50 L.

[35] 35. The molded polyurethane hydrogel condom according to item 34, wherein the air burst volume is 5 L to 40 L.

[36] 36. The molded polyurethane hydrogel condom of any one of items 30 to 35, having an air burst pressure of about 0.75 kPa to about 5 kPa.

[37] 37. The molded polyurethane hydrogel condom according to item 36, wherein the air burst pressure is 1.6 kPa to 3.6 kPa.

Claims

1. 1. A method for making a molded polyurethane hydrogel, comprising: forming a first solution of at least one polyurethane having a weight average molecular weight between 40,000 and 500,000 in an aqueous:organic polar solvent containing less than 40% (v / v) water; applying a layer of said first solution to a mold; drying the layer of the first solution to form a polyurethane film on the mold; and contacting the polyurethane film with a swelling agent under conditions whereby the film forms a polyurethane hydrogel having a swelling agent content of between 1% and 95%. Including, The polyurethane is —CH ２ - (CH ２ -O-CH ２ ) ｎ -CH ２ -[O-OCHN(C ６ H １０ ) CH ２ (C ６ H １０ )NHCO-O-(CH ２ CH ２ -O-CH ２ CH ２ )-O-OCHN(C ６ H １０ ) CH ２ (C ６ H １０ )NHCO-NH-(C ６ H １０ ) CH ２ (C ６ H １０ )NHCO-O-CH ２ CH ２ -O-CH ２ CH ２ -O-OCHN(C ６ H １０ ) CH ２ (C ６ H １０ )NHCO-O] ｍ -CH ２ - (CH ２ -O-CH ２ ) ｎ -CH ２ and containing methyl and / or hydroxy end groups wherein n is an average independently selected from any number from 1 to 35; m is an average independently selected from any number from 15 to 500; method.

2. The method of claim 1, wherein the polyurethane has a weight average molecular weight of 40,000 to 200,000, 150,000 to 350,000, or 300,000 to 500,000.

3. The method of claim 1 or 2, wherein the polyurethane is derived from the polymerization of 4,4'-dicyclohexylmethane diisocyanate.

4. The method of claim 1 or 2, wherein the polyurethane is a polyether-based polyurethane.

5. The method of claim 4, wherein the polyether-based polyurethane is derived from the polymerization of 4,4'-dicyclohexylmethane diisocyanate and a polyether.

6. The method of claim 5, wherein the polyether comprises 1 to 35 ethyl ether groups.

7. 7. The method of any one of claims 1 to 6, wherein the organic polar solvent is selected from the group consisting of ethanol, methanol, isopropanol, butanol, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, acetone, acetonitrile, and any combination thereof.

8. 8. The method of claim 7, wherein the organic polar solvent is ethanol.

9. 9. The method of any one of claims 1 to 8, wherein the ratio of water to organic polar solvent is selected from 5:95 (v / v), 10:90 (v / v), 15:85 (v / v), 20:80 (v / v), 25:75 (v / v), 30:70 (v / v), or 35:65 (v / v).

10. 10. The method of claim 9, wherein the ratio of water to organic polar solvent is 10:90 (v / v).

11. 11. The method of any one of claims 1 to 10, wherein the swelling agent is selected from at least one of water, a glycol solution, a hydroxyethyl cellulose solution, a paraben-based solution, a glycol-based solution, a glycerin-based solution, an oil-based solution, or a silicone-based solution.

12. 12. The method of claim 11, wherein the bulking agent comprises one or more of a spermicide, a lubricant, an antiviral agent, an antifungal agent, an antibacterial agent, a prebiotic, a probiotic, a microbiome enhancer, a flavor compound, an aroma compound, a sensory enhancer, a sterilant, or a disinfectant.

13. The method of any one of claims 1 to 12, wherein the polyurethane film is contacted with the swelling agent for at least 1 second at ambient temperature.

14. forming a second solution of at least one polyurethane having a weight average molecular weight of 40,000 to 200,000, 150,000 to 350,000, or 300,000 to 500,000 in an aqueous:organic polar solvent containing less than 40% (v / v) water; applying a layer of the second solution to the polyurethane film on the mold; drying the layers of the second solution to form a polyurethane film on the mold; and contacting the polyurethane film with a swelling agent under conditions whereby the film forms a polyurethane hydrogel having a swelling agent content of between 1% and 95%. further comprising The polyurethane contains -CH ２ -(CH ２ -O-CH ２ ) ｎ -CH ２ -[O-OC HN(C ６ H １０ )CH ２ (C ６ H １０ )NHCO-O-(CH ２ CH ２ -O-CH ２ CH ２ )-O-OC HN(C ６ H １０ )CH ２ (C ６ H １０ )NHCO-NH-(C ６ H １０ )CH ２ (C ６ H １０ )NHCO-O-CH ２ CH ２ -O-CH ２ CH ２ -O-OC HN(C ６ H １０ )CH ２ (C ６ H １０ )NHCO-O] ｍ -CH ２ -(CH ２ -O-CH ２ ) ｎ -CH ２ and contains n is an average independently selected from any number from 1 to 35; m is an average independently selected from any number from 15 to 500; The method according to any one of claims 1 to 13.

15. 15. The method of any one of claims 1 to 14, wherein the ratio of n:m is from 1:0.1 to 1:

75.

16. 16. The method of claim 14 or 15, wherein the at least one polyurethane in the second solution is not the same as the at least one polyurethane in the first solution.

17. 17. The method of any one of claims 14 to 16, further comprising applying a subsequent layer of the first or second solution to the polyurethane film on the mold to increase the thickness of or create particular characteristics of the polyurethane film.

18. 18. The method of any one of claims 14 to 17, further comprising applying a subsequent layer of the first or second solution to a portion of the polyurethane film on the mold to increase the thickness of the portion of the polyurethane film or to create a particular feature in the portion of the polyurethane film.

19. 20. The method of claim 18, wherein the particular feature formed from the subsequent layer has a different modulus, tensile strength, and / or linear expansion range than the hydrogel formed from the layer to which the subsequent layer is applied.

20. 20. The method of any one of claims 14 to 19, wherein one or both of the weight average molecular weight and n:m ratio of the at least one polyurethane in the first solution is different from the weight average molecular weight and n:m ratio of the at least one polyurethane in the second solution.

21. A method according to any one of claims 14 to 20, wherein further subsequent layers are applied to increase the thickness to a predetermined value.

22. 22. The method of any one of claims 1 to 21, wherein the molded polyurethane hydrogel has a linear expansion range of 1% to 100%.

23. 23. The method of any one of claims 1 to 22, wherein the molded polyurethane hydrogel has a tensile strength of 1 MPa to 100 MPa; 1 MPa to 20 MPa, 20 MPa to 60 MPa, or 60 MPa to 80 MPa.

24. 24. The method of any one of claims 1 to 23, wherein the molded polyurethane hydrogel has an elongation at break range of 200% to 2000%.

25. 25. The method of any one of claims 1 to 24, wherein the molded polyurethane hydrogel has at least one of a 50% modulus of 80 kPa to 15 MPa, a 100% modulus of 200 kPa to 15 MPa, and a 300% modulus of 700 kPa to 15 MPa.

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