condom

Abstract

The invention relates to a condom comprising a copolymer X obtainable by polymerization of monomers A, B, C and D, in which monomer A has the formula JPEG2025512433000009.jpg4755 (in the formula, R 1 and R 2 are independently H and C optionally substituted by hydroxyl, primary amine, or secondary amine groups; 1- C 20 alkyl, where R 1 and R 2 one of which has a hydroxyl, primary amine, or secondary amine group and monomer B is one or more compounds of the formula OCN-R 3 -NCO(in the formula, R 3 =C4-C 20 monomer C is one or more telechelic hydroxy-terminated polyalkylene glycol compounds having a number average molecular weight of 1000 to 10,000, preferably linear; and monomer D is one or more diisocyanate compounds of the formula HO-R 4 -OH(in the formula, R 4 is a C2-C alkyl group optionally interrupted by 1 to 5 heteroatoms selected from the group consisting of O, N, and S, preferably one O atom; 20 alkylene and / or preferably R 4 is linear), and the molar ratio of monomers D to C is in the range of 0.1:1 to 10:1.

Description

[Technical field]

[0001] The present invention is in the field of condoms. In particular, the present invention relates to hydrogel condoms, packaged forms thereof, and methods of manufacturing same. [Background technology]

[0002] Currently, consumers have a wide selection of different contraceptive devices that can be used to prevent pregnancy. However, condoms are the only ones that can also protect against sexually transmitted diseases such as chlamydia and HIV. Condoms form a physical barrier against the transfer of bodily fluids, viruses, and other microorganisms between sexual partners. Therefore, the selection of materials for manufacturing condoms is very important, which must also have low permeability to such bodily fluids and microorganisms, and sufficient strength so as not to burst, break, or tear during sexual activity. On the other hand, condom materials should ideally be flexible and able to stretch to accommodate users of different sizes. In addition, the softness of the material is a very important parameter. A significant percentage of people who choose not to use condoms do so because they do not like the feel. From a public health perspective, and for the individual consumer, it would be highly beneficial to develop a material that feels softer, more natural, and more like skin, yet is still strong enough for condom use. Most condoms on the current market are made from either natural rubber latex ("NRL"), synthetic polyisoprene ("PI"), or polyurethane ("PU"). While all these materials are capable of fulfilling the basic barrier function of a condom, each has its own disadvantages. NRL has an unpleasant odor and taste that needs to be attenuated, and causes latex allergies in a certain percentage of the population. Of the so-called "latex-free" materials, PU feels harder, less stretchy, and often less comfortable to wear than NRL and PI. PI still has some of the unpleasant odor and taste of NRL, and cannot currently be made as thin as PU. In addition, all three of these materials have an inherent tackiness and some degree of friction so that they do not feel slippery to the touch, and commercially available condoms made from these materials generally have a separate lubricant pre-applied to their surface.

[0003] Several alternative materials have been investigated in the art. For example, carboxylated nitrile butadiene rubber has been proposed for condoms, see, for example, U.S. Pat. No. 5,195,537 (Tillotson Corporation). Other materials described in this document include polyvinylidene chloride or low density polyethylene mixed with polyisobutene and / or polyethylene-vinyl acetate copolymers (see U.S. Pat. App. Pub. No. 2015 / 0313752 (Abadi)), and styrene-polyisoprene-styrene latex (see WO 2021 / 124215 (Church & Dwight)).

[0004] WO 2020 / 257880 (Eudaemon Technologies) describes condoms formed from polyether- or polyester-based polyurethane hydrogels. The polyurethanes have a molecular weight between about 40,000 and 500,000 Da and are preferably derived from the polymerization of 4.4'-dicyclohexylmethane diisocyanate with ethyl ethers or ethyl esters. WO 2021 / 130625 (Church & Dwight) sought to increase the inherent lubricity of latex condoms by coating them with a hydrogel / latex blend layer. The blend layer is, for example, polyethylene oxide blended with natural rubber latex. None of these materials have come close to challenging the established commercial NRL, PI, or PU materials in the market. Many materials that are pleasant to the touch are inherently weak and unsuitable in the condom field where minimizing breakage is paramount. It is therefore a challenge to provide a condom that meets such conflicting technical requirements. Summary of the Invention

[0005] In a first aspect of the present invention, there is provided a condom as claimed in claim 1. In a second aspect of the present invention, there is provided a package enclosing a condom according to the present invention in its first aspect. In a third aspect of the present invention, there is provided a method for manufacturing a condom, as claimed in claim 14. In a fourth aspect of the invention there is provided the use of a membrane comprising the copolymer used in the first aspect of the invention, in hydrogel form, as a physical barrier during sexual activity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] The embodiments described herein in the context of one aspect of the invention may be combined with one another and may apply equally to other aspects of the invention, unless specified to the contrary or unless the context requires otherwise. The inventors have developed condoms made from the copolymers described herein, which are based on the copolymers outlined in WO 2006 / 118460, EP 1972661, and WO 2014 / 185779. These documents are particularly interested in providing hydrogels that can reversibly switch between liquid and gel states (e.g., by changing the temperature, concentration of the polymer, or the polarity / ionic strength of the solvent). Materials are disclosed for a variety of applications, including biomedical applications such as scaffolds for tissue engineering and biodegradable implants, but no use for condoms or in sexual activity is disclosed.

[0007] Hydrogels are typically highly crosslinked polymers that can swell and absorb high water content (over 95% by weight) into the polymer network. The water in hydrogels provides advantageous lubrication properties. However, a trade-off must be made between the lubricity and mechanical strength of the material. In traditional types of hydrogels, a higher level of crosslinking can produce a material with greater strength but lower capacity to hold water, and therefore less lubricity, while a lower level of crosslinking can produce a more lubricious but weaker material.

[0008] In the present invention, the copolymer is reversibly crosslinked via hydrogen bonds. Monomer A reacts with monomer B to form a species containing a ureidopyrimidone or UPy unit. Two UPy units can form a quadruple hydrogen bond pair as a strong, reversible crosslinker, as exemplified below. [ka]

[0009] In one embodiment, monomer A has the formula [ka] (In the formula, R 1 and R 2are independently substituted by H and a single hydroxyl, primary amine, or secondary amine group; 1- C 20 alkyl) Preferably, the hydroxyl or amine group is located at a terminal carbon atom. 1 and R 2 One of R has a single hydroxyl group, preferably on a terminal carbon. 1 and R 2 and the other of R is unsubstituted. 2 In one embodiment, R 1 and R 2 are independently selected from H, and C1, C2, C3, C4, C5, C6, C7, C8, C9, and C10, each of which may be substituted with a single hydroxyl, primary amine, or secondary amine group; 10 In one embodiment, R 1 and R 2 Preferably one of R 1 is H or C1-C3 alkyl, preferably methyl or ethyl, preferably methyl. In one embodiment, R 1 and R 2 (preferably the other of those defined in the preceding embodiment), preferably R 2 is a C1-C5 alkyl (preferably C2-C4 alkyl, preferably C2 or C3 alkyl, preferably C2 alkyl) substituted with a hydroxyl group, preferably by a hydroxyl group on a terminal carbon atom, preferably -CH2CH2OH. 1 is H or C1-C3 alkyl, R 2 is a C1-C5 alkyl substituted with a (preferably terminal) hydroxyl or primary amine group, preferably with a hydroxyl group.

[0010] Preferably, monomer A has the formula [ka] has.

[0011] Monomer B has the formula OCN-R 3 -NCO(in the formula, R 3 is C4-C 20 R is a diisocyanate of 3 may be linear, cyclic or branched. In one embodiment, monomer B has the formula OCN-R 3 -NCO(in the formula, R 3 is an alkylene group having at least 5 C atoms, at least 6 C atoms, at least 7 C atoms, at least 8 C atoms, at least 9 C atoms, at least 10 C atoms, at least 11 C atoms, at least 12 C atoms, or at least 13 C atoms, and / or up to 19 C atoms, up to 18 C atoms, up to 17 C atoms, up to 16 C atoms, up to 15 C atoms, up to 14 C atoms, or up to 13 C atoms. 3 is C5-C 18 Alkylene, preferably C6-C 15 In one embodiment, R 3 is C9-C 14 Alkylene or C 10 -C 13 For example, R 3 is C6 alkylene, C9 alkylene, C 10 Alkylene or C 13 In one embodiment, R 3 is a C5-C8 linear alkylene. In one embodiment, monomer B is hexamethylene diisocyanate (HDI).

[0012] In one embodiment, R 3 comprises cyclic alkylene, preferably cyclohexylene. In one embodiment, R 3 contains one or two cyclohexylene groups. 3is a methylene-dicyclohexylene group. Preferably, monomer B is methylene-dicyclohexyl-4,4'-diisocyanate (HMDI). Alternatively, R 3 When R 3 is C9 or C 10 Preferably, monomer B is isophorone diisocyanate (IPDI).

[0013] Monomer C is a telechelic hydroxy-terminated polyalkylene glycol having a number average molecular weight of 1000 to 10,000 Da. In one embodiment, the telechelic hydroxy-terminated polyalkylene glycol monomer C is linear. In one embodiment, it is a polyethylene glycol, a polypropylene glycol, or a polyethylene-polypropylene glycol (which may be, for example, a random copolymer, an alternating copolymer, or a block copolymer). In one embodiment, it has a number average molecular weight, determined from its hydroxyl number, of at least 1500, at least 2000, at least 2500, at least 3000, at least 3500, or at least 4000 Da, and / or 8000 or less, 7000 or less, 6000 or less, 5000 or less, or 4500 or less. For example, it may have a number average molecular weight of 2000 to 7000, or 2500 to 4500 Da. In one embodiment, monomer C has a number average molecular weight of 2500-3500, preferably 2800-3200, preferably 3000 Da, or about 3000 Da. In one embodiment, it has a number average molecular weight of 3500-4500, preferably 3800-4200, preferably 4000 Da, or about 4000 Da. In one embodiment, monomer C has a number average molecular weight of 3000-4000, preferably 3200-3800, preferably 3400-3600, preferably 3500 Da, or about 3500 Da.

[0014] Monomer D has the formula HO-R 4 -OH(in the formula, R 4C2-C may be interrupted by 1 to 5 heteroatoms selected from the group consisting of O, N, and S. 20 R is a diol of 4 may be linear or branched, cyclic or may contain cyclic groups. In one embodiment, R 4 is linear. In one embodiment, R 4 is an alkylene having at least 4 C atoms, at least 5 C atoms, at least 6 C atoms, at least 7 C atoms, at least 8 C atoms, at least 9 C atoms, at least 10 C atoms, at least 11 C atoms, or at least 12 C atoms, and / or up to 18 C atoms, up to 17 C atoms, up to 16 C atoms, up to 15 C atoms, up to 14 C atoms, up to 13 C atoms, up to 12 C atoms, up to 11 C atoms, up to 10 C atoms, up to 9 C atoms, or up to 8 C atoms, which may be interrupted by 1 to 5 heteroatoms (preferably 1 or 2 heteroatoms) selected from the group consisting of O, N, and S, preferably O. For example, R 4 may be alkylene having 4 to 16 C atoms, 5 to 15 C atoms, 6 to 12 C atoms, 6 to 8 C atoms, or 10 to 14 C atoms. 4 is not interrupted by any heteroatom. Monomer D may be, for example, 1,6-hexanediol, 1,10-decanediol, or 1,12-dodecanediol. In one embodiment, R 4 is a cyclic alkylene, preferably a cyclohexylene, preferably R 4 is not interrupted by any heteroatom. 4 is a dimethylene-cyclohexyl group. Preferably, monomer D is 1,4-cyclohexanedimethanol (preferably a cis-trans racemic mixture). Without wishing to be bound by theory, it is believed that the cyclohexylene group may increase the toughness of the resulting polymer.

[0015] In another embodiment, R 4 is interrupted by 1 or 2 O atoms, preferably 1 O atom. For example, R 4 may be alkylene having 2 to 8 C atoms, 3 to 7 C atoms or 4 to 6 C atoms, in each case interrupted by one or two O atoms. Thus, the monomer D may be, for example, diethylene glycol or triethylene glycol. In one embodiment, monomer D is solid at 25° C. Preferably, monomer D has a melting point of 30° C. or more, 40° C. or more, 50° C. or more, 60° C. or more, 70° C. or more, 75° C. or more, or 80° C. or more, and / or 120° C. or less, 110° C. or less, 100° C. or less, 90° C. or less, or 85° C. or less. For example, monomer D may have a melting point of 40 to 100° C., 50 to 90° C., or 70 to 85° C., or 75 to 83° C. Without wishing to be bound by theory, it is believed that the relatively long chain R 4 The groups and / or relatively high melting points may contribute to the formation of copolymers with excellent stability against thermal degradation on storage. The resulting materials may also result in condoms that are particularly pleasant to the touch and / or less sticky when worn.

[0016] In one embodiment, the molar ratio of monomers D to C is at least 0.5:1, at least 1:1, at least 1.5:1, at least 2:1, at least 3:1, at least 4:1, or at least 5:1, and / or no more than 9:1, no more than 8:1, no more than 7:1, no more than 6:1, no more than 5:1, no more than 4.7:1, or no more than 4.5:1. In one embodiment, the molar ratio of monomers D to C is in the range of 3:1 to 6:1, 3.2:1 to 5:1, or 3.5:1 to 4.7:1. The optimum ratio of monomer D to C may depend on the number average molecular weight of monomer C and / or the selection of monomer D. In one embodiment, monomer C has a number average molecular weight of 2500-3500 Da and the molar ratio of monomer D to C is 1.5-6.5, preferably, monomer C has a number average molecular weight of 3000 Da and the molar ratio of monomer D to C is 2-6, 3-5, or 4. In one embodiment, monomer C has a number average molecular weight of 3500-4500 Da and the molar ratio of monomer D to C is 4.5-8.5, 5-8, or 5.5-7, preferably, monomer C has a number average molecular weight of 4000 Da and the molar ratio of monomer D to C is 4-8, 5-7, or 6. Preferably, in the embodiment of this paragraph, monomer D is 1,6-hexanediol.

[0017] In one embodiment, a) Monomer C has a number average molecular weight of 2500 to 5000 Da, 2700 to 4500 Da, 2800 to 4200 Da, 3000 to 4000 Da, 3000 Da, or about 3000 Da; b) the molar ratio of monomers D to C is at least 3, at least 3.2, at least 3.5, at least 4, at least 4.5, or at least 4.7, and / or up to 6, up to 5.5, up to 5.0, or up to 4.8, preferably 3-6, 3.2-5, 3.5-4.8, 4-4.7, 4.5, or about 4.5; c) Monomer D has the formula HO-R 4 -OH(in the formula, R 4 is an alkylene having 10 to 14 C atoms, preferably 11 to 13 C atoms, preferably 12 C atoms), preferably monomer D is 1,12-dodecanediol or has a melting point above 70 ° C, preferably 75 to 85 ° C.

[0018] In one embodiment, the molar ratio of monomer B to the sum of monomers A+C+D is at least 0.9, at least 0.95, or at least 0.98, and / or up to 1.1, up to 1.05, or up to 1.02. Preferably, the molar ratio of monomer B to the sum of monomers A+C+D is between 0.9 and 1.1, between 0.95 and 1.05, between 0.98 and 1.02, about 1, or 1.00. In one embodiment, copolymer X has a weight average molecular weight of 5 to 140 kDa, preferably 10 kDa or more, 20 kDa or more, 30 kDa or more, 40 kDa or more, 50 kDa or more, 60 kDa or more, or 70 kDa or more, and / or 130 kDa or less, 120 kDa or less, 110 kDa or less, 100 kDa or less, 95 kDa or less, 90 kDa or less, 85 kDa or less, or 80 kDa or less, preferably 50 to 80 kDa, determined using size exclusion chromatography in DMF containing 10 mM LiBr at 50° C. using PEO / PEG standards. However, the weight average molecular weight of copolymer X will be affected by the molecular weight of the monomers used to form it. Preferably, the weight average molecular weights described in this paragraph apply to embodiments in which monomer D is 1,6-hexanediol.

[0019] In one embodiment, a) Monomer D has the formula HO-R 4 -OH(in the formula, R 4 is an alkylene having 10 to 14 C atoms, preferably 11 to 13 C atoms, preferably 12 C atoms), preferably monomer D is 1,12-dodecanediol or has a melting point of 70° C. or more, preferably 75 to 85° C., b) Copolymer X has a mass average molecular weight of 70 kDa or more, 75 kDa or more, 80 kDa or more, 85 kDa or more, 90 kDa or more, 95 kDa or more, 100 kDa or more, or 105 kDa or more, and / or 130 kDa or less, 120 kDa or less, or 110 kDa or less, preferably 80 to 120 kDa, 85 to 115 kDa, or 90 to 110 kDa. In an embodiment, the copolymer X is a random copolymer.

[0020] In one embodiment, copolymer X can be obtained by reacting monomers A (or a tautomer thereof), B, and C together in the same reaction mixture to form a reaction product, preferably followed by polymerizing the reaction product with monomer D.

[0021] In another embodiment, copolymer X can be obtained by reacting monomers A (or a tautomer thereof), B, C, and D together in the same reaction mixture to form a reaction product. The reaction may be catalyzed, such as by using catalysts known in the art for the reaction of isocyanates with hydroxyl groups. Examples of suitable catalysts are given in WO 2006 / 118460 and WO 2014 / 185779, and include tin compounds such as tin dibutyl dilaurate. Alternatively, the reaction may proceed without a tin catalyst or without any catalyst at all.

[0022] In a particularly preferred embodiment, 2-amino-4-hydroxy-5-(2-hydroxyethyl)-6-methyl-pyrimidine (or its tautomer) is reacted with polyethylene glycol, a diisocyanate, and a diol (HO-R-OH). The diisocyanate is preferably HMDI, methylenedicyclohexyl-4,4'-diisocyanate. The diol is preferably 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, or 1,12-dodecanediol, preferably 1,6-hexanediol, 1,4-cyclohexanedimethanol, or 1,12-dodecanediol. The polyethylene glycol is preferably PEG1000 to PEG6000, preferably PEG3000 to PEG4000. In one embodiment, monomer A is 2-amino-4-hydroxy-5-(2-hydroxyethyl)-6-methyl-pyrimidine, monomer B is methylenedicyclohexyl-4,4'-diisocyanate, monomer C is a linear polyethylene glycol having a number average molecular weight of 2000 to 6000, monomer D is 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, or 1,12-dodecanediol, and the molar ratio of monomer D to C is 3:1 to 8:1.

[0023] In one embodiment, monomer A is 2-amino-4-hydroxy-5-(2-hydroxyethyl)-6-methyl-pyrimidine, monomer B is methylenedicyclohexyl-4,4'-diisocyanate, monomer C is PEG 2800-4500 (preferably PEG 3000-4200, preferably PEG 4000), monomer D is 1,6-hexanediol, and the molar ratio of monomer D to C is 3-7 (preferably 4-6.5 or 5-6). In one embodiment, monomer A is 2-amino-4-hydroxy-5-(2-hydroxyethyl)-6-methyl-pyrimidine, monomer B is methylenedicyclohexyl-4,4'-diisocyanate, monomer C is PEG 2800-3500 (preferably PEG 2900-3200, preferably PEG 3000), monomer D is 1,12-dodecanediol, and the molar ratio of monomer D to C is 2-6 (preferably 3-5, 3.5-4.7, or 4-4.5). In each of the above cases, the present invention may use a mixture of various monomers A and / or a mixture of various monomers B and / or a mixture of various monomers C and / or a mixture of various monomers D. However, preferably, only a single monomer A and / or B and / or C and / or D is used (preferably a single of each of the monomers A, B, C and D). When a mixture of various monomers A, B, C and / or D is used, the amounts mentioned above relate to the total amount of each monomer type, e.g. the molar ratio D:C means the molar ratio of all monomers D:all monomers C.

[0024] In one embodiment, the condom comprises more than one type of copolymer X. For example, different layers of the condom may comprise different copolymers X. In one embodiment, the various copolymers X are present together as a blend. For example, the blend may comprise a first copolymer X and a second copolymer X in a weight ratio of at least 1:1, at least 1.5:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, or at least 9:1, and / or up to 50:1, up to 40:1, up to 30:1, up to 20:1, up to 15:1, up to 10:1, or up to 9:1. In one embodiment, the blend comprises a first copolymer X and a second copolymer X in a weight ratio of 1:1 to 50:1, 1.5:1 to 20:1, or 2:1 to 9:1. In one embodiment, a first copolymer X has a higher tensile strength but a higher E100 than a second polymer X. Thus, blending a softer material with a stronger material may achieve a good balance of properties.

[0025] In one embodiment, the condom is hydrated and the one or more copolymers X are in hydrogel form. Preferably, the condom comprises 20% or more water, 30% or more water, 40% or more water, 50% or more water, 60% or more water, 65% or more water, or 70% or more water, and / or 95% or less water, 90% or less water, 85% or less water, 80% or less water, or 75% or less water, by weight of the total weight of the condom. For example, it may comprise 60-95% water, 65-85% water, or 70-80% water. If the water content is too high, the condom may become too weak, but a water content higher than that of the skin is desired for a soft and lubricous feel. In one embodiment, the condom has an equilibrium water content of the value described in this paragraph after swelling in water at 25° C. for 24 hours. It will be appreciated that the actual moisture content of a condom may vary over time depending on the environmental conditions in which it is stored.

[0026] The condom may take the typical shape of a tubular body with an open end and a closed end. It may be a "male" condom (intended to be worn on the penis) or an "internal" condom (intended to be inserted into the vagina or anus prior to sexual activity). Preferably, it is a male condom. The condom may be generally straight-walled or shaped, for example with variable width along its length. It may have a nipple or reservoir at the closed end to retain semen.

[0027] In an embodiment of the invention, the condom is at least 120mm long, or at least 130mm long, or at least 140mm long, or at least 150mm long, or at least 160mm long, or at least 170mm long, or at least 180mm long, and / or up to 230mm long, or up to 220mm long, or up to 210mm long, or up to 200mm long. In one embodiment, the condom is 120-230mm long, or 160-200mm long. These lengths are measured as the longest dimension from the open end to the closed end of the condom.

[0028] The condom may have a maximum width (measured flat) of at least 40mm, at least 45mm, at least 50mm, at least 51mm, at least 52mm, at least 53mm, at least 54mm, at least 55mm, at least 56mm, at least 57mm, at least 58mm, at least 59mm, or at least 60mm, and / or no more than 80mm, no more than 75mm, no more than 70mm, no more than 65mm, no more than 64mm, no more than 63mm, no more than 62mm, no more than 61mm, or no more than 60mm. In one embodiment, the condom has a maximum width of between 40 and 80mm, or between 45 and 70mm. By "maximum width" it is meant the width of the condom at its widest point (taking into account that in the case of moulded condoms the width may vary).

[0029] In the past, consumers have been seeking thinner and thinner condoms, due to the belief that they will provide a more natural sensation during sexual activity. Thinner condoms made from traditional materials also tend to be more transparent. However, the condom of the present invention may have an inherently pleasant feel and high transparency, so that its thickness is less harmful. In one embodiment, the condom has a thickness of at least 20 μm, at least 30 μm, at least 40 μm, at least 50 μm, at least 60 μm, at least 70 μm, at least 80 μm, at least 90 μm, or at least 100 μm, and / or up to 300 μm, up to 250 μm, up to 200 μm, up to 150 μm, or up to 120 μm. For example, it may have a thickness of 20 to 300 μm, 70 to 200 μm, 80 to 150 μm, or 90 to 120 μm. In an embodiment of the invention, the condom has a pore size of less than 30 nm, less than 29 nm, less than 28 nm, less than 27 nm, less than 26 nm, or less than 25 nm. In the process of rolling the condom, the material may be stretched. The condom may be allowed to stretch while being worn, and the rolling process may also slightly stretch the material, so the dimensions described herein are measured when the condom is in an unrolled, relaxed state. In addition, because absorption of water causes the hydrogel material to swell, the dimensions described herein are measured with the condom unloaded, at its equilibrium water content at 25°C.

[0030] The condom may consist only of one or more copolymers X and water. In one embodiment, the condom may be transparent and / or colorless. Because no chemical crosslinkers, hardeners, or other additives are required to form the condom from an aqueous formulation of the copolymer, the condom of the present invention can be made with a high degree of transparency compared to natural rubber latex condoms. Preferably, the condom has a thickness of 1 mm at 350 nm per mm of condom thickness. -1 Below, 0.9mm -1 Below, 0.8mm-1 Below, 0.7mm -1 Below, 0.6mm -1 Below, 0.4mm -1 Below, 0.3mm -1 Below, 0.2mm -1 Below, 0.1mm -1 Less than or equal to 0.05 mm -1 The following absorbance and / or thickness at 400 nm is 1 mm per mm of condom thickness: -1 Below, 0.9mm -1 Below, 0.8mm -1 Below, 0.7mm -1 Below, 0.6mm -1 Below, 0.4mm -1 Below, 0.3mm -1 Below, 0.2mm -1 Below, 0.1mm -1 Below, 0.05mm -1 Less than or equal to 0.02 mm -1 It has the following absorbance, measured using UV / vis spectroscopy on a 1 cm x 1 cm film cut from the unrolled condom:

[0031] On the other hand, it is possible to include desirable additives in the condom to increase its appeal to consumers. For example, the condom may be colored, for example, by hydrating the condom in an aqueous formulation containing one or more colorants, preferably hydrophilic colorants. Similarly, the condom may include any one or more of flavoring agents, fragrances, sensates (such as agents that provide a warming, cooling, or tingling sensation), antibacterial agents, spermicides, or pH adjusters. It may include agents to prevent premature ejaculation, such as medicinal agents such as benzocaine, or agents to provide orgasm-enhancing effects. Alternatively, or both, incorporated into the condom hydration fluid, one or more of these additives may be present in the liquid that forms the initial membrane, for example the liquid in which the condom former is immersed. Another option is to include additives in the reaction mixture for the synthesis of copolymer X, provided that these additives do not interfere with the copolymerization reaction.

[0032] If it is desired that the additive remain in a localized area of ​​the condom and not spread throughout the entire condom, this can be accomplished by applying a suitable formulation after the condom is formed and hydrated. For example, a high viscosity benzocaine formulation can be administered to the tip of the condom after manufacture.

[0033] In its hydrated state, the condom may have a high inherent lubricity. However, if additional lubricity is desired, the condom may contain, in addition to water, further lubricating agents, such as water-absorbing polysaccharides. The lubricating agents may be synthetic or derived from natural sources. Examples of suitable lubricating agents include carrageenan, alginate, agar, agarose, pectin, dextran, xanthan gum, gum arabic, hyaluronic acid, chondroitin sulfate, starch, chitosan, cyclodextrin, guar gum, cellulose, polyacrylic acid, or polyacrylamide. The lubricating agent is preferably non-gelling at the concentration used. When the lubricating agent is carrageenan, lamba carrageenan is preferred over iota carrageenan, which in turn is preferred over kappa carrageenan. The lubricating agent may be introduced into the condom by hydrating it in water containing the lubricating agent in a dissolved or dispersed state, preferably in a dissolved state. Compared with traditional lubricants that are applied only to the surface of latex condoms, when lubricants are introduced into hydrogels in this way, the lubricants are incorporated into the body of the condom, not just on the surface, and therefore are less likely to fall off during sexual activity. Alternatively, lubricants (preferably hydrophilic lubricants, such as traditional water-based lubricants) or other fluid materials can be applied to the surface of the condom after hydration. Or the lubricants can be dissolved or dispersed in the liquid that forms the initial film, such as the immersion fluid. Another option can be to include the lubricant in the reaction mixture for the synthesis of copolymer X.

[0034] The lubricant may be incorporated into the condom in any suitable amount. In one embodiment, the condom comprises lubricant in an amount of 5% by weight or less, preferably 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less, and / or 0.01% by weight or more, 0.02% by weight or more, 0.05% by weight or more, 0.1% by weight or more, 0.2% by weight or more, or 0.25% by weight or more. The desired concentration may vary according to the pH of the solution to minimize gelling. In its hydrated state, the condom may be able to be easily rolled and unrolled without the need for the use of any finishing powder. Preferably, no finishing powder is used on the condom.

[0035] In one embodiment, the condom has a Young's modulus at 100% strain (E100) of 5 MPa or less, 4 MPa or less, 3.5 MPa or less, 3 MPa or less, 2.5 MPa or less, or 2.0 MPa or less. In one embodiment, the condom has a Young's modulus at 100% strain (E100) of 5 mJ / mm 3 More than 10mJ / mm 3 More than 15mJ / mm 3 More than 20mJ / mm 3 More than 25mJ / mm 3 More than 30mJ / mm 3 More than 35mJ / mm 3 More than 40mJ / mm 3 More than 45mJ / mm 3 More than 50mJ / mm 3 or more than 55 mJ / mm 3 In one embodiment, the condom has a tensile strength of 5 MPa or more, 8 MPa or more, 10 MPa or more, 12 MPa or more, 13 MPa or more, 14 MPa or more, or 15 MPa or more. In one embodiment, the condom has a breaking elongation of 400% or more, 500% or more, 600% or more, 700% or more, 800% or more, 900% or more, or 1000% or more. The condom of the first aspect of the invention may be made by a process involving dipping a former into a liquid formulation comprising copolymer X by conventional techniques. Alternatively, a film comprising copolymer X may be processed into a condom by thermoforming and / or vacuum forming. Condoms may also be made by processes involving extrusion or injection molding.

[0036] If the condom is formed by dipping the former, then the end of the material at the open end of the condom while still on the former may be subsequently curled to form a "bead". Preferably, after the basic condom shape is formed and the membrane is dried and / or cooled (depending on the molding process), it is swollen with an aqueous formulation or water. In one embodiment, the condom is hydrated and reaches its equilibrium moisture content in water or an aqueous formulation for at least 1 minute, at least 5 minutes, at least 10 minutes, at least 30 minutes, at least 1 hour, at least 4 hours, at least 8 hours, at least 12 hours, or at least 24 hours. Preferably, the hydration occurs at room temperature or at a temperature between 20-60°C, between 20-50°C, or between 30-50°C. The required hydration time / temperature may vary depending on the thickness of the condom membrane.

[0037] The hydrated condom may then be sealed in a package. The condom may be rolled prior to packaging, either before or after the hydration step. The second aspect of the present invention provides a condom of the first aspect enclosed in a package. This may be any suitable package known in the art, such as a foil package or a plastic container with a lid. Preferably, the condom is provided in the package in a rolled state. In one embodiment, there is no separate lubricant included in the package.

[0038] In a third aspect of the invention, the condom is formed by dipping. Conventional dipping techniques may be used. For example, the former may be dipped once or more than once into a liquid comprising copolymer X. The liquid may be, for example, an aqueous dispersion of copolymer X, a solution of copolymer X in an organic solvent (e.g. a polar solvent such as ethanol), or copolymer X dissolved or dispersed in an organic solvent / water mixture (e.g. water in ethanol, preferably 1-20% v / v, 6-15% v / v, or 8-12% v / v water in ethanol). The liquid may comprise copolymer X in a concentration of at least 1%, at least 2%, at least 3%, at least 4%, or at least 5%, and / or up to 15%, up to 14%, up to 13%, up to 12%, up to 11%, up to 10%, or up to 9% by weight. For example, it may comprise copolymer X in a concentration of 1-15%, 3-12%, or 5-9% by weight. The liquid may be prepared by dissolving or dispersing copolymer X in water and / or organic solvent at elevated temperature, for example at least 40° C., at least 50° C., at least 60° C., or at least 70° C., and / or up to 100° C., up to 90° C., or up to 80° C. As mentioned above, the former may be immersed in liquids containing different copolymers X sequentially and / or in liquids containing blends of different copolymers X.

[0039] The copolymer may be dried at room temperature to form a film on the surface of the former. Alternatively, it may be dried under heat and / or vacuum. If the former is dipped more than once, it may be subjected to a drying step after each dipping. Once the film is formed, it is hydrated in water or an aqueous formulation and the condom is removed from the former. The condom may be rolled (dry or hydrated) and a fluid material (e.g., a lubricant) may be applied to the closed end of the condom in the rolled state. The condom may go through an electrical testing process before being rolled. Given the tendency of condom materials to swell and expand in water, it may be necessary to use a former that is smaller than the desired size of the finished condom.

[0040] The fourth aspect of the present invention relates to the use of a film comprising copolymer X in hydrogel form as a physical barrier during sexual intercourse. The film may be in the form of a condom, as described in the first aspect of the present invention. The film may also be a flat film used as a barrier during sexual intercourse, for example, placed between the mouth and genitals or anus during oral intercourse. Such products may be known in the art as dental dams. The present invention may provide enhanced sensation and pleasure, and therefore may be more attractive to consumers compared to existing commercialized dental dams. EXAMPLES

[0041] The following non-limiting examples are intended to illustrate the present invention. Example 1 A) Preparation of Monomer A (UPy Precursor) 2.38 g (19 mmol) of 2-acetylbutyrolactone and 3.3 g (37 mmol) of guanidine carbonate were refluxed in 20 ml of absolute ethanol in the presence of 5.2 ml of triethylamine. The solution turned yellow and cloudy. After heating at reflux overnight, the solid was filtered, washed with ethanol, and suspended in water. The pH was adjusted to a value of 6-7 using HCl solution, and the mixture was stirred. Filtration, rinsing the residue with water and ethanol, followed by drying of the solid, gave the pure monomer A, 2-amino-4-hydroxy-5-(2-hydroxyethyl)-6-methyl-pyrimidine.

[0042] B) Synthesis of supramolecular polymers using hexanediol 20 g (6.67 mmol) of telechelic hydroxy-terminated PEG-3000 (M = 3000) as monomer C n) was dried at 120°C under vacuum for 2 hours. Then, 1.13g (6.67mmol) of monomer A of Example 1A, 6.99g (26.7mmol) of methylenedicyclohexane 4,4'-diisocyanate (HMDI) as monomer B, 50ml of dimethylformamide, and 1 drop of dibutyltin dilaurate were added. The reaction mixture was stirred at 90°C. After 1 hour, 1.56g (13.3mmol) of 1,6-hexanediol was added as monomer D (molar ratio of hexanediol:PEG=2:1; molar ratio of monomer B:sum of monomers A+C+D=1). The reaction mixture was stirred at 90°C for 8 hours. Then, the reaction mixture was diluted with 50ml of methanol and poured into 500ml of diethyl ether. The precipitated polymer was dissolved in 70ml of chloroform and 70ml of methanol and poured into 500ml of diethyl ether. The precipitated polymer was dried in vacuum to give a white solid with a weight average molecular weight of 52 kDa.

[0043] C) Condom manufacturing A solution of 8-12% (v / v) water in ethanol was prepared in which the polymer of Example 1B was dissolved at 70°C with stirring until a homogenous solution was obtained at a concentration of about 5-9% by weight. This was allowed to cool to 40°C to form a solution with the required viscosity for immersion. A glass former was immersed in the polymer-containing liquid and pulled back, leaving a layer of liquid on the surface. This was dried at room temperature with rotation for 1 hour, followed by a second immersion in the same liquid. This was dried at room temperature with rotation for 16 hours, forming a second layer of hydrogel on the former's surface. The condom and former were immersed together in room temperature water, and after swelling for 5 minutes, the hydrogel condom spontaneously separated from the glass. This was allowed to equilibrate in water for an additional 24 hours. Upon taking up water, the condom swelled and increased in diameter. The water content of the finished hydrogel was approximately 73%, and the condom was approximately 240 μm thick. In the rolled state, the condom does not stick to itself and can be easily unrolled onto the penis without the need for any dusting agent.

[0044] D) Mechanical property testing To illustrate the mechanical properties of the condom, a 2 cm wide ring was cut from its middle. This ring was measured using a tensile tester by stretching the material at 50 mm / min until it broke. Both the % elongation at break and F max (the maximum force measured during stretching) depends on the thickness of the condom. Because thickness was not precisely controlled during this model condom production process, its value is not reported here. However, the following parameters are independent of condom thickness: Stiffness - Tangent to the tensile curve from 0 to 2.5% elongation E100 - Young's modulus at 100% strain Toughness - Area under the tensile curve Tensile strength

[0045] (Examples 2 to 13) The procedure of Example 1 was repeated using varying PEG and varying molar ratios of hexanediol, and the results are summarized in the table below. It can be seen that, with a constant hexanediol to PEG molar ratio, increasing the molecular weight of the PEG monomer used has a general tendency to increase water absorption. This is hypothesized to be due to an increase in the hydrophilic content of the copolymer. Similarly, with a constant PEG molecular weight, increasing the hexanediol to PEG molar ratio decreases water absorption. However, this effect becomes less pronounced at higher PEG molecular weights. Thus, for PEG6000, the water absorption is already quite high and shows less variation with the change in the hexanediol to PEG molar ratio compared to PEG1000, which has a lower average water absorption and is more strongly affected by the hexanediol to PEG molar ratio.

[0046] Young's modulus generally shows a small increase for a given PEG molecular weight as the molar ratio of hexanediol to PEG increases, except for PEG 1000, which is strongly affected by this ratio. With respect to tensile strength, PEG 1000 appears to show a non-linear trend with the molar ratio of hexanediol to PEG, whereas the results for PEG 3000 and PEG 4000 appear to be better than PEG 6000. [Table 1] (Examples 14 to 22) The procedure of Example 1 was similarly repeated using varying PEG and varying molar ratios of 1,12-dodecanediol instead of hexanediol, and the results are summarized in the table below.

[0047] It can be seen that the same general trend applies when using dodecanediol. Comparing Examples 15, 18, and 21, and 14 vs. 17, and 16 vs. 19, increasing the molecular weight of the PEG monomer used at a constant dodecanediol to PEG molar ratio increases water absorption, making the condom softer and less rigid, but also reducing toughness and strength. At a constant PEG molecular weight, increasing the dodecanediol to PEG molar ratio reduces water absorption, at least for PEG6000 and PEG4000. For PEG6000, stiffness, toughness, and tensile strength all increase as the diol:PEG molar ratio increases. However, for PEG4000, toughness and tensile strength are better when the diol:PEG molar ratio is 4 than when this ratio is either 2 or 6. For PEG3000, a diol:PEG molar ratio of 4.5 yields the best toughness, softness, and low stiffness of the ratios tested, while a ratio of 4 results in the highest tensile strength of the ratios tested.

[0048] It is therefore clear that it is important to select the best balance of all required mechanical properties. Of the examples tested above, when hexanediol is used, the best overall results appear to be achieved by PEG3000 and a molar ratio of hexanediol to PEG of 2-4, and by PEG4000 and a molar ratio of hexanediol to PEG of 5-6. Examples 11 and 12 (PEG4000, a molar ratio of hexanediol to PEG of 5 or 6) are the most preferred of these due to the balance of high tensile strength and reasonably low E100. When dodecanediol is used, the best overall results appear to be achieved by PEG4000 and a molar ratio of diol to PEG of 4, and by PEG3000 and a molar ratio of diol to PEG of 4-4.5. It is hypothesized that ratios up to 5 may also produce good results for PEG3000. Of all the tested examples, Example 12 has the highest tensile strength, while Example 22 has the highest toughness combined with good tensile strength, sufficiently low stiffness and E100, and sufficiently high water absorption, followed closely by Example 21. [Table 2] The thickness of the condom can be adjusted by adjusting the solids content of the liquid in which the former is dipped and / or by varying the number of dippings.

[0049] Porosity Test Condom samples were tested for leakage by filling with squid ink and visually observing any migration of ink through the condom (at approximately 3000 Pa) according to the procedure of Appl. Env. Microbiol., 1922, 3180. No migration of ink was observed for any of the condoms tested.

[0050] Transparency Test Examples 12 and 13 were repeated to obtain condom samples with various thicknesses (Example 12a- 60 μm, Example 13a- 400 μm). The condom samples were tested for their transparency and color using UV / vis spectroscopy. Membranes with typical dimensions of 1 cm×1 cm were cut from the condoms. These cut specimens were placed on glass microscopic examination slides with a thickness of 1 mm. The absorbance of these glass slides with the various condom specimens was measured at 350 nm and 400 nm using a double beam UV / vis spectrophotometer, using a microscopic examination slide without a condom membrane as a reference. The measured absorbance was divided by the thickness of the condom membrane to calculate the absorbance per mm thickness. The results were compared with those for two commercially available condoms made from natural rubber latex and synthetic polyisoprene, respectively. The results show that while for NRL and PI condoms it is important to aim for the thinnest possible condom to achieve high transparency, with the condoms of the present invention it is possible to achieve very high transparency even in rather thick condoms. The option to use a thicker condom may also provide a different tactile effect to the consumer.

[0051] [Table 3]

[0052] Thermal Stability Test A rolled condom according to the present invention was placed in a beaker and fully immersed in water at 20° C. for 24 hours. The resulting fully swollen condom was placed in a 70° C. oven for 24 hours, taking care that the condom remained fully immersed in water the entire time. The beaker was then removed from the oven and allowed to cool to room temperature for 4 hours. The rolled condom was then removed from the water and placed over a glass former and slowly unrolled thereon and observed.

[0053] Condoms made with hexanediol work well at room temperature, but some stickiness and brittleness were observed in the condoms when subjected to stability testing (although this is a very extreme stability condition and the condoms can still function). In this regard, condoms made with dodecanediol showed increased heat resistance. This is hypothesized to be related to the fact that dodecanediol is more non-polar and has a higher melting point (80°C vs. 40°C). There is stronger microphase separation from the hydrophilic PEG segments, and due to the more non-polar local environment, the H-bonds of the UPy units become stronger.

Claims

1. A condom comprising copolymer X, which can be obtained by polymerization of monomers A, B, C, and D, Monomer A is, 【Chemistry 1】 (In the formula, R 1 and R 2 C may be independently substituted with H and a hydroxyl, primary amine, or secondary amine group. 1- C 20 Selected from alkyl, however, R 1 and R 2 One of them has a hydroxyl, primary amine, or secondary amine group. It is one or more (preferably one) compounds of the following: Monomer B is a compound of the formula OCN-R 3 -NCO (where R 3 =C 4 -C 20 is alkylene, which may be cyclic or branched) and is one or more (preferably one) diisocyanate compounds Monomer C is one or more (preferably one) telechelic hydroxy-terminated polyalkylene glycol compounds having a number average molecular weight of 1,000 to 10,000, and is preferably linear. Monomer D is of formula HO-R 4 -OH (wherein, R 4 C may be interrupted by 1 to 5 heteroatoms selected from the group consisting of O, N, and S, preferably by one O atom. 2 -C 20 It is an alkylene, and / or preferably R 4 It is one or more diol compounds (which are linear in chain), The molar ratio of monomer D to C is in the range of 0.1:1 to 10:

1. condom.

2. The condom according to claim 1, wherein the molar ratio of monomer D to C is at least 0.5:1, at least 1:1, at least 2:1, at least 3:1, at least 4:1, or at least 5:1, and / or 9:1 or less, 8:1 or less, 7:1 or less, or 6:1 or less.

3. The condom according to claim 1, wherein monomer C is one or more compounds each having a number average molecular weight of at least 1500, at least 2000, at least 2500, at least 3000, at least 3500, or at least 4000 Da, and / or 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, or 4500 Da or less, preferably monomer C is one or more compounds each having a number average molecular weight of 3000 to 5000 Da, and the molar ratio of monomer D to C is in the range of 3:1 to 6:

1.

4. R 1 and R 2 One of them is H, and the other is an unsubstituted C. 1 -C 20 Selected from alkyl groups, R 1 and R 2 The other of these C is substituted with a hydroxyl group. 1 -C 20 It is alkyl, preferably R 1 However, H or C 1- C 3 Alkyl, preferably methyl, and / or R 2 However, due to the hydroxyl group, preferably -CH 2 CH 2 C is substituted by OH 1- C 5 The condom according to claim 1, wherein it is alkyl.

5. R 3 However, C 9 -C 15 Alkylene, preferably C 13 The condom according to claim 1, wherein the alkylene, preferably monomer B, or the compound of monomer B, comprises methylene-dicyclohexyl-4,4'-diisocyanate.

6. In at least one compound of monomer D, R 4 However, C 4 -C 18 Alkylene, preferably C 5 -C 14 Alkylene, preferably C 6 -C 12 The condom according to claim 1, wherein the monomer D is alkylene, preferably not interrupted by any heteroatom, and monomer D may be 1,6-hexanediol, 1,4-cyclohexanedimethanol, or 1,12-dodecanediol.

7. The condom according to claim 1, wherein the copolymer X can be obtained by reacting monomers A, B, and C together in the same reaction mixture to form a reaction product, and then polymerizing the reaction product with monomer D, or by reacting monomers A, B, C, and D together in the same reaction mixture to form a reaction product.

8. The condom according to claim 1, wherein the copolymer X is a random copolymer.

9. The condom according to claim 1, wherein the copolymer X has a mass-average molecular weight of 5 to 140 kDa, preferably 10 kDa or more, 20 kDa or more, 30 kDa or more, 40 kDa or more, 50 kDa or more, 60 kDa or more, or 70 kDa or more, and / or 130 kDa or less, 120 kDa or less, 110 kDa or less, 100 kDa or less, 95 kDa or less, 90 kDa or less, 85 kDa or less, or 80 kDa or less, preferably 50 to 110 kDa, as determined by size exclusion chromatography in DMF containing 10 mM LiBr at 50°C using a PEO / PEG standard.

10. The condom according to claim 1, wherein the copolymer X is hydrated to be in a hydrogel form, and preferably the condom contains water in an amount of 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 65% by mass or more, or 70% by mass or more, and / or 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, or 75% by mass or less, preferably 55 to 85% by mass, based on the total mass of the condom.

11. The condom according to claim 10, which is hydrated with water containing a dissolved or dispersed lubricant, preferably the lubricant being carrageenan.

12. A package for enclosing a condom according to any one of claims 1 to 11.

13. The package according to claim 12, which does not contain a separate lubricant inside.

14. A method for manufacturing condoms, A liquid containing copolymer X as defined in any one of claims 1 to 9, Immersing the molding tool in the aforementioned liquid, The process involves drying the material to form a film of copolymer X on the molding tool, The aforementioned membrane is hydrated to form a hydrogel. Methods that include...

15. Use of a membrane comprising copolymer X as defined in any one of claims 1 to 11 in hydrogel form as a physical barrier during sexual intercourse.

Images