Crosslinked styrenic block copolymer

Abstract

To provide copolymer compositions that are useful in forming immersion articles such as surgical gloves.SOLUTION: Elastomeric styrenic block copolymer (SBC) compositions are provided. The compositions comprise one or more SBCs and one or more polymers miscible with styrenic end blocks of the one or more SBCs, the block copolymer compositions being both physically and chemically crosslinked, where the chemical crosslinking comprises covalent bonds between chains of SBC and the physical crosslinking comprises non-covalent interaction between styrenic end blocks of the one or more SBCs and the one or more polymers miscible with the styrenic end blocks.

Description

FIELD OF THEINVENTION

[0001] This disclosure relates to physically and chemically crosslinked styrenic block copolymers that are advantageous in the manufacture of elastic dipped products such as gloves and condoms.

[0002] Background technology Thin-walled elastomeric dipped products are traditionally made from natural rubber (NR), polychloroprene (CR), polyisoprene (IR), polyurethane (PU), nitrile butadiene rubber (NBR), styrenic block copolymers (SBC), blends thereof, or laminates thereof.

[0003] Natural rubber is used in such applications because it is a natural product with excellent performance. However, its use is limited by the presence of sensitizing proteins that cause immediate hypersensitivity (type 1 allergy). To address this shortcoming, synthetic materials have been developed as alternatives.

[0004] Typical Processing Thin elastic membranes are usually formed for the intended application (gloves, condoms, etc.) by dipping a suitably shaped former into a liquid mixture of the polymer, which may be either an aqueous dispersion (latex) or a solution in one or more suitable solvents. A rigid membrane is formed after evaporation of the water or other solvent.

[0005] Enhanced performance in terms of mechanical and chemical properties, elasticity, and durability of materials is achieved through crosslinking mechanisms. Vulcanization is the traditional chemical crosslinking mechanism for most elastomeric materials such as NR and IR. Vulcanization creates sulfur covalent bonds that connect one polymer chain to another. However, vulcanization with sulfur alone requires too long reaction conditions and very high temperatures, so chemical additives such as "accelerators" are added. There are many types of accelerators, usually classified into the following groups: thiazoles, carbamates, guanidines, thioureas, and thiurams. It is common to use a mixture of different accelerators selected from different groups to optimize the rate and performance of vulcanization.

[0006] The sulfur is covalently incorporated into the polymer network, whereas the accelerator is not. A typical composition of a polyisoprene glove may contain up to 2% accelerator. Accelerator molecules have low solubility in water and cannot be removed from the glove by washing. Also, they may "bloom" on the membrane surface over time due to their limited compatibility with the rubber. Accelerators are also strong skin sensitizers and can cause allergic contact dermatitis (delayed type hypersensitivity, type 4).

[0007] Product performance Typically, the combination of materials, formulation conditions, and the process of conversion into a thin film determines the performance of the resulting product.

[0008] NR, CR, IR and NBR are the more common elastomers, and they are all converted into thin films from aqueous dispersions, also known as latex. However, thin films made with latex have the disadvantage that the resulting product sometimes tends to have pinholes. These pinholes, often on the order of micrometers in diameter, may be the result of low concentrations of impurities in the latex that are difficult to remove, and the method converts a heterogeneous system (a dispersion) into a film. There are some inherent micropores in the rubber that may result from the inability of all the latex particles that make up the film to completely fuse with each other and form a continuous film without gaps. Natural proteins (present in NR) and chemicals used in the stabilization and manufacturing process of latex (surfactants, mainly in the case of synthetic polymers) tend to prevent fusion.

[0009] Advantageously, some other synthetic polymers can be dissolved in solvents such as hydrocarbon solvents to form true solutions, making the solvent casting technique attractive for producing membranes with extremely high quality and minimal micropores. There is also less chance of pinholes being present.

[0010] Multiblock rubber copolymers, especially styrenic block copolymers (SBC), are particularly suitable for use in solvent casting due to their ability to form solutions of suitable viscosity that can be utilized for dipping.

[0011] Styrenic block copolymer SBCs are classified as thermoplastic elastomers, with the mechanical properties of rubber and the processing properties of thermoplastics. These properties are due to their molecular structure. SBCs consist of at least three blocks, usually two hard polystyrene endblocks and one soft elastomeric (polybutadiene, polyisoprene - hydrogenated or non-hydrogenated) midblock. The more common SBCs are linear triblock copolymers such as styrene-ethylene / butylene-styrene (SEBS), styrene-butadiene-styrene (SBS) and styrene-isoprene-styrene (SIS), although other architectures (e.g. copolymers composed of more than three blocks) and other structures (star or radial) are also possible.

[0012] On a microscopic scale, the polystyrene blocks form separate domains in the rubber matrix due to the immiscibility of the hard and soft blocks, and therefore SBCs exhibit two glass transition temperatures (Tg) characteristic of each homopolymer (e.g., 90-100°C for polystyrene endblocks and approximately -90°C for the rubbery midblock of polybutadiene).

[0013] In addition to the advantage of being made from true solution, SBCs also have polystyrene segments at both ends of each rubbery block, and these rigid domains act as multifunctional junctions to create a "physically" crosslinked elastomeric network that is in many ways similar to conventional vulcanized rubber, allowing them to form elastic membranes with high mechanical performance without the use of chemical crosslinkers or accelerators such as sulfur.

[0014] Finally, these elastomers can be advantageously compounded with appropriate plasticizers to provide the desired combination of tensile strength, elasticity and tactility required, for example, in surgical gloves.

[0015] Ultimate breaking force and tensile strength are important factors in assessing the performance of thin-walled stretched membranes such as condoms or gloves, and must be evaluated according to international standards. Surgical gloves must also provide high sensitivity over time and at the same time not compress the wearer's hand. To prevent hand compression, a 100% elongation of less than 1.0 MPa, ideally less than 0.7 MPa, is preferred.

[0016] With the right blend of plasticizers, SBC can meet all international standards and achieve flexibility and mechanical properties comparable and in many cases superior to other elastomers such as NRL, CR, IR, etc. This means that the material can perform mechanically in a manner comparable or superior to other elastomers while avoiding the drawbacks of latex-based elastomers such as accelerators and pinholes.

[0017] In summary, SBC is particularly suitable for use in thin membrane applications such as medical gloves, offering superior properties such as a synthetic rubber free of natural rubber proteins, no accelerators, softness and an extremely high quality membrane with minimal pinholes or hydration.

[0018] Suitable SBC compositions for surgical gloves are described in EP 0 488 021 A which discloses a combination of two or more S-EB-S block copolymers, and in EP 1 472 315 A which discloses a combination of one S-EB-S block copolymer and one S-EP-S-EP block copolymer.

[0019] The limitations of styrene block copolymers Products made with the SBCs described in the above patents have an important drawback: because the network is formed solely by physical, not chemical, crosslinks, the glassy polystyrene domains soften and lose cohesion when in contact with certain organic solvents.

[0020] For example, surgical gloves made from SBC are destroyed when in direct contact with organic solvents. Several organic solvents and "aggressive" chemicals may be used in the medical field. One example is methyl methacrylate monomer (MMA), present in uncured bone cement used in joint arthroplasty. The Hansen solubility parameter of MMA is 17.9 MPa. 1 / 2 , a value close to PS (18.6). Another example is diethyl ether, which is used as a solvent in some preparations such as collodion. The poor chemical resistance to these solvents is an important limitation for this type of elastomer for use in surgical gloves.

[0021] The physical network can be strengthened by adding a permanent covalent chemical network that links the chains of the elastomeric phase together and makes them insoluble. One example is described by Decker et al., Journal of Applied Polymer Science, vol. 77, 1902-1912, 2000, which uses a commercially available triblock copolymer of SBS and SIS crosslinked by UV irradiation in the presence of a radical photoinitiator. The crosslinking process may be significantly accelerated by the addition of multifunctional organic molecules such as acrylate or thiol monomers that can copolymerize with the polybutadiene or polyisoprene unsaturations.

[0022] However, this chemical cross-linking process dramatically reduces the mechanical properties of the membrane, since the coexistence of two networks (one "physical" and one "chemical") reduces the mechanical resistance of the material and increases its stiffness.

[0023] For example, such materials have not been able to achieve international standards for surgical gloves, such as the minimum tensile strength set forth in ASTM D3577.

[0024] It would therefore be desirable to provide an alternative SBC composition and method for making the same that addresses one or more of the above-mentioned problems and shortcomings.

[0025] Any reference herein to a prior art document (or information derived therefrom) or known matter is not, and should not be, taken as a form of admission or acknowledgment, or an indication that the prior art document (or information derived therefrom) or known matter forms part of the common general knowledge in the field relevant to this specification.

[0026] Summary of the Invention In one aspect, the disclosure provides an elastomeric styrenic block copolymer (SBC) composition comprising one or more SBCs and one or more polymers compatible with the styrenic endblocks of the one or more SBCs, the block copolymer composition being physically and chemically crosslinked, the chemical crosslinks comprising covalent bonds between chains of the SBC and the physical crosslinks comprising non-covalent interactions between the styrenic endblocks of the one or more SBCs and one or more polymers compatible with the endblocks.

[0027] In another aspect, the disclosure provides a compatible polymer blend comprising one or more SBCs and one or more polymers compatible with the styrenic endblocks of the one or more SBCs, the compatible polymer blend being physically and chemically crosslinked, the chemical crosslinks comprising covalent bonds between the chains of the SBC and the physical crosslinks comprising non-covalent interactions between the styrenic endblocks of the one or more SBCs and one or more polymers compatible with the endblocks.

[0028] The unique compositions or blends comprising the physically and chemically crosslinked styrenic block copolymers disclosed herein are used in the manufacture of thin-walled dipped products such as condoms and medical gloves, which overcome the chemical resistance shortcomings of currently available SBCs while maintaining a high level of mechanical resistance and flexibility.

[0029] In another aspect, the disclosure provides elastomeric styrenic block copolymer compositions that include (a) one or more SBCs, (b) one or more polymers compatible with the polystyrene end blocks of the one or more SBCs, and (c) one or more crosslinkers capable of inducing covalent bonds between chains of the one or more SBCs.

[0030] In another aspect, a method for making an SBC composition is provided that includes combining one or more SBCs, one or more polymers compatible with the one or more polystyrene end blocks of the one or more SBCs, and one or more crosslinkers capable of inducing covalent bonds between chains of the one or more SBCs.

[0031] The composition or blend may further include one or more plasticizers and / or flexibilizers that are compatible with the elastomeric midblock of the one or more SBCs.

[0032] The compositions or blends may further comprise one or more compatibilizers that enhance the compatibility between the styrenic endblocks of the one or more SBCs and the one or more compatible polymers. Such compatibilizers may be, for example, surfactants, especially polymeric surfactants such as diblock copolymers containing PS segments or low molecular weight polymers or resins having suitable solubility parameters.

[0033] One or more of the SBCs may have a fully unsaturated, partially unsaturated elastomeric midblock, or may have a fully saturated elastomeric midblock.

[0034] The one or more SBCs may be selected from the group consisting of SIS, SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS, or SBCs functionalized with reactive groups grafted to the intermediate rubber block, such as carboxylic acids, amines, alcohols, maleic anhydride, epoxies, isocyanates, and aziridines, or combinations thereof.

[0035] Preferably, the SBC is composed of one or a mixture of SBCs with a molecular weight (Mn) of more than 100,000 g / mol. Preferably, at least one elastomeric midblock contains reactive functional groups such as double bonds, e.g., carbon-carbon double bonds, that allow chemical crosslinking.

[0036] A polymer compatible with polystyrene end blocks may be a polymer that can form, to some extent, a molecular intimate blend with the polystyrene end blocks. A compatible polymer may be a polymer that is miscible with polystyrene. That is, the SBC and the compatible polymer can form a homogeneous blend due to chemical similarity and / or specific interactions such as pi-bond interactions of arene rings. This interaction may be non-covalent in nature. This interaction may not involve covalent bonds between the SBC and the compatible polymer.

[0037] Preferably, the number average molecular weight (Mn) of the compatible polymer is less than 10,000 g / mol, more preferably less than 3,000 g / mol.

[0038] Preferably, the compatible polymer has a broad molecular weight polydispersity index, for example, greater than 2.0, greater than 3.0, greater than 4.0, or greater than 5.0. Preferably, the compatible polymer has a polarity similar to that of polystyrene.

[0039] In a preferred embodiment, the compatible polymer is selected from low molecular weight copolymers of alkylarene monomers.

[0040] The compatible polymer may be selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha methylstyrene resins, alpha methylstyrene resins, polyphenylene ethers, copolymers of alkylarene monomers such as alpha methylstyrene and para methylstyrene, rosin esters, styrenated terpenes, polyterpenes, terpene phenols, and mixtures thereof.

[0041] The crosslinking agent may be selected from the group consisting of aromatic, aliphatic and heteroatom monomers and oligomers containing at least two carbon-carbon double bonds, for example, polyfunctional acrylates such as trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), epoxy acrylates, urethane acrylates, triallyl cyanurate, triallyl isocyanurate, functional thiols such as 1,8-dimercapto-3,6-dioxaoctane, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), ethoxylated trimethylolpropane tri(3-mercaptopropionate), and other polyfunctional compounds having vinyl or allyl groups, and mixtures thereof.

[0042] The crosslinker may also be an amine selected from the group consisting of metal salts, organic amines, organic diamines, and organic polyamines, or a polyol.

[0043] Chemical crosslinking may also be performed by so-called "vulcanization", where the crosslinking agents may be conventional sulfur, metal oxides, and accelerators commonly used in the vulcanization of rubbers contained in thin elastic membranes such as condoms and gloves. Vulcanization is not considered a preferred crosslinking route as far as this disclosure is concerned, since accelerators that are strong skin sensitizers are not contained within the chemical network and may "bloom" to the surface.

[0044] In a preferred embodiment, the crosslinking reaction is a thiol-ene reaction, a so-called "click" reaction that is carried out as a radical-mediated addition reaction.

[0045] Preferably, the crosslinker is selected from dithiol, trithiol, and tetrathiol molecules, eg, containing ether or ester groups in the backbone.

[0046] Advantageously, the crosslinking reaction may be induced by radiation, for example UV, gamma radiation, X-ray or electron beam radiation. Radiation offers several advantages: the energy is high enough to create radicals from existing chemicals, there is less risk of shadowing effects that may be observed with UV curing, and the technique provides adequate and precise control of the dose. It should also be noted that most surgical gloves are sterilized with radiation (electron beam or gamma radiation), so crosslinking can advantageously occur during the same process as the sterilization of the gloves.

[0047] In another embodiment, the crosslinking reaction may be initiated or accelerated by one or a mixture of radical type photoinitiators.

[0048] If used, the photoinitiator is preferably selected from compounds that have a broad UV absorption spectrum, efficiently generate reactive radicals upon irradiation, have good solubility in resin systems, and have good resistance upon contact with human skin. The photoinitiator may be selected from the group consisting of, for example, acylphosphine oxides such as monoacylphosphine oxides, bisacylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, or others such as 2-hydroxymethyl-1-phenylpropanone, methyl benzoylformate, and phenylglyoxylic acid methyl ester.

[0049] The plasticizer may enhance the elasticity and flexibility of the SBC compositions and polymer blends disclosed herein. Preferably, the plasticizer comprises a liquid saturated polyolefin or mixtures thereof that are compatible with the midblock (elastomeric block) of the SBC. More preferably, the plasticizer may be selected from compounds with a pour point of 35° C. or less. It is preferred to use plasticizing oils, preferably mineral plasticizing oils, especially mineral oils formed from refined mixtures of liquid saturated hydrocarbons formed from paraffinic or naphthenic compounds or mixtures thereof, in various proportions.

[0050] The preferred mineral plasticizing oil is a clear, water-white product that is free of toxic impurities and MOAHs (mineral oil aromatic hydrocarbons) and complies with the US FDA 21 CFR 178.3620(a), White Mineral Oil, the United States Pharmacopoeia, the European Pharmacopoeia (liquid paraffinum) and the European Regulation (EU) 10 / 2011 on plastic materials and articles intended for contact with food, White Mineral Oil. The preferred mineral oil is a medicinal white oil with a specific gravity of 0.85-0.90 at 15°C.

[0051] The plasticizer may also be an oligomer or other elastomer that has sufficient compatibility with the rubbery midblock, and in this case may be considered a "flexibilizer". Such flexibilizers may be selected from the family of polybutadiene, polyisoprene, polyisobutene, amorphous polyolefin copolymers of propylene and ethylene, butyl rubber, and other polymers known to have sufficient compatibility with the rubbery block. Functionalized or reactive flexibilizers such as acrylic or hydroxyl modified polybutadienes may also be used. These reactive flexibilizers may participate in a chemically crosslinked network.

[0052] According to an embodiment of this disclosure, the SBC composition or compatible polymer blend is expressed in PHR (per hundred rubbers), where a rubber is one or more SBCs. Exemplary ranges of components in the composition include:· Compatible polymer: 0.25-100 phr, preferably 5-50 phr· Plasticizer / flexibilizer: 0-200 phr, preferably 20-75 phr· Crosslinker: 0.01-5 phr, preferably 0.05-1 phr· Photoinitiator: 0-5 phr, preferably 0-2 phr.

[0053] In another aspect, a method is provided for producing a dipped article from at least one SBC composition or compatible polymer blend disclosed herein, wherein an outer mold corresponding to the outer shape of the dipped article to be produced is dipped in a dipping solution comprising one or more SBC compositions or compatible polymer blends for a pre-determinable period of time, after which the dipped article is removed from the solution and dried.

[0054] The product, especially the dried product, may then be exposed to radiation, for example electron beam, gamma, UV or X-ray irradiation.

[0055] In another aspect, a thin film comprising one or more SBC compositions or compatible polymer blends is provided, where the thin film has a tensile strength of greater than 17 MPa as measured according to ASTM 3577, and the thin film is substantially insoluble in organic solvents.

[0056] "Substantially insoluble" may mean that at least 80% of the film is insoluble, or at least 95% of the film is insoluble, in organic solvents that may be used in the medical field, such as, for example, methyl methacrylate (MMA) or diethyl ether.

[0057] In another aspect, an elastomeric styrenic block copolymer composition or compatible polymer blend is provided, wherein the composition has a tensile strength of at least 17 MPa, and the composition is substantially insoluble in organic solvents.

[0058] "Substantially insoluble" may mean that at least 80% of the composition is insoluble, or at least 95% of the composition is insoluble, in organic solvents that may be used in the medical field, such as, for example, methyl methacrylate (MMA) or diethyl ether.

[0059] In another aspect, according to any one of the embodiments disclosed herein, there is provided a thin film comprising one or more SBC compositions or compatible polymer blends.

[0060] According to any of the embodiments disclosed herein, the thin film may be from about 10 to about 500 microns or from about 150 to about 250 microns thick.

[0061] According to any of the embodiments disclosed herein, the thin film may be less than 500 microns, less than 400 microns, less than 300 microns, or less than 200 microns thick.

[0062] In another aspect, there is provided a multilayer film, the multilayer film comprising one or more layers or films, the one or more layers or films comprising an SBC composition or compatible polymer blend disclosed herein.

[0063] In another aspect, a multilayer film is provided, wherein the multilayer film comprises one or more layers or films, the one or more layers or films comprising an SBC composition or a compatible polymer blend, the composition or compatible polymer blend having a tensile strength of at least 17 MPa, and the composition or compatible polymer blend is substantially insoluble in organic solvents.

[0064] A multilayer film may be obtained by superposition of several thin layers made of the same or different SBC compositions. Different SBC compositions as currently disclosed may be combined in different layers. Also, at least one layer having the currently disclosed composition may be combined with other elastomers selected from the group consisting of natural rubber, polybutadiene, polyisoprene, polychloroprene, butyl rubber, polyurethane, acrylic polymers and copolymers, silicone elastomers, other SBCs, cyclic block copolymers (CBCs) and mixtures thereof. It is understood that the nature of the elastomers constituting each of said layers may be the same or different from each other.

[0065] According to this disclosure, SBS, SEBS and butyl rubber are preferred components of the multi-layer film. In some embodiments, a multi-layer glove comprising stacked layers made from the compositions disclosed herein and butyl rubber provides enhanced resistance to permeation of chemicals such as methyl methacrylate monomer. Such a glove may, for example, include a thin butyl rubber layer on an outer layer and / or intermediate other layers including the presently disclosed SBC compositions.

[0066] Each layer, including the thin elastic membrane, may also contain other adjuvants conventionally used in the polymer industry, particularly the glove industry, such as, for example, lubricants, antistatic agents, primary and secondary antioxidants, colorants or treatment agents.

[0067] In another aspect, an article of manufacture is provided that includes one or more SBC compositions or compatible polymer blends disclosed herein.

[0068] The article of manufacture may be a medical device, such as a medical glove, a condom, or personal protective equipment, such as a laboratory glove or a clean industrial glove.

[0069] The film or multilayer may also contain active chemicals.

[0070] The nature of the active substance may be selected depending on the desired properties. The active chemical may be selected in particular from anticorrosive agents, lubricants, chemical markers, phase change products, energetic particle (radiation) moderators, agents with disinfecting properties, odorants or moisturizers, dyes for detecting discontinuities, metal particles, and mixtures thereof.

[0071] When the active chemical substance is an agent with disinfecting ability, it is preferably selected from substances that denature proteins substantially and instantly by simple contact, either by chemical reaction or by physicochemical effects such as changes in surface tension.Among such substances, mention may be made in particular of biocides such as quaternary ammonium salts, more particularly dimethyldidecylammonium chloride and benzalkonium chloride, water-soluble salts of chlorhexidine, for example chlorhexidine digluconate, biguanides such as phthalaldehyde, phenol derivatives such as hexachlorophene or benzyl derivatives, formaldehyde, non-ionic surfactants that contain at least one polyoxyethylene moiety such as octoxynol (Triton® X100), hexamidine, iodized polyvinylpyrrolidone compounds, non-ionic surfactants with virucidal activity, sodium or potassium salts of dichromate or hypochlorous acid, and mixtures thereof.

[0072] This disclosure relates to compositions including SBCs capable of forming chemically and physically crosslinked, thin-walled, elastomeric articles having improved mechanical properties.

[0073] Detailed Description of the Invention Before the present compositions, components, articles, and / or methods are disclosed and described, it is to be understood that, unless otherwise specified, this invention is not limited to the particular compositions, components, articles, methods, etc., which may vary, unless otherwise stated. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only, and is not intended to be limiting.

[0074] It should also be noted that, as used in the specification and claims, the singular forms "a," "an," and "the" include plural referents unless specifically stated otherwise. Thus, for example, reference to "SBC" can include one or more SBCs, and so forth.

[0075] Advantageous SBC compositions, compatible polymer blends and methods for their preparation are disclosed herein.

[0076] In an exemplary embodiment, an elastomeric styrenic block copolymer (SBC) composition is provided that includes one or more SBCs and one or more polymers compatible with the styrenic end blocks of the one or more SBCs, where the block copolymer composition is physically and chemically crosslinked, the chemical crosslinks including covalent bonds between chains of the SBCs and the physical crosslinks including non-covalent interactions between the styrenic end blocks of the one or more SBCs and one or more polymers compatible with the end blocks; the one or more SBCs are SIS, SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS, or intermediate rubber blocks. The SBC is selected from the group consisting of SBC functionalized with a reactive group grafted onto the polymer, such as carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate, and aziridine, or a combination thereof, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha methylstyrene resins, alpha methylstyrene resins, polyphenylene ethers, copolymers of alkyl arene monomers such as alpha methylstyrene and para methylstyrene, rosin esters, styrenated terpenes, polyterpenes, terpene phenols, and mixtures thereof.

[0077] In another exemplary embodiment, an elastomeric styrenic block copolymer (SBC) composition is provided that includes one or more SBCs and one or more polymers compatible with the styrenic end blocks of the one or more SBCs, wherein the block copolymer composition is physically and chemically crosslinked, the chemical crosslinks comprising covalent bonds between chains of the SBC and the physical crosslinks comprising non-covalent interactions between the styrenic end blocks of the one or more SBCs and one or more polymers compatible with the end blocks, and the one or more SBCs are selected from the group consisting of SIS, SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS, or intermediate rubbers. the SBC is selected from the group consisting of SBC functionalized with reactive groups grafted onto the block, such as carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate, and aziridine, or combinations thereof, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha methylstyrene resins, alpha methylstyrene resins, polyphenylene ethers, copolymers of alkyl arene monomers such as alpha methylstyrene and para methylstyrene, rosin esters, styrenated terpenes, polyterpenes, terpene phenols, and mixtures thereof, the SBC having a molecular weight (Mn) greater than 100,000 g / mol, and the compatible polymer having a molecular weight (Mn) less than 10,000 g / mol.

[0078] In another exemplary embodiment, an elastomeric styrenic block copolymer (SBC) composition is provided that includes one or more SBCs and one or more polymers compatible with the styrenic end blocks of the one or more SBCs, wherein the block copolymer composition is physically and chemically crosslinked, the chemical crosslinks include covalent bonds between chains of the SBC, the physical crosslinks include non-covalent interactions between the styrenic end blocks of the one or more SBCs and one or more polymers compatible with the end blocks, the at least one SBC includes reactive functional groups in its elastomeric midblock that enable chemical crosslinking, such as double bonds, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha methylstyrene resins, alpha methylstyrene resins, polyphenylene ethers, copolymers of alkyl arene monomers such as alpha methylstyrene and para methylstyrene, rosin esters, styrenated terpenes, polyterpenes, terpenes, and the like. phenols, and mixtures thereof, wherein the SBC has a molecular weight (Mn) greater than 100,000 g / mol and the compatible polymer has a molecular weight (Mn) less than 10,000 g / mol.

[0079] In another exemplary embodiment, an elastomeric styrenic block copolymer (SBC) composition is provided that includes one or more SBCs and one or more polymers compatible with the styrenic end blocks of the one or more SBCs, wherein the block copolymer composition is physically and chemically crosslinked, the chemical crosslinks include covalent bonds between chains of the SBC, the physical crosslinks include non-covalent interactions between the styrenic end blocks of the one or more SBCs and one or more polymers compatible with the end blocks, the at least one SBC includes reactive functional groups in its elastomeric midblock that enable chemical crosslinking, such as double bonds, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, alpha-methylstyrene resins, copolymers of alkyl arene monomers such as alpha-methylstyrene and para-methylstyrene, and mixtures thereof, the SBC having a molecular weight (Mn) greater than 100,000 g / mol, and the compatible polymers having a molecular weight (Mn) less than 10,000 g / mol.

[0080] In another exemplary embodiment, a compatible polymer blend is provided that includes one or more SBCs and one or more polymers compatible with the styrenic endblocks of the one or more SBCs, wherein the compatible polymer blend is physically and chemically crosslinked, the chemical crosslinks comprising covalent bonds between the chains of the SBCs, the physical crosslinks comprising non-covalent interactions between the styrenic endblocks of the one or more SBCs and one or more polymers compatible with the endblocks, and the one or more SBCs are SIS, SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS, or grafted to an intermediate rubber block. and the one or more compatible polymers are selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha methylstyrene resins, alpha methylstyrene resins, polyphenylene ethers, copolymers of alkyl arene monomers such as alpha methylstyrene and para methylstyrene, rosin esters, styrenated terpenes, polyterpenes, terpene phenols, and mixtures thereof.

[0081] In another exemplary embodiment, a compatible polymer blend is provided that includes one or more SBCs and one or more polymers compatible with the styrenic endblocks of the one or more SBCs, wherein the compatible polymer blend is physically and chemically crosslinked, the chemical crosslinks comprising covalent bonds between the chains of the SBCs, the physical crosslinks comprising non-covalent interactions between the styrenic endblocks of the one or more SBCs and one or more polymers compatible with the endblocks, and the one or more SBCs are SIS, SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS, or grafted to an intermediate rubber block. and the one or more compatible polymers are selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha methylstyrene resins, alpha methylstyrene resins, polyphenylene ethers, copolymers of alkyl arene monomers such as alpha methylstyrene and para methylstyrene, rosin esters, styrenated terpenes, polyterpenes, terpene phenols, and mixtures thereof, wherein the SBC has a molecular weight (Mn) greater than 100,000 g / mol and the compatible polymer has a molecular weight (Mn) less than 10,000 g / mol.

[0082] In another exemplary embodiment, a compatible polymer blend is provided that includes one or more SBCs and one or more polymers compatible with the styrenic endblocks of the one or more SBCs, wherein the compatible polymer blend is physically and chemically crosslinked, the chemical crosslinks include covalent bonds between the chains of the SBCs, and the physical crosslinks include non-covalent interactions between the styrenic endblocks of the one or more SBCs and one or more polymers compatible with the endblocks, the at least one SBC includes reactive functional groups in its elastomeric midblock that enable chemical crosslinking, such as double bonds, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha methylstyrene resins, alpha methylstyrene resins, polyphenylene ethers, copolymers of alkyl arene monomers such as alpha methylstyrene and para methylstyrene, rosin esters, styrenated terpenes, polyterpenes, terpenes, and the like. phenols, and mixtures thereof, wherein the SBC has a molecular weight (Mn) greater than 100,000 g / mol and the compatible polymer has a molecular weight (Mn) less than 10,000 g / mol.

[0083] In another exemplary embodiment, a compatible polymer blend is provided that includes one or more SBCs and one or more polymers compatible with the styrenic end blocks of the one or more SBCs, where the compatible polymer blend is physically and chemically crosslinked, the chemical crosslinks include covalent bonds between the chains of the SBC, and the physical crosslinks include non-covalent interactions between the styrenic end blocks of the one or more SBCs and one or more polymers compatible with the end blocks, the at least one SBC includes reactive functional groups in its elastomeric midblock that enable chemical crosslinking, such as double bonds, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, alpha-methylstyrene resins, copolymers of alkylarene monomers such as alpha-methylstyrene and para-methylstyrene, and mixtures thereof, the SBC has a molecular weight (Mn) greater than 100,000 g / mol, and the compatible polymer has a molecular weight (Mn) less than 10,000 g / mol.

[0084] In another exemplary embodiment, an elastomeric styrenic block copolymer composition is provided that includes: (a) one or more SBCs; (b) one or more polymers compatible with the polystyrene end blocks of the one or more SBCs; and (c) one or more crosslinkers capable of inducing covalent bonds between the chains of the one or more SBCs, wherein the one or more SBCs are selected from the group consisting of SIS, SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS, or SBCs functionalized with reactive groups grafted to the intermediate rubber block, such as carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate, and aziridine, or combinations thereof; and the one or more compatible polymers are selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha methylstyrene resins, alpha methylstyrene resins, polyphenylene ethers, copolymers of alkyl arene monomers such as alpha methylstyrene and para methylstyrene, rosin esters, styrenated terpenes, polyterpenes, ... and mixtures thereof, and the one or more crosslinking agents are selected from the group consisting of aromatic, aliphatic and heteroatom monomers and oligomers containing at least two carbon-carbon double bonds, for example, polyfunctional acrylates such as trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), epoxy acrylates, urethane acrylates, triallyl cyanurate, triallyl isocyanurate, functional thiols such as 1,8-dimercapto-3,6-dioxaoctane, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), ethoxylated trimethylolpropane tri(3-mercaptopropionate), and other polyfunctional compounds having vinyl or allyl groups, and mixtures thereof.

[0085] In another exemplary embodiment, an elastomeric styrenic block copolymer composition is provided that includes: (a) one or more SBCs; (b) one or more polymers compatible with the polystyrene end blocks of the one or more SBCs; and (c) one or more crosslinkers capable of inducing covalent bonds between the chains of the one or more SBCs, wherein the one or more SBCs are selected from the group consisting of SIS, SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS, or SBCs functionalized with reactive groups grafted to the intermediate rubber block, such as carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate, and aziridine, or combinations thereof, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha methylstyrene resins, alpha methylstyrene resins, polyphenylene ethers, copolymers of alkyl arene monomers such as alpha methylstyrene and para methylstyrene, rosin esters, styrenated terpenes, polyterpenes, ... and mixtures thereof, wherein the one or more crosslinking agents are selected from the group consisting of aromatic, aliphatic and heteroatom monomers and oligomers containing at least two carbon-carbon double bonds, such as trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), epoxy acrylates, urethane acrylates, multifunctional acrylates such as triallyl cyanurate, triallyl isocyanurate, 1,8-dimercapto-3,6-dioxaoctadecane, trimethylolpropane trimethacrylate (TMPTMA), ... functional thiols such as trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), ethoxylated trimethylolpropane tri(3-mercaptopropionate), and other multifunctional compounds having vinyl or allyl groups, and mixtures thereof, wherein the SBC has a molecular weight (Mn) greater than 100,000 g / mol and the compatible polymer has a molecular weight (Mn) less than 10,000 g / mol.

[0086] In another exemplary embodiment, an elastomeric styrenic block copolymer composition is provided that includes: (a) one or more SBCs; (b) one or more polymers compatible with the polystyrene end blocks of the one or more SBCs; and (c) one or more crosslinkers capable of inducing covalent bonds between the chains of the one or more SBCs, wherein the at least one SBC includes reactive functional groups in its elastomeric midblock that enable chemical crosslinking, such as double bonds, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha methylstyrene resins, alpha methylstyrene resins, polyphenylene ethers, copolymers of alkyl arene monomers such as alpha methylstyrene and para methylstyrene, rosin esters, styrenated terpenes, polyterpenes, terpenes, and the like. and mixtures thereof, and the one or more crosslinking agents are selected from the group consisting of aromatic, aliphatic and heteroatom monomers and oligomers containing at least two carbon-carbon double bonds, such as trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), epoxy acrylates, urethane acrylates, multifunctional acrylates such as triallyl cyanurate, triallyl isocyanurate, 1,8-dimercapto-3,6-dioxanoic acid esters, trimethylolpropane trimethacrylate (TMPTMA), ... The SBC is selected from the group consisting of functional thiols such as butyl ether, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), ethoxylated trimethylolpropane tri(3-mercaptopropionate), and other multifunctional compounds having vinyl or allyl groups, and mixtures thereof, wherein the SBC has a molecular weight (Mn) greater than 100,000 g / mol and the compatible polymer has a molecular weight (Mn) less than 10,000 g / mol.

[0087] In another exemplary embodiment, an elastomeric styrenic block copolymer composition is provided that includes: (a) one or more SBCs; (b) one or more polymers compatible with the polystyrene end blocks of the one or more SBCs; and (c) one or more crosslinkers capable of inducing covalent bonds between the chains of the one or more SBCs, wherein the at least one SBC includes reactive functional groups in its elastomeric midblock, such as double bonds, that enable chemical crosslinking; the one or more compatible polymers are selected from the group consisting of polystyrene resins, alpha-methylstyrene resins, copolymers of alkyl arene monomers, such as alpha-methylstyrene and para-methylstyrene, and mixtures thereof; and the one or more crosslinkers are selected from the group consisting of aromatic, aliphatic, and heteroatom monomers and oligomers containing at least two carbon-carbon double bonds, such as, for example, trimethylolpropane triacrylate (TMPTA), ... and the SBC has a molecular weight (Mn) greater than 100,000 g / mol and the compatible polymer has a molecular weight (Mn) less than 10,000 g / mol.

[0088] In another exemplary embodiment, the layer comprising the thin elastic membrane may further comprise other adjuvants conventionally used in the polymer industry, particularly in the glove industry, such as, for example, lubricants, antistatic agents, primary and secondary antioxidants, colorants or treatment agents.

[0089] In another exemplary embodiment, an elastomeric styrenic block copolymer composition is provided that includes: (a) one or more SBCs; (b) one or more polymers compatible with the polystyrene end blocks of the one or more SBCs; and (c) one or more crosslinkers capable of inducing covalent bonds between the chains of the one or more SBCs, wherein the one or more SBCs are selected from the group consisting of SIS, SBS, or mixtures thereof, wherein the at least one SBC contains reactive functional groups in its elastomeric midblock, such as double bonds, that enable chemical crosslinking, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, alpha-methylstyrene resins, copolymers of alkylarene monomers such as alpha-methylstyrene and para-methylstyrene, and mixtures thereof. and the one or more crosslinkers are selected from the group consisting of functional thiols such as 1,8-dimercapto-3,6-dioxaoctane, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), ethoxylated trimethylolpropane tri(3-mercaptopropionate), and mixtures thereof, wherein the SBC has a molecular weight (Mn) greater than 100,000 g / mol and the compatible polymer has a molecular weight (Mn) less than 10,000 g / mol.

[0090] In another exemplary embodiment, a method for preparing an SBC composition is provided that includes combining one or more SBCs, one or more polymers compatible with one or more polystyrene end blocks of the one or more SBCs, and one or more crosslinkers capable of inducing covalent bonds between the chains of the one or more SBCs, wherein the one or more SBCs are selected from the group consisting of SIS, SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS, or SBCs functionalized with reactive groups grafted to the intermediate rubber block, such as carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate, and aziridine, or combinations thereof, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha methylstyrene resins, alpha methylstyrene resins, polyphenylene ethers, copolymers of alkyl arene monomers such as alpha methylstyrene and para methylstyrene, rosin esters, styrenated terpenes, polyterpenes, ... and mixtures thereof, and the one or more crosslinking agents are selected from the group consisting of aromatic, aliphatic and heteroatom monomers and oligomers containing at least two carbon-carbon double bonds, for example, polyfunctional acrylates such as trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), epoxy acrylates, urethane acrylates, triallyl cyanurate, triallyl isocyanurate, functional thiols such as 1,8-dimercapto-3,6-dioxaoctane, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), ethoxylated trimethylolpropane tri(3-mercaptopropionate), and other polyfunctional compounds having vinyl or allyl groups, and mixtures thereof.

[0091] In another exemplary embodiment, a method for preparing an SBC composition is provided that includes combining one or more SBCs, one or more polymers compatible with one or more polystyrene end blocks of the one or more SBCs, and one or more crosslinkers capable of inducing covalent bonds between the chains of the one or more SBCs, wherein the one or more SBCs are selected from the group consisting of SIS, SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS, or SBCs functionalized with reactive groups grafted to the intermediate rubber block, such as carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate, and aziridine, or combinations thereof, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha methylstyrene resins, alpha methylstyrene resins, polyphenylene ethers, copolymers of alkyl arene monomers such as alpha methylstyrene and para methylstyrene, rosin esters, styrenated terpenes, polyterpenes, ... and mixtures thereof, and the one or more crosslinking agents are selected from the group consisting of aromatic, aliphatic and heteroatom monomers and oligomers containing at least two carbon-carbon double bonds, such as trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), epoxy acrylates, urethane acrylates, multifunctional acrylates such as triallyl cyanurate, triallyl isocyanurate, 1,8-dimercapto-3,6-dioxanoic acid esters, trimethylolpropane trimethacrylate (TMPTMA), ... The SBC is selected from the group consisting of functional thiols such as butyl ether, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), ethoxylated trimethylolpropane tri(3-mercaptopropionate), and other multifunctional compounds having vinyl or allyl groups, and mixtures thereof, wherein the SBC has a molecular weight (Mn) greater than 100,000 g / mol and the compatible polymer has a molecular weight (Mn) less than 10,000 g / mol.

[0092] In another exemplary embodiment, a method for preparing an SBC composition is provided that includes combining one or more SBCs, one or more polymers compatible with one or more polystyrene end blocks of the one or more SBCs, and one or more crosslinkers capable of inducing covalent bonds between the chains of the one or more SBCs, where the at least one SBC contains reactive functional groups in its elastomeric midblock that allow for chemical crosslinking, such as double bonds, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha methylstyrene resins, alpha methylstyrene resins, polyphenylene ethers, copolymers of alkyl arene monomers such as alpha methylstyrene and para methylstyrene, rosin esters, styrenated terpenes, polyterpenes, terpenes, and the like. and mixtures thereof, and the one or more crosslinking agents are selected from the group consisting of aromatic, aliphatic and heteroatom monomers and oligomers containing at least two carbon-carbon double bonds, such as trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), epoxy acrylates, urethane acrylates, multifunctional acrylates such as triallyl cyanurate, triallyl isocyanurate, 1,8-dimercapto-3,6-dioxanoic acid esters, trimethylolpropane trimethacrylate (TMPTMA), ... The SBC is selected from the group consisting of functional thiols such as butyl ether, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), ethoxylated trimethylolpropane tri(3-mercaptopropionate), and other multifunctional compounds having vinyl or allyl groups, and mixtures thereof, wherein the SBC has a molecular weight (Mn) greater than 100,000 g / mol and the compatible polymer has a molecular weight (Mn) less than 10,000 g / mol.

[0093] In another exemplary embodiment, a method for making an SBC composition is provided that includes combining one or more SBCs, one or more polymers compatible with one or more polystyrene end blocks of the one or more SBCs, and one or more crosslinking agents capable of inducing covalent bonds between the chains of the one or more SBCs, where the at least one SBC contains reactive functional groups in its elastomeric midblock, such as double bonds, that enable chemical crosslinking, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, alpha-methylstyrene resins, copolymers of alkyl arene monomers, such as alpha-methylstyrene and para-methylstyrene, and mixtures thereof, and the one or more crosslinking agents are aromatic, aliphatic, and heteroatom monomers and oligomers containing at least two carbon-carbon double bonds, such as trimethylolpropane. triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), epoxy acrylate, urethane acrylate, multifunctional acrylates such as triallyl cyanurate, triallyl isocyanurate, functional thiols such as 1,8-dimercapto-3,6-dioxaoctane, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), ethoxylated trimethylolpropane tri(3-mercaptopropionate), and other multifunctional compounds having vinyl or allyl groups, and mixtures thereof, wherein the SBC has a molecular weight (Mn) greater than 100,000 g / mol and the compatible polymer has a molecular weight (Mn) less than 10,000 g / mol.

[0094] In another exemplary embodiment, a method for preparing an SBC composition is provided that includes combining one or more SBCs, one or more polymers compatible with one or more polystyrene end blocks of the one or more SBCs, and one or more crosslinking agents capable of inducing covalent bonds between the chains of the one or more SBCs, where the at least one SBC contains reactive functional groups in its elastomeric midblock that allow for chemical crosslinking, such as double bonds, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, alpha-methylstyrene resins, copolymers of alkyl arene monomers such as alpha-methylstyrene and para-methylstyrene, and the like. and mixtures thereof, and the one or more crosslinkers are selected from the group consisting of functional thiols such as 1,8-dimercapto-3,6-dioxaoctane, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), ethoxylated trimethylolpropane tri(3-mercaptopropionate), and mixtures thereof, the SBC having a molecular weight (Mn) greater than 100,000 g / mol and the compatible polymer having a molecular weight (Mn) less than 10,000 g / mol.

[0095] In another exemplary embodiment, a method is provided for producing a dipped article from at least one SBC composition or compatible polymer blend according to the disclosure of any one of the exemplary embodiments described herein, wherein an outer mold corresponding to the outer shape of the dipped article to be produced is dipped in a dipping solution comprising one or more SBC compositions or compatible polymer blends for a pre-determinable period of time, after which the dipped article is removed from the solution and dried.

[0096] The product, especially the dried product, may then be exposed to radiation, for example electron beam, gamma, UV or X-ray irradiation.

[0097] In another exemplary embodiment, a thin film is provided comprising one or more SBC compositions or compatible polymer blends according to the disclosure of any one of the exemplary embodiments described herein, wherein the thin film has a tensile strength of greater than 17 MPa as measured according to ASTM 3577, and the thin film is substantially insoluble in organic solvents.

[0098] In another exemplary embodiment, a thin film is provided that includes one or more SBC compositions, or compatible polymer blends, according to any one of the preferred embodiments disclosed herein.

[0099] Thin films according to any of the representative embodiments disclosed herein may be from about 10 to about 500 microns or from about 150 to about 250 microns thick.

[0100] Thin films according to any of the exemplary embodiments disclosed herein may be less than 500 microns, less than 400 microns, less than 300 microns, or less than 200 microns thick.

[0101] In another exemplary embodiment, an article of manufacture, such as a glove or a condom, is provided, where the article of manufacture comprises one or more SBC compositions or compatible polymer blends according to any one of the exemplary embodiments disclosed herein.

[0102] mechanical properties According to this disclosure, the SBC composition or compatible polymer blend may have a 100% elongation of less than 1.0 MPa or less than 0.70 MPa.

[0103] According to this disclosure, a thin-walled elastic product may have an elongation at 100% of less than 1.0 MPa or less than 0.70 MPa.

[0104] According to this disclosure, the thin walled elastomeric products may be compliant with EN455-2 and ISO 10282, i.e., have a breaking force of greater than 9N (measured on an undegraded membrane).

[0105] According to this disclosure, the thin-walled elastomeric products may conform to ASTM D3577, i.e., have a tensile strength of greater than 17 MPas (undegraded film).

[0106] The SBC composition, compatible polymer blend, or thin walled elastomeric article may have any combination of the mechanical properties described above.

[0107] composition According to an embodiment of this disclosure, the composition is expressed in PHR (per hundred rubber), where the rubber is an SBC of 1 or more. Exemplary ranges of components in the composition include:· Compatible polymer: 0.25-100 phr, preferably 5-50 phr· Plasticizer / flexibilizer: 0-200 phr, preferably 20-75 phr· Crosslinker: 0.01-5 phr, preferably 0.05-1 phr· Photoinitiator: 0-5 phr, preferably 0-2 phr.

[0108] Definition and composition The thin walled elastic dipped products disclosed herein, such as gloves, particularly medical gloves, and condoms, may be from about 10 to about 500 microns or from about 150 to about 250 microns thick.

[0109] The dipped product may be single layer or multi-layered. Multi-layer products may include layers with the same or different polymer compositions.

[0110] Working Example The following examples illustrate the compositions disclosed herein and are intended to illustrate this disclosure, and should not be construed in any way as limiting the scope of this disclosure.

[0111] Although this disclosure has been described with respect to certain embodiments, it is to be understood that this description is intended to illustrate, and not to limit, the scope of the disclosure. Other aspects, advantages, and modifications will be apparent to those of skill in the art to which this disclosure pertains. Thus, the examples are set forth so as to provide those of skill in the art with a complete disclosure and description of how to make and use the disclosed compositions, and are not intended to limit the scope of the disclosure.

[0112] Example 1 The following examples demonstrate the improved performance (mechanical properties and chemical resistance) of compositions according to this disclosure.

[0113] Styrene-butadiene-styrene copolymer (SBS) with a viscosity of 150 mPas (10% in toluene at 25°C), a compatible polymer based on styrene and substituted styrenes (Mn=800 g / mol, polydispersity index=2.8), a plasticizer as white mineral oil with a viscosity of 68 mPas at 40°C, and a crosslinker as trimethylpropane tris(3-mercaptopropionate) were dissolved in a mixture of methylcyclohexane and toluene (8:2) to prepare a solution with a solids content of 18% by weight.

[0114] Different amounts of crosslinker and compatible polymer ("P") were used, as shown in the table below.

[0115] The amount of plasticizer was 50 phr and 1 phr of polyphenol antioxidant was added to the polymer solution.

[0116] The solution was stored at ambient temperature in a suitable container with a lid to prevent evaporation of the solvent. After immersion of a porcelain mould in the solution using a dipping robot with controlled immersion rate, the solvent was evaporated to obtain a membrane. Before stripping, the membrane was dried at 70°C for 1 h, followed by a final drying at 50°C for 6 h to remove traces of residual solvent.

[0117] The membrane was then subjected to electron beam irradiation at a dose of 25±2 kGy.

[0118] The chemical resistance of the irradiated films was evaluated by a variety of means. Ideally, the test methods should replicate real-world exposure conditions to chemicals.

[0119] In this example, the SBC composition was intended for use in gloves, so the following tests were employed to evaluate the chemical resistance of the membrane: 1) Swab test: 0.5 g of pure methyl methacrylate monomer was soaked in a cotton swab and applied to a pre-tensioned membrane. The contact time was 10 seconds under slight pressure. The test was repeated three times, after which the membrane was tested for resistance. 2) Swelling test: A disk with a diameter of 25 mm was cut from the membrane and placed in a beaker containing 20 ml of MEK for 5 minutes with slight stirring. After 5 minutes, the disk was removed, its outer surface was cleaned with tissue, and the diameter of the disk was measured. The swelling ratio was measured as 100 x (diameter after swelling (mm) - 25) / 25. The mechanical properties were measured according to ASTM 3577 for surgical gloves. For unaged synthetic type 2 material, the lower limit of the tensile strength is 17 MPa. The results are shown in the table below.

[0120] [Table 1]

[0121] These results indicate that SBS can be efficiently chemically crosslinked with trimethylolpropane tris(3-mercaptopropionate).

[0122] This example demonstrates that compositions combining SBC, crosslinker and a compatible polymer exhibit greater mechanical properties than: - SBC alone (Sample 1); - SBC combined with a compatible polymer but without a crosslinker (Sample 2); - SBC combined with a crosslinker but without a compatible polymer (Sample 4).

[0123] Sample 3 also shows a significant improvement in chemical resistance compared to Samples 1 or 2. Finally, it can be seen that the glove of Sample 3 is the only sample that passes the ASTM specifications for tensile strength, and the resulting membrane is very soft (100% elongation = 0.68 MPa).

[0124] Example 2 A styrene-isoprene-styrene copolymer (SIS) containing a styrene-isoprene diblock copolymer with a viscosity of 45 mPas (10% in toluene at 25°C) was used to replace the SBS copolymer used in samples 1-4.

[0125] The compatible polymer is based on 20 phr of styrene and substituted styrenes (Mn=800 g / mol, polydispersity index=2.8) and does not contain any plasticizers or flexibilizers. The crosslinker is trimethylolpropane trimethacrylate at 1 phr.

[0126] For samples 1-4, films were obtained after solvent evaporation and then dried to remove traces of residual solvent before being irradiated with an electron beam at a dose of 50±3 kGy.

[0127] The mechanical properties of the membrane are 17.1 MPa, and the swab test shows that it has excellent chemical resistance.

[0128] Example 3 A multilayer film was produced using the following combination of polymers: - a first layer of 80±10 μm thickness consisting of the styrene-butadiene-styrene block copolymer composition described in sample 3 above - a second layer of 140±20 μm thickness consisting of high molecular weight styrene-ethylene / butylene-styrene (SEBS) with a radial structure of 75 cp viscosity (5% toluene) and 31% polystyrene. The compatible polymer is based on 25 phr of styrene and substituted styrene (Mn=800 g / mol, polydispersity index=2.8) and the amount of plasticizer is 60 phr. The crosslinker is 0.2 phr of trimethylpropane tris(3-mercaptopropionate). The multilayer film was subjected to electron beam irradiation of 40 kGy±3. Analysis of the film showed a tensile strength of 20.5 MPa and good resistance in swab tests.

[0142] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit, or any lower limit with any other lower limit, or any upper limit with any other upper limit, to imply a range that is not expressly stated. tree do.

[0143] All cited documents are incorporated herein by reference in their entirety, under all statutes permitting incorporation, and to the extent consistent with the disclosure herein.

[0144] The invention as originally claimed is set forth below. [1] An elastomeric styrenic block copolymer composition comprising one or more styrenic block copolymers (SBCs) and one or more polymers compatible with the styrenic endblocks of the one or more SBCs, The block copolymer composition is physically and chemically crosslinked; The chemical crosslinks include covalent bonds between the chains of the SBC, and The physical crosslinks comprise non-covalent interactions between one or more styrenic endblocks of the SBC and one or more polymers compatible with the endblocks. [2] An elastomeric styrenic block copolymer composition comprising one or more SBCs, one or more polymers compatible with the one or more polystyrene end blocks of the one or more SBCs, and one or more crosslinkers capable of inducing covalent bonds between chains of the one or more SBCs. [3] A compatible polymer blend comprising one or more SBCs and one or more polymers compatible with the styrenic endblocks of the one or more SBCs, the compatible polymer blend is physically and chemically crosslinked; The chemical crosslinks include covalent bonds between the chains of the SBC, and The physical crosslinks include non-covalent interactions between one or more styrenic endblocks of the SBC and one or more polymers that are compatible with the endblocks, forming a compatible polymer blend. [4] A method for making an SBC composition comprising combining one or more SBCs, one or more polymers compatible with the one or more polystyrene end blocks of the one or more SBCs, and one or more crosslinkers capable of inducing covalent bonds between chains of the one or more SBCs. [5] The composition of [1] or [2], the mixture of [3], or the method of [4], further comprising one or more plasticizers and / or flexibilizers compatible with the elastomeric midblock of the one or more SBCs. [6] The composition of any of [1], [2] or [5], the mixture of any of [3] or [5], or the method of any of [4] or [5], wherein the one or more SBCs independently comprise a fully unsaturated, partially unsaturated, or fully saturated elastomeric midblock. [7] The composition according to any one of [1], [2], [5] or [6], wherein the one or more SBCs comprise a fully saturated elastomeric midblock, which is cleavable when exposed to radiation, e.g., when exposed to electron beam irradiation; the mixture according to any one of [3], [5] or [6]; or the method according to any one of [4] to [6]. [8] The composition according to any one of [1], [2] or [5] to [7], the mixture according to any one of [3] or [5] to [7], or the method according to any one of [4] to [7], wherein the one or more SBS is selected from the group consisting of SIS, SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS, or SBC functionalized with reactive groups grafted to the intermediate rubber block, such as carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate, and aziridine, and combinations thereof. [9] The composition according to any one of [1], [2] or [5] to [8], the mixture according to any one of [3] to [8], or the method according to any one of [4] to [8], wherein the one or more SBCs have a molecular weight (Mn) of more than 100,000 g / mol.

[10] The composition according to any one of [1], [2] or [5] to [9], the mixture according to any one of [3] to [9], or the method according to any one of [4] to [9], wherein the at least one SBC has an elastomeric midblock containing a reactive functional group such as a carbon-carbon double bond.

[11] The composition according to any one of [1], [2] or [5] to

[10] , the mixture according to any one of [3] to

[10] , or the method according to any one of [4] to

[10] , wherein the number average molecular weight (Mn) of the compatible polymer is less than 10,000 g / mol, more preferably less than 3,000 g / mol.

[12] The composition according to any one of [1], [2] or [5] to

[11] , the mixture according to any one of [3] to

[11] , or the method according to any one of [4] to

[11] , wherein the compatible polymer has a polydispersity index over a wide range of molecular weights, for example, greater than 2.0, greater than 3.0, greater than 4.0, or greater than 5.0.

[13] The composition according to any one of [1], [2], or [5] to

[12] , or the mixture according to any one of [3] to

[12] , or the method according to any one of [4] to

[12] , wherein the compatible polymer is selected from the group consisting of polystyrene resin, coumarone-indene resin, polyindene resin, poly(methylindene) resin, vinyltoluene-α-methylstyrene resin, α-methylstyrene resin, polyphenylene ether, copolymers of alkylarenes such as α-methylstyrene and para-methylstyrene, rosin ester, styrenated terpenes, polyterpenes, terpene phenols, and mixtures thereof.

[14] The composition according to any one of [1], [2], or [5] to

[12] , or the mixture according to any one of [3] to

[12] , or the method according to any one of [4] to

[12] .

[14] The composition according to any one of [1], [2] or [5] to

[13] , wherein the at least one SBC contains double bonds in its elastomeric midblock which allow for chemical crosslinking, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha-methylstyrene resins, alpha-methylstyrene resins, polyphenylene ethers, copolymers of alkyl arene monomers such as alpha-methylstyrene and para-methylstyrene, rosin esters, styrenated terpenes, polyterpenes, terpene phenols, and mixtures thereof, wherein the SBC has a molecular weight (Mn) greater than 100,000 g / mol, and the compatible polymer has a molecular weight (Mn) less than 10,000 g / mol; the mixture according to any one of [3] to

[13] ; or the method according to any one of [4] to

[13] .

[15] The composition according to any one of [2] and [5] to

[14] or the method according to any one of [4] to

[14] , wherein the crosslinking agent is selected from the group consisting of polyfunctional acrylates such as trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), epoxy acrylate, urethane acrylate, triallyl cyanurate, and triallyl isocyanurate, functional thiols such as 1,8-dimercapto-3,6-dioxaoctane, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and ethoxylated trimethylolpropane tri(3-mercaptopropionate), and other polyfunctional compounds having a vinyl group or an allyl group, and mixtures thereof.

[16] The composition according to any one of [2] and [5] to

[14] or the method according to any one of [4] to

[14] , wherein the crosslinking agent is an amine crosslinking agent selected from the group consisting of a metal salt, an organic amine, an organic diamine, and an organic polyamine, or a polyol.

[17] The composition according to any one of [2] and [5] to

[14] or the method according to any one of [4] to

[14] , wherein the crosslinking agent is selected from conventional sulfur, metal oxides, and accelerators commonly used in the vulcanization of rubber.

[18] The composition according to any one of [2] and [5] to

[14] or the method according to any one of [4] to

[14] , wherein the crosslinking agent is selected from dithiol, trithiol, and tetrathiol molecules containing an ether or ester group in the main chain.

[19] The method according to any one of [5] to

[18] , wherein the composition is crosslinked by exposure to radiation such as ultraviolet light, electron beams, gamma rays or X-rays.

[20] The method according to any of [5] to

[19] , wherein the crosslinking reaction is initiated or accelerated by one or a mixture of radical type photoinitiators.

[21] The method of

[20] , wherein the crosslinking photoinitiator is selected from the group consisting of acylphosphine oxides, such as monoacylphosphine oxides, bisacylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, or others, such as 2-hydroxymethyl-1-phenylpropanone, methyl benzoylformate, and phenylglyoxylic acid methyl ester.

[22] The composition according to any one of [5] to

[18] , the mixture according to any one of [3] to

[14] , or the method according to any one of [5] to

[21] , wherein the plasticizer comprises a liquid saturated polyolefin or a mixture thereof that is compatible with the midblock (elastomeric block) of the SBC.

[23] The composition according to any one of [5] to

[18] or

[22] , the mixture according to any one of [3] to

[14] or

[22] , or the method according to any one of [5] to

[22] , wherein the plasticizer comprises a plasticizing oil, preferably a mineral plasticizing oil, in particular a mineral oil formed from a refined mixture of liquid saturated hydrocarbons formed from paraffinic or naphthenic compounds or mixtures thereof.

[24] The composition according to any one of [5] to

[18] ,

[22] or

[23] , the mixture according to any one of [3] to

[14] ,

[22] or

[23] , or the method according to any one of [5] to

[23] , wherein the flexibilizing agent is selected from polybutadiene, polyisoprene, polyisobutene, amorphous polyolefin copolymers of propylene and ethylene, butyl rubber, and other elastomers known to have sufficient compatibility with the elastomeric block.

[25] The composition according to any one of [1], [2], [5] to

[18] or

[22] to

[24] , the mixture according to any one of [3] to

[14] or

[22] to

[24] , or the method according to any one of [4] to

[24] , further comprising other adjuvants conventionally used in the polymer industry, in particular in the glove industry, such as lubricants, antistatic agents, primary and secondary antioxidants, colorants or processing agents.

[26] A method for producing a dipped product from at least one SBC composition according to any one of [1], [2], [5] -

[18] , or

[22] -

[25] , or a mixture according to [3] -

[14] or

[22] -

[25] , comprising immersing an outer mould corresponding to the external shape of the dipped product to be produced in a dipping solution comprising one or more SBC compositions or a compatible polymer mixture for a predeterminable period of time, after which the dipped product is removed from the solution and dried.

[27] The method of

[26] , further comprising exposing the dried product to radiation, preferably electron beam radiation.

[28] A film comprising one or more SBC compositions or compatible polymer blends, the film having a tensile strength greater than 17 MPa when tested in accordance with ASTM 3577, and the film being substantially insoluble in organic solvents.

[29] The thin film according to

[28] , wherein the film has a thickness of about 10 microns to about 500 microns.

[30] The thin film according to

[28] or

[29] , wherein at least 80% or 95% of the film is insoluble in organic solvents.

[31] A thin film comprising one or more SBC compositions according to any one of [1], [2], [5]-

[18] or

[22] -

[24] , or a compatible polymer mixture according to any one of [3]-

[14] or

[22] -

[24] .

[32] The thin film according to

[31] , wherein the film has a thickness of about 10 microns to about 500 microns.

[33] The thin film according to

[31] , wherein the film has a thickness of about 150 microns to about 250 microns.

[34] The thin film according to any one of

[30] to

[33] , wherein the thin film has a tensile strength of greater than 17 MPa when evaluated according to ASTM 3577, and the thin film is substantially insoluble in organic solvents.

[35] A multilayer film comprising one or more layers, the one or more layers comprising an SBC composition according to any one of [1], [2], [5] to

[18] , or

[22] to

[25] , or a compatible polymer mixture according to any one of [3] to

[14] , or

[22] to

[25] .

[36] A multilayer film, the multilayer film comprising one or more layers, the one or more layers comprising an SBC composition or a compatible polymer blend, the composition or compatible polymer blend having a tensile strength of at least 17 MPa, and the composition or compatible polymer blend being substantially insoluble in organic solvents.

[37] A multilayer film comprising several thin films according to any one of

[28] to

[34] .

[38] The multilayer film according to any one of

[35] to

[37] , wherein the one or more layers are selected from the group consisting of natural rubber, polybutadiene, polyisoprene, polychloroprene, butyl rubber, polyurethane, acrylic acid polymers and copolymers, silicone elastomers, other SBCs, cyclic block copolymers (CBCs), and mixtures thereof.

[39] An article of manufacture comprising one or more SBC compositions according to any one of [1], [2], [5]-

[18] , or

[22] -

[25] , or a compatible polymer blend according to any one of [3]-

[14] or

[22] -

[25] .

[40] The article of manufacture of

[39] , wherein the article is a medical device such as a medical glove, a condom, or personal protective equipment such as a laboratory glove or a clean industrial glove.

Claims

1. 1. An elastomeric styrenic block copolymer composition for use in making an elastic dipped article, comprising one or more styrenic block copolymers (SBCs) and one or more polymers compatible with the styrenic endblocks of the one or more SBCs, the one or more SBCs have a molecular weight (Mn) greater than 100,000 g / mol; The number average molecular weight (Mn) of the compatible polymer is less than 3,000 g / mol; The polydispersity index of the molecular weight of the compatible polymer is 2.8; the block copolymer composition is physically and chemically crosslinked, the chemical crosslinks comprising covalent bonds between chains of SBC and the physical crosslinks comprising non-covalent interactions between one or more styrenic endblocks of SBC and the one or more polymers compatible with the styrenic endblocks; the block copolymer composition comprises one or more crosslinking agents for chemical crosslinking capable of inducing covalent bonds between the chains of the one or more SBCs; the block copolymer composition comprises one or more plasticizers and / or flexibilizers compatible with the elastomeric midblock of the one or more SBCs, the one or more plasticizers and / or flexibilizers being used in an amount of 20 to 75 phr; The styrenic block copolymer composition, wherein the compatible polymer has an arene ring and is selected from the group consisting of polystyrene resin, coumarone-indene resin, polyindene resin, poly(methylindene) resin, vinyltoluene-α-methylstyrene resin, α-methylstyrene resin, polyphenylene ether, and copolymers of alkylarene monomers, and the arene ring of the compatible polymer and the styrene ring of the styrenic end block of the one or more SBCs form a uniform mixture of the compatible polymer and the one or more SBCs by π-bond interaction therebetween.

2. 10. The styrenic block copolymer composition of claim 1, wherein the one or more SBCs independently comprise a fully unsaturated, partially unsaturated, or fully saturated elastomeric midblock.

3. 3. The styrenic block copolymer composition of claim 2, wherein the one or more SBCs comprise a fully saturated elastomeric midblock, the fully saturated elastomeric midblock being cleavable when exposed to radiation.

4. 2. The styrenic block copolymer composition of claim 1, wherein the one or more SBCs are selected from the group consisting of SIS, SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS, or SBCs functionalized with reactive groups grafted to an intermediate rubber block.

5. 10. The styrenic block copolymer composition of claim 1, wherein at least one SBC has an elastomeric midblock that contains a reactive functional group.

6. 2. The styrenic block copolymer composition of claim 1, wherein the at least one SBC contains double bonds in its elastomeric midblock that allow for chemical crosslinking, and the one or more compatible polymers are selected from the group consisting of polystyrene resins, coumarone-indene resins, polyindene resins, poly(methylindene) resins, vinyltoluene-alpha methylstyrene resins, alpha methylstyrene resins, polyphenylene ethers, copolymers of alkyl arene monomers, and the SBC has a molecular weight (Mn) greater than 100,000 g / mol and the compatible polymer has a molecular weight (Mn) less than 3,000 g / mol.

7. 10. The styrenic block copolymer composition of claim 1, wherein said plasticizer comprises a liquid saturated polyolefin blend that is compatible with said midblock of the SBC.

8. 10. The styrenic block copolymer composition of claim 1, wherein the plasticizer comprises a plasticizing oil.

9. 2. The styrenic block copolymer composition of claim 1, wherein the flexibilizer is selected from polybutadiene, polyisoprene, polyisobutene, amorphous polyolefin copolymers of propylene and ethylene, butyl rubber.

10. 10. The styrenic block copolymer composition of claim 1 further comprising a lubricant, an antistatic agent, a primary and secondary antioxidant, a colorant or a treating agent.

11. A thin film for use in the manufacture of elastic dipped products, comprising one or more styrenic block copolymer compositions according to any one of claims 1 to 10.

12. The film of claim 11, wherein the film is between 10 microns and 500 microns thick.

13. The film of claim 11, wherein the film is between 150 microns and 250 microns thick.

14. A multilayer film for use in the manufacture of an elastic dipped product, the multilayer film comprising one or more layers, the one or more layers comprising the styrenic block copolymer composition according to any one of claims 1 to 10.

15. 15. The multilayer film of claim 14, wherein the one or more layers are selected from the group consisting of natural rubber, polybutadiene, polyisoprene, polychloroprene, butyl rubber, polyurethane, acrylic polymers and copolymers, silicone elastomers, cyclic block copolymers (CBC), and mixtures thereof.

16. An elastic dipped product comprising one or more styrenic block copolymer compositions according to any one of claims 1 to 10.

17. 17. The elastic immersion product of claim 16, wherein the elastic immersion product is a medical device.

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