Classifications

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  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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  • A61F6/00—Contraceptive devices; Pessaries; Applicators therefor
  • A61F6/06—Contraceptive devices; Pessaries; Applicators therefor for use by females
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Definitions

• the present disclosure relates to styrenic block copolymers which are both physically and chemically cross-linked.
• the copolymers find advantageous use in the manufacture of elastic dipped articles, for example gloves and condoms.
• Thin-walled elastic dipped articles are traditionally made of natural rubber (NR), polychloroprene (CR), polyisoprene (IR), polyurethane (PU), nitrile butadiene rubber (NBR), styrenic block copolymers (SBC), mixtures thereof or laminations thereof.
• NR natural rubber
• CR polychloroprene
• IR polyisoprene
• PU polyurethane
• NBR nitrile butadiene rubber
• SBC styrenic block copolymers
• Natural rubber is used in such applications as it is a natural product which offers exceptional performance.
• sensitizing proteins which are responsible for immediate type hypersensitivity (type I allergies) has restricted its use.
• synthetic materials have been developed as alternatives.
• Thin-walled elastic films are usually shaped for the intended application (glove, condom, etc) by dipping a form of an appropriate shape into a liquid mixture of the polymer, which may be either a dispersion in water (latex) or a solution in one or more appropriate solvents. A solid film is formed following the evaporation of water or other solvents.
• Vulcanization is the traditional chemical cross-linking mechanism for most elastomeric materials such as NR or IR. Vulcanization creates sulphur covalent bonds that link one polymer chain to another.
• chemical additives such as "accelerators” are added. Accelerators may be of many types and are usually classified within the following families: thiazoles, carbamates, guanidines, thiourea and thiurams. It is common practice to use a mixture of different accelerators selected from the different families to optimize the vulcanization speed and performance.
• accelerators are not.
• a typical glove formulation made of polyisoprene can comprise up to 2% of accelerators.
• the accelerator molecules have poor solubility in water and cannot be removed from the glove by washing. Also, they may "bloom" at the surface of the film over time, due to their limited compatibility with the rubber. Accelerators are also strong skin sensitizers and can cause allergic contact dermatitis (delayed hypersensitivity, type IV).
• NR, CR, IR and NBR are the more common elastomers and are all transformed into thin walled films starting from water dispersions, also known as lattices.
• thin walled films produced from lattices have the disadvantage that the resulting products are sometimes prone to having pinholes. These pinholes, often on the order of micrometers in diameter, may be the result of low levels of impurities in the latex which are difficult to filter out, and to the fact that the process converts a heterogeneous system (dispersion) into a film.
• some other synthetic polymers can be dissolved in solvents, such as hydrocarbon solvents, to form a true solution. Accordingly, solvent cast technology is attractive for the production of films with extremely high-quality requirements and almost no microporosity. Pinholes are also much less likely to be present.
• Multiblock rubber based copolymers and especially styrenic block copolymer (SBCs), are particularly suitable to be used for solvent casting as they can form solutions with acceptable viscosities that can be utilised for dipping.
• SBCs styrenic block copolymer
• SBCs are classified as thermoplastic elastomers, which possess the mechanical properties of rubbers and the processing characteristics of thermoplastics. These properties result from their molecular structure. SBCs consist of at least three blocks, generally two hard polystyrene end blocks and one soft, elastomeric (polybutadiene, polyisoprene - hydrogenated or not) midblock.
• More common SBCs comprise linear triblock copolymers such as styrene-ethylene/butylene-styrene (SEBS), styrene-butadiene-styrene (SBS) and styrene-isoprene-styrene (SIS), but other architectures (for example copolymers composed of more than 3 blocks) and other structures (star or radial) are also possible.
• SEBS styrene-ethylene/butylene-styrene
• SBS styrene-butadiene-styrene
• SIS styrene-isoprene-styrene
• the hard and soft blocks are immiscible, so that, on a microscopic scale, the polystyrene blocks form separate domains in the rubber matrix. Therefore, SBCs exhibit two glass transition temperatures (Tg) which are characteristic of the respective homopolymer (polystyrene end-block, 90-100°C and rubbery mid-block at around -90°C in the case of polybutadiene, for example).
• Tg glass transition temperatures
• SBCs are capable of forming elastic films with high mechanical performance without the use of any chemical cross-linking such as sulphur and accelerators, since both ends of each rubbery block are terminated by polystyrene segments and these rigid domains act as multifunctional junction points to produce a "physically" crosslinked elastomer network, similar in many respects of that of a conventional vulcanized rubber ("chemical crosslinking").
• these elastomers can advantageously be formulated with suitable plasticizers to provide a desirable combination of tensile strength, elasticity and tactility, such as is required, for example, for surgical gloves.
• the ultimate force at break and tensile strength are important factors in assessing the performance of thin walled extensible films such as condoms or gloves, which should be evaluated following international standards.
• a surgical glove should provide a high sensitivity while at the same time not compressing the wearer's hand over a prolonged period of time.
• a Modulus at 100% elongation below 1.0 MPa, and ideally below 0.7 MPa is preferred.
• SBCs Suitably formulated with plasticizer, SBCs can meet all international standards and can achieve comparable, and in many cases superior, flexibility and mechanical properties to those of other elastomers such as NRL, CR, IR. This means that the material can perform mechanically in a manner comparable or superior to other elastomers while avoiding the shortcomings of latex-based elastomers such as accelerators and pinholes.
• SBCs are particularly suitable for use in thin-walled film applications such as medical gloves providing excellent properties including, synthetic rubber free of natural rubber proteins, accelerator free, softness, as well as films with extremely high quality having almost no pinholes and no hydration.
• EP0488021 discloses a combination of two or more S-EB-S block copolymers
• EP1472315 discloses a combination of one S-EB-S block copolymer and one S-EP-S-EP block copolymer.
• MMA methyl methacrylate monomer
• PS 18.6
• diethyl ether which is used as a solvent in some preparations, such as collodion.
• the weak chemical resistance to these solvents is a major limitation of this family of elastomers for gloves for surgical usage.
• Such materials could not, for example, achieve the international standards for the case of surgical gloves, such as the minimum tensile strength as described in the ASTM D3577.
• the present disclosure provides an elastomeric styrenic block copolymer (SBC) composition comprising one or more SBCs and one or more polymers miscible with styrenic end blocks of the one or more SBCs;
• SBC elastomeric styrenic block copolymer
• block copolymer composition is both physically and chemically crosslinked
• said chemical crosslinking comprises covended bonds between chains of SBC and;
• said 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.
• the present disclosure provides a miscible polymer blend comprising one or more SBCs and one or more polymers miscible with styrenic end blocks of the one or more SBCs;
• miscible polymer blend is both physically and chemically crosslinked; wherein said chemical crosslinking comprises covended bonds between chains of SBC and;
• said 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.
• compositions or blends comprising physically and chemically cross-linked styrene block copolymers find use in, for example, the manufacture of thin-walled dipped articles such as condoms and medical gloves.
• the unique compositions or blends overcome the shortcoming of chemical resistance in presently available SBCs, while maintaining a high level of mechanical resistance and flexibility.
• an elastomeric styrenic block copolymer composition comprising:
• a method of preparing a SBC composition comprising the step of: combining one or more SBCs, one or more polymers miscible with polystyrene end blocks of the one or more SBCs; and one or more cross-linking agents capable of inducing covalent bonding between chains of the one or more SBCs.
• compositions or blends may further comprise one or more plasticizers
• compositions or blends may further comprise one or more
• compatibilizers which enhance the miscibility between styrenic end blocks of the one or more SBCs and the one or more miscible polymers.
• Such compatibilizers may be, for example, surfactants and particularly polymeric surfactants such as di-block copolymers comprising a PS segment, or a low molecular weight polymer or resin having an appropriate solubility parameter.
• the one or more SBCs may have a fully unsaturated or partially unsaturated elastomeric mid-block or may have a fully saturated elastomeric mid- block.
• the one or more SBCs may be selected from the group consisting of SIS, SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS or a SBC functionalized with reactive groups grafted in the middle rubber block such as, for example, carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate and aziridine groups or mixtures thereof.
• the SBC is composed of one or a mixture of SBCs of molecular weight (Mn) above 100,000g/mol.
• the elastomeric mid-block of at least one SBC comprises reactive functionalities, such as double bonds, for example, carbon-carbon double bonds, to enable chemical crosslinking.
• the polymer miscible with the polystyrene end blocks may be a polymer capable of forming, to a certain extent, an intimate blend at the molecular level with the polystyrene end blocks.
• the miscible polymer may be a polymer that is miscible with polystyrene, that is, the SBC and the miscible polymer can form a homogeneous blend, either by chemical similarity and/or by specific interactions, such as between ⁇ bonds in arene rings.
• the interactions may be non-covalent in nature.
• the interactions may not include covalent bonds between the SBC and the miscible polymer.
• the number average molecular weight of the miscible polymer (Mn) is below 10,000 g/mol and more preferably below 3,000 g/mol.
• the miscible polymer has a broad molecular weight
• the miscible polymer preferably has a polarity similar to that of polystyrene.
• the miscible polymers are selected from low molecular weight copolymers of alkyl arene monomers.
• the miscible polymer may be selected from the group consisting of polystyrene resin, coumarone-indene resin, polyindene resin, poly(methylindene) resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin, polyphenylene ether, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, rosin ester, styrenated terpenes, polyterpenes, terpene phenolics and mixtures thereof.
• the crosslinking agent may be selected from the group consisting of aromatic, aliphatic and heteroatomic monomers and oligomers containing at least two carbon-carbon double bonds, such as, for example: multifunctional 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), as well as other multifunctional compounds with vinyl or allyl groups, and mixtures thereof.
• multifunctional acrylates such as trimethylolprop
• the chemical crosslinking may also be performed through so-called "vulcanization", and in this case the crosslinking agent may be selected from conventional sulphur, metallic oxides and accelerators commonly utilized for vulcanization of rubber in thin walled elastic films such as condoms and gloves. Vulcanization is not considered as a preferred cross-linking route in respect of the present disclosure because the accelerators, which are strong skin sensitizers, are not integrated into the chemical network and may bloom to the surface.
• the cross-linking reaction is a thiol-ene reaction.
• a thiol-ene reaction is a so-called "click" reaction that can take place as a radical-mediated addition reaction.
• the cross-linker is selected from, for example, di-thiol, tri-thiol and tetra-thiol molecules containing ether or ester groups in their backbone.
• the cross-linking reaction may be triggered by radiation, for example UV, gamma irradiation, X-Ray or electron beam radiation.
• Radiation offers multiple advantages: the energy is high enough to create radicals from the existing chemicals, there is less risk of shadowing effects as may be observed with UV curing, and the technology also offers good and accurate control of the dose. It should also be noted that most surgical gloves are sterilized by radiation (either electron beam or gamma radiation) therefore the crosslinking may advantageously occur during the same process as the glove sterilization itself.
• the cross-linking reaction may be initiated or enhanced by one or a mixture of radical-type photo-initiators.
• the photo-initiator is preferably selected from those compounds offering broad UV absorption spectra and effective production of reactive radicals upon irradiation, combined with good solubility in resin systems, as well as good tolerance when in contact with human skin.
• the photo-initiator may, for example, be selected from the group consisting of acylphosphine oxides, for example monoacylphosphine oxides, bisacylphosphine oxides, 2,4,6- trimethylbezoyldiphenylphosphine oxide or others such as 2-hydroxy-methyl-1- phenylpropanone, methylbenzoylformate, and phenylglyoxylic acid methyl ester.
• the plasticizer may enhance the stretching and flexibility of the herein disclosed SBC compositions and polymer blends.
• the plasticizer consists of a liquid or a mixture of liquid saturated polyolefins compatible with the midblock (elastomeric block) of the SBC. More preferably the said plasticizer may be selected from compounds that have a pour point less than or equal to 35°C.
• plasticizing oils preferably mineral plasticizing oils and especially mineral oils formed from a purified mixture of liquid saturated hydrocarbons formed from compounds of paraffinic or naphthenic nature or mixtures thereof in varying proportions.
• Preferred plasticizing mineral oils are crystal clear, water-white products that contain no toxic impurities and no MOAH (Mineral Oil Aromatic Hydrocarbon) and comply with USA FDA 21 CFR 178.3620(a), White Mineral Oil, US Pharmacopeia, European Pharmacopoeia (Liquid Paraffin) as well as Europe Regulation (EU) 10/201 1 on plastic material and articles intended to come into contact with foodstuff, White mineral oil.
• a preferred mineral oil is a medicinal white oil which has a specific gravity of 0.85-0.90 at 15°C.
• the plasticizer may also be an oligomer or other elastomer that possess a sufficient compatibility with the rubbery mid-blocks and in this case, may be considered more as a "flexibilizer".
• a flexibilizer 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 a sufficient compatibility with the rubbery block.
• Functionalized or reactive flexibilizers such as acrylic or hydroxyl modified polybutadiene may also be used. These reactive flexibilizers may participate in the chemically crosslinked network.
• SBC compositions or miscible polymer blends in accordance with embodiments of the present disclosure are expressed in PHR (Per Hundred Rubber) with rubber being the one or more SBCs.
• PHR Per Hundred Rubber
• Exemplary ranges for components in the compositions include:
• Miscible polymer 0.25 to 100phr, preferably 5 to 50phr
• Plasticizer/Flexibilizer 0 to 200phr, preferably 20 to 75phr
• Cross-linking agent 0.01 to 5phr, preferably 0.05 to 1 phr
• Photo-initiator 0 to 5phr, preferably 0 to 2phr.
• immersion article from at least one SBC composition or miscible polymer blend as herein disclosed in which a mold with an external contour which corresponds to that of the immersion article to be produced is immersed for a pre-specifiable period of time in an immersion solution comprising the one or more SBC compositions or miscible polymer blends, and where subsequently the immersion article is removed from the solution and dried.
• the article, particularly the dried article may subsequently be exposed to radiation, for example electron beam, gamma, UV or X-Ray radiation.
• radiation for example electron beam, gamma, UV or X-Ray radiation.
• a thin film comprising one or more SBC compositions or miscible polymer blends wherein said thin film has a tensile strength of greater than 17 MPa measured according to ASTM 3577 and wherein said thin film is substantially insoluble in an organic solvent.
• substantially insoluble it may be meant, for example, that at least
• MMA methyl methacrylate
• diethyl ether methyl methacrylate
• an elastomeric styrenic block copolymer composition or miscible polymer blend wherein said composition has a tensile strength of at least 17 MPa and wherein said composition is substantially insoluble in an organic solvent
• substantially insoluble it may be meant, for example, that at least
• composition is insoluble, or at least 95% of the composition is insoluble in organic solvents that may be used in medical fields, such as methyl methacrylate (MMA) or diethyl ether.
• MMA methyl methacrylate
• diethyl ether diethyl ether
• a thin film comprising one or more
• compositions or miscible polymer blends according to any one of the herein disclosed embodiments.
• the thin film may have a thickness between about 10 microns and about 500 microns or between about 150 microns and about 250 microns.
• the thin film may have a thickness less than 500 microns, or less than 400 microns or less than 300 microns or less than 200 microns.
• a multilayer film comprising one or more layers or thin films, said one or more layers or thin films comprising the herein disclosed SBC compositions or miscible polymer blends.
• a multilayer film comprising one or more layers or thin films, said one or more layers or thin films comprising SBC compositions or miscible polymer blends, wherein said composition or miscible polymer blend has a tensile strength of at least 17 MPa and wherein said composition or miscible polymer blend is substantially insoluble in an organic solvent.
• the multilayer film may be obtained by superposition of several thin layers made from the same SBC composition, or different SBC compositions. Different SBC compositions as presently disclosed may be combined in different layers. Also, at least one layer having the presently disclosed compositions may be combined with other elastomer(s) 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 (CBC) and blends therefrom. It is understood that the nature of the elastomer(s) constituting each of the said layers may be identical to or different from each other.
• SBS, SEBS and butyl rubber are preferred constituents of a multilayer film.
• a multilayer glove comprising superposed layers made from the herein disclosed compositions and butyl rubber offers increased resistance to permeation of chemicals such as methyl methacrylate monomer.
• Such gloves may comprise, for example, a thin butyl rubber layer on the outside layer or/and sandwiched in the middle of other layers comprising the presently disclosed composition of SBC.
• Each of the layers comprising the thin-walled elastic film may also comprise other adjuvants conventionally used in the polymer industry and specifically in the glove industry, such as, for example, lubricants and anti-tack agents, anti-static agents, primary and secondary antioxidants, colorants, processing agents and so forth.
• an article of manufacture comprising one or more of the SBC compositions or miscible polymer blends as disclosed herein.
• the article of manufacture may be a medical device, such as medical glove, a condom or personal protective equipment, such as laboratory gloves or clean industry gloves.
• the film or multilayer film may also include active chemical substances.
• this active substance may be chosen as a function of the properties that are desired.
• This active chemical substance may be chosen especially from anticorrosion agents, lubricants, chemical markers, phase-change products, energetic-particle (radiation) decelerators, agents with disinfecting power, odoriferous agents or moisturizers, dyes for detecting cuts, metallic particles, and mixtures thereof.
• the active chemical substance is a product with disinfecting power
• it is preferably chosen from substances capable of causing a virtually instantaneous denaturation of proteins by simple contact, either by chemical reaction or by a physicochemical effect such as a modification of the surface tension.
• biocides such as quaternary ammoniums and more particularly dimethyldidecylammonium chloride and benzalkonium chloride
• biguanides such as water-soluble salts of chlorhexidine, for instance chlorhexidine digluconate, phthalaldehyde, phenolic derivatives such as hexachlorophene or benzylic derivatives, formaldehyde, nonionic surfactants comprising at least one polyoxyethylene sequence such as octoxynol (Triton®X100), hexamidine, iodinated polyvinylpyrrolidone compounds, nonionic surfactants with virucidal activity, sodium and potassium dichromates and hypochlorites, and mixtures thereof.
• compositions comprising SBCs capable of forming chemically and physically crosslinked thin-walled elastic articles with improved mechanical properties.
• an elastomeric styrenic block copolymer (SBC) composition comprising one or more SBCs and one or more polymers miscible with styrenic end blocks of the one or more SBCs; wherein said block copolymer composition is both physically and chemically crosslinked;
• said chemical crosslinking comprises covalent bonds between chains of SBC; wherein said 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;
• the one or more SBCs is selected from the group consisting of SIS,
• SBS SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS or a SBC functionalized with reactive groups grafted in the middle rubber block such as, for example, carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate and aziridine groups or mixtures thereof; and
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, coumarone-indene resin, polyindene resin, poly(methylindene) resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin, polyphenylene ether, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, rosin ester, styrenated terpenes, polyterpenes, terpene phenolics and mixtures thereof.
• an elastomeric styrenic block copolymer (SBC) composition comprising one or more SBCs and one or more polymers miscible with styrenic end blocks of the one or more SBCs;
• block copolymer composition is both physically and chemically crosslinked
• said chemical crosslinking comprises covalent bonds between chains of SBC; wherein said 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;
• the one or more SBCs is selected from the group consisting of SIS,
• SBS SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS or a SBC functionalized with reactive groups grafted in the middle rubber block such as, for example, carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate and aziridine groups or mixtures thereof; and
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, coumarone-indene resin, polyindene resin, poly(methylindene) resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin, polyphenylene ether, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, rosin ester, styrenated terpenes, polyterpenes, terpene phenolics and mixtures thereof, said SBCs having a molecular weight (Mn) above 100,000 g/mol and said miscible polymers having a molecular weight (Mn) less than 10,000 g/mol.
• an elastomeric styrenic block copolymer (SBC) composition comprising one or more SBCs and one or more polymers miscible with styrenic end blocks of the one or more SBCs;
• block copolymer composition is both physically and chemically crosslinked
• said chemical crosslinking comprises covalent bonds between chains of SBC; wherein said 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;
• At least one SBC comprises, in its elastomeric mid-block, reactive functionalities, such as double bonds, to enable chemical crosslinking;
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, coumarone-indene resin, polyindene resin, poly(methylindene) resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin, polyphenylene ether, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, rosin ester, styrenated terpenes, polyterpenes, terpene phenolics and mixtures thereof, said SBCs having a molecular weight (Mn) above 100,000 g/mol and said miscible polymers having a molecular weight (Mn) less than 10,000 g/mol.
• an elastomeric styrenic block copolymer (SBC) composition comprising one or more SBCs and one or more polymers miscible with styrenic end blocks of the one or more SBCs;
• block copolymer composition is both physically and chemically crosslinked
• said chemical crosslinking comprises covalent bonds between chains of SBC; wherein said 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;
• At least one SBC comprises, in its elastomeric mid-block, reactive functionalities, such as double bonds, to enable chemical crosslinking;
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, alphamethylstyrene resin, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene and mixtures thereof, said SBCs having a molecular weight (Mn) above 100,000 g/mol and said miscible polymers having a molecular weight (Mn) less than 10,000 g/mol.
• a miscible polymer blend comprising one or more SBCs and one or more polymers miscible with styrenic end blocks of the one or more SBCs;
• miscible polymer blend is both physically and chemically crosslinked; wherein said chemical crosslinking comprises covalent bonds between chains of SBC; wherein said 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;
• the one or more SBCs is selected from the group consisting of SIS,
• SBS SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS or a SBC functionalized with reactive groups grafted in the middle rubber block such as, for example, carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate and aziridine groups or mixtures thereof; and
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, coumarone-indene resin, polyindene resin, poly(methylindene) resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin, polyphenylene ether, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, rosin ester, styrenated terpenes, polyterpenes, terpene phenolics and mixtures thereof.
• a miscible polymer blend comprising one or more SBCs and one or more polymers miscible with styrenic end blocks of the one or more SBCs;
• miscible polymer blend is both physically and chemically crosslinked; wherein said chemical crosslinking comprises covalent bonds between chains of SBC; wherein said 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;
• the one or more SBCs is selected from the group consisting of SIS,
• a miscible polymer blend comprising one or more SBCs and one or more polymers miscible with styrenic end blocks of the one or more SBCs;
• miscible polymer blend is both physically and chemically crosslinked; wherein said chemical crosslinking comprises covalent bonds between chains of SBC; wherein said 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;
• At least one SBC comprises, in its elastomeric mid-block, reactive functionalities, such as double bonds, to enable chemical crosslinking;
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, coumarone-indene resin, polyindene resin, poly(methylindene) resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin, polyphenylene ether, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, rosin ester, styrenated terpenes, polyterpenes, terpene phenolics and mixtures thereof, said SBCs having a molecular weight (Mn) above 100,000 g/mol and said miscible polymers having a molecular weight (Mn) less than 10,000 g/mol.
• a miscible polymer blend comprising one or more SBCs and one or more polymers miscible with styrenic end blocks of the one or more SBCs;
• miscible polymer blend is both physically and chemically crosslinked; wherein said chemical crosslinking comprises covalent bonds between chains of SBC; wherein said 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;
• At least one SBC comprises, in its elastomeric mid-block, reactive functionalities, such as double bonds, to enable chemical crosslinking; and wherein the one or more miscible polymers is selected from the group consisting of polystyrene resin, alphamethylstyrene resin, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, and mixtures thereof, said SBCs having a molecular weight (Mn) above 100,000 g/mol and said miscible polymers having a molecular weight (Mn) less than 10,000 g/mol.
• an elastomeric styrenic block copolymer composition comprising:
• the one or more SBCs is selected from the group consisting of SIS,
• SBS SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS or a SBC functionalized with reactive groups grafted in the middle rubber block such as, for example, carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate and aziridine groups or mixtures thereof;
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, coumarone-indene resin, polyindene resin, poly(methylindene) resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin, polyphenylene ether, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, rosin ester, styrenated terpenes, polyterpenes, terpene phenolics and mixtures thereof; and
• the one or more cross-linking agents is selected from the group consisting of aromatic, aliphatic and heteroatomic monomers and oligomers containing at least two carbon-carbon double bonds, such as, for example: multifunctional 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), as well as other multifunctional compounds with vinyl or allyl groups, and mixtures thereof.
• multifunctional acrylates such as trimethyl
• an elastomeric styrenic block copolymer composition comprising: (a) one or more SBCs;
• the one or more SBCs is selected from the group consisting of SIS,
• SBS SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS or a SBC functionalized with reactive groups grafted in the middle rubber block such as, for example, carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate and aziridine groups or mixtures thereof;
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, coumarone-indene resin, polyindene resin, poly(methylindene) resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin, polyphenylene ether, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, rosin ester, styrenated terpenes, polyterpenes, terpene phenolics and mixtures thereof; and
• the one or more cross-linking agents is selected from the group consisting of aromatic, aliphatic and heteroatomic monomers and oligomers containing at least two carbon-carbon double bonds, such as, for example: multifunctional 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), as well as other multifunctional compounds with vinyl or allyl groups, and mixtures thereof, said SBCs having a molecular
• an elastomeric styrenic block copolymer composition comprising:
• cross-linking agents capable of inducing covalent bonding between chains of the one or more SBCs; wherein at least one SBC comprises, in its elastomeric mid-block, reactive functionalities, such as double bonds, to enable chemical crosslinking;
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, coumarone-indene resin, polyindene resin, poly(methylindene) resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin, polyphenylene ether, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, rosin ester, styrenated terpenes, polyterpenes, terpene phenolics and mixtures thereof; and
• the one or more cross-linking agents is selected from the group consisting of aromatic, aliphatic and heteroatomic monomers and oligomers containing at least two carbon-carbon double bonds, such as, for example: multifunctional acrylates, such as trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPT A), 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), as well as other multifunctional compounds with vinyl or allyl groups, and mixtures thereof, said SBCs having a molecular
• an elastomeric styrenic block copolymer composition comprising:
• At least one SBC comprises, in its elastomeric mid-block, reactive functionalities, such as double bonds, to enable chemical crosslinking;
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, alphamethylstyrene resin, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene and mixtures thereof; and wherein the one or more cross-linking agents is selected from the group consisting of aromatic, aliphatic and heteroatomic monomers and oligomers containing at least two carbon-carbon double bonds, such as, for example: multifunctional 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, pen
• the layers comprising the thin-walled elastic film may also comprise other adjuvants conventionally used in the polymer industry and specifically in the glove industry, such as, for example, lubricants, anti- tack agents, anti-static agents, primary and secondary antioxidants, colorants, processing agents and so forth.
• an elastomeric styrenic block copolymer composition comprising:
• the one or more SBCs is selected from the group consisting of SIS or SBS or mixtures thereof;
• At least one SBC comprises, in its elastomeric mid-block, reactive functionalities, such as double bonds, to enable chemical crosslinking;
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, alphamethylstyrene resin, copolymers of alkyi arene monomers such as alpha methyl styrene and para methyl styrene and mixtures thereof; and wherein the one or more cross-linking agents is 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, said SBCs having a molecular weight (Mn) above 100,000 g/mol and said miscible polymers having a molecular weight (Mn) less than 10,000 g/mol.
• a method of preparing a SBC composition comprising the step of: combining one or more SBCs, one or more polymers miscible with one or more polystyrene end blocks of the one or more SBCs; and one or more cross-linking agents capable of inducing covalent bonding between chains of the one or more SBCs;
• the one or more SBCs is selected from the group consisting of SIS,
• SBS SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS or a SBC functionalized with reactive groups grafted in the middle rubber block such as, for example, carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate and aziridine groups or mixtures thereof;
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, coumarone-indene resin, polyindene resin, poly(methylindene) resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin, polyphenylene ether, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, rosin ester, styrenated terpenes, polyterpenes, terpene phenolics and mixtures thereof; and
• the one or more cross-linking agents is selected from the group consisting of aromatic, aliphatic and heteroatomic monomers and oligomers containing at least two carbon-carbon double bonds, such as, for example: multifunctional 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), as well as other multifunctional compounds with vinyl or allyl groups, and mixtures thereof.
• multifunctional acrylates such as trimethyl
• a method of preparing a SBC composition comprising the step of: combining one or more SBCs, one or more polymers miscible with one or more polystyrene end blocks of the one or more SBCs; and one or more cross-linking agents capable of inducing covalent bonding between chains of the one or more SBCs;
• the one or more SBCs is selected from the group consisting of SIS,
• SBS SBS, SIBS, S-isobutylene-S, SEBS, SEPS, SEEPS or a SBC functionalized with reactive groups grafted in the middle rubber block such as, for example, carboxylic acid, amine, alcohol, maleic anhydride, epoxy, isocyanate and aziridine groups or mixtures thereof;
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, coumarone-indene resin, polyindene resin, poly(methylindene) resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin, polyphenylene ether, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, rosin ester, styrenated terpenes, polyterpenes, terpene phenolics and mixtures thereof; and
• the one or more cross-linking agents is selected from the group consisting of aromatic, aliphatic and heteroatomic monomers and oligomers containing at least two carbon-carbon double bonds, such as, for example: multifunctional 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), as well as other multifunctional compounds with vinyl or allyl groups, and mixtures thereof, said SBCs having a molecular
• a method of preparing a SBC composition comprising the step of: combining one or more SBCs, one or more polymers miscible with one or more polystyrene end blocks of the one or more SBCs; and one or more cross-linking agents capable of inducing covalent bonding between chains of the one or more SBCs;
• At least one SBC comprises, in its elastomeric mid-block, reactive functionalities, such as double bonds, to enable chemical crosslinking;
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, coumarone-indene resin, po!yindene resin, poly(methylindene) resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin, polyphenylene ether, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, rosin ester, styrenated terpenes, polyterpenes, terpene phenolics and mixtures thereof; and
• the one or more cross-linking agents is selected from the group consisting of aromatic, aliphatic and heteroatomic monomers and oligomers containing at least two carbon-carbon double bonds, such as, for example: multifunctional 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), as well as other multifunctional compounds with vinyl or allyl groups, and mixtures thereof, said SBCs having a molecular
• a method of preparing a SBC composition comprising the step of: combining one or more SBCs, one or more polymers miscible with one or more polystyrene end blocks of the one or more SBCs; and one or more cross-linking agents capable of inducing covalent bonding between chains of the one or more SBCs;
• At least one SBC comprises, in its elastomeric mid-block, reactive functionalities, such as double bonds, to enable chemical crosslinking;
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, alphamethylstyrene resin, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, and mixtures thereof; and wherein the one or more cross-linking agents is selected from the group consisting of aromatic, aliphatic and heteroatomic monomers and oligomers containing at least two carbon-carbon double bonds, such as, for example: multifunctional 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,
• a method of preparing a SBC composition comprising the step of: combining one or more SBCs, one or more polymers miscible with one or more polystyrene end blocks of the one or more SBCs; and one or more cross-linking agents capable of inducing covalent bonding between chains of the one or more SBCs;
• At least one SBC comprises, in its elastomeric mid-block, reactive functionalities, such as double bonds, to enable chemical crosslinking;
• the one or more miscible polymers is selected from the group consisting of polystyrene resin, alphamethylstyrene resin, copolymers of alkyl arene monomers such as alpha methyl styrene and para methyl styrene, and mixtures thereof; and wherein the one or more cross-linking agents is 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, said SBCs having a molecular weight (Mn) above 100,000 g/mol and said miscible polymers having a molecular weight (Mn) less than 10,000 g/mol.
• a method for producing an immersion article from at least one SBC composition or miscible polymer blend as disclosed in any one of the herein described exemplary embodiments in which a mold with an external contour which corresponds to that of the immersion article to be produced is immersed for a pre-specifiable period of time in an immersion solution comprising the one or more SBC compositions or miscible polymer blends, and where subsequently the immersion article is removed from the solution and dried.
• the article may subsequently be exposed to radiation, for example electron beam, gamma, UV or X-Ray radiation
• radiation for example electron beam, gamma, UV or X-Ray radiation
• a thin film comprising one or more SBC compositions or miscible polymer blends as disclosed in any one of the herein described exemplary embodiments wherein said thin film has a tensile strength of greater than 17 MPa measured according to ASTM 3577 and wherein said thin film is substantially insoluble in an organic solvent.
• a thin film comprising one or more SBC compositions or miscible polymer blends according to any one of the herein disclosed preferred embodiments.
• the thin film may have a thickness between about 10 microns and about 500 microns or between about 150 microns and about 250 microns.
• the thin film may have a thickness less than 500 microns, or less than 400 microns or less than 300 microns or less than 200 microns.
• an article of manufacture such as a glove or a condom, said article of manufacture comprising one or more SBC compositions or miscible polymer blends as disclosed in any one of the herein disclosed exemplary embodiments.
• the SBC compositions or miscible polymer blends according to the present disclosure may have a modulus at 100% elongation below 1.0 MPa or below 0.70 MPa.
• Thin-walled elastic articles according to the present disclosure may have a modulus at 100% elongation below 1.0 MPa or below 0.70 MPa.
• Thin-walled elastic articles according to the present disclosure may have a force at break compliant with EN455-2 and ISO10282, that is, above 9N (measured on unaged film).
• Thin-walled elastic articles according to the present disclosure may have a tensile strength compliant with ASTMD3577, that is, above 17 MPas (unaged film).
• compositions, or miscible polymer blends or thin-walled elastic articles may have any combination of the above disclosed mechanical properties.
• compositions in accordance with embodiments of the present disclosure are expressed in PHR (Per Hundred Rubber) with rubber being the one or more SBCs.
• PHR Per Hundred Rubber
• Exemplary ranges for components in the compositions include:
• Miscible polymer 0.25 to 100phr, preferably 5 to 50phr
• Plasticizer/Flexibilizer 0 to 200phr, preferably 20 to 75phr
• Cross-linking agent 0.01 to 5phr, preferably 0.05 to 1 phr
• Photo-initiator 0 to 5phr, preferably 0 to 2phr.
• Thin-walled elastic dipped articles for example gloves, particularly medical
• gloves, and condoms as disclosed herein may have a thickness in the range from between about 10 to about 500 microns or from about 150 to about 250 microns.
• the dipped articles may comprise a single layer or may be multilayered.
• the multilayered articles may comprise layers comprising the same polymer composition or different polymer compositions.
• SBS Styrene-butadiene-styrene copolymer
• plasticizer as a white mineral oil with a viscosity of 68 mPas at 40°C
• a crosslinking agent as trimethylpropane tris (3-mercaptopropionate) were dissolved in a mixture of methylcyclohexane and toluene (8:2) to form a solution having 18% solid content by weight.
• the amount of plasticizer was 50phr and 1 phr of polyphenolic antioxidant was added to the polymer solution.
• the solution was stored at ambient temperature in an appropriate vessel covered to prevent solvent evaporation. Films were obtained following solvent evaporation after dipping a porcelain mold into the solution using a dipping robot with controlled dipping speeds. The film was dried at 70°C for 1 hour before stripping and then a final drying at 50°C during 6 hours was performed to remove trace amounts of residual solvent.
• the film was then exposed to electron beam radiation at a dose of 25 ⁇ 2 kGy.
• the SBC composition was intended to be used for a glove so the following tests were employed to assess the chemical resistance of the film: - 1 ) swab test: 0.5g of pure methyl methacrylate monomer was deposited on a cotton swab which was then applied on a film previously brought under slight tension. The contact time was 10 seconds, under slight pressure. The test was repeated three times and then the film resistance was checked.
• the minimum limit of tensile strength is 17 MPa.
• the example indicates that a composition combining a SBC, a
• cross-linker and a miscible polymer exhibits a greater mechanical performance than:
• Reference 3 also indicates a significantly improved chemical resistance as compared with references 1 or 2.
• the reference 3 glove is the only sample that passes the ASTM specifications regarding tensile strength.
• SIS Styrene-lsoprene-Styrene copolymer
• the crosslinking agent is trimethylolpropane trimethacrylate used at a quantity of 1 phr.
• the films were obtained following solvent evaporation then dried to remove any traces of residual solvent before exposure to electron beam radiation at a dose of 50 ⁇ 3 kGy.
• the mechanical properties of the film is 17.1 MPa, with excellent chemical resistance on swab test.
• a multilayer film was produced using the following combinations of polymers:
• SEBS Styrene-Ethylene/Butylene-Styrene
• This SEBS has a radial structure with a viscosity of 75cp in toluene at 5% and contains 31 % of Polystyrene.
• the crosslinking agent is trimethylpropane tris (3-mercaptopropionate) at a quantity of 0.2phr.
• the multilayer film is exposed to electron-beam at 40kGy ⁇ 3.
• ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.

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