# US 11,898,030 B2 · Crosslinked styrenic block copolymer > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,898,030 B2 - Document ID: US11898030B2 - Status: Granted - Kind: B2 - Application number: 16/619,115 - Filed: 2018-05-28 - Published: 2020-04-02 - Granted: 2024-02-13 - Earliest claimed: 2017-06-06 - Assignees: Top Glove Global Sdn Bhd - Applicants: Top Glove Global Sdn Bhd - Inventors: Sebastien Treilhes; Pierre Hoerner; Chin Guan Low - Web page: https://patentgrep.com/patent/US11898030B2 ## CPC - C08L 53/02: of vinyl-aromatic monomers and conjugated dienes - B32B 7/02: Physical, chemical or physicochemical properties - B32B 25/042: {of natural rubber or synthetic rubber} - B32B 25/12: comprising natural rubber - B32B 25/14: comprising {synthetic rubber copolymers (B32B25/18 and B32B25/20 take precedence)} - B32B 25/16: comprising polydienes {homopolymers} or poly-halodienes {homopolymers (B32B25/12 takes precedence)} - B32B 25/20: comprising silicone rubber - B32B 27/08: of synthetic resin - B32B 27/22: using plasticisers - B32B 27/285: {comprising polyethers} - B32B 27/30: comprising vinyl {(co)polymers; comprising acrylic (co)polymers} - B32B 27/302: {comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers} - B32B 27/36: comprising polyesters - B32B 27/42: comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines - C08J 3/242: {Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements} - C08L 25/06: Polystyrene - A61B 42/10: Surgical gloves - A61B 2017/00526: {Methods of manufacturing} - A61F 6/04: Condoms, sheaths or the like {, e.g. combined with devices protecting against contagion} - A61F 6/06: for use by females (A61F6/20 takes precedence) - B32B 2270/00: Resin or rubber layer containing a blend of at least two different polymers - B32B 2307/50: having particular mechanical properties - B32B 2307/51: Elastic - B32B 2307/54: Yield strength; Tensile strength - B32B 2307/546: Flexural strength; Flexion stiffness - B32B 2307/714: Inert, i.e. inert to chemical degradation, corrosion - B32B 2307/732: Dimensional properties - B32B 2437/02: Gloves, shoes - B32B 2535/00: Medical equipment, e.g. bandage, prostheses or catheter - B32B 2571/00: Protective equipment - C08K 3/011: Crosslinking or vulcanising agents, e.g. accelerators - C08K 3/06: Sulfur - C08K 5/0016: {Plasticisers} - C08K 5/0025: {Crosslinking or vulcanising agents; including accelerators} - C08K 5/5397: Phosphine oxides - C08L 2203/16: used for films - C08L 2312/06: by radiation - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - A61B: DIAGNOSIS; SURGERY; IDENTIFICATION (usefulness limited to only animals A61D) - A61F: FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS (dental prosthetics A61C) - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) ## Abstract Elastomeric styrenic block copolymer (SBC) 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 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. The block copolymer compositions are useful in forming immersion articles such as surgical gloves. ## Claims ### Claim 1 An elastomeric styrenic block copolymer (SBC) composition comprising one or more SBCs and one or more polymers having a molecular weight polydispersity index greater than 2.0 miscible with styrenic end blocks of the one or more SBCs; wherein said block copolymer composition is both physically and chemically crosslinked; wherein said chemical crosslinking comprises covalent bonds between chains of SBC and; 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. ### Claim 2 (depends on 1) The composition according to claim 1, further comprising one or more plasticizers and/or flexibilizers compatible with an elastomeric mid-block of the one or more SBCs. ### Claim 3 (depends on 2) The composition according to claim 2, wherein the plasticizer comprises a liquid or a mixture of liquid saturated polyolefins compatible with the midblock (elastomeric block) of the SBC. ### Claim 4 (depends on 2) The composition according to claim 2, wherein the plasticizer comprises plasticizing oils. ### Claim 5 (depends on 2) The composition according to claim 2, wherein the flexibilizer is selected from polybutadiene, polyisoprene, polyisobutene, amorphous polyolefin copolymers of propylene and ethylene, butyl rubber and other elastomers known to have a sufficient compatibility with the elastomeric block. ### Claim 6 (depends on 1) The composition according to claim 1, wherein, independently, the one or more SBCs comprise a fully unsaturated or fully saturated elastomeric mid-block. ### Claim 7 (depends on 6) The composition according to claim 6, wherein the one or more SBCs comprise a fully saturated elastomeric mid-block, said fully saturated elastomeric mid-block being cleavable when exposed to radiation. ### Claim 8 (depends on 1) The composition according to claim 1, wherein the one or more SBCs is 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. ### Claim 9 (depends on 1) The composition according to claim 1, wherein the one or more SBCs has a molecular weight (Mn) above 100,000 g/mol. ### Claim 10 (depends on 1) The composition according to claim 1, wherein at least one SBC has an elastomeric mid-block containing reactive functionalities. ### Claim 11 (depends on 1) The composition according to claim 1, wherein the number average molecular weight of the miscible polymer (Mn) is below 10,000 g/mol. ### Claim 12 (depends on 1) The composition according to claim 1, wherein the one or more miscible polymers have a molecular weight polydispersity index greater than 5.0. ### Claim 13 (depends on 1) The composition according to claim 1, wherein the miscible polymer 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. ### Claim 14 (depends on 1) The composition according to claim 1, wherein at least one SBC comprises, in its elastomeric mid-block, double bonds, to enable chemical crosslinking; and wherein 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, 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. ### Claim 15 (depends on 1) The composition according to claim 1, wherein the block copolymer composition is crosslinked using a crosslinking agent is selected from the group consisting of multifunctional acrylates, functional thiols, as well as other multifunctional compounds with vinyl or allyl groups, and mixtures thereof. ### Claim 16 (depends on 1) The composition according to claim 1, wherein the block copolymer composition is crosslinked using a crosslinking agent is a metal salt, an amine cross-linker selected from the group consisting of organic amine, organic diamine and organic polyamine or a polyol. ### Claim 17 (depends on 1) The composition according to claim 1, wherein the block copolymer composition is crosslinked using a crosslinking agent is selected from conventional sulphur, metallic oxides and accelerators commonly utilized for vulcanization of rubber. ### Claim 18 (depends on 1) The composition according to claim 1, wherein the block copolymer composition is crosslinked using a cross-linker is selected from di-thiol, tri-thiol and tetra-thiol molecules containing ether or ester groups in their backbone. ### Claim 19 (depends on 1) The composition according to claim 1, further comprising an adjuvant. ### Claim 20 (depends on 1) An article of manufacture comprising one or more of the elastomeric SBC compositions according to claim 1. ### Claim 21 (depends on 20) The article of manufacture according to claim 20, wherein the article is a medical device, or personal protective equipment. ### Claim 22 (depends on 1) A method of preparing the elastomeric SBC composition according to claim 1 comprising the step of: combining the one or more SBCs, the one or more polymers having a molecular weight polydispersity index greater than 2.0 miscible with the 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. ### Claim 23 (depends on 22) The method according to claim 22, wherein the composition is cross-linked by the application of radiation. ### Claim 24 (depends on 22) The method according to claim 22, wherein the crosslinking reaction is initiated or enhanced by one or a mixture of radical-type photo-initiators. ### Claim 25 (depends on 24) The method according to claim 24, wherein the crosslinking photo-initiators are selected from the group consisting of acylphosphine oxides. ### Claim 26 (depends on 1) A method for producing an immersion article from at least one elastomeric SBC composition according to claim 1, 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 elastomeric SBC compositions, and where subsequently the immersion article is removed from the solution and dried. ### Claim 27 (depends on 26) The method according to claim 26 further comprising exposing the dried article to radiation. ### Claim 28 (depends on 1) A thin film comprising one or more elastomeric SBC compositions according to claim 1, wherein said thin film has a tensile strength of greater than 17 MPa when evaluated according to ASTM 3577 and wherein said thin film is substantially insoluble in an organic solvent. ### Claim 29 (depends on 28) The thin film according to claim 28, wherein at least 80% of the thin film is insoluble, or at least 95% of the film is insoluble in an organic solvent. ### Claim 30 (depends on 28) The thin film according to claim 28, wherein the film has a thickness between about 10 microns and about 500 microns. ### Claim 31 (depends on 28) The thin film according to claim 28, wherein the film has a thickness between about 150 microns and about 250 microns. ### Claim 32 (depends on 28) A multilayer film, said multilayer film comprising several thin films according to claim 28. ### Claim 33 (depends on 1) A multilayer film, said multilayer film comprising one or more layers, said one or more layers comprising one or more elastomeric SBC compositions according to claim 1, wherein said one or more elastomeric SBC compositions has a tensile strength of at least 17 MPa. ### Claim 34 (depends on 33) The multilayer film according to claim 33, wherein at least one layer is 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. ### Claim 35 A miscible polymer blend comprising one or more SBCs and one or more polymers having a molecular weight polydispersity index greater than 2.0 miscible with styrenic end blocks of the one or more SBCs; wherein said miscible polymer blend is both physically and chemically crosslinked; wherein said chemical crosslinking comprises covalent bonds between chains of SBC and; 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.