# US 9,752,017 B2 · Air permeation resistant film and pneumatic tire > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,752,017 B2 - Document ID: US9752017B2 - Status: Granted - Kind: B2 - Application number: 14/346,142 - Filed: 2011-09-21 - Published: 2014-08-28 - Granted: 2017-09-05 - Earliest claimed: 2011-09-21 - Assignees: Toyo Tire & Rubber Co., Ltd.; Toyobo Co., Ltd. - Applicants: Toshiki Shimizu; Shigenori Inata; Tomohiko Kurahashi; Junzo Matsuno; Tatsuya Endo; Shigeo Ukyo; Momoko Daitoku - Inventors: Toshiki Shimizu; Shigenori Inata; Tomohiko Kurahashi; Junzo Matsuno; Tatsuya Endo; Shigeo Ukyo; Momoko Daitoku - Web page: https://patentgrep.com/patent/US9752017B2 ## CPC - C08L 15/00: Compositions of rubber derivatives (C08L11/00, C08L13/00 take precedence) - B29D 30/0681: {Parts of pneumatic tyres; accessories, auxiliary operations} - B60C 1/0008: {Compositions of the inner liner} - B60C 5/14: with impervious liner or coating on the inner wall of the tyre - C08J 5/18: Manufacture of films or sheets - C08L 21/00: Compositions of unspecified rubbers - C08L 23/0884: Epoxide-containing esters - C08L 67/00: Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain (of polyester-amides C08L77/12; of polyester-imides C08L79/08); Compositions of derivatives of such polymers - C08L 67/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds (C08L67/06 takes precedence) - C08L 67/025: {containing polyether sequences} - C08L 69/005: {Polyester-carbonates} - B29D 2030/0682: {Inner liners} - C08J 2321/00: Characterised by the use of unspecified rubbers - C08J 2367/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds; (C08J2367/06 takes precedence) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - B29D: PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE (making granules B29B9/00; making preforms B29B11/00) - B60C: VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES - 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) ## Abstract Provided is an air permeation resistant film in which flexibility can be imparted to the film without remarkably increasing the proportion of a rubber constituting a dispersed phase. An air permeation resistant film comprising (A) a thermoplastic polyester elastomer which comprises a block copolymer containing a polyester as a hard segment and has a melting point of from 180 to 230° C., and (B) a rubber, in a mass ratio (A)/(B) of from 90/10 to 40/60, wherein the component (A) and the component (B) are melt-kneaded to perform dynamic crosslink, thereby forming a continuous phase composed of the component (A) and a dispersed phase composed of the component (B), and the film has an air permeation coefficient at 80° C. of 5×1013 fm2/Pa·s or less and Young's modulus of 120 MPa or less. ## Claims ### Claim 1 An air permeation resistant film consisting essentially of: (A) a thermoplastic polyester elastomer which is a block copolymer containing a hard segment and a soft segment, and has a melting point of from 180 to 230° C., and (B) at least one rubber, in a mass ratio (A)/(B) of from 90/10 to 40/60, wherein the component (A) and the component (B) are melt-kneaded to perform dynamic crosslink, thereby forming a continuous phase composed of the component (A) and a dispersed phase composed of the component (B), wherein the hard segment comprises polybutylene terephthalate, wherein the soft segment comprises aliphatic polycarbonate, the film has an air permeation coefficient at 80° C. of 5×1013 fm2/Pa·s or less and Young's modulus of 120 MPa or less, wherein a number average molecular weight of aliphatic polycarbonate diol, which is a raw material of the aliphatic polycarbonate, is from 3,000 to 60,000. ### Claim 2 (depends on 1) The air permeation resistant film according to claim 1, wherein the component (B) is at least one rubber selected from butyl rubber, halogenated butyl rubber, nitrile rubber and hydrogenated nitrile rubber. ### Claim 3 (depends on 1) The air permeation resistant film according to claim 1, wherein the component (A) has an air permeation coefficient at 80° C. of 5×1013 fm2/Pa·s or less and Young's modulus of from 100 to 500 MPa, and the component (B) has Young's modulus of 50 MPa or less. ### Claim 4 (depends on 1) The air permeation resistant film according to claim 1, which further contains a compatibilizing agent. ### Claim 5 (depends on 4) The air permeation resistant film according to claim 4, wherein the compatibilizing agent has an ethylene main chain framework and a side chain containing an epoxy group. ### Claim 6 (depends on 1) The air permeation resistant film according to claim 1, further contains a crosslinking agent for dynamically crosslinking the at least one rubber of component (B), wherein the crosslinking agent is a phenolic resin. ### Claim 7 (depends on 1) The air permeation resistant film according to claim 1, wherein a mass ratio of the hard segment to the soft segment is from 45/55 to 87/13. ### Claim 8 (depends on 1) The air permeation resistant film according to claim 1, wherein the mass ratio (A)/(B) is from 90/10 to 50/50. ### Claim 9 (depends on 1) The air permeation resistant film according to claim 1, wherein the hard segment is polybutylene terephthalate, and the soft segment is aliphatic polycarbonate. ### Claim 10 (depends on 1) The air permeation resistant film according to claim 1, wherein the aliphatic polycarbonate diol is produced from carbonate ester and aliphatic glycol having from 2 to 12 carbon atoms. ### Claim 11 (depends on 1) A pneumatic tire having the air permeation resistant film according to claim 1 as an inner liner or other air permeation inhibiting layer. ### Claim 12 A method for producing an air permeation resistant film, which comprises melt-kneading a composition consisting essentially of (A) a thermoplastic polyester elastomer that is a block copolymer containing a hard segment and a soft segment, and has a melting point of from 180 to 230° C., and (B) at least one a rubber, in a mass ratio (A)/(B) of from 90/10 to 40/60 to perform dynamic crosslink, thereby obtaining a polymer composition comprising a continuous phase composed of the component (A) and a dispersed phase composed of the component (B), and forming a film comprising the polymer composition, wherein the hard segment comprises polybutylene terephthalate, wherein the soft segment comprises aliphatic polycarbonate, and wherein a number average molecular weight of aliphatic polycarbonate diol, which is a raw material of the aliphatic polycarbonate, is from 3,000 to 60,000. ### Claim 13 (depends on 12) The production method according to claim 12, wherein the air permeation resistant film has an air permeation coefficient at 80° C. of 5×1013 fm2/Pa·s or less and Young's modulus of 120 MPa or less. ### Claim 14 (depends on 12) The production method according to claim 12, wherein the component (A) has an air permeation coefficient at 80° C. of 5×1013 fm2/Pa·s or less and Young's modulus of from 100 to 500 MPa, and the component (B) has Young's modulus of 50 MPa or less. ### Claim 15 (depends on 12) The production method according to claim 12, which comprises mixing a compatibilizing agent together with the component (A) and the component (B). ### Claim 16 (depends on 15) The production method according to claim 15, wherein the compatibilizing agent has an ethylene main chain framework and a side chain containing an epoxy group. ### Claim 17 (depends on 12) The production method according to claim 12, comprising adding a crosslinking agent for dynamically crosslinking the rubber of component (B), wherein the crosslinking agent is a phenolic resin. ### Claim 18 (depends on 12) The production method according to claim 12, wherein the mass ratio (A)/(B) is from 90/10 to 50/50. ### Claim 19 (depends on 12) The production method according to claim 12, wherein the hard segment is polybutylene terephthalate, and the soft segment is aliphatic polycarbonate. ### Claim 20 (depends on 12) The production method according to claim 12, wherein the aliphatic polycarbonate diol is produced from carbonate ester and aliphatic glycol having from 2 to 12 carbon atoms. ### Claim 21 (depends on 12) The production method according to claim 12, wherein the component (B) is at least one rubber selected from butyl rubber, halogenated butyl rubber, nitrile rubber and hydrogenated nitrile rubber. ### Claim 22 (depends on 12) A method for producing a pneumatic tire, which comprises obtaining an air permeation resistant film by the production method according to claim 12, preparing a cylindrical inner liner comprising the air permeation resistant film, fixing a carcass ply and other rubber members including a tread rubber to an outer peripheral side of the inner liner to prepare a green tire, and vulcanization molding the green tire in a mold.