JP2009528178A - Structure containing tie layer - Google Patents

Abstract

  This disclosure relates to a vulcanizable layered composition comprising at least two layers and at least one tie layer. The first of the two layers includes a fluid permeation prevention layer and the second of the two layers includes at least one high diene rubber. The tie layer comprises an appropriate amount in parts by weight per 100 parts by weight of rubber: (1) epoxidized natural rubber, (2) at least one high diene elastomer, (3) at least one filler, (4) at least Contains a mixture of one tackifier and (5) a curing system for rubber. The fluid permeation prevention layer preferably comprises (A) at least one thermoplastic engineering resin component, preferably one or more nylon resins and (B) at least one elastomer component, preferably brominated isobutylene p-methyl. A styrene copolymer, wherein the total amount of component (A) and component (B) is 30% by weight or more, and (B) is in a vulcanized or partially vulcanized state as a discontinuous phase , Dispersed in the matrix of component (A).

Description

Cross Reference to Related Applications This patent application includes PCT patent applications filed September 29, 2006 (unnumbered, Aoki's Ref. YR. EXOC-S835-PCT) and PCT / PC applications filed October 27, 2005. Claims the benefit of US 2005/38705, the disclosure of which is incorporated herein by reference.
The present invention relates to compositions useful in multilayer structures, such as tire structures, and in particular to tire tie layers between an innerliner and a carcass. In particular, the present disclosure relates to rubber compositions using blends of high diene containing elastomers or rubbers, such as natural rubber (NR) and styrene butadiene rubber (SBR), and epoxidized natural rubber.

  A carcass layer containing a textile or steel cord to prevent a strike-through of the tire cord, i.e., a condition where the reinforced tire cord penetrates the inner liner layer and leads to air leakage and tire breakage; It is common practice to add a buffer layer between the innerliner layer. This buffer layer is referred to as a tie rubber, tie layer, cushion compound or liner backing layer and typically contains a blend of natural rubber (NR) and styrene butadiene rubber (SBR). For purposes of this disclosure, this tire component is referred to as a “tie layer”. Typically, the composition of the tie layer provides the necessary tack formation to maintain a coherent tire structure in uncured or “green” state, cured adhesion and satisfactory dynamic properties during tire use. It is similar to the composition of carcass compound to give. However, general-purpose tie layers based on NR and SBR, for example, provide sufficient adhesion between the vulcanized blended thermoplastic elastomer tire innerliner composition and carcass layer of halogenated isobutylene including engineering resins and elastomers. Can not give vulcanized adhesion. The present disclosure relates to a general innerliner composition based on a halogenated isobutylene-containing elastomer component, as well as an engineering resin produced by using, for example, dynamic vulcanization, as disclosed in US Pat. For example, it is useful in tires using a thermoplastic elastomeric tire innerliner composition based on a vulcanized blend of polyamide and BIMS. Accordingly, the present disclosure is accomplished by an innerliner on a tire carcass with a layer based on a dynamically vulcanized alloy of a polyamide and a brominated copolymer of isobutylene-para-methylstyrene, such as an innerliner composition. A tie layer is provided that is suitable for adhering without compromising the improved permeability characteristics. This can also hold, for example, gases or liquids where the air or fluid retention layer is used in combination with other layers, especially when the other layers contain reinforcing fibers or cords. It is also useful in the necessary hoses and other containers.

  Patent Document 2 discloses a thermoplastic polyester comprising a block copolymer of polybutylene terephthalate and polyoxyalkylene diimide diacid at a weight ratio of at least 20% by weight of polybutylene terephthalate / polyoxyalkylene diimide diacid of 85/15 or less. A pneumatic tire having an air permeation preventive layer or an inner liner layer composed of a thin film of a resin composition containing an elastomer is disclosed. The resin composition may further contain dispersed and dynamically vulcanized rubber particles. The concept of using a resin composition as the inner liner layer was further developed by various inventors of the same assignee. See, for example, U.S. Patent No. 6,057,037, which claims a pneumatic tire including such an inner liner and discloses the use of various thermoplastic resins for use in the composition. This patent also discloses the presence of tie layers and other layers to promote the bonding or adhesive strength of the innerliner layer in the overall structure. Further development of the technology for improving the adhesion of the inner liner layer in the structure is described in Patent Document 4, and in Patent Document 4, the melt viscosity and solubility of the thermoplastic resin component and the elastomer component are described. The parameter is controlled according to a specific mathematical formula.

  Patent Document 5 describes a carcass comprising a ply of cord defining an innermost reinforcing cord layer extending between bead portions and along the inner surface of the tire, covering substantially the entire inner surface of the tire. Disclosed is a pneumatic tire comprising a hermetic layer disposed inside a carcass ply cord, wherein the hermetic layer comprises at least 10 wt% halogenated butyl rubber and / or halogenated isobutylene in its rubber base. The thickness of the hermetic layer, produced from an air-impermeable rubber containing paramethylstyrene copolymer and measured from the inner surface of the tire towards the carcass ply cord, is in the range of 0.2-0.7 mm is there. This patent also describes an “airtight layer” defined by a rubber layer between the tire inner surface and the innermost tire cord or carcass cord, the inner layer of the air impermeable rubber compound and the air impermeable. It is disclosed that it may be a bilayer consisting of an outer layer of a diene rubber that is not.

  Alternatively, the outer layer may be of the same air impermeable rubber compound or similar air impermeable rubber compound, which is further described in this patent document as halogenated butyl rubber and / or halogen. Isobutylene-paramethylstyrene copolymer and diene rubber and carbon black (see paragraphs 28-34).

  Other documents of interest include Patent Literature 6, Patent Literature 7, Patent Literature 8, Patent Literature 9, Patent Literature 10, Patent Literature 11, Patent Literature 12, Patent Literature 13, and Patent Literature 3.

European Patent 0 722 850 US Pat. No. 5,738,158 US Pat. No. 6,079,465 US Pat. No. 6,062,283 US Patent Application Publication No. 2002/0066512 International Patent Application Publication No. 2004/081107 International Patent Application Publication No. 2004/081106 International Patent Application Publication No. 2004/081108 International Patent Application Publication No. 2004/081116 International Patent Application Publication No. 2004/081099 JP 200023188 European Patent No. 01 424 219 US Pat. No. 6,759,136

Some aspects of this disclosure are vulcanizable layered compositions including at least two layers and at least one tie layer, wherein the first of the two layers includes a fluid permeation prevention layer. The second layer of the two layers comprises at least one high diene rubber, and the tie layer is based on 100 parts by weight of rubber in the mixture,
(1) about 10 to about 70 parts by weight of epoxidized natural rubber,
(2) about 30 to about 90 parts by weight of at least one high diene elastomer;
(3) about 20 to about 90 parts by weight of at least one filler;
(4) about 1 to about 20 parts by weight of at least one tackifier, and (5) at least about 0.2 to about 15 parts by weight of a mixture of said elastomer and rubber curing system, said fluid permeation prevention The layer comprises a polymer composition having an air permeability coefficient of 25 × 10 ⁻¹² cc · cm / cm ² sec cmHg (30 ° C.) or lower and a Young's modulus of 1 to 500 MPa, wherein the polymer composition comprises:
(A) at least 10% by weight based on the total weight of the polymer composition, at least one air permeability coefficient of 25 × 10 ⁻¹² cc · cm / cm ² sec cmHg (30 ° C.) or lower and less than 500 MPa Thermoplastic engineering resin component having a large Young's modulus (this resin component is selected from the group consisting of polyamide resin, polyester resin, polynitrile resin, polymethacrylate resin, polyvinyl resin, cellulose resin, fluororesin and imide resin) and ( B) at least 10% by weight based on the total weight of the polymer composition, at least one air permeability coefficient greater than 25 × 10 ⁻¹² cc · cm ² / cm ² sec cmHg (30 ° C.) and 500 MPa or less Elastomer component with Young's modulus (this elastomer component is diene And hydrides thereof, selected from the group consisting of halogen-containing rubbers, silicone rubbers, sulfur-containing rubbers, fluororubbers, hydrin rubbers, acrylic rubbers, ionomers and thermoplastic elastomers, and component (A) and component (B ) Is 30% by weight or more based on the total weight of the polymer composition, and the elastomer component (B) is a vulcanized or partially vulcanized state as a discontinuous phase. In order to produce an acceptable multilayered structure, the amount and type of the at least one tackifier dispersed in the matrix of the thermoplastic resin component (A) in the proper adhesion between the layers Sufficient to allow assembly of the multi-layer structure without substantial delamination of the tie layer with respect to adjacent layers prior to cross-linking. The present invention relates to a structure that is effective for providing an uncured adhesive strength.

  In a preferred aspect, the present disclosure provides a tire that includes a carcass, an inner liner, and a tie layer between the inner liner and the carcass, wherein the inner liner includes a thermoplastic engineering resin, an isoolefin, and a halogen of para-alkylstyrene. Relates to a tire comprising a dynamically vulcanized alloy with a vulcanized copolymer and a tie layer comprising epoxidized natural rubber, natural rubber and a mixed tackifier. In another aspect, the present disclosure is directed to a hose comprised of this improved vulcanizable layered structure.

  The present disclosure provides a relatively impermeable tie layer between an innerliner and a carcass for tire weight reduction while maintaining the heat resistance, durability and flexibility required for a pneumatic tire. The present invention relates to a rubber composition. The present disclosure is also directed to reducing the permeability of a tie layer having improved durability while maintaining its excellent adhesion to the carcass and inner liner and / or its fatigue resistance.

  The new numbering system for the periodic table family used herein is that disclosed in CHEMICAL AND ENGINEERING NEWS, Vol. 63 (5), p. 27 (1985). All molecular weights are weight average molecular weights unless otherwise indicated.

  Polymer can be used to refer to homopolymers, copolymers, interpolymers, terpolymers, and the like. Similarly, a copolymer can refer to a polymer consisting of at least two monomers, optionally with other monomers.

  When a polymer is referred to as comprising a monomer, the monomer is present in the polymer in the polymerized form of the monomer or in the derivative form of the monomer. However, for ease of reference, the phrase “comprising (respectively) monomers” etc. is used as an abbreviation. Similarly, when a catalyst component is described as consisting of a neutral stable form of the component, it is well understood by those skilled in the art that the active form of the component is the form that reacts with the monomer to produce the polymer. .

  Isoolefin refers to any olefin monomer having two substituents on the same carbon.

  Multiolefin refers to any monomer having two or more double bonds. In some embodiments, the multiolefin is any monomer that contains two double bonds, preferably two conjugated double bonds, eg, a conjugated diene such as isoprene.

  As used herein, elastomer (s) refers to any polymer or composition of polymers consistent with ASTM D1566 definition. This term can be used interchangeably with the term “rubber (s)”.

Alkyl refers to a paraffinic hydrocarbon group, such as a methyl group (CH ₃ ) or an ethyl group (CH ₃ CH ₂ ), which can be derived from an alkane by dropping one or more hydrogens from the formula. .

Aryl refers to a hydrocarbon group that forms a ring structure characteristic of an aromatic compound such as benzene, naphthalene, phenanthrene, anthracene, etc., and typically has alternating double bonds (“unsaturated”) in the structure. . An aryl group thus, by dropping one or more hydrogens from the formula, a group derived from an aromatic compound, for example, phenyl or C ₆ H _5.

  “Substituted” means that at least one hydrogen group is, for example, halogen (chlorine, bromine, fluorine or iodine), amino, nitro, sulfoxy (sulfonate or alkyl sulfonate), thiol, alkyl thiol and hydroxy; alkyl, carbon number 1-20 straight chain or branched chain (including methyl, ethyl, propyl, tert-butyl, isopropyl, isobutyl, etc.); alkoxy, 1-20 carbon straight chain or branched chain alkoxy such as methoxy, ethoxy , Propoxy, isopropoxy, butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy; haloalkyl (which contains at least one Containing halogen Means a linear or branched alkyl having 1 to 20 carbon atoms, such as chloromethyl, bromomethyl, fluoromethyl, iodomethyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 3-chloropropyl, 3-bromopropyl , 3-fluoropropyl, 4-chlorobutyl, 4-fluorobutyl, dichloromethyl, dibromomethyl, difluoromethyl, diiodomethyl, 2,2-dichloroethyl, 2,2-dibromoethyl, 2,2-difluoroethyl, 3,3 -Dichloropropyl, 3,3-difluoropropyl, 4,4-dichlorobutyl, 4,4-difluorobutyl, trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,3,3-trifluoro Propyl, 1,1,2,2-tetrafluoroethyl and 2, Refers to are replaced by at least one substituent selected from including) 3,3 tetrafluoropropyl. Thus, for example, “substituted styrene units” include p-methylstyrene, p-ethylstyrene, and the like.

  In various preferred embodiments, the present disclosure provides at least one thermoplastic engineering resin as a continuous phase (also referred to as “engineering resin” or “thermoplastic resin”) and vulcanized as a dispersed phase ( (Or partly vulcanized) directed to a layered structure comprising a layer comprising an elastomer. Such a composition is produced, for example, by using a technique known as dynamic vulcanization, and the resulting composition is known as a dynamically vulcanized alloy (DVA), which Details of such compositions and their method of manufacture are described herein. This structure further comprises (a) a high diene rubber, such as natural rubber and / or styrene butadiene rubber, (b) a halogenated elastomer or a layer of elastomer composition comprising a mixture of (a) and (b) Further described in the specification). Each of these layers typically has additional components such as reinforcements and process aids such as carbon black and / or each exfoliated, intercalated or Contains simply dispersed clay and rubber process oils. High diene rubber-containing layers are typically made by standard rubber compounding methods and contain a curing agent or curing system so that the composition is vulcanizable. Between the two layers is a tie layer (which is so named because it ties the two layers together). This is also preferably a vulcanizable composition containing at least one reinforcing filler and optional additives such as process aids, and for the purposes of this disclosure, the tie layer is Includes halogenated isobutylene-containing elastomers. The thermoplastic engineering resin layer of the present disclosure may be comprised of at least one reinforcing filler and other components so that it functions to prevent the permeation of fluids through it. In connection with its use in pneumatic tires, this typically functions as a liner on the innermost surface of the tire structure and is referred to as the inner liner in the tire industry. Its composition and manufacturing method is designed by the rubber compounder to prevent the passage of air or oxygen through the layers and maintain tire pressure over a long period of time.

  When an engineering resin-containing layer is used as a layer (typically the innermost layer) of the hose structure, it will also prevent the passage of fluid therethrough. Such fluids may include air, oxygen and other gases and liquids such as water and industrial liquids. The nature of the contained fluid will dictate the choice of components of the engineering resin-containing layer, including the choice of vulcanizable rubber used to produce the DVA composition. Such selection is well known to those skilled in the formulation arts in the hose industry.

  When the engineering resin-containing layer is used as a tire inner liner, the tire inner liner composition of the present disclosure is used for power vehicle tires such as truck tires, bus tires, passenger cars, motorcycle tires, moped tires, rough terrain vehicle tires, and the like. It can be used when manufacturing the inner liner. Furthermore, such layers can be used in tires intended for non-powered vehicles, for example bicycles.

  The first layer in the structure, or fluid permeation prevention layer, is typically a dynamically vulcanized alloy (DVA) composition as described in detail below, typically a sheet or Although present in the form of a film, it can be present in the form of a tubular layer of a hose structure.

  The second layer (eg film or sheet or tire carcass layer) in the structure is typically a composition comprising a high diene rubber. Such a second layer may be a tubular layer of a hose structure. This layer may also contain reinforcing fibers such as tire cords, carbon black or other suitable reinforcements useful in tire or hose applications.

  The tie layer typically exists as a sheet or film formed, for example, by use of extrusion or calendering.

Halogenated rubber is defined as a rubber having at least about 0.1 mole percent halogen, such halogen being selected from the group consisting of bromine, chlorine and iodine. Preferred halogenated rubbers useful in the present disclosure include halogenated isobutylene-containing elastomers (referred to as halogenated isobutylene homopolymers or copolymers). These elastomers can be described as random copolymers of C _{4 to} C ₇ isomonoolefin derived units, such as isobutylene derived units and at least one other polymerizable unit. In one embodiment of the present disclosure, the halogenated isobutylene-containing elastomer is a butyl rubber or a branched butyl rubber, particularly a brominated version of these elastomers. (Useful unsaturated butyl rubbers, such as olefin or isoolefin homopolymers and copolymers, and other types of elastomers suitable for this disclosure are known, RUBBER TECHNOLOGY 209-581 (Maurice Morton, Ed. Chapman & Hall) 1995), THE VANDERBILT RUBBER HANDBOOK 105-122 (Edited by Robert F. Ohm, RT Vanderbilt Co., Inc. 1990) and 8 KIRK-OTHMER ENCYCLO (registered trademark) PEDIA OF CHEMICAL TE 93 Sons, Inc. 4th Edition, Edward Kresge and HC Wang in 1993). ) Preferred halogenated isobutylene homopolymers or copolymers useful in the present disclosure include halobutyl rubbers such as bromobutyl rubber and chlorobutyl rubber.

Butyl rubber is typically produced by reacting a mixture of monomers, the mixture having at least (1) a C _{4 to} C ₁₂ isoolefin monomer component, such as isobutylene and (2) a multiolefin monomer component. . The isoolefin is in one embodiment within the range of 70-99.5% by weight of the total monomer mixture and in another embodiment within the range of 85-99.5% by weight. The multiolefin component is present in the monomer mixture at 30 to 0.5 wt% in one embodiment and 15 to 0.5 wt% in another embodiment. In yet another embodiment, 8 to 0.5 weight percent of the monomer mixture is multiolefin. The isoolefin is preferably a C _{4 to} C ₁₂ compound, non-limiting examples of which are isobutylene, isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1- Compounds such as butene, 2-butene, methyl vinyl ether, indene, vinyl trimethylsilane, hexene and 4-methyl-1-pentene. Multiolefins include C _{4 to} C ₁₄ multiolefins such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene and piperylene and EP 279. , 456 and U.S. Pat. No. 5,506,316 and U.S. Pat. No. 5,162,425. Other polymerizable monomers such as styrene and dichlorostyrene are also suitable for homopolymerization or copolymerization with butyl rubber. One embodiment of a butyl rubber polymer useful in the present disclosure is from 95 to 99.5 wt% isobutylene, from 0.5 to 8 wt% isoprene, or in yet another embodiment from 0.5 wt% to 5 wt%. Obtained by reacting with 0.0% by weight of isoprene. Butyl rubbers and methods for their production are described, for example, in US Pat. No. 2,356,128, US Pat. No. 3,968,076, US Pat. No. 4,474,924, US Pat. No. 4,068,051 and This is described in detail in US Pat. No. 5,532,312.

Halogenated butyl rubber is produced by halogenation of the above butyl rubber product. Halogenation can be performed by any means, and the present disclosure is not limited here by the halogenation method. Methods for halogenating polymers such as butyl polymers are described in US Pat. No. 2,631,984, US Pat. No. 3,099,644, US Pat. No. 4,288,575, US Pat. No. 4,554, 326, US Pat. No. 4,632,963, US Pat. No. 4,681,921, US Pat. No. 4,650,831, US Pat. No. 4,384,072, US Pat. No. 4,513 116 and US Pat. No. 5,681,901. In one embodiment, butyl rubber is halogenated in hexane diluent at 4-60 ° C. using bromine (Br ₂ ) or chlorine (Cl ₂ ) as the halogenating agent. Post-treated halogenated butyl rubber as disclosed in U.S. Pat. No. 4,288,575 can also be used. Halogenated butyl rubber typically has a Mooney viscosity of about 20 to about 70 (ML _{1 + 8} at 125 ° C.), for example, a Mooney viscosity of about 25 to about 55 in other embodiments. The halogen content is typically about 0.1 to 10% by weight based on the weight of the halogenated rubber, such as about 0.5 to 5% by weight, alternatively about 0.8 to about 2.5% by weight. For example, 1 to about 2% by weight.

A commercial embodiment of a halogenated isobutylene-containing elastomer useful in the present invention is Bromobutyl 2222 (ExxonMobil Chemical Company). Its Mooney viscosity is typically about 27-37 (ML 1 + 8 at 125 ° C., ASTM 1646) and its bromine content is about 1.8-2.2% by weight with respect to Bromobutyl 2222. Further, the cure characteristics of Bromobutyl 2222 as shown by the manufacturer are as follows. The MH is about 28-40 dN m and the ML is about 7-18 dN m (ASTM D2084). Another commercial embodiment of a halogenated isobutylene-containing elastomer useful in the present disclosure is Bromobutyl 2255 (ExxonMobil Chemical Company). Its Mooney Viscosity is about _{41~51 (ML 1 + 8, ASTM} D1646 at 125 ° C.), and its bromine content is about 1.8 to 2.2 wt%. Furthermore, its curing characteristics as disclosed by the manufacturer are as follows. The MH is about 34-48 dN m and the ML is about 11-21 dN m (ASTM D2084).

  Another embodiment of the halogenated isobutylene-containing elastomer is a halogenated branched or “star-branched” butyl rubber. These rubbers are described, for example, in European Patent 0 678 529 B1, US Pat. No. 5,182,333 and US Pat. No. 5,071,913, each incorporated herein by reference. Yes. In one embodiment, star-branched butyl rubber (“SBB”) is a composition comprising butyl rubber and a polydiene or block copolymer. For the purposes of this disclosure, the method of forming the SBB is not a limitation. Polydienes, block copolymers or branching agents (hereinafter “polydienes”) are typically cationically reactive and are present during polymerization of butyl or halogenated butyl rubber or with butyl rubber to form SBB. Can be blended. The branching agent or polydiene may be any suitable branching agent and the present disclosure is not limited to the type of polydiene or branching agent used to make the SBB.

  In one embodiment, SBB comprises butyl rubber or halogenated butyl rubber, styrene, polybutadiene, polyisoprene, polypiperylene, natural rubber, styrene-butadiene rubber, ethylene-propylene diene rubber (EPDM), ethylene-propylene. A composition with a polydiene selected from the group consisting of rubber (EPM), styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers and copolymers of partially hydrogenated polydienes. The polydiene is typically greater than 0.3% by weight, based on the total monomer content in weight percent, and instead is about 0.3 to about 3% or about 0.4 to 2.7% by weight. May be present.

  Preferably, the branched or “star-branched” butyl rubber used in the present disclosure is halogenated. In one embodiment, the halogenated star-branched butyl rubber (“HSBB”) comprises a halogenated or non-halogenated butyl rubber and a halogenated or non-halogenated polydiene or block copolymer. This halogenation method is described in US Pat. No. 4,074,035, US Pat. No. 5,071,913, US Pat. No. 5,286,804, US Pat. No. 5,182,333 and US Pat. , 228,978. The present invention is not limited by the method of forming HSBB. The polydiene / block copolymer or branching agent (hereinafter “polydiene”) is typically cationically reactive and is present during the polymerization of butyl or halogenated butyl rubber or butyl or halogen to form HSBB. Can be blended with butyl rubber. The branching agent or polydiene may be any suitable branching agent and the present invention is not limited by the type of polydiene used to produce the HSBB.

  In one embodiment, HSBB is typically a halogenated butyl rubber as described above as well as styrene, polybutadiene, polyisoprene, polypiperylene, natural rubber, styrene-butadiene rubber, ethylene-propylene diene rubber, styrene-butadiene- A composition comprising a polydiene selected from the group consisting of styrene and a styrene-isoprene-styrene block copolymer and a copolymer of partially hydrogenated polydiene. The polydiene is typically greater than 0.3% by weight, based on the total monomer content in weight percent, and instead is about 0.3 to about 3% or about 0.4 to 2.7% by weight. May be present.

A commercial embodiment of HSBB useful in the present disclosure has a Mooney viscosity of about 27-37 (ML _{1 + 8} at 125 ° C., ASTM D1646) and a bromine content of about 2.2-2.6% by weight. Bromobutyl 6222 (ExxonMobil Chemical Company). In addition, the cure characteristics of Bromobutyl 6222 as disclosed by the manufacturer are as follows. The MH is 24 to 38 dN · m, and the ML is 6 to 16 dN · m (ASTM D2084).

As the halogenated isobutylene-containing elastomer, preferred isoolefin / para useful in the present disclosure - the alkylstyrene copolymers, C ₄ -C ₇ isoolefin, include, for example, a random copolymer comprising isobutylene and a halomethyl styrene. The halomethylstyrene may be an ortho-, meta- or para-alkyl substituted styrene. In one embodiment, the halomethyl styrene is p-halomethyl styrene containing at least 80 wt%, more preferably at least 90 wt% para isomer. A “halo” group may be any halogen, desirably chlorine or bromine. The copolymer also includes a functionalized copolymer in which at least some of the alkyl substituents present on the styrene monomer units contain benzylic halogens or other functional groups as described further below. It's okay. These copolymers are referred to herein as “isoolefin copolymers consisting of halomethylstyrene” or simply “isoolefin copolymers”.

Preferred isoolefin copolymers include isobutylene or isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-butene, 2-butene, methyl vinyl ether, indene, vinyl trimethyl Monomers selected from the group consisting of silane, hexene and 4-methyl-1-pentene may be included. Preferred isoolefin copolymers may also further multiolefin, preferably C ₄ -C ₁₄ multiolefin such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethyl - fulvene, It may consist of hexadiene, cyclopentadiene and piperylene and other monomers as disclosed in EP 279,456 and US 5,506,316 and US 5,162,425. Desirable styrenic monomers in the isoolefin copolymer include styrene, methylstyrene, chlorostyrene, methoxystyrene, indene and indene derivatives and combinations thereof.

  Preferred isoolefin copolymers have the following monomer units randomly spaced along the polymer chain:

Wherein R and R ¹ are independently hydrogen, lower alkyl, preferably C ₁ -C ₇ alkyl and primary or secondary alkyl halide, and X is a functional group such as halogen.
It can be characterized as a copolymer containing Desirable halogens are chlorine, bromine or combinations thereof, preferably bromine. R and R ¹ are preferably each hydrogen. The —CRR ₁ H and —CRR ₁ X groups may be substituted on the styrene ring in the ortho, meta or para position, preferably in the para position. In one embodiment, up to 60 mole percent of the p-substituted styrene present in the copolymer structure may be the functionalized structure (2) above, and in another embodiment, 0. It may be 1-5 mol%. In yet another embodiment, the amount of functionalized structure (2) is 0.4-1 mol%. Functional group X can be a benzyl, by halogen or other groups such as carboxylic acids; carboxy salts; carboxy esters, amides and imides; hydroxy; alkoxides; phenoxides; thiolates; thioethers; There may be several other functional groups that can be included by nucleophilic substitution of the functional halogen. These functionalized isomonoolefin copolymers, their production methods, functionalization methods and curing are more particularly disclosed in US Pat. No. 5,162,445.

  Particularly useful copolymers of isobutylene and p-methylstyrene are those containing 0.5-20 mol% p-methylstyrene (provided that no more than 60 mol% of the methyl substituents present on the benzyl ring are bromine Or a chlorine atom, preferably containing a bromine atom (p-bromomethylstyrene)) and their acid or ester functionalized versions, provided that the halogen atom is substituted by maleic anhydride or by acrylic acid or methacrylic acid functional groups. Is). These copolymers are named “halogenated poly (isobutylene-co-p-methylstyrene)” or “brominated poly (isobutylene-co-methylstyrene)” and have the trade name EXXPRO® Elastomer (Exxon). Commercially available from Mobile Chemical Company, Houston, Texas. The use of the term “halogenated” or “brominated” is not limited to the method of halogenation of the copolymer, but merely describes a copolymer comprising isobutylene derived units, p-methylstyrene derived units and p-halomethylstyrene derived units. Is.

  These functionalized polymers preferably contain at least 95% by weight of the polymer (as determined as shown in US Pat. No. 5,162,445) average p-alkylstyrene content of the polymer. It has a substantially homogeneous composition distribution so as to have a p-alkylstyrene content within 10% of the amount. More preferred polymers also have a narrow molecular weight distribution (Mw / Mn) less than 5, more preferably less than 2.5, a preferred viscosity average molecular weight in the range of about 200,000 to about 2,000,000, and Characterized by a preferred number average molecular weight in the range of about 25,000 to about 750,000 as determined by gel permeation chromatography.

Preferred halogenated poly (isobutyl-co-p-methylstyrene) polymers are generally brominated polymers containing from about 0.1 to about 5 weight percent bromomethyl groups. In yet another embodiment, the amount of bromomethyl groups is from about 0.2 to about 2.5% by weight. Expressed in other ways, preferred copolymers contain about 0.05 to about 2.5 mole percent bromine, more preferably about 0.1 to about 1.25 mole percent bromine, based on the weight of the polymer. And substantially free of ring halogen or halogen in the polymer backbone. In one embodiment of the present disclosure, the copolymer is a copolymer of C ₄ -C ₇ isomonoolefin derived units, p- methylstyrene derived units and p- halomethylstyrene derived units, wherein the p- halo The methylstyrene unit is present in the copolymer from about 0.4 to about 1 mole percent on a copolymer basis. In other embodiments, the p-halomethylstyrene is p-bromomethylstyrene. The Mooney viscosity (1 + 8, 125 ° C., ASTM D1646) is about 30 to about 60 Mooney units.

  In another embodiment, the relationship between the triolefin fraction of isoolefin and p-alkyl styrene contained in the copolymer and the mole percent of p-alkyl styrene is: It is described by the equation and is characterized by the copolymer order distribution parameter, m.

F = 1- {mA / (1 + mA)}
Where m is the copolymer order distribution parameter,
A is the molar ratio of p-alkylstyrene to isoolefin in the copolymer, and F is the p-alkylstyrene-isoolefin-p-alkylstyrene triad fraction in the copolymer. )

  Parameters F and A can be determined experimentally. The m value (positive number) is obtained by solving this equation for the copolymerization of isoolefin and p-alkylstyrene in a particular diluent. In some embodiments, m is less than 38, instead less than 36, instead less than 35, and alternatively less than 30. In other embodiments, m is 1-38, 1-36 instead, 1-35 instead, 1-30 instead. Copolymers having such characteristics are disclosed in International Patent Application Publication No. 2004058825 and International Patent Application Publication No. 2004058835.

In other embodiments, the isoolefin / para-alkylstyrene copolymer is substantially free of long chain branching. For purposes of the present invention, polymers that are substantially free of long chain branching are 0.978 when g ′ _vis.avg. Is determined by triple detection size exclusion chromatography (SEC) as described below _. Above, instead 0.980 or higher, instead 0.985 or higher, instead 0.990 or higher, instead 0.995 or higher, instead 0.998 or higher, instead 0.999 or higher It is defined as a polymer that is determined to be. Such polymers and methods for measuring such characteristics are disclosed in International Patent Application Publication No. 2004058825 and International Patent Application Publication No. 2004058835.

  In another embodiment, the relationship between the isoolefin and multiolefin triad fractions contained in the halogenated rubber copolymer and the mole percent of the multiolefin is illustrated by the following copolymer order distribution equation: Characterized by copolymer order distribution parameter, m.

F = mA / (1 + mA) ²
Where m is the copolymer order distribution parameter,
A is the molar ratio of multiolefin to isoolefin in the copolymer, and F is the isoolefin-multiolefin-multiolefin triad fraction in the copolymer. )

  The measurement of isoolefin and multiolefin triad fractions contained in the copolymer and the mole% of multiolefin will be described later. Parameters F and A can be determined experimentally. It is obtained by solving this equation for the copolymerization of isoolefin and multiolefin in each diluent. In some embodiments, m is greater than 1.5, instead greater than 2.0, instead greater than 2.5, instead greater than 3.0, and instead 3 Greater than .5. In other embodiments, m is 1.10 to 1.25, alternatively 1.15 to 1.20, instead 1.15 to 1.25, and instead m is about 1.20. It is. Halogenated rubbers having these characteristics and methods for measuring such characteristics are disclosed in International Patent Application Publication No. 2004058825 and International Patent Application Publication No. 2004058835.

In other embodiments, the halogenated rubber is substantially free of long chain branching. For purposes of this disclosure, polymers that are substantially free of long chain branching will have 0.978 or higher instead, as g ′ _vis.avg. Is determined by triple detection SEC as described below _. 0.980 or higher, instead 0.985 or higher, instead 0.990 or higher, instead 0.995 or higher, instead 0.998 or higher, instead Is defined as a polymer determined to be 0.999 or higher. The presence or absence of long chain branching in the polymer is determined using triple detection SEC. The triple detection SEC was equipped with Precision Detectors (Bellingham, Mass.) PD2040 light scattering detector, Viscotek (Houston, TX) model 150R viscometer detector and Waters differential refractive index detector (integrated at 150C), 40 Performed on a Waters (Milford, Mass.) 150C chromatograph operating at 0C. The detectors are connected in series, first to a light scattering detector, second to a viscometer detector, and third to a differential refractive index detector. Tetrahydrofuran was used as the eluent (0.5 mL / min) and three Polymer Laboratories, Ltd. (Shropshire, UK) Use with a set of 10 micron mixed-B / LS GPC columns. The instrument is calibrated against 16 narrow polystyrene standards (Polymer Laboratories, Ltd.). Data is acquired with TriSEC software (Viscotek) and imported into the WaveMetric's Igor Pro program (Lake Oswego, OR) for analysis. Linear polyisobutylene is used to establish the relationship between intrinsic viscosity ([η] _linear determined by viscometer detector) and molecular weight (M _w determined by light scattering detector). The relationship between [η] _linear and M _w is expressed by the Mark-Houwink equation.

[Η] _linear = KM _w ^α
The parameters K and α are obtained from a double logarithmic plot of intrinsic viscosity versus M _w , where alpha is the slope and K is the intercept. A significant deviation from the established relationship for linear standards indicates the presence of long chain branching. In general, samples that show more significant deviations from the linear relationship contain more prominent long chain branches. The scale factor g ′ also indicates the deviation from the determined linear relationship.

[Η] _sample = g ′ [η] _linear
The value of g ′ is defined to be 1 or less and 0 or more. When g 'is equal to 1 or approximately equal to 1, the polymer is considered linear. When g 'is significantly less than 1, the sample is a branched long chain. For example, E.I. F. Casassa and G.C. C. Berry, “Comprehensive Polymer Science”, Volume 2, (71-120), G.C. Allen and J.M. C. See Beverton, Pergamon Press, New York, 1988. In triple detection SEC, g ′ is calculated for each data slice of the chromatography curve. The viscosity average g ′ or g ′ _vis.avg. Is calculated over the entire molecular weight distribution. The scale factor g ′ _vis.avg. Is calculated from the average intrinsic viscosity number of the sample.

g ′ _vis.avg. = [η] _avg. / (KM _w ^α )
Other preferred halogenated rubbers include halogenated isobutylene-p-methylstyrene-isoprene copolymers as described in WO 01/21672 A1.

  In another embodiment, a halogenated elastomer, preferably a halogenated isobutylene-containing elastomer, can be included in the tie layer. The elastomer useful in the air permeation prevention layer and the halogenated isobutylene-containing elastomer useful in the tie layer may be the same or different elastomers. In a preferred embodiment, the elastomer present in the air permeation prevention layer and the halogenated isobutylene-containing elastomer present in the tie layer are the same elastomer. In another preferred embodiment, the elastomer present in the air permeation prevention layer and the halogenated isobutylene containing elastomer present in the tie layer are different elastomers. Similarly, the high diene elastomer present in the second layer may be the same or different high diene elastomer as the high diene elastomer present in the tie layer. In another preferred embodiment, the high diene elastomer present in the second layer is the same high diene elastomer present in the tie layer. In a preferred embodiment, the high diene elastomer present in the second layer is different from the high diene elastomer present in the tie layer. By “same” is meant that the elastomers each have a comonomer and halogen content within 2% by weight of each other. By “different” is meant that the elastomer consists of different halogens or comonomers, or that the elastomers have a comonomer or halogen content that is not within 2% by weight of each other. For example, a BIMS copolymer having 3 wt% para-methylstyrene (PMS) and 5 wt% bromine is considered different from a BIMS copolymer having 11 wt% PMS and 5 wt% bromine. In a preferred embodiment, the elastomer present in the air permeation prevention layer is a brominated copolymer of isobutylene and para-methylstyrene, and the halogenated isobutylene containing elastomer present in the tie layer is the same or different, Brominated copolymer of isobutylene and para-methylstyrene. In other embodiments, the elastomer present in the air permeation prevention layer is a brominated copolymer of isobutylene and para-methylstyrene, and the halogenated isobutylene-containing elastomer present in the tie layer is brominated butyl rubber. is there.

For the purposes of this disclosure, engineering resins (also referred to as “engineering thermoplastic resins”, “thermoplastic resins” or “thermoplastic engineering resins”) have a Young's modulus greater than 500 MPa and preferably 60 × 10 ^−12. having an air permeability coefficient less than cc cm / cm ² sec cm Hg (at 30 ° C.), preferably less than 25 × 10 ⁻¹² cc cm / cm ² sec cm Hg (at 30 ° C.) Without limitation, the following:
a) Polyamide resin: nylon 6 (N6), nylon 66 (N66), nylon 46 (N46), nylon 11 (N11), nylon 12 (N12), nylon 610 (N610), nylon 612 (N612), nylon 6 / 66 copolymer (N6 / 66), nylon 6/66/610 (N6 / 66/610), nylon MXD6 (MXD6), nylon 6T (N6T), nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS Copolymer;
b) Polyester resin: polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyacrylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene Diimide diacid / polybutylene terephthalate copolymer and other aromatic polyesters;
c) Polynitrile resin: polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile-styrene copolymer (AS), methacrylonitrile-styrene copolymer, methacrylonitrile-styrene-butadiene copolymer;
d) Polymethacrylate resin: polymethyl methacrylate, polyethyl acrylate;
e) Polyvinyl resin (for illustrative purposes, but not limited): vinyl acetate (EVA), polyvinyl alcohol (PVA), vinyl alcohol / ethylene copolymer (EVOA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyvinyl / Polyvinylidene copolymer, polyvinylidene chloride / methacrylate copolymer;
f) Cellulose resin: cellulose acetate, cellulose acetate butyrate;
g) Fluororesin: polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE);
h) Polyimide resin: aromatic polyimide;
i) polysulfone;
j) polyacetal;
k) Polyacton;
l) polyphenylene oxide and polyphenylene sulfide;
m) styrene-maleic anhydride;
n) Aromatic polyketones and o) any and all mixtures of a) to n) (including) and any mixture of exemplary or illustrative engineering resins within each of a) to n) (including) Defined as being all thermoplastic polymers, copolymers or mixtures thereof, including species or more.

  For purposes of this disclosure, this definition of engineering resin excludes olefin polymers such as polyethylene and polypropylene.

  Preferred engineering resins include polyamide resins and mixtures thereof, and particularly preferred resins include nylon 6, nylon 66, nylon 666 copolymer, nylon 11, nylon 12 and blends thereof.

Also, high diene content rubbers or elastomers, referred to as high diene monomer rubbers, are typically at least 50 mol%, typically at least about 60 mol% to about 100 mol%, more preferably at least about 70 mol%. A rubber comprising from mole percent to about 100 mole percent, more preferably from at least about 80 mole percent to about 100 mole percent C _{4 to} C ₁₂ diene monomer.

  Useful high diene monomer rubbers include olefins or isoolefins and multiolefin homopolymers and copolymers or multiolefin homopolymers. These are known and are described in RUBBER TECHNOLOGY, 179-374 (Maurice Morton, Chapman & Hall 1995) and THE VANDERBILT RUBER HANDBOOK 22-80 (Robert F. Ohm, Ed. RT Co. Int. Are listed. Preferred examples of the high diene monomer rubber include polyisoprene, polybutadiene rubber, styrene-butadiene rubber, natural rubber, chloroprene rubber, acrylonitrile-butadiene rubber and the like, which can be used alone or in combination and mixture. .

  Another useful group of high diene monomer rubbers includes styrenic block copolymers, such as those containing 5% to 95%, preferably 10% to 85%, more preferably 15% to 70% by weight styrene. Those having a quantity are included. Preferred styrenic block copolymers (SBC) generally include those comprising a thermoplastic block portion A and an elastomeric block portion B. Block portion A is a hard block and is derived from a material having a glass transition temperature that is high enough to form crystalline or glassy domains at the use temperature of the polymer. Such hard blocks generally form strong physical “crosslinks” or agglomerates with other hard blocks in the copolymer. The hard block portion A generally comprises polyvinyl arenes derived from monomers such as styrene, α-methyl styrene, other styrene derivatives or mixtures thereof. The hard block portion A may also be a copolymer derived from styrenic monomers such as those described above and olefinic monomers such as ethylene, propylene, butene, isoprene, butadiene and mixtures thereof. Such polymers useful for the present invention typically contain less than about 50% glassy phase so that the glass transition temperature, Tg, of the polymer must be less than about −50 ° C. Is included.

  In one embodiment, the hard block portion A has a number average of about 1,000 to about 200,000, preferably about 2,000 to about 100,000, more preferably about 5,000 to about 60,000. Polystyrene with molecular weight. Typically, the hard block portion A comprises about 5% to about 80%, preferably about 10% to about 70%, more preferably about 10 to about 50% of the total weight of the copolymer.

  The material forming the B block preferably has a glass transition temperature that is sufficiently low at the use temperature of the polymer so that no crystalline or glassy domains are formed at these working temperatures. Thus, the B block is typically considered as a soft block. The soft block portion B is typically an olefinic polymer derived from a conjugated aliphatic diene monomer having from about 4 to about 6 carbon atoms or a linear alkene monomer having from about 2 to about 6 carbon atoms. Suitable diene monomers include butadiene, isoprene and the like, while suitable alkene monomers include ethylene, propylene, butene and the like, and in each case a mixture is also suitable. The soft block portion B preferably comprises a substantially amorphous polyolefin, such as ethylene / propylene polymer, ethylene / butene polymer, polyisoprene, polybutadiene, etc., or mixtures thereof. (By the term “substantially amorphous”, the polymer is less than 25%, preferably less than 20%, preferably less than 15%, preferably less than 10%, as measured by differential scanning calorimetry. % Means less crystallinity). The number average molecular weight of the soft block B is typically about 1,000 to about 300,000, preferably about 10,000 to about 200,000, more preferably about 20,000 to about 100,000. .

  Typically, the soft block portion B comprises from about 20% to about 90%, preferably from about 30% to about 80%, more preferably from about 40 to about 80% of the total weight of the copolymer.

  Suitable SBCs for use in the compositions described herein include at least one substantially thermoplastic block portion A and at least one substantially elastomeric block portion B. The SBC may have a number of blocks.

  In one embodiment, the SBC may be an AB diblock copolymer. In other embodiments, the block copolymer may be an ABA triblock copolymer. In yet another embodiment, the SBC can be selected as an ABABA tetrablock copolymer or an ABBABA block copolymer.

  In another embodiment, the SBC is a triblock copolymer having an elastomeric intermediate block B and thermoplastic end blocks A and A ′, where A and A ′ may be derived from different vinylarene monomers. It is. In other embodiments, the SBC has more than one A block and / or more than one B block, wherein each A block is derived from the same or different vinylarene monomers. And each B block may be derived from the same or different olefinic monomers.

  SBC also has three or more arms, each arm being a B-A, B-A-B-A or similar type of copolymer, and the B block being the central portion of the radical polymer or It may be a radical in the vicinity. In other embodiments, the SBC may have 4, 5 or 6 arms.

  In one embodiment, the olefinic polymer block comprises at least about 50% by weight block copolymer. Unsaturation in the olefinic double bond can be selectively hydrogenated to reduce its susceptibility to oxidative cracking, and such hydrogenation also has a beneficial impact on elastomeric properties. For example, polyisoprene blocks can be selectively hydrogenated or reduced to form ethylene-propylene blocks. In one embodiment, the vinyl arene block typically comprises at least about 10% by weight SBC. However, a higher vinylarene content can be selected for high elastic properties and low stress relaxation properties.

  Typical suitable SBCs used for inclusion in the polymer compositions described herein are styrene-olefin-styrene triblock copolymers, such as styrene-butadiene-styrene (SBS), styrene-ethylene / butylene. -Styrene (S-EB-S), styrene-ethylene / propylene-styrene (S-EP-S), styrene-isoprene-styrene (S-I-S) and mixtures thereof. The SBC may be a selected SBC or a blend of SBCs.

  In one embodiment, the SBC for use in the polymer compositions described herein is a polystyrene-ethylene / butylene-polystyrene block copolymer having a styrene content greater than about 10% by weight. With higher styrene content, the polystyrene block portion generally has a relatively high molecular weight.

  In one embodiment, the SBC has a melt flow rate of about 0.01 to about 150 dg / min. In other embodiments, the SBC has a melt flow rate of about 0.1 to about 100 dg / min. In yet another embodiment, the SBC has a melt flow rate of about 1 to about 75 dg / min (each of the melt flow rates is measured by ASTM D1238, 2.16 kg and 230 ° C.).

  In one embodiment, the composition comprises a triblock segment comprising styrene derived units and at least one other unit selected from the group consisting of ethylene derived units, butadiene derived units, isoprene derived units and isobutylene derived units. Wherein the styrenic block copolymer is composed of less than 20 wt% diblock segments. In another embodiment, the composition includes SBC comprising a segment selected from the group consisting of SIS, SBS, SEBS, SEPS and SIBS (styrene-isoprene-butadiene-styrene) units, wherein About 5% to about 95% of the diene units in the block copolymer are hydrogenated.

  Representative SBCs used in the polymer compositions described herein are commercially available from Dexco Polymers LP under the name Vector® and from Kraton Polymers in Houston, Texas under the name Kraton®. ing.

  A particularly useful rubber component of the tie layer is epoxidized natural rubber, ENR. Epoxidized rubber is a modified rubber in which a part of the unsaturation of the rubber is replaced with an epoxy group. This modification is typically achieved by an epoxidation reaction.

  The epoxidation reaction can be carried out by reacting natural rubber or unsaturated rubber with an epoxidizing agent. Useful epoxidizing agents are peracids such as m-chloroperbenzoic acid and peracetic acid. Other examples include carboxylic acids such as acetic acid and formic acid, or carboxylic anhydrides such as acetic anhydride, and hydrogen peroxide. A catalyst such as sulfuric acid, p-toluenesulfonic acid, or a cation exchange resin such as sulfonated polystyrene may be used as necessary. The epoxidation reaction is preferably carried out at a temperature of from about 0 ° C to about 150 ° C, and preferably from about 25 ° C to about 80 ° C. The time required to carry out the epoxidation reaction is typically from about 0.25 hours to about 10 hours, and preferably from about 0.5 hours to about 3 hours.

  The epoxidation reaction is preferably carried out in a solvent capable of substantially dissolving the rubber both in its original state and after epoxidation. Suitable solvents include aromatic solvents such as benzene, toluene, xylene and chlorobenzene and cycloaliphatic solvents such as cyclohexane, cyclopentane and mixtures thereof. After epoxidation, the epoxidized rubber is preferably removed or isolated from an acidic environment that may contain oxidizing agents and acidic catalysts. This isolation can be achieved by filtration or by adding dilute aqueous base to neutralize the acid followed by flocculation of the polymer. Epoxidized rubber can be agglomerated by using alcohols such as methanol, ethanol or propanol. After the isolation procedure, typically an anti-aging agent is added and the final product can be dried using techniques such as vacuum distillation. Alternatively, other known methods for removing the polymer from the hydrocarbon solvent or the like, for example, steam stripping or drum drying can be used.

  Useful epoxidized rubbers have a degree of epoxidation of from about 5 mol% to about 95 mol%, preferably from about 15 mol% to about 80 mol%, and more preferably from about 25 mol% to about 50 mol%. The degree of epoxidation is here defined as the mole% of olefinic unsaturation originally present in the rubber converted to oxirane, hydroxyl or ester groups. Epoxidized natural rubber can also be characterized by Mooney viscosity (large rotor (ML), 1 minute preheat, 4 minutes read (1 + 4), measured at 100 ° C.), which is typically about 85 To about 170, preferably about 95 to about 155, and more preferably about 105 to about 145, but can vary widely.

Useful epoxidized natural rubber is typically from about 10 mol% to about 75 mol% epoxide, preferably from about 15 mol% to about 60 mol%, more preferably from about 20 mol% to about 55 mol%, more preferably Is a product comprising from about 25 mole% to about 50 mole%, for example having from about 25 mole% to about 50 mole% epoxide. Epoxidized natural rubber is trade name “Epoxyprene” (Kumpulan Guthrie Beshad, Malaysia), Grade ENR25 (including about 25 ± 2 mol% epoxide), ENR50 (including about 50 ± 2 mol% epoxide) Are commercially available. Similar products are also commercially available from River Research Institute (RRIM), Malaysia. Both of these commercial products exhibit a Mooney viscosity (ML _{1 + 4} (100 ° C.)) of about 70 to about 90. The layered composition according to the present disclosure preferably uses an epoxidized natural rubber containing about 50 mole% epoxide (eg, ENR50).

  Epoxidized natural rubber is typically present in the tie layer composition at an ENR level of about 10 to about 70 parts by weight, based on 100 parts by weight of the total rubber present in the mixture. Preferred amounts are from about 20 parts to about 60 parts, more preferably from about 30 parts to about 50 parts, such as from about 25 parts to about 55 parts, or from about 33 parts to about 48 parts, such as 40 parts. is there. Preferably, the tie layer composition of the present disclosure is selected from natural rubber, ethylene butadiene rubber, polyisoprene rubber, polybutadiene rubber, and mixtures thereof, preferably including natural rubber. Typically, the tie layer composition is about 30 to about 90 parts by weight, preferably about 35 to 80 parts, more preferably about 40 to about 100 parts by weight of total rubber present in the tie layer composition. About 70 parts, still more preferably about 45 to about 70 parts natural rubber, for example about 50 to about 65 parts natural rubber, such as 60 parts.

  As discussed in detail below, particularly preferred compositions include additives that improve the unvulcanized tack of the tie layer composition in addition to the use of ENR. Such additives improve the processability of the unvulcanized composition and facilitate the construction of the multilayer structure by maintaining the structural integrity of the structure until vulcanized, and the vulcanized adhesion between the layers Establish.

  Without wishing to be bound by theory, the use of ENR provides cure or vulcanization adhesion of the tie layer to the fluid permeation prevention layer (eg, the inner liner layer of the tire), especially when using polyamide in the inner liner composition. To improve. Similarly, the presence of natural rubber in the tie layer improves vulcanization adhesion to other layers in contact with the tie layer, such as the carcass layer or sidewall layer of the tire. Furthermore, the use of ENR reduces the air permeability of the tie layer, considering that ENR is substantially impermeable to air compared to NR and SBR.

Generally, polymer compositions, such as those used in the manufacture of tires, are crosslinked into the finished tire product. Crosslinking or vulcanization is accomplished by the inclusion of curing agents and / or accelerators, and a total mixture of such reagents is typically referred to as a curing “system”. It is known that the physical properties, performance characteristics and durability of a vulcanized rubber compound are directly related to the number (crosslink density) and type of crosslinks formed during the vulcanization reaction. (See, for example, Helt et al., The Post Vulcanization Stabilization for NR, RUBBER WORLD 18-23 (1991)). Curing agents include those components that facilitate or affect the curing of elastomers and generally include metals, accelerators, sulfur, peroxides, and the like in the art. Other common reagents are included. Crosslinking or curing agents include, for example, at least one of sulfur, zinc oxide and fatty acids and mixtures thereof. Peroxide-containing curing systems can also be used. In general, polymer compositions are crosslinked by adding a curing agent such as sulfur, metal oxides (ie, zinc oxide, ZnO), organometallic compounds, radical initiators, etc. and heating the composition or mixture. Can be made. When using a method known as “dynamic vulcanization”, this method involves the addition of at least one vulcanizable rubber, elastomer or polymer and at least one vulcanizable component. At least one vulcanizable component in a composition comprising at least one elastomer or polymer that cannot be vulcanized using the vulcanizing agent (s) is mixed substantially simultaneously and vulcanized or Can be changed to cross-link. (For example, see Patent Literature 3 and literature cited therein). In particular, the following are common curing agents that can function in the present disclosure: ZnO, CaO, MgO, Al ₂ O ₃ , CrO ₃ , FeO, Fe ₂ O ₃ and NiO. These metal oxides can be used in conjunction with the corresponding metal stearate complexes (eg stearates of Zn, Ca, Mg and Al) or stearic acid and sulfur or alkyl peroxide compounds. (See, for example, Formulation Design and Curing Characteristics of NBR Mixes for Seals, RUBBER WORLD 25-30 (1993)). To this curing agent (s) is often added an accelerator for vulcanization of the elastomeric composition. Curing agent (s) with or without the use of at least one accelerator is often referred to in the art as a curing “system” for the elastomer (s). Curing systems typically use more than one curing agent for advantageous effects, especially when mixtures of high diene rubbers and low reactivity elastomers are used.

For the purpose of dynamic vulcanization in the presence of engineering resins to form a highly impermeable layer, any common curing agent system capable of vulcanizing saturated halogenated polymers, at least one, C ₄ -C ₇ isomonoolefin and para - can be used to vulcanize the elastomeric halogenated copolymer of alkyl styrene. However, when the selected thermoplastic engineering resin (s) are such that the peroxide crosslinks these resins themselves, the engineering resins themselves vulcanize or crosslink, thereby excessively Peroxide curing agents are excluded unless specifically excluded from the practice of this disclosure because they result in a cured non-thermoplastic composition. Suitable curing agent systems for the elastomeric halogenated copolymer components of the present disclosure include zinc stearate or zinc oxide in combination with stearic acid, and optionally in combination with the following accelerators or vulcanizing agents, ie sulfur: Permalux (di-ortho-tolylguanidine salt of dicatechol borate); HVA-2 (m-phenylenebismaleimide); Zisnet (2,4,6-trimercapto-5-triazine); ZDEDC (zinc Diethyldithiocarbamate) and also other dithiocarbamates for purposes of this disclosure; Tetrone A (dipentamethylene thiuram hexasulfide); Vultac5 (alkylated phenol disulfide); SP1045 (phenol formaldehyde resin); SP1056 ( Bromination DPPD (diphenylphenylenediamine); salicylic acid, ortho-hydroxybenzoic acid; wood rosin, abietic acid and one or more of TMTDS (tetramethylthiuram disulfide).

  Dynamic vulcanization is carried out at conditions for at least partially, preferably fully vulcanizing, the elastomeric halogen-containing copolymer of the fluid (gas or liquid, preferably air) permeation prevention layer.

  With reference to the polymers and / or elastomers referred to herein, the term “cured”, “vulcanized” or “crosslinked” refers to, for example, chain extension or polymers or polymers including elastomers. During cross-linking between chains, the elastomer undergoing such a process includes forming bonds to the extent that it can provide the necessary functional properties resulting from the curing reaction when the tire is put into use. Refers to a chemical reaction. For purposes of this disclosure, absolute completion of such a curing reaction is not necessary in order for an elastomer-containing composition to be considered “cured”, “vulcanized”, or “crosslinked”. Absent. For example, for the purposes of this disclosure, a tire consisting of a tie layer is sufficiently cured and used in a vehicle when the tire it is a component of passes the required product specification test during and after manufacture. When you do it, it will perform so that you can be satisfied. Further, even though the additional cure time creates additional crosslinks, the composition is sufficiently or substantially cured, vulcanized or cross-linked to be satisfactory when the tire is put to use. With limited experimentation using known tools and standard techniques, one of ordinary skill in the art will recognize the appropriate elastomeric (s) and polymer (s) selected for use in the tie layer composition. Alternatively, the optimum cure time and the amount and type of crosslinking agent (s) and accelerator (s) used to produce the tire and the curing temperature can be readily determined.

  Accelerators useful in the present disclosure include amines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenimides, thiocarbamates, xanthates and the like. Acceleration of the curing process can be achieved by adding a certain amount of accelerator to the composition. Mechanisms for accelerated vulcanization of natural rubber include complex interactions between curing agents, accelerators, activators and polymers. Ideally, all of the available curing agent is consumed to form effective crosslinks that join the two polymer chains together and enhance the overall strength of the polymer matrix. A number of accelerators are known in the art, including but not limited to the following: stearic acid, diphenylguanidine (DPG), tetramethylthiuram disulfide (TMTD), 4,4 ′. -Dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBTD), 2,2'-benzothiazyl disulfide (MBTS), hexamethylene-1,6-bisthiosulfate disodium salt dihydrate, 2- (morpholino Thio) benzothiazole (MBS or MOR), composition of 90% MOR and 10% MBTS (MOR90), N-tertiarybutyl-2-benzothiazolesulfenamide (TBBS) and N-oxydiethylenethio Carbamyl-N-oxydiethylenesulfonamide (OTOS), 2-ethyl San zinc (ZEH), N, include N'- diethyl thiourea. Curing agents, accelerators and curing systems useful with one or more crosslinkable polymers are known in the art.

  In one embodiment of the present disclosure, the at least one curing agent is typically present from about 0.1 to about 15 phr, alternatively from about 0.5 to about 10 phr.

  The compositions described herein include one or more filler ingredients such as calcium carbonate, clay, mica, silica and silicates, talc, titanium dioxide, starch and other organic fillers such as wood flour. As well as carbon black. Suitable filler materials include carbon black, such as channel black, furnace black, thermal black, acetylene black, lamp black and the like. Reinforced grade carbon black is most preferred. The filler may also contain other reinforcing or non-reinforcing materials such as silica, clay, calcium carbonate, talc, titanium dioxide and the like. The filler is usually present in the composition (preferably the innerliner) at a level of from about 20 to about 50% by weight of the total composition, more preferably from about 25 to 40% by weight. In one embodiment, the filler is carbon black or modified carbon black. A preferred filler is semi-reinforced grade carbon black, typically used at a level of about 10 to 150 phr (parts per hundred parts by weight of rubber), more preferably about 30 to about 120 phr. Carbon black grades useful in the present disclosure include N110-N990, as described in RUBBER TECHNOLOGY, 59-85 (1995). More desirably, carbon black grades useful in, for example, tire treads, such as N229, N351, N339, N220, N234 and N110, as defined in ASTM (D3037, D1510 and D3765) are useful here. . Carbon black embodiments useful, for example, in tire sidewalls, such as N330, N351, N550, N650, N660 and N762 are particularly useful here. Carbon black embodiments useful in, for example, inner liners or inner tubes, such as N550, N650, N660, N762, N990, and Regal 85 (Cabot Corporation, Alpharetta, Georgia) are also particularly useful here.

Flaked, inserted or dispersed clay may also be present in the composition. These clays are also referred to as “nanoclays” and are known and their identification, production methods and blends with polymers are described, for example, in JP2000109635, JP2000109605, JP11310643, DE19726278, WO 98/53000 and U.S. Pat. No. 5,091,462, U.S. Pat. No. 4,431,755, U.S. Pat. No. 4,472,538 and U.S. Pat. No. 5,910,523. Swellable layered clay materials suitable for the purposes of the present disclosure include natural or synthetic phyllosilicates, particularly smectic clays such as montmorillonite, nontronite, beidellite, vorkonskite, laponite, Examples include hectorite, saponite, sauconite, magadite, kenyaite, stevensite, etc., as well as vermiculite, halloysite, aluminate oxide, hydrotalcite and the like. In one embodiment, these layered clays generally contain exchangeable cations, such as Na ⁺ , Ca ⁺² , K ⁺ or Mg ⁺² , bonded together and present on the interlayer surface. It consists of particles containing a plurality of silicate platelets, typically having a thickness of about 4 to about 20 mm, and in other embodiments about 8 to about 12 mm.

The layered clay can be inserted or sliced by treatment with an organic molecule (swelling agent) capable of undergoing an ion exchange reaction with cations present on the surface of the layered silicate interlayer. Suitable swelling agents include cationic surfactants such as ammonium, alkylamines or alkylammonium (primary, secondary, tertiary) of aliphatic, aromatic or arylaliphatic amines, phosphines and sulfides. And quaternary), phosphonium or sulfonium derivatives. Desirable amine compounds (or the corresponding ammonium ions) have the structure R ₁ R ₂ R ₃ N, wherein R ₁ , R ₂ and R ₃ can be the same or different C ₁ -C ₃₀ alkyl or alkene. Is). In one embodiment, the exfoliating agent is a so-called long chain tertiary amine where at least R ₁ is a C ₁₂ -C ₂₀ alkyl or alkene.

Another class of swelling agents includes those that can be covalently bound to the intermediate layer surface. These include the structure —Si (R ′) ₂ R ² , where R ′, if present, may be the same or different and is selected from alkyl, alkoxy, or oxysilane, and R ² is a composite Polysilanes which are organic groups compatible with the matrix polymer of Other suitable swelling agents include C2-C30 protonated amino acids and their salts such as 12-aminododecanoic acid, [epsilon] -caprolactam and similar materials. Suitable swelling agents and layered silicate insertion methods are described in US Pat. No. 4,472,538, US Pat. No. 4,810,734, US Pat. No. 4,889,885 and International Patent Application Publication No. 92. No. 02582.

  In a preferred embodiment of the present disclosure, the exfoliating agent or swelling agent is combined with a halogenated polymer. In one embodiment, the reagents include all primary, secondary and tertiary amines and phosphines; alkyl and aryl sulfides and thiols and their multifunctional versions. Desirable additives include long chain tertiary amines such as N, N-dimethyloctadecylamine, N, N-dioctadecyl-methylamine, dihydrogenated tallow alkyl-methylamine and the like, and amine-terminated polytetrahydrofuran; And thiosulfate compounds, such as hexamethylene sodium thiosulfate. In another embodiment of the present invention, improved copolymer impermeability is achieved through the use of multifunctional curing agents such as hexamethylene bis (sodium thiosulfate) and hexamethylene bis (cinnamaldehyde). The

  The amount of exfoliated, intercalated or dispersed clay contained in the composition in accordance with the present disclosure can improve the mechanical or barrier properties of the composition, such as tensile strength or air / oxygen permeability. It is an amount sufficient to cause The amount is typically from about 0.5 to about 15% by weight in one embodiment or from about 1 to about 10% by weight and in other embodiments based on the polymer content of the composition. In embodiments, it may be from about 1 to about 5% by weight. Expressed in parts per hundred parts of rubber, the flaked, inserted or dispersed clay is present from about 1 to about 30 phr in one embodiment and from about 3 to about 20 phr in another embodiment. You can. In one embodiment, the exfoliated clay is an alkylamine exfoliated clay.

  The term “process oil” as used herein refers to both petroleum derived process oils and synthetic plasticizers. Process oil or plasticizer oil may be present in the air barrier composition. Such oils are mainly used to improve the processing of the composition during the production of the layer, for example mixing, calendering, etc. Suitable plasticizer oils include aliphatic acid ester or hydrocarbon plasticizer oils such as paraffinic or naphthenic petroleum oils. A preferred plasticizer oil for use in a standard, non-DVA, non-engineering resin-containing innerliner composition is a paraffinic petroleum oil and a suitable hydrocarbon plasticizer for use in such an innerliner. Oils include oils having the following general characteristics.

In general, the process oil can be selected from paraffinic oil, aromatic oil, naphthenic oil and polybutene oil. The polybutene process oil is a low molecular weight (less than 15,000 Mn) homopolymer or copolymer of olefin derived units having from about 3 to about 8 carbon atoms, more preferably from about 4 to about 6 carbon atoms. In another embodiment, the polybutene oil is a homopolymer or copolymer of C ₄ raffinate. Low molecular weight “polybutene” polymers are described, for example, in SYNTHETIC LUBRICATS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS 357-392 (Leslie R. Rudnick and Ronald L. Shubkin, edited by Marcel Dek, 1999). "Polybutene"). A useful example of polybutene oil is the PARAPOL® series of process oils (formerly available from ExxonMobil Chemical Company, Houston, TX, now from Infineum International Limited, Milton Hill, UK, under the trade name “INFINEUM”. c, d, f or g), including grades previously identified as PARAPOL® 450, 700, 950, 1300, 2400 and 2500. An additional preferred polybutene oil is SUNEX® polybutene oil available from Sun Chemicals. A preferred polybutene process oil is typically a synthetic liquid polybutene having a constant molecular weight, preferably from about 420 Mn to about 2700 Mn. A preferred polybutene oil has a molecular weight distribution, Mw / Mn ("MWD"), typically from 1.8 to about 3, preferably from about 2 to about 2.8. Useful polybutene process oil density (g / mL) varies from about 0.85 to about 0.91. The bromine number (CG / G) for the preferred polybutene oil ranges from about 40 for the 450 Mn process oil to about 8 for the 2700 Mn process oil.

  Rubber process oils also have ASTM names that depend on whether they fall into the class of paraffin, naphthene or aromatic hydrocarbon process oils. The type of process oil used is customarily used in conjunction with the type of elastomer component, and rubber chemists with ordinary knowledge in the art may have special requirements for special applications. You will recognize what kind of oil should be used with rubber. For the innerliner composition, the oil is typically present at a level of 0 to about 25%, preferably about 5 to 20% by weight of the total composition.

  In addition, plasticizers such as organic esters and other synthetic plasticizers can be used. Particularly preferred plasticizers for use in DVA compositions are N-butylsulfonamide or other plasticizers suitable for polyamides. In other embodiments, rubber process oils such as naphthenic, aromatic or paraffinic extender oils may be present at about 1 to about 5 phr. In yet other embodiments, naphthenic, aliphatic, paraffinic and other aromatic oils are substantially absent from the composition. “Substantially absent” means that naphthenic, aliphatic, paraffinic and other aromatic oils, if present, can be present to the extent of 1 phr or less in the composition. Is meant. In still other embodiments, naphthenic, aliphatic, paraffinic and other aromatic oils are present in less than 2 phr.

  The term “dynamic vulcanization” is used herein to indicate a vulcanization method in which engineering resins and rubbers are mixed in the presence of a curing agent under conditions of high shear and elevated temperature. The As a result, the rubber is simultaneously cross-linked and dispersed as fine particles, for example in the form of a microgel, into an engineering resin that forms a continuous matrix and the resulting composition is a “dynamically vulcanized alloy”. Or known as DVA in the art. Dynamic vulcanization uses components such as roll mills, Banbury® mixers, continuous mixers, kneaders or mixed extruders (eg, twin screw extruders) to cure the rubber at or above the curing temperature of the rubber. Is carried out by mixing at a certain temperature. The unique property of dynamically crosslinked compositions is that, despite the fact that the rubber is cured, the composition can be processed by common thermoplastic processing techniques such as extrusion, injection molding, compression molding, etc. It can be processed and reworked. Scrap and / or flushing can also be recovered and reprocessed.

  The dynamic vulcanization process is carried out at conditions for at least partially, preferably fully vulcanizing the elastomeric halogen-containing copolymer. To accomplish this, the thermoplastic engineering resin, elastomeric copolymer and any other polymer are at a temperature sufficient to soften the resin, or more generally, above the melting point of the crystalline or semi-crystalline resin. Mix together at high temperature. Preferably, the curing system is premixed in the elastomer component. Heating and kneading at the vulcanization temperature is generally adequate to complete the vulcanization within about 0.5 to about 10 minutes. By increasing the vulcanization temperature, the vulcanization time can be shortened. A suitable range for the vulcanization temperature is typically from about the melting point of the thermoplastic resin to about 300 ° C., for example, this temperature may range from about the melting point of the matrix resin to about 275 ° C. Preferably, the vulcanization is carried out in a temperature range of about 10 ° C. to about 50 ° C. above the melting temperature of the matrix resin.

  The mixing process is preferably continued until the desired level of vulcanization or crosslinking is complete. If it is allowed to continue vulcanization after mixing is stopped, the composition cannot be reworked as a thermoplastic resin. However, dynamic vulcanization can be carried out in stages. For example, vulcanization can be initiated in a twin screw extruder and an underwater pelletizer can be used to form pellets from the DVA material or material, thereby quenching the vulcanization before vulcanization is complete. . This vulcanization can be completed at a later time under dynamic vulcanization conditions. Those skilled in the art will be aware of the appropriate amount, type and degree of mixing time of the curing agent needed to effect rubber vulcanization. Using a varying amount of curing agent that may contain one or more curing agents and / or accelerators, as necessary or desirable to establish appropriate concentrations and conditions, the rubber It can be vulcanized alone to determine the optimal curing system to be used and the appropriate curing conditions to achieve substantially complete curing.

  Although it is preferred that all components be present in the mixture prior to performing the dynamic vulcanization process, this is not a requirement. For example, in one embodiment, the elastomer to be cured can be dynamically vulcanized in the presence of some or all of the thermoplastic engineering resin. This blend can then be dissolved or dispersed in additional thermoplastic engineering resin under appropriate conditions. Similarly, when used, it is not necessary to add all of the filler and oil prior to the dynamic vulcanization stage. Some or all of the filler and oil can be added after vulcanization is complete. Certain components, such as stabilizers and process aids, function more effectively when they are added after curing.

  The degree of cure of the vulcanized rubber can be described in terms of gel content, crosslink density, amount of extractable component or this is achieved in the rubber when cured in the absence of resin. It can be based on the state of cure to be made. For example, in the present disclosure, halogenated elastomers are used, for example, by tensile strength or oscillating disc cure meter test (ASTM D 2084, rubber properties using an oscillating disc cure meter-vulcanization of It is preferred to achieve about 50 to about 85% of the total cure based on the elastomer itself, as measured by using standard test methods for).

  Typically, the vulcanizable tie layer composition comprises (1) about 10 to about 70 parts epoxidized natural rubber, (2) about 30 to about 100 parts by weight of total rubber present in the mixture. About 90 parts of at least one high diene elastomer, (3) about 20 to about 90 parts of at least one filler, and (4) about 1 to about 20 parts of at least one tackifier (tackifying). Agent) and (5) at least about 0.1 to about 15 parts of a mixture of the curing system for the elastomer. Optionally, the tie layer composition can include more than about 0 parts and up to about 20 parts of at least one process oil. In a preferred embodiment, the epoxidized natural rubber contains about 50 ± 2 mole percent epoxide. Alternatively, the amount of epoxidized natural rubber suitable for use in the tie layer composition is expressed as parts by weight per 100 parts of total rubber in the mixture, 10-70, 20-60, 30-50, 25-55, Selected from the group of 33-48 and 40 parts by weight.

  High diene elastomers suitable for use in the tie layer compositions of the present disclosure are preferably natural rubber or a synthetic rubber containing at least 50 mole percent diene monomer, such as polyisoprene, polybutadiene, poly (styrene-co-). Butadiene), poly (styrene-butadiene-styrene) block copolymers, natural rubber, and mixtures thereof. The amount of at least one high diene elastomer suitable for use in the tie layer composition is expressed in parts by weight relative to 100 parts by weight of the total rubber in the mixture, 30-90, 35-80, 40-70, Selected from the group of 45-70, 50-65 and 60 parts by weight.

  Useful fillers in tie layers include carbon black, clay, exfoliated clay, intercalated clay, dispersed clay, calcium carbonate, mica, silica, silicate, talc, titanium dioxide, wood At least one filler selected from the group consisting of flour and mixtures thereof is included. Preferably, the filler is selected from the group consisting of carbon black, exfoliated clay, intercalated and dispersed clay, and mixtures thereof. The amount of the at least one filler is typically about 20 to about 90 parts by weight, preferably about 25 to about 85 parts by weight, for example about 30 parts by weight, relative to 100 parts by weight of the total weight of rubber. -80 parts or about 35 to about 70 parts, for example 60 parts, or 50 parts.

  The tie layer optionally contains a rubber process oil or plasticizer oil selected from those mentioned above. Suitable plasticizer oils include aliphatic acid ester or hydrocarbon plasticizer oils such as paraffinic or naphthenic petroleum oils or polybutene oils. The amount of rubber process oil or plasticizer oil is typically from about 0 to about 20 parts, preferably from about 0 to about 15 parts, more preferably, based on weight based on 100 parts by weight of total rubber present in the composition. Is from about 0 to about 10 parts per total weight of the tie layer composition. When used, the preferred process oil is a naphthenic oil or a polybutene type oil, most preferably a polybutene oil.

  The tie layer is cured or added using a curing system consisting of at least one curing agent and at least one accelerator useful for the halogenated isobutylene-containing elastomers and high diene elastomers that make up the composition. Sulfurated. Such curing agents and accelerators have been previously described and can be found in standard reference books for materials that are useful for formulating rubber. For example, “Blue Book 2000 (and later editions), materials, compounding excipients, machinery and services for rubber” D. R. Edited by Smith, 2000, Lippincott & Peto Inc. See Publication. Typically, the curing system is present in an amount of at least about 0.1 to about 15 phr (parts per hundred parts of rubber), but as those skilled in the art are aware, certain amounts of the curing system are limited. Rather, the amount used will depend to a great extent on the specific components of the selected curing system.

  Further optional, useful additives are typically added at levels below about 10 phr, from pigments, anti-aging agents, anti-ozonants, processing aids, compound compatibilizers and the like and mixtures thereof. Can be selected from the group consisting of Such optional additives, such as anti-aging agents to improve the heat aging properties of the cured composition, can be included at the formulator's discretion to achieve certain advantages in the composition. .

  In a preferred embodiment, at least one tackifier is included in the tie layer composition. For purposes of this disclosure, tackifiers include a variety of materials such as acetylene-phenolic compounds known as tackifiers for materials identified as rosins or rosin derivatives and elastomer or polymer-containing compositions. Derivatives are included. Particularly useful tackifiers include condensation products of butylphenol and acetylene, such as acetylene-p-tert-butylphenol commercially available as “Koresin” (BASF) and “MR1085A” (Mobile Rose Oil Company, Mobile, Alabama). ) Rosin tackifier, tall oil rosin and fatty acid blends that are commercially available as) (for purposes of this disclosure, blends containing rosin are included in the description of “rosin derivatives”). Tackifiers useful in the elastomer compound and rubber compounding industry are generally described in, for example, “Blue Book 2000” D.C. R. Listed and described in Smith, pp. 245-253 (Lippincott & Peto Inc., 2000). Several tackifiers have been specified as being particularly useful for imparting tack to a particular polymer or elastomer, but they are also determined to be useful for the compounds of the present invention. Can do. Stickiness is generally determined by the adhesion of the uncured rubber compound to itself or other compounds when the compound is contacted using only a relatively short holding time and a moderate amount of pressure. (Rubber Technology: Compounding and Testing for Performance, edited by JS Dick, 42, 2001). The holding time and pressure are often determined by the equipment used for this purpose or by the possibility for the sheet of uncured composition to be damaged by excessive pressure and holding time. Adhesion can also be affected by the solubility of the various rubber components in each other and in the overall composition. In some examples, the components of the composition may diffuse to the surface of the calendered or extruded sheet or film, for example, if it is inorganic particles, it can interfere with sticking (in some cases, “ Referred to as "bloom"). On the other hand, such diffusion can improve adhesion, for example, if the diffusing component is itself adhesive. It is recognized by those skilled in the art that stickiness is a difficult property to measure, and sometimes the skilled person evaluates the performance of the composition (s) in a factory trial or the environment in which the final product is manufactured. By this, it will be required to determine whether the composition has achieved a sufficient level of tack. Typically, in the case of the present disclosure, which includes determining the actual tire assembly and whether the tie layer exhibits sufficient tire assembly adhesion, the uncured tire structure is the initial component during the tire assembly phase and during vulcanization. During staged expansion, the structure cured and thus cured to each other of the various tire layers, including adhesion of the tie layer to the layer it is in adjacent contact with (eg, including the carcass layer and the innerliner layer). They will hold together until a sufficient level of adhesion is reached. Although there is no standardized test procedure for measuring rubber compound adhesion, a widely used instrument is the “Tel-Tak Tackmeter” introduced by Monsanto in 1969. Another test instrument is the PICMA tack tester manufactured by Toyo Seiki Seisakusho (Japan). In preferred embodiments of the present disclosure, at least one tackifier is added to the tie layer composition from about 1 phr to about 20 phr, preferably from about 2 phr to about 18 phr, more preferably from about 3 phr to about 16 phr, such as about 4 phr. Added at a concentration of ~ 14 phr. Instead, the at least one tackifier is typically about 15 phr or less, preferably about 12 phr or less, more preferably about 10 phr or less, even more preferably about 9 phr or less, Most preferably about 1 phr, including individual values and ranges of about 8 phr or less, eg, phr, including values of about 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10, respectively. To about 10 phr, about 1 phr to about 9 phr, about 2 phr to about 9 phr, about 2 phr to about 8 phr, about 2 phr to about 7 phr, and the like. Similarly, if a mixture of tackifiers is used, eg, two tackifiers of the same or different chemical types, each of the tackifiers may be present in equal or unequal amounts. The total amount of tackifier used is preferably constrained by the total amount listed immediately above.

  The tie layer composition is a mixing device such as a Banbury mixer, a mill roll mixer, an extruder mixer, for mixing elastomers, filler (s), process oils and other additives and for dispersing curing system components. Etc. can be used individually and in combination. Typically, components other than the curing system component are added at elevated temperatures and high shear to obtain a satisfactory dispersion of all non-elastomeric components in the elastomer and satisfactory dispersion of the elastomers in each other. Mixed. After such a mixing step, sometimes referred to as a masterbatch, the composition containing no curing system components uses, for example, a lower mill, lower shear section of a rubber mill or mixing extruder or internal mixer. Then it is cooled to a lower temperature and the curing system components are dispersed in the masterbatch. The temperature for mixing the curing agent is typically less than about 120 ° C, and preferably less than about 100 ° C.

  The vulcanizable tie layer composition can be formed into a layer suitable for end use applications, for example, using an extruder or calender. Where convenient or useful, extrusion may include the use of equipment that allows double or multiple extrusion of a fluid (preferably air) permeation prevention layer, a tie layer and an outer high diene rubber layer. In a preferred embodiment, the tie layer is manufactured for use in a tire structure, typically about 5 mm or less, preferably about 2.5 mm or less, more preferably about 0.2 to about It has a thickness that is 2.0 mm, most preferably from about 0.2 to about 1.5 mm, such as from about 0.3 to about 0.9 mm. The thickness of the tie layer for use in the hose structure may be the same or different depending on the application in which the hose is used. For example, an unreinforced low pressure hose may have different performance requirements than a high pressure reinforced hose, and similarly, a hose intended for use with liquids is not intended for use with gases. It can be different. Thickness adjustment is within the technical scope of the product designer, engineer or chemist, if necessary, based on limited experimentation.

  Ingredient mixing can be achieved when the polymer component and the filler is clay, and the clay in the form of an insert is replaced with any suitable mixing device, such as a Banbury® mixer, a Brabender® mixer (laboratory mixing). Or preferably by bringing them together in a mixer / extruder. Mixing is typically performed at temperatures above the softening point of the elastomer and / or secondary elastomer or rubber used in the composition, such as in other embodiments from about 80 ° C to about 300 ° C, In other embodiments, at 120 ° C. to about 250 ° C. or less, the clay is exfoliated from insertion and performed under conditions of sufficient shear to uniformly disperse in the polymer to form a nanocomposite. When preparing a composition that is not dynamically vulcanized, typically about 70% to about 100% of the elastomer or group of elastomers is first prepared for about 20 to about 90 seconds or at a temperature of about 40 to about 60 ° C. Mix until reached. The remaining amount of filler and elastomer, if any, is then typically added to the mixer and mixing is continued until the temperature reaches about 90 ° C to about 150 ° C. The finished mixture is then sheeted on an open mill and allowed to cool to about 60 ° C. to about 100 ° C. at which point a curing system or curing agent is added. Instead, the curing system can be mixed in the internal mixer of the mixing extruder, provided that appropriate care is taken to control the temperature.

  Clay mixing is performed by techniques known to those skilled in the art, where in one embodiment, the clay is added to the polymer (s) simultaneously with the carbon black. If used, process oils are typically added later in the mixing cycle after the carbon black and clay have achieved proper dispersion in the elastomeric or polymer matrix.

  The compositions of the present disclosure and layered structures formed using such compositions are useful in tire applications; tire curing bladders; And can be used. This composition and a tie layer comprising such a composition are particularly useful in pneumatic tires to promote adhesion of the tire inner liner to the inner surface of the tire and air retention characteristics. Particularly useful structures are those in which the tire inner liner layer forms the innermost surface of the tire and the inner liner layer surface opposite the one that forms the air retention chamber is in contact with the tie layer of the present disclosure. It is. Alternatively, an adhesive layer can be used between the inner liner layer and the tie layer. The surface of the tie layer opposite the one in contact with the innerliner (or adhesive layer) is in contact with a tire layer referred to as a carcass, in other words, a tire layer typically made of reinforced tire cord. is there. As explained in detail earlier, the innerliner layer exhibits advantageously low permeability properties and is preferably dynamically vulcanized, including engineering resins, particularly polyamides and halogenated isobutylene-paramethylstyrene copolymers. Including a composition. In addition, as a result of the unique composition of the tie layer based on epoxidized natural rubber and tackifier, it is particularly unvulcanized adhesive strength and high vulcanization to the inner liner layer surface where it is in contact. The ability to generate good adhesion allows the use of a thin tie layer compared to prior art compositions. The resulting overall structure based on such an innerliner and tie layer allows tire structures (and other structures including air or fluid retaining layers and tie layers) with reduced weight. Such weight savings in the tire structure are significant.

  Tire innerliner compositions (ie, preferably nylon and BIMS DVA) can be applied to common mixing techniques including, for example, kneading, roll milling, extruder mixing, internal mixing (eg, with a Banbury® mixer), and the like. Can be manufactured by using. The order of mixing and temperature used is well known to rubber compounders having ordinary skill in the art, the purpose of which is to engineer the innerliner in combination with DVA technology as described above. Of fillers, activators and hardeners in a polymer matrix under temperature controlled conditions that will vary depending on whether the resin is based or based on non-DVA technology Distributed. For the production of inner liners based on non-DVA technology, a useful mixing procedure utilizes a Banbury mixer in which copolymer rubber, carbon black and plasticizer are added to achieve proper dispersion of the components To do so, the composition is mixed for a desired time or at a specific temperature. Instead, a portion of the rubber and carbon black (eg 1/3 to 2/3) is mixed for a short time (eg about 1 to 3 minutes), followed by the remainder of the carbon black and the oil. Mixing continues at a high rotor speed for about 5 to 10 minutes during the time that the mixed components reach a temperature of about 140 ° C. Following cooling, the ingredients are added in a second stage, for example on a rubber mill or in a Banbury mixer, in order to avoid premature curing or “scorching” of the composition, such as curing agents and optional accelerators. Mix at a relatively low temperature, eg, about 80 ° C. to about 105 ° C., while being fully and uniformly dispersed. Variations in mixing will be readily apparent to those skilled in the art and the present disclosure is not limited to any particular mixing procedure. This mixing is performed in order to disperse all the components of the composition sufficiently and uniformly.

  The innerliner layer or “stock” is then calendered with the compounded rubber composition into a sheet material having a thickness of about 0.5 mm to about 2 mm, and the sheet material is made to a specific size and Manufactured by cutting into pieces of appropriate width and length for innerliner application in type tires. This inner liner is then ready for use as an element in the assembly of a pneumatic tire. Pneumatic tires typically consist of an outer surface containing tread and sidewall elements, an intermediate consisting of a number of plies containing tire reinforcing fibers (eg rayon, polyester, nylon or metal fibers) embedded in a rubbery matrix. It comprises a multilayer laminate comprising a carcass layer, a tie layer as described herein, an optional adhesive layer, and an inner liner layer. Tires are typically assembled on tire molding drums using the layers described above. After assembling the uncured tire with this drum, it is removed and placed in a heated mold. The mold includes an inflatable tire shaping bladder that is installed within the internal environment of the uncured tire. After closing the mold, it shapes the tire by inflating the bladder and pressing it against the inner surface of the closed mold during the initial stages of the curing process. The temperature of the tire is raised to the vulcanization temperature by heat in the bladder and the mold. The vulcanization temperature is typically about 100 ° C to about 250 ° C, preferably about 150 ° C to about 200 ° C. The curing time can vary from about 1 minute to several hours, preferably from about 5 minutes to 30 minutes. Cure time and temperature depend on a number of variables known in the art, including the composition of the tire components, the cure system in each of the layers, the overall tire size and thickness, and the like. Vulcanization parameters include test procedures and stress-strain tests, adhesion tests, flex tests, etc. described in ASTM D2048 (Rubber Properties Using Oscillating Disc Curing Meter—Standard Test Method for Vulcanization) It can be established with the help of various known laboratory test methods. Vulcanization of the assembled tire results in complete or substantially complete vulcanization or crosslinking of all elements or layers of the tire assembly, i.e., inner liner, carcass and outer tread and sidewall layers. In addition to the development of the desired strength properties of each layer and the overall structure, vulcanization enhances the adhesion between these elements, resulting in a cured, unitary tire with multiple layers separated from it. .

  FIG. 1 is a half-sectional view along the meridian of a tire showing a typical example of air permeation prevention or inner liner layer arrangement of a pneumatic tire. In FIG. 1, the carcass layer 2 includes a left bead core 1 and a right bead core 1 (for simplicity, only one half of a symmetric cross-sectional view is included, so that the second bead core is not shown. I want to pay attention). An inner liner layer 3 is provided on the tire inner surface inside the carcass layer 2. The tie layer 5 of the present disclosure is interposed between the inner liner layer and the carcass layer. The inner liner layer is indicated by 3 and the tire sidewall is indicated by 4.

The following examples are given as specific illustrations of the embodiments of the present disclosure as set forth in the claims. It should be understood, however, that the disclosure is not limited to the specific details set forth in the examples. All parts and percentages in the examples and specification are by weight unless otherwise specified. In addition, any numerical range recited in the specification or claims, such as those representing a particular set of properties, unit of measure, condition, physical state or percentage, is so recited. All numbers falling within such ranges, including any subset of numbers within any range, are intended to be explicitly included herein by reference or otherwise. For example, whenever a numerical range having a lower limit R _L and an upper limit R _U is disclosed, any number R falling within this range is specifically disclosed. In particular, the following number R within this range is specifically disclosed. R = R _L + k (R _U −R _L ) (where k is a variable in the range of 1% to 100% in 1% increments, for example, k is 1%, 2%, 3% 4%, 5%, ... 50%, 51%, 52%, ... 95%, 96%, 97%, 98%, 99% or 100%). Moreover, any numerical range represented by any two R values as calculated above is also specifically disclosed.

  For the purposes of this disclosure, the term “substantially” when applied to all criteria, such as properties, features or variables, unless otherwise defined with respect to a particular property, feature or variable. It is meant to meet the stated criteria on a scale such that the person skilled in the art understands that the benefits to be achieved or the conditions or properties desired are met.

  Throughout the specification, including the claims, the word “comprise” and variations of that word as well as “having”, “including”, “including” and variations thereof refer to the name to which it relates. The listed steps, elements or materials are essential, but other steps, elements or materials can be added, and still form a composition, composition or step within the scope of the claims or disclosure. means. When describing a disclosure and when recited in the claims, what is disclosed and claimed means to follow and potentially be considered more than that. These terms, particularly when applied to the claims, are not exhaustive or limitative and do not exclude additional unlisted elements or method steps.

  In this context, “consisting essentially of” is any element or combination of elements and any combination of elements or elements that changes the fundamental and novel features of the present disclosure. It also means to exclude the amount. Thus, for example, a high-diene rubber or other polymer or polymer combination is used for the elimination of epoxidized natural rubber in the tie layer, and / or the layered construction and / or the air permeation prevention layer is an engineering resin-containing composition. Layered structures produced from compositions other than by dynamically vulcanizing the article would be excluded. Similarly, again for illustrative purposes only, a tie layer comprising one or more additional additives that does not interfere with achieving the appropriate level of tack strength and vulcanization adhesion of the resulting layered structure. It will not be excluded. For example, small amounts of compatibilizers, anti-aging agents, process oils or other low molecular weight additives to the extent that they do not significantly change the tack, adhesion or air or fluid permeability of the layered structure or tie layer Could still be used.

  As used throughout the specification, including the described aspects, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, “tackifier” includes a single tackifier and two or more different tackifiers combined, and “epoxidized natural rubber” includes two or more epoxidations. Included are mixtures of natural rubber and one epoxidized natural rubber.

  The term “about” is specifically recited so long as the value of the property or condition concerned is reasonably readily compatible with the technical purpose (s) of the present disclosure as detailed in the specification and claims. Includes values larger and smaller than those. More specifically, the term “about” when used as a modifier for a variable or in conjunction with a variable indicates that the numerical values and ranges disclosed herein are flexible and is within the stated ranges. This disclosure by those skilled in the art using outside or different from a single value, eg concentration, amount, content, carbon number, temperature, pressure, properties such as density, purity, strength, stickiness etc. An elastomeric composition comprising a desired result, ie an epoxidized natural rubber suitable for use in a tire tie layer, preferably in combination with at least one tackifier, wherein the composition Is intended to convey that it will achieve improved tire assembly tack, cured adhesion, and impervious properties useful in the construction of pneumatic tires and the like.

  In an alternative embodiment, the composition described herein can be a pressure vessel, such as any vessel designed to hold a pressure above the atmospheric pressure of a fluid (liquid or gas, such as air or water). Can be used within. Preferably, the vessel holds a pressure of at least 10 psi, more preferably at least 20 psi, at 230 ° C. for 24 hours.

  A composition was prepared according to the following examples. The amount of each component used is based on parts per hundred (phr) of rubber present in the composition. The following commercial products were used for the ingredients used in the example compositions:

  In accordance with the compositions or formulations listed in Table I, Comparative Examples 1-6 were prepared using a Banbury® internal mixer and mixed using a standard non-DVA mixing procedure. In a typical mixing cycle, the Banbury internal mixer is preheated between 40 ° C. and 60 ° C., the polymer is added and mixed. In 1 minute, the rest of the ingredients (excluding the curing agent) are added and mixing is continued to a temperature of about 130 ° C. to about 150 ° C., at which point the composition is drained and cooled. The cooled material is then placed back into the Banbury mixer at a temperature below that at which the curing system component reacts, the curing system component is added to the composition in the Banbury mixer, and the composition is heated to a temperature of about 100 ° C. And then dumped from the mixer and cooled.

  The test methods used to evaluate the performance of the compositions in Table I and the tables that follow are described below.

Adhesion Test to DVA A DVA film (thickness: 200 μm) shown in Table III was placed on a 2 mm unvulcanized rubber sheet shown in Table I and vulcanized at 180 ° C. for 10 minutes. This was set in a dematcher crack tester manufactured by Ueshima Seisakusho and subjected to continuous tensile strain for 500,000 cycles using a 60 mm chuck distance and a 10 mm stroke. The peeling of the film from the knife cut portion was observed with the naked eye and evaluated according to the following criteria.
++ No peeling of film + Slight peeling from cut (but not broken)
-Significant peeling from the cut and interfacial peeling

Adhesion Test for Diene Rubber An unvulcanized rubber sheet shown in Table I was set on the top of the measuring device. The rubber sheet affixed to the bottom sample (DVA film such as a tire inner liner or other fluid permeation prevention layer composition) at the mounting position of the measuring device was pressed together with the unvulcanized sheet. The force required to peel the sheet from the DVA film is reported as tacky. The measuring device was a PICMA tack tester manufactured by Toyo Seiki Seisakusho, and the measurement was performed under the following conditions.
Reference sample (top) dimensions: 12.7 mm x 152 mm
Press force: 4.90N
Peeling speed: 120mm / min
Press time: 10 seconds Temperature: 20 ° C
Humidity: 65%

  Compositions of the present disclosure were prepared for the compositions shown in Table I as described above according to the compositions or formulations described in Table Ia.

  The diene rubber compositions shown in Table II were prepared as described above for the compositions in Table I and Table Ia.

The thermoplastic DVA compositions shown in Table III were prepared as follows.
A thermoplastic elastomer innerliner layer was prepared at 230 ° C. using a dynamic vulcanization mixing method and a twin screw extruder. DVA was prepared according to the method described in the section entitled “Production of Thermoplastic Elastomer Composition θ” in EP0969039. The elastomer component and vulcanization system were fed to a kneader, mixed for about 3.5 minutes, and discharged at about 90 ° C. to prepare an elastomer component having a vulcanization system. The mixture was then pelletized with a rubber pelletizer. Subsequently, the elastomer component and the resin component were supplied to a twin-screw mixing extruder and dynamically vulcanized to prepare a thermoplastic elastomer composition.

  All documents mentioned in this specification, including all priority documents and / or test procedures, are hereby incorporated by reference to the extent they do not conflict with this specification. The principles, preferred embodiments and modes of operation of the present disclosure have been described in the specification. Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present disclosure. Accordingly, it is understood that numerous modifications can be made to the exemplary embodiments and other arrangements can be devised without departing from the spirit and scope of the present disclosure as defined by the appended claims. It should be. Similarly, the term “consisting of” is considered synonymous with the term “including” for purposes of Australian law.

FIG. 3 is a simplified cross-sectional view showing the position of various layers in a tire including a tie layer.

Claims (78)

A vulcanizable layered composition comprising at least two layers and at least one tie layer, the first of the two layers including a fluid permeation prevention layer and the second of the two layers at least Containing one high diene rubber and the tie layer is 100 parts by weight of rubber in the mixture,
(1) about 10 to about 70 parts by weight of epoxidized natural rubber,
(2) about 30 to about 90 parts by weight of at least one high diene elastomer;
(3) about 20 to about 90 parts by weight of at least one filler;
(4) about 1 to about 20 parts by weight of at least one tackifier, and (5) at least about 0.2 to about 15 parts by weight of a mixture of elastomer and rubber curing system, said fluid permeation The prevention layer comprises a polymer composition having an air permeability coefficient of 25 × 10 ⁻¹² cc · cm / cm ² sec cmHg (30 ° C.) or lower and a Young's modulus of 1 to 500 MPa, ,
(A) At least 10% by weight, based on the total weight of the polymer composition, at least one air permeability coefficient of 25 × 10 ⁻¹² cc · cm / cm ² sec cmHg (30 ° C.) or lower and 500 MPa A thermoplastic engineering resin component selected from the group consisting of a polyamide resin, a polyester resin, a polynitrile resin, a polymethacrylate resin, a polyvinyl resin, a cellulose resin, a fluororesin, and an imide resin, and (B) a polymer composition Having an air permeability coefficient greater than 25 × 10 ⁻¹² cc · cm / cm ² sec cmHg (30 ° C.) and a Young's modulus of 500 MPa or less, at least 10% by weight, based on the total weight of Diene rubber and its hydride, halogen-containing rubber, silicone rubber, Comprising an elastomer component selected from the group consisting of yellow-containing rubber, fluororubber, hydrin rubber, acrylic rubber, ionomer and thermoplastic elastomer, wherein the total amount of component (A) and component (B) is the total weight of the polymer composition The thermoplastic resin component (30% by weight or more) in the polymer composition as a discontinuous phase when the elastomer component (B) is vulcanized or partially vulcanized. Dispersed in the matrix of A),
The amount and type of the at least one tackifier is such that it provides adequate adhesion between the layers, and the tie layer substantially delaminates adjacent layers prior to crosslinking. And the composition is effective to provide a desired multilayer structure with sufficient uncured adhesive strength to allow assembly of the multilayer structure.   The epoxidized natural rubber is selected from the group consisting of about 10-75 mol%, about 15-60 mol%, about 20-55 mol%, about 25-50 mol%, about 25 mol% and about 50 mol% epoxide. The composition of claim 1 comprising an amount of epoxide.   Component (2) is natural rubber or synthetic rubber containing at least 50 mol% diene monomer, polyisoprene, polybutadiene, poly (styrene-co-butadiene), poly (styrene-butadiene-styrene) block copolymer, natural rubber And the composition according to any one of claims 1 to 3, which is selected from the group consisting of and mixtures thereof.   The composition according to claim 3, wherein the component (2) is natural rubber.   The at least one filler is selected from the group consisting of carbon black, clay, exfoliated clay, calcium carbonate, mica, silica, silicate, talc, titanium dioxide, wood flour, and mixtures thereof. The composition of any one of 1-4.   The composition of claim 5, wherein the at least one filler is selected from the group consisting of carbon black, exfoliated clay, and mixtures thereof.   7. A composition according to any one of the preceding claims, wherein the at least one curing system comprises at least one curing agent and optionally at least one accelerator.   The composition according to any one of claims 1 to 7, further comprising an additive selected from the group consisting of a pigment, an anti-aging agent, an anti-ozonation agent, a processing aid, a compound compatibilizer, and a mixture thereof. .   9. Any of claims 1-8 suitable for use in a tire wherein the layer containing at least one engineering resin is an inner liner layer and the layer containing the high diene rubber is a carcass layer or a sidewall layer or both. The composition according to claim 1.   The composition according to any one of claims 1 to 9, wherein the engineering resin is selected from the group consisting of polyamide resins.   The engineering resin is nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66 copolymer, nylon 6/66/610 copolymer, nylon MXD6, nylon 6T, nylon 6 / 6T copolymer. , Nylon 66 / PP copolymer, nylon 66 / PPS copolymer, polybutylene terephthalate, polyethylene terephthalate, polyethylene isophthalate, polyethylene terephthalate / polyethylene isophthalate copolymer, polyacrylate, polybutylene naphthalate, liquid crystal polyester, polyoxyalkylene diimidate / Polybutylene terephthalate copolymer, polyacrylonitrile, polymethacrylonitrile, acrylonitrile / styrene Copolymer, methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene copolymer, polymethyl methacrylate, polyethyl methacrylate, ethylene vinyl acetate, polyvinyl alcohol, vinyl alcohol / ethylene copolymer, polyvinylidene chloride, polyvinyl chloride, vinyl chloride / Selected from the group consisting of vinylidene chloride copolymer, vinylidene chloride / methacrylate copolymer, cellulose acetate, cellulose acetate butyrate, polyvinylidene fluoride, polyvinyl fluoride, polychlorofluoroethylene, tetrafluoroethylene / ethylene copolymer, aromatic polyimide and mixtures thereof The composition according to any one of claims 1 to 9.   The elastomer component (B) is natural rubber, synthetic polyisoprene rubber, epoxidized natural rubber, styrene-butadiene rubber (SBR), polybutadiene rubber (BR), nitrile-butadiene rubber (NBR), hydrogenated NBR, hydrogenated SBR; ethylene Propylene diene monomer rubber (EPDM), ethylene propylene rubber (EPM), maleic acid modified ethylene propylene rubber (M-EPM), butyl rubber (IIR), isobutylene-aromatic vinyl or diene monomer copolymer, brominated IIR, chlorinated IIR, Brominated isobutylene p-methylstyrene copolymer, chloroprene rubber, epichlorohydrin homopolymer rubber, epichlorohydrin-ethylene oxide or allyl glycidyl ether copolymer rubber, epichlorohydrin-ethyleneoxy -Allyl glycidyl ether terpolymer rubber, chlorosulfonated polyethylene, chlorinated polyethylene, maleic acid modified chlorinated polyethylene, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber, polysulfide rubber, vinylidene fluoride rubber, tetrafluoroethylene The composition according to claim 1, which is selected from the group consisting of propylene rubber, fluorinated silicone rubber, fluorinated phosphagen rubber, styrene elastomer, thermoplastic olefin elastomer, polyester elastomer, urethane elastomer and polyamide elastomer. object. Said at least one elastomer component (B) is a halide of C _{4 to} C ₇ isomonoolefin and p-alkylstyrene copolymer, brominated isobutylene-p-methylstyrene copolymer, hydrogenated nitrile-butadiene rubber, acrylonitrile butadiene rubber, The composition according to any one of claims 1 to 12, which is selected from the group consisting of chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, chlorinated butyl rubber and brominated butyl rubber.   The composition according to any one of claims 1 to 13, wherein the elastomer component of the air permeation preventive layer is substantially completely vulcanized.   The composition according to claim 1, wherein the at least one tackifier comprises at least one selected from the group consisting of rosin, rosin derivatives, tert-butylphenol and acetylene condensates, and mixtures thereof.   16. The composition of claim 15, wherein the tackifier comprises at least two mixtures selected from the group consisting of rosin, rosin derivatives, tert-butylphenol and acetylene condensates, and mixtures thereof.   The composition according to claim 16, wherein the tackifier comprises a mixture of at least one of rosin or rosin derivatives and a condensate of tert-butylphenol and acetylene.   18. Each of the tackifiers is present in phr at a concentration selected from the group consisting of about 1 to about 20, about 2 to about 18, about 3 to about 16, and about 4 to about 14. Composition.   19. A composition according to claim 18 wherein each tackifier is present in a substantially equal amount.   20. A composition according to claim 19 present in about 4 to about 10 phr of each tackifier.   19. The composition of claim 18, wherein the at least two tackifiers are present in a weight ratio to the other of about 1 to about 10: about 10 to about 1. (A) a first layer containing an elastomer,
(B) a second layer comprising a dynamically vulcanized alloy of an engineering resin and a copolymer of isoolefin and para-alkylstyrene; and (C) (1) about 10 to about 70 parts by weight of epoxidized natural rubber;
(2) about 30 to about 90 parts by weight of at least one high diene elastomer;
(3) about 20 to about 90 parts by weight of at least one filler;
(4) about 1 to about 20 phr (parts per 100 parts) of at least one tackifier; and (5) at least about 0.2 to about 15 phr (parts per 100 parts of rubber) of the elastomer and rubber. An article comprising a tie layer comprising a curable mixture, the tie layer being disposed between the first layer and the second layer, wherein the at least one tackifier The amount and type is sufficient to provide adequate adhesion between the layers, allowing assembly of the article without substantial detachment of the tie layer relative to adjacent layers prior to crosslinking. Articles that are effective in providing the desired article with sufficient uncured adhesive strength to do.   23. The article of claim 22, wherein the engineering resin is selected from the group consisting of polyamide resin, polyester resin, polynitrile resin, poly (meth) acrylate resin, polyvinyl resin, cellulose resin, fluororesin, imide resin, and mixtures thereof. A halogen-containing random copolymer of para-alkylstyrene, C _{4 to} C ₁₂ isomonoolefin, wherein the elastomer of the first layer comprises C _{4 to} C ₇ isomonoolefin and about 0.5 to about 20% by weight of the copolymer; And a halogen-containing random copolymer of C _{4 to} C ₁₄ multiolefin (wherein the halogen is selected from the group consisting of chlorine, bromine and mixtures thereof), natural rubber or at least 50 mol% diene monomer, polyisoprene, 23. The method of claim 22, wherein the rubber is selected from the group consisting of polybutadiene, poly (styrene-co-butadiene), poly (styrene-butadiene-styrene) block copolymer, natural rubber, and mixtures thereof. Goods.   The engineering resin is nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66 copolymer, nylon 6/66/610 copolymer, nylon MXD6, nylon 6T, nylon 6 / 6T copolymer. , Nylon 66 / PP copolymer, nylon 66 / PPS copolymer, polybutylene terephthalate, polyethylene terephthalate, polyethylene isophthalate, polyethylene terephthalate / polyethylene isophthalate copolymer, polyacrylate, polybutylene naphthalate, liquid crystal polyester, polyoxyalkylene diimidate / Polybutylene terephthalate copolymer, polyacrylonitrile, polymethacrylonitrile, acrylonitrile / styrene Copolymer, methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene copolymer, polymethyl methacrylate, polyethyl methacrylate, ethylene vinyl acetate, polyvinyl alcohol, vinyl alcohol / ethylene copolymer, polyvinylidene chloride, polyvinyl chloride, polyvinyl / poly Selected from the group consisting of vinylidene copolymers, vinylidene chloride / methacrylate copolymers, cellulose acetate, cellulose acetate butyrate, polyvinylidene fluoride, polyvinyl fluoride, polychlorofluoroethylene, tetrafluoroethylene / ethylene copolymers, aromatic polyimides and mixtures thereof The article according to claim 22 or 24.   The at least one diene elastomer in the tie layer is selected from the group consisting of polyisoprene, polybutadiene, poly (styrene-co-butadiene), poly (styrene-butadiene-styrene) block copolymers, natural rubber, and mixtures thereof. Item 22. The article according to Item 22.   27. The article of claim 26, wherein the at least one high diene elastomer comprises natural rubber.   28. The article of claim 22, 26, or 27, wherein the at least one tackifier comprises at least one selected from the group consisting of rosin, rosin derivatives, tert-butylphenol and acetylene condensates, and mixtures thereof. .   29. The article of claim 28, wherein the tackifier comprises at least two mixtures selected from the group consisting of rosin, rosin derivatives, tert-butylphenol and acetylene condensates, and mixtures thereof.   30. The article of claim 29, wherein the tackifier comprises a mixture of at least one rosin or rosin derivative and a condensate of tert-butylphenol and acetylene.   31. Each of the tackifiers is present in phr at a concentration selected from the group consisting of about 1 to about 20, about 2 to about 18, about 3 to about 16, and about 4 to about 14. Goods.   32. The article of claim 31, wherein each tackifier is present in a substantially equal amount.   The article of claim 32, wherein each of said tackifiers is present at about 4 to about 10 phr.   32. The article of claim 31, wherein the at least two tackifiers are present in a weight ratio to the other of about 1 to about 10: about 10 to about 1.   35. Article according to any one of claims 22 to 34, which is substantially in the form of a hose.   A pneumatic tire comprising an outer tread and a sidewall portion, an inner carcass portion bonded to the tread sidewall portion, a tie layer having a top surface and a bottom surface, and an inner liner layer having a top surface and a bottom surface. A top surface of the inner liner layer is bonded to a bottom surface of the tie layer, a top surface of the tie layer is bonded to a carcass portion, the inner liner layer includes an engineering resin, and the tie layer A pneumatic tire comprising the composition according to any one of claims 1 to 21. The innerliner layer includes a dynamically vulcanized alloy of an engineering resin and a halogen-containing random elastomeric copolymer of C _{4 to} C ₇ isoolefin and para-alkyl styrene, wherein the para-alkyl styrene is about 37. The pneumatic tire of claim 36, comprising 0.5 to about 20 wt%, wherein the elastomeric copolymer is dispersed in the engineering resin matrix as a discontinuous phase in a vulcanized state. The inner liner layer comprises a dynamically vulcanized alloy of an engineering resin and a halogen-containing random elastomer copolymer of C _{4 to} C ₁₂ isomonoolefin and C _{4 to} C ₁₄ multiolefin, the elastomer copolymer being vulcanized 37. The pneumatic tire according to claim 36, wherein the pneumatic tire is dispersed as a discontinuous phase in a matrix of the engineering resin.   The pneumatic tire according to any one of claims 36 to 38, wherein the tire is vulcanized.   40. Tire according to any one of claims 36 to 39, selected from the group consisting of tires suitable for use in automobiles, trucks, construction vehicles, recreational vehicles and farm vehicles. A method for producing a pneumatic tire comprising a carcass element containing a high diene rubber and an inner liner layer as the innermost layer of the pneumatic tire, comprising 100 parts by weight of rubber in the mixture,
(A) (1) about 10 to about 70 parts by weight of at least one halogenated isobutylene-containing elastomer,
(2) about 30 to about 90 parts by weight of at least one high diene elastomer;
(3) about 20 to about 90 parts by weight of at least one filler;
(4) about 1 to about 20 phr (parts per 100 parts) of at least one tackifier; and (5) at least about 0.1 to about 15 parts by weight of a mixture of the elastomer and rubber curing system. Forming a tie layer from a composition comprising:
(B) forming an inner liner layer containing a halogenated isomonoolefin-containing elastomer and an engineering resin;
(C) contacting the tie layer with the carcass element to form a laminate structure;
(D) contacting the inner liner layer with the tie layer to form a further laminate structure, wherein the amount and type of the at least one tackifier is the appropriate adhesion between the layers Sufficient to allow assembly of the tire without substantial delamination of the tie layer to the innerliner layer or the carcass element prior to crosslinking in an amount to provide Effective in providing desired strength by providing adhesive strength, and (E) substantially vulcanizing the structure at a temperature of about 100 ° C. to about 250 ° C. Heating and shaping the tire into the desired shape under sufficient time and pressure.   42. The method of claim 41, wherein the at least one tackifier comprises at least one selected from the group consisting of rosin, rosin derivatives, condensates of tert-butylphenol and acetylene, and mixtures thereof. (I) An air permeation prevention layer comprising a polymer composition having an air permeability coefficient of about 25 × 10 ⁻¹² cc · cm / cm ² sec cmHg (30 ° C.) or less and a Young's modulus of about 1 to about 500 MPa. The layer of the polymer composition is
(A) at least 10% by weight, based on the total weight of the polymer composition, of at least one air permeability coefficient of about 25 × 10 ⁻¹² cc · cm / cm ² sec cmHg (30 ° C.) or less and 500 MPa A thermoplastic resin component selected from the group consisting of a polyamide resin, a polyester resin, a polynitrile resin, a polymethacrylate resin, a polyvinyl resin, a cellulose resin, a fluororesin, and an imide resin, and (B) the polymer composition Having an air permeability coefficient greater than about 25 × 10 ⁻¹² cc · cm / cm ² sec cmHg (30 ° C.) and a Young's modulus of 500 MPa or less, at least 10% by weight, based on the total weight of , Diene rubber and its hydride, halogen-containing rubber, silicone rubber, sulfur-containing rubber An elastomer component selected from the group consisting of fluorine rubber, hydrin rubber, acrylic rubber, ionomer and thermoplastic elastomer, wherein the total amount of component (A) and component (B) (A) + (B) is the polymer. The thermoplastic resin component (A) in the polymer composition is about 30% by weight or more based on the total weight of the composition, and the elastomer component (B) is in a vulcanized state as a discontinuous phase. An air permeation prevention layer, dispersed in a matrix of
(Ii) a layer facing at least one surface of the air permeation prevention layer; and (iii) a tie layer stacked between the air permeation prevention layer and the layer (ii), the tie layer comprising a mixture For 100 parts by weight of rubber inside
(1) about 10 to about 70 parts by weight of epoxidized natural rubber,
(2) about 30 to about 90 parts by weight of at least one high diene elastomer;
(3) about 20 to about 90 parts by weight of at least one filler;
(4) about 1 to about 20 phr (parts per 100 parts) of at least one tackifier; and (5) at least about 0.1 to about 15 phr (parts per 100 parts of rubber) of the elastomer and rubber. A pneumatic tire comprising a curable mixture, wherein the amount and type of the at least one tackifier is an amount to provide adequate adhesion between the layers, and before the crosslinking, the inner liner layer Or effective in producing the desired tire with sufficient uncured adhesive strength to allow assembly of the tire without substantial delamination of the tie layer to the carcass element. Pneumatic tires that are things.   The epoxidized natural rubber is selected from the group consisting of about 10-75 mol%, about 15-60 mol%, about 20-55 mol%, about 25-50 mol%, about 25 mol% and about 50 mol% epoxide. 44. A pneumatic tire according to claim 43, comprising an amount of epoxide.   The at least one high diene elastomer in the tie layer is natural rubber or a synthetic rubber containing at least 50 mol% diene monomer, and is polyisoprene, polybutadiene, poly (styrene-co-butadiene), poly (styrene-butadiene) 45. A pneumatic tire according to claim 44, selected from the group consisting of (styrene) block copolymers, natural rubber and mixtures thereof.   The pneumatic tire according to claim 44 or 45, wherein the tie layer component (2) contains natural rubber. Wherein component (i) (A) is at least one polyamide resin, said component (i) (B) is C ₄ -C ₇ isomonoolefin and para - bromine-containing random elastomeric copolymer of an alkylstyrene, and The pneumatic tire according to claim 46, wherein the tie layer component (1) is an epoxidized natural rubber containing about 50 mol% of epoxide.   The at least one tackifier is at least one selected from the group consisting of rosin, rosin derivatives, condensates of tert-butylphenol and acetylene, and mixtures thereof. The described pneumatic tire.   38. A tire structure according to any one of claims 35 to 37, sufficient to substantially vulcanize the tire including the portions and layers therein at a temperature of about 100C to about 250C. Vulcanized pneumatic tire manufactured by heating for a long time.   Interposing a tie layer (iii) between the air permeation prevention layer (i) and the layer (ii) facing at least one surface of the air permeation prevention layer and then processing the tire; The method for manufacturing a pneumatic tire according to any one of claims 43 to 47, further comprising a vulcanizing step. A vulcanizable layered structure comprising at least two layers and at least one tie layer, wherein one of the two layers comprises a fluid permeation prevention layer and the second layer of the at least two layers is at least one kind. Comprising high diene rubber, wherein the tie layer is based on 100 parts by weight of rubber in the mixture;
(1) about 10 to about 70 parts by weight of epoxidized natural rubber,
(2) about 30 to about 90 parts by weight of at least one high diene elastomer;
(3) about 20 to about 90 parts by weight of at least one filler;
(4) about 1 to about 20 phr (parts per 100 parts) of at least one tackifier; and (5) at least about 0.1 to about 15 phr (parts per 100 parts of rubber) of the elastomer and rubber. A mixture of curing systems, wherein the amount and type of the at least one tackifier is an amount to provide adequate adhesion between the layers, and the tie to the adjacent layer prior to crosslinking. To produce the desired vulcanizable layered structure with sufficient uncured adhesive strength to allow assembly of the vulcanizable layered structure without causing substantial delamination of the layer. Effective, wherein the fluid permeation prevention layer comprises a polymer composition having a Young's modulus of 1 to 500 MPa, and the layer of the polymer composition comprises:
(A) at least 10% by weight based on the total weight of the polymer composition, at least one polyamide resin, polyester resin, polynitrile resin, polymethacrylate resin, polyvinyl resin, cellulose resin having a Young's modulus greater than 500 MPa, A thermoplastic resin component selected from the group consisting of a fluororesin and an imide resin; and (B) at least 10% by weight, based on the total weight of the polymer composition, of at least one 500 MPa or less Young's modulus; Comprising an elastomer component selected from the group consisting of diene rubber and its hydride, halogen-containing rubber, silicone rubber, sulfur-containing rubber, fluorine rubber, hydrin rubber, acrylic rubber, ionomer and thermoplastic elastomer, component (A) and component The total amount of (B) (A) + (B) is The thermoplastic resin component (A) in the polymer composition is 30% by weight or more based on the total weight of the polymer composition, and the elastomer component (B) is in a vulcanized state as a discontinuous phase. Structures dispersed in a matrix.   The epoxidized natural rubber is selected from the group consisting of about 10-75 mol%, about 15-60 mol%, about 20-55 mol%, about 25-50 mol%, about 25 mol% and about 50 mol% epoxide. 52. The composition of claim 51, comprising an amount of epoxide.   The at least one high diene elastomer in the tie layer is natural rubber or a synthetic rubber containing at least 50 mol% diene monomer, and is polyisoprene, polybutadiene, poly (styrene-co-butadiene), poly (styrene-butadiene- 53. The structure of claim 52, selected from the group consisting of (styrene) block copolymers, natural rubber, and mixtures thereof.   54. A structure according to claim 52 or 53, wherein said component (2) comprises natural rubber.   The said at least one filler is selected from the group consisting of carbon black, clay, exfoliated clay, calcium carbonate, mica, silica, silicate, talc, titanium dioxide, wood flour and mixtures thereof. The structure according to any one of 51 to 54.   56. The structure of claim 55, wherein the at least one filler is selected from the group consisting of carbon black, flaked clay, and mixtures thereof.   57. A structure according to any one of claims 51 to 56, wherein the at least one curing system comprises at least one curing agent and at least one accelerator.   58. The structure of any one of claims 51 to 57, further comprising an additive selected from the group consisting of pigments, antioxidants, antiozonants, processing aids, compound compatibilizers and mixtures thereof. body.   The at least one tackifier is at least one selected from the group consisting of rosin, rosin derivatives, condensates of tert-butylphenol and acetylene, and mixtures thereof. The structure described in 1.   60. The structure of claim 59, wherein the tackifier comprises at least two mixtures selected from the group consisting of rosin, rosin derivatives, condensates of tert-butylphenol and acetylene, and mixtures thereof.   61. The structure of claim 60, wherein the tackifier comprises a mixture of at least one rosin or rosin derivative and a condensate of tert-butylphenol and acetylene.   62. Each of the tackifiers is present in phr at a concentration selected from the group consisting of about 1 to about 20, about 2 to about 18, about 3 to about 16, and about 4 to about 14. Structure.   64. The structure of claim 62, wherein the tackifier is present in substantially equal amounts.   64. The structure of claim 63, wherein each of the tackifiers is present at about 4 to about 10 phr.   64. The structure of claim 62, wherein the at least two tackifiers are present in a weight ratio of about 1 to about 10: about 10 to about 1 to the other.   67. A structure according to any one of claims 51 to 66 suitable for use in a tire, wherein the layer comprising at least one engineering resin is a tire inner liner layer, and the high A structure in which the layer containing diene rubber is a tire carcass layer, a tire sidewall layer, or both.   The engineering resin is any one of claims 51 to 66 selected from the group consisting of a polyamide resin, a polyester resin, a polynitrile resin, a polymethacrylate resin, a polyvinyl resin, a cellulose resin, a fluororesin, an imide resin, and a mixture thereof. The structure described.   The engineering resin is nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66 copolymer, nylon 6/66/610 copolymer, nylon MXD6, nylon 6T, nylon 6 / 6T copolymer. , Nylon 66 / PP copolymer, nylon 66 / PPS copolymer, polybutylene terephthalate, polyethylene terephthalate, polyethylene isophthalate, polyethylene terephthalate / polyethylene isophthalate copolymer, polyacrylate, polybutylene naphthalate, liquid crystal polyester, polyoxyalkylene diimidate / Polybutylene terephthalate copolymer, polyacrylonitrile, polymethacrylonitrile, acrylonitrile / styrene Copolymer, methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene copolymer, polymethyl methacrylate, polyethyl methacrylate, ethylene vinyl acetate, polyvinyl alcohol, vinyl alcohol / ethylene copolymer, polyvinylidene chloride, polyvinyl chloride, vinyl chloride / Selected from the group consisting of vinylidene chloride copolymer, vinylidene chloride / methacrylate copolymer, cellulose acetate, cellulose acetate butyrate, polyvinylidene fluoride, polyvinyl fluoride, polychlorofluoroethylene, tetrafluoroethylene / ethylene copolymer, aromatic polyimide and mixtures thereof The structure according to any one of claims 51 to 66.   The at least one elastomer component B is natural rubber, synthetic polyisoprene rubber, epoxidized natural rubber, styrene-butadiene rubber (SBR), polybutadiene rubber (BR), nitrile-butadiene rubber (NBR), hydrogenated NBR, hydrogenated. SBR: ethylene propylene diene monomer rubber (EPDM), ethylene propylene rubber (EPM), maleic acid modified ethylene propylene rubber (M-EPM), butyl rubber (IIR), isobutylene-aromatic vinyl or diene monomer copolymer, brominated IIR, chlorine IIR, brominated isobutylene p-methylstyrene copolymer, chloroprene rubber, epichlorohydrin homopolymer rubber, epichlorohydrin-ethylene oxide or allyl glycidyl ether copolymer rubber, epichlorohydrin Ethylene oxide-allyl glycidyl ether terpolymer rubber, chlorosulfonated polyethylene, chlorinated polyethylene, maleic acid modified chlorinated polyethylene, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber, polysulfide rubber, vinylidene fluoride rubber, tetrafluoro 69. The method according to any one of claims 51 to 68, which is selected from the group consisting of ethylene-propylene rubber, fluorinated silicone rubber, fluorinated phosphagen rubber, styrene elastomer, thermoplastic olefin elastomer, polyester elastomer, urethane elastomer and polyamide elastomer. Structure. The at least one elastomer component B is a halide of C _{4 to} C ₇ isomonoolefin and p-alkylstyrene copolymer, brominated isobutylene-p-methylstyrene copolymer, hydrogenated nitrile-butadiene rubber, acrylonitrile butadiene rubber, chlorosulfone 70. The structure according to any one of claims 51 to 69, selected from the group consisting of chlorinated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, chlorinated butyl rubber and brominated butyl rubber.   The structure according to any one of claims 51 to 70, wherein the elastomer component of the fluid permeation preventive layer is substantially completely vulcanized.   72. A vulcanized structure according to any one of claims 51 to 71.   An article comprising the vulcanizable structure according to any one of claims 51 to 72.   74. The article of claim 73, selected from the group consisting of a hose and a pneumatic tire component.   The pressure vessel which consists of a composition of any one of Claims 1-21.   36. The article according to any one of claims 22 to 35, wherein the article is a pressure vessel. (I) An air permeation prevention layer comprising a polymer composition having an air permeability coefficient of about 25 × 10 ⁻¹² cc · cm / cm ² sec cmHg (30 ° C.) or less and a Young's modulus of about 1 to about 500 MPa. A layer of the polymer composition
(A) about 40 parts by weight, based on the total weight of the polymer composition, having an air permeability coefficient of about 25 × 10 ⁻¹² cc · cm / cm ² sec cmHg (30 ° C.) or less and a Young's modulus greater than 500 MPa. A nylon 6/66 copolymer polyamide resin component having (B) about 60 parts by weight based on the total weight of the polymer composition, air greater than about 25 × 10 ⁻¹² cc · cm / cm ² sec cmHg (30 ° C.) An elastomer component comprising a brominated random elastomeric copolymer of isobutylene containing about 1.2 wt% bromine and about 7.5 wt% para-methylstyrene having a permeability coefficient and a Young's modulus of 500 MPa or less; The matrix of the polyamide resin component (A) in the polymer composition as a discontinuous phase in a vulcanized state (B) They are dispersed in,
(Ii) a layer comprising at least one high diene elastomer facing at least one surface of the air permeation prevention layer; and (iii) layered between the air permeation prevention layer and the layer (ii). Tie layer (this tie layer is based on 100 parts by weight of rubber in the mixture,
(1) about 40 parts by weight of epoxidized natural rubber containing about 50 mol% of epoxide,
(2) about 60 parts by weight of natural rubber,
(3) about 50 parts by weight of carbon black,
(4) about 6 parts by weight of rosin,
(5) A pneumatic tire comprising about 15 parts by weight of an acetylene p-tert-butylphenol condensation product and (6) about 7.5 parts by weight of the rubber curing system mixture.   45. The composition of claim 1, the article of claim 22, the pneumatic tire of claim 36 or 43, or the claim, wherein the tie layer further comprises greater than about 0 parts by weight and about 20 parts by weight of at least one process oil. Item 51. The vulcanizable layered structure according to Item 51.

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