JP6238990B2 - Structure containing tie layer - Google Patents

Description

Cross-reference to related applications This application is incorporated herein by reference in its entirety, international application PCT / US2005 / 38705 filed October 27, 2005, and 2006-10. Claims the benefit of US patent application Ser. No. 12/091608, filed on Jan. 26.

  The present invention relates to a composition useful in a multilayer structure, such as a tire structure, particularly a tire tie layer between an inner liner and a carcass. More particularly, the present invention relates to rubber compositions that use halogenated isobutylene-containing elastomers, optionally blended with high diene-containing elastomers or rubbers, such as natural rubber (NR) and styrene butadiene rubber (SBR). Related to things.

  In order to prevent the tire cord from striking through, where the reinforced tire cord penetrates the inner liner layer and leads to air leakage and tire failure, the carcass layer including the textile cord or steel cord and the inner In general, a buffer layer is added between the liner layer. This buffer layer is called a tie rubber, tie layer, cushion compound, or liner backing layer and generally comprises a mixture of natural rubber (NR) and styrene-butadiene rubber (SBR). For the purposes of the present invention, this tire component is referred to as a “tie layer”. In general, the composition of the tie layer determines the molding tack required to maintain uncured, i.e., matched tire structure in the "green" state, cured adhesion, and satisfactory dynamic properties during tire use ( It is similar to the composition of a carcass compound to provide a building tack). However, both NR and SBR are highly permeable rubbers. Thus, a thicker cross-section is required to reduce the air permeability of this layer and maintain tire pressure. In order to achieve an overall tire weight reduction by using a thin, highly impermeable inner liner, it is necessary to find a means to reduce the cross-sectional thickness of the tie layer.

  U.S. Pat. No. 5,738,158 describes at least 20% by weight of a thermoplastic polyester elastomer consisting of a block copolymer of polybutylene terephthalate and polyoxyalkylene diimide diacid, with a polybutylene terephthalate / polyoxyalkylene diimide diester of 85/15 or less. A pneumatic tire having an air permeation preventive layer or an inner liner layer, which is made of a thin film of a resin composition containing a mass ratio of acid, is disclosed. The resin composition may further include dispersed rubber particles that are dynamically vulcanized. The concept of using a resin composition as an inner liner layer has been further developed by various inventors of the same assignee (eg, claiming a pneumatic tire containing such an inner liner, See US Pat. No. 6,079,465, which discloses the use of various thermoplastic resins for use in The patent also discloses the presence of a tie layer and another layer to promote adhesion or adhesive strength of the innerliner layer in the overall structure. Further progress in this technology to improve the adhesion of the innerliner layer in the structure is described in US Pat. No. 6,062,283, in which the melting of thermoplastic and elastomeric components Viscosity and solubility parameters are controlled according to specific formulas.

US 2002/0066512 is arranged inside a carcass ply cord along the inner surface of a carcass and a carcass including a ply of cord defining an innermost reinforcing cord layer between bead portions. , A pneumatic tire comprising an air tight layer covering substantially the entire tire inner surface, wherein the air tight layer is in its rubber base at least 10% by weight halogenated butyl rubber and / or halogenated isobutylene-para. The air tight layer is made of air-impermeable rubber containing methylstyrene copolymer, and the thickness of the air tight layer measured from the inner surface of the tire to the carcass ply cord is in the range of 0.2 to 0.7 mm. The published application discloses a diene system in which an “air tight layer” defined by a rubber layer between an inner surface of a tire and an innermost tire cord or carcass cord is an air-impermeable rubber compound and an air-impermeable layer. It is also disclosed that it can be a bilayer comprising an outer layer of rubber.
Alternatively, the outer layer may be a layer made of the same air-impermeable rubber compound or a similar air-impermeable rubber compound, and the compound is a halogenated butyl rubber and / or a halogenated isobutylene paramethylstyrene copolymer. And diene rubber and carbon black are further disclosed in the published application (see paragraphs 28-34).

  Other notable references include International Publication No. 2004/081107, International Publication No. 2004/081106, International Publication No. 2004/081108, International Publication No. 2004/081116, International Publication No. 2004/081099, JP-A 2000-238188, European Patent No. 0144219, US Pat. No. 6,759,136, and US Pat. No. 6,079,465 can be mentioned.

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 Publication No. 2004/081107 International Publication No. 2004/081106 International Publication No. 2004/081108 International Publication No. 2004/081116 International Publication No. 2004/081099 JP 2000-238188 A European Patent No. 1424219 US Pat. No. 6,759,136

  The present invention provides a solution by using at least one highly impermeable isobutylene-based elastomer in the tie layer, a particularly preferred impermeable elastomer being a brominated isobutylene-isoprene copolymer (BIIR), i.e. bromo. Butyl copolymer. The present invention is useful, for example, in tires using a thermoplastic elastomeric tire innerliner composition based on a vulcanized mixture of engineering resins such as polyamide and BIMS made using dynamic vulcanization. is there. The tie layer is directly bonded to the dynamic vulcanized alloy layer without compromising the improved transmission properties achieved by the innerliner and without using additional bonding means to bond the two layers. The

  One embodiment of the disclosed invention is a method for forming a layered structure in which a fluid permeation prevention film and an adhesive tie layer are directly bonded. Prior to laminating the two layers, the fluid permeation prevention layer is treated to remove any residual plasticizer or oil on the surface of the film. The two layers of the layered structure may be extruded separately and then adhered to each other during a calendering operation, and the adhesive tie layer composition is coated onto the treated film.

  In any embodiment of the disclosed invention, the tie layer comprises 100% by weight of at least one halogenated isobutylene-containing elastomer and from about 1 to about 20 phr (parts per 100 parts rubber) of at least one tackifier. Contains a mixture.

  In any aspect of the disclosed invention, the fluid permeation prevention film is dispersed as a discontinuous phase in a vulcanized or partially vulcanized state in a matrix of a thermoplastic resin component. Contains an elastomeric component.

  The present invention may also be used in other applications where an air or liquid holding layer is used in combination with another layer, particularly such as other containers where the other layer needs to hold a gas or liquid, for example. This is useful when it contains reinforcing fibers or cords.

FIG. 4 is a schematic view of a multi-zone oven for processing a DVA film to remove residual plasticizer;

A typical calendering system for adhesive tie rubber layer applications; and

It is a simplified sectional view of a tire showing the position of various layers in a tire including a tie layer.

  The present invention is for a relatively impervious tie layer between an inner liner and a carcass for reducing tire weight while maintaining heat resistance, durability and flexibility required for a pneumatic tire. It relates to the rubber composition. The present invention also relates to reducing the permeability of a tie layer having improved durability while achieving excellent adhesion to both the carcass and the innerliner.

  Polymer may be used to refer to homopolymers, copolymers, interpolymers, terpolymers, and the like. Similarly, a copolymer can refer to a polymer comprising at least two monomers, optionally with other monomers. When a polymer includes a monomer, the monomer exists in the form of a polymerized monomer or derivative of the monomer. However, for the sake of simplicity, the expression “comprising the (respective) monomers”, or the like, is used as an abbreviation. Similarly, if the catalyst component includes 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 form a 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 a preferred embodiment, the multiolefin is any monomer that contains two double bonds, preferably two conjugated double bonds, for example conjugated dienes such as isoprene.

  Elastomer as used herein refers to any polymer or composition of polymers consistent with the definition of ASTM D1566-06. The term is used interchangeably with the term “rubber”.

  The present invention includes a thermoplastic engineering resin (also referred to as an “engineering resin” or “thermoplastic resin”) as a continuous phase and a vulcanized (or partially vulcanized) elastomer as a dispersed phase. The present invention relates to a layered structure having one layer. Such compositions are prepared, for example, using a technique known as dynamic vulcanization, and the resulting composition is known as dynamic vulcanization alloy (DVA), and such compositions and Details of its preparation method are described herein. When used in a pneumatic tire, the DVA layer serves as a tire inner liner. Since this layer is the layer having the lowest permeation rate, the layer is generally referred to as an air permeation prevention layer or a barrier layer.

  Adjacent to the air permeation prevention layer is an adhesive tie layer, which is referred to as such in order to bond the DVA inner liner with the adjacent layer in the constructed tire and is generally referred to as the adjacent layer. Is the innermost surface in the radial direction of the carcass and the innermost coating rubber in the radial direction of the carcass layer. The tie layer is preferably a vulcanizable composition that generally includes at least one reinforcing filler, and additives such as optional processing aids, and for the purposes of the present invention, the tie layer is Includes halogenated isobutylene-containing elastomers.

  In accordance with the present invention, the formulation and / or treatment of the air permeation prevention layer allows the adhesive tie layer to be directly bonded to the air permeation prevention layer without the need to use an intermediary adhesive layer between the two layers. it can.

Fluid Permeation Prevention Layer The fluid permeation prevention layer is generally present in the form of a sheet or film for a tire structure, but may be present in the form of a tubular layer of a hose structure. The sheet or film may be extruded as a blown sheet or tubular layer, or formed into a film. Either layer formation method can form a layer of desired constant thickness or various thicknesses, which is superior in different areas, corresponding to areas with varying flexibility of the article in which it is used. Thickness can be achieved.

  As described above, the fluid permeation prevention layer is formed from a DVA having a vulcanized or partially vulcanized elastomer dispersed as dispersed particles in a continuous phase of a thermoplastic engineering resin.

Elastomers Elastomers useful in the DVA of the present invention are all C4-7 alkene monomers derived from elastomers. One such elastomer useful in the present invention generally reacts as a monomer component at least (1) an alkene monomer having 4 to 7 carbon atoms and (2) a mixture of monomers having at least one multiolefin. It is prepared by. In one embodiment, the alkene ranges from 70 to 99.5% by weight of the total weight of the monomer mixture, and in another embodiment from 85 to 99.5% by weight. Alkenes are compounds of 4 to 7 carbon atoms, non-limiting examples of which are isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-butene, Compounds such as 2-butene, hexene, and 4-methyl-1-pentene. The preferable alkene of this invention is a C4-C7 isoolefin or a C4-C7 isomonoolefin. A useful monomer is isobutylene, resulting in an isobutylene-based polymer. In one embodiment, the multiolefin component is present at 30-0.5% by weight in the monomer mixture, and in another embodiment at 15-0.5% by weight. In yet another embodiment, 8 to 0.5% by weight of the monomer mixture is multiolefin. The multiolefin is a C4-14 multiolefin such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, and piperylene. is there. Useful in the present invention is the reaction of 92-99.5% by weight of isobutylene with 0.5-8% by weight of isoprene, or 99.5% by weight to 95% by weight of isobutylene of 0.5% by weight to An elastomer obtained by reacting with 5.0% by weight isoprene, this isobutylene-isoprene copolymer (IIR) is conventionally called butyl rubber / elastomer.

  In the present invention, it is useful to use a halogenated rubber. Halogenated rubber is conventionally defined as a rubber having at least about 0.1 mole percent halogen relative to the total moles of monomer and comonomer, such halogen being selected from the group consisting of, for example, bromine, chlorine and iodine. The Halogenated rubbers useful in the present invention include halogenated isobutylene-containing elastomers (also referred to as halogenated isobutylene copolymers). These elastomers can be described as random copolymers of units having 4 to 7 carbon atoms, such as units derived from isobutylene, and at least one other polymerizable unit. In one embodiment of the present invention, the halogenated isobutylene-containing elastomer is a butyl rubber or a branched butyl rubber, particularly a brominated form of these elastomers. Preferred halogenated isobutylene homopolymers or copolymers useful in the present invention include halobutyl rubbers, such as bromobutyl rubber and chlorobutyl rubber.

Halogenated butyl rubber is produced by halogenation of the butyl rubber product described above. Halogenation can be carried out by any means, and the present invention is not limited by the method of halogenation. Methods for halogenating polymers such as butyl polymers are disclosed in US Pat. Nos. 3,099,644, 4,513,116, and 5,681,901. In the conventional method, butyl rubber is halogenated using bromine (Br ₂ ) or chlorine (Cl ₂ ) as a halogenating agent in a hexane diluent at 4 to 60 ° C. Halogenated butyl rubber generally has a Mooney viscosity (ML 1 + 8 at 125 ° C.) of about 27 to about 51. The halogen content is generally about 0.1 to 10% by weight, for example about 0.5 to 5% by weight, alternatively about 0.8 to about 2.5% by weight, for example about 1 to about 2% by mass. A commercial embodiment of a halogenated isobutylene-containing elastomer useful in the present invention is Bromobutyl 2222 (ExxonMobil Chemical Company). Its Mooney viscosity is generally about 27-37 (ML 1 + 8 at 125 ° C., ASTM D1646-04, modified), and its bromine content is about 1.8-2.2 for halogenated elastomers. % By mass. Further, the cure characteristics of Bromobutyl 2222 provided by the manufacturer are as follows: MH is about 28-40 dNm, ML is about 7-18 dNm (ASTM D2084-92A). Another commercial embodiment of a halogenated isobutylene containing elastomer useful in the present invention is Bromobutyl 2255 (ExxonMobil Chemical Company). Its Mooney viscosity is about 41-51 (ML 1 + 8 at 125 ° C., ASTM D1646-04), and its bromine content is about 1.8-2.2% by weight. Further, its curing properties disclosed by the manufacturer are as follows: MH is 34-48 dNm, ML is 11-21 dNm (ASTM D2084-92A).

  Another useful embodiment of the halogenated isobutylene-containing elastomer is a halogenated branched or “star-branched” butyl rubber. In one embodiment, star-branched butyl rubber ("SBB") is a composition comprising butyl rubber and a polydiene or block copolymer. For the purposes of the present invention, the method of forming the SBB is not a limitation. Polydienes, block copolymers, or branching agents (hereinafter referred to as “polydienes”) are generally cationically reactive and may be present during the polymerization of butyl rubber or halogenated butyl rubber or mixed with butyl rubber to form SBB. it can. The branching agent or polydiene may be any suitable branching agent, and the present invention is not limited to the type of polydiene or branching agent used to make the SBB.

  In one embodiment, the SBB comprises butyl rubber or halogenated butyl rubber, styrene, polybutadiene, polyisoprene, polypiperylene, natural rubber, styrene-butadiene rubber, ethylene-propylene diene rubber (EPDM), ethylene-propylene rubber (EPM). ), Polydienes selected from the group consisting of styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers and copolymers of partially hydrogenated polydienes. The polydiene is generally present in an amount of greater than 0.3%, alternatively from about 0.3 to about 3%, or from about 0.4 to 2.7% by weight, based on the total monomer content in weight%. obtain.

  Preferably, the branched or “star-branched” butyl rubber used in the present invention is halogenated. In one embodiment, halogenated star branched butyl rubber (“HSBB”) comprises either halogenated or non-halogenated butyl rubber, and either halogenated or non-halogenated polydiene or block copolymer. The present invention is not limited by the formation method of HSBB. A polydiene / block copolymer, or branching agent (hereinafter referred to as “polydiene”) is generally cationically reactive and is present during the polymerization of butyl rubber or halogenated butyl rubber, or mixed with butyl rubber or halogenated butyl rubber to produce HSBB. Can be formed. The branching agent or polydiene may be any suitable branching agent and the present invention is not limited by the type of polydiene used in the preparation of HSBB.

  A commercial embodiment of HSBB useful in the present invention has a Mooney viscosity of about 27-37 (ML 1 + 8, 125 ° C., ASTM D1646-04, modified), and about 2.2-2.6 wt% Bromobutyl 6222 (ExxonMobil Chemical Company) with bromine content. Further, the cure characteristics of Bromobutyl 6222 disclosed by the manufacturer are as follows: MH is 24-38 dNm, ML is 6-16 dNm (ASTM D2084-92A).

Another elastomer useful in the present invention is an isoolefin styrenic polymer. Useful isoolefin monomers include, for example, 4 to 7 carbon atoms such as isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, and 4-methyl-1-pentene. Is an isoolefin. Useful styrenic monomers in the isoolefin copolymer include styrene, alkyl styrene, alkyloxy styrene, indene and indene derivatives, and combinations thereof. The alkyl styrene may be an ortho, meta, or paraalkyl substituted styrene. In one embodiment, the alkyl styrene is p-alkyl styrene comprising at least 80%, more preferably at least 90% by weight of the para isomer. The polymer is derived from a multiolefin having 4 to 14 carbon atoms such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, and piperylene. Units may be included. The polymer may also include a functionalized interpolymer, and at least some of the alkyl substituents present on the styrene monomer unit may include halogen or another functional group as described further below. These interpolymers are referred to herein as “isoolefin copolymers comprising halomethylstyrene” or simply “isoolefin copolymers”.
Such isoolefin polymers can be characterized as interpolymers, randomly spaced along the polymer chain and comprising the following monomer units:

In the formula, R and R ¹ are independently hydrogen, lower alkyl, preferably alkyl having 1 to 7 carbon atoms and primary or secondary halogenated alkyl, and X is a functional group such as halogen. Desirable halogens are chlorine, bromine or combinations thereof, preferably bromine. Preferably R and R ¹ are each hydrogen. The —CRR ₁ H and CRR ₁ X groups may be substituted at any of the ortho, meta, or para positions of the styrene ring, preferably at the para position. In one embodiment, up to 60 mol% of the p-substituted styrene present in the interpolymer structure may be the functionalized structure (2) described above, in another embodiment 0.1-5 mol%. It may be. In yet another embodiment, the amount of functionalized structure (2) is 0.4-1 mol%. The functional group X may be halogen or other groups such as carboxylic acids; carboxy salts; carboxy esters, amides and imides; hydroxy; alkoxides; phenoxides; thiolates; thioethers; xanthates; And several other functional groups that can be incorporated by nucleophilic substitution of benzylic halogens, and mixtures thereof. These functionalized isomonoolefin copolymers, methods for their preparation, functionalization and curing are disclosed in particular in US Pat. No. 5,162,445.
Useful in the present invention is a copolymer of isobutylene and p-methylstyrene containing 0.5 to 20 mole percent p-methylstyrene, provided that up to 60 mole percent 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 forms, provided that the halogen atom is substituted by maleic anhydride or acrylic acid or methacrylic acid functional groups Is). These interpolymers are called “halogenated poly (isobutylene-co-p-methylstyrene)” or “brominated poly (isobutylene-co-p-methylstyrene)”. The use of the terms “halogenated” or “brominated” is not limited to the method of halogenation of the copolymer, but simply refers to units derived from isobutylene, units derived from p-methylstyrene, and units derived from p-halomethylstyrene. It will be understood that it only describes the copolymers comprising.

  These functionalized polymers have a substantially uniform composition distribution such that at least 95% by weight of the polymer has a p-alkylstyrene content within 10% of the average p-alkylstyrene content of the polymer. It is preferable to have. More preferred polymers also have a narrow molecular weight distribution (Mw / Mn) as measured by gel permeation chromatography of less than 5, more preferably less than 2.5, a preferred viscosity average molecular weight of about 200,000 to about 2, And a preferred number average molecular weight in the range of about 25,000 to about 750,000.

  Preferred halogenated poly (isobutylene-co-p-methylstyrene) polymers are brominated polymers that generally contain from about 0.1 to about 5 weight percent bromomethyl groups. In still another embodiment, the amount of bromomethyl group is from about 0.2 to about 2.5% by weight. In other words, 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 the polymer backbone chain Substantially free of a halogen ring or halogen. In one embodiment of the present invention, the interpolymer is a copolymer of a unit having 4 to 7 carbon atoms derived from an isomonoolefin, a unit derived from p-methylstyrene, and a unit derived from p-halomethylstyrene. The methylstyrene units are present in the interpolymer in an amount of about 0.4 to about 1 mole percent based on the interpolymer. In another embodiment, the p-halomethylstyrene is p-bromomethylstyrene. The Mooney viscosity (1 + 8, 125 ° C., ASTM D1646-04, modified) is about 30 to about 60 MU.

  The elastomer useful in the air permeation prevention layer and the halogenated isobutylene-containing elastomer useful in the tie layer may be the same elastomer 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 a 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. Preferably, the elastomer present in the air permeation prevention layer is a brominated copolymer of isobutylene and paramethylstyrene, and the isobutylene containing elastomer present in the tie layer is a brominated butyl rubber.

Thermoplastic engineering resin For the purposes of the present invention, a thermoplastic engineering resin (also referred to as a “thermoplastic resin” or “thermoplastic”) has a Young's modulus greater than 500 MPa, and Preferably, the air permeability coefficient is less than 60 × 10 ⁻¹² 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.) Defined as any thermoplastic polymer, copolymer or mixture thereof including, but not limited to, one or more of 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 / polybutyrate terephthalate copolymers 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: Vinyl acetate (EVA), polyvinyl alcohol (PVA), ethylene vinyl alcohol copolymer (EVOH), 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) an aromatic polyketone; and o) any of all of the a) to n) and all mixtures a) to n) are included in any of the illustrated or exemplified engineering resins. ,included.

  For the purposes of the present invention, this definition of engineering resin does not include polymers of olefins having any crystallinity, such as polyethylene and polypropylene.

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

Additional Components Generally, elastomeric polymers, such as those used to make tires, are crosslinked or vulcanized. Crosslinking or vulcanization is accomplished by incorporating curing agents and / or accelerators, and the overall mixture of such agents is commonly referred to as a curing “system”. It is known that the physical properties, performance characteristics, and durability of vulcanized rubber compounds are directly related to the number of crosslinks (crosslink density) and type formed during the vulcanization reaction. Curing agents include the above-described components that promote or affect the curing of the elastomer, and generally include metals, accelerators, sulfur, peroxides, and other agents common in the art, and Contains the agents described above. The crosslinker or curing agent includes, 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, for example, by adding a curing agent such as sulfur, metal oxides (ie, zinc oxide, ZnO), organometallic compounds, radical initiators, and heating the composition or mixture, the polymer composition Can be cross-linked. When using a process known as “dynamic vulcanization”, vulcanization may be carried out using at least one vulcanizable rubber, elastomer or polymer and a vulcanizing agent for at least one vulcanizable component. The process is modified so that at least one vulcanizable component in a composition comprising at least one elastomer or polymer that cannot be mixed and vulcanized or crosslinked substantially simultaneously. (See, eg, US Pat. No. 6,079,465 and references cited therein). In particular, common curing agents that can function in the present invention are: ZnO, CaO, MgO, Al ₂ O ₃ , CrO ₃ , FeO, Fe ₂ O ₃ , and NiO. These metal oxides are used with the corresponding metal stearate complexes (eg, stearates of Zn, Ca, Mg, and Al), or stearic acid, and either sulfur compounds or alkyl peroxide compounds. be able to. Accelerators for vulcanization of the elastomer composition are often added to the curing agent. Curing agents, with or without the use of at least one accelerator, are often referred to in the art as curing “systems” for elastomers. The reason why the curing system is used is that two or more curing agents are generally used to obtain a beneficial effect, particularly when using a mixture of high diene rubber and less reactive elastomer.

  Using any conventional curing system capable of vulcanizing saturated halogenated polymers for the purpose of dynamic vulcanization in the presence of engineering resins to form highly impermeable layers At least one elastomeric halogenated copolymer of 4 to 7 carbon isomonoolefin and paraalkyl styrene may be vulcanized. However, when the selected thermoplastic engineering resin is such that the peroxide crosslinks the resin itself, the engineering resin is itself vulcanized or cross-linked and thereby non-heated and excessively cured. Peroxide curing agents are specifically excluded from the practice of the present invention to provide a plastic composition. A suitable curing system for the elastomeric halogenated copolymer component of the present invention comprises zinc stearate or stearic acid, and zinc oxide optionally combined with one or more of the following accelerators or vulcanizing agents: Permalux ( Dicatechol borate di-ortho-tolylguanidine salt); HVA-2 (m-phenylene bismaleimide); Zisnet (2,4,6-trimercapto-5-triazine); ZDEDC (zinc diethyldithiocarbamate) and the present invention Other dithiocarbamates are also included for this purpose; Tetrone A (dipentamethylene thiuram hexasulfide); Vultac 5 (alkylated phenol disulfide), SP1045 (phenol formaldehyde resin); SP1056 (brominated alkylphenol form) Aldehyde resin); DPPD (diphenylphenylenediamine); salicylic acid (ortho-hydroxybenzoic acid); wood rosin (abietic acid); and TMTDS (tetramethylthiuram disulfide) used in combination with sulfur.

  Dynamic vulcanization is carried out under conditions that vulcanize the elastomeric halogen-containing copolymer of the liquid (gas or liquid, preferably air) permeation prevention layer, at least in part, preferably completely.

  With respect to the polymers and / or elastomers referred to herein, the terms “cured”, “vulcanized”, or “crosslinked” refer to the elastomer that undergoes such a process when the tire is put into use. , Refers to a chemical reaction that includes the formation of bonds during the chain reaction or cross-linking between polymer chains, including polymers or elastomers, to an extent that can provide the required functional properties as a result of the curing reaction. For the purposes of the present invention, such a curing reaction need not be completely completed in order for an elastomer-containing composition to be considered “cured”, “vulcanized” or “crosslinked”. For example, for the purpose of the present invention, when a tire having a tie layer as a constituent element passes a required product specification test during or after manufacture and exhibits satisfactory performance when used in a vehicle, the tie layer Is fully cured. Furthermore, the composition is satisfactorily or substantially cured, vulcanized or crosslinked if the tire can be ready for use, even if additional curing results in additional crosslinking. By limited experimentation using known tools and standard techniques, those skilled in the art will be able to determine the appropriate or optimal cure time required for elastomers and polymers selected for use in tie layer compositions, and tires. The amount and type of crosslinkers and accelerators used to produce and the curing temperature can be readily determined.

  Accelerators useful in the present invention include amines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenimides, thiocarbamates, xanthates and the like. Acceleration of the curing process can be achieved by adding an amount of accelerator to the composition. The mechanism for the accelerated vulcanization of natural rubber involves a complex interaction between curing agents, accelerators, activators and polymers. Ideally, all available curing agents are consumed in the formation of effective crosslinks connecting the two polymer chains, improving the overall strength of the polymer matrix. A number of accelerators are known in the art and examples include, but are not limited to, 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- (morpholinothio) benzothiazole (MBS or MOR), 90% MOR and 10% MBTS composition (MOR90), N-tertiarybutyl-2-benzothiazolesulfenamide (TBBS), and N-oxydiethylenethiocarbamyl-N -Oxydiethylenesulfonamide (OTOS), zinc 2-ethyl Hexanoate (ZEH), N, N'- diethyl thiourea. Curing agents, accelerators and curing systems useful for one or more crosslinkable polymers are known in the art.

  In one embodiment of the present invention, the at least one curing agent is generally present in an amount of about 0.1 to about 15 phr, alternatively about 0.5 to about 10 phr.

  The compositions described herein include one or more filler components such as calcium carbonate, clay, mica, silica and silicates, talc, titanium dioxide, starch, and other organic fillers such as wood flour, and Can have carbon black. Suitable filler materials include carbon black such as channel black, furnace black, thermal black, acetylene black, lamp black. Reinforced grade carbon black is most preferred. The filler may also include other reinforced or non-reinforced materials such as silica, clay, calcium carbonate, talc, titanium dioxide and the like. Fillers are usually present in the composition (preferably the inner liner) at a level of about 20 to about 50% by weight of the total composition, more preferably about 25 to 40% by weight. In one embodiment, the filler is carbon black or modified carbon black. A preferred filler is semi-reinforcing grade carbon black, generally used at a level of about 10 to 150 phr (parts by weight per 100 parts rubber), more preferably about 30 to about 120 phr. Carbon black grades useful in the present invention 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 described in ASTM (D3037, D1510, and D3765) are useful in the present invention. . For example, carbon black embodiments useful in tire sidewalls, such as N330, N351, N550, N650, N660, and N762, are particularly useful in the present invention. For example, carbon black embodiments useful in inner liners or inner tubes, such as N550, N650, N660, N762, N990, and Regal 85 (Cabot Corporation, Alpharetta, Ga.) Are also included in the present invention. Also particularly useful.

  Since there is a difference in solubility between the thermoplastic resin and the elastomer in DVA, a compatibilizer may be used. Such compatibilizers are believed to function by changing, in particular reducing, the surface tension between the rubber and thermoplastic components of the composition. Suitable compatibilizers include ethylenically unsaturated nitrile-conjugated diene based highly saturated copolymer rubber (HNBR), epoxidized natural rubber (ENR), acrylate rubber, and mixtures thereof, as well as thermoplastic or elastomeric polymers and Mention may be made of copolymers having the same structure or the structure of a copolymer having an epoxy group, a carbonyl group, a halogen group, an amine group, a maleated group, an oxazoline group, or a hydroxyl group, which can react with a thermoplastic resin or elastomer.

  The amount of the compatibilizer is generally about 0.5 to about 10 parts by weight, preferably about 3 to about 8 parts by weight, based on 100 parts by weight of the total mass of the elastomer.

  Uniform mixing and fineness that significantly enhances good mixing mechanical properties and desired permeation properties by minimizing the viscosity difference between the elastomer and thermoplastic components during mixing and / or processing The mixing form is promoted. However, due to the inherent flow activation characteristics and shear thinning properties of elastomeric polymers, the decrease in viscosity of elastomeric polymers at elevated temperatures and the decrease in shear rate that occurs during mixing is the result of the thermoplastic component being mixed with the elastomer. It is much more pronounced than the decrease in viscosity. In order to obtain a DVA with an acceptable elastomer dispersion size, it is desirable to reduce this viscosity difference between the materials.

  Ingredients conventionally used to match the viscosity between the elastomer and the thermoplastic component include low molecular weight polyamides, polymers having a molecular weight of about 10,000 or more grafted with maleic anhydride, methacrylate copolymers, tertiary amines and tertiary amines. Secondary diamines are included. As an example, an ethylene-ethyl acrylate copolymer grafted with maleic anhydride (obtained from Mitsui-DuPont as AR-201 having a melt flow rate of 7 g / 10 min measured according to JIS K6710) A possible solid rubber material) and butylbenzylsulfonamide (BBSA). These compounds may act to increase the “effective” amount of thermoplastic material in the elastomeric / thermoplastic compound. The amount of additive is selected to achieve a desired viscosity that does not negatively affect the properties of the DVA. If the compatibilizer is present in excess, the impermeability may be reduced and the excess may have to be removed during post processing. In the absence of sufficient compatibilizer, the elastomer may not reverse the phase to become a dispersed phase in the thermoplastic resin matrix.

  The amount of plasticizer present in the DVA ranges from a minimum amount of about 2 phr, 5 phr, or 10 phr to a maximum amount of 15 phr, 20 phr, 25 phr, 30 phr, or 35 phr.

DVA Preparation As used herein, the term “dynamic vulcanization” refers to a vulcanization process in which an engineering resin and rubber are mixed under high shear and elevated temperature conditions in the presence of a curing agent. As a result, the rubber is simultaneously cross-linked and dispersed, for example, as fine particles in the form of a microgel, in an engineering resin that forms a continuous matrix, and the resulting composition is known in the art as a “dynamic vulcanization alloy”, ie Known as DVA. Dynamic vulcanization uses a roll mill, a Banbury (registered trademark) mixer, a continuous mixer, a kneader, or a mixing extruder (for example, a twin-screw extruder) to mix components at a temperature equal to or higher than the rubber curing temperature. It is carried out by doing. The unique property of dynamically cured compositions is that, despite the fact that the rubber is cured, the composition can be obtained by conventional thermoplastic processing techniques such as extrusion, injection molding and compression molding. Can be processed and reworked. Scrap and / or flushing can also be recovered and reprocessed.

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

  The mixing process is preferably continued until the desired level of vulcanization or crosslinking is complete. When vulcanization is continued after mixing is stopped, the composition may not be reprocessed 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 pellets can be formed from a DVA material or material using an underwater pelletizer, thereby quenching the vulcanization before vulcanization is complete. The vulcanization process can be completed at a later time under dynamic vulcanization conditions. Those skilled in the art will understand the appropriate amount, type and mixing time range of curing agents needed to effect rubber vulcanization. If it is necessary or desirable to determine the proper concentration and conditions, only rubber is vulcanized and used with various amounts of curing agent, which may include one or more curing agents and / or accelerators. The optimal curing system to do and the appropriate curing conditions to achieve substantially complete curing can be determined.

  It is preferred that all components be present in the mixture prior to performing the dynamic vulcanization process, but this is not a necessary condition. For example, when used, not all fillers and oils need be added before the dynamic vulcanization stage. Some or all of the filler and oil can also be added after vulcanization is complete. Certain components, such as stabilizers and processing aids, work more effectively when added after vulcanization.

Adhesive Tie Layer The tie layer generally exists as a sheet or film formed using an extrusion or calendering method. The tie layer may be coextruded with DVA or may be extruded or calendered onto an already formed DVA layer.

  The adhesive tie layer composition comprises: (1) 100% by weight halogenated isobutylene-containing elastomer; (2) about 20 to about 50% by weight of at least one filler; (3) about 0 to about 30% by weight of at least 1 (4) a curing system for elastomers of at least about 0.1 to about 15 phr (parts per 100 parts rubber); and (5) at least about 0.1 to about 10 phr (parts per 100 parts rubber). A mixture of one tackifier; In a preferred embodiment, the halogenated isobutylene-containing elastomer is a halogen-containing random copolymer of isobutylene and a C 4-14 multiolefin. In each case, the halogen is selected from the group consisting of chlorine, bromine and mixtures thereof. Useful elastomers may be selected from the group consisting of chlorinated butyl rubber, brominated butyl rubber, chlorinated star branched butyl rubber, brominated star branched butyl rubber, and mixtures thereof. By selecting 100% by weight of the halogenated isobutylene-containing elastomer as the sole elastomer in the tie layer, low permeability in the tie layer is obtained.

  Useful fillers in the tie layer include carbon black, clay, exfoliated clay, intercalated clay, disperse clay, calcium carbonate, mica, silica, silicate, talc, titanium dioxide, At least one filler selected from the group consisting of wood flour and mixtures thereof is included. Preferably, the filler is selected from the group consisting of carbon black, exfoliated clay, intercalated clay, and dispersed clay, and mixtures thereof. The amount of the at least one filler is generally about 20 to about 50% by weight, preferably about 25 to about 40% by weight, based on the total weight of the tie layer composition.

  The tie layer may contain rubber process oil or plasticizer oil. As used herein, the term “process oil” refers to both petroleum-derived process oils and synthetic plasticizers. Such oils are mainly used to improve the processing of the composition during the preparation of the layer, for example mixing, calendering and the like. Generally, 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 units derived from olefins 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 4 raffinates. Preferred polybutene process oils are generally synthetic liquid polybutenes having a molecular weight, preferably from about 420 Mn to about 2700 Mn. Preferred polybutene oils have a molecular weight distribution -Mw / Mn- ("MWD") generally from about 1.8 to about 3, preferably from about 2 to about 2.8. The preferred density (g / ml) of useful polybutene process oil varies between about 0.85 and about 0.91. Preferred polybutene oil bromine numbers (CG / G) range from about 40 for 450 Mn process oil to about 8 for 2700 Mn process oil.

  Rubber process oils also have ASTM names depending on whether they are in the class of paraffinic, naphthenic or aromatic hydrocarbon based process oils. The types of process oils used are those conventionally used to match the type of elastomer component, and rubber chemists with ordinary skills can use any type of oil for a specific rubber in a specific application. You will recognize what to use.

  Suitable plasticizer oils include aliphatic acid ester or hydrocarbon plasticizer oils such as paraffinic or naphthenic petroleum or polybutene oils.

  In yet another embodiment, naphthenic, aliphatic, paraffinic and other aromatic oils are substantially absent from the composition. The expression “substantially absent” means that naphthenic, aliphatic, paraffinic and other aromatic oils may be present, but if present, amounts in the composition of 1 phr or less. It means that. In yet another embodiment, naphthenic, aliphatic, paraffinic and other aromatic oils are present in an amount less than 2 phr.

  The amount of rubber process oil or plasticizer oil is generally about 0 to about 30% by weight, preferably about 0 to about 20% by weight, more preferably about 0 to about 10% by weight, based on the total weight of the tie layer composition. %. Preferably, the process oil is a naphthenic or polybutene based oil.

  The adhesive tie layer is cured or vulcanized using a curing system comprising at least one curing agent and at least one accelerator useful for halogenated isobutylene-containing elastomers comprising the composition. The curing system for the adhesive tie layer includes all of the above-described curing agents and accelerators that have been previously described as useful in DVA. The curing systems in the DVA and tie layers may be the same or different, but if each layer is adjacent during formation and subsequent article construction and article curing, one layer to the adjacent layer Since the curing system components are transferred between layers, they should match. Generally, 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 the specific amount of the curing system is not limited and the amount used is selected. One skilled in the art will appreciate that it is highly dependent on the specific components of the curing system.

  In addition, any useful additives are generally added at a level of less than about 10 phr, such as pigments, antioxidants, antiozonants, processing aids, compound compatibilizers, and the like, and mixtures thereof. Can be selected from the group consisting of Such optional additives can be added at the discretion of the dispenser to achieve a particular advantage in the composition, for example to improve contact adhesion during tire molding. Use of a tackifier or an antioxidant for improving the heat aging resistance of the cured composition.

  In a preferred embodiment, at least one tackifier is included in the tie layer composition. For the purposes of the present invention, tackifiers are materials identified as rosin or rosin derivatives and various derivatives, such as acetylene-phenolic compounds known as tackifiers for elastomer or polymer-containing compositions. Including. Particularly useful tackifiers include condensates of butylphenol and acetylene, such as acetylene-p-tert-butylphenol, commercially available as “Koresin” (BASF), and mixtures of tall oil rosin and fatty acids. Rosin tackifiers commercially available as "MR1085A" (Mobile, Rosin Oil Company, Mobile, AL). Some tackifiers have been designated as particularly useful for imparting tack to certain polymers or elastomers, but can be judged to be useful for the compounds of the present invention.

  Stickiness generally refers to the ability of an uncured rubber compound to stick to another compound when the compound is contacted using only a relatively short residence time and moderate pressure ("Rubber Technology: Compounding"). and Testing for Performance, "JS Dick, Ed., 42, 2001). Residence time and pressure are often determined by the equipment used for that purpose and by the possibility that the sheet of uncured composition will be damaged by excessive pressure and residence time. Adhesion can also be affected by the solubility of the various rubber components in each other and in the overall composition. In some cases, the components of the composition may diffuse to the surface of the calendered or extruded sheet or film, for example, if it is inorganic particulates, all prevent stickiness (" Sometimes called "bloom"). On the other hand, if the diffusing component itself exhibits tackiness, such diffusion may improve the tackiness. It is understood by those skilled in the art that stickiness is a difficult property to measure, and by assessing the performance of the composition in a factory test or environment where the final product is manufactured, the composition is adequate. It may be necessary to determine whether a certain level of tack has been achieved. In this case, the evaluation generally involves actually molding the tire; and the uncured tire structure is in the tire molding stage and the expansion during vulcanization until the structure achieves a sufficient cure level. Determining whether the tie layer exhibits sufficient tire building tack so that it can remain bonded during the initial phase; and the resulting cured adhesion of the various tire layers to each other Determination (including adhesion of the tie layer to the layer in contact with the tie layer adjacent to the tie layer, such as adhesion between the carcass layer and the inner liner layer). There is no standardized test procedure for measuring the tackiness of rubber compounds, but a widely used device is the “Tel-Tak Tackmeter” introduced by Monsanto in 1969. . Another test apparatus is a PICMA tack tester manufactured by Toyo Seiki Seisakusho Co., Ltd. (Japan).

  In a preferred embodiment of the present invention, the at least one tackifier is at a concentration of about 1 phr to about 20 phr, preferably about 2 phr to about 18 phr, more preferably about 3 phr to about 16 phr, such as about 4 phr to about 14 phr. Added to the tie layer composition. Alternatively, the at least one tackifier is generally 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 8 phr or less, such as about 1 phr 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, etc., about 1, 2, 3, 4, 5, 6, 7, 8, 9, And 10 individual values of phr and ranges containing each value are also included. Similarly, when using a mixture of tackifiers, for example a mixture of two tackifiers of the same or different chemical type, each tackifier may be present in equal or unequal amounts. Often, the total amount of tackifier used is preferably within the constraints of the total amount described directly above.

  The adhesive tie layer composition is a mixture of, for example, a Banbury (registered trademark) mixer, a mill roll mixer, an extrusion mixer, etc., for mixing elastomers, fillers, process oils and other additives, and dispersing curing system components. The devices can be prepared individually and in combination. In general, components other than the curing system components are mixed at elevated temperature and high shear to achieve a satisfactory dispersion of all non-elastomeric components into the elastomer and a satisfactory dispersion of the elastomers into each other. Is done. After such a mixing step, a composition that does not contain a curing system component (sometimes referred to as a masterbatch) is used, for example, a rubber roll machine or a low temperature, low shear section of a mixing extruder or closed mixer Then, it is cooled to a lower temperature, and the curing system components are dispersed in this master batch. The temperature at which the curing agent is mixed is generally less than about 120 ° C, preferably less than about 100 ° C.

  The adhesive tie layer composition can be formed into a layer suitable for the end use using, for example, an extruder or a calendar. Where convenient or useful, extrusion may involve the use of a device that allows double or multiple extrusion of a liquid (preferably air) permeation prevention layer and an adhesive tie layer. Alternatively, the mixed rubber composition is calendered into a sheet material having a desired thickness, and the sheet material is cut into strips of width and length appropriate for the specific size or tire type innerliner application. By doing so, an adhesive tie layer may be produced.

  In the present invention, the tie layer is made for use in a tire structure and is generally about 5 mm or less, preferably about 2.5 mm or less, more preferably about 1.0 mm or less, about 0.9 mm or less, or About 0.8 mm or less, even more preferably from about 0.2 to about 2.0 mm, most preferably from about 0.2 to about 1.5 mm or from about 0.2 mm to about 0.8 mm, such as from about 0.3 to It has a thickness of 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 for which the hose is used. For example, a non-reinforced low pressure hose may have different performance requirements than a high pressure reinforced hose, and similarly, a hose intended for liquid use may be different from a hose for gas use. Thickness adjustment is within the skill of a product designer, engineer or chemist, and can be performed based on experimentation if necessary.

Layered Composition / Laminated Structure After the DVA is mixed to achieve the desired composition and morphology, it is common to pass the material through a pelletizer to form DVA pellets. These pellets are then fed to a film extruder to prepare an extruded / blown film, or fed to a mixer to prepare a molded film. In the present invention, DVA is extruded or molded by itself; that is, the sheet is not coextruded with the adhesive film layer to provide additional adhesion between the DVA and the adhesive tie layer.

  After formation of the DVA film, the film is processed to remove any residual plasticizer or oil; in the present invention, “residual plasticizer or oil” is grafted onto the DVA during mixing in the extruder or during film preparation. Is defined as a plasticizer or oil that is not present and is present on the film surface due to the thinness of the film. Residual plasticizer / oil removal is performed to obtain a film that is substantially free of any plasticizer / oil present on the film surface, and “substantially free” means a plasticizer on the film. Is defined as less than 0.1% by weight.

  One method of removing the plasticizer / oil from the DVA film is by exposing the heat to flashing, evaporation, sublimation, and / or oxidation of the plasticizer from at least one side of the film. . This is initially prepared by heating the film to a temperature below 15 ° C or 10 ° C or 5 ° C or 1 ° C above the flash point of the plasticizer / oil, and then cooling the DVA film. This is accomplished by forming a heat treated film having a plasticizer level below that of the DVA film. It is desirable to expose the film to oxygen during the heating process. In any embodiment of the invention, a continuous or substantially continuous gas stream is blown over the length of the continuous elastomer during heating. The gas may be air, a nitrogen / oxygen mixture, or other gas mixed with an oxidant.

  FIG. 1 illustrates a method for processing a DVA film to remove residual plasticizer. The DVA film 10 is passed through a multi-zone oven 12. The DVA film 10 is unwound from the roll 14 and rewound onto the roll 16. Four zones are shown in the multi-zone oven 12; however, the actual number of zones useful in the present invention can vary between 2-10 zones. By using the oven 12 zone, the temperature of the DVA material can be gradually increased or decreased to achieve either immediate or delayed removal of residual plasticizer / oil, while at the same time any DVA film The desired staged cooling can also be provided. In any embodiment of the invention, plasticizer / oil flashing occurs in zone N-2, where N is the total number of zones in oven 12, and the zone is to the zone of film 10. It is counted in the order from the entrance to the exit.

  The rewind roll 16 is shown to be located immediately next to the outlet of the oven 12; however, the processed film 18 with reduced plasticizer is sufficient to allow rewinding to the film 10. If the cooled temperature is not reached, those skilled in the art will understand and additional take-up rolls, wrap rolls, and other conventional cooling means can be used.

  Alternatively, instead of unwinding the plasticizer-reduced film 18 onto the roll 16, the film 18 may be sent to a calendering operation for adhesive tie rubber layer applications. A typical calendering system for adhesive tie rubber layer applications is shown in FIG. 2; calendering applications are known, various calendering systems may be useful in the present invention, and the present invention is illustrated. Those skilled in the art will understand that the present invention is not limited to such systems. The DVA film 18 passes around a bank 20 of calendar rolls. As the DVA film 18 passes through several roll gaps made by adjacent rolls, it passes under a set of pencil banks 22 containing an adhesive tie layer composition. The roll is adjusted to give the desired thickness to the adhesive tie layer.

  The roll of calendar bank 20 is at a temperature sufficient to warm the DVA film 18 and the adhesive tie layer composition in the pencil bank 22 allows flow of the elastomeric composition and smooth coating of the DVA film. Heated to ensure that there is. The temperature and pressure of the bank 20 roll should be sufficient to produce some degree of bonding between the DVA film 18 and the adhesive tie composition. The temperature of the roll can vary from 50 ° C to 150 ° C, preferably from 65 ° C to 85 ° C. The temperature should be kept below the vulcanization temperature of the tie layer composition to prevent any curing of the adhesive tie layer composition.

  The film exits the calendar bank 20 as a film 24 (also referred to as a DVA laminate) coated with a tie layer. Because the adhesive tie composition is tacky in nature, an optional handling film 26 is applied to the coated film 24 to simplify winding and DVA lamination during subsequent roll winding and storage. The body 24 may be prevented from adhering to itself. If a handling film is present, remove the handling film from the DVA laminate 24 before using the DVA laminate 24.

  Compositions of the present invention and layered structures formed using such compositions can be used in tire applications; examples include tire cured bladders; air sleeves such as air shock absorbers, diaphragms, etc. And hose applications, including gas and liquid transport hoses.

  FIG. 3 is a half-sectional view (semi-cross-section view) along the meridian direction of the tire 28 showing a general example of the configuration of the air permeation preventive layer or the inner liner layer of the pneumatic tire. At least one carcass layer 30 extends between the left and right bead cores 32 (note that the second bead core is not shown because only half of the symmetrical cross section is included for clarity. Wanna) An inner liner layer 34 is provided inside the carcass layer 30 on the inner surface of the tire. An adhesive tie layer 36 is inserted between the inner liner layer 34 and the carcass layer 30. The adhesive tie layer 36 promotes the adhesion and air retention quality of the DVA air permeation prevention layer to the inner surface of the tire. The surface of the tie layer 36 opposite to the surface in contact with the inner liner layer 34 is in direct contact with the innermost carcass layer 30, that is, the adhesive tie layer 36 is more specifically the innermost carcass layer 30. In direct contact with 30 radially innermost coating compounds.

  Pneumatic tires also include a tread, a multi-layer belt structure, and an outer surface including sidewall elements, and tire reinforcing fibers (eg, rayon, polyester, nylon or metal fibers) embedded in a rubbery matrix. It consists of a possible intermediate carcass layer consisting of several plies. Differences in tread, belt and carcass layers and tire sizes (ie, overall diameter and sidewall height) are acceptable and not limited by the present invention. Tires are typically molded on tire forming drums using the layers described above. After the uncured tire is molded on the drum, it is removed and placed in a heated mold. The mold includes an inflatable tire molding bladder located within the inner circumference of the uncured tire. After closing the mold, the bladder expands and forms the tire by pressing the tire against the inner surface of the closed mold during the initial stages of the curing process. The heat in the bladder and mold raises the temperature of the tire to the vulcanization temperature. The vulcanization temperature is generally about 100 ° C to about 250 ° C, preferably about 150 ° C to about 200 ° C. Curing time can vary from about 1 minute to several hours, preferably from about 5 to 30 minutes. Cure time and temperature depend on many variables known in the art, including the composition of the tire components including the cure system in each layer, the overall tire size and thickness, and the like. Vulcanization parameters include test procedures described in ASTM D2084-01 (Rubber properties using vibration disc vulcanization tester-standard test method for vulcanization), stress-strain test, adhesion test, bending test, etc. Can be established using a variety of known laboratory testing methods. Vulcanization of the assembled tire results in complete or substantially complete vulcanization or cross-linking of all elements or layers of the tire assembly, i.e. inner liner, carcass and outer tread and sidewall layers. In addition to developing the desired strength characteristics of each layer and the overall structure, vulcanization promotes adhesion between these elements, resulting in cured and integrated tires from separate layers. Is obtained.

  As detailed above, the innerliner layer advantageously exhibits low permeation properties and preferably comprises a dynamic vulcanization comprising an engineering resin, in particular a polyamide, and a halogenated isobutylene-paramethylstyrene copolymer. Of the prepared composition. In addition, the unique composition of the tie layer based on the vulcanizable halogenated isobutylene elastomer results in its low air permeability characteristics and the ability to produce high vulcanizable adhesion to the surface of the inner liner layer it contacts. Allows the use of a thin tie layer compared to compositions containing predominantly high diene rubber. The resulting overall structure based on such innerliner and tie layers results in a reduced weight tire structure (and other structures including air or liquid retaining layers and tie layers). to enable. In general, weight reductions of about 2% to about 16%, or about 4% to about 13%, can be achieved. Such an improvement is particularly significant in applications such as pneumatic tires.

The following examples are provided as specific illustrations of embodiments of the claimed invention. However, it should be understood that the invention is not limited to the specific details set forth in the examples. In addition, any numerical range, such as a property, unit of measure, condition, physical state, or percentage of a particular set of percentages, as described in the specification or claims is within the stated range. Any number included in such a range, including any number subset, is intended to be expressly included herein, explicitly or by reference, or by other means. For example, whenever a numerical range having a lower limit R _L and an upper limit R _u is disclosed, every number R included in the range is specifically disclosed. More specifically, the following number R within the range is specifically disclosed: if 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%. . . . When 95%, 96%, 97%, 98%, 99%, or 100%, R = R _L + k (R _u −R _L ). Furthermore, any numerical range represented by any two values of R, calculated as described above, is also specifically disclosed.

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

  The test methods used to evaluate the following samples are shown in Table 2.

  Thermoplastic elastomeric DVA having the composition shown in Table 3 was prepared. The elastomer component and vulcanization system were charged to the first kneader, mixed for about 3.5 minutes, and discharged at about 90 ° C. to prepare an accelerated elastomer component containing the vulcanization system. The mixture was then pelletized with a rubber pelletizer. Next, the pelletized elastomer and resin component were charged into a twin-screw mixing extruder and dynamically vulcanized to prepare a thermoplastic elastomer composition. DVA was prepared according to the procedure described in EP 0969039, with specific reference to the section entitled “Production of Thermoplastic Elastomer Composition”. Vulcanization in a twin screw extruder was performed at 230 ° C. After the DVA was prepared and pelletized, it was then sent to a film blowing operation where the DVA was extruded and extruded as a thin film. In the present invention, the DVA film is not coextruded with the adhesive coating, and the DVA film does not contain an adhesive.

  After the DVA film was coextruded as a film, the residual plasticizer was removed by a heating operation as described above, and a DVA film containing no residual plasticizer / oil on the film surface was produced.

  Adhesive tie layer compositions and representative carcass compounds were prepared as described above for conventional elastomer formulations. The composition is shown in Table 4 below. The amounts of all components in Table 4 are given in parts per hundred parts of rubber (phr).

  All adhesive tie layers showed excellent adhesion to the treated DVA layer when adhered directly to the DVA film. In the peel adhesion test, the adhesion between the adhesive tie layer and the DVA film actually decreased as the amount of tackifier in the adhesive tie layer increased, but the adhesion between the adhesive tie layer and the ply compound was all The adhesive composition was relatively comparable. Compared to other DVA laminate structures, such as those disclosed, for example, in US 2008/314492, the above data indicates that the DVA has been processed to remove residual plasticizer / oil. In this case, even when the thin film adhesive layer is not present, it is not necessary to use a plurality of tackifiers in the tie rubber layer.

Therefore, according to the present invention, it is not necessary to use a thin film adhesive layer between the DVA film and the tie rubber layer in order to achieve excellent adhesion to the DVA-containing laminate. Removal of residual plasticizer and / or oil from the DVA film allowed the adhesive tie layer to more easily adhere to the DVA film, resulting in improved adhesion of the DVA film in the article. More specifically, due to improved adhesion, tires that include bonded and processed DVA films have improved durability.
The present invention includes the following aspects.
[1] A method for producing a laminated structure, the method comprising:
(A) A step of forming an adhesive tie composition, wherein the adhesive tie composition is
(1) 100% by weight of at least one halogenated isobutylene-containing elastomer,
(2) about 20 to about 50% by weight of at least one filler;
(3) about 0 to about 30% by weight of at least one process oil;
(4) about 1 to about 20 phr (parts per 100 parts rubber) of at least one tackifier, and
(5) about 0.1 to about 15 phr (parts per 100 parts of rubber) of a curing system for the elastomer,
A process comprising a mixture of
(B) forming a fluid permeation preventive composition, wherein the fluid permeation preventive composition comprises:
(1) At least one thermoplastic engineering resin component having a Young's modulus greater than 500 MPa, at least 10% by mass relative to the total mass of the polymer composition, wherein the thermoplastic engineering resin component is a polyamide resin A thermoplastic engineering resin component selected from the group consisting of polyester resin, polynitrile resin, polymethacrylate resin, polyvinyl resin, cellulose resin, fluororesin, and imide resin,
(2) At least one elastomer component having a Young's modulus of 500 MPa or less, at least 10% by mass based on the total mass of the polymer composition, wherein the elastomer component is a diene rubber, a halogen-containing rubber, or a silicone rubber An elastomer component selected from the group consisting of sulfur-containing rubber, and fluororubber, and
(3) 2-30 phr (parts per 100 parts of rubber) plasticizer for component (2),
Including
The thermoplastic engineering resin, the elastomer, and the plasticizer are mixed under dynamic vulcanization conditions, and the elastomer is dispersed as a discontinuous phase in a continuous matrix of the thermoplastic engineering resin;
(C) forming a film of the fluid permeation preventive composition;
(D) treating the fluid permeation prevention film to remove residual plasticizer or oil from the surface of the film to form a treated film; and
(E) directly coating the adhesive tie composition on one surface of the treated film to form the laminated structure;
Including a method.
[2] The method of [1], wherein the adhesive tie composition is calendered or extruded on the surface of the treated film.
[3] The method according to [1] or [2], wherein the step (E) is performed under heat and pressure conditions in order to bond the treated film and the adhesive tie composition.
[4] Component (1) of the adhesive tie composition is (i) a halogen-containing random copolymer of 4 to 7 carbon isomonoolefin and paraalkyl styrene, wherein the paraalkyl styrene is about 1% of the copolymer. A halogen-containing random copolymer comprising 0.5 to about 20% by weight, or (ii) a halogen-containing random copolymer of isomonoolefin having 4 to 12 carbon atoms and multiolefin having 4 to 14 carbon atoms, in each case The method according to any one of [1] to [3], wherein the halogen is selected from the group consisting of chlorine, bromine and mixtures thereof.
[5] The at least one elastomer component of the fluid permeation preventive composition is a halide of 4 to 7 carbon isomonoolefin and p-alkylstyrene copolymer, brominated isobutylene p-methylstyrene copolymer, hydrogenated nitrile- [1] to [4], selected from the group consisting of butadiene rubber, acrylonitrile butadiene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, chlorinated butyl rubber, and brominated butyl rubber. Method.
[6] The at least one tackifier includes at least one selected from the group consisting of rosin, rosin derivatives, tert-butylphenol and acetylene condensates, and mixtures thereof [1] to [5] The method in any one of.
[7] The at least one tackifier includes at least two mixtures selected from the group consisting of rosin, rosin derivatives, tert-butylphenol and acetylene condensates, and mixtures thereof. 6] The method according to any one of the above.
[8] A vulcanizable layered composition comprising two directly adjacent layers, wherein the first layer of the two layers includes a fluid permeation prevention layer, and the second of the two layers. Layer
(1) 100% by weight of at least one halogenated isobutylene-containing elastomer,
(2) about 20 to about 50% by weight of at least one filler;
(3) about 0 to about 30% by weight of at least one process oil;
(4) about 1 to about 20 phr (parts per 100 parts rubber) of at least one tackifier, and
(5) about 0.2 to about 15 phr (parts per 100 parts of rubber) of a curing system for the elastomer,
A mixture of
The fluid permeation prevention layer includes a polymer composition having a Young's modulus of 1 to 500 MPa, and the polymer composition includes:
(A) At least one thermoplastic engineering resin component having a Young's modulus greater than 500 MPa, at least 10% by mass relative to the total mass of the polymer composition, wherein the thermoplastic engineering resin component is a polyamide resin A thermoplastic engineering resin component selected from the group consisting of polyester resin, polynitrile resin, polymethacrylate resin, polyvinyl resin, cellulose resin, fluororesin, and imide resin,
(B) At least one elastomer component having a Young's modulus of 500 MPa or less and at least 10% by mass based on the total mass of the polymer composition, wherein the elastomer component is a diene rubber, a halogen-containing rubber, or a silicone rubber An elastomer component selected from the group consisting of sulfur-containing rubber, and fluororubber, and
2 to 30 phr (parts per 100 parts of rubber) plasticizer relative to component (B),
Including
The total mass of the component (A) and the component (B) is 30% by mass or more based on the total mass of the polymer composition, and the elastomer component (B) is the heat in the polymer composition. Dispersed in the matrix of the plastic resin component (A) as a discontinuous phase in a vulcanized or partially vulcanized state, and
The fluid permeation prevention layer is treated to remove residual plasticizer from the surface of the layer;
Vulcanizable layered composition.
[9] Component (1) is (i) a halogen-containing random copolymer of an isomonoolefin having 4 to 7 carbon atoms and paraalkyl styrene, wherein the paraalkyl styrene is about 0.5 to about 20 mass of the copolymer. A random copolymer, or (ii) a halogen-containing random copolymer of an isomonoolefin having 4 to 12 carbon atoms and a multiolefin having 4 to 14 carbon atoms, wherein in each case said halogen is chlorine, bromine and The composition according to [8], which is selected from the group consisting of mixtures thereof.
[10] The at least one elastomer component B is a halogenated product of isomonoolefin and p-alkylstyrene copolymer having 4 to 7 carbon atoms, brominated isobutylene p-methylstyrene copolymer, hydrogenated nitrile-butadiene rubber, acrylonitrile butadiene rubber. The composition according to [8] or [9], which is selected from the group consisting of chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, chlorinated butyl rubber, and brominated butyl rubber.
[11] The at least one tackifier includes at least one selected from the group consisting of rosin, rosin derivatives, tert-butylphenol and acetylene condensates, and mixtures thereof. [8] to [10] The composition in any one of.
[12] The at least one tackifier comprises at least two mixtures selected from the group consisting of rosin, rosin derivatives, tert-butylphenol and acetylene condensates, and mixtures thereof. 11].
[13] The fluid permeation prevention layer has an air permeability coefficient of 25 × 10 ⁻¹² cc cm / cm ² sec cmHg (at 30 degrees) or less, and the at least one thermoplastic engineering of the polymer composition. The resin has an air permeability coefficient of 25 × 10 ⁻¹² cc-cm / cm ² sec cmHg (at 30 degrees) or less, and the at least one elastomer of the polymer composition is 25 × 10 ⁻¹² cc The composition according to any one of [8] to [12], having an air permeability coefficient of greater than or equal to −cm / cm ² sec cmHg (at 30 degrees).
[14] The composition according to any one of [8] to [13], suitable for use in a tire, wherein the layer containing at least one engineering resin is an inner liner layer.
[15] A pneumatic tire, wherein the tire is
(I) Air permeation prevention comprising a polymer composition having an air permeability coefficient of about 25 × 10 ⁻¹² cc-cm / cm ² sec cmHg (at 30 ° C.) or less and a Young's modulus of about 1 to about 500 MPa. A layer comprising the polymer composition,
(A) At least one air permeability coefficient less than about 25 × 10 ⁻¹² cc cm / cm ² sec cmHg (at 30 ° C.) and greater than 500 MPa , at least 10% by weight, based on the total weight of the polymer composition. A thermoplastic resin component having a Young's modulus, wherein the 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 , Thermoplastic resin components,
(B) At least one air permeability coefficient greater than about 25 × ⁻¹² cc-cm / cm ² sec cmHg (at 30 ° C.) and 500 MPa or less , at least 10% by weight, based on the total weight of the polymer composition. An elastomer component having a Young's modulus of: wherein the elastomer component is selected from the group consisting of diene rubber, halogen-containing rubber, silicone rubber, sulfur-containing rubber, and fluororubber, and
(C) 2-30 phr (parts per 100 parts of rubber) plasticizer with respect to component (B),
Including, and
The total amount (A) + (B) of the component (A) and the component (B) is about 30% by mass or more based on the total mass of the polymer composition, and the elastomer component (B) is the polymer. Dispersed as a discontinuous phase in a vulcanized state in the matrix of the thermoplastic resin component (A) in the composition; and
The air permeation prevention layer is substantially free of residual plasticizer,
An air permeation prevention layer, and
(Ii) an adhesive tie layer that is in direct contact with the air permeation prevention layer, wherein the tie layer comprises:
(1) 100% by weight of at least one halogenated isobutylene-containing elastomer,
(2) about 20 to about 50% by weight of at least one filler;
(3) about 0 to about 30% by weight of at least one process oil;
(4) about 1 to about 20 phr (parts per 100 parts rubber) of at least one tackifier, and
(5) about 0.1 to about 15 phr (parts per 100 parts of rubber) of a curing system for the elastomer,
Tie layer, including a mixture of
Including pneumatic tires.
[16] Bromine-containing random of isomonoolefin having 4 to 7 carbon atoms and paraalkylstyrene, wherein component (i) (A) is at least one polyamide resin and component (i) (B) is at least one The pneumatic tire according to [15], which is an elastomeric copolymer and wherein the tie layer component (1) is (i) a bromine-containing random copolymer of an isomonoolefin having 4 to 7 carbon atoms and a paraalkylstyrene.
[17] The at least one tackifier includes at least one selected from the group consisting of rosin, rosin derivatives, tert-butylphenol and acetylene condensates, and mixtures thereof. [15] or [16 ] The pneumatic tire of description.

Claims (8)

A method for manufacturing a laminated structure, the method comprising:
(A) A step of forming an adhesive tie composition, wherein the adhesive tie composition is
(1) 100% by weight of brominated isobutylene-isoprene copolymer ,
(2) 20-50% by weight of at least one filler,
(3) 0-30% by weight of at least one process oil;
(4) 1-20 phr (parts per 100 parts of rubber), at least one tackifier, and (5) 0.1-15 phr (parts per 100 parts of rubber) of the curing system for the elastomer,
A process comprising a mixture of
(B) forming a fluid permeation preventive composition, wherein the fluid permeation preventive composition comprises:
(1) At least one thermoplastic engineering resin component having a Young's modulus greater than 500 MPa, at least 10% by mass, based on the total mass of the fluid permeation prevention composition, wherein the thermoplastic engineering resin component is A thermoplastic engineering resin component selected from the group consisting of polyamide resin, polyester resin, polynitrile resin, polymethacrylate resin, polyvinyl resin, cellulose resin, fluororesin, and imide resin;
(2) At least one elastomer component having a Young's modulus of 500 MPa or less, at least 10% by mass with respect to the total mass of the fluid permeation prevention composition, wherein the elastomer component is a diene rubber, a halogen-containing rubber, An elastomer component selected from the group consisting of silicone rubber, sulfur-containing rubber, and fluororubber, and (3) 2-30 phr (parts per 100 parts of rubber) plasticizer for component (2),
Including
The thermoplastic engineering resin, the elastomer, and the plasticizer are mixed under dynamic vulcanization conditions, and the elastomer is dispersed as a discontinuous phase in a continuous matrix of the thermoplastic engineering resin;
(C) forming a film of the fluid permeation preventive composition;
(D) treating the fluid permeation prevention film to remove residual plasticizer from the surface of the film to form a treated film; and (E) one surface of the treated film on the surface. Coating the adhesive tie composition directly to form the laminated structure;
Including a method.   The method of claim 1, wherein the adhesive tie composition is calendered or extruded onto the surface of the treated film.   The method according to claim 1 or 2, wherein step (E) is performed under conditions of heat and pressure to bond the treated film and the adhesive tie composition. The at least one tackifier is at least one selected from the group consisting of i) rosin, rosin derivatives, condensates of tert-butylphenol and acetylene, and mixtures thereof; or ii) rosin, rosin derivatives, tert- condensates of phenol and acetylene, and mixtures of at least two selected from the group consisting of mixtures thereof, including a method according to any one of claims 1-3. A vulcanizable layered composition comprising two directly adjacent layers, wherein the first of the two layers includes a fluid permeation prevention layer, and the second of the two layers comprises:
(1) 100% by weight of brominated isobutylene-isoprene copolymer ,
(2) 20-50% by weight of at least one filler,
(3) 0-30% by weight of at least one process oil;
(4) 1-20 phr (parts per 100 parts of rubber), at least one tackifier, and (5) 0.2-15 phr (parts per 100 parts of rubber) of the curing system for the elastomer,
A mixture of
The fluid permeation prevention layer includes a polymer composition having a Young's modulus of 1 to 500 MPa, and the polymer composition includes:
(A) At least one thermoplastic engineering resin component having a Young's modulus greater than 500 MPa, at least 10% by mass relative to the total mass of the polymer composition, wherein the thermoplastic engineering resin component is a polyamide resin A thermoplastic engineering resin component selected from the group consisting of polyester resin, polynitrile resin, polymethacrylate resin, polyvinyl resin, cellulose resin, fluororesin, and imide resin,
(B) At least one elastomer component having a Young's modulus of 500 MPa or less and at least 10% by mass based on the total mass of the polymer composition, wherein the elastomer component is a diene rubber, a halogen-containing rubber, or a silicone rubber An elastomer component selected from the group consisting of sulfur-containing rubbers and fluororubbers, and 2-30 phr (parts per 100 parts rubber) plasticizer for component (B),
Including
The total mass of the component (A) and the component (B) is 30% by mass or more based on the total mass of the polymer composition, and the elastomer component (B) is the heat in the polymer composition. In the matrix of the plastic resin component (A), dispersed as a discontinuous phase in a vulcanized or partially vulcanized state, and the fluid permeation preventive layer is formed from the surface of the layer with residual plasticity. Being processed to remove the agent,
Vulcanizable layered composition. The at least one tackifier is at least one selected from the group consisting of i) rosin, rosin derivatives, condensates of tert-butylphenol and acetylene, and mixtures thereof; or ii) rosin, rosin derivatives, tert- 6. The composition of claim 5 , comprising at least two mixtures selected from the group consisting of condensates of butylphenol and acetylene, and mixtures thereof. The composition according to claim 5 or 6 , suitable for use in a tire, wherein the layer comprising at least one engineering resin is an inner liner layer. A pneumatic tire comprising the composition according to any one of claims 5 to 7 , wherein the fluid permeation preventive layer is an inner liner layer.

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