JP2009220793A - Tire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tire having a high stripping resistance at a high temperature between a thermoplastic resin film and a rubber-like elastic layer used for an inner liner and an excellent durability. <P>SOLUTION: The tire is provided with an inner liner 1 has one or more of the thermoplastic resin film layer (A)2 and the rubber-like elasticity layer (B)3 disposed adjacent to the surface of the thermoplastic resin film layer (A)2, both layers being provided on an inner surface. An average stripping resistance between the thermoplastic resin film layer (A)2 and the rubber-like elasticity layer (B)3 at a temperature of 150°C is 0.05 kN/m or more. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a tire having an inner liner including a thermoplastic resin film layer and a rubber-like elastic layer on the inner surface of the tire, and in particular, increases the peel resistance between the thermoplastic resin film layer and the rubber-like elastic layer at a high temperature and is durable. This relates to a tire with improved properties.

  Conventionally, a rubber composition mainly composed of butyl rubber, halogenated butyl rubber or the like is used for an inner liner disposed as an air barrier layer on the inner surface of the tire in order to prevent air leakage and maintain the internal pressure of the tire. . However, when the content of these butyl rubbers is increased, the strength of the unvulcanized rubber is decreased, and rubber breakage, sheet punching, etc. are likely to occur. There is a problem that the cord of this is easily exposed. For this reason, the content of the butyl rubber is limited, and when the rubber composition using the butyl rubber as a main raw material is used for the inner liner, the thickness of the inner liner needs to be about 1 mm. Therefore, the weight of the inner liner in the tire is about 5%, which is an obstacle to reducing the tire weight and improving the fuel efficiency of the automobile.

  Therefore, in accordance with the social demand for energy saving in recent years, a method for reducing the thickness of the inner liner has been proposed for the purpose of reducing the weight of the automobile tire. For example, a technique of using a nylon film layer or a vinylidene chloride layer as an inner liner instead of a conventional butyl rubber is disclosed (for example, see Patent Document 1 and Patent Document 2). Further, it is disclosed that a film of a composition comprising a blend of a thermoplastic resin such as a polyamide resin or a polyester resin and an elastomer is used for the inner liner.

  However, the methods using these films, even if the weight of the tire can be reduced to some extent, since the matrix agent is a crystalline resin material, crack resistance and resistance particularly when used at a low temperature of 5 ° C. or lower. There is a drawback that the bending fatigue property is inferior to that of a rubber composition layer containing butyl rubber which is usually used, and the manufacture of the tire is complicated.

  On the other hand, an ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH) is known to have excellent gas barrier properties. The EVOH has an air permeation amount that is 1/100 or less of the rubber composition for an inner liner in which a butyl rubber is blended. Therefore, even if the thickness is 50 μm or less, the internal pressure retention property of the tire can be greatly improved. In addition, it is possible to reduce the weight of the tire. Therefore, it can be said that it is effective to use EVOH for the tire inner liner in order to improve the air permeability of the pneumatic tire. For example, a pneumatic tire having a tire inner liner made of EVOH is disclosed (see, for example, Patent Document 3).

  However, when normal EVOH is used as an inner liner, the effect of improving the internal pressure retention of the tire is great, but normal EVOH has a significantly higher elastic modulus than rubber normally used for tires, so when bent, Breaking or cracking may occur due to deformation. Therefore, when the inner liner made of EVOH is used, the internal pressure retention before using the tire is greatly improved, but the internal pressure retention is lower than that before using the tire after being subjected to bending deformation during rolling of the tire. There was something to do.

  As a means for solving this problem, for example, a resin comprising an ethylene content of 20 to 70 mol%, an ethylene-vinyl alcohol copolymer having a saponification degree of 85% or more and 60 to 99 wt% and a hydrophobic plasticizer of 1 to 40 wt% A technique for using the composition in an inner liner is disclosed (see, for example, Patent Document 4). However, the bending resistance of such an inner liner is not always satisfactory. Accordingly, there has been a demand for the development of an inner liner that has a high degree of bending resistance and can be made thinner while maintaining gas barrier properties.

Japanese Patent Laid-Open No. 7-40702 JP-A-7-81306 JP-A-6-40207 JP 2002-52904 A

  Under such circumstances, the present inventors have examined, and as such an inner liner, a laminate obtained by joining and integrating a rubber-like elastic layer having excellent bending resistance and a thermoplastic resin film layer having excellent gas barrier properties. Was found to be effective.

  However, when a laminate formed by joining and integrating the rubber-like elastic layer and the thermoplastic resin film layer is used as an inner liner, the adhesive strength between the rubber-like elastic layer and the thermoplastic resin film layer at a high temperature is low. For example, there is a tendency that separation occurs at the joint surface between the rubber-like elastic layer and the thermoplastic resin film layer during vulcanization.

  Accordingly, an object of the present invention is to provide a tire having high durability at high temperatures and excellent durability between a rubber-like elastic layer used for an inner liner and a thermoplastic resin film layer.

  As a result of intensive studies to achieve the above object, the present inventors include a thermoplastic resin film layer (A) and a rubber-like elastic layer (B), and the thermoplastic resin film layer (A) and the rubber-like layer. By placing an inner liner on the tire inner surface with an average peel force of 0.05 kN / m or more at 150 ° C with the elastic layer (B), the durability of the tire is improved and the gas barrier property is improved. The headline and the present invention have been completed.

That is, the tire of the present invention has one or more thermoplastic resin film layers (A) on the tire inner surface and a rubber-like elastic layer (B) disposed adjacent to the surface of the thermoplastic resin film layer (A). ) Including an inner liner including:
An average peeling force between the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) at 150 ° C. is 0.05 kN / m or more.

  The tire of the present invention is preferably produced by vulcanization molding in a mold without applying a release agent to both the inner liner and the tire vulcanization bladder surface.

  In a preferred example of the tire of the present invention, the inner liner is formed by joining the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) via an adhesive layer (C).

  In the tire of the present invention, it is preferable that an average peeling force at 150 ° C. between the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) is 0.2 kN / m or more.

  In another preferred embodiment of the tire of the present invention, at least one of the thermoplastic resin film layers (A) is an epoxy with respect to 100 parts by mass of an ethylene-vinyl alcohol copolymer having an ethylene content of 20 to 50 mol%. It consists of a layer containing a modified ethylene-vinyl alcohol copolymer obtained by reacting 1 to 50 parts by mass of the compound. Here, the layer containing the modified ethylene-vinyl alcohol copolymer is made of a resin composition in which a flexible resin or an elastomer having a Young's modulus of 500 MPa or less is dispersed in a matrix made of the modified ethylene-vinyl alcohol copolymer. The content of the flexible resin or elastomer in the resin composition is preferably 10 to 60% by mass.

  In another preferred embodiment of the tire of the present invention, the thermoplastic resin film layer (A) is crosslinked.

  In another preferred embodiment of the tire of the present invention, the thermoplastic resin film layer (A) includes a layer made of a thermoplastic urethane-based elastomer in at least one of the outermost layer and the innermost layer.

  In another preferred embodiment of the tire of the present invention, the rubber-like elastic layer (B) includes at least one of butyl rubber and halogenated butyl rubber.

  In another preferable example of the tire of the present invention, the rubber-like elastic layer (B) contains a diene elastomer.

In the inner liner used in the tire of the present invention, when the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) are bonded via an adhesive layer (C),
Adhesive composition in which at least one of poly-p-dinitrosobenzene and 1,4-phenylenedimaleimide is blended in an amount of 0.1 parts by mass or more with 100 parts by mass of the rubber component (a) in the adhesive layer (C). It is preferable to use a product.

In the inner liner used in the tire of the present invention, when the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) are bonded via an adhesive layer (C),
The rubber component (a) of the adhesive composition used for the adhesive layer (C) contains 10% by mass or more of chlorosulfonated polyethylene or 50% by mass or more of at least one of butyl rubber and halogenated butyl rubber. Further preferred.

In the inner liner used in the tire of the present invention, when the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) are bonded via an adhesive layer (C),
More preferably, the adhesive composition used for the adhesive layer (C) further contains 2 to 50 parts by mass of a filler with respect to 100 parts by mass of the rubber component (a). Here, as the filler, carbon black is more preferable.

In the inner liner used in the tire of the present invention, when the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) are bonded via an adhesive layer (C),
More preferably, the adhesive composition used for the adhesive layer (C) further contains 0.1 parts by mass or more of a rubber vulcanization accelerator with respect to 100 parts by mass of the rubber component (a). Here, as the rubber vulcanization accelerator, a thiuram vulcanization accelerator and a substituted dithiocarbamate vulcanization accelerator are more preferable.

In the inner liner used in the tire of the present invention, when the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) are bonded via an adhesive layer (C),
More preferably, the adhesive composition used for the adhesive layer (C) further contains 0.1 parts by mass or more of at least one of a resin and a low molecular weight polymer with respect to 100 parts by mass of the rubber component (a). Here, as the resin, C ₅ resins, phenol resins, terpene resins, modified terpene resins, even more preferably a hydrogenated terpene resins and rosin based resins.

  According to the present invention, one or more thermoplastic resin film layers (A) and a rubber-like elastic layer (B) are included, and the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) at 150 ° C. It is possible to provide a tire having an inner liner having an average peeling force of 0.05 kN / m or more and having excellent durability and improved gas barrier properties.

  Below, the inner liner used for the tire of this invention is demonstrated in detail, referring a figure. FIG. 1 is a cross-sectional view of an example of an inner liner used in the tire of the present invention, FIG. 2 is a cross-sectional view of another example of the inner liner used in the tire of the present invention, and FIG. 3 is a tire of the present invention. It is sectional drawing of the other example of the inner liner used for. The inner liner 1 shown in FIG. 1 includes a thermoplastic resin film layer (A) 2 and a rubber-like elastic layer (B) 3 disposed adjacent to the surface of the thermoplastic resin film layer (A) 2. Including. Here, the inner liner 1 used in the tire of the present invention has an average peeling force between the thermoplastic resin film layer (A) 2 and the rubber-like elastic layer (B) 3 at 150 ° C. of 0.05 kN / m or more. And is preferably 0.2 kN / m or more. If the average peel force at 150 ° C. between the thermoplastic resin film layer (A) 2 and the rubber-like elastic layer (B) 3 in the inner liner 1 is 0.05 kN / m or more, the peel resistance at high temperatures is high, It is possible to suppress the occurrence of peeling observed on the joint surface between the rubber-like elastic layer (B) and the thermoplastic resin film layer (A) during vulcanization. For this reason, a tire including such an inner liner is excellent in durability and can improve gas barrier properties. Some conventional inner liners use a commercially available adhesive to prevent the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) from peeling, but the thermoplastic resin film layer (A). And the reactivity between the functional group present on the surface of the rubber-like elastic layer (B) and the conventional adhesive is low, and the average peeling force at 150 ° C. was less than 0.05 kN / m, so the rubber-like elastic layer (B) Separation was observed on the joint surface between the thermoplastic resin film layer and the thermoplastic resin film layer (A), and the durability as a tire was not high.

  Further, as shown in FIG. 2, the inner liner used in the tire of the present invention is formed by joining a thermoplastic resin film layer (A) 2 and a rubber-like elastic layer (B) 3 via an adhesive layer (C) 4. It is preferred that By joining the thermoplastic resin film layer (A) 2 and the rubber-like elastic layer (B) 3 via the adhesive layer (C) 4, the thermoplastic resin film layer (A) 2 and the rubber-like elastic layer (B ) Adhesive strength between the three layers can be easily secured, and the average peeling force at 150 ° C. between these layers can be improved. Furthermore, the average peeling force at 150 ° C. between the thermoplastic resin film layer (A) 2 and the rubber-like elastic layer (B) 3 is determined by appropriately selecting the kinds and blending ratios of various compounding agents constituting each layer. It is also possible to adjust to the range.

  The inner liner shown in FIGS. 1 and 2 has only one thermoplastic resin film layer (A), but the inner liner used in the tire of the present invention has two or more thermoplastic resin film layers (A). May be.

  In the innerliner used in the tire of the present invention, at least one of the thermoplastic resin film layers (A) has an epoxy compound of 1 to 100 parts by mass of an ethylene-vinyl alcohol copolymer having an ethylene content of 20 to 50 mol%. It preferably comprises a layer containing a modified ethylene-vinyl alcohol copolymer obtained by reacting 50 parts by mass. When a layer containing the modified ethylene-vinyl alcohol copolymer is used for at least one layer of the thermoplastic resin film layer (A) of the inner liner used in the tire of the present invention, the elastic modulus of the thermoplastic resin film layer (A) is increased. The resistance to breakage is increased, and the resistance to breakage at the time of bending is increased, and cracks are less likely to occur.

  The ethylene-vinyl alcohol copolymer requires an ethylene content of 25 to 50 mol%, preferably 30 to 48 mol%, and more preferably 35 to 45 mol%. If the ethylene content is less than 25 mol%, the bending resistance, fatigue resistance and melt moldability may be deteriorated. On the other hand, if it exceeds 50 mol%, the gas barrier properties may not be sufficiently secured. The ethylene-vinyl alcohol copolymer preferably has a saponification degree of 90% or more, more preferably 95% or more, and still more preferably 99% or more. If the degree of saponification is less than 90%, gas barrier properties and thermal stability during molding may be insufficient. Further, the ethylene-vinyl alcohol copolymer preferably has a melt flow rate (MFR) of 0.1 to 30 g / 10 min at 190 ° C. under a load of 2160 g, more preferably 0.3 to 25 g / 10 min. .

  In the present invention, a method for producing the modified ethylene-vinyl alcohol copolymer is not particularly limited, but a production method in which the ethylene-vinyl alcohol copolymer and an epoxy compound are reacted in a solution is preferably exemplified. More specifically, a modified ethylene-vinyl alcohol copolymer is produced by adding an epoxy compound to a solution of an ethylene-vinyl alcohol copolymer in the presence of an acid catalyst or an alkali catalyst, preferably in the presence of an acid catalyst, and reacting. can do. Examples of the reaction solvent include aprotic polar solvents such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Examples of the acid catalyst include p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, and boron trifluoride. Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, Examples include sodium methoxide. The catalyst amount is preferably in the range of 0.0001 to 10 parts by mass with respect to 100 parts by mass of the ethylene-vinyl alcohol copolymer.

  As the epoxy compound to be reacted with the ethylene-vinyl alcohol copolymer, a monovalent epoxy compound is preferable. A divalent or higher valent epoxy compound may crosslink with the ethylene-vinyl alcohol copolymer to generate gels, blisters, and the like, which may deteriorate the quality of the inner liner. Note that glycidol and epoxypropane are particularly preferable among the monovalent epoxy compounds from the viewpoints of ease of production of the modified ethylene-vinyl alcohol copolymer, gas barrier properties, flex resistance, and fatigue resistance. The epoxy compound requires 1 to 50 parts by mass with respect to 100 parts by mass of the ethylene-vinyl alcohol copolymer, preferably 2 to 40 parts by mass, and 5 to 35 parts by mass. It is more preferable to react.

  For the layer containing the modified ethylene-vinyl alcohol copolymer, a resin composition in which a flexible resin or elastomer having a Young's modulus of 500 MPa or less is dispersed in a matrix made of the modified ethylene-vinyl alcohol copolymer. preferable. When the flexible resin or elastomer is dispersed in the matrix made of the modified ethylene-vinyl alcohol copolymer, the elastic modulus is greatly reduced, and the occurrence of breakage and cracks during bending can be suppressed. Here, in order to disperse | distribute the said flexible resin or elastomer uniformly in a matrix, it is preferable to have a functional group which reacts with a hydroxyl group. Examples of the functional group that reacts with a hydroxyl group include a maleic anhydride residue, a hydroxyl group, a carboxyl group, and an amino group. Specific examples of the flexible resin or elastomer having a functional group that reacts with a hydroxyl group include maleic anhydride-modified hydrogenated styrene-ethylene-butadiene-styrene block copolymer, maleic anhydride-modified ultra-low density polyethylene, and the like. If the Young's modulus of the flexible resin or elastomer is 500 MPa or less, the Young's modulus is generally lower than that of the modified ethylene-vinyl alcohol copolymer, and the elastic modulus of the thermoplastic resin film layer (A) can be reduced.

  In addition, the content of the flexible resin or elastomer in the resin composition used for the layer containing the modified ethylene-vinyl alcohol copolymer is preferably in the range of 10 to 60% by mass from the viewpoint of enhancing the bending resistance and gas barrier properties. . Furthermore, the flexible resin or elastomer preferably has an average particle size of 2 μm or less from the viewpoint of enhancing the bending resistance and gas barrier properties. In addition, the average particle diameter of the flexible resin or the elastomer in the resin composition is observed, for example, by freezing a sample, sectioning the sample with a microtome, and using a transmission electron microscope (TEM).

  When the thermoplastic resin film layer (A) is composed of a plurality of layers, the thermoplastic resin film layer (A) may be composed of only the layer containing the modified ethylene-vinyl alcohol copolymer, or may have another layer. The thermoplastic resin film layer (A) of the inner liner used in the tire of the invention is not only a layer containing a modified ethylene-vinyl alcohol copolymer, but also other layers as shown in FIG. 3, preferably a thermoplastic urethane elastomer. You may have the layer which consists of.

  FIG. 3 is a cross-sectional view of another example of the inner liner used in the tire of the present invention. The illustrated inner liner 1 includes, as a thermoplastic resin film layer (A) 2, a layer 5 containing the modified ethylene-vinyl alcohol copolymer, and a two-layer thermoplastic disposed adjacent to the layer 5. And a layer 6 made of urethane elastomer. The inner liner used in the tire according to the present invention is provided on at least one of the outermost layer and the innermost layer of the thermoplastic resin film layer (A), preferably adjacent to the layer containing the modified ethylene-vinyl alcohol copolymer. By providing a layer made of a plastic urethane elastomer, for example, even if a layer containing a modified ethylene-vinyl alcohol copolymer breaks or cracks, it is difficult for the cracks to extend and suppresses adverse effects such as large breaks and cracks. In addition, the internal pressure retention of the tire can be sufficiently maintained.

  In addition, the said thermoplastic urethane type elastomer is obtained by reaction of a polyol, an isocyanate compound, and a short chain diol, for example. A polyol and a short chain diol form a linear polyurethane by an addition reaction with an isocyanate compound. Here, the polyol becomes a flexible part in the thermoplastic urethane elastomer, and the isocyanate compound and the short chain diol become a hard part. Note that the properties of thermoplastic urethane elastomers can be changed over a wide range by changing the type, blending amount, polymerization conditions, and the like of raw materials.

  The thermoplastic resin film layer (A) is preferably further crosslinked. If the thermoplastic resin film layer (A) is not cross-linked, the inner liner may be significantly deformed and non-uniform during the vulcanization process of the tire, and the gas barrier properties, flex resistance, and fatigue resistance of the inner liner may be reduced. is there. Here, as a crosslinking method, a method of irradiating energy rays is preferable. Examples of the energy rays include ionizing radiation such as ultraviolet rays, electron beams, X-rays, α rays, γ rays, and among these, electron beams are used. Particularly preferred. The electron beam irradiation is preferably performed after the thermoplastic resin film layer (A) is processed into a molded body such as a film or a sheet. Here, the dose of the electron beam is preferably in the range of 10 to 60 Mrad, and more preferably in the range of 20 to 50 Mrad. In addition, the thermoplastic resin film layer (A) may be subjected to a surface treatment by an oxidation method, a concavo-convex method or the like in order to improve the adhesiveness with the adhesive layer (C). Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, and the like. Is mentioned. Among these, corona discharge treatment is preferable.

The thermoplastic resin film layer (A) preferably has an oxygen transmission rate at 20 ° C. and 65% RH of 3.0 × 10 ⁻¹² cm ³ · cm ² · sec · cmHg or less, and 1.0 × 10 ⁻¹² more preferably cm ³ · cm / cm is ² · sec · cmHg or less, and more preferably not more than ^{5.0 × 10 -13 cm 3 · cm} / cm 2 · sec · cmHg.

  The method for forming the thermoplastic resin film layer (A) is not particularly limited, and in the case of a single layer film, a conventionally known method such as a solution casting method, a melt extrusion method, a calendering method, etc. may be adopted. Among these, melt extrusion methods such as a T-die method and an inflation method are preferable. On the other hand, in the case of a multilayer film, a laminating method by coextrusion is preferably employed. The total thickness of the thermoplastic resin film layer (A) is preferably 1 to 200 μm, more preferably 10 to 150 μm, and even more preferably 20 to 100 μm from the viewpoint of reducing the gauge of the inner liner.

  In the inner liner used in the tire of the present invention, the rubber-like elastic layer (3) preferably contains butyl rubber and / or halogenated butyl rubber as a rubber component. Here, examples of the halogenated butyl rubber include chlorinated butyl rubber, brominated butyl rubber, and modified rubbers thereof. The halogenated butyl rubber may be a commercially available product. For example, “Enjay Butyl HT10-66” (registered trademark) [manufactured by Enjay Chemical Co., Ltd., chlorinated butyl rubber], “Bromobutyl 2255” (registered trademark). [Brominated butyl rubber manufactured by JSR Corporation], “Bromobutyl 2244” (registered trademark) [Brominated butyl rubber manufactured by JSR Corporation], and the like. Examples of the chlorinated or brominated modified rubber include “Expro 50” (registered trademark) [manufactured by Exxon Corporation].

  The content of butyl rubber and / or halogenated butyl rubber in the rubber component in the rubber-like elastic layer (B) is preferably 50% by mass or more from the viewpoint of improving air permeation resistance, and is 70 to 100% by mass. More preferably. Here, as the rubber component, in addition to butyl rubber and halogenated butyl rubber, a diene elastomer or the like may be used. These rubber components may be used alone or in combination of two or more.

  Specific examples of the diene elastomer include natural rubber (NR), isoprene rubber (IR), cis-1,4-polybutadiene (BR), syndiotactic-1,2-polybutadiene (1,2BR), and styrene. -Butadiene copolymer rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), etc. are mentioned.

  The rubber-like elastic layer (B) is a compounding agent usually used in the rubber industry, such as a reinforcing filler, a softening agent, an anti-aging agent, a vulcanizing agent, a rubber vulcanization accelerator, A scorch inhibitor, zinc white, stearic acid, and the like can be produced by appropriately selecting and blending them within a range that does not impair the object of the present invention, and kneading, heating, extruding, and the like. As these compounding agents, commercially available products can be suitably used.

  In the inner liner used for the tire of the present invention, when the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) are bonded via the adhesive layer (C), the adhesive layer (C) It is preferable to use an adhesive composition in which at least one of poly-p-dinitrosobenzene and 1,4-phenylene dimaleimide is blended in an amount of 0.1 parts by mass or more per 100 parts by mass of the rubber component (a). By using poly-p-dinitrosobenzene and / or 1,4-phenylene dimaleimide as the crosslinking agent and crosslinking aid in the adhesive composition, the thermoplastic resin film layer (A) and the rubber-like elastic layer (B ) To the adhesive layer (C) can be improved, and the peel resistance at high temperatures between the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) can be improved. Further, the blending amount of poly-p-dinitrosobenzene and / or 1,4-phenylene dimaleimide is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the rubber component (a), and is 2 parts by mass or more. More preferably it is. When the blending amount of poly-p-dinitrosobenzene and / or 1,4-phenylene dimaleimide is less than 0.1 parts by mass with respect to 100 parts by mass of the rubber component (a), the peel resistance at high temperature cannot be sufficiently improved. .

  The rubber component (a) used in the adhesive composition is not particularly limited, and examples thereof include chlorosulfonated polyethylene, butyl rubber, halogenated butyl rubber, and diene rubber. Among these, chlorosulfonated polyethylene, butyl rubber and / or Or halogenated butyl rubber is preferable. The chlorosulfonated polyethylene is a synthetic rubber having a saturated main chain structure obtained by chlorinating and chlorosulfonated polyethylene using chlorine and sulfurous acid gas, and has excellent weather resistance, ozone resistance, heat resistance, etc. Gas barrier properties are also high. Moreover, as said chlorosulfonated polyethylene, a commercial item can be utilized, for example, a brand name "Hypalon" [made by DuPont] etc. is mentioned. Furthermore, the content of chlorosulfonated polyethylene in the rubber component (a) is preferably 10% by mass or more, and preferably 10 to 40% by mass from the viewpoint of improving the average peeling force. On the other hand, butyl rubber and halogenated butyl rubber are as described in the rubber-like elastic layer (B), and the content of butyl rubber and / or halogenated butyl rubber in the rubber component (a) is the same as that of the adhesive layer (c). From the viewpoint of workability, average peeling force, etc., 50% by mass or more is preferable. In addition, the said rubber component (a) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The adhesive composition preferably further contains a rubber vulcanization accelerator, a filler, a resin, a low molecular weight polymer, and the like. In addition to the above components, for example, a softener, an anti-aging agent, an additive, and the like. A sulfurizing agent, a scorch inhibitor, zinc white, stearic acid and the like may be appropriately blended depending on the purpose.

  Examples of the rubber vulcanization accelerator include thiuram vulcanization accelerator, substituted dithiocarbamate vulcanization accelerator, guanidine vulcanization accelerator, thiazole vulcanization accelerator, sulfenamide vulcanization accelerator, Examples include thiourea vulcanization accelerators, xanthate vulcanization accelerators, and among these, thiuram vulcanization accelerators and substituted dithiocarbamate vulcanization accelerators are preferred. These rubber vulcanization accelerators may be used alone or in combination of two or more. The blending amount of the rubber vulcanization accelerator is preferably 0.1 parts by mass or more and more preferably in the range of 0.3 to 3 parts by mass with respect to 100 parts by mass of the rubber component (a).

  Thiuram-based vulcanization accelerators suitable as rubber vulcanization accelerators include tetramethylthiuram monosulfide, tetramethylthiuram disulfide, activated tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram monosulfide, tetrabutylthiuram. Examples thereof include disulfide, dipentamethylene thiuram tetrasulfide, dipentamethylene thiuram hexasulfide, tetrabenzyl thiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide and the like.

  On the other hand, suitable substituted dithiocarbamate vulcanization accelerators as the rubber vulcanization accelerators include sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium di-n-butyldithiocarbamate, potassium dimethyldithiocarbamate, ethylphenyl Lead dithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, zinc ethylphenyldithiocarbamate, tellurium diethyldithiocarbamate, dimethyldithiocarbamine Examples include acid copper and pentamethylene dithiocarbamate piperidine.

  Preferred examples of the filler include inorganic fillers and carbon black. Here, as the inorganic filler, wet silica, aluminum hydroxide, aluminum oxide, magnesium oxide, montmorillonite, mica, smectite, organic montmorillonite, organic mica, organic smectite and the like are preferable. On the other hand, carbon black is preferably SRF, GPF, FEF, HAF, ISAF, or SAF grade. These fillers may be used alone or in combination of two or more. Moreover, the blending amount of the filler is preferably 2 to 50 parts by mass and more preferably 5 to 35 parts by mass with respect to 100 parts by mass of the rubber component (a).

  In order to improve both the adhesiveness of the adhesive composition and the workability of attaching the thermoplastic resin film layer (A) and the rubber-like elastic layer (B), the adhesive composition has a rubber component (a ) The resin and / or low molecular weight polymer is preferably contained in an amount of 0.1 parts by mass or more, more preferably 5 to 40 parts by mass, and even more preferably 10 to 30 parts by mass with respect to 100 parts by mass.

As the resin, C ₅ resins, phenol resins, terpene resins, modified terpene resins, hydrogenated terpene resins, rosin resins and the like are preferable, phenolic resins Among these, particularly preferred. The phenolic resin is obtained, for example, by condensation of pt-butylphenol and acetylene or condensation of alkylphenol and formaldehyde in the presence of a catalyst. Examples of the terpene resin include terpene resins such as β-pinene resin and α-pinene resin. A hydrogenated terpene resin can be obtained by hydrogenating the terpene resin. Furthermore, the modified terpene resin can be obtained by the reaction of terpene and phenol in the presence of a Friedel-Craft type catalyst or by condensation with formaldehyde. Examples of the rosin resin include natural rosin or a rosin derivative obtained by modifying the natural rosin by hydrogenation, disproportionation, dimerization, esterification, limeization, or the like. These resins may be used alone or in combination of two or more.

  The low molecular weight polymer preferably has a polystyrene-equivalent weight average molecular weight of 1,000 to 100,000, and more preferably 1,000 to 50,000. The low molecular weight polymer is preferably a styrene-butadiene copolymer. Here, the method for producing the styrene-butadiene copolymer is not particularly limited. For example, in a hydrocarbon solvent such as cyclohexane, an organic lithium compound is used as a randomizer and an ether or a tertiary amine is used as a randomizer. A styrene-butadiene copolymer can be produced by using it in the presence and copolymerizing butadiene and styrene at a temperature of 50 to 90 ° C. In the obtained copolymer, the weight average molecular weight can be controlled by adjusting the amount of the polymerization initiator, and the microstructure of the conjugated diene compound portion of the copolymer is controlled using a randomizer. be able to. In addition, the said low molecular weight polymer may be used individually by 1 type, and may be used in combination with the said resin.

  As a method for producing the inner liner used in the tire of the present invention, for example, a coating liquid in which the adhesive composition is dispersed or dissolved in an organic solvent is applied and dried on the surface of the thermoplastic resin film layer (A). The inner liner used for the tire of the present invention is formed by forming the adhesive layer (C), and then bonding the rubber-like elastic layer (B) to the surface of the adhesive layer (C) and performing vulcanization treatment. Can be manufactured. The inner liner is produced by applying and drying the coating liquid on the surface of the rubber-like elastic layer (B) to form an adhesive layer (C), and forming the adhesive layer (C) on the surface. The thermoplastic resin film layer (A) may be bonded together and vulcanized. Further, in the method for producing the inner liner, the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) may be directly bonded and vulcanized. The vulcanization temperature is preferably 100 ° C. or higher, more preferably in the range of 125 to 200 ° C., and still more preferably in the range of 130 to 180 ° C. The vulcanization time is preferably in the range of 10 to 120 minutes.

The mixing method of the adhesive composition and the organic solvent is performed by a conventional method, and the concentration of the adhesive composition in the coating solution prepared by such a method is preferably in the range of 5 to 50% by mass, and 10 to 30. A range of mass% is more preferred. Here, examples of the organic solvent include toluene, xylene, n-hexane, cyclohexane, chloroform, methyl ethyl ketone, and the like. These organic solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them. Moreover, in the said organic solvent, it is preferable that the Hildebrand solubility parameter (delta value) is the range of 14-20 MPa1 ^{/ 2} . Here, when the Hildebrand solubility parameter (δ value) is within the specific range, the affinity between the organic solvent and the rubber component (a) increases.

  Next, the tire of the present invention will be described in detail with reference to the drawings. FIG. 4 is a partial cross-sectional view of an example of the tire of the present invention. The tire shown in FIG. 4 has a pair of bead portions 7 and a pair of sidewall portions 8, and a tread portion 9 connected to both sidewall portions 8, and extends in a toroid shape between the pair of bead portions 7. Embedded in the bead portion 7, a carcass 10 for reinforcing these portions 7, 8, 9, a belt 11 composed of two belt layers disposed on the outer side in the tire radial direction of the crown portion of the carcass 10, respectively. And a bead filler 13 disposed on the outer side in the tire radial direction of the ring-shaped bead core 12, and an inner liner 14 is disposed on the inner surface of the tire inside the carcass 10. Here, the tire of the present invention is characterized in that the inner liner described above is applied to the inner liner 14. By providing the inner liner, the tire of the present invention is excellent in durability by suppressing the occurrence of peeling seen during vulcanization.

  In the tire shown in FIG. 4, it is preferable to use an inner liner having the structure shown in FIGS. 1, 2, and 3 as the inner liner 14, and the rubber-like elastic layer 3 in FIGS. It is preferable to be joined to the inner tire inner surface.

  Further, the carcass 10 of the tire shown in FIG. 4 is composed of a single carcass ply, and a main body portion extending in a toroid shape between a pair of bead cores 12 embedded in the bead portion 7, respectively. Each bead core 12 includes a turn-up portion wound radially outward from the inner side to the outer side in the tire width direction. In the tire of the present invention, the number of plies and the structure of the carcass 10 are limited to this. is not.

  Further, the belt 11 of the tire shown in FIG. 4 is composed of two belt layers, and each belt layer is usually a rubberized layer of a cord, preferably steel, extending incline with respect to the tire equatorial plane. The belt 11 is composed of a rubberized layer of cords, and two belt layers are laminated so that the cords constituting the belt layers intersect with each other across the tire equatorial plane. Although the belt 11 in the figure is composed of two belt layers, the number of belt layers constituting the belt 11 in the tire of the present invention is not limited to this.

  The tire of the present invention can be produced by, for example, appropriately stacking an inner liner, a carcass, a belt, a tread, and the like on the circumference of a molding drum to produce a raw tire, and then vulcanizing and molding the raw tire. Here, in the vulcanization molding of the raw tire, usually, at least one of the inner liner and the tire vulcanization bladder surface is used to prevent the tire vulcanization bladder from sticking to the inner liner that forms the inner surface of the raw tire. Further, a release agent such as silicone oil is applied. However, since the inner liner used in the tire of the present invention includes one or more thermoplastic resin film layers (A), it is difficult to adhere to the surface of the tire vulcanization bladder, thereby eliminating the cause of peeling failure. . Therefore, the tire of the present invention can be vulcanized and molded in a mold without applying a release agent to both the inner liner and the tire vulcanization bladder surface. For this reason, the process of apply | coating a mold release agent can be skipped and manufacturing cost can be reduced.

  In the tire of the present invention, any gas capable of exhibiting its function can be used as the gas for maintaining the tire internal pressure, and examples thereof include air, nitrogen, and helium.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<Production Example 1 Production of Modified Ethylene-Vinyl Alcohol Copolymer>
In a pressurized reaction vessel, 2 parts by mass of ethylene-vinyl alcohol copolymer (MFR: 5.5 g / 10 min (190 ° C., 21.18 N load)) having an ethylene content of 44 mol% and a saponification degree of 99.9 mol% and N − 8 parts by mass of methyl-2-pyrrolidone was charged and stirred at 120 ° C. for 2 hours to completely dissolve the ethylene-vinyl alcohol copolymer. To this was added 0.4 parts by mass of epoxypropane as an epoxy compound, and then heated at 160 ° C. for 4 hours. After the heating, it was precipitated in 100 parts by mass of distilled water, and N-methyl-2-pyrrolidone and unreacted epoxypropane were sufficiently washed with a large amount of distilled water to obtain a modified ethylene-vinyl alcohol copolymer. Further, the resulting modified ethylene-vinyl alcohol copolymer was fined to a particle size of about 2 mm with a pulverizer, and then sufficiently washed with a large amount of distilled water again. The washed particles were vacuum-dried at room temperature for 8 hours, and then melted at 200 ° C. using a twin-screw extruder and pelletized.

The ethylene content and saponification degree of the ethylene-vinyl alcohol copolymer were measured by ¹ H-NMR measurement using deuterated dimethyl sulfoxide as a solvent [using “JIM-GX-500 type” manufactured by JEOL Ltd.] This is a value calculated from the spectrum obtained in (1). The ethylene-vinyl alcohol copolymer has a melt flow rate (MFR) of a melt indexer L244 (manufactured by Takara Kogyo Co., Ltd.) filled with a sample in a cylinder with an inner diameter of 9.55 mm and a length of 162 mm, and melted at 190 ° C. After that, using a plunger with a weight of 2160g and a diameter of 9.48mm, apply a load evenly and the amount of resin extruded per unit time from the 2.1mm diameter orifice provided in the center of the cylinder (g / 10min) I asked for it. However, when the melting point of the ethylene-vinyl alcohol copolymer is around 190 ° C or exceeds 190 ° C, it is measured at a plurality of temperatures above the melting point under a load of 2160g. Is plotted on the vertical axis, and the value calculated by extrapolating to 190 ° C. was taken as the melt flow rate (MFR).

<Production Example 2 Production of 3-layer film>
Using the modified EVOH obtained in Production Example 1 and thermoplastic polyurethane (made by Kuraray Co., Ltd., Kuramiron 3190) as an elastomer, using a two-type three-layer coextrusion device, three layers under the following coextrusion molding conditions: A film (thermoplastic polyurethane layer / modified EVOH layer / thermoplastic polyurethane layer) was prepared. The thickness of each layer is 20 μm for both the modified EVOH layer and the thermoplastic polyurethane layer.
The coextrusion molding conditions are as follows.
Layer structure:
Thermoplastic polyurethane / modified EVOH / thermoplastic polyurethane (thickness 20/20/20, unit is μm)
Extrusion temperature of each resin:
C1 / C2 / C3 / die = 170/170/220/220 ° C
Extruder specifications for each resin:
Thermoplastic polyurethane:
25mmφ extruder P25-18AC (Osaka Seiki Machine Co., Ltd.)
Modified EVOH:
20mmφ extruder Lab type ME CO-EXT (manufactured by Toyo Seiki Co., Ltd.)
T-die specification:
For 500mm width, 2 types and 3 layers (Plastic Engineering Laboratory Co., Ltd.)
Cooling roll temperature: 50 ℃
Pickup speed: 4m / min

<Production Example 2 ′ Production of Single Layer Film>
Using the modified EVOH obtained in Production Example 1, a monolayer film having a thickness of 20 μm was obtained in accordance with the conditions of Production Example 2.

<Production Example 3 Production of Unvulcanized Rubber Elastic Layer>
30 parts by mass of natural rubber and 70 parts by mass of brominated butyl rubber (Br-IIR) [manufactured by JSR Corporation, Bromobutyl 2244], 60 parts by mass of GPF carbon black [Asahi Carbon Co., Ltd., # 55], SUNPAR 2280 [Japan Sun Petroleum Corporation] 7 parts by mass, stearic acid [Asahi Denka Kogyo Co., Ltd.] 1 part by mass, vulcanization accelerator [Ouchi Shinsei Chemical Co., Ltd., Noxeller DM] 1.3 parts by mass, zinc oxide [Shiramizu Chemical Industries, Ltd. ] A rubber composition was prepared by blending 3 parts by mass and 0.5 parts by mass of sulfur [manufactured by Karuizawa Smelter] to prepare an unvulcanized rubber-like elastic sheet having a thickness of 500 μm.

<Production Example 4 Production of Unvulcanized Rubber Elastic Layer>
For 100 parts by mass of natural rubber, GPF carbon black [Asahi Carbon Co., # 55] 60 parts by mass, SUNPAR 2280 [Nihon Sun Sekiyu Co., Ltd.] 7 parts by mass, stearic acid [Asahi Denka Kogyo Co., Ltd.] 1 part by mass, A rubber composition containing 1.3 parts by mass of a vulcanization accelerator [Ouchi Shinsei Chemical Co., Ltd., Noxeller DM], 3 parts by mass of zinc oxide [Shiramizu Chemical Co., Ltd.] and 0.5 parts by mass of sulfur [Karuizawa Smelter] To prepare an unvulcanized rubber-like elastic sheet having a thickness of 500 μm.

<Preparation of Production Example 5 Adhesive Composition-1 and Coating Solution>
After preparing an adhesive composition having the formulation shown in Table 1 by a conventional method, 100 parts by mass of the obtained adhesive composition was added to 1000 parts by mass of toluene (δ value: 18.2 MPa ^1/2 ), and dissolved or dispersed. Thus, an adhesive coating solution was prepared.

<Preparation of Production Example 6 Adhesive Composition-2 and Coating Solution>
After preparing an adhesive composition having the formulation shown in Table 2 by a conventional method, 100 parts by mass of the obtained adhesive composition was added to 1000 parts by mass of toluene (δ value: 18.2 MPa ^1/2 ), and dissolved or dispersed. Thus, an adhesive coating solution was prepared.

<Preparation of Production Example 7 Adhesive Composition-3 and Coating Solution>
After preparing an adhesive composition having the formulation shown in Table 3 by a conventional method, 100 parts by mass of the obtained adhesive composition was added to 1000 parts by mass of toluene (δ value: 18.2 MPa ^1/2 ), and dissolved or dispersed. Thus, an adhesive coating solution was prepared.

Example 1
Using the Nisshin High Voltage Co., Ltd. electron beam irradiation device “Curetron EBC200-100 for production”, the three-layer film (thermoplastic polyurethane / modified EVOH / thermoplastic polyurethane) obtained in Production Example 2 was accelerated. The film was irradiated with an electron beam under the conditions of a voltage of 200 kV and an irradiation energy of 30 Mrad, subjected to crosslinking treatment, and used as a multilayer thermoplastic film. The adhesive coating solution prepared in Production Example 5 is applied to one side of the crosslinked multilayer thermoplastic resin film, dried, and then bonded to the unvulcanized rubber-like elastic sheet obtained in Production Example 3. As a result, an inner liner was produced. Using the obtained inner liner, a pneumatic tire for passenger cars (195 / 65R15) was prototyped through a vulcanization process by a conventional method.
The average peeling force at 150 ° C. and the tire inner surface properties after running the drum were measured and evaluated by the following methods. The results are shown in Table 4.

(1) Measurement of average peeling force In accordance with JIS K6854-3 [Adhesive-peeling adhesion strength test method (T-type peeling)], a T-type peeling test was conducted at 150 ° C, and the average peeling force (kN / m ) Was measured. Note that a test piece having a width of 10 mm was used.

(2) Evaluation of tire inner surface property after running The prototype tire was pushed at a load of 6 kN on a drum having an air pressure of 140 kPa and a rotational speed corresponding to a speed of 80 km / h, and run for 10,000 km. The appearance of the inner liner of the tire after running the drum was visually observed, and the peeled state of the thermoplastic resin film layer was evaluated based on the following evaluation criteria.
◎ No problem with film layer peeling (no problem for all 10 prototype tires)
○ No peeling of film layer and almost no problem (only 1 out of 10 prototype tires showed slight peeling, but there was no problem in durability)
× With peeling of film layer

(Example 2)
Evaluation was performed in the same manner as in Example 1 except that the coating solution of adhesive composition-1 prepared in Production Example 5 was changed to the coating solution of adhesive composition-2 prepared in Production Example 6. . The results are shown in Table 4.

(Example 3)
Evaluation was performed in the same manner as in Example 1 except that the coating solution of adhesive composition-1 prepared in Production Example 5 was changed to the coating solution of adhesive composition-3 prepared in Production Example 7. . The results are shown in Table 4.

Example 4
Evaluation was performed in the same manner as in Example 3 except that the unvulcanized rubber-like elastic sheet obtained in Production Example 3 was changed to the unvulcanized rubber-like elastic sheet obtained in Production Example 4. The results are shown in Table 4.

(Example 5)
Evaluation was performed in the same manner as in Example 3 except that the single-layer film obtained in Production Example 2 ′ was used in place of the three-layer film obtained in Production Example 2. The results are shown in Table 4.

(Comparative Example 1)
In Example 1, evaluation was performed in the same manner as in Example 1 except that the coating liquid of adhesive composition-1 prepared in Production Example 5 was not applied. The results are shown in Table 4.

(Comparative Example 2)
It replaces with the coating liquid of adhesive composition-1 prepared in manufacture example 5, and is the same as that of Example 1 except having apply | coated the commercially available adhesive composition [The Toyo Chemical Laboratory make, Metalloc R-46]. And evaluated. The results are shown in Table 4.

  As is clear from Table 4, the tires of the examples have higher peel resistance at high temperatures than the tires of the comparative examples, and the peeling between the rubber-like elastic layer and the thermoplastic resin film layer during vulcanization is suppressed, It can be seen that the durability is improved.

It is sectional drawing of an example of the inner liner used for the tire of this invention. It is sectional drawing of the other example of the inner liner used for the tire of this invention. It is sectional drawing of the other example of the inner liner used for the tire of this invention. It is sectional drawing of an example of the tire of this invention.

Explanation of symbols

1 Inner liner 2 Thermoplastic resin film layer (A)
3 Rubber elastic layer (B)
4 Adhesive layer (C)
5 Layer containing modified ethylene-vinyl alcohol copolymer 6 Layer made of thermoplastic urethane elastomer 7 Bead portion 8 Side wall portion 9 Tread portion 10 Carcass 11 Belt 12 Bead core 13 Bead filler 14 Inner liner

Claims (19)

An inner liner including one or more thermoplastic resin film layers (A) and a rubber-like elastic layer (B) disposed adjacent to the surface of the thermoplastic resin film layer (A) is provided on the tire inner surface. In the tire
A tire characterized in that an average peeling force at 150 ° C. between the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) is 0.05 kN / m or more.   2. The tire according to claim 1, wherein the tire is produced by vulcanization molding in a mold without applying a release agent to both the inner liner and the tire vulcanization bladder surface. 3.   The inner liner is formed by joining the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) through an adhesive layer (C). tire.   The tire according to claim 1 or 3, wherein an average peeling force at 150 ° C between the thermoplastic resin film layer (A) and the rubber-like elastic layer (B) is 0.2 kN / m or more.   At least one layer of the thermoplastic resin film layer (A) is obtained by reacting 1 to 50 parts by mass of an epoxy compound with 100 parts by mass of an ethylene-vinyl alcohol copolymer having an ethylene content of 20 to 50 mol%. The tire according to claim 1, comprising a layer containing a modified ethylene-vinyl alcohol copolymer. The layer containing the modified ethylene-vinyl alcohol copolymer consists of a resin composition in which a flexible resin or elastomer having a Young's modulus of 500 MPa or less is dispersed in a matrix made of the modified ethylene-vinyl alcohol copolymer,
The tire according to claim 5, wherein a content of the flexible resin or the elastomer in the resin composition is 10 to 60% by mass.   The tire according to claim 1, wherein the thermoplastic resin film layer (A) is crosslinked.   The tire according to claim 1 or 5, wherein the thermoplastic resin film layer (A) includes a layer made of a thermoplastic urethane-based elastomer in at least one of the outermost layer and the innermost layer.   The tire according to claim 1, wherein the rubber-like elastic layer (B) contains at least one of butyl rubber and halogenated butyl rubber.   The tire according to claim 1, wherein the rubber-like elastic layer (B) contains a diene elastomer.   Adhesive composition in which at least one of poly-p-dinitrosobenzene and 1,4-phenylenedimaleimide is blended in an amount of 0.1 parts by mass or more with 100 parts by mass of the rubber component (a) in the adhesive layer (C). The tire according to claim 3, wherein an object is used.   The tire according to claim 11, wherein the rubber component (a) contains 10% by mass or more of chlorosulfonated polyethylene.   The tire according to claim 11, wherein the rubber component (a) contains 50% by mass or more of at least one of butyl rubber and halogenated butyl rubber.   The tire according to claim 11, wherein the adhesive composition further contains 2 to 50 parts by mass of a filler with respect to 100 parts by mass of the rubber component (a).   The tire according to claim 14, wherein the filler is carbon black.   The tire according to claim 11, wherein the adhesive composition further contains 0.1 parts by mass or more of a rubber vulcanization accelerator with respect to 100 parts by mass of the rubber component (a).   The tire according to claim 16, wherein the rubber vulcanization accelerator includes at least one of a thiuram vulcanization accelerator and a substituted dithiocarbamate vulcanization accelerator.   The tire according to claim 11, wherein the adhesive composition further includes at least one of a resin and a low molecular weight polymer in an amount of 0.1 parts by mass or more with respect to 100 parts by mass of the rubber component (a). The resin, C ₅ resins, phenol resins, terpene resins, modified terpene resins, in claim 18, characterized in that at least one selected from the group consisting of hydrogenated terpene resins and rosin based resins The described tire.

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