JP2013086295A - Strip and manufacturing method for pneumatic tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To achieve the uniform thickness of an inner liner, molded by forming ear parts on a strip, in order to improve adhesion of a carcass ply and suppress the crack growth due to the repeated bending deformation during the tire running.SOLUTION: A strip 10 is made of a polymer composition and spirally wound on a cylindrical drum to form a tire inner liner. The strip 10 is composed of a polymer sheet made of a polymer composition containing ≥0.1 and ≤5 pts. of sulfur based on 100 pts. of a polymer component containing ≥5 and ≤40 mass% of a styrene-isobutylene-styrene triblock copolymer and ≥60 and ≤95 mass% of at least one kind of rubber component selected from a group comprising natural rubber, isoprene rubber, and butyl rubber. The thickness of the strip 10 body is 0.05-1.0 mm. The thickness of the ear part is thinner than the thickness of the body. The width of the ear part is 0.5-5.0 mm.

Description

  The present invention relates to a strip for an inner liner used in a pneumatic tire and a method for producing a pneumatic tire using the strip.

  In recent years, tires have been made lighter due to the strong social demand for low fuel consumption of vehicles, and among the tire members, the amount of air leakage from the inside of the pneumatic tire to the outside is arranged inside the tire. In the inner liner having a function of reducing the weight, weight reduction and the like have been performed.

  Thermoplastic elastomers that are thinner than butyl rubber and exhibit high air permeation resistance are inferior to butyl rubber in vulcanization adhesion to insulation rubber and carcass rubber adjacent to the inner liner. If the vulcanization adhesive strength of the inner liner is low, an air-in phenomenon occurs in which air is mixed between the inner liner and the insulation or the carcass and many small bubbles appear. This phenomenon gives the user the impression that the appearance is poor due to the small spotted pattern inside the tire. Furthermore, since air becomes a starting point during running and the inner liner and the insulation or carcass peel off, the inner liner may crack and the tire internal pressure may decrease.

  In order to reduce the weight of the tire, a film made of a material containing a thermoplastic resin has been proposed. However, if a tire is manufactured using a thin inner liner made of a thermoplastic resin, the pressure in the vulcanization process is partially reduced so that the finished gauge of the inner liner of the tire product becomes thinner than the design. The inner liner with a thin finish has the phenomenon that the carcass cord is raised at the location (open thread), giving the user the impression that the inner appearance is poor. Therefore, the tire internal pressure decreases, and in the worst case, the tire may burst.

  The inner liner is subjected to a large shear strain in the vicinity of the shoulder when the tire is running. When a material containing a thermoplastic resin is used as the inner liner, there is a problem that due to this shear strain, peeling is likely to occur at the adhesive interface between the inner liner and the carcass ply, resulting in tire air leakage.

  In Patent Document 1 (Japanese Patent Laid-Open No. 9-165469), an inner liner layer is formed using nylon having a low air permeability to improve adhesion to a tire inner surface or a carcass layer that is a rubber composition. Proposed. However, in the technique of Patent Document 2, in order to form a nylon film layer, after the nylon film is RFL-treated, it is necessary to bond a rubber paste made of a rubber composition, which causes a problem that the process becomes complicated. . Furthermore, in the vulcanization process, the bladder is expanded from the inside of the unvulcanized tire, but the nylon of the inner liner layer comes into contact with the bladder in a heated state, and the inner liner adheres to and adheres to the bladder and breaks. There's a problem.

  Patent Document 2 (International Publication No. 2008/029781) manufactures a tire with a strip of a film laminate obtained by blending a thermoplastic resin and a thermoplastic elastomer. By using a laminate, gas barrier properties and adhesiveness can be improved, and bonding between ribbon-like strips is possible. However, with this technique, the gauge at the unvulcanized green cover of the film laminate is constant, and if the gauge is thinned, the tire finish after vulcanization at the buttress portion or the like may be thinned.

  Patent Document 3 (Japanese Patent Application Laid-Open No. 2009-220460) discloses a cross-sectional shape of a die slit by extruding a thermoplastic elastomer composition in which a thermoplastic resin is a sea component and rubber is an island component from an extrusion die into a sheet shape. In addition to having a thick extruded portion between the center portion of the slit and both ends of the slit, the ratio (%) of the thickness increase Δt to the thickness change portion length Δl in the slit length direction is 0.01 to 10%. A method for producing an inner liner material that is extruded using the above-described extrusion die is disclosed. Such a configuration is intended to have a large air leakage prevention effect and is difficult to peel off.

  However, it is difficult to change the dimensions of the extrusion die, and the tire size to be manufactured is limited. Even if several types of extrusion dies are prepared, it takes time to change the size when changing the size and the productivity is lowered.

  Patent Document 4 (Japanese Patent Laid-Open No. 2000-254980) discloses that a rubber member is formed with a contour shape close to a desired finished cross-sectional shape by sequentially winding a ribbon-like unvulcanized rubber strip on a cylindrical drum. Disclosure.

  Conventionally, inner liners used in pneumatic tires are generally continuously extruded from rubber extruders with a predetermined finished cross-sectional shape, and the finished cross-sectional shape is determined by a base provided at the head of the rubber extruder. Has been. In the conventional method of extruding with a finished cross-sectional shape, since the cross-sectional size of the rubber member is large, a large rubber extruder is required, and as a result, the production line cannot be reduced in size. In addition, many types of bases must be prepared according to the type of tire, etc., and every time the type of tire to be manufactured is changed, the base must be replaced or adjusted, etc. This is to solve the above problems.

  However, when the tire member is formed of a ribbon-like rubber strip, there is a problem in processability due to the adhesiveness between the rubber compositions, and the shape of the rubber member formed of the rubber strip loses its shape during storage. There was a problem that caused.

  Patent Document 5 (Japanese Patent Laid-Open No. 2010-058437) discloses a method in which a molten resin is extruded from a die into a sheet shape, and the extruded resin sheet is sandwiched between a mold roller and a nip roller having a convex shape formed on at least one side. Is disclosed, and a sheet is formed by forming a cut groove and solidifying by cooling.

  Patent Document 6 (Japanese Patent Laid-Open No. 9-19987) discloses a laminate for improving the adhesion between the inner liner layer and the rubber layer. By providing an adhesive layer on both sides of the inner liner layer, the adhesive layers come into contact with each other at the overlapping portion of the inner liner layer, and are firmly bonded by heating, thereby improving air pressure retention. . However, the adhesive layer for overlapping the inner liner layer comes into contact with the bladder in a heated state in the vulcanization process, and there is a problem of sticking to the bladder.

JP-A-9-165469 International Publication No. 2008/029781 JP 2009-220460 A JP 2000-254980 A JP 2010-058437 A JP-A-9-19987

  The present invention provides a strip used for an inner liner and a method for producing a pneumatic tire using the same. When a ribbon-shaped strip with a flat rectangular cross-sectional shape is stacked to form a wider sheet-shaped inner liner, the thickness of the overlapping portion at both ends of the strip becomes thick and irregularities are formed on the surface of the finished sheet Is done. The first object of the present invention is to make the thickness of the inner liner formed by forming the ears on the ribbon-shaped strip uniform.

  The present invention also uses a thermoplastic elastomer and a mixture of at least one of natural rubber, isoprene rubber and butyl rubber as a polymer component, and vulcanizes it with sulfur to reduce the inner liner weight and reduce rolling resistance. Furthermore, the inner liner is prevented from being broken or deformed by the heat and pressure of the bladder during the vulcanization process, and the generation of scratches on the surface and residual air inside. Furthermore, the adhesiveness between the inner liner and the carcass ply is improved, and crack growth is reduced with repeated bending deformation during tire running.

  The present invention relates to a strip of a polymer composition for forming an inner liner for a tire having a shape close to a finished cross-sectional shape by being spirally wound on a cylindrical drum, the strip comprising styrene-isobutylene-styrene 100% by mass of a polymer component containing 5% by mass to 40% by mass of a triblock copolymer and 60% by mass to 95% by mass of at least one rubber component selected from the group consisting of natural rubber, isoprene rubber and butyl rubber The strip is made of a polymer sheet of a polymer composition containing 0.1 to 5 parts by mass of sulfur, and the strip has a strip body and ears disposed on both sides thereof, and the thickness of the strip body The thickness (T1) is 0.05 mm to 1.0 mm, and the thickness (T2) of the ear is the thickness of the strip body. Thinner than (T1), the ear portion of the width (W2) relates strip for an inner liner formed is 0.5 mm to 5.0 mm.

  The polymer sheet further comprises 1 part by mass or more and 5 parts by mass or less of stearic acid, 0.1 part by mass or more and 8 parts by mass or less of zinc oxide, and 0.1 part by mass or more and 5 parts by mass of anti-aging agent with respect to 100 parts by mass of the polymer component. It is preferable to contain 0.1 part by mass or more and 5 parts by mass or less of a vulcanization accelerator.

  Further, the styrene-isobutylene-styrene triblock copolymer preferably has a weight average molecular weight of 50,000 to 400,000 and a styrene unit content of 10% by mass to 30% by mass.

  Another embodiment of the present invention is a strip of a polymer composition for forming an inner liner for a tire having a shape close to a finished cross-sectional shape by being spirally wound on a cylindrical drum, the strip comprising: 5 mass% to 40 mass% of styrene-isobutylene-styrene triblock copolymer and 60 mass% to 95 mass% of at least one rubber component selected from the group consisting of natural rubber, isoprene rubber and butyl rubber Consists of a laminate of a first layer of a polymer sheet of a polymer composition containing 0.1 to 5 parts by mass of sulfur and 100 parts by mass of a polymer component, and a second layer made of a thermoplastic elastomer composition. The strip has a strip body and ears disposed on both sides thereof, and the thickness of the strip body (T1 Is 0.05 mm to 1.0 mm, the thickness (T2) of the ear is thinner than the thickness (T1) of the strip body, and the width (W2) of the ear is 0.5 mm to 5.0 mm. The present invention relates to a strip for forming an inner liner.

  The second layer includes at least one selected from the group consisting of a styrene-isoprene-styrene triblock copolymer, a styrene-isobutylene diblock copolymer, and an epoxidized styrene-butylene diblock copolymer, A thermoplastic elastomer and at least one rubber component selected from the group consisting of natural rubber, isoprene rubber, and butyl rubber are included, and the rubber component is 20% by mass or more based on the total of the thermoplastic elastomer and the rubber component It is preferable to contain 90 mass% or less.

  In an embodiment of the present invention, the width (W0) of the strip is preferably 5 mm to 40 mm, and the thickness (T2) of the ear portion of the strip is preferably 0.02 mm to 0.5 mm.

  According to the present invention, the strip is spirally wound on a cylindrical drum so that an inner liner having a shape close to the finished cross-sectional shape is formed on the inner surface of the raw tire, and the raw tire is vulcanized. The present invention relates to a method for manufacturing a pneumatic tire.

  In the method for producing a pneumatic tire according to the present invention, the strip is formed by (a) an extrusion process of extruding a thermoplastic elastomer composition to form a sheet having a horizontally long rectangular cross-section by an extrusion apparatus including an extruder body and an extrusion head. And (b) passing the sheet through a pair of mold rollers, transferring the shape of the mold roller to the sheet and providing a strip end portion with an ear portion, and (c) forming the strip into the mold roller. And a peeling step for peeling from the substrate.

It is a schematic sectional drawing of the right half of the pneumatic tire of this invention. 1 is a schematic view of an apparatus for producing the strip of the present invention. It is sectional drawing which shows the space | interval of a type | mold roll and a nip roll in the manufacturing apparatus shown in FIG. (A)-(d) is a schematic sectional drawing of the strip of this invention. It is the schematic which shows the method of manufacturing an inner liner using the strip of this invention. It is a schematic sectional drawing which shows the arrangement | positioning state of an inner liner. It is the schematic which shows the method of manufacturing an inner liner using the conventional strip.

<Tire structure>
The present invention relates to a strip for an inner liner disposed inside a pneumatic tire, a method for manufacturing the strip, and a method for manufacturing a pneumatic tire including the strip. The inner liner is manufactured by spirally winding a ribbon-like strip having ears at both ends on a cylindrical drum. Here, the ribbon-like strip is extruded in a state close to the finished cross-sectional shape.

  The strip is formed of a one-layer or two-layer laminate. In the strip, the polymer sheet in the case of a single layer or the first layer in the case of a laminate is mainly composed of a styrene-isobutylene-styrene triblock copolymer (SIBS). And the 2nd layer in the case of a laminated body is comprised with the composition containing a thermoplastic elastomer, for example, a styrene-isoprene-styrene triblock copolymer (SIS) or a styrene-isobutylene block copolymer (SIB). Here, the thickness (T1) of the strip body is 0.05 mm to 1.0 mm, and the thickness (T2) of the ear portion is thinner than the thickness (T1) of the strip body.

  An embodiment of a pneumatic tire manufactured by the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view of the right half of a pneumatic tire. In the figure, a pneumatic tire 1 has a tread portion 2 and sidewall portions 3 and bead portions 4 so as to form a toroid shape from both ends of the tread portion. Further, a bead core 5 is embedded in the bead portion 4. In addition, a carcass ply 6 provided from one bead portion 4 to the other bead portion, with both ends wound around the bead core 5 and locked, and at least two sheets on the outer side of the crown portion of the carcass ply 6 A belt layer 7 made of a ply is arranged.

  The belt layer 7 usually intersects two plies made of steel cords or cords such as aramid fibers with respect to the tire circumferential direction so that the cords are usually at an angle of 5 to 30 °. Are arranged as follows. Note that a topping rubber layer can be provided on both outer sides of the belt layer to reduce peeling at both ends of the belt layer. In the carcass ply, organic fiber cords such as polyester, nylon, and aramid are arranged at approximately 90 ° in the tire circumferential direction. In the region surrounded by the carcass ply and the folded portion, the bead core 5 extends from the upper end to the sidewall direction. An extending bead apex 8 is arranged. Further, an inner liner 9 extending from one bead portion 4 to the other bead portion 4 is disposed inside the carcass ply 6 in the tire radial direction.

<Strip shape>
4A to 4D show cross-sectional views of the embodiment of the strip 10. The strip 10 has a thickness (T1) of the strip body 10A of 0.05 mm to 1.0 mm. When the thickness (T1) of the strip body 10A is less than 0.05 mm, extrusion molding becomes difficult, and the number of times is unnecessarily increased to form an inner liner having a predetermined thickness, and when the thickness exceeds 1.0 mm. It will not be possible to reduce the bending durability and weight of the inner liner. The thickness (T1) of the strip is preferably in the range of 0.1 mm to 0.6 mm. And the width | variety (W0) of the whole strip is adjusted in the range of 5 mm-40 mm, Preferably it is the range of 10-40 mm.

  The thickness (T2) of the ear portion 10B formed on both sides of the strip body 10A is formed to be thinner than the thickness (T1) of the strip body, and is preferably in the range of 0.02 mm to 0.5 mm. The range is 0.02 mm to 0.3 mm. If the ear thickness (T2) is less than 0.02 mm, the dimensional accuracy of the extrusion may decrease, whereas if the ear thickness (T2) is greater than 0.5 mm, the adjacent strip may The unevenness of the surface to be formed may become large. Here, the thickness (T2) of the ear portion is defined as an average thickness in the width direction when changing in the width direction of the strip.

  And the width (W2) of the ear | edge part 10B has the preferable range of 0.5 mm-5.0 mm in order to smooth the unevenness | corrugation formed on the surface wound on a drum, and the value of (W2 * 2) is , (W0 × 0.5) or less. When the width (W2) of the ear portion is out of the range of 0.5 mm to 5.0 mm, the thickness dimension of the cross section of the inner liner formed by joining the strips may be nonuniform. Here, the strip ears 10B can be symmetric or asymmetric at the left and right ends of the strip body.

  In FIG. 4A, the cross section of the strip has a substantially parallelogram. The left ear portion 10B has a shape in which the thickness gradually decreases in the downward direction, and the right ear portion 10B has a shape in which the thickness gradually decreases in the upward direction.

  In FIG. 4B, an ear portion 10B having a thickness gradually reduced toward the lower surface of the strip is formed in the left end direction and the right end direction of the strip body 10A. In this strip shape, when the strips are joined on the drum, a step is formed at the end where the adjacent strips are joined to each other, but an inner liner sheet with a reduced surface irregularity shape can be obtained. .

  In FIG. 4C, the left ear is formed with a certain thickness on the lower surface, and the right ear is formed with a certain thickness on the upper surface. By adopting such a shape, when the strip is rewound on the drum to form the inner liner, the adjacent strip ears relieve the step formed at the end of the strip and can be joined with small unevenness. The strip body 10A has a rectangular shape with a horizontally long flat shape whose thickness (T1) is constant in the length direction.

  In FIG. 4 (d), a step is formed at the left end and the right end of the strip body 10A to form an ear portion 10b having a reduced thickness, and the strip has a constant thickness on the lower surface. In this case, when the strips are joined on the drum, a step is formed at the end of the adjacent strip, but the unevenness can be reduced.

  By forming the strip of the present invention into the above-mentioned shape, when the strip is rewound on the drum to form the inner liner, the adjacent strip ears are properly fitted to form a joint with no thickness unevenness. it can. Note that the thickness (T1) of the strip body 10A has a rectangular shape that is horizontally long and flat in the length direction. In addition, the ear | edge part of this invention can employ | adopt not only these shapes but various modifications.

<Strip: Polymer sheet>
The strip of the present invention is a styrene-isobutylene-styrene triblock copolymer (hereinafter also referred to as SIBS) of at least one selected from the group consisting of 5% by mass to 40% by mass and natural rubber, isoprene rubber and butyl rubber. This is a polymer composition containing 0.1 to 5 parts by mass of sulfur with respect to 100 parts by mass of the polymer component containing 60 to 95% by mass of the rubber component.

  The polymer composition includes SIBS, a rubber component, and sulfur. When a rubber component and sulfur are added to SIBS and heated and mixed, the rubber component and sulfur are vulcanized during the heating and mixing to form a sea-island structure in which SIBS is a matrix (sea) and the rubber component is an island.

  The polymer composition having a sea-island structure has air permeation resistance derived from a matrix phase composed of SIBS. Furthermore, the rubber component forming the island phase has adhesiveness before vulcanization with an adjacent member containing the rubber component, and also vulcanizes with the rubber component of the adjacent member during heating and mixing. Also has adhesiveness. Therefore, the polymer sheet made of the polymer composition is excellent in air permeation resistance, and at the same time has pre-vulcanization tackiness and vulcanization adhesiveness with adjacent members.

(Styrene-isobutylene-styrene triblock copolymer)
Due to the isobutylene block of SIBS, the polymer sheet containing SIBS has excellent air permeation resistance. Therefore, when a polymer sheet containing SIBS is used for the inner liner, a pneumatic tire excellent in air permeation resistance can be obtained.

  Further, SIBS has excellent durability because its molecular structure other than aromatic is completely saturated, thereby preventing deterioration and hardening. Therefore, when a polymer sheet containing SIBS is used for the inner liner, a pneumatic tire having excellent durability can be obtained.

  When a pneumatic tire is manufactured by applying a polymer sheet containing SIBS to the inner liner, conventional air permeation resistance such as halogenated butyl rubber is imparted to ensure air permeation resistance by incorporating SIBS. Therefore, the amount of use can be reduced even when the high specific gravity halogenated rubber which has been used for this purpose is not used or used. As a result, the weight of the tire can be reduced, and the effect of improving fuel consumption can be obtained.

  The molecular weight of SIBS is not particularly limited, but the weight average molecular weight by GPC method is preferably 50,000 or more and 400,000 or less from the viewpoint of fluidity, molding process, rubber elasticity and the like. If the weight average molecular weight is less than 50,000, the tensile strength and the tensile elongation may be lowered, and if it exceeds 400,000, the extrusion processability may be deteriorated.

  SIBS generally contains 10% to 40% by mass of styrene units. The content of styrene units in SIBS is preferably 10% by mass or more and 30% by mass or less from the viewpoint of better air permeation resistance and durability.

  SIBS can be obtained by a general polymerization method of vinyl compounds. For example, it can be obtained by a living cationic polymerization method. Since SIBS does not have double bonds other than aromatics in the molecule, it is more stable to ultraviolet rays and has weather resistance than a polymer having double bonds in the molecule such as polybutadiene. It is good.

  The content of SIBS is 5% by mass or more and 40% by mass or less in the polymer component of the polymer composition. If the SIBS content is less than 5% by mass, the air permeation resistance of the polymer sheet may be lowered. On the other hand, when the content of SIBS exceeds 40% by mass, the vulcanization adhesive strength with the adjacent member may be insufficient. The content of SIBS is preferably 10% by mass or more and 30% by mass or less in the polymer component from the viewpoint of ensuring air permeation resistance.

(Rubber component)
The polymer composition constituting the inner liner polymer sheet contains a rubber component. The rubber component can give the polymer composition tackiness before vulcanization with an adjacent member containing the rubber component. Furthermore, the vulcanization reaction with sulfur can provide the polymer composition with vulcanization adhesion to adjacent members such as carcass and insulation. The rubber component contains at least one selected from the group consisting of natural rubber, isoprene rubber and butyl rubber, and among them, natural rubber is preferable from the viewpoint of breaking strength and adhesiveness.

  The content of the rubber component is 60% by mass or more and 95% by mass or less in the polymer component of the polymer composition. When the content of the rubber component is less than 60% by mass, the viscosity of the polymer composition is increased and the extrusion processability is deteriorated, so that there is a possibility that the polymer sheet cannot be thinned during the production of the polymer sheet. On the other hand, when the content of the rubber component exceeds 95% by mass, the air permeation resistance of the polymer sheet may be lowered. The content of the rubber component is preferably 70% by mass or more and 90% by mass or less in the polymer component from the viewpoints of tackiness before vulcanization and vulcanization adhesion.

(sulfur)
The polymer composition can use sulfur which is widely used, but it is preferable to use insoluble sulfur. Here, the insoluble sulfur is obtained by heating and quenching natural sulfur S ₈ to increase the molecular weight so as to be S _x (x = 100,000 to 300,000). By using insoluble sulfur, blooming that normally occurs when sulfur is used as a rubber vulcanizing agent can be prevented.

  The sulfur content is 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polymer component. When the sulfur content is less than 0.1 parts by mass, the vulcanization effect of the rubber component cannot be obtained. On the other hand, when the sulfur content exceeds 5 parts by mass, the hardness of the polymer composition increases, and when used for the inner liner, the durability performance of the pneumatic tire may be reduced. The sulfur content is further preferably 0.3 parts by mass or more and 3.0 parts by mass or less.

(Polymer composition additive)
The polymer composition constituting the strip can contain additives such as stearic acid, zinc oxide, anti-aging agents, vulcanization accelerators and the like. Stearic acid functions as a vulcanization aid for the rubber component. The content of stearic acid is preferably 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polymer component. If the content of stearic acid is less than 1 part by mass, the effect as a vulcanization aid cannot be obtained. On the other hand, when the content of stearic acid exceeds 5 parts by mass, the viscosity of the polymer composition is lowered, and the breaking strength may be lowered. The content of stearic acid is further preferably 1 part by mass or more and 4 parts by mass or less.

  Zinc oxide functions as a vulcanization aid for the rubber component. The content of zinc oxide is preferably 0.1 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the polymer component. When the content of zinc oxide is less than 0.1 part by mass, the effect as a vulcanization aid cannot be obtained. On the other hand, when the content of zinc oxide exceeds 8 parts by mass, the hardness of the polymer composition increases, and when the polymer sheet is used for the inner liner, the durability performance of the pneumatic tire may be lowered. The content of zinc oxide is further preferably 0.5 parts by mass or more and 6 parts by mass or less.

  The anti-aging agent has a function of preventing a series of deteriorations such as oxidative deterioration, heat deterioration, ozone deterioration, fatigue deterioration and the like called aging. Anti-aging agents are classified into primary anti-aging agents composed of amines and phenols and secondary anti-aging agents composed of sulfur compounds and phosphites. The primary anti-aging agent has the function of stopping hydrogenation to various polymer radicals to stop the chain reaction of auto-oxidation, and the secondary anti-aging agent shows a stabilizing action by changing hydroxy peroxide to a stable alcohol. is there.

  Examples of the anti-aging agent include amines, phenols, imidazoles, phosphorus and thioureas. The above antioxidants may be used alone or in combination of two or more. Of these, N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine is preferably used.

  The content of the antioxidant is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polymer component. When the content of the anti-aging agent is less than 0.1 parts by mass, the anti-aging effect cannot be obtained. On the other hand, when the content of the anti-aging agent exceeds 5 parts by mass, a blooming phenomenon occurs in the polymer composition. The content of the antioxidant is further preferably 0.3 parts by mass or more and 4 parts by mass or less.

  As the vulcanization accelerator, thiurams, thiazoles, thioureas, dithiocarbamates, guanidines and sulfenamides can be used. The above vulcanization accelerators may be used alone or in combination of two or more. Of these, dibenzothiazyl sulfide is preferably used.

  The content of the vulcanization accelerator is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polymer component. When the content of the vulcanization accelerator is less than 0.1 parts by mass, the vulcanization acceleration effect cannot be obtained. On the other hand, when the content of the vulcanization accelerator exceeds 5 parts by mass, the hardness of the polymer composition increases, and when the polymer sheet is used for the inner liner, the durability performance of the pneumatic tire may be reduced. Furthermore, the raw material cost of the polymer composition increases. The content of the vulcanization accelerator is further preferably 0.3 parts by mass or more and 4 parts by mass or less.

<Strip: Laminate>
In the present invention, a laminate of a first layer and a second layer is used for the strip. Here, the first layer may be a polymer composition that is substantially the same as the polymer sheet, and is a polymer composition mainly composed of a styrene-isobutylene-styrene triblock copolymer (SIBS).

(Second layer)
In the laminate, the second layer is composed of a thermoplastic elastomer composition containing a thermoplastic elastomer and sulfur. In the second layer, at least one rubber component selected from the group consisting of natural rubber, isoprene rubber and butyl rubber can be mixed with the thermoplastic elastomer. By adding sulfur to the thermoplastic elastomer, the adhesive strength before vulcanization and the vulcanized adhesive strength with the first layer are improved. Furthermore, the pre-vulcanization adhesive force and vulcanization adhesion force with adjacent members such as carcass and insulation are also improved.

  As the thermoplastic elastomer, styrene-isoprene-styrene triblock copolymer, styrene-isobutylene diblock copolymer, styrene-butadiene-styrene triblock copolymer, styrene-isoprene / butadiene-styrene triblock copolymer, Styrene-ethylene / butene-styrene triblock copolymer, styrene-ethylene / propylene / styrene triblock copolymer, styrene / ethylene / ethylene / propylene / styrene triblock copolymer, styrene / butadiene / butylene / styrene triblock copolymer At least one selected from the group consisting of copolymers can be used. These thermoplastic elastomers may be epoxy-modified thermoplastic elastomers having an epoxy group.

  In particular, it is preferable to use a styrene-isoprene-styrene triblock copolymer, a styrene-isobutylene diblock copolymer, or an epoxidized styrene-butadiene-styrene triblock copolymer.

  Since the isoprene block of the styrene-isoprene-styrene triblock copolymer (hereinafter also referred to as SIS) is a soft segment, the thermoplastic elastomer composition containing SIS is easily vulcanized and bonded to the rubber component. Therefore, when a thermoplastic elastomer composition containing SIS is used for a polymer laminate for an inner liner, the polymer laminate is excellent in adhesiveness with, for example, a carcass or an adjacent rubber forming an insulation. Thus, a pneumatic tire having excellent durability can be obtained.

  The molecular weight of SIS is not particularly limited, but from the viewpoint of rubber elasticity and moldability, the weight average molecular weight by GPC method is preferably 100,000 or more and 290,000 or less. If the weight average molecular weight is less than 100,000, the tensile strength may be lowered, and if it exceeds 290,000, the extrusion processability is deteriorated. The content of styrene units in the SIS is preferably 10% by mass or more and 30% by mass or less from the viewpoints of tackiness, adhesiveness, and rubber elasticity.

  Since the isobutylene block of the styrene-isobutylene diblock copolymer (hereinafter also referred to as SIB) is a soft segment, the thermoplastic elastomer composition containing SIB is easily vulcanized and bonded to the rubber component. Therefore, when a thermoplastic elastomer composition containing SIB is used for a polymer laminate for an inner liner, the inner liner is excellent in adhesion to, for example, a carcass or an adjacent rubber forming an insulation. A pneumatic tire that can be prevented and has excellent durability can be obtained.

  As SIB, it is preferable to use a linear molecular chain from the viewpoint of rubber elasticity and adhesiveness. As for the molecular weight of SIB, it is preferable that the weight average molecular weight by GPC method is 40,000 or more and 120,000 or less from a viewpoint of rubber elasticity and moldability. If the weight average molecular weight is less than 40,000, the tensile strength may be lowered, and if it exceeds 120,000, the extrusion processability may be deteriorated. The content of styrene units in the SIB is preferably 10% by mass or more and 35% by mass or less from the viewpoints of tackiness, adhesiveness, and rubber elasticity.

  In the epoxidized styrene-butadiene-styrene triblock copolymer (hereinafter, epoxidized SBS), the hard segment is a polystyrene block and the soft segment is a butadiene block, and an unsaturated double bond portion contained in the butadiene block is epoxidized. It is a thermoplastic elastomer. Since the epoxidized SBS has a soft segment, the thermoplastic elastomer composition containing the epoxidized SBS is easily vulcanized and bonded to the rubber component. Therefore, when a thermoplastic elastomer composition containing epoxidized SBS is used for a polymer laminate for an inner liner, the polymer laminate is excellent in adhesiveness with an adjacent rubber that forms, for example, carcass and insulation. Air-in can be prevented, and a pneumatic tire excellent in durability can be obtained.

  As for the molecular weight of the epoxidized SBS, it is preferable that the weight average molecular weight by GPC method is 10,000 or more and 400,000 or less from the viewpoint of rubber elasticity and moldability. If the weight average molecular weight is less than 10,000, the reinforcing effect may be reduced, and if it exceeds 400,000, the viscosity of the thermoplastic elastomer composition may increase, such being undesirable.

  The content of styrene units in the epoxidized SBS is preferably 10% by mass or more and 30% by mass or less from the viewpoints of tackiness, adhesiveness, and rubber elasticity. The epoxidized SBS preferably has a molar ratio of butadiene units to styrene units (butadiene units / styrene units) of 90/10 to 70/30. In the epoxidized SBS, the degree of polymerization of each block is preferably about 500 to 5,000 for a butadiene block and about 500 to 1,500 for a styrene block from the viewpoint of rubber elasticity and handling.

  When the second layer includes a rubber component, the rubber component is preferably 20% by mass or more and 90% by mass or less, and more preferably 30% by mass with respect to the total of the thermoplastic elastomer and the rubber component. % To 80% by mass. If it is less than 20% by mass, the second layer may be difficult to vulcanize and bond to the carcass layer, and if it exceeds 90% by mass, the second layer and the carcass layer may be too vulcanized and bonded.

  The sulfur content is 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer. If the sulfur content is less than 0.1 parts by mass, the crosslinking reaction may not occur. On the other hand, if the sulfur content exceeds 5 parts by mass, the crosslinking density of the thermoplastic elastomer composition may increase and the viscosity may increase. The sulfur content is further preferably 0.3 parts by mass or more and 3 parts by mass or less.

(Additive for thermoplastic elastomer composition)
The thermoplastic elastomer composition may contain additives such as stearic acid, zinc oxide, antioxidants, vulcanization accelerators and the like. These additives can employ the formulation of the first layer.

<Strip manufacturing equipment>
A manufacturing method for manufacturing the strip 10 will be described with reference to FIG. The strip manufacturing apparatus 11 includes an extrusion apparatus 13 for extruding a sheet 12 of a thermoplastic elastomer having a horizontally long rectangular cross section, and a pair of mold rollers 14 disposed in the vicinity of the extrusion port 16.

  The extrusion device 13 includes an extruder main body 13A having a screw shaft 15 and an extrusion head 13B that forms a thermoplastic elastomer sheet discharged from the extruder main body 13A and extrudes it from an extrusion port 16. The extruder main body 13A kneads and melts the injected thermoplastic elastomer by the screw shaft 15 driven by an electric motor having a speed reducing function.

  The extrusion head 13B is provided with a die 17 for extrusion which is attached to the tip of the extruder body 13A and constitutes the extrusion port 16. Next, the pair of mold rollers 14 has a configuration having upper and lower rolls 14 </ b> A and 14 </ b> B, and is held in a lateral direction perpendicular to the direction of extrusion from the extrusion port 16. The upper and lower mold rolls 14A and 14B are driven and controlled to be rotatable at the same speed and in synchronization with each other.

  The shape of the gap between the upper and lower mold rolls 14A and 14B approximates the cross-sectional shape of the strip 10 as shown in FIG. Here, “approximate” is substantially similar to the cross-sectional shape of the strip 10, and considering the expansion, the similarity ratio is usually in the range of 0.50 to 0.90 and the gaps K 1 and K 2 Is smaller.

  That is, one or both of the upper and lower mold rolls 14A and 14B are provided with recessed portions 14a and 14b corresponding to the strip body 10A on the peripheral surface of the right cylindrical cylindrical roll body. Accordingly, the ear portion 10B is formed by the gap portion K1 between the mold rolls 14A and 14B, and the strip body 10A is formed by the gap portion K2 formed by the recessed portions 14a and 14b.

  As described above, in the manufacturing apparatus 11, first, the horizontally long rectangular sheet 12 is formed using the extrusion apparatus 13, and the shape of the mold roll is transferred to the sheet under the condition that no heat is generated in the mold roll molding. Then, the strip 12A on which the ear portion is formed is peeled from the mold roller 14B by the free roller 18 and processed into a final shape. Therefore, the accuracy and stability of the dimensions are improved, and the manufacturing efficiency can be improved, such as the need for a knife cutting operation for adjusting the width, which is usually required in calendar molding. In addition, the variation in the thickness T2 in the ear portion 10B can be reduced, and the high-quality strip 10 can be manufactured.

  For this purpose, the opening height HA1 of the extrusion port 16 in the extrusion head 13B is 2 to 7 times the thickness T1 of the strip, and the opening width WA1 of the extrusion port 16 is 0 of the width W0 of the strip. 0.7 to 1.0 times is preferable.

When the opening height HA1 exceeds 7 times T1, and when the opening width WA1 is smaller than 0.7 times W0, the processing rate in the mold roll forming becomes excessive, and the quality and accuracy of the strip 10 are lowered. In particular, the width accuracy becomes unstable, and it is necessary to maintain the width accuracy by knife cutting. Further, when the opening height HA1 is smaller than twice T1, in order to obtain a strip 10 of 1.0 mm or less, the sheet thickness at the time of extrusion becomes thin, so that the extrusion pressure becomes high, and the dimensions are not good. It becomes stable. On the other hand, when the opening width WA1 exceeds 1 times W0, the processing rate is excessively reduced, and there is a problem that the strip 10 is cut, and the dimensional stability is also lowered.
<Strip manufacturing method>
(Production of polymer sheet or laminate)
The strip for an inner liner of the present invention can be produced by the following method. A polymer composition in which each compounding agent is charged into a twin-screw extruder and kneaded under conditions of about 150 to 280 ° C. and 50 to 300 rpm, and SIBS, a rubber component, sulfur, and various additives are dynamically cross-linked as necessary. A pellet of the product is obtained. The obtained pellets are put into a T-die extruder to obtain a sheet-like polymer sheet (or first layer) made of a polymer composition and a sheet-like second layer made of a thermoplastic elastomer composition.

  In the twin screw extruder, SIBS, which is a thermoplastic elastomer, becomes a matrix phase and the rubber component becomes an island phase and is dispersed. Further, in the twin-screw extruder, the rubber component and the additive component react, and the rubber component that is an island phase undergoes a crosslinking reaction. A so-called dynamic crosslinking is formed in which the rubber component is dynamically crosslinked in a twin screw extruder. Even if the rubber component is cross-linked in a twin-screw extruder, the matrix phase of the system is composed of a thermoplastic elastomer component, so that the shear viscosity of the entire system is low and extrusion is possible.

  The pellets of the dynamically crosslinked polymer composition obtained by the twin-screw extruder have the rubber component crosslinked, but the thermoplastic elastomer component in the matrix phase retains the plasticity, and the plasticity of the entire polymer composition It plays a role to produce. Therefore, since the polymer composition exhibits plasticity even in T-die extrusion, it can be formed into a sheet shape.

  Further, since the rubber component of the pellet of the dynamically crosslinked polymer composition is crosslinked, the pneumatic tire is used when a pneumatic tire is manufactured by applying the polymer sheet prepared using the pellet to the inner liner. Even when heated, it is possible to prevent the polymer composition of the inner liner from entering the carcass layer.

  When the strip is formed of a laminate, the first layer and the second layer are bonded together. Here, a polymer sheet can be used for the first layer. Alternatively, the pellets of the polymer composition and the thermoplastic elastomer composition can be formed by lamination extrusion such as laminate extrusion or coextrusion to form a laminate, thereby obtaining a ribbon-like sheet. Thereafter, a strip in which the ears of a predetermined shape are formed at both ends in the width direction of the sheet is manufactured.

<Molding of inner liner>
As shown in FIG. 5A, the strips 10 are sequentially wound spirally on the cylindrical drum D, and adjacent strips 10 form an inner liner while forming overlapping portions within a range of 3 mm to 38 mm. Here, when the strip 10 is wound, a step is formed between adjacent strips as shown in the enlarged view of FIG. 5B, but the uneven step d is relaxed by the ear. Become. On the other hand, as shown in FIG. 7, the uneven step d0 in the case of using a conventional strip having a rectangular cross section without an ear is about twice as large as the unevenness in the case of a strip having an ear. Yes.

  Thus, when the strip having the ear portion is used, it is easy to approximate the finished cross-sectional shape required for the inner liner. Moreover, a smooth contour shape can be obtained, and the occurrence of surface flaws after vulcanization can be prevented. On the other hand, the inner liner can be formed with the number of windings approximately the same as that of the conventional strip having the same thickness, and a reduction in production efficiency and generation of remaining air can be suppressed.

<Pneumatic tire manufacturing method>
A general manufacturing method can be used for the pneumatic tire of the present invention. A strip is produced using the laminate, and an inner liner is produced by the method described above. As described above, it can be produced by vulcanization molding of a green tire formed with an inner liner. When the laminate is disposed on the raw tire, the second layer of the laminate is disposed outward in the tire radial direction so as to be adjacent to the carcass ply. With this arrangement, the adhesive strength between the second layer and the carcass ply can be increased in the tire vulcanization process. The obtained pneumatic tire can have excellent air permeation resistance and durability since the inner liner and the rubber layer of the carcass ply are well bonded.

<Inner liner arrangement>
In the vulcanized tire of the present invention, the arrangement state of the inner liner formed by the laminate is shown in FIG. In FIG. 6, the stacked body PL is composed of a SIBS layer PL1 as a first layer and a SIS layer or SIB layer PL2 as a second layer. When the laminated body PL is applied to the inner liner of a pneumatic tire, if the second layer PL2 is installed facing outward in the tire radial direction so as to be in contact with the carcass ply C, the second layer PL2 The adhesive strength with the carcass ply C can be increased. Therefore, the obtained pneumatic tire has excellent air permeation resistance and durability because the inner liner and the rubber layer of the carcass ply C are well bonded.

<Manufacture of inner liner>
According to the formulation shown in Tables 1 and 2, various compounding agents were put into a twin screw extruder (screw diameter: φ50 mm, L / D: 30, cylinder temperature: 220 ° C.) to be pelletized. Using this extruder (screw diameter: φ80 mm, L / D: 50, die gap width: 40 mm, cylinder temperature: 220 ° C.) shown in FIGS. 2 and 3, the screw rotation speed is 80 RPM, and the extrusion speed is about 9 m / In minutes, a ribbon-like sheet was extruded. And it passed through the mold rolls 14A and 14B, and manufactured the strip 12A which formed the ear | edge part of the predetermined shape at both ends.

  When the ribbon-shaped sheet 12 is only one layer of polymer sheet, the ribbon-shaped sheet 12 is manufactured using one extruder, and in the case of a laminate, the first layer polymer sheet and the second layer thermoplastic elastomer. Are coextruded to produce a laminate. Thereafter, the strip was peeled from the mold roller via a free roller 18 to obtain a strip 12A. An enlarged cross-sectional structure of the strip 12A is shown as the strip 10 in FIG. Here, the width W0 and thickness T1 of the strip 10, the width W2 of the ear portion 10B, and the ear thickness T2 are as shown in Tables 1 and 3 to 5.

  Tables 1 and 2 show the composition of the first and second layers of the strip manufactured by the above manufacturing method. Table 1 shows the composition of the polymer sheet (first layer of the laminate). Formulations A1 to A6 are examples in which a mixture of IIR and / or natural rubber is used for SIBS as a polymer component. Formulations B1-B7 are SIBS or IIR alone or a mixture of these and NR, but are out of the scope of the present invention.

  Table 2 shows the composition of the second layer, and is an example using SIS, SIB, epoxidized SBS alone or a mixture of these with natural rubber or butyl rubber as the polymer component.

<Manufacture of tires>
The above strip is wound on the drum shown in FIG. 5 and formed into a wide sheet by forming a joint portion between adjacent strips so that adjacent strips overlap each other by 5 mm. A sheet for an inner liner was manufactured.

  Examples of pneumatic tires using one polymer sheet as a strip are shown in Examples S1 to S6 and Comparative Examples S1 to S7 in Table 1. Examples of pneumatic tires used for laminate strips are shown in Examples 1 to 23 and Comparative Examples 1 to 8 in Tables 3 to 5. A pneumatic tire having a tire size of 195 / 65R15 was prototyped by molding these strips on an inner liner on a drum. Vulcanization was performed by pressing at 170 ° C. for 20 minutes, cooling at 100 ° C. for 3 minutes without removing from the vulcanization mold, and then removing from the vulcanization mold. Tables 1 and 3 to 5 show the specifications of tires of the examples of the present invention and comparative examples and the performance test results thereof.

(Note 1) IIR: “Exon Chlorobutyl 1066” manufactured by ExxonMobil Co., Ltd.
(Note 2) NR: Natural rubber TSR20
(Note 3) SIBS: “Sibstar SIBSTAR 102T” manufactured by Kaneka Corporation (styrene-isobutylene-styrene triblock copolymer, weight average molecular weight 100,000, styrene unit content 25 mass%, Shore A hardness 25)
(Note 4) Carbon black: “Seast V” manufactured by Tokai Carbon Co., Ltd. (N660, nitrogen adsorption specific surface area: 27 m ² / g)
(Note 5) Stearic acid: “Lunac stearate S30” manufactured by Kao Corporation
(Note 6) Zinc oxide: “Zinc Hana 1” manufactured by Mitsui Mining & Smelting Co., Ltd.
(Note 7) Anti-aging agent: “NOCRACK 6C” (N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine) manufactured by Ouchi Shinsei Chemical Co., Ltd.
(Note 8) Vulcanization accelerator: “Noxeller DM” (di-2-benzothiazolyl disulfide) manufactured by Ouchi Shinsei Chemical Co., Ltd.
(Note 9) Sulfur: “Powder sulfur” manufactured by Tsurumi Chemical Co., Ltd.
(Note 10) SIS: “D1161JP” manufactured by Kraton Polymer Co., Ltd. (styrene-isoprene-styrene triblock copolymer, weight average molecular weight 150,000, styrene unit content 15 mass%)
(Note 11) SIB: SIB (styrene-isobutylene diblock copolymer, weight average molecular weight 70,000, styrene unit content 15% by mass) obtained in the above (manufacturing SIB)
(Note 12) Epoxidized SBS: “Epofriend A1020” manufactured by Daicel Chemical Industries, Ltd. (epoxy-modified styrene-butadiene-styrene copolymer, weight average molecular weight 100,000, epoxy equivalent 500)
(Note 13) Natural rubber: TSR20
(Note 14) Butyl rubber: “Exon Chlorobutyl 1066” manufactured by ExxonMobil Co., Ltd.

  In Tables 1 to 5, the evaluation methods for strips and pneumatic tires are as follows.

(A) Mooney viscosity of the first layer According to JISK-6300 “Testing method for unvulcanized rubber”, a Mooney viscosity tester “Moony Viscometer SMV-202” manufactured by Shimadzu Corporation was used for 1 minute. Under the temperature condition of 130 ° C. heated by preheating, the small rotor was rotated, and the Mooney viscosity (ML _{1 + 4} , 130 ° C.) of the polymer composition after 4 minutes was measured. A smaller Mooney viscosity indicates better workability.

(B1) Unvulcanized adhesion index with carcass layer A sheet of a carcass layer (compounding: 100 parts by mass of styrene butadiene rubber, 50 parts by mass of carbon black, 2 parts by mass of sulfur, thickness: 2.0 mm) was prepared. The polymer sheet and the carcass layer sheet were bonded and held at 100 gf for 30 seconds, and then the peeled force was measured as an adhesive force before vulcanization. According to the following calculation formula, the first layer indicated the adhesive strength before vulcanization of each formulation as an index based on the formulation B1 as the reference (100) and the second layer based on the formulation No1 (100). The larger the adhesive strength index before vulcanization, the stronger the adhesive strength before vulcanization, which is preferable.
(Adhesive strength index before vulcanization) = (Adhesive strength before vulcanization of each formulation) ÷ (Adhesive strength before vulcanization of Comparative Example 1) × 100.

(B2) Unvulcanized adhesive strength index of the first layer and the second layer The polymer sheets of the first layer and the second layer are bonded together and held for 100 seconds for 30 seconds, and then the peeled force is used as the adhesive strength before vulcanization. It was measured. From the following calculation formula, the comparative example 1 was used as a reference (100), and the adhesive strength before vulcanization of each blend was expressed as an index. The larger the adhesive strength index before vulcanization, the stronger the adhesive strength before vulcanization, which is preferable.
(Adhesive strength index before vulcanization) = (Adhesive strength before vulcanization of each formulation) ÷ (Adhesive strength before vulcanization of Comparative Example 1) × 100.

(C1) Vulcanization adhesive force with carcass layer The polymer sheet and the carcass layer sheet are bonded together and heated at 170 ° C. for 20 minutes to prepare a sample for vulcanization adhesive force measurement. The peel strength was measured by a tensile peel test to obtain a vulcanized adhesive strength. According to the following calculation formula, the first layer displayed the vulcanization adhesive strength of each formulation as an index based on Comparative Example S1 as the reference (100) and the second layer based on the formulation No1 (100). The larger the vulcanized adhesive strength index, the stronger and more preferable the vulcanized adhesive strength.
(Vulcanization adhesion index) = (Vulcanization adhesion of each formulation) ÷ (Vulcanization adhesion of Comparative Example 1) × 100.

(C2) Vulcanization adhesive strength of first layer and second layer The polymer sheets of the first layer and second layer are bonded together and heated at 170 ° C. for 20 minutes to prepare a sample for measuring vulcanization adhesive strength. The peel strength was measured by a tensile peel test to obtain a vulcanized adhesive strength. By the following formula, the vulcanization adhesive strength of each formulation was displayed as an index using Comparative Example 1 as a reference (100). The larger the vulcanized adhesive strength index, the stronger and more preferable the vulcanized adhesive strength.
(Vulcanization adhesion index) = (Vulcanization adhesion of each formulation) ÷ (Vulcanization adhesion of Comparative Example 1) × 100.

Moreover, evaluation of the pneumatic tire was implemented based on the following method.
(D) Lightweighting effect index The weight of the pneumatic tire using each formulation was displayed as an index according to the following formula, using Comparative Example 1 as a reference (100). The larger the weight reduction effect index, the lighter the tire weight, the better.
(Weight reduction effect index) = (tire weight of Comparative Example 1) ÷ (tire weight of each formulation) × 100.

(E) Rolling resistance index Using a rolling resistance tester manufactured by Kobe Steel Co., Ltd., the manufactured 195 / 65R15 size pneumatic tire was assembled into a JIS standard rim 15 × 6JJ, load 3.4 kN, air pressure 230 kPa, speed The rolling resistance was measured by running at room temperature (38 ° C.) under the condition of 80 km / hour. The rolling resistance of each formulation was displayed as an index using the following calculation formula, with Comparative Example 1 as a reference (100). The larger the rolling resistance index, the lower the rolling resistance, which is preferable.
(Rolling resistance index) = (Rolling resistance of Comparative Example 1) ÷ (Rolling resistance of each formulation) × 100.

(F) Static air pressure reduction rate The manufactured 195 / 65R15 size tire is assembled into a JIS standard rim 15 x 6 JJ, sealed with an initial air pressure of 300 Kpa, and left at room temperature for 90 days. Calculated.

(G) Uniformity Radial force variation (RFV) was measured using a tire uniformity tester in accordance with JASO-C607: 2000 “Uniformity test method for automobile tires”. Relative values with Comparative Example 1 as 100 were displayed as an index. The larger the index, the better the uniformity. The measurement conditions were 8.0 × 17 for the rim, 60 rpm for the tire rotation speed, 200 kPa for the air pressure, and 4000 kN for the longitudinal load.

(Comprehensive judgment)
Table 6 shows the criteria for comprehensive judgment.

<Examples S1-S6>
Examples S1 to S6 are comparative examples S1 to S7, which are examples of pneumatic tires using a single layer of polymer sheet for the strip. Each of Examples S1 to S6 is inferior to the unvulcanized tack index and vulcanized adhesion index of the strip as compared with Comparative Example S1, but it is clear that the performance of the pneumatic tire is excellent.

  Examples 5 to 23 and Comparative Examples 1 to 8 are examples in which the combination of the first layer and the second layer is changed with the cross-sectional shape of the strip as shown in FIG. Examples 1 to 23 include a strip having an unvulcanized tackiness index and a vulcanized adhesion index that are inferior to those of Comparative Example 1, but is excellent in overall performance of the pneumatic tire.

  The pneumatic tire of the present invention can be used as a pneumatic tire for trucks and buses, heavy machinery, etc. in addition to a pneumatic tire for passenger cars.

  DESCRIPTION OF SYMBOLS 1 Pneumatic tire, 2 tread part, 3 side wall part, 4 bead part, 5 bead core, 6 carcass ply, 7 belt layer, 8 bead apex, 9 inner liner, 10 strip, 11 strip manufacturing apparatus, 12 sheets, 13 Extrusion equipment.

Reference examples S1 to S6 and Comparative Examples S1 to S7 in Table 1 show examples of pneumatic tires using a single layer polymer sheet as a strip. Moreover, the reference examples 1-23 of Tables 3-5 and the comparative examples 1-8 show the example of the pneumatic tire used for the strip of a laminated body. A pneumatic tire having a tire size of 195 / 65R15 was prototyped by molding these strips on an inner liner on a drum. Vulcanization was performed by pressing at 170 ° C. for 20 minutes, cooling at 100 ° C. for 3 minutes without removing from the vulcanization mold, and then removing from the vulcanization mold. Tables 1 and 3 to 5 show the specifications of tires of the examples, reference examples, and comparative examples of the present invention, and the performance test results thereof.

< Reference Examples S1 to S6>
Reference examples S1 to S6 are examples of pneumatic tires in which comparative examples S1 to S7 use a single layer of a polymer sheet for the strip. Although all of Reference Examples S1 to S6 are inferior to the unvulcanized tack index and vulcanized adhesion index of the strip as compared with Comparative Example S1, it is clear that the performance of the pneumatic tire is excellent.

Claims (9)

A strip of a polymer composition for forming an inner liner for a tire having a shape close to a finished cross-sectional shape by being spirally wound on a cylindrical drum,
The strip comprises 5% by mass or more and 40% by mass or less of a styrene-isobutylene-styrene triblock copolymer, and 60% by mass or more of at least one rubber component selected from the group consisting of natural rubber, isoprene rubber and butyl rubber. It consists of a polymer sheet of a polymer composition containing 0.1 to 5 parts by mass of sulfur with respect to 100 parts by mass of the polymer component containing 95% by mass or less,
The strip has a strip body and ears disposed on both sides thereof, the thickness (T1) of the strip body is 0.05 mm to 1.0 mm, and the thickness (T2) of the ear part is the strip. A strip for forming an inner liner, which is thinner than the thickness (T1) of the main body and the width (W2) of the ear is 0.5 mm to 5.0 mm.   The polymer sheet further comprises 1 part by mass or more and 5 parts by mass or less of stearic acid, 0.1 part by mass or more and 8 parts by mass or less of zinc oxide, and 0.1 part by mass or more and 5 parts by mass of anti-aging agent with respect to 100 parts by mass of the polymer component. The strip according to claim 1, comprising not more than 0.1 part and not more than 0.1 part by weight and not more than 5 parts by weight of a vulcanization accelerator.   The strip according to claim 1, wherein the styrene-isobutylene-styrene triblock copolymer has a weight average molecular weight of 50,000 to 400,000 and a styrene unit content of 10% by mass to 30% by mass. A strip of a polymer composition for forming an inner liner for a tire having a shape close to a finished cross-sectional shape by being spirally wound on a cylindrical drum,
The strip comprises 5% by mass or more and 40% by mass or less of a styrene-isobutylene-styrene triblock copolymer, and 60% by mass or more of at least one rubber component selected from the group consisting of natural rubber, isoprene rubber and butyl rubber. The first layer of the polymer sheet of the polymer composition containing 0.1 parts by mass or more and 5 parts by mass or less of sulfur with respect to 100 parts by mass of the polymer component containing 95% by mass or less, and the second layer comprising the thermoplastic elastomer composition It consists of a laminate,
The strip has a strip body and ears disposed on both sides thereof, the thickness (T1) of the strip body is 0.05 mm to 1.0 mm, and the thickness (T2) of the ear part is the strip. A strip for forming an inner liner, which is thinner than the thickness (T1) of the main body and the width (W2) of the ear is 0.5 mm to 5.0 mm.   The second layer is a thermoplastic containing at least one selected from the group consisting of a styrene-isoprene-styrene triblock copolymer, a styrene-isobutylene diblock copolymer, and an epoxidized styrene-butylene diblock copolymer. An elastomer and at least one rubber component selected from the group consisting of natural rubber, isoprene rubber, and butyl rubber, and the rubber component is 20% by mass or more and 90% by mass with respect to the total of the thermoplastic elastomer and the rubber component. The strip of claim 4 comprising no more than%.   The strip according to claim 1 or 4, wherein a width (W0) of the strip is 5 mm to 40 mm.   The strip according to claim 1 or 4, wherein the thickness (T2) of the ear portion of the strip is 0.02 mm to 0.5 mm.   The strip according to claim 1 or 4 is spirally wound on a cylindrical drum to form an inner liner having a shape close to a finished cross-sectional shape on the inner surface of the raw tire, and the raw tire is vulcanized A method of manufacturing a pneumatic tire, characterized by: The strip is
(A) an extrusion step of extruding the thermoplastic elastomer composition to form a sheet having a horizontally long rectangular cross-sectional shape by an extrusion apparatus including an extruder body and an extrusion head;
(B) The sheet is passed through a pair of mold rollers, the shape of the mold roller is transferred to the sheet, and a strip forming step provided with an ear at the end of the strip;
(C) a peeling step of peeling the strip from the mold roller;
The manufacturing method of the pneumatic tire of Claim 8 manufactured by the process containing these.

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