WO2017209207A1 - Revêtement interne de pneumatique, pneumatique, et procédé de production de pneumatique - Google Patents

Revêtement interne de pneumatique, pneumatique, et procédé de production de pneumatique Download PDF

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Publication number
WO2017209207A1
WO2017209207A1 PCT/JP2017/020340 JP2017020340W WO2017209207A1 WO 2017209207 A1 WO2017209207 A1 WO 2017209207A1 JP 2017020340 W JP2017020340 W JP 2017020340W WO 2017209207 A1 WO2017209207 A1 WO 2017209207A1
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Prior art keywords
inner liner
tire
pneumatic tire
layer
rubber
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PCT/JP2017/020340
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English (en)
Japanese (ja)
Inventor
賢太郎 萱嶋
宏行 横倉
俊和 杉本
康弘 野中
鈴木　真
七歩才 林
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株式会社ブリヂストン
株式会社クラレ
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Publication of WO2017209207A1 publication Critical patent/WO2017209207A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/08—Building tyres
    • B29D30/20—Building tyres by the flat-tyre method, i.e. building on cylindrical drums
    • B29D30/30—Applying the layers; Guiding or stretching the layers during application
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C5/00—Inflatable pneumatic tyres or inner tubes
    • B60C5/12—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim
    • B60C5/14—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim with impervious liner or coating on the inner wall of the tyre

Definitions

  • the present invention relates to an inner liner of a pneumatic tire, a pneumatic tire, and a method for manufacturing a pneumatic tire.
  • 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 tire inner surface in order to maintain the internal pressure of the tire.
  • these rubber compositions using butyl rubber as the main raw material have low gas barrier properties, and therefore when the rubber composition is used for an inner liner, the thickness of the inner liner has to be about 1 mm.
  • the weight of the inner liner in the tire is, for example, about 5%, which is an obstacle to reducing the weight of the tire and improving the fuel efficiency of the automobile.
  • thermoplastic resin such as an ethylene-vinyl alcohol copolymer (hereinafter sometimes simply referred to as “EVOH”) has an excellent gas barrier property compared to rubber.
  • EVOH has an air permeation amount that is 1/100 or less of the butyl rubber composition for an inner liner. Therefore, even if the thickness is 100 ⁇ m or less, the internal pressure retention of the tire can be improved. Therefore, when EVOH is used as the inner liner, it can be used even with a thickness of 100 ⁇ m or less, and the weight of the tire can be reduced.
  • thermoplastic resin such as EVOH for the inner liner of the tire in order to improve the internal pressure retention of the pneumatic tire.
  • thermoplastic resin such as EVOH has poor adhesion to a rubber member used in a tire, and therefore, an epoxidized natural rubber (ENR) or the like is separately provided between the inner liner made of the thermoplastic resin and the rubber member.
  • EMR epoxidized natural rubber
  • An adhesive layer made of is provided (see Patent Document 1).
  • the present invention solves the above-mentioned problems of the prior art, and is an inner liner of a pneumatic tire having high durability at low temperatures (low temperature resistance) and high crack resistance, as well as adhesion between adjacent rubber members. It is an object of the present invention to provide an inner liner for a pneumatic tire that is high in durability and crack resistance at low temperatures. Further, the present invention provides a pneumatic tire using such an inner liner, which has high durability and crack resistance at low temperatures, and further has high adhesion between the inner liner and the adjacent rubber member. It is a further object to provide a pneumatic tire having a low temperature durability and crack resistance of the liner, and a method for producing the same.
  • the gist configuration of the present invention for solving the above-described problems is as follows.
  • An inner liner of a pneumatic tire of the present invention is an inner liner of a pneumatic tire comprising a film layer and an adhesive layer disposed on at least one surface of the film layer,
  • the film layer has a gas barrier layer and an elastic layer disposed on at least one surface of the gas barrier layer
  • the gas barrier layer includes at least a thermoplastic resin
  • the elastic layer includes at least a polyurethane-based thermoplastic elastomer
  • the adhesive layer includes at least a polystyrene-based thermoplastic elastomer
  • the polystyrene-based thermoplastic elastomer has a styrene content of more than 0% by mass and less than 40% by mass.
  • Such an inner liner of the pneumatic tire of the present invention has high adhesiveness between adjacent rubber members, and also has low temperature durability and crack resistance.
  • the adhesive layer is disposed on both surfaces of the film layer.
  • the adhesive layers at the end portions come into contact with each other, and the adhesive layer Since the adhesive force between each other is higher than the adhesive force between the film layer and the adhesive layer, it is possible to suppress peeling between the end portions of the inner liner in the tire circumferential direction.
  • the film layer is formed by alternately laminating the gas barrier layer and the elastic layer, and the elastic layer is formed on both outermost surfaces of the film layer. Located in. In this case, the crack resistance of the inner liner is further improved.
  • a rubber-like elastic layer having a thickness of 0.1 mm to 1.0 mm is laminated on at least one surface of the inner liner. In this case, it is possible to more reliably suppress the occurrence of cracks in the inner liner.
  • the pneumatic tire of the present invention is characterized by using the above inner liner.
  • Such a pneumatic tire of the present invention has high adhesiveness between the inner liner and the adjacent rubber member, and also has low temperature durability and crack resistance.
  • the inner liner includes the inner liner of the pneumatic tire described above, On the inner surface of the tire, the inner liner extends in the tire circumferential direction, and ends of the inner liner in the tire circumferential direction are arranged so as to overlap in the tire radial direction, Both ends in the tire circumferential direction of the inner liner are parallel to the tire width direction, The overlapping width of the ends of the inner liner in the tire circumferential direction is in the range of 5 mm to 20 mm. In this case, the adhesiveness between the inner liner and the adjacent rubber member is further increased, and the durability of the inner liner at low temperature and the crack resistance are further increased.
  • the inner liner includes the inner liner of the pneumatic tire described above, On the inner surface of the tire, the inner liner extends in the tire circumferential direction, and ends of the inner liner in the tire circumferential direction are arranged so as to overlap in the tire radial direction, The end of the inner liner has alternating peaks and valleys, In the end portion of the inner liner, the angle of the top of the peak and the angle of the bottom of the valley are in the range of 45 ° to 120 °, The overlapping width between the ends of the inner liner in the tire circumferential direction is in the range of 1 mm to 13 mm. Also in this case, the adhesion between the inner liner and the adjacent rubber member is higher, and the durability of the inner liner at low temperature and the crack resistance are also higher.
  • the pneumatic tire of the present invention preferably includes a rubber-like elastic layer having a thickness of 0.1 mm to 1.0 mm on the outer side in the tire radial direction of the inner liner.
  • a rubber-like elastic layer having a thickness of 0.1 mm to 1.0 mm on the outer side in the tire radial direction of the inner liner.
  • the thickness of the rubber-like elastic layer is more preferably 0.2 mm to 0.6 mm. In this case, it is possible to further improve the peel resistance between the end portions of the inner liner while further suppressing the occurrence of cracks in the inner liner.
  • the manufacturing method of the pneumatic tire of the present invention is the manufacturing method of the pneumatic tire described above, On the inner liner of the pneumatic tire, a process of laminating other tire members to form a raw tire; Vulcanizing the green tire; It is characterized by including.
  • a raw tire may be formed by laminating other tire members on the inner liner having a rubber-like elastic layer laminated thereon.
  • a pneumatic tire having high adhesion between the inner liner and the adjacent rubber member can be manufactured.
  • the inner liner of a pneumatic tire with high adhesiveness between adjacent rubber members and high durability at low temperature and crack resistance can be provided. Further, according to the present invention, it is possible to provide a pneumatic tire and a method for manufacturing the same, in which the adhesiveness between the inner liner and the adjacent rubber member is high, and the inner liner has high durability at low temperatures and high crack resistance. it can.
  • FIG. 1 is a partial cross-sectional view of an example of an inner liner of a pneumatic tire according to the present invention.
  • An inner liner 100 shown in FIG. 1 includes a film layer 10 and an adhesive layer 20 disposed on both surfaces of the film layer 10.
  • the adhesive layers 20 are disposed on both surfaces of the film layer 10.
  • the adhesive layer is formed only on one surface of the film layer. May be provided.
  • the adhesive layer 20 is disposed on both surfaces of the film layer 10 as in the inner liner 100 shown in FIG. It is preferable that At this time, a rubber-like elastic layer can be laminated on one surface of the film layer 10.
  • the inner liner extends in the tire circumferential direction, and when the tire circumferential direction ends of the inner liner are arranged so as to overlap each other in the tire radial direction, the adhesive layers at the ends are in contact with each other.
  • the adhesive layer at one end adheres to the rubber-like elastic body layer at the other end, and peeling between the end portions of the inner liner in the tire circumferential direction can be suppressed.
  • the adhesive layer of the inner liner of the present invention is not too sticky at room temperature, even if the adhesive layer is disposed on both sides of the film layer, in the green tire molding process, Adhesion of the adhesive layer is suppressed and workability can be improved.
  • the film layer 10 of the inner liner 100 shown in FIG. 1 has a gas barrier layer 11 and an elastic layer 12 disposed on both surfaces of the gas barrier layer 11, and the gas barrier layer 11 and the elastic layer 12 are alternately arranged.
  • the elastic layer 12 is disposed on both sides of the gas barrier layer 11, but the film layer of the inner liner of the pneumatic tire of the present invention is only on one side of the gas barrier layer.
  • An elastic layer may be provided.
  • the elastic layer 12 is disposed on both surfaces of the gas barrier layer 11 as in the inner liner 100 shown in FIG.
  • the film layer of the inner liner of the pneumatic tire of the present invention may further include other layers in addition to the gas barrier layer and the elastic layer.
  • the gas barrier layer includes at least a thermoplastic resin, and may include other components in addition to the thermoplastic resin, or may be composed only of the thermoplastic resin.
  • a flexible resin having a dynamic storage elastic modulus E ′ at ⁇ 20 ° C. lower than that of the thermoplastic resin is preferable.
  • thermoplastic resin used for the gas barrier layer is not particularly limited, and examples thereof include ethylene-vinyl alcohol copolymer resins, polyamide resins, polyvinylidene chloride resins, polyester resins, and the like.
  • An ethylene-vinyl alcohol copolymer resin is preferred.
  • Such an ethylene-vinyl alcohol copolymer resin has a low oxygen permeation amount and a very good gas barrier property.
  • these thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the ethylene-vinyl alcohol copolymer-based resin examples include an ethylene-vinyl alcohol copolymer, and a modified ethylene-vinyl alcohol copolymer obtained by reacting, for example, an epoxy compound with the ethylene-vinyl alcohol copolymer. Etc.
  • a modified ethylene-vinyl alcohol copolymer has a lower elastic modulus than a normal ethylene-vinyl alcohol copolymer, so it has high fracture resistance when bent and also has excellent crack resistance in a low-temperature environment. .
  • the ethylene-vinyl alcohol copolymer preferably has an ethylene content of 25 mol% to 50 mol%, more preferably 30 mol% to 48 mol%, and 35 mol% to 45 mol%. It is even more preferable. If the ethylene content is 25 mol% or more, the bending resistance, fatigue resistance and melt moldability are good, and if it is 50 mol% or less, the gas barrier properties are sufficiently high.
  • the ethylene-vinyl alcohol copolymer has a saponification degree (that is, a ratio of the number of vinyl alcohol units to the total number of vinyl alcohol units and vinyl ester units in the ethylene-vinyl alcohol copolymer) of 80 mol% or more.
  • the ethylene-vinyl alcohol copolymer has a melt flow rate (MFR) of 190 g / min and a load of 0.1 g / 10 min to 30 g / 30 g under a load of 2160 g from the viewpoint of obtaining gas barrier properties, flex resistance and fatigue resistance. It is preferably 10 minutes, more preferably 0.3 g / 10 minutes to 25 g / 10 minutes, and even more preferably 0.5 g / 10 minutes to 20 g / 10 minutes.
  • MFR melt flow rate
  • the method for producing the modified ethylene-vinyl alcohol copolymer is not particularly limited, but a method of reacting the ethylene-vinyl alcohol copolymer and an epoxy compound in a solution is preferable. 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.
  • 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 alkaline 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.
  • the epoxy compound to be reacted with the ethylene-vinyl alcohol copolymer is preferably a monovalent epoxy compound.
  • a divalent or higher-valent epoxy compound may undergo a crosslinking reaction with the ethylene-vinyl alcohol copolymer to generate gels, blisters and the like, thereby deteriorating the quality of the inner liner.
  • the monovalent epoxy compounds glycidol and epoxypropane are particularly preferred 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 is preferably reacted in an amount of 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, with respect to 100 parts by mass of the ethylene-vinyl alcohol copolymer. It is even more preferable to react part by mass to 35 parts by mass.
  • the modified ethylene-vinyl alcohol copolymer has a melt flow rate (MFR) of 190 ° C. under a load of 2160 g and a load of 0.1 g / 10 min to 30 g / 10 from the viewpoint of obtaining gas barrier properties, flex resistance and fatigue resistance. Minutes, preferably 0.3 g / 10 min to 25 g / 10 min, more preferably 0.5 g / 10 min to 20 g / 10 min.
  • MFR melt flow rate
  • the flexible resin has a dynamic storage elastic modulus E ′ at ⁇ 20 ° C. lower than that of the thermoplastic resin, preferably 6 ⁇ 10 8 Pa or less.
  • E ′ a dynamic storage elastic modulus
  • the elastic modulus of the gas barrier layer is lowered and the crack resistance and the bending resistance in a low temperature environment are improved. Can do.
  • the flexible resin preferably has a functional group that reacts with a hydroxyl group.
  • the flexible resin has a functional group that reacts with a hydroxyl group, the flexible resin is uniformly dispersed in the thermoplastic resin.
  • 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 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.
  • the flexible resin preferably has an average particle size of 5 ⁇ m or less. If the average particle diameter of the flexible resin is 5 ⁇ m or less, the bending resistance of the gas barrier layer can be sufficiently improved, and the internal pressure retention of the tire can be sufficiently improved. In addition, the average particle diameter of the flexible resin in the gas barrier layer can be observed with a transmission electron microscope (TEM), for example, by freezing the sample, cutting the sample with a microtome.
  • TEM transmission electron microscope
  • the content of the flexible resin in the gas barrier layer is preferably in the range of 10% by mass to 80% by mass, and more preferably in the range of 10% by mass to 30% by mass. If the content of the flexible resin is 10% by mass or more, the effect of improving the bending resistance is large, and if it is 80% by mass or less, the gas permeability is sufficiently low.
  • the resin composition used for the gas barrier layer is not limited to the purpose of the present invention, but includes various materials such as a thermal stabilizer, an ultraviolet absorber, an antioxidant, a colorant, and a filler in addition to the thermoplastic resin and the flexible resin.
  • the additive may be included.
  • the amount is preferably 50% by mass or less, more preferably 30% by mass or less, and more preferably 10% by mass with respect to the total amount of the resin composition. % Or less is particularly preferable.
  • the gas barrier layer preferably has an air permeability at 20 ° C. and 65% RH of 3.0 ⁇ 10 ⁇ 12 cm 3 ⁇ cm 2 ⁇ sec ⁇ cmHg or less, and 1.0 ⁇ 10 6 More preferably, it is -12 cm 3 ⁇ cm / cm 2 ⁇ sec ⁇ cm Hg or less.
  • the air permeability is measured according to JIS K 7126-1: 2006 (isobaric method). If the air permeability at 20 ° C. and 65% RH is 3.0 ⁇ 10 ⁇ 12 cm 3 ⁇ cm / cm 2 ⁇ sec ⁇ cmHg or less, even if the gas barrier layer is thin, the internal pressure retention characteristics of the tire are high. The weight of the tire can be sufficiently reduced.
  • the gas barrier layer preferably has an average thickness of 0.001 ⁇ m to 10 ⁇ m. If the average thickness of one layer of the gas barrier layer is within this range, the number of layers constituting the inner liner can be increased, and the inner liner is compared with an inner liner having the same overall thickness but a small number of layers. The gas barrier property and crack resistance can be improved.
  • the elastic layer 12 includes at least a polyurethane-based thermoplastic elastomer.
  • the elastic layer contains the polyurethane-based thermoplastic elastomer, cracks are further prevented from entering the gas barrier layer, and the crack resistance of the inner liner is further improved.
  • the elastic layer includes at least a polyurethane-based thermoplastic elastomer, but may include other components in addition to the polyurethane-based thermoplastic elastomer, or may include only the polyurethane-based thermoplastic elastomer.
  • the other components include thermoplastic elastomers (TPE) other than polyurethane thermoplastic elastomers, soft materials having a Young's modulus at 23 ° C. lower than that of the polyurethane thermoplastic elastomer, and the like.
  • the film layer 10 is formed by alternately laminating gas barrier layers 11 and elastic layers 12, and the elastic layers 12 are formed as films. It is preferably located on both outermost surfaces of the layer 10. Although not shown, it is also preferable that the gas barrier layers are located on both outermost surfaces of the film layer. In this case, the gas barrier layer 11 or the elastic layer 12 is closer to the adhesive layer 20 than the adhesive made of a conventional diene rubber, and therefore the adhesive layer 20 and the film layer 10 (that is, the outermost surface). The adhesive strength of the layer to the gas barrier layer 11 or the elastic layer 12) is large and hardly peels off.
  • the polyurethane-based thermoplastic elastomer (TPU) used for the elastic layer includes (1) polyurethane obtained by a reaction of a short-chain glycol and isocyanate as a hard segment, and (2) a reaction of a long-chain glycol and an isocyanate as a soft segment. It is a linear multi-block copolymer comprising the resulting polyurethane.
  • polyurethane is a general term for compounds having a urethane bond (—NHCOO—) obtained by a polyaddition reaction (urethanization reaction) of isocyanate (—NCO) and alcohol (—OH).
  • the elastic layer contains TPU, it is possible to improve stretchability and thermoformability by laminating the elastic layer. Also, with such an inner liner, the interlayer adhesion between the elastic layer and the gas barrier layer is improved, so the durability such as crack resistance is high, and the gas barrier property and stretchability are maintained even when the inner liner is deformed and used. can do.
  • the TPU is composed of a polymer polyol, an organic polyisocyanate, a chain extender and the like.
  • the polymer polyol is a substance having a plurality of hydroxyl groups, and is obtained by polycondensation, addition polymerization (for example, ring-opening polymerization), polyaddition or the like.
  • Examples of the polymer polyol include polyester polyol, polyether polyol, polycarbonate polyol, or a cocondensate thereof (for example, polyester-ether-polyol).
  • polyester polyol or polycarbonate polyol is preferable, and polyester polyol is particularly preferable.
  • these polymer polyols may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the polyester polyol is obtained by condensing a compound capable of forming an ester such as a dicarboxylic acid, an ester thereof, and an anhydride thereof with a low molecular polyol by a direct esterification reaction or a transesterification reaction.
  • a direct esterification reaction or a transesterification reaction Alternatively, it can be produced by ring-opening polymerization of a lactone.
  • the dicarboxylic acid that can be used to produce the polyester polyol is not particularly limited, and examples thereof include dicarboxylic acids that are generally used in the production of polyester.
  • Specific examples of the dicarboxylic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, methylsuccinic acid, 2-methylglutaric acid, trimethyladipic acid, 2- Aliphatic dicarboxylic acids having 4 to 12 carbon atoms such as methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; terephthalic acid, isophthalate Examples thereof include aromatic dicarboxylic acids such as acid, orthophthalic acid, and naphthalenedicarbox
  • dicarboxylic acids may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • aliphatic dicarboxylic acids having 6 to 12 carbon atoms are preferable, and adipic acid, azelaic acid or sebacic acid is particularly preferable.
  • These dicarboxylic acids have a carbonyl group that is more easily reacted with a hydroxyl group, and can greatly improve the interlayer adhesion with the gas barrier layer.
  • the low molecular polyol that can be used to produce the polyester polyol is not particularly limited, and examples thereof include low molecular polyols that are generally used in the production of polyester.
  • Specific examples of the low molecular polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butylene glycol, 1, 4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octane Diol, 2,7-dimethyl-1,8-octanediol, 1,9-nonanediol, 2-methyl-1,9-nonanediol, 2,8-dimethyl
  • low molecular polyols may be used alone or in a combination of two or more.
  • 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 1,9-nonanediol, 2,8- C5-C12 aliphatic diols having a methyl group in the side chain such as dimethyl-1,9-nonanediol are preferred.
  • Polyester polyols obtained using such aliphatic diols are likely to react with hydroxyl groups, and can greatly improve interlayer adhesion with the gas barrier layer.
  • a small amount of a trifunctional or higher functional low molecular polyol can be used in combination with the low molecular polyol.
  • the trifunctional or higher functional low molecular polyol include trimethylolpropane, trimethylolethane, glycerin, 1,2,6-hexanetriol, and the like.
  • polyether polyol examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (methyltetramethylene) glycol, and the like. These polyether polyols may be used individually by 1 type, and 2 or more types may be mixed and used for them. Among these, polytetramethylene glycol is preferable.
  • polycarbonate polyol examples include fats having 2 to 12 carbon atoms such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and 1,10-decanediol.
  • Preferable examples include compounds obtained by polycondensation of a group diol or a mixture thereof by the action of diphenyl carbonate or phosgene.
  • the polymer polyol preferably has a number average molecular weight of 500 or more, more preferably 600 or more, further preferably 700 or more, and preferably 8,000 or less. Is more preferably 3,000 or less, and still more preferably 3,000 or less. If the number average molecular weight of the polymer polyol is 500 or more, the resulting TPU has high elasticity and good mechanical properties such as stretchability of the inner liner and thermoformability. On the other hand, when the number average molecular weight of the polymer polyol is 8,000 or less, the compatibility with the organic polyisocyanate is high, the mixing in the polymerization process is easy, and a uniform TPU can be obtained.
  • the number average molecular weight of the polymer polyol is a number average molecular weight measured based on JIS K 1577 and calculated based on the hydroxyl value.
  • the organic polyisocyanate is not particularly limited, and a known organic polyisocyanate generally used in the production of TPU, for example, organic diisocyanate can be used.
  • organic diisocyanate examples include 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dichloro-4,4′-diphenylmethane diisocyanate, and toluic acid.
  • aromatic diisocyanates such as diisocyanate
  • aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and hydrogenated xylylene diisocyanate.
  • 4,4'-diphenylmethane diisocyanate is preferable from the viewpoint of improving the strength and flex resistance of the obtained inner liner.
  • These organic polyisocyanates may be used alone or in combination of two or more.
  • the chain extender is not particularly limited, and a known chain extender generally used in the production of TPU can be used, and the molecular weight is 300 having two or more active hydrogen atoms capable of reacting with an isocyanate group in the molecule.
  • the following low molecular weight compounds are preferably used.
  • the chain extender include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis ( ⁇ -hydroxyethoxy) benzene, 1,4-cyclohexanediol, and the like. .
  • 1,4-butanediol is particularly preferable from the viewpoint of further improving the stretchability and thermoformability of the obtained inner liner.
  • These chain extenders may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • a polymer polyol, an organic polyisocyanate, and a chain extender are used, and a production method using a known urethanization reaction technique is used, and any of the prepolymer method and the one-shot method is used. Also good.
  • the ratio of the mass of the organic polyisocyanate to the total mass of the polymer polyol and the chain extender is preferably 1.02 or less. If this ratio is 1.02 or less, the long-term operational stability during molding is also good.
  • thermoplastic elastomer other than the polyurethane-based thermoplastic elastomer described above
  • examples of the thermoplastic elastomer (TPE) other than the polyurethane-based thermoplastic elastomer described above include, for example, a polystyrene-based thermoplastic elastomer, a polyolefin-based thermoplastic elastomer, a polydiene-based thermoplastic elastomer, a polyvinyl chloride-based thermoplastic elastomer, and a chlorinated product.
  • examples include polyethylene-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, fluororesin-based thermoplastic elastomers, etc. These thermoplastic elastomers may be used alone or in combination of two or more. May be used.
  • the soft material has a Young's modulus at 23 ° C. lower than that of the polyurethane-based thermoplastic elastomer, preferably 1000 MPa or less, more preferably in the range of 0.01 MPa to 500 MPa.
  • a soft material having a Young's modulus at 23 ° C. of 1000 MPa or less crack resistance is improved.
  • the soft material is preferably a compound having a functional group capable of reacting with a hydroxyl group.
  • the soft material has a functional group capable of reacting with a hydroxyl group, the soft material is uniformly dispersed in the polyurethane-based thermoplastic elastomer, and the average particle diameter of the soft material can be reduced.
  • functional groups capable of reacting with hydroxyl groups include hydroxyl groups, carboxyl groups, carboxylate groups, isocyanate groups, isothiocyanate groups, epoxy groups, amino groups, boron-containing groups, maleic acid, maleic anhydride, and alkoxysilanes.
  • the functional group can be directly reacted with the polyurethane-based thermoplastic elastomer molecule, or is not limited to those having high affinity, and can be reacted with the polyurethane-based thermoplastic elastomer molecule by pre-reacting with another agent. Examples are also included. Note that the soft material may have two or more of such functional groups.
  • the soft material is preferably a compound having a molecular weight of 10,000 or less, more preferably a compound having a molecular weight of 5,000 or less, still more preferably a compound having a molecular weight of 2,000 or less, particularly preferably.
  • the molecular weight of the soft material is preferably 750 or more.
  • the molecular weight of this soft material refers to the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).
  • the soft materials include butadiene rubber (BR), isoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), natural rubber (NR), butyl rubber (IIR), isobutylene, particularly from the viewpoint of improving crack resistance.
  • BR butadiene rubber
  • IR isoprene rubber
  • SBR styrene-butadiene copolymer rubber
  • NR natural rubber
  • IIR butyl rubber
  • isobutylene particularly from the viewpoint of improving crack resistance.
  • -P-methylstyrene chlorosulfonated polyethylene rubber (CSM), ethylene-propylene rubber (EPM, EPDM), ethylene-butene rubber, ethylene-octene rubber, chloroprene rubber (CR), acrylic rubber (ACM), nitrile rubber (NBR)
  • these hydrogenated rubbers for example, hydrogenated SBR
  • modified rubbers for example, modified natural rubber, brominated butyl rubber (Br-IIR), chlorinated butyl rubber (Cl-IIR), bromine Isobutylene-p-methylstyrene, etc.
  • liquid rubber ie, low molecular weight And a rubber or the like.
  • the soft material includes polyethylene (PE), polypropylene (PP), ethylene-butene copolymer, styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-ethylene-propylene.
  • PE polyethylene
  • PP polypropylene
  • SEBS ethylene-butene copolymer
  • SEBS styrene-ethylene-butene-styrene block copolymer
  • SEPS styrene block copolymer
  • SEPS styrene-isobutylene-chloromethylstyrene block copolymer
  • polyamide etc.
  • maleic anhydride-modified hydrogenated styrene-ethylene-butadiene-styrene block copolymer and maleic anhydride-modified ultra-low density polyethylene.
  • these soft materials may be used individually by 1 type, and may blend and use 2 or more types.
  • a known plasticizer may be used as the soft material from the viewpoint of excellent compatibility with the polyurethane-based thermoplastic elastomer and lowering the glass transition point (Tg).
  • phthalic acid plasticizers such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate (DOP), ditridecyl phthalate and trioctyl phthalate; phosphate plastics such as tricresyl phosphate and trioctyl phosphate Agents; fatty acid plasticizers such as tributyl citrate, dioctyl adipate, dioctyl sebacate, methylacetyl ricinolate; epoxy plasticizers such as epoxidized soybean oil and diisodecyl-4,5-epoxytetrahydrophthalate; N-butylbenzenesulfone
  • amide plasticizers such as amides, chlorinated paraffin
  • the content of the soft material in the elastic layer is preferably 10% by mass to 30% by mass. If the content of the soft material is 10% by mass or more, the crack resistance can be sufficiently improved, and the low-temperature hardness of the elastic layer can be sufficiently reduced. Moreover, if the content rate of a soft material is 30 mass% or less, film-forming property can fully be improved.
  • the composition used for the elastic layer includes the above-described polyurethane-based thermoplastic elastomer, thermoplastic elastomers other than polyurethane-based thermoplastic elastomers, soft materials, thermal stabilizers, ultraviolet absorbers, antioxidants, colorants, Additives such as fillers can be appropriately selected and contained within a range that does not impair the object of the present invention.
  • the content of these additives in the composition used for the elastic layer is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 10% by mass or less.
  • the elastic layer preferably has an air permeability at 20 ° C. and 65% RH of 3.0 ⁇ 10 ⁇ 8 cm 3 ⁇ cm 2 ⁇ sec ⁇ cmHg or less.
  • the air permeability is measured according to JIS K7126-1: 2006 (isobaric method).
  • the average thickness of the elastic layer is preferably 0.001 ⁇ m to 40 ⁇ m.
  • the film layer of the inner liner of the pneumatic tire of the present invention preferably has a total number of layers of 7 or more of the gas barrier layer and the elastic layer.
  • a film layer it is possible to prevent defects such as pinholes and cracks generated in a certain layer from progressing to adjacent layers, so that cracks and breaks throughout the film layer can be prevented, and high gas barrier properties In addition, durability such as crack resistance can be maintained.
  • the gas barrier layers and the elastic layers are preferably laminated alternately, and the surface of the film layer is preferably formed of the elastic layer. It is also preferred that the surface of the film layer is formed by a gas barrier layer.
  • the number of gas barrier layers is preferably 3 or more, and the number of elastic layers is preferably 4 or more.
  • the total number of gas barrier layers and elastic layers is preferably 7 or more, more preferably 11 or more, More preferably, it is 15 layers or more.
  • the upper limit of the total number of gas barrier layers and elastic layers is not particularly limited.
  • the thickness of the film layer is preferably from 0.1 ⁇ m to 1,000 ⁇ m, more preferably from 0.5 ⁇ m to 750 ⁇ m, further preferably from 1 ⁇ m to 500 ⁇ m, and even more preferably from 1 ⁇ m to 150 ⁇ m.
  • the thickness of the film layer is obtained by measuring the thickness of the cross section at an arbitrarily selected point of the film layer.
  • the adhesive layer of the inner liner of the pneumatic tire of the present invention contains at least a polystyrene-based thermoplastic elastomer, and may contain other components in addition to the polystyrene-based thermoplastic elastomer, or only from the polystyrene-based thermoplastic elastomer. It may be.
  • the adhesive layer contains at least a polystyrene-based thermoplastic elastomer, the adhesiveness with the rubber member is high, and the adhesiveness of the adhesive layer at room temperature is not too high, so that the workability is good.
  • the adhesive layer of the inner liner of the present invention is not too sticky at room temperature, even if the adhesive layer is disposed on both sides of the film layer, in the green tire molding process, Adhesion (excessive adhesion) of the adhesive layer is suppressed, and workability can be improved.
  • the above-mentioned polystyrene-based thermoplastic elastomer has an aromatic vinyl polymer block (hard segment) and a rubber block (soft segment), and the aromatic vinyl polymer portion forms a physical cross-link and becomes a crosslinking point.
  • the rubber block imparts rubber elasticity.
  • the polystyrene-based thermoplastic elastomer can be classified according to the arrangement pattern of the soft segments in the molecule.
  • SBS styrene-butadiene-styrene block copolymer
  • SIBS styrene-isoprene-styrene block copolymer
  • SIBS Styrene-isobutylene-styrene block copolymer
  • SEBS styrene-ethylene-butene-styrene block copolymer
  • SEPS styrene-ethylene-propylene-styrene block copolymer
  • SIBS styrene-isobutylene-styrene block copolymer
  • SIBS styrene-isobutylene-styrene block copolymer
  • SIBS styrene-isoprene-styrene block copolymer
  • the styrene content of the polystyrene-based thermoplastic elastomer is more than 0 mass% and less than 40 mass%, preferably 15 mass% to 35 mass%. Adhesiveness between the adhesive layer and the rubber member is improved by using a polystyrene-based thermoplastic elastomer having a styrene content exceeding 0% by mass for the adhesive layer.
  • the polystyrene-based thermoplastic elastomer having a styrene content of less than 40% by mass is softer at a lower temperature than the polystyrene-based thermoplastic elastomer having a styrene content of 40% by mass or more, the styrene content is less than 40% by mass.
  • a polystyrene-based thermoplastic elastomer having a styrene content of more than 0% by mass and less than 40% by mass has a large difference in adhesiveness at high temperature and normal temperature.
  • the adhesive layer does not stick too closely to the molding drum, and the film layer and the adjacent rubber member can be more closely adhered to each other in the vulcanization process usually performed at a high temperature. It is possible to improve both the property and the adhesion between the film layer after vulcanization and the adjacent rubber member.
  • the adhesive layer preferably has an average thickness of 0.001 ⁇ m to 40 ⁇ m. If the average thickness of one adhesive layer is 0.001 ⁇ m or more, the adhesion between adjacent rubber members can be further improved, and if it is 40 ⁇ m or less, unnecessary weight increase is avoided. Can do.
  • additives such as a metal salt, a radical crosslinking agent, a phosphoric acid compound, a carboxylic acid, and a boron compound are added. It can be appropriately selected and included within a range that does not impair the object of the present invention.
  • the raw material composition used for the gas barrier layer, elastic layer, and adhesive layer contains a metal salt
  • very good interlayer adhesion is exhibited. Due to such very excellent interlayer adhesion, the inner liner has high durability.
  • the reason why the metal salt improves interlaminar adhesion is not necessarily clear, but, for example, the bond formation reaction that occurs between the thermoplastic resin and the like in the raw material composition and the thermoplastic elastomer is caused by the presence of the metal salt. It can be accelerated.
  • Examples of such a bond formation reaction include a hydroxyl group exchange reaction occurring between a carbamate group of a polyurethane-based thermoplastic elastomer (TPU) and a hydroxyl group of an ethylene-vinyl alcohol copolymer (EVOH), and a polyurethane-based thermoplastic elastomer.
  • TPU polyurethane-based thermoplastic elastomer
  • EVOH ethylene-vinyl alcohol copolymer
  • TPU residual isocyanate group in
  • the metal salt is not particularly limited, but an alkali metal salt, an alkaline earth metal salt, or a d block metal salt described in the fourth period of the periodic table is preferable in terms of further improving interlayer adhesion. .
  • alkali metal salts or alkaline earth metal salts are more preferable, and alkali metal salts are particularly preferable.
  • alkali metal salts include aliphatic carboxylates such as lithium, sodium, and potassium, aromatic carboxylates, phosphates, and metal complexes.
  • alkali metal salt examples include sodium acetate, potassium acetate, sodium phosphate, lithium phosphate, sodium stearate, potassium stearate, sodium salt of ethylenediaminetetraacetic acid, and the like.
  • sodium acetate, potassium acetate, and sodium phosphate are particularly preferable because they are easily available.
  • alkaline earth metal salt examples include acetates or phosphates such as magnesium, calcium, barium, and beryllium. Among these, magnesium or calcium acetate or phosphate is particularly preferable because it is easily available.
  • the die adhesion amount of the molding machine of the resin or the thermoplastic elastomer which has deteriorated at the time of melt molding can be reduced.
  • the metal salt of the d block metal described in the fourth period of the periodic table include carboxylates, phosphates such as titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, An acetylacetonate salt etc. are mentioned.
  • the content of the metal salt in the raw material composition is preferably 1 mass ppm or more, more preferably 5 mass ppm or more, still more preferably 10 mass ppm or more, and even more preferably 20 mass ppm or more, in terms of metal element. 50 mass ppm or more is particularly preferable.
  • the content of the metal salt in the raw material composition is preferably 10,000 mass ppm or less, more preferably 5,000 mass ppm or less, further preferably 1,000 mass ppm or less, and 500 mass in terms of metal element. ppm or less is even more preferable, and 300 mass ppm or less is particularly preferable. If the content of the metal salt in the raw material composition is 1 mass ppm to 10,000 mass ppm in terms of metal element, the adhesion with other adjacent layers is further enhanced, so that the gas barrier property and the bending resistance are improved. Further improvement can be achieved.
  • the raw material composition contains a radical crosslinking agent
  • the crosslinking effect at the time of irradiation with active energy rays is promoted, and the interlayer adhesion is further improved, Gas barrier properties are further enhanced.
  • radical crosslinking agent examples include poly (meth) acrylates of polyhydric alcohols such as trimethylolpropane trimethacrylate, diethylene glycol diacrylate, neophenylene glycol diacrylate, triallyl isocyanurate, triallyl cyanurate, and the like. it can. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the content of the radical crosslinking agent in the raw material composition is preferably in the range of 0.01% by mass to 10% by mass, more preferably in the range of 0.05% by mass to 9% by mass, and 0.1% by mass to 8% by mass. The mass% range is particularly preferable from the viewpoint of the balance between the crosslinking effect and the economical efficiency.
  • the thermal stability at the time of the melt molding of a film layer and a contact bonding layer can be improved by containing a phosphoric acid compound in the said raw material composition.
  • the phosphoric acid compound include various acids such as phosphoric acid and phosphorous acid, and salts thereof.
  • the phosphate may be included in any form of, for example, a first phosphate, a second phosphate, and a third phosphate, and the counter cation species is not particularly limited. Alkaline earth metal ions are preferred.
  • sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate, or potassium hydrogen phosphate is preferred because of its high thermal stability improving effect.
  • 1 mass ppm or more is preferable, as for content (the phosphate radical conversion content of the phosphoric acid compound in a dry raw material composition) of the said phosphoric acid compound, 10 mass ppm or more is more preferable, and 30 mass ppm or more is further more preferable.
  • the content of the phosphoric acid compound is preferably 10,000 mass ppm or less, more preferably 1,000 mass ppm or less, and further preferably 300 mass ppm or less. If the content of the phosphoric acid compound is lower than 1 ppm by mass, coloring during melt molding may become severe. In particular, since the tendency is remarkable when the heat histories are repeated, the molded product obtained by molding the composition pellet may be poor in recoverability. On the other hand, when the content of the phosphoric acid compound exceeds 10,000 ppm by mass, there is a risk that gels and blisters are likely to occur during molding.
  • carboxylic acid in the said raw material composition, there exists an effect which controls the pH of a composition, prevents gelatinization, and improves thermal stability.
  • carboxylic acid acetic acid or lactic acid is preferable from the viewpoint of cost and the like.
  • the content of the carboxylic acid is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more, and further preferably 50 ppm by mass or more. Further, the content of the carboxylic acid is preferably 10,000 mass ppm or less, more preferably 1,000 mass ppm or less, and even more preferably 500 mass ppm or less. If the content of the carboxylic acid is lower than 1 mass ppm, coloring may occur during melt molding. Moreover, if content of carboxylic acid is 10,000 mass ppm or less, favorable interlayer adhesiveness can be obtained.
  • a boron compound in the raw material composition has an effect of improving thermal stability.
  • a boron compound when added to the raw material composition, it is considered that a chelate compound is generated between the thermoplastic resin or thermoplastic elastomer and the boron compound, and by using such a thermoplastic resin or thermoplastic elastomer, It is possible to improve thermal stability and mechanical properties as compared with ordinary thermoplastic resins and thermoplastic elastomers.
  • the boron compound include boric acids, boric acid esters, borates, hydrogenated boric acids, and the like.
  • boric acids include orthoboric acid (H 3 BO 3 ), metaboric acid, and tetraboric acid.
  • boric acid esters include triethyl borate and trimethyl borate.
  • the borate include alkali metal salts, alkaline earth metal salts, and borax of the various boric acids.
  • orthoboric acid is preferable. 1 mass ppm or more is preferable, as for content of the said boron compound (boron conversion content of the boron compound in a dry raw material composition), 10 mass ppm or more is more preferable, and 50 mass ppm or more is further more preferable. Further, the content of the boron compound is preferably 2,000 mass ppm or less, more preferably 1,000 mass ppm or less, and further preferably 500 mass ppm or less.
  • the content of the boron compound is lower than 1 ppm by mass, the effect of improving the thermal stability due to the addition of the boron compound may not be obtained.
  • the content of the boron compound exceeds 2,000 ppm by mass, gelation tends to occur and there is a risk of forming defects.
  • the method for containing the metal salt, phosphate compound, carboxylic acid, and boron compound in the raw material composition is not particularly limited.
  • the method of adding to the raw material composition is not particularly limited, but the method of adding as a dry powder, the method of adding in a paste impregnated with a solvent, the method of adding in a suspended state in a liquid, or dissolving in a solvent.
  • the method of adding as a solution is exemplified. Among these, from the viewpoint of homogeneous dispersion, a method of dissolving in a solvent and adding as a solution is preferable.
  • the solvent used in these methods is not particularly limited, but water is preferably used from the viewpoint of the solubility of the additive, cost, ease of handling, completeness of the working environment, and the like.
  • a method of containing the metal salt, phosphate compound, carboxylic acid, and boron compound a method of immersing pellets or strands of the raw material composition in a solution in which those substances are dissolved can be uniformly dispersed. This is preferable. Also in this method, water is preferably used as the solvent for the same reason as described above.
  • the raw material composition preferably contains a compound having a conjugated double bond having a molecular weight of 1,000 or less.
  • a compound having a conjugated double bond having a molecular weight of 1,000 or less By containing such a compound, since the hue of the composition is improved, a film layer having a good appearance can be obtained.
  • examples of such a compound include a conjugated diene compound having a structure in which at least two carbon-carbon double bonds and one carbon-carbon single bond are alternately connected, and three carbon-carbon double bonds.
  • Triene compound with a structure in which two carbon-carbon single bonds are alternately connected, and conjugated polyene compound with a structure in which a larger number of carbon-carbon double bonds and carbon-carbon single bonds are alternately connected Conjugated triene compounds such as 2,4,6-octatriene and the like.
  • the compound having a conjugated double bond may have a plurality of conjugated double bonds independently in one molecule. For example, a compound having three conjugated triene
  • Examples of the compound having a conjugated double bond include a carboxy group and a salt thereof, a hydroxyl group, an ester group, a carbonyl group, an ether group, an amino group, an imino group, an amide group, a cyano group, a diazo group, a nitro group, a sulfone group, It may have other various functional groups such as sulfoxide group, sulfide group, thiol group, sulfonic acid group and salt thereof, phosphoric acid group and salt thereof, phenyl group, halogen atom, double bond, triple bond and the like.
  • Such a functional group may be directly bonded to the carbon atom in the conjugated double bond, or may be bonded to a position away from the conjugated double bond.
  • the multiple bond in the functional group may be in a position capable of conjugating with the conjugated double bond.
  • 1-phenylbutadiene having a phenyl group, sorbic acid having a carboxy group, etc. Included in compounds with heavy bonds.
  • the compound examples include 2,4-diphenyl-4-methyl-1-pentene, 1,3-diphenyl-1-butene, 2,3-dimethyl-1,3-butadiene, 4-methyl- Examples include 1,3-pentadiene, 1-phenyl-1,3-butadiene, sorbic acid, myrcene and the like.
  • the conjugated double bond in the compound having a conjugated double bond is not only an aliphatic conjugated double bond such as 2,3-dimethyl-1,3-butadiene and sorbic acid, but also 2,4-diphenyl. Also included are aliphatic and aromatic conjugated double bonds such as -4-methyl-1-pentene and 1,3-diphenyl-1-butene. However, from the viewpoint of obtaining a film layer having a more excellent appearance, a compound containing a conjugated double bond between aliphatic groups is preferable, and a conjugated double bond having a polar group such as a carboxy group and a salt thereof or a hydroxyl group is included. Also preferred are compounds. Furthermore, a compound having a polar group and containing an aliphatic conjugated double bond is particularly preferable.
  • the molecular weight of the compound having a conjugated double bond is preferably 1,000 or less. When the molecular weight exceeds 1,000, the surface smoothness and extrusion stability of the film layer may be deteriorated.
  • the content of the compound having a conjugated double bond having a molecular weight of 1,000 or less is preferably 0.1 ppm by mass or more, more preferably 1 ppm by mass or more, and more preferably 3 ppm by mass or more from the viewpoint of the effect exerted. Further preferred is 5 ppm by mass or more.
  • the content of the compound is preferably 3,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, further preferably 1,500 ppm by mass or less, and 1,000 masses from the viewpoint of the effect exerted. ppm or less is particularly preferable.
  • the method for adding the compound having a conjugated double bond is not particularly limited.
  • a thermoplastic resin is polymerized.
  • saponification it is preferable to add them after saponification.
  • the compound having a conjugated double bond has an action of preventing the thermoplastic resin from being deteriorated before saponification and / or during the saponification reaction.
  • the inner liner of the pneumatic tire of the present invention preferably has a peel resistance between adjacent layers (for example, a gas barrier layer and an elastic layer, a gas barrier layer and an adhesive layer, an elastic layer and an adhesive layer, etc.) from the viewpoint of interlayer adhesion. It is 25N / 25mm or more, More preferably, it is 27N / 25mm or more, More preferably, it is 30N / 25mm or more.
  • the peel resistance is a value measured by a T-type peel test under a 23 ° C., 50% RH atmosphere and a pulling speed of 50 mm / min in accordance with JIS K 6854.
  • the method for producing the inner liner is not particularly limited as long as the film layer and the adhesive layer can be laminated and adhered satisfactorily.
  • known methods such as co-extrusion, bonding, coating, bonding, and adhesion are known.
  • the method is mentioned.
  • (1) Prepare a raw material for a gas barrier layer containing at least a thermoplastic resin, a raw material for an elastic layer containing at least a polyurethane-based thermoplastic elastomer, and a raw material for an adhesive layer containing at least a polystyrene-based thermoplastic elastomer.
  • a method for producing an inner liner having a gas barrier layer, an elastic layer and an adhesive layer by a multilayer coextrusion method (2) Prepare a gas barrier layer raw material containing at least a thermoplastic resin, an elastic layer raw material containing at least a polyurethane-based thermoplastic elastomer, and an adhesive layer raw material containing at least a polystyrene-based thermoplastic elastomer, and use these raw materials.
  • the method (1) is preferable from the viewpoint of high productivity and excellent interlayer adhesion.
  • the raw material for forming the gas barrier layer, the raw material for forming the elastic layer, and the raw material for forming the adhesive layer are heated and melted and passed through different flow paths from different extruders and pumps.
  • the inner liner is formed by being supplied to the extrusion die and laminated and adhered after being extruded in multiple layers from the extrusion die.
  • this extrusion die for example, a multi-manifold die, a field block, a static mixer or the like can be used.
  • the inner liner of the present invention it is preferable to irradiate the inner liner thus obtained with active energy rays.
  • the cross-linking reaction between the film layer and the adhesive layer is promoted, and the interlayer adhesion between the film layer and the adhesive layer can be further improved.
  • the cross-linking reaction between the gas barrier layer and the elastic layer in the film layer is also promoted, and the interlayer adhesion between the gas barrier layer and the elastic layer can be improved.
  • the adhesiveness between layers is enhanced by irradiating the inner liner with active energy rays.
  • irradiating the inner liner with active energy rays improves the shape retention of each layer of the inner liner in the vulcanization process at the time of tire manufacture, and also adheres to the bladder when the inner liner peels from the bladder Can be improved.
  • the active energy rays are those having energy quanta among electromagnetic waves or charged particle beams, specifically, ultraviolet rays, ⁇ rays, electron beams and the like.
  • an electron beam is preferable from the viewpoint of improving the interlayer adhesion.
  • various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used as an electron beam source.
  • ultraviolet rays when ultraviolet rays are used as the active energy rays, it is preferable to irradiate those containing ultraviolet rays having a wavelength of 190 nm to 380 nm.
  • the ultraviolet light source is not particularly limited, and for example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or the like is used.
  • FIG. 2 is a partial cross-sectional view of an example of the pneumatic tire of the present invention.
  • the tire shown in FIG. 2 has a pair of bead portions 1 and a pair of sidewall portions 2, and a tread portion 3 connected to both sidewall portions 2, and extends in a toroidal shape between the pair of bead portions 1.
  • a carcass 4 that reinforces each of these parts 1, 2, and 3, and a belt 5 comprising two belt layers disposed on the outer side of the crown portion of the carcass 4 in the tire radial direction.
  • An inner liner 6 is disposed on the inner surface of the tire.
  • the inner liner 6 includes the inner liner of the pneumatic tire of the present invention described above.
  • the inner liner having high adhesion between the adjacent rubber members described above is used. Therefore, peeling of the inner liner 6 is suppressed, and internal pressure retention is high.
  • the carcass 4 is composed of a single carcass ply, and extends around a bead core 7 from a main body portion that extends in a toroidal manner between a pair of bead cores 7 embedded in the bead portion 1.
  • the number of plies and the structure of the carcass 4 are not limited to this.
  • the belt 5 includes two belt layers.
  • the number of belt layers constituting the belt 5 is not limited to this.
  • materials, shapes, and arrangements used for those portions of a normal tire can be appropriately employed for the tread portion, sidewall portion, bead portion, and the like of the pneumatic tire of the present invention.
  • inert gas such as nitrogen, argon, helium other than normal or the air which adjusted oxygen partial pressure, can be used.
  • the inner liner extends in the tire circumferential direction, and ends of the inner liner in the tire circumferential direction are arranged so as to overlap in the tire radial direction, It is preferable that both ends of the inner liner in the tire circumferential direction are parallel to the tire width direction, and an overlap width between the ends of the inner liner in the tire circumferential direction is in a range of 5 mm to 20 mm. In the case where both end portions of the inner liner in the tire circumferential direction are parallel to the tire width direction, if the overlapping width is in the range of 5 mm to 20 mm, peeling of the joint portion after running the tire can be suppressed.
  • the inner liner extends in the tire circumferential direction on the tire inner surface, and ends of the inner liner in the tire circumferential direction are in the tire radial direction. It is also preferable that the end portions of the inner liner alternately have peaks and valleys. By having the end portions of the inner liner alternately have peaks and valleys (that is, the shape of the end portions is so-called “jagged”), the shear stress applied to the joint portion between the end portions is dispersed and reduced. Thus, it is possible to suppress the peeling of the bonded portion during the molding of the raw tire and the peeling of the bonded portion after running the tire.
  • FIG. 3 is a partial cross-sectional view of an example of a pneumatic tire according to the present invention, as seen from the tire inner surface, where the inner liner end portion is joined.
  • one end portion (indicated by a dotted line in FIG. 3) 100a of the inner liner located on the outer side in the tire radial direction is on the inner side in the tire radial direction (that is, the innermost surface of the tire).
  • one end 100a of the inner liner has alternating with crests T a and valley portions B a, also, the other end portion 100b of the inner liner Also have peaks T b and valleys B b alternately.
  • the cut surfaces of the end portions 100a, 100b in the tire circumferential direction of the inner liner extend as a whole along the tire width direction.
  • the inner liner tire The cut surface at the end in the circumferential direction may be inclined with respect to the tire width direction.
  • ridges T a of the one end portion 100a of the inner liner, valleys B a also, crests T b of the other end portion 100b of the inner liner, valley B b is two both the cut surface
  • the angle T ⁇ of the peak of the peak part T a , the angle T ⁇ of the peak of the peak part T b , and the angle B of the valley bottom of the valley part B a , which are formed by intersecting two planes ⁇ and the angle B ⁇ of the valley bottom of the valley portion B b are both preferably in the range of 45 ° to 120 °. If the angle of the peak of the peak and the angle of the valley bottom of the valley is 45 ° or more, the peak of the peak and the valley of the valley are not sharp.
  • the joint can be further prevented from peeling, and if it is 120 ° or less, the joint can be further prevented from peeling after running the tire.
  • the overlap width D between the end portions 100a, 100b of the inner liner in the tire circumferential direction is preferably in the range of 1 mm to 13 mm. If the overlap width D is 1 mm or more, peeling of the joint portion during molding of the raw tire can be further suppressed, and if it is 13 mm or less, peeling of the joint portion after running the tire can be further suppressed.
  • a rubber-like elastic layer having a thickness of 0.1 mm to 1.0 mm on the outer side in the tire radial direction of the inner liner, and the thickness is 0.2 mm. It is more preferable to provide a rubbery elastic layer of up to 0.6 mm.
  • a rubber-like elastic layer having a thickness of 0.1 mm to 1.0 mm By disposing a rubber-like elastic layer having a thickness of 0.1 mm to 1.0 mm on the outer side of the inner liner in the radial direction of the tire, it is possible to suppress the occurrence of cracks in the inner liner and It is possible to improve the peel resistance between each other, and when the rubber-like elastic layer has a thickness of 0.2 mm to 0.6 mm, it is possible to further suppress the occurrence of cracks in the inner liner, The peel resistance between the end portions can be further improved.
  • FIG. 4 is a partial cross-sectional view of an example of a pneumatic tire according to the present invention, as seen from the tire width direction, where the inner liner end portion is joined.
  • a rubber-like elastic layer having a thickness of 0.1 mm or more By attaching a rubber-like elastic layer having a thickness of 0.1 mm or more to the inner liner, it is possible to suppress the occurrence of cracks in the inner liner.
  • FIG. When a composite with the body layer 8 attached thereto is prepared and the composite is extended in the tire circumferential direction on the tire inner surface, the rubber-like elastic body layer 8 is formed at the overlapping portion between the ends of the composite.
  • the peeling resistance between the ends of the composite may decrease due to the moment M generated by the shear stress in the direction perpendicular to the expansion force F of the tire.
  • the thickness H of the rubber-like elastic layer 8 is set to 1.0 mm or less, the moment M generated by the shear stress in the direction perpendicular to the tire expansion force F can be reduced. The peel resistance between the end portions can be improved.
  • the inner liner extends in the tire circumferential direction, and ends of the inner liner in the tire circumferential direction overlap and contact with each other in the tire radial direction. It is preferable that a rubber-like elastic layer having a thickness of 0.1 mm to 1.0 mm is further provided on the outer side in the tire radial direction of the overlapping portion between the ends in the tire circumferential direction of the inner liner. It is more preferable to further include a rubber-like elastic layer having a thickness of 0.2 mm to 0.6 mm.
  • FIG. 5 is a partial cross-sectional view of a joining portion at the end of the inner liner, as seen from the tire width direction, as another example of the pneumatic tire of the present invention.
  • one end portion 100a of the inner liner located on the outer side in the tire radial direction is an inner liner located on the inner side in the tire radial direction (that is, the innermost surface of the tire).
  • the rubber-like elastic body layer 8 is disposed on the outer side in the tire radial direction of the overlapping portion between the end portions 100a and 100b of the inner liner, which is covered with the other end portion 100b.
  • an inner liner that is, a gas barrier layer + an elastic layer + an adhesive layer
  • a form in which one end part and the other end part are bonded via a rubber-like elastic layer is mentioned, and another form is a form in which both end parts of the inner liner are arranged in direct contact with each other.
  • the thickness H of the rubber-like elastic layer 8 is preferably in the range of 0.1 to 1 mm, and more preferably in the range of 0.2 mm to 0.6 mm.
  • the thickness H of the rubber-like elastic layer 8 is in the above range, the stress generated in the gas barrier layer constituting the inner liner is relaxed at ⁇ 20 ° C. while maintaining the followability to the carcass, Generation of cracks can be suppressed. Moreover, even if the gas barrier layer breaks and cracks occur, the progress of the breaks and cracks can be suppressed.
  • the rubber-like elastic layer is previously attached to the inner liner.
  • the attached composite is prepared, and when the composite is extended in the tire circumferential direction on the inner surface of the tire, the thickness H of the rubber-like elastic layer 8 is set at the overlapping portion between the ends of the composite.
  • the peeling resistance between the ends of the composite may be reduced.
  • the rubber-like elastic body layer is pasted on the inner liner in advance, as shown in FIG.
  • the thickness H of the rubber-like elastic body layer 8 is 0.1 mm or more, the occurrence of cracks in the inner liner can be suppressed, and if it is 1.0 mm or less, an increase in tire weight can be suppressed. .
  • the dynamic storage elastic modulus E ′ at ⁇ 20 ° C. of the rubber-like elastic layer 8 is preferably 1.0 ⁇ 10 5 to 1.0 ⁇ 10 7 Pa, and 1.0 ⁇ 10 5 to 1. 0 ⁇ 10 6 Pa is more preferable, and 1.0 ⁇ 10 5 Pa to 5.0 ⁇ 10 5 Pa is even more preferable.
  • the dynamic storage elastic modulus E ′ is 1.0 ⁇ 10 5 Pa or more, workability in kneading the rubber composition used for the rubber-like elastic body layer 8 can be sufficiently ensured, and dynamic storage is also possible.
  • the elastic modulus E ′ is 1.0 ⁇ 10 7 Pa or less, the deformation of the carcass can be relaxed, the deformation of the gas barrier layer is suppressed, and the crack resistance in a low temperature environment is improved.
  • the rubber component of the rubber composition used for the rubber-like elastic layer 8 is not particularly limited, and for example, diene rubber is used.
  • diene rubber include natural rubber (NR), isoprene rubber (IR), cis-1,4-polybutadiene rubber (BR), and syndiotactic-1,2-polybutadiene rubber (1, 2BR). And styrene-butadiene copolymer rubber (SBR). These diene rubbers may be used alone or in combination of two or more.
  • the rubber composition used for the rubber-like elastic body layer 8 is a compounding agent usually used in the rubber industry, such as a softener, a vulcanizing agent, a vulcanization accelerator, a filler, and a tackifier. Resins, anti-aging agents, anti-scorching agents, zinc white, stearic acid, and the like can be appropriately blended depending on the purpose. As these compounding agents, commercially available products can be suitably used.
  • the rubber composition used for the rubber-like elastic layer 8 can be prepared by mixing each component using, for example, a Banbury mixer or a roll.
  • the rubber composition used for the rubber-like elastic layer 8 preferably contains a softener.
  • a softener any of mineral oil softeners, vegetable oil softeners, and synthetic softeners can be used.
  • Mineral oil softeners include petroleum softeners and coal tar softeners. Examples of petroleum softeners include process oil, extender oil, asphalt, paraffins, liquid paraffin, petrolatum, and petroleum resin. Examples of the coal tar softener include coal tar and coumarone indene resin.
  • Vegetable oil softeners include fatty oil softeners such as soybean oil, palm oil, pine oil, castor oil, linseed oil, rapeseed oil, coconut oil and tall oil, and waxes such as factis, beeswax, carnauba wax and lanolin , Fatty acids such as linoleic acid, palmitic acid, stearic acid and lauric acid.
  • Synthetic softeners include synthetic resin softeners, liquid rubbers or oligomers, low molecular plasticizers, high molecular plasticizers, and reactive plasticizers. Examples of the synthetic resin softener include phenol aldehyde resin, styrene resin, and atactic polypropylene.
  • liquid rubber or oligomer examples include polybutene, liquid butadiene rubber, liquid isoprene rubber, and liquid acrylonitrile butadiene rubber.
  • low molecular plasticizer examples include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like.
  • the softening agent described above is preferably contained in an amount of 5 to 50 parts by weight, more preferably 5 to 40 parts by weight, and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the rubber component. Even more preferred.
  • the rubber-like elastic body layer 8 is 1.0 ⁇ 10 5 to 1.0 ⁇ 10 7 Pa. It can be.
  • the softening agent one selected from the softening agents described above can be used, or a plurality of softening agents can be used in combination.
  • the rubber composition used for the rubber-like elastic layer 8 contains a vulcanizing agent and a vulcanization accelerator.
  • the vulcanizing agent include sulfur.
  • sulfur is used as the vulcanizing agent, the blending amount thereof is preferably in the range of 0.1 to 10.0 parts by weight, and 1.0 to 5.0 parts by weight with respect to 100 parts by weight of the rubber component. A range is more preferred.
  • vulcanization accelerator examples include thiazoles such as M (2-mercaptobenzothiazole), DM (dibenzothiazolyl disulfide), CZ (N-cyclohexyl-2-benzothiazolylsulfenamide), Examples thereof include guanidine-based vulcanization accelerators such as DPG (diphenylguanidine).
  • thiazoles such as M (2-mercaptobenzothiazole), DM (dibenzothiazolyl disulfide), CZ (N-cyclohexyl-2-benzothiazolylsulfenamide)
  • guanidine-based vulcanization accelerators such as DPG (diphenylguanidine).
  • the blending amount of these vulcanization accelerators is preferably in the range of 0.1 to 5.0 parts by weight, more preferably in the range of 0.2 to 3.0 parts by weight with respect to 100 parts by weight of the rubber component.
  • the rubber composition used for the rubber-like elastic body layer 8 preferably contains a filler.
  • a filler an inorganic filler and / or carbon black is used.
  • the inorganic filler is not particularly limited, and preferred examples include silica, aluminum hydroxide, aluminum oxide, magnesium oxide, montmorillonite, mica, smectite, organic montmorillonite, organic mica, and organic smectite by a wet method. it can. These may be used individually by 1 type, and may be used in combination of 2 or more types.
  • carbon black any of those conventionally used as reinforcing fillers for rubber can be appropriately selected and used, for example, FEF, SRF, HAF, ISAF, SAF, GPF, etc. Is mentioned.
  • the blending amount of the filler preferably includes 5 parts by mass or more of an inorganic filler, together with carbon black, from the viewpoint of tackiness and peeling resistance with respect to 100 parts by mass of the rubber component.
  • the rubber composition used for the rubber-like elastic body layer 8 preferably contains a tackifier resin.
  • the pressure-sensitive adhesive imparting resin e.g., phenolic resins, terpene resins, modified terpene resins, hydrogenated terpene resins, rosin resins, C 5 petroleum resins, C 9 petroleum resins, xylene resins, coumarone - indene resin, Dicyclopentadiene resin, styrene resin, and the like can be mentioned.
  • phenol resin, terpene resin, modified terpene resin, hydrogenated terpene resin, and rosin resin are preferable.
  • phenolic resin examples include a resin obtained by condensing pt-butylphenol and acetylene in the presence of a catalyst, and a condensate of alkylphenol and formaldehyde.
  • terpene resin, modified terpene resin, and hydrogenated terpene resin include, for example, terpene resins such as ⁇ -pinene resin and ⁇ -pinene resin, hydrogenated terpene resins obtained by hydrogenating these, A modified terpene resin obtained by reacting terpene and phenol with a Friedel-Craft type catalyst or condensing with formaldehyde can be mentioned.
  • rosin-based resin examples include natural resin rosin and rosin derivatives modified by hydrogenation, disproportionation, dimerization, esterification, limeization, and the like. These resins may be used alone or in combination of two or more. Among these resins, phenolic resins are particularly preferable.
  • the tackifying resin is preferably used in an amount of 5 parts by mass or more, more preferably 5 to 40 parts by mass, and still more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the rubber component.
  • the method for producing a pneumatic tire of the present invention includes a step of laminating another tire member on the inner liner of the pneumatic tire to form a raw tire, Vulcanizing the green tire; It is characterized by including.
  • the adhesion between the adjacent rubber members is high, and in order to laminate another tire member on the inner liner of the pneumatic tire of the present invention described above,
  • the adhesive force between the other tire member and the inner liner is high, and peeling of the inner liner from the other tire member can be suppressed even when the green tire is molded or after running the tire.
  • the green tire molding step is not particularly limited except that another tire member is laminated on the inner liner of the pneumatic tire of the present invention described above, and is performed in the same manner as normal green tire molding. be able to.
  • a raw tire may be formed by laminating other tire members on the inner liner obtained by laminating a rubber-like elastic body layer.
  • the overlap width between the ends of the inner liner in the tire circumferential direction is in a range of 5 mm to 20 mm.
  • the overlap width is in the range of 5 mm to 20 mm, it is possible to suppress peeling of the joint after running the tire.
  • the overlapping width of the end portions in the tire circumferential direction of the inner liner is in the range of 1 mm to 13 mm. If the overlap width is 1 mm or more, peeling of the joint during molding of the raw tire can be sufficiently suppressed, and if it is 13 mm or less, peeling of the joint after running of the tire can be sufficiently suppressed.
  • the shape of the raw tire can be appropriately selected according to the shape of the pneumatic tire to be the product.
  • the adhesive layer of the inner liner of the pneumatic tire is not too sticky at normal temperature, and is usually performed at normal temperature.
  • the workability in the green tire molding process is high, and the adhesive layer is highly tacky at high temperatures.
  • the film layer and the adjacent rubber member can be more closely adhered to each other.
  • the adhesion between the vulcanized inner liner and the adjacent rubber member is also high.
  • the raw tire vulcanization step may be performed at a temperature at which the raw tire is vulcanized, and a normal raw tire vulcanization temperature may be employed.
  • the shape of the mold used for vulcanization can be appropriately selected according to the shape of the pneumatic tire that is the product.
  • EVOH Ethylene-vinyl alcohol copolymer
  • TPU thermoplastic polyurethane elastomer
  • TPS polystyrene-based thermoplastic elastomer
  • TPS layer adheresive layer
  • the inside of the adhesive layer is a TPU layer (elastic layer)
  • a TPU layer (elastic layer) and an EVOH layer (gas barrier layer) are alternately repeated in a 21-layer structure
  • Inner liner TPS layer / TPU layer / EVOH layer / TPU layer /.../ EVOH layer / TPU layer / TPS layer, TPS layer 2 layers, T U layer 10 layers, to prepare a EVOH layer 9 layers.
  • the molding conditions for coextrusion are as follows. Moreover, the film forming property in the case of coextrusion was evaluated.
  • the thickness of the TPS layer (each of the two layers) is 5 ⁇ m
  • the thickness of the EVOH layer (each of the nine layers) is 0.5 ⁇ m
  • the thickness of the TPU layer (each of the two layers) adjacent to the TPS layer is 10 ⁇ m.
  • the thickness of each of the other TPU layers was 4.2 ⁇ m.
  • An inner liner produced as described above is wound on a molding drum, a carcass is pasted thereon, another tire member is further pasted to form a raw tire, and the raw tire is vulcanized.
  • a pneumatic tire having a size of 195 / 65R15 having the structure shown in FIG. 2 was produced.
  • the carcass-covered rubber as a part of the carcass adjacent to the inner liner is made of 50 parts by mass of natural rubber, SBR [manufactured by JSR Corporation, SBR 1712, and 100 parts by mass of rubber component with 37. 5 parts by mass]
  • SBR manufactured by JSR Corporation
  • SBR 1712 100 parts by mass of rubber component with 37. 5 parts by mass
  • GPF grade carbon black (N-660) [Asahi Carbon Co., Ltd., 50S] 40 parts by mass
  • the inner liner was cut out from the obtained tire, and the peel resistance between the TPS layer (adhesive layer) and the TPU layer (elastic layer) in the inner liner was evaluated by the following method. The results are shown in Table 1.
  • Examples 2 to 4, Comparative Examples 2 to 6 An inner liner was produced in the same manner as in Example 1 except that the material shown in Table 1 was used as a raw material for the adhesive layer, and a pneumatic tire was produced using the inner liner. Moreover, the same evaluation as Example 1 was performed with respect to the obtained pneumatic tire. In Comparative Example 6, a polyurethane-based thermoplastic elastomer (TPU) was also used for the adhesive layer.
  • TPU thermoplastic elastomer
  • both outermost layers are made TPU layers (elastic layers) in the same manner as in Example 1, and further, TPU layers (elastic layers) and EVOH layers (gas barrier layers) are alternately repeated 19
  • An inner liner having a layer structure (TPU layer / EVOH layer / TPU layer /... / EVOH layer / TPU layer, TPU layer 10 layers, EVOH layer 9 layers) was produced. Further, 75 parts by mass of epoxidized natural rubber 1 (trade name: ENR25, manufactured by RRIM, epoxidation degree (epoxidation rate) 25%) and epoxidized natural rubber 2 (trade name: ENR50) are provided on both sides of the inner liner.
  • Example 1 Manufactured by RRIM, and coated with a composition mixed with 25 parts by mass of epoxidation degree (epoxidation rate: 50%) to form an adhesive layer having a thickness of 5 ⁇ m, thereby obtaining an inner liner.
  • a pneumatic tire was produced in the same manner as in Example 1 except that the obtained inner liner was used, and the same evaluation as in Example 1 was performed on the obtained pneumatic tire.
  • the inner liner of the present invention has high crack resistance, high adhesion between the adhesive layer and the TPU layer (elastic layer), and high durability at low temperatures.
  • the inner surface of the green tire was observed to confirm whether or not the overlapping portion (joint portion) of the end portion of the inner liner was peeled off. Further, in the same manner as in Example 1, the peel resistance between the adhesive layer and the TPU layer (elastic layer) was measured, and further, the presence or absence of cracks after the low-temperature drum test was evaluated. The results are shown in Table 2.
  • Example 10 Comparative Examples 10 to 15 and Examples 5 to 9
  • the inner liner is cut into so-called “jagged edges” so that the ends of the inner liner alternately have crests and troughs.
  • a pneumatic tire was produced in the same manner as in Example 1 except that the tires were arranged so as to be close to each other. Note that the overlapping width of the end portions of the inner liner, the angle of the peak of the peak, and the angle of the valley of the valley are as shown in Table 2.
  • a pneumatic tire obtained in Example 1, Examples 5 to 9 and Comparative Examples 7 to 15 is mounted on a rim of 6J-15, adjusted to an internal pressure of 100 kPa lower than the specified internal pressure, and a drum having a smooth surface Durability tests were carried out using a drum testing machine equipped with In the test, each tire is pressed against the drum and a load of 615 kgf is applied, and the tire (sidewall portion) runs (rotates) on the drum at the same predetermined speed until a failure (crack) occurs. This is the internal pressure Rongrand ram test. In addition, the test was stopped at 10,000 km, and the inner surface of the tire was observed to confirm the peeling of the overlapping portion (joint portion) of the end portion of the inner liner. The case where there was no peeling was judged as good ( ⁇ ), and although there was some peeling, the case where it was practical was acceptable ( ⁇ ), and the case where there was peeling and impractical was impossible (x). The results are shown in Table 2.
  • the cutting surface of the end of the inner liner is parallel to the tire width direction, and the overlapping width of the ends is in the range of 5 mm to 20 mm, or (2) the inner Crests and troughs are alternately formed at the end of the liner, the angle between the top of the crest and the angle at the bottom of the trough is in the range of 45 ° to 120 °, and the overlap width between the ends is 1 mm. It can be seen that by setting the thickness in the range of ⁇ 13 mm, peeling of the joint portion at the end of the inner liner after forming the green tire and after the room temperature drum test can be prevented.
  • Example 10 to 12 Except for preparing a composite in which a rubber-like elastic layer having a thickness shown in Table 3 was attached to the outer side of the inner liner in the tire radial direction, and applying a carcass on the composite, the same procedure as in Example 1 was performed. Thus, a pneumatic tire having the structure shown in FIG. 4 at the end of the inner liner was produced. Further, the peel resistance between the adhesive layer and the TPU layer (elastic layer) was measured in the same manner as in Example 1. The results are shown in Table 3.
  • the rubber-like elastic layer contains 50 parts by mass of natural rubber, SBR [manufactured by JSR Co., Ltd., SBR 1712, 37.5 parts by mass of extension oil with respect to 100 parts by mass of rubber component] and 68.75 parts by mass.
  • GPF grade carbon black N-660 [Asahi Carbon Co., Ltd., 50S] 40 parts by mass, softener [TOP, manufactured by Daihachi Chemical Industry Co., Ltd.] 55 parts by mass, anti-aging agent [Nocrac224- S, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.] 1.0 part by mass, stearic acid [produced by Asahi Denka Kogyo Co., Ltd.] 1.5 part by mass, vulcanization accelerator 1 [Accel M, Kawaguchi Chemical Industry Co., Ltd.] 0.5 parts by mass, vulcanization accelerator 2 [Accel CZ, manufactured by Kawaguchi Chemical Industry Co., Ltd.] 1 part by mass, 5 parts by mass of zinc oxide [manufactured by Hitech], 3 parts by mass of sulfur [manufactured by Karuizawa Smelter] Was used.
  • Example 13 A pneumatic tire having the structure shown in FIG. 5 at the end of the inner liner was prepared in the same manner as in Example 1 except that a rubber-like elastic layer was separately attached to the inner liner.
  • the composition of the rubber-like elastic layer is the same as in Examples 10-12.
  • the peel resistance between the adhesive layer and the TPU layer (elastic layer) was measured in the same manner as in Example 1. The results are shown in Table 3.
  • the inner liner of the pneumatic tire of the present invention can be used for a pneumatic tire.
  • the pneumatic tire of the present invention can be used as a tire for various vehicles.
  • Inner liner 10: Film layer, 11: Gas barrier layer, 12: Elastic layer, 20: Adhesive layer, 1: Bead part, 2: Side wall part, 3: Tread part, 4: Carcass, 5: Belt, 6 : Inner liner, 7: Bead core, 100a: One end part of the inner liner, 100b: Other one end part of the inner liner, T a : Peak part of one end part of the inner liner, B a : Valley part of one end part of the inner liner, T b : Peak of the other end of the inner liner, B b : Valley of the other end of the inner liner, T ⁇ : Angle of the apex of the peak of the one end of the inner liner, B ⁇ : Angle of valley bottom of valley at one end, T ⁇ : Angle of peak of peak at other one end of inner liner, B ⁇ : Angle of valley bottom of valley at other one end of inner liner D: Overlap width of tire inner circumferential end

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Tires In General (AREA)
  • Tyre Moulding (AREA)

Abstract

La présente invention aborde le problème de proposer un revêtement interne de pneumatique qui est hautement durable et qui présente une résistance élevée aux fissures à basse température. En tant que solution à ce problème, la présente invention propose un revêtement interne de pneumatique (100) qui comprend une couche de film (10) et une couche adhésive (20) qui est disposée sur au moins une surface de la couche de film (10). Le revêtement interne de pneumatique (100) est caractérisé en ce que : la couche de film (10) présente une couche barrière contre les gaz (11) et une couche élastique (12) qui est disposée sur au moins une surface de la couche barrière contre les gaz (11) ; la couche barrière contre les gaz (11) comprend au moins une résine thermoplastique ; la couche élastique (12) comprend au moins un élastomère thermoplastique de polyuréthane ; et la couche adhésive (20) comprend au moins un élastomère thermoplastique de polystyrène, la teneur en styrène de l'élastomère thermoplastique de polystyrène étant supérieure à 0 % en masse mais inférieure à 40 % en masse.
PCT/JP2017/020340 2016-05-31 2017-05-31 Revêtement interne de pneumatique, pneumatique, et procédé de production de pneumatique WO2017209207A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012236388A (ja) * 2011-05-13 2012-12-06 Sumitomo Rubber Ind Ltd 空気入りタイヤの製造方法
JP2013057016A (ja) * 2011-09-08 2013-03-28 Bridgestone Corp 粘接着剤組成物及びそれを用いた接着方法
JP2013233850A (ja) * 2012-05-08 2013-11-21 Yokohama Rubber Co Ltd:The 空気入りタイヤ
JP2013256287A (ja) * 2010-12-22 2013-12-26 Yokohama Rubber Co Ltd:The 空気入りタイヤおよび空気入りタイヤの製造方法

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KR20130056914A (ko) * 2010-10-01 2013-05-30 가부시키가이샤 브리지스톤 다층 구조체, 이것을 이용한 이너 라이너 및 공기식 타이어
JP6208927B2 (ja) * 2011-05-31 2017-10-04 株式会社ブリヂストン 多層構造体、空気入りタイヤ用インナーライナー及び空気入りタイヤ
JP6155084B2 (ja) * 2013-04-30 2017-06-28 株式会社ブリヂストン 乗用車用空気入りラジアルタイヤ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013256287A (ja) * 2010-12-22 2013-12-26 Yokohama Rubber Co Ltd:The 空気入りタイヤおよび空気入りタイヤの製造方法
JP2012236388A (ja) * 2011-05-13 2012-12-06 Sumitomo Rubber Ind Ltd 空気入りタイヤの製造方法
JP2013057016A (ja) * 2011-09-08 2013-03-28 Bridgestone Corp 粘接着剤組成物及びそれを用いた接着方法
JP2013233850A (ja) * 2012-05-08 2013-11-21 Yokohama Rubber Co Ltd:The 空気入りタイヤ

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