WO2017110012A1 - Air-impermeable film and method for producing pneumatic tire - Google Patents

Air-impermeable film and method for producing pneumatic tire Download PDF

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Publication number
WO2017110012A1
WO2017110012A1 PCT/JP2016/003628 JP2016003628W WO2017110012A1 WO 2017110012 A1 WO2017110012 A1 WO 2017110012A1 JP 2016003628 W JP2016003628 W JP 2016003628W WO 2017110012 A1 WO2017110012 A1 WO 2017110012A1
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WO
WIPO (PCT)
Prior art keywords
air
rubber
rubber composition
thermoplastic resin
resistant film
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PCT/JP2016/003628
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French (fr)
Japanese (ja)
Inventor
竜也 遠藤
敏喜 清水
哲也 坪井
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東洋ゴム工業株式会社
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Publication of WO2017110012A1 publication Critical patent/WO2017110012A1/en

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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)
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • Embodiments of the present invention relate to an air permeation-resistant film and a pneumatic tire using the same.
  • Patent Document 1 discloses air permeation resistance made of a dynamic cross-linked body of a thermoplastic resin as a continuous phase and an elastomer as a dispersed phase. Sex films have been proposed.
  • This type of air permeation-resistant film particularly a film used for an inner liner, is required to have improved durability.
  • Patent Document 2 discloses that the fatigue resistance is improved by bringing the melt viscosity of the thermoplastic resin and the rubber closer to finely disperse the rubber and increasing the amount of the rubber to reduce the elastic modulus. Therefore, it has been proposed to increase the viscosity by adding a filler or the like to rubber and to blend an appropriate amount of a low viscosity component into the thermoplastic resin. However, it is conceivable that the strength is reduced by adding a low-viscosity component to the thermoplastic resin, and cracks are caused by adding a filler to the rubber.
  • Patent Document 3 discloses that a modified ethylene vinyl alcohol copolymer is used as a resin constituting a continuous phase, and that rubber is highly dispersed as a low modulus viscoelastic material to improve durability. However, it can only be applied to specific polymers.
  • An object of the embodiment of the present invention is to obtain an air-permeable film having excellent durability.
  • the method for producing an air permeable resistant film according to the present embodiment includes a thermoplastic resin, a melt viscosity lower at 230 ° C. than that of the thermoplastic resin, and a vulcanization rate at 200 ° C. of 0.70 dN ⁇ m / min. It includes melt-kneading and dynamically crosslinking the rubber composition as described above to obtain a dynamically crosslinked product having the thermoplastic resin as a continuous phase and the rubber composition as a dispersed phase.
  • the melt viscosity of the rubber composition is a melt viscosity measured excluding the crosslinking agent.
  • the method for manufacturing a pneumatic tire according to the present embodiment uses an air-permeable-resistant film obtained by the manufacturing method as an inner liner or other air permeation suppression layer.
  • thermoplastic resin having a higher melt viscosity than the rubber composition and a rubber composition having a high vulcanization rate, an air-permeable resistant film having excellent durability can be obtained. Can do.
  • the air permeable resistant film according to the present embodiment is composed of a dynamic cross-linked body having a sea-island structure in which a thermoplastic resin is a continuous phase (matrix phase) and a rubber composition is a dispersed phase (domain phase).
  • a thermoplastic resin a high-viscosity resin having a higher melt viscosity at 230 ° C. than the rubber composition is used, and as the rubber composition, the vulcanization rate at 200 ° C. is 0.70 dN ⁇ m / min or more. It is characterized by using a faster one than before.
  • the thermoplastic resin when the melt viscosity of the thermoplastic resin is lower than that of the rubber composition, the thermoplastic resin can be a continuous phase and the rubber composition can be a dispersed phase.
  • the thermoplastic resin has a low viscosity, the durability is generally low and it does not become a highly durable air-permeable film.
  • a general-purpose rubber composition having a low vulcanization rate is used as the rubber composition, the rubber composition becomes a continuous phase at the initial stage of mixing with the thermoplastic resin, and a high shear force necessary for high dispersion is obtained. I can't.
  • the continuous phase and the dispersed phase are unlikely to reverse, and the rubber composition tends to become the continuous phase in the finished composite.
  • the rubber composition is a continuous phase, it is difficult to form as a film and the air permeability resistance is poor.
  • the viscosity of the rubber composition is increased at the initial stage of mixing, so The plastic resin can be a continuous phase. Thereby, sufficient shearing force can be given also to a rubber composition, and a rubber dispersed phase can be refined.
  • a thermoplastic resin having a higher viscosity (higher durability) than that of the conventional one can be used for the continuous phase while making the rubber dispersed phase highly dispersed, high durability can be expressed.
  • thermoplastic resin examples include nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66 copolymer, and nylon 6/66/610 copolymer.
  • Aliphatic polyamide resin such as coalescence, nylon MXD6, nylon 6T, nylon 6 / 6T copolymer; ethylene-vinyl alcohol copolymer (EVOH), ethylene-vinyl acetate copolymer (EVA), polyvinyl Polyvinyl resins such as alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC); polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), polyarylate (PAR), Polybuchi Polyester resins such as nonaphthalate (PBN); Polynitrile resins such as polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile-styrene copolymer, and nylon 6/
  • the thermoplastic resin may be at least one selected from the group consisting of aliphatic polyamide resins and polyvinyl resins, or selected from the group consisting of aliphatic polyamide resins and ethylene-vinyl alcohol copolymers. It may be at least one kind.
  • thermoplastic resin it is preferable to use an air permeable thermoplastic resin having an air permeability coefficient at 80 ° C. of 5 ⁇ 10 13 fm 2 / Pa ⁇ s or less, and imparts excellent air permeability resistance to the film. can do.
  • the air permeability coefficient of the thermoplastic resin may be 0.05 ⁇ 10 13 to 2 ⁇ 10 13 fm 2 / Pa ⁇ s.
  • the air permeability coefficient is a value measured at a test gas: air and at a test temperature: 80 ° C. according to JIS K7126-1 “Plastics—Films and Sheets—Gas Permeability Test Method—Part 1: Differential Pressure Method”. is there.
  • thermoplastic resin forming the continuous phase requires additives such as a plasticizer, a softener, a filler, a reinforcing agent, a processing aid, a stabilizer, and an antioxidant as long as the effects of the present embodiment are not impaired. You may mix
  • NR natural rubber
  • EMR epoxidized natural rubber
  • IR isoprene rubber
  • SBR styrene butadiene rubber
  • BR butadiene rubber
  • NBR nitrile rubber
  • H-NBR hydrogenated nitrile rubber
  • Diene rubber such as hydrogenated styrene butadiene rubber and its hydrogenated rubber
  • EPDM ethylene propylene rubber
  • IIR maleic acid modified ethylene butylene rubber
  • ACM acrylic rubber
  • Halogenated butyl rubber for example, brominated butyl rubber (Br-IIR), chlorinated butyl rubber (Cl-IIR)), chloroprene rubber (CR), halogen-containing rubber such as chlorosulfonated polyethylene; Fluoro rubber, police Fidogomu and the like.
  • halogenated butyl rubber such as butyl rubber (IIR) and brominated butyl rubber (Br-IIR), nitrile rubber (NBR) and hydrogenated nitrile rubber (H-NBR) are selected. It is preferable to use at least one kind.
  • the rubber composition forming the dispersed phase is blended with a crosslinking agent for dynamically crosslinking the rubber component. That is, the rubber composition contains at least a rubber component and a crosslinking agent.
  • the crosslinking agent include vulcanizing agents such as sulfur and sulfur-containing compounds, vulcanization accelerators, and phenol resins.
  • a phenol resin is used from the viewpoint of heat resistance and the like.
  • the phenol resin include resins obtained by condensation reaction of phenols and formaldehyde, and examples thereof include alkylphenol-formaldehyde resins.
  • a halogenated phenol resin such as a brominated alkylphenol-formaldehyde resin.
  • the amount of the crosslinking agent is not particularly limited as long as it can appropriately crosslink the rubber component, but may be 0.1 to 10 parts by mass, or 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component. But you can.
  • the rubber composition forming the dispersed phase may contain only the rubber component and the crosslinking agent described above, but in addition to these, the rubber composition generally includes a filler, a softening agent, an anti-aging agent, a processing aid, and the like.
  • Various additives to be blended may be blended.
  • blend a filler from the meaning which eliminates the factor of crack generation as much as possible, for example, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of rubber components, More preferably, it is 10 mass parts or less. Yes, more preferably 5 parts by mass or less.
  • the blending ratio of the thermoplastic resin and the rubber composition is not particularly limited, and is, for example, a mass ratio (thermoplasticity).
  • Resin / rubber composition which may be 90/10 to 30/70, 70/30 to 40/60, or 60/40 to 40/60.
  • thermoplastic resin having a higher melt viscosity at 230 ° C. than the rubber composition is used as the thermoplastic resin. That is, a thermoplastic resin and a rubber composition satisfying ⁇ 1 > ⁇ 2 are used, where ⁇ 1 is the melt viscosity of the thermoplastic resin at 230 ° C. and ⁇ 2 is the melt viscosity of the rubber composition at 230 ° C.
  • the ratio of these melt viscosities satisfies ⁇ 1 / ⁇ 2 ⁇ 1.20, that is, the ratio ⁇ 1 / ⁇ 2 is 1.20 or more, and more preferably the ratio ⁇ 1 / ⁇ 2 Is 1.40 or more, and may be 1.50 or more.
  • the higher the melt viscosity the better the durability of the thermoplastic resin. Therefore, the durability of the air permeation-resistant film can be improved by using a thermoplastic resin having a high melt viscosity.
  • the upper limit of the melt viscosity ratio ⁇ 1 / ⁇ 2 is not particularly limited, and may be 10.0 or less, or 7.0 or less, for example.
  • the melt viscosity ⁇ 1 of the thermoplastic resin is not particularly limited, but is preferably 70 to 400 Pa ⁇ s, more preferably 100 to 300 Pa ⁇ s, and further preferably 150 to 300 Pa ⁇ s from the viewpoint of durability. s.
  • the melt viscosity ⁇ 2 of the rubber composition is not particularly limited as long as it is smaller than the melt viscosity ⁇ 1 of the thermoplastic resin, and may be, for example, 40 to 250 Pa ⁇ s or 50 to 170 Pa ⁇ s.
  • the melt viscosity of a thermoplastic resin can be adjusted with additives, such as the kind of resin, molecular weight, and a plasticizer, for example.
  • the melt viscosity of the rubber composition can be adjusted by, for example, the type and molecular weight of the rubber component, and additives such as softeners and fillers.
  • the melt viscosity is a value measured using a capillary rheometer at a cylinder temperature of 230 ° C. and an extrusion speed of 800 s ⁇ 1 .
  • the melt viscosity ⁇ 1 of the thermoplastic resin is a value measured for the additive containing the additive when the additive is added to the thermoplastic resin as described above. However, the additive does not include a compatibilizer described later. Further, the melt viscosity ⁇ 2 of the rubber composition is a value measured excluding the crosslinking agent.
  • a rubber composition having a vulcanization rate (also referred to as a crosslinking rate) at 200 ° C. of 0.70 dN ⁇ m / min or more is used.
  • the vulcanization rate of the rubber composition is more preferably 0.80 dN ⁇ m / min or more.
  • the upper limit of the vulcanization rate of the rubber composition is not particularly limited, and may be, for example, 2.5 dN ⁇ m / min or less, or 1.7 dN ⁇ m / min or less.
  • rate can be adjusted with the kind and quantity of a crosslinking agent, for example.
  • the vulcanization speed of the rubber composition is a value obtained by measuring the viscosity at a test temperature of 200 ° C. using a rheometer and obtaining a torque increase gradient for 1 minute from the minimum viscosity ML.
  • a compatibilizing agent may be blended together with the thermoplastic resin and the rubber composition.
  • the compatibilizing agent lowers the interfacial tension between the thermoplastic resin and the rubber composition and makes them compatible.
  • a compatibilizing agent as one embodiment, an ethylene-glycidyl (meth) acrylate copolymer (that is, an ethylene-glycidyl methacrylate copolymer and / or an ethylene-glycidyl acrylate copolymer) may be used.
  • the compounding amount of the compatibilizer is not particularly limited, but may be 0.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin and the rubber composition (amount as a polymer excluding additives), It may be 0.5 to 5 parts by mass.
  • the thermoplastic resin and the rubber composition are melt-kneaded and the rubber composition is dynamically crosslinked (TPV) with a crosslinking agent.
  • TPV dynamically crosslinked
  • the timing of addition of the various additives (for example, fillers, crosslinking agents, etc.) to these resin compositions and rubber compositions may be added and mixed in advance before the melt kneading, for example. It may be added inside.
  • a rubber composition (masterbatch) pellet is prepared by adding a crosslinking agent or the like to the rubber component, and the pellet is put into a kneader together with a thermoplastic resin and a compatibilizer, and melt kneaded to operate. Dynamically crosslinked pellets may be obtained by mechanical crosslinking.
  • the kneader used for kneading is not particularly limited, and examples thereof include a twin screw extruder, a screw extruder, a kneader, and a Banbury mixer.
  • the kneading temperature should just be more than the temperature which a thermoplastic resin fuse
  • An air permeation-resistant film can be obtained by forming the dynamic cross-linked product thus obtained into a film.
  • the method of forming the dynamically crosslinked pellets into a film is not particularly limited.
  • a method of forming a normal thermoplastic resin into a film such as extrusion molding or calendar molding, can be used.
  • the air permeation-resistant film according to the present embodiment preferably has an air permeability coefficient at 80 ° C. of 5 ⁇ 10 13 fm 2 / Pa ⁇ s or less, and the weight of the tire is reduced by thinning the inner liner. Can do.
  • the air permeability coefficient may be 0.1 ⁇ 10 13 to 4 ⁇ 10 13 fm 2 / Pa ⁇ s, or may be 0.1 ⁇ 10 13 to 1.0 ⁇ 10 13 fm 2 / Pa ⁇ s.
  • the thickness of the air permeable resistant film is not particularly limited, and may be, for example, 0.02 to 1.0 mm, 0.05 to 0.5 mm, or 0.1 to 0.3 mm.
  • the air permeable resistant film according to the present embodiment is applied to various pneumatic tires such as tires for passenger cars, various automobile tires including heavy load tires such as trucks and buses, and motorcycle tires including bicycles. can do.
  • FIG. 1 is a cross-sectional view of a pneumatic tire 1 according to an embodiment.
  • a pneumatic tire 1 includes a pair of bead portions 2 and 2 that are assembled to a rim, a pair of sidewall portions 3 and 3 that extend outward from the bead portion 2 in the tire radial direction, and the pair of sidewalls. And a tread portion 4 that contacts the road surface provided between the portions 3 and 3.
  • a ring-shaped bead core 5 is embedded in each of the pair of bead portions 2 and 2.
  • a carcass ply 6 using an organic fiber cord is folded around the bead cores 5 and 5 and locked between the left and right bead portions 2 and 2.
  • a belt 7 made of two belt plies using a tire cord such as a steel cord is provided on the outer peripheral side of the tread portion 4 of the carcass ply 6.
  • An inner liner 8 is provided inside the carcass ply 6 over the entire inner surface of the tire.
  • the air permeable resistant film is used as the inner liner 8.
  • the inner liner 8 is bonded to the inner surface of the carcass ply 6 that is a rubber layer on the inner surface of the tire, and more specifically, a topping rubber that covers the cord of the carcass ply 6. Affixed to the inner surface of the layer.
  • an air-permeable film is used as an inner liner, and the inner liner is attached to the outer periphery of the molding drum in a cylindrical shape.
  • a green tire (unvulcanized tire) is produced by attaching a carcass ply on the inner liner and further attaching and inflating each tire member such as a belt, tread rubber, and sidewall rubber.
  • a pneumatic tire is obtained by vulcanizing the green tire in a mold.
  • the air permeation-resistant film is provided on the inner surface side of the carcass ply.
  • the air pressure from the inside of the tire can be prevented and the air pressure of the tire can be maintained, that is, the internal pressure.
  • the air permeation-resistant film can be provided at various positions such as the outer surface side of the carcass ply.
  • IIR Butyl rubber, “IIR268” manufactured by ExxonMobil Chemical ⁇ NBR: Nitrile rubber, "JSR N230S” manufactured by JSR Corporation Nylon-A: Nylon 6/66 copolymer, “Novamid 2010J” manufactured by DSM Nylon-B: Nylon 6/66 copolymer, “Novamid 2020J” manufactured by DSM ⁇ Nylon-C: nylon 6/66 copolymer, “Amilan CM6041XF” manufactured by Toray Industries, Inc.
  • Nylon-D 50 parts by mass of Nylon-A pellets and 50 parts by mass of Nylon-B pellets were dry blended and melted in a twin-screw extruder set at 220 ° C (Plastics Engineering Laboratory Co., Ltd.) Kneaded and pelletized (nylon blend 50/50)
  • Nylon-E 25 parts by mass of Nylon-A pellets and 75 parts by mass of Nylon-B pellets were dry blended and melted in a twin-screw extruder set at 220 ° C (Plastics Engineering Laboratory Co., Ltd.) Kneaded and pelletized (nylon blend 25/75)
  • EVOH-A ethylene-vinyl alcohol copolymer, “Soarnol 3203RB” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
  • EVOH-B ethylene-vinyl alcohol copolymer, “Soarnol 3212B” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
  • Compatibilizer “Bond First E” manufactured by Sumitomo Chemical Co., Ltd., ethylene-glycidyl methacrylate copolymer
  • Carbon black “Seast 3” manufactured by Tokai Carbon Co., Ltd.
  • Zinc flower "Zinc flower 3” manufactured by Mitsui Mining & Smelting Co., Ltd.
  • Stearic acid “Lunac S-20” manufactured by Kao Corporation
  • Sulfur “Powder sulfur” manufactured by Tsurumi Chemical Co., Ltd.
  • Vulcanization accelerator “Soxinol CZ” manufactured by Sumitomo Chemical Co., Ltd.
  • Crosslinking agent-1 Alkylphenol-formaldehyde resin, "Tactrol 201” manufactured by Taoka Chemical Co., Ltd.
  • Crosslinking agent-2 Brominated alkylphenol-formaldehyde resin, “Tactrol 201-III” manufactured by Taoka Chemical Co., Ltd.
  • Retarder “Kyowa Mug 150” manufactured by Kyowa Chemical Industry Co., Ltd.
  • evaluation measurement method The evaluation measurement methods in the following examples are as follows.
  • Vulcanization rate The rubber composition mixed in a lab plast mill (manufactured by Toyo Seiki Seisakusho) was tested at 200 ° C. for 60 minutes using a rheometer “MDR2000” (manufactured by Alpha Technology Co., Ltd.). The vulcanization speed was determined from the slope of the torque increase for 1 minute from the minimum viscosity ML.
  • test piece (dumbbell-shaped No. 3 test piece), and use a tensile tester to make the test piece 3 cm between chucks. Then, the film was repeatedly stretched by 50% at a frequency of 5 Hz at an ambient temperature of 40 ° C. The number of test pieces is 10, 50% elongation is repeated 1,000,000 times, and when the number of breaks in the film is 3 or less, the pass is “ ⁇ ”, and when it is 4 or more, it is “fail”. did.
  • melt viscosity of thermoplastic resin and rubber components The melt viscosity at 230 ° C. of the thermoplastic resin and the rubber component and the air permeability coefficient of the thermoplastic resin were as shown in Table 1.
  • the air permeability coefficient of a thermoplastic resin is the value measured about the film shape
  • melt viscosity of the thermoplastic resin is higher than the melt viscosity of the rubber composition ( ⁇ 1 / ⁇ 2 > 1), and the initial vulcanization rate of the rubber composition is 0.70 dN ⁇ m / min or more.
  • the phase image was confirmed by SPM (scanning probe microscope), it is a sea-island structure which uses a thermoplastic resin as a continuous phase and a crosslinked (vulcanized) rubber composition as a dispersed phase. Yes, the dispersed phase was made finer than in Comparative Example 5.

Abstract

A method for producing an air-impermeable film according to one embodiment comprises melt-kneading and thereby dynamically crosslinking a thermoplastic resin, and a rubber composition having a melt viscosity lower than that of the thermoplastic resin at 230°C and a vulcanization rate of 0.70 dN·m/min or higher at 200°C, to obtain a dynamically crosslinked product in which the thermoplastic resin is in a continuous phase, and the rubber composition is in a dispersed phase. As a result, an air-impermeable film having excellent durability is obtained.

Description

耐空気透過性フィルム及び空気入りタイヤの製造方法Air permeation resistant film and method for producing pneumatic tire
　本発明の実施形態は、耐空気透過性フィルム、及びそれを用いた空気入りタイヤに関するものである。 Embodiments of the present invention relate to an air permeation-resistant film and a pneumatic tire using the same.
　空気入りタイヤの内側面には、タイヤの空気圧を一定に保持するために空気透過抑制層としてインナーライナーが設けられている。タイヤの軽量化等を目的として、インナーライナーの薄肉化を図るべく、例えば、特許文献１には、連続相である熱可塑性樹脂と分散相であるエラストマーとの動的架橋体からなる耐空気透過性フィルムが提案されている。 An inner liner is provided on the inner side surface of the pneumatic tire as an air permeation suppressing layer in order to keep the tire air pressure constant. In order to reduce the thickness of the inner liner for the purpose of reducing the weight of the tire, for example, Patent Document 1 discloses air permeation resistance made of a dynamic cross-linked body of a thermoplastic resin as a continuous phase and an elastomer as a dispersed phase. Sex films have been proposed.
　この種の耐空気透過性フィルム、とりわけインナーライナーに用いられるフィルムにおいては、耐久性を向上することが求められる。 This type of air permeation-resistant film, particularly a film used for an inner liner, is required to have improved durability.
　そこで、特許文献２では、熱可塑性樹脂とゴムの溶融粘度を近づけてゴムを微分散化させるとともに、ゴム配合量を増加させて弾性率を低減することで、耐疲労性を向上することが開示されており、そのために、ゴムに充填剤等を加えて粘度を増加させるとともに、熱可塑性樹脂に低粘度成分を適量ブレンドすることが提案されている。しかしながら、熱可塑性樹脂に低粘度成分を添加することによる強度低下や、ゴムに充填剤を添加することによる亀裂発生の要因となることが考えられる。 Therefore, Patent Document 2 discloses that the fatigue resistance is improved by bringing the melt viscosity of the thermoplastic resin and the rubber closer to finely disperse the rubber and increasing the amount of the rubber to reduce the elastic modulus. Therefore, it has been proposed to increase the viscosity by adding a filler or the like to rubber and to blend an appropriate amount of a low viscosity component into the thermoplastic resin. However, it is conceivable that the strength is reduced by adding a low-viscosity component to the thermoplastic resin, and cracks are caused by adding a filler to the rubber.
　一方、特許文献３には、連続相を構成する樹脂として変性エチレンビニルアルコール共重合体を用い、これにモジュラスの低い粘弾性体としてゴムを高分散化させて、耐久性を向上することが開示されているが、特定のポリマーにしか適用できない。 On the other hand, Patent Document 3 discloses that a modified ethylene vinyl alcohol copolymer is used as a resin constituting a continuous phase, and that rubber is highly dispersed as a low modulus viscoelastic material to improve durability. However, it can only be applied to specific polymers.
日本国特開平０８－２５９７４１号公報Japanese Laid-Open Patent Publication No. 08-259741 日本国特開２００３－０２６９３１号公報Japanese Unexamined Patent Publication No. 2003-026931 日本国特開２００９－２６３６５３号公報Japanese Unexamined Patent Publication No. 2009-263653
　本発明の実施形態は、耐久性に優れた耐空気透過性フィルムを得ることを目的とする。 An object of the embodiment of the present invention is to obtain an air-permeable film having excellent durability.
　本実施形態に係る耐空気透過性フィルムの製造方法は、熱可塑性樹脂と、前記熱可塑性樹脂よりも２３０℃での溶融粘度が低くかつ２００℃での加硫速度が０．７０ｄＮ・ｍ／分以上であるゴム組成物と、を溶融混練し動的架橋させることにより、前記熱可塑性樹脂を連続相とし、前記ゴム組成物を分散相とした動的架橋体を得ることを含むものである。ここで、ゴム組成物の溶融粘度は、架橋剤を除いて測定される溶融粘度である。 The method for producing an air permeable resistant film according to the present embodiment includes a thermoplastic resin, a melt viscosity lower at 230 ° C. than that of the thermoplastic resin, and a vulcanization rate at 200 ° C. of 0.70 dN · m / min. It includes melt-kneading and dynamically crosslinking the rubber composition as described above to obtain a dynamically crosslinked product having the thermoplastic resin as a continuous phase and the rubber composition as a dispersed phase. Here, the melt viscosity of the rubber composition is a melt viscosity measured excluding the crosslinking agent.
　本実施形態に係る空気入りタイヤの製造方法は、該製造方法により得られた耐空気透過性フィルムを、インナーライナー又はその他の空気透過抑制層として用いるものである。 The method for manufacturing a pneumatic tire according to the present embodiment uses an air-permeable-resistant film obtained by the manufacturing method as an inner liner or other air permeation suppression layer.
　本実施形態によれば、ゴム組成物よりも高い溶融粘度を持つ熱可塑性樹脂と、加硫速度の速いゴム組成物と、を組み合わせることにより、耐久性に優れた耐空気透過性フィルムを得ることができる。 According to this embodiment, by combining a thermoplastic resin having a higher melt viscosity than the rubber composition and a rubber composition having a high vulcanization rate, an air-permeable resistant film having excellent durability can be obtained. Can do.
一実施形態に係る空気入りタイヤの断面図である。It is sectional drawing of the pneumatic tire which concerns on one Embodiment.
　以下、本発明の実施に関連する事項について詳細に説明する。 Hereinafter, matters related to the implementation of the present invention will be described in detail.
　本実施形態に係る耐空気透過性フィルムは、熱可塑性樹脂を連続相（マトリックス相）とし、ゴム組成物を分散相（ドメイン相）とした海島構造を持つ動的架橋体からなるものである。該熱可塑性樹脂として、ゴム組成物よりも２３０℃での溶融粘度が高い高粘度の樹脂を使用するとともに、ゴム組成物として、２００℃での加硫速度が０．７０ｄＮ・ｍ／分以上と従来よりも速いものを用いることを特徴とする。 The air permeable resistant film according to the present embodiment is composed of a dynamic cross-linked body having a sea-island structure in which a thermoplastic resin is a continuous phase (matrix phase) and a rubber composition is a dispersed phase (domain phase). As the thermoplastic resin, a high-viscosity resin having a higher melt viscosity at 230 ° C. than the rubber composition is used, and as the rubber composition, the vulcanization rate at 200 ° C. is 0.70 dN · m / min or more. It is characterized by using a faster one than before.
　これにより、耐空気透過性フィルムの耐久性を向上することができるが、その理由は次のように考えられる。 This can improve the durability of the air permeation-resistant film, and the reason is considered as follows.
　すなわち、熱可塑性樹脂の溶融粘度がゴム組成物よりも低い場合、熱可塑性樹脂を連続相とし、ゴム組成物を分散相とすることができる。しかしながら、熱可塑性樹脂が低粘度であるが故に一般に耐久性が低く、高耐久な耐空気透過性フィルムにはならない。耐久性を向上するために、ゴム組成物よりも溶融粘度の大きな熱可塑性樹脂を使用することが考えられる。しかし、その場合に、ゴム組成物として加硫速度の遅い汎用のゴム組成物を用いると、熱可塑性樹脂との混合初期にゴム組成物が連続相となり、高分散に必要な高いせん断力が得られない。また、この場合、加硫によるゴム組成物の粘度上昇が遅いため、連続相と分散相の反転が起こりにくく、できあがった複合体においてゴム組成物が連続相となりやすい。ゴム組成物が連続相では、フィルムとしての成形が難しく、耐空気透過性に劣るものになってしまう。 That is, when the melt viscosity of the thermoplastic resin is lower than that of the rubber composition, the thermoplastic resin can be a continuous phase and the rubber composition can be a dispersed phase. However, since the thermoplastic resin has a low viscosity, the durability is generally low and it does not become a highly durable air-permeable film. In order to improve durability, it is conceivable to use a thermoplastic resin having a melt viscosity larger than that of the rubber composition. However, in this case, if a general-purpose rubber composition having a low vulcanization rate is used as the rubber composition, the rubber composition becomes a continuous phase at the initial stage of mixing with the thermoplastic resin, and a high shear force necessary for high dispersion is obtained. I can't. Further, in this case, since the viscosity increase of the rubber composition due to vulcanization is slow, the continuous phase and the dispersed phase are unlikely to reverse, and the rubber composition tends to become the continuous phase in the finished composite. When the rubber composition is a continuous phase, it is difficult to form as a film and the air permeability resistance is poor.
　これに対し、本実施形態によれば、高粘度の熱可塑性樹脂を用いながら加硫速度の速いゴム組成物を用いることにより、混合初期にゴム組成物の粘度を上昇させて、高粘度の熱可塑性樹脂を連続相にすることができる。また、これにより、ゴム組成物にも十分なせん断力を与えることができ、ゴム分散相を微細化することができる。このように、ゴム分散相を高分散としつつ、連続相に従来よりも高粘度（高耐久）の熱可塑性樹脂を用いることができるので、高い耐久性を発現することができる。 On the other hand, according to the present embodiment, by using a rubber composition having a high vulcanization speed while using a high-viscosity thermoplastic resin, the viscosity of the rubber composition is increased at the initial stage of mixing, so The plastic resin can be a continuous phase. Thereby, sufficient shearing force can be given also to a rubber composition, and a rubber dispersed phase can be refined. As described above, since a thermoplastic resin having a higher viscosity (higher durability) than that of the conventional one can be used for the continuous phase while making the rubber dispersed phase highly dispersed, high durability can be expressed.
　本実施形態において、熱可塑性樹脂としては、例えば、ナイロン６、ナイロン６６、ナイロン４６、ナイロン１１、ナイロン１２、ナイロン６１０、ナイロン６１２、ナイロン６／６６共重合体、ナイロン６／６６／６１０共重合体、ナイロンＭＸＤ６、ナイロン６Ｔ、ナイロン６／６Ｔ共重合体などの脂肪族ポリアミド系樹脂（ナイロン樹脂）；　エチレン－ビニルアルコール共重合体（ＥＶＯＨ）、エチレン－酢酸ビニル共重合体（ＥＶＡ）、ポリビニルアルコール（ＰＶＡ）、ポリ塩化ビニリデン（ＰＶＤＣ）、ポリ塩化ビニル（ＰＶＣ）などのポリビニル系樹脂；　ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンイソフタレート（ＰＥＩ）、ポリアリレート（ＰＡＲ）、ポリブチレンナフタレート（ＰＢＮ）などのポリエステル系樹脂；　ポリアクリロニトリル（ＰＡＮ）、ポリメタクリロニトリル、アクリロニトリル－スチレン共重合体（ＡＳ）などのポリニトリル系樹脂；　酢酸セルロース、酢酸酪酸セルロースなどのセルロース系樹脂；　ポリフッ化ビニリデン（ＰＶＤＦ）、ポリフッ化ビニル（ＰＶＦ）、ポリクロルフルオロエチレン（ＰＣＴＦＥ）などのフッ素系樹脂；　芳香族ポリイミド（ＰＩ）などのイミド系樹脂が挙げられ、これらはそれぞれ単独又は２種以上組み合わせて用いることができる。一実施形態において、熱可塑性樹脂としては、脂肪族ポリアミド系樹脂及びポリビニル系樹脂からなる群から選択される少なくとも一種でもよく、脂肪族ポリアミド系樹脂及びエチレン－ビニルアルコール共重合体からなる群から選択される少なくとも一種でもよい。 In this embodiment, examples of the thermoplastic resin include nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66 copolymer, and nylon 6/66/610 copolymer. Aliphatic polyamide resin (nylon resin) such as coalescence, nylon MXD6, nylon 6T, nylon 6 / 6T copolymer; ethylene-vinyl alcohol copolymer (EVOH), ethylene-vinyl acetate copolymer (EVA), polyvinyl Polyvinyl resins such as alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC); polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), polyarylate (PAR), Polybuchi Polyester resins such as nonaphthalate (PBN); Polynitrile resins such as polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile-styrene copolymer (AS); Cellulosic resins such as cellulose acetate and cellulose acetate butyrate; Polyfluoride Fluorine resins such as vinylidene fluoride (PVDF), polyvinyl fluoride (PVF), and polychlorofluoroethylene (PCTFE); and imide resins such as aromatic polyimide (PI), which are used alone or in combination of two or more. Can be used. In one embodiment, the thermoplastic resin may be at least one selected from the group consisting of aliphatic polyamide resins and polyvinyl resins, or selected from the group consisting of aliphatic polyamide resins and ethylene-vinyl alcohol copolymers. It may be at least one kind.
　熱可塑性樹脂としては、８０℃での空気透過係数が５×１０13ｆｍ2／Ｐａ・ｓ以下である耐空気透過性熱可塑性樹脂を用いることが好ましく、フィルムに優れた耐空気透過性を付与することができる。熱可塑性樹脂の空気透過係数は、０．０５×１０13～２×１０13ｆｍ2／Ｐａ・ｓでもよい。空気透過係数は、ＪＩＳ　Ｋ７１２６－１「プラスチック－フィルム及びシート－ガス透過度試験方法－第１部：差圧法」に準じて、試験気体：空気、試験温度：８０℃にて測定される値である。 As the thermoplastic resin, it is preferable to use an air permeable thermoplastic resin having an air permeability coefficient at 80 ° C. of 5 × 10 13 fm 2 / Pa · s or less, and imparts excellent air permeability resistance to the film. can do. The air permeability coefficient of the thermoplastic resin may be 0.05 × 10 13 to 2 × 10 13 fm 2 / Pa · s. The air permeability coefficient is a value measured at a test gas: air and at a test temperature: 80 ° C. according to JIS K7126-1 “Plastics—Films and Sheets—Gas Permeability Test Method—Part 1: Differential Pressure Method”. is there.
　連続相を形成する熱可塑性樹脂には、本実施形態による効果を損なわない限り、可塑剤、軟化剤、充填剤、補強剤、加工助剤、安定剤、酸化防止剤などの添加剤を必要に応じて適宜配合してもよい。 The thermoplastic resin forming the continuous phase requires additives such as a plasticizer, a softener, a filler, a reinforcing agent, a processing aid, a stabilizer, and an antioxidant as long as the effects of the present embodiment are not impaired. You may mix | blend suitably according to it.
　本実施形態において、分散相に用いられる未架橋のゴム組成物に含まれるゴム成分としては、一般に架橋（加硫）して使用される各種の未架橋（未加硫）ゴムポリマーが用いられる。例えば、天然ゴム（ＮＲ）、エポキシ化天然ゴム（ＥＮＲ）、イソプレンゴム（ＩＲ）、スチレンブタジエンゴム（ＳＢＲ）、ブタジエンゴム（ＢＲ）、ニトリルゴム（ＮＢＲ）、水素化ニトリルゴム（Ｈ－ＮＢＲ）、水素化スチレンブタジエンゴムなどのジエン系ゴム及びその水素添加ゴム；　エチレンプロピレンゴム（ＥＰＤＭ）、マレイン酸変性エチレンプロピレンゴム、マレイン酸変性エチレンブチレンゴム、ブチルゴム（ＩＩＲ）、アクリルゴム（ＡＣＭ）などのオレフィン系ゴム；　ハロゲン化ブチルゴム（例えば、臭素化ブチルゴム（Ｂｒ－ＩＩＲ）、塩素化ブチルゴム（Ｃｌ－ＩＩＲ））、クロロプレンゴム（ＣＲ）、クロロスルホン化ポリエチレンなどの含ハロゲンゴム；　その他、シリコーンゴム、フッ素ゴム、ポリスルフィドゴムなどが挙げられる。これらはいずれか１種を単独で用いても、２種以上を併用してもよい。これらの中でも、耐空気透過性の点から、ブチルゴム（ＩＩＲ）、臭素化ブチルゴム（Ｂｒ－ＩＩＲ）などのハロゲン化ブチルゴム、ニトリルゴム（ＮＢＲ）及び水素化ニトリルゴム（Ｈ－ＮＢＲ）から選択される少なくとも１種を用いることが好ましい。 In the present embodiment, as the rubber component contained in the uncrosslinked rubber composition used for the dispersed phase, various uncrosslinked (unvulcanized) rubber polymers generally used after being crosslinked (vulcanized) are used. For example, natural rubber (NR), epoxidized natural rubber (ENR), isoprene rubber (IR), styrene butadiene rubber (SBR), butadiene rubber (BR), nitrile rubber (NBR), hydrogenated nitrile rubber (H-NBR) , Diene rubber such as hydrogenated styrene butadiene rubber and its hydrogenated rubber; ethylene propylene rubber (EPDM), maleic acid modified ethylene propylene rubber, maleic acid modified ethylene butylene rubber, butyl rubber (IIR), acrylic rubber (ACM), etc. Olefin-based rubber; Halogenated butyl rubber (for example, brominated butyl rubber (Br-IIR), chlorinated butyl rubber (Cl-IIR)), chloroprene rubber (CR), halogen-containing rubber such as chlorosulfonated polyethylene; Fluoro rubber, police Fidogomu and the like. These may be used alone or in combination of two or more. Among these, from the viewpoint of air permeation resistance, halogenated butyl rubber such as butyl rubber (IIR) and brominated butyl rubber (Br-IIR), nitrile rubber (NBR) and hydrogenated nitrile rubber (H-NBR) are selected. It is preferable to use at least one kind.
　分散相を形成するゴム組成物には、上記ゴム成分を動的架橋するための架橋剤が配合される。すなわち、該ゴム組成物は、少なくともゴム成分と架橋剤を含むものである。架橋剤としては、硫黄や硫黄含有化合物等などの加硫剤、加硫促進剤の他、フェノール樹脂などが挙げられる。好ましくは、耐熱性等の点から、フェノール樹脂を用いることである。フェノール樹脂としては、フェノール類とホルムアルデヒドとの縮合反応により得られる樹脂が挙げられ、例えば、アルキルフェノール－ホルムアルデヒド樹脂が挙げられる。また、加硫速度を速くすることができる点から、臭素化アルキルフェノール－ホルムアルデヒド樹脂などのハロゲン化フェノール樹脂を用いることが好ましい。架橋剤の配合量は、ゴム成分を適切に架橋できるものであれば、特に限定されないが、ゴム成分１００質量部に対して、０．１～１０質量部でもよく、０．５～５質量部でもよい。 The rubber composition forming the dispersed phase is blended with a crosslinking agent for dynamically crosslinking the rubber component. That is, the rubber composition contains at least a rubber component and a crosslinking agent. Examples of the crosslinking agent include vulcanizing agents such as sulfur and sulfur-containing compounds, vulcanization accelerators, and phenol resins. Preferably, a phenol resin is used from the viewpoint of heat resistance and the like. Examples of the phenol resin include resins obtained by condensation reaction of phenols and formaldehyde, and examples thereof include alkylphenol-formaldehyde resins. Further, from the viewpoint that the vulcanization rate can be increased, it is preferable to use a halogenated phenol resin such as a brominated alkylphenol-formaldehyde resin. The amount of the crosslinking agent is not particularly limited as long as it can appropriately crosslink the rubber component, but may be 0.1 to 10 parts by mass, or 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component. But you can.
　分散相を形成するゴム組成物は、上記のゴム成分及び架橋剤のみを含むものでもよいが、これらに加えて、充填剤や軟化剤、老化防止剤、加工助剤などの一般にゴム組成物に配合される各種添加剤を配合してもよい。なお、充填剤は、亀裂発生の要因を極力排除する趣旨より配合しないことが好ましく、例えば、ゴム成分１００質量部に対して２０質量部以下であることが好ましく、より好ましくは１０質量部以下であり、更に好ましくは５質量部以下である。 The rubber composition forming the dispersed phase may contain only the rubber component and the crosslinking agent described above, but in addition to these, the rubber composition generally includes a filler, a softening agent, an anti-aging agent, a processing aid, and the like. Various additives to be blended may be blended. In addition, it is preferable not to mix | blend a filler from the meaning which eliminates the factor of crack generation as much as possible, for example, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of rubber components, More preferably, it is 10 mass parts or less. Yes, more preferably 5 parts by mass or less.
　本実施形態に係る耐空気透過性フィルムにおいて、上記の熱可塑性樹脂とゴム組成物との配合比（添加剤を除いたポリマーとしての比率）は、特に限定されず、例えば、質量比（熱可塑性樹脂／ゴム組成物）で、９０／１０～３０／７０でもよく、７０／３０～４０／６０でもよく、６０／４０～４０／６０でもよい。 In the air permeable resistant film according to the present embodiment, the blending ratio of the thermoplastic resin and the rubber composition (ratio as a polymer excluding additives) is not particularly limited, and is, for example, a mass ratio (thermoplasticity). Resin / rubber composition), which may be 90/10 to 30/70, 70/30 to 40/60, or 60/40 to 40/60.
　本実施形態では、上記のように、熱可塑性樹脂として、ゴム組成物よりも２３０℃での溶融粘度が高い高粘度の樹脂を使用する。すなわち、熱可塑性樹脂の２３０℃での溶融粘度をη1とし、ゴム組成物の２３０℃での溶融粘度をη2として、η1＞η2を満足する熱可塑性樹脂及びゴム組成物を用いる。より好ましくは、これら溶融粘度の比がη1／η2≧１．２０を満足すること、即ち、比η1／η2が１．２０以上であり、更に好ましくは、比η1／η2が１．４０以上であり、１．５０以上でもよい。一般に、熱可塑性樹脂は溶融粘度が高いほど耐久性に優れるので、溶融粘度の高い熱可塑性樹脂を用いることにより、耐空気透過性フィルムの耐久性を向上することができる。なお、溶融粘度の比η1／η2の上限は、特に限定されず、例えば１０．０以下でもよく、７．０以下でもよい。 In the present embodiment, as described above, a high-viscosity resin having a higher melt viscosity at 230 ° C. than the rubber composition is used as the thermoplastic resin. That is, a thermoplastic resin and a rubber composition satisfying η 1 > η 2 are used, where η 1 is the melt viscosity of the thermoplastic resin at 230 ° C. and η 2 is the melt viscosity of the rubber composition at 230 ° C. More preferably, the ratio of these melt viscosities satisfies η 1 / η 2 ≧ 1.20, that is, the ratio η 1 / η 2 is 1.20 or more, and more preferably the ratio η 1 / η 2 Is 1.40 or more, and may be 1.50 or more. In general, the higher the melt viscosity, the better the durability of the thermoplastic resin. Therefore, the durability of the air permeation-resistant film can be improved by using a thermoplastic resin having a high melt viscosity. The upper limit of the melt viscosity ratio η 1 / η 2 is not particularly limited, and may be 10.0 or less, or 7.0 or less, for example.
　熱可塑性樹脂の溶融粘度η1は、特に限定されないが、耐久性の観点より、７０～４００Ｐａ・ｓであることが好ましく、より好ましくは１００～３００Ｐａ・ｓであり、更に好ましくは１５０～３００Ｐａ・ｓである。ゴム組成物の溶融粘度η2は、熱可塑性樹脂の溶融粘度η1よりも小さい限り、特に限定されず、例えば、４０～２５０Ｐａ・ｓでもよく、５０～１７０Ｐａ・ｓでもよい。なお、熱可塑性樹脂の溶融粘度は、例えば、樹脂の種類や分子量、可塑剤などの添加剤により調整することができる。また、ゴム組成物の溶融粘度は、例えば、ゴム成分の種類や分子量、軟化剤や充填剤等の添加剤により調整することができる。 The melt viscosity η 1 of the thermoplastic resin is not particularly limited, but is preferably 70 to 400 Pa · s, more preferably 100 to 300 Pa · s, and further preferably 150 to 300 Pa · s from the viewpoint of durability. s. The melt viscosity η 2 of the rubber composition is not particularly limited as long as it is smaller than the melt viscosity η 1 of the thermoplastic resin, and may be, for example, 40 to 250 Pa · s or 50 to 170 Pa · s. In addition, the melt viscosity of a thermoplastic resin can be adjusted with additives, such as the kind of resin, molecular weight, and a plasticizer, for example. The melt viscosity of the rubber composition can be adjusted by, for example, the type and molecular weight of the rubber component, and additives such as softeners and fillers.
　ここで、溶融粘度は、キャピラリーレオメータを用いて、シリンダー温度２３０℃、押出速度８００ｓ-1で測定される値である。なお、熱可塑性樹脂の溶融粘度η1は、上記のように熱可塑性樹脂に添加剤が配合される場合、添加剤を含んだものについて測定される値である。但し、該添加剤には、後述する相溶化剤は含まれない。また、ゴム組成物の溶融粘度η2は、架橋剤を除いて測定される値である。 Here, the melt viscosity is a value measured using a capillary rheometer at a cylinder temperature of 230 ° C. and an extrusion speed of 800 s −1 . The melt viscosity η 1 of the thermoplastic resin is a value measured for the additive containing the additive when the additive is added to the thermoplastic resin as described above. However, the additive does not include a compatibilizer described later. Further, the melt viscosity η 2 of the rubber composition is a value measured excluding the crosslinking agent.
　本実施形態では、また、上記のように、ゴム組成物として、２００℃での加硫速度（架橋速度とも称される。）が０．７０ｄＮ・ｍ／分以上であるものを用いる。ゴム組成物の加硫速度は、より好ましくは０．８０ｄＮ・ｍ／分以上である。ゴム組成物の加硫速度の上限は、特に限定されず、例えば２．５ｄＮ・ｍ／分以下でもよく、１．７ｄＮ・ｍ／分以下でもよい。なお、加硫速度は、例えば、架橋剤の種類や量により調整することができる。 In the present embodiment, as described above, a rubber composition having a vulcanization rate (also referred to as a crosslinking rate) at 200 ° C. of 0.70 dN · m / min or more is used. The vulcanization rate of the rubber composition is more preferably 0.80 dN · m / min or more. The upper limit of the vulcanization rate of the rubber composition is not particularly limited, and may be, for example, 2.5 dN · m / min or less, or 1.7 dN · m / min or less. In addition, a vulcanization | cure speed | rate can be adjusted with the kind and quantity of a crosslinking agent, for example.
　ここで、ゴム組成物の加硫速度は、レオメータを用いて試験温度２００℃で粘度を測定し、最低粘度ＭＬから１分間のトルク上昇の傾きにより求められる値である。 Here, the vulcanization speed of the rubber composition is a value obtained by measuring the viscosity at a test temperature of 200 ° C. using a rheometer and obtaining a torque increase gradient for 1 minute from the minimum viscosity ML.
　本実施形態においては、熱可塑性樹脂及びゴム組成物とともに、相溶化剤を配合してもよい。相溶化剤は、熱可塑性樹脂とゴム組成物との界面張力を低下させて、両者を相溶化させるものである。相溶化剤としては、一実施形態として、エチレン－グリシジル（メタ）アクリレート共重合体（即ち、エチレン－グリシジルメタクリレート共重合体、及び／又は、エチレン－グリシジルアクリレート共重合体）を用いてもよい。該相溶化剤の配合量は特に限定されないが、熱可塑性樹脂とゴム組成物の合計量（添加剤を除いたポリマーとしての量）１００質量部に対して０．５～１０質量部でもよく、０．５～５質量部でもよい。 In the present embodiment, a compatibilizing agent may be blended together with the thermoplastic resin and the rubber composition. The compatibilizing agent lowers the interfacial tension between the thermoplastic resin and the rubber composition and makes them compatible. As a compatibilizing agent, as one embodiment, an ethylene-glycidyl (meth) acrylate copolymer (that is, an ethylene-glycidyl methacrylate copolymer and / or an ethylene-glycidyl acrylate copolymer) may be used. The compounding amount of the compatibilizer is not particularly limited, but may be 0.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin and the rubber composition (amount as a polymer excluding additives), It may be 0.5 to 5 parts by mass.
　本実施形態において、耐空気透過性フィルムを製造するに際しては、上記熱可塑性樹脂とゴム組成物とを溶融混練し、架橋剤でゴム組成物を動的架橋（ＴＰＶ）させる。これらの樹脂組成物及びゴム組成物への上記各種添加剤（例えば、充填剤、架橋剤等）の添加時期は、例えば、該溶融混練前に予め添加混合しておいてもよく、該溶融混練中に添加してもよい。一実施形態として、ゴム成分に架橋剤等を添加してゴム組成物（マスターバッチ）のペレットを作製し、該ペレットを熱可塑性樹脂及び相溶化剤とともに混練機に投入し、溶融混練して動的架橋することにより動的架橋体のペレットを得てもよい。 In this embodiment, when producing an air permeation-resistant film, the thermoplastic resin and the rubber composition are melt-kneaded and the rubber composition is dynamically crosslinked (TPV) with a crosslinking agent. The timing of addition of the various additives (for example, fillers, crosslinking agents, etc.) to these resin compositions and rubber compositions may be added and mixed in advance before the melt kneading, for example. It may be added inside. As an embodiment, a rubber composition (masterbatch) pellet is prepared by adding a crosslinking agent or the like to the rubber component, and the pellet is put into a kneader together with a thermoplastic resin and a compatibilizer, and melt kneaded to operate. Dynamically crosslinked pellets may be obtained by mechanical crosslinking.
　混練に使用する混練機としては、特に限定されず、例えば、二軸押出機、スクリュー押出機、ニーダー、バンバリーミキサーなどが挙げられる。混練温度は、熱可塑性樹脂が溶融する温度以上であればよい。 The kneader used for kneading is not particularly limited, and examples thereof include a twin screw extruder, a screw extruder, a kneader, and a Banbury mixer. The kneading temperature should just be more than the temperature which a thermoplastic resin fuse | melts.
　このようにして得られた動的架橋体をフィルム化することにより、耐空気透過性フィルムが得られる。動的架橋体のペレットをフィルム化する方法は特に限定されず、例えば押し出し成形やカレンダー成形など、通常の熱可塑性樹脂をフィルム化する方法を用いることができる。 An air permeation-resistant film can be obtained by forming the dynamic cross-linked product thus obtained into a film. The method of forming the dynamically crosslinked pellets into a film is not particularly limited. For example, a method of forming a normal thermoplastic resin into a film, such as extrusion molding or calendar molding, can be used.
　本実施形態に係る耐空気透過性フィルムは、８０℃での空気透過係数が５×１０13ｆｍ2／Ｐａ・ｓ以下であることが好ましく、インナーライナーの薄肉化によるタイヤの軽量化を図ることができる。該空気透過係数は、０．１×１０13～４×１０13ｆｍ2／Ｐａ・ｓでもよく、０．１×１０13～１．０×１０13ｆｍ2／Ｐａ・ｓでもよい。 The air permeation-resistant film according to the present embodiment preferably has an air permeability coefficient at 80 ° C. of 5 × 10 13 fm 2 / Pa · s or less, and the weight of the tire is reduced by thinning the inner liner. Can do. The air permeability coefficient may be 0.1 × 10 13 to 4 × 10 13 fm 2 / Pa · s, or may be 0.1 × 10 13 to 1.0 × 10 13 fm 2 / Pa · s.
　耐空気透過性フィルムの厚みは、特に限定されず、例えば、０．０２～１．０ｍｍでもよく、０．０５～０．５ｍｍでもよく、０．１～０．３ｍｍでもよい。 The thickness of the air permeable resistant film is not particularly limited, and may be, for example, 0.02 to 1.0 mm, 0.05 to 0.5 mm, or 0.1 to 0.3 mm.
　本実施形態に係る耐空気透過性フィルムは、例えば、乗用車用タイヤ、トラックやバスなどの重荷重用タイヤを含む各種の自動車用タイヤ、また自転車を含む二輪車用タイヤなど、各種の空気入りタイヤに適用することができる。 The air permeable resistant film according to the present embodiment is applied to various pneumatic tires such as tires for passenger cars, various automobile tires including heavy load tires such as trucks and buses, and motorcycle tires including bicycles. can do.
　図１は、一実施形態に係る空気入りタイヤ１の断面図である。図示するように、空気入りタイヤ１は、リム組みされる一対のビード部２，２と、該ビード部２からタイヤ径方向外側に延びる一対のサイドウォール部３，３と、該一対のサイドウォール部３，３間に設けられた路面に接地するトレッド部４とから構成される。一対のビード部２，２には、それぞれリング状のビードコア５が埋設されている。有機繊維コードを用いたカーカスプライ６が、ビードコア５，５の周りを折り返して係止されるとともに、左右のビード部２，２間に架け渡して設けられている。また、カーカスプライ６のトレッド部４における外周側には、スチールコードなどのタイヤコードを用いた２枚のベルトプライからなるベルト７が設けられている。 FIG. 1 is a cross-sectional view of a pneumatic tire 1 according to an embodiment. As shown in the figure, a pneumatic tire 1 includes a pair of bead portions 2 and 2 that are assembled to a rim, a pair of sidewall portions 3 and 3 that extend outward from the bead portion 2 in the tire radial direction, and the pair of sidewalls. And a tread portion 4 that contacts the road surface provided between the portions 3 and 3. A ring-shaped bead core 5 is embedded in each of the pair of bead portions 2 and 2. A carcass ply 6 using an organic fiber cord is folded around the bead cores 5 and 5 and locked between the left and right bead portions 2 and 2. Further, a belt 7 made of two belt plies using a tire cord such as a steel cord is provided on the outer peripheral side of the tread portion 4 of the carcass ply 6.
　カーカスプライ６の内側にはタイヤ内面の全体にわたってインナーライナー８が設けられている。本実施形態では、このインナーライナー８として上記耐空気透過性フィルムが用いられている。インナーライナー８は、図１中の拡大図に示すように、タイヤ内面側のゴム層であるカーカスプライ６の内面に貼り合わされており、より詳細には、カーカスプライ６のコードを被覆するトッピングゴム層の内面に貼り合わされている。 An inner liner 8 is provided inside the carcass ply 6 over the entire inner surface of the tire. In the present embodiment, the air permeable resistant film is used as the inner liner 8. As shown in the enlarged view in FIG. 1, the inner liner 8 is bonded to the inner surface of the carcass ply 6 that is a rubber layer on the inner surface of the tire, and more specifically, a topping rubber that covers the cord of the carcass ply 6. Affixed to the inner surface of the layer.
　かかる空気入りタイヤの製造方法としては、例えば、耐空気透過性フィルムをインナーライナーとして用いて、成形ドラムの外周にインナーライナーを筒状に装着する。該インナーライナーの上にカーカスプライを貼り付け、更にベルト、トレッドゴム及びサイドウォールゴムなどの各タイヤ部材を貼り重ね、インフレートすることによりグリーンタイヤ（未加硫タイヤ）が作製される。該グリーンタイヤをモールド内で加硫成形することにより、空気入りタイヤが得られる。なお、図１に示す例では、耐空気透過性フィルムをカーカスプライの内面側に設けたが、タイヤ内部からの空気の透過を防止して、タイヤの空気圧を保持することができる態様、即ち内圧保持のための空気透過抑制層として設けられるものであれば、特に限定されない。耐空気透過性フィルムは、例えば、カーカスプライの外面側などの種々の位置に設けることができる。 As a method for manufacturing such a pneumatic tire, for example, an air-permeable film is used as an inner liner, and the inner liner is attached to the outer periphery of the molding drum in a cylindrical shape. A green tire (unvulcanized tire) is produced by attaching a carcass ply on the inner liner and further attaching and inflating each tire member such as a belt, tread rubber, and sidewall rubber. A pneumatic tire is obtained by vulcanizing the green tire in a mold. In the example shown in FIG. 1, the air permeation-resistant film is provided on the inner surface side of the carcass ply. However, the air pressure from the inside of the tire can be prevented and the air pressure of the tire can be maintained, that is, the internal pressure. There is no particular limitation as long as it is provided as an air permeation suppression layer for holding. The air permeation-resistant film can be provided at various positions such as the outer surface side of the carcass ply.
　以下に、本発明を実施例に基づき具体的に説明するが、本発明はこれら実施例により限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
　［使用原材料］
　以下の実施例で使用した原材料の詳細は以下の通りである。 [Raw materials used]
Details of the raw materials used in the following examples are as follows.
　・ＩＩＲ：ブチルゴム、エクソンモービルケミカル社製「IIR268」
　・ＮＢＲ：ニトリルゴム、ＪＳＲ（株）製「JSR N230S」
　・ナイロン－Ａ：ナイロン６／６６共重合体、ＤＳＭ社製「Novamid 2010J」
　・ナイロン－Ｂ：ナイロン６／６６共重合体、ＤＳＭ社製「Novamid 2020J」
　・ナイロン－Ｃ：ナイロン６／６６共重合体、東レ（株）製「アミランCM6041XF」
　・ナイロン－Ｄ：５０質量部のナイロン－Ａのペレットと５０質量部のナイロン－Ｂのペレットをドライブレンドし、２２０℃に設定した２軸押出機（（株）プラスチック工学研究所）にて溶融混練しペレット化したもの（ナイロンブレンド５０／５０）
　・ナイロン－Ｅ：２５質量部のナイロン－Ａのペレットと７５質量部のナイロン－Ｂのペレットをドライブレンドし、２２０℃に設定した２軸押出機（（株）プラスチック工学研究所）にて溶融混練しペレット化したもの（ナイロンブレンド２５／７５）
　・ＥＶＯＨ－Ａ：エチレン－ビニルアルコール共重合体、日本合成化学工業（株）製「ソアノール3203RB」
　・ＥＶＯＨ－Ｂ：エチレン－ビニルアルコール共重合体、日本合成化学工業（株）製「ソアノール3212B」
　・相溶化剤：住友化学（株）製「ボンドファーストＥ」、エチレン－グリシジルメタクリレート共重合体
　・カーボンブラック：東海カーボン（株）製「シースト３」
　・亜鉛華：三井金属鉱業（株）製「亜鉛華３号」
　・ステアリン酸：花王（株）製「ルナックＳ－２０」
　・硫黄：鶴見化学工業（株）製「粉末硫黄」
　・加硫促進剤：住友化学（株）製「ソクシノールＣＺ」
　・架橋剤－１：アルキルフェノール－ホルムアルデヒド樹脂、田岡化学工業（株）製「タッキロール２０１」
　・架橋剤－２：臭素化アルキルフェノール－ホルムアルデヒド樹脂、田岡化学工業（株）製「タッキロール２０１－III」
　・リターダー：協和化学工業（株）製「キョウワマグ150」 IIR: Butyl rubber, “IIR268” manufactured by ExxonMobil Chemical
・ NBR: Nitrile rubber, "JSR N230S" manufactured by JSR Corporation
Nylon-A: Nylon 6/66 copolymer, “Novamid 2010J” manufactured by DSM
Nylon-B: Nylon 6/66 copolymer, “Novamid 2020J” manufactured by DSM
・ Nylon-C: nylon 6/66 copolymer, “Amilan CM6041XF” manufactured by Toray Industries, Inc.
・ Nylon-D: 50 parts by mass of Nylon-A pellets and 50 parts by mass of Nylon-B pellets were dry blended and melted in a twin-screw extruder set at 220 ° C (Plastics Engineering Laboratory Co., Ltd.) Kneaded and pelletized (nylon blend 50/50)
・ Nylon-E: 25 parts by mass of Nylon-A pellets and 75 parts by mass of Nylon-B pellets were dry blended and melted in a twin-screw extruder set at 220 ° C (Plastics Engineering Laboratory Co., Ltd.) Kneaded and pelletized (nylon blend 25/75)
EVOH-A: ethylene-vinyl alcohol copolymer, “Soarnol 3203RB” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
EVOH-B: ethylene-vinyl alcohol copolymer, “Soarnol 3212B” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
・ Compatibilizer: “Bond First E” manufactured by Sumitomo Chemical Co., Ltd., ethylene-glycidyl methacrylate copolymer ・ Carbon black: “Seast 3” manufactured by Tokai Carbon Co., Ltd.
・ Zinc flower: "Zinc flower 3" manufactured by Mitsui Mining & Smelting Co., Ltd.
・ Stearic acid: “Lunac S-20” manufactured by Kao Corporation
・ Sulfur: “Powder sulfur” manufactured by Tsurumi Chemical Co., Ltd.
・ Vulcanization accelerator: “Soxinol CZ” manufactured by Sumitomo Chemical Co., Ltd.
・ Crosslinking agent-1: Alkylphenol-formaldehyde resin, "Tactrol 201" manufactured by Taoka Chemical Co., Ltd.
・ Crosslinking agent-2: Brominated alkylphenol-formaldehyde resin, “Tactrol 201-III” manufactured by Taoka Chemical Co., Ltd.
・ Retarder: “Kyowa Mug 150” manufactured by Kyowa Chemical Industry Co., Ltd.
　［評価測定方法］
　以下の実施例での評価測定方法は以下の通りである。 [Evaluation measurement method]
The evaluation measurement methods in the following examples are as follows.
　・溶融粘度：キャピラリーレオメータ（（株）安田精機製作所製）を用い、シリンダー温度＝２３０℃、押出速度＝８００ｓ-1、ダイ径＝１ｍｍ、ダイ長＝１ｃｍでの溶融粘度を算出した。 Melt viscosity: A capillary rheometer (manufactured by Yasuda Seiki Seisakusho) was used to calculate the melt viscosity at a cylinder temperature = 230 ° C., an extrusion rate = 800 s −1 , a die diameter = 1 mm, and a die length = 1 cm.
　・加硫速度：ラボプラストミル（（株）東洋精機製作所製）にて混合したゴム組成物をレオメータ「MDR2000」（アルファテクノロジー社製）を用いて２００℃６０分で試験した。加硫速度は、最低粘度ＭＬから１分間のトルク上昇の傾きより求めた。 Vulcanization rate: The rubber composition mixed in a lab plast mill (manufactured by Toyo Seiki Seisakusho) was tested at 200 ° C. for 60 minutes using a rheometer “MDR2000” (manufactured by Alpha Technology Co., Ltd.). The vulcanization speed was determined from the slope of the torque increase for 1 minute from the minimum viscosity ML.
　・耐久性：ＪＩＳ　Ｋ６２７０を参考にして、耐空気透過性フィルムを配向方向に打ち抜き試験片（ダンベル状３号形試験片）を作製し、引張試験機を用いて、試験片をチャック間３ｃｍにて挟み込み、雰囲気温度４０℃にて、５Ｈｚの振動数で５０％の繰り返し伸張をかけた。試験片の数は１０個とし、５０％伸張を１００万回繰り返し、フィルムの破断が起こったものが３個以下の場合を合格「○」とし、４個以上の場合を不合格「×」とした。 -Durability: Refer to JIS K6270, punch out the air permeable film in the orientation direction to make a test piece (dumbbell-shaped No. 3 test piece), and use a tensile tester to make the test piece 3 cm between chucks. Then, the film was repeatedly stretched by 50% at a frequency of 5 Hz at an ambient temperature of 40 ° C. The number of test pieces is 10, 50% elongation is repeated 1,000,000 times, and when the number of breaks in the film is 3 or less, the pass is “◯”, and when it is 4 or more, it is “fail”. did.
　・耐空気透過性：ＪＩＳ　Ｋ７１２６－１「プラスチック－フィルム及びシート－ガス透過度試験方法－第１部：差圧法」に準じて、試験気体：空気、試験温度：８０℃にて空気透過係数を測定した。数値が小さいほど、空気が透過しにくく、耐空気透過性に優れる。 -Air permeability resistance: According to JIS K7126-1 "Plastics-Film and sheet-Gas permeability test method-Part 1: Differential pressure method" Test gas: Air, Test temperature: Air permeability coefficient at 80 ° C It was measured. The smaller the numerical value, the less air permeates and the better the air permeation resistance.
　［熱可塑性樹脂及びゴム成分の溶融粘度］
　熱可塑性樹脂及びゴム成分の２３０℃での溶融粘度、及び熱可塑性樹脂の空気透過係数は表１に示す通りであった。なお、熱可塑性樹脂の空気透過係数は、厚み０．２ｍｍに成形したフィルムについて測定した値である。 [Melt viscosity of thermoplastic resin and rubber components]
The melt viscosity at 230 ° C. of the thermoplastic resin and the rubber component and the air permeability coefficient of the thermoplastic resin were as shown in Table 1. In addition, the air permeability coefficient of a thermoplastic resin is the value measured about the film shape | molded by thickness 0.2mm.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　［耐空気透過性フィルムの作製・評価］
　下記表２～４に示す配合（質量部）に従い、熱可塑性樹脂と相溶化剤をドライブレンドしたものと、予めマスターバッチ化したゴム組成物のペレットとを、２２０℃に設定した２軸押出機（（株）プラスチック工学研究所製）にて溶融混練し、動的架橋体のペレットを作製した。得られた動的架橋体ペレットを単軸押出機にて幅１４ｃｍ×厚み０．２ｍｍに成形し、得られたフィルムの耐久性及び耐空気透過性を評価した。結果を表２～４に示す。なお、表２～４には、各耐空気透過性フィルムの作製に用いたゴム組成物の加硫速度も示す。 [Production and evaluation of air-permeable film]
In accordance with the composition (parts by mass) shown in Tables 2 to 4 below, a twin-screw extruder in which a thermoplastic resin and a compatibilizer are dry-blended and a rubber batch pellet preliminarily masterbatch set at 220 ° C. The mixture was melt-kneaded in (Plastics Engineering Laboratory Co., Ltd.) to produce dynamically crosslinked pellets. The obtained dynamic cross-linked pellets were formed into a width of 14 cm and a thickness of 0.2 mm using a single screw extruder, and the durability and air permeation resistance of the obtained film were evaluated. The results are shown in Tables 2-4. Tables 2 to 4 also show the vulcanization rate of the rubber composition used for the production of each air permeable resistant film.
　表２～４に示すように、ゴム組成物の溶融粘度よりも熱可塑性樹脂の溶融粘度が低い場合（比較例１～３、１７～１９及び２１～２３）、耐空気透過性フィルムの耐久性が低かった。また、ゴム組成物の溶融粘度よりも熱可塑性樹脂の溶融粘度が高い場合において、ゴム組成物の初期の加硫速度が０．７０ｄＮ・ｍ／分未満である場合、比較例９～１６のようにゴム組成物が連続相となってフィルム成形が困難となり、均一なフィルムは作製できなかった。そのため、比較例９～１６では耐久性と耐空気透過性は評価しなかった。また、比較例４～８，２０及び２４のように、均一なフィルムが成形できた場合でも、耐久性に劣っていた。 As shown in Tables 2 to 4, when the melt viscosity of the thermoplastic resin is lower than the melt viscosity of the rubber composition (Comparative Examples 1 to 3, 17 to 19, and 21 to 23), the durability of the air permeation-resistant film Was low. Further, when the melt viscosity of the thermoplastic resin is higher than the melt viscosity of the rubber composition, when the initial vulcanization rate of the rubber composition is less than 0.70 dN · m / min, as in Comparative Examples 9 to 16 In addition, the rubber composition became a continuous phase and film formation became difficult, and a uniform film could not be produced. Therefore, in Comparative Examples 9 to 16, durability and air permeation resistance were not evaluated. Further, even when a uniform film could be formed as in Comparative Examples 4 to 8, 20, and 24, the durability was poor.
　これに対し、ゴム組成物の溶融粘度よりも熱可塑性樹脂の溶融粘度が高く（η1／η2＞１）、かつゴム組成物の初期の加硫速度が０．７０ｄＮ・ｍ／分以上である実施例１～１３では、耐空気透過性に優れ、かつ高耐久性のフィルムが得られた。なお、実施例２のフィルムについて、ＳＰＭ（走査型プローブ顕微鏡）により位相像を確認したところ、熱可塑性樹脂を連続相とし、架橋（加硫）されたゴム組成物を分散相とする海島構造であり、比較例５よりも分散相が微細化されていた。 In contrast, the melt viscosity of the thermoplastic resin is higher than the melt viscosity of the rubber composition (η 1 / η 2 > 1), and the initial vulcanization rate of the rubber composition is 0.70 dN · m / min or more. In Examples 1 to 13, films having excellent air permeation resistance and high durability were obtained. In addition, about the film of Example 2, when the phase image was confirmed by SPM (scanning probe microscope), it is a sea-island structure which uses a thermoplastic resin as a continuous phase and a crosslinked (vulcanized) rubber composition as a dispersed phase. Yes, the dispersed phase was made finer than in Comparative Example 5.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　以上、いくつかの実施形態を説明したが、これらの実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら新規な実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。 Although some embodiments have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention.
１…空気入りタイヤ、６…カーカスプライ、８…インナーライナー 1 ... Pneumatic tire, 6 ... Carcass ply, 8 ... Inner liner

Claims (9)

  1. 　熱可塑性樹脂と、前記熱可塑性樹脂よりも２３０℃での溶融粘度が低くかつ２００℃での加硫速度が０．７０ｄＮ・ｍ／分以上であるゴム組成物と、を溶融混練し動的架橋させることにより、前記熱可塑性樹脂を連続相とし、前記ゴム組成物を分散相とした動的架橋体を得ることを含む、
    　耐空気透過性フィルムの製造方法。     Dynamic crosslinking by melt-kneading a thermoplastic resin and a rubber composition having a melt viscosity lower than that of the thermoplastic resin at 230 ° C. and a vulcanization rate at 200 ° C. of 0.70 dN · m / min or more. Including obtaining a dynamic cross-linked body having the thermoplastic resin as a continuous phase and the rubber composition as a dispersed phase,
    A method for producing an air permeation-resistant film.
  2. 　前記熱可塑性樹脂の２３０℃での溶融粘度η1と前記ゴム組成物の２３０℃での溶融粘度η2の比が、η1／η2≧１．２０を満足する、
    　請求項１記載の耐空気透過性フィルムの製造方法。     The ratio of the melt viscosity η 1 at 230 ° C. of the thermoplastic resin to the melt viscosity η 2 at 230 ° C. of the rubber composition satisfies η 1 / η 2 ≧ 1.20.
    The manufacturing method of the air-permeable-resistant film of Claim 1.
  3. 　前記熱可塑性樹脂が、脂肪族ポリアミド系樹脂及びポリビニル系樹脂からなる群から選択される少なくとも一種を含み、前記ゴム組成物が、ブチルゴム、ハロゲン化ブチルゴム、ニトリルゴム及び水素化ニトリルゴムからなる群から選択される少なくとも１種のゴム成分を含む、
    　請求項１又は２に記載の耐空気透過性フィルムの製造方法。     The thermoplastic resin includes at least one selected from the group consisting of an aliphatic polyamide resin and a polyvinyl resin, and the rubber composition is selected from the group consisting of butyl rubber, halogenated butyl rubber, nitrile rubber, and hydrogenated nitrile rubber. Including at least one rubber component selected,
    The manufacturing method of the air-permeable-resistant film of Claim 1 or 2.
  4. 　前記ゴム組成物が架橋剤を含み、前記架橋剤がフェノール樹脂を含む、
    　請求項１～３のいずれか１項に記載の耐空気透過性フィルムの製造方法。     The rubber composition contains a crosslinking agent, and the crosslinking agent contains a phenolic resin;
    The method for producing an air permeable resistant film according to any one of claims 1 to 3.
  5. 　前記架橋剤がハロゲン化フェノール樹脂を含む、
    　請求項４に記載の耐空気透過性フィルムの製造方法。     The crosslinking agent comprises a halogenated phenol resin,
    The manufacturing method of the air-permeable-resistant film of Claim 4.
  6. 　前記ゴム組成物は、充填剤を含まないか、又は、充填剤をゴム成分１００質量部に対して２０質量部以下含む、
    　請求項１～５のいずれか１項に記載の耐空気透過性フィルムの製造方法。     The rubber composition does not contain a filler or contains a filler in an amount of 20 parts by mass or less based on 100 parts by mass of the rubber component.
    The method for producing an air-permeable-resistant film according to any one of claims 1 to 5.
  7. 　前記ゴム組成物の２００℃での加硫速度が０．８０ｄＮ・ｍ／分以上である、
    　請求項１～６のいずれか１項に記載の耐空気透過性フィルムの製造方法。     The rubber composition has a vulcanization rate at 200 ° C. of 0.80 dN · m / min or more.
    The method for producing an air permeable resistant film according to any one of claims 1 to 6.
  8. 　前記熱可塑性樹脂及び前記ゴム組成物とともに、相溶化剤を加えて溶融混練する、
    　請求項１～７のいずれか１項に記載の耐空気透過性フィルムの製造方法。     Along with the thermoplastic resin and the rubber composition, a compatibilizer is added and melt kneaded.
    The method for producing an air-permeable-resistant film according to any one of claims 1 to 7.
  9. 　請求項１～８のいずれか１項に記載の製造方法により得られた耐空気透過性フィルムを、インナーライナー又はその他の空気透過抑制層として用いる、空気入りタイヤの製造方法。 A method for producing a pneumatic tire, wherein the air permeable resistant film obtained by the production method according to any one of claims 1 to 8 is used as an inner liner or other air permeation suppression layer.
PCT/JP2016/003628 2015-12-22 2016-08-05 Air-impermeable film and method for producing pneumatic tire WO2017110012A1 (en)

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WO2006057333A1 (en) * 2004-11-26 2006-06-01 Daikin Industries, Ltd. Thermoplastic polymer composition and process for production thereof
WO2007100157A1 (en) * 2006-03-03 2007-09-07 The Yokohama Rubber Co., Ltd. Elastomer composition, method for producing same, and pneumatic tire using same
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JP2013237760A (en) * 2012-05-14 2013-11-28 Tokyo Univ Of Agriculture & Technology Method of manufacturing rubber-polyolefin composite

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WO2006057333A1 (en) * 2004-11-26 2006-06-01 Daikin Industries, Ltd. Thermoplastic polymer composition and process for production thereof
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JP2013237760A (en) * 2012-05-14 2013-11-28 Tokyo Univ Of Agriculture & Technology Method of manufacturing rubber-polyolefin composite

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