WO2018230097A1 - タイヤ用金属樹脂複合部材及びタイヤ - Google Patents

タイヤ用金属樹脂複合部材及びタイヤ Download PDF

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Publication number
WO2018230097A1
WO2018230097A1 PCT/JP2018/013021 JP2018013021W WO2018230097A1 WO 2018230097 A1 WO2018230097 A1 WO 2018230097A1 JP 2018013021 W JP2018013021 W JP 2018013021W WO 2018230097 A1 WO2018230097 A1 WO 2018230097A1
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WIPO (PCT)
Prior art keywords
resin
tire
metal
polyester
composite member
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/013021
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English (en)
French (fr)
Japanese (ja)
Inventor
壮一 京
鈴木　隆弘
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bridgestone Corp
Original Assignee
Bridgestone Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bridgestone Corp filed Critical Bridgestone Corp
Priority to CN201880039791.5A priority Critical patent/CN110770037A/zh
Priority to EP18816962.7A priority patent/EP3640045A4/en
Publication of WO2018230097A1 publication Critical patent/WO2018230097A1/ja
Priority to US16/699,067 priority patent/US20200238763A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
    • B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
    • B60C9/22—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre
    • B60C9/2204—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre obtained by circumferentially narrow strip winding
    • 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
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • 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
    • B60C5/01—Inflatable pneumatic tyres or inner tubes without substantial cord reinforcement, e.g. cordless tyres, cast tyres
    • 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
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
    • 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
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
    • B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
    • B60C9/22—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre
    • 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
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C2001/0066—Compositions of the belt layers
    • 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
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
    • B60C2009/0021—Coating rubbers for steel cords
    • 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
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
    • B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
    • B60C9/22—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre
    • B60C2009/2238—Physical properties or dimensions of the ply coating rubber
    • 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
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
    • B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
    • B60C9/22—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre
    • B60C2009/2238—Physical properties or dimensions of the ply coating rubber
    • B60C2009/2242—Modulus; Hardness; Loss modulus or "tangens delta"

Definitions

  • the present invention relates to a metal resin composite member for a tire and a tire.
  • Patent Document 1 proposes a tire having a tire skeleton formed using a polyester-based thermoplastic resin as a resin material.
  • Patent Document 1 describes that a coated portion of a metal cord (reinforcing member) covered with a thermoplastic resin of the same type as a thermoplastic resin forming a tire frame body is melted by heat and bonded to the tire frame body. ing. By using the same kind of thermoplastic resin for the reinforcing member and the tire frame body, good bonding properties between the tire frame body and the reinforcing cord are realized.
  • a metal-resin composite member for a tire that is excellent in bondability with a tire skeleton including a thermoplastic resin and that can improve the cornering power of the tire, and a tire including the metal-resin composite member for a tire. It is rare.
  • a metal cord and a resin layer are provided, and the resin layer is formed from a resin mixture including a polyester-based thermoplastic elastomer and an amorphous resin having a glass transition temperature (Tg) of 40 ° C. or more and having an ester bond.
  • Tg glass transition temperature
  • the metal resin composite member for tires which is excellent in bondability with the tire frame body containing a thermoplastic resin, and can improve the cornering power of a tire, and a tire provided with this metal resin composite member for tires are provided. Is done.
  • the “resin” is a concept including a thermoplastic resin (including a thermoplastic elastomer) and a thermosetting resin, and does not include a vulcanized rubber.
  • thermoplastic elastomer means a crystalline polymer having a high melting point hard segment or a high cohesion hard segment, and an amorphous polymer having a low glass transition temperature soft segment. It means a polymer compound having a rubber-like elasticity, which becomes a relatively hard and strong state when cooled, and which softens and flows as the temperature rises.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the term “process” includes not only an independent process but also a process that can be clearly distinguished from other processes as long as the purpose is achieved. include.
  • a metal resin composite member for tires of the present disclosure (hereinafter also referred to as a metal resin composite member) includes a metal cord and a resin layer, and the resin layer has a polyester-based thermoplastic elastomer and a glass transition temperature (Tg) of 40. And a non-crystalline resin having an ester bond (hereinafter also referred to as a specific non-crystalline resin), and the content of the non-crystalline resin is 50% by mass of the resin mixture. It is as follows.
  • a metal resin composite member comprising a resin layer formed from a resin mixture containing a polyester-based thermoplastic elastomer and a specific amorphous resin is a resin formed only from a polyester-based thermoplastic elastomer. It was found that the effect of improving the cornering power of a tire provided with the layer was superior to that of a metal resin composite member for a tire provided with a layer. This is presumably because the rigidity of the resin mixture is increased by blending an amorphous resin having a Tg of 40 ° C. or higher with a polyester-based thermoplastic elastomer.
  • the metal resin composite member having the above-described structure is better for the tire frame than the case of increasing the rigidity of the polyester-based thermoplastic elastomer itself (for example, changing the polyester-based thermoplastic elastomer to one having higher rigidity). It was found that the bondability was maintained. The reason for this is not always clear, but when an amorphous resin that does not have a clear melting point is blended with a polyester-based thermoplastic elastomer to increase its rigidity, the resin is better than when the type of polyester-based thermoplastic elastomer is changed. This is presumably because the melting point of the mixture is less likely to fluctuate and the deviation from the melting point of the resin material forming the tire frame body is less likely to occur. Furthermore, by setting the content of the amorphous resin to 50% by mass or less of the resin mixture, it is considered that the affinity with the resin material forming the tire skeleton is maintained and the deterioration of the bondability is suppressed.
  • the metal resin composite member may be disposed on the outer peripheral portion (crown portion) of the tire frame body, for example.
  • the method for disposing the metal resin composite member on the outer periphery of the tire frame body is not particularly limited.
  • the metal resin composite member may be wound around the outer peripheral portion of the tire frame body by a method as described in Examples described later. At this time, it is preferable to melt the resin layer of the metal-resin composite member and the crown portion of the tire frame body by heating, thereby improving the bondability between them.
  • the metal resin composite member may comprise only a metal cord and a resin layer, or may include a member other than the metal cord and the resin layer.
  • an adhesive layer may be provided between the metal cord and the resin layer.
  • the cross-sectional shape of the metal resin composite member is not particularly limited. For example, a circle, a rectangle, etc. are mentioned. In view of ease of arrangement in the crown portion of the tire skeleton, a quadrangular shape is preferable. Further, the metal resin composite member may have one metal cord or may have a plurality of (for example, two) metal cords.
  • the metal cord is not particularly limited, and a metal cord that can be generally used for tire reinforcement can be used.
  • the metal cord include a monofilament (single wire) made of a single metal cord, a multifilament (twisted wire) in which a plurality of metal cords are twisted, and the like.
  • the cross-sectional shape, diameter, etc. of the metal cord are not particularly limited and can be selected according to the use of the composite member.
  • the material of the metal cord is not particularly limited, and examples thereof include steel.
  • the number of the plurality of cords is not particularly limited. For example, it can be selected from the range of 2 to 10 and is preferably 5 to 9.
  • the diameter of the metal cord is preferably 0.2 mm to 2 mm, and more preferably 0.8 mm to 1.6 mm.
  • the measured value of the diameter of the metal cord is the diameter of the cross section of the metal cord (the distance between two points arbitrarily selected on the contour line of the cross section of the metal cord is the maximum). (Distance between the two points).
  • the metal cord is composed of a plurality of metal cords, the diameter of the smallest circle among the circles including all the cross-sections of the plurality of metal cords observed in the cross-section of the metal cord is used.
  • the tensile elastic modulus of the metal cord itself (hereinafter, unless otherwise specified, “elastic modulus” means a tensile elastic modulus) is usually about 100,000 to 300,000 MPa, and 120,000 to 270000 MPa. Preferably, it is 150,000 MPa to 250,000 MPa.
  • the tensile elastic modulus of the metal cord is calculated from the slope of a stress-strain curve drawn on a tensile tester using a ZWICK chuck.
  • the breaking elongation (tensile breaking elongation) of the metal cord itself is usually about 0.1% to 15%, preferably 1% to 15%, more preferably 1% to 10%.
  • the tensile elongation at break of the metal cord can be obtained from the strain by drawing a stress-strain curve using a ZWICK chuck with a tensile tester.
  • the resin layer is formed from a resin mixture containing a polyester-based thermoplastic elastomer and a specific amorphous resin, and the content of the specific amorphous resin is 50% by mass or less of the resin mixture.
  • the content of the specific amorphous resin in the resin mixture is 50% by mass or less, preferably 40% by mass or less, and preferably 30% by mass or less. More preferred.
  • the lower limit of the content of the specific amorphous resin in the resin mixture is not particularly limited, but is preferably 10% by mass or more and more preferably 20% by mass or more from the viewpoint of sufficiently obtaining the effect of increasing rigidity. Preferably, it is more preferably 30% by mass or more.
  • the content of the specific amorphous resin in the resin mixture can be examined by, for example, a nuclear magnetic resonance (NMR) method.
  • NMR nuclear magnetic resonance
  • the method for confirming whether or not the resin mixture contains a polyester-based thermoplastic elastomer and a specific amorphous resin is not particularly limited. For example, it can be performed by a technique such as thermal analysis or observation of a cross section of the resin mixture.
  • the melting point of the resin mixture is usually about 100 ° C. to 350 ° C., but is preferably about 100 ° C. to 250 ° C., more preferably 120 ° C. to 250 ° C. from the viewpoint of tire durability and productivity.
  • the melting point of the resin mixture is a value measured according to JIS K 7121: 2012 by differential scanning calorimetry (DSC). The measurement can be performed, for example, using “DSC Q100” manufactured by TA Instruments Co., Ltd. at a sweep rate of 10 ° C./min.
  • the melting point of the component having the largest mass ratio in the resin mixture is defined as the melting point of the resin mixture. The same applies to the melting point of the resin material forming the tire skeleton described later.
  • the resin mixture may contain components other than the resin.
  • components other than the resin include various fillers (for example, silica, calcium carbonate, clay, etc.), antioxidants, oils, plasticizers, color formers, weathering agents, and the like.
  • the total content rate is 10 mass% or less of the whole resin mixture, and it is more preferable that it is 5 mass% or less.
  • the elastic modulus of the resin layer is preferably 400 MPa or more. On the other hand, from the viewpoint of durability, it is preferably 1500 MPa or less.
  • the elastic modulus of the resin layer is a value obtained by measuring the tensile elastic modulus of the resin composition in accordance with JIS K 7113: 1995.
  • the thickness of the resin layer is not particularly limited. From the viewpoint of water barrier properties, it is preferable that the minimum thickness of the resin layer (the thickness of the portion having the smallest thickness) is 1.3 mm or more. From the viewpoint of durability, it is preferable that the maximum thickness of the resin layer (the thickness of the portion with the largest thickness) is 5.0 mm or less.
  • the “amorphous resin” means a thermoplastic resin that has a very low crystallinity or cannot be crystallized.
  • the specific amorphous resin contained in the resin mixture may be one type or two or more types.
  • the Tg of the specific amorphous resin is 40 ° C. or higher, preferably 60 ° C. or higher, and more preferably 80 ° C. or higher.
  • the Tg of the specific amorphous resin is a value measured by DSC in accordance with JIS K 6240: 2011. Specifically, the temperature at the intersection of the original baseline at the DSC measurement and the tangent at the inflection point is defined as Tg.
  • the measurement can be performed, for example, using “DSC Q100” manufactured by TA Instruments Co., Ltd. at a sweep rate of 10 ° C./min.
  • amorphous resin those having an ester bond are used from the viewpoint of affinity with the polyester-based thermoplastic elastomer.
  • the amorphous resin having an ester bond include polyester-based thermoplastic resins, polycarbonate-based thermoplastic resins, and polyurethane-based thermoplastic resins.
  • amorphous polyester resin Commercial products of specified amorphous resins include Toyobo's amorphous polyester resin "Byron” series, Mitsubishi Engineering Plastics' amorphous polycarbonate resin “Novalex” series, Mitsubishi Gas Chemical Co., Ltd. ) Amorphous polyester resin “ALTERSTER” series and the like.
  • polyester thermoplastic elastomer examples include a high molecular compound in which at least a polyester forms a crystalline hard segment having a high melting point, and another polymer forms an amorphous soft segment having a low glass transition temperature.
  • the polyester-based thermoplastic elastomer contained in the resin mixture may be one type or two or more types.
  • the content of the polyester-based thermoplastic elastomer in the resin mixture is preferably more than 50% by mass, more preferably 60% by mass or more, and still more preferably 70% by mass or more.
  • Aromatic polyester is mentioned as polyester which forms the hard segment of a polyester-type thermoplastic elastomer.
  • the aromatic polyester can be formed, for example, from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol.
  • the aromatic polyester is preferably polybutylene terephthalate derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol, and further, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid Dicarboxylic acid components such as naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or ester-forming derivatives thereof, and a molecular weight of 300 or less Diols such as aliphatic diols such as ethylene glycol, trimethylene glyco
  • polyester forming the hard segment examples include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like, and polybutylene terephthalate is preferable.
  • Examples of the polymer forming the soft segment include aliphatic polyesters and aliphatic polyethers.
  • Aliphatic polyethers include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, poly (propylene oxide) And ethylene oxide addition polymer of glycol, and a copolymer of ethylene oxide and tetrahydrofuran.
  • Examples of the aliphatic polyester include poly ( ⁇ -caprolactone), polyenantlactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate.
  • poly (tetramethylene oxide) glycol poly (propylene oxide) glycol are polymers that form soft segments from the viewpoint of the elastic properties of the resulting polyester block copolymer.
  • Preferred are ethylene oxide adducts, poly ( ⁇ -caprolactone), polybutylene adipate, polyethylene adipate and the like.
  • the number average molecular weight of the polymer forming the soft segment is preferably 300 to 6000 from the viewpoint of toughness and low temperature flexibility. Furthermore, the mass ratio (x: y) between the hard segment (x) and the soft segment (y) is preferably 99: 1 to 20:80, more preferably 98: 2 to 30:70, from the viewpoint of moldability. .
  • the hard segment is at least one selected from the group consisting of polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polybutylene naphthalate (PBN), and polyethylene naphthalate (PEN).
  • PBT polybutylene terephthalate
  • PET polyethylene terephthalate
  • PBN polybutylene naphthalate
  • PEN polyethylene naphthalate
  • PTMG polytetramethylene glycol
  • polyester-based thermoplastic elastomers examples include “Hytrel” series (for example, 3046, 5557, 6347, 4047, 4767, etc.) manufactured by Toray DuPont Co., Ltd., and “Perprene” series manufactured by Toyobo Co., Ltd. (For example, P30B, P40B, P40H, P55B, P70B, P150B, P280B, P450B, P150M, S1001, S2001, S5001, S6001, S9001, etc.) can be used.
  • Hytrel for example, 3046, 5557, 6347, 4047, 4767, etc.
  • Perprene manufactured by Toyobo Co., Ltd.
  • the resin mixture may include a resin (other resin) other than the polyester-based thermoplastic elastomer and the specific amorphous resin.
  • the total proportion of the polyester-based thermoplastic elastomer and the specific amorphous resin in the entire resin is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. It is more preferable.
  • the resin mixture includes other resins
  • the “polyester-based thermoplastic resin” here does not include the above-described polyester-based thermoplastic elastomer.
  • both a resin composed only of a structural unit corresponding to polyester and a resin having a structural unit corresponding to polyester of 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more of the whole are included. .
  • the polyester thermoplastic resin B is preferably polybutylene terephthalate, polyethylene terephthalate, polybutylene naphthalate, polyethylene naphthalate or the like, and polybutylene terephthalate is More preferred.
  • polyester-based thermoplastic resins examples include “Duranex” series (for example, 201AC, 2000, 2002, etc.) manufactured by Polyplastics Co., Ltd., and “Novaduran” series (manufactured by Mitsubishi Engineering Plastics Co., Ltd.). For example, 5010R5, 5010R3-2, etc.), “Toraycon” series (for example, 1401X06, 1401X31, etc.) manufactured by Toray Industries, Inc. can be used.
  • the metal resin composite member may include an adhesive layer between the metal cord and the resin layer.
  • the material for the adhesive layer is not particularly limited.
  • a thermoplastic resin a thermoplastic resin elastomer is included
  • the thermoplastic resin that forms the adhesive layer may be one type or two or more types.
  • the thermoplastic resin forming the adhesive layer is a thermoplastic resin having the same type of structural unit as the hard segment of the polyester-based thermoplastic resin elastomer contained in the resin mixture forming the resin layer. It is preferable that For example, a polyester-based thermoplastic elastomer or a polyester-based thermoplastic resin is preferable.
  • thermoplastic resin forming the adhesive layer is preferably modified with a functional group, and more preferably acid-modified.
  • a tire according to the present disclosure includes an annular tire frame and the above-described metal-resin composite member disposed on an outer peripheral portion of the tire frame, and the tire frame includes a resin material including a polyester-based thermoplastic resin. Formed from.
  • the resin material forming the tire frame includes at least a polyester-based thermoplastic elastomer as a polyester-based thermoplastic resin.
  • the polyester-based thermoplastic elastomer contained in the resin mixture forming the resin layer and the polyester-based contained in the resin material forming the tire skeleton The closer the structure of the thermoplastic resin is, the better.
  • the hard segment of the polyester thermoplastic elastomer contained in the resin mixture forming the resin layer is polybutylene terephthalate
  • the hard segment is A thermoplastic elastomer such as polybutylene terephthalate or polybutylene naphthalate is preferable, and a thermoplastic elastomer whose hard segment is polybutylene terephthalate is more preferable.
  • the melting point of the resin material is not particularly limited, and is usually 100 ° C to 350 ° C. From the viewpoint of tire durability and productivity, it is preferably selected from 100 ° C. to 250 ° C., more preferably from 120 ° C. to 250 ° C., respectively.
  • the melting point difference ( ⁇ Tm) between the resin mixture forming the resin layer of the metal resin composite member and the resin material forming the tire frame body is within 6 ° C. It is preferably 3 ° C. or less.
  • the difference in melting point is obtained by measuring the melting point a of the resin mixture forming the resin layer of the metal resin composite member and the melting point b of the resin used for forming the tire frame by DSC (ab). Value (° C).
  • the melting point of the resin mixture forming the resin layer of the metal resin composite member or the melting point of the resin material forming the tire frame body may be higher.
  • the melting point of the resin mixture is a value measured by DSC.
  • the resin material forming the tire skeleton may include a resin other than the polyester-based thermoplastic resin.
  • the ratio of the polyester-based thermoplastic resin in the entire resin is preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more.
  • thermoplastic elastomers such as polyamide-based thermoplastic elastomer, olefin-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, and polystyrene-based thermoplastic elastomer. Is mentioned.
  • thermoplastic resins such as polyamide-based thermoplastic resins, olefin-based thermoplastic resins, polyurethane-based thermoplastic resins, and polystyrene-based thermoplastic resins composed of structural units corresponding to the hard segments of these thermoplastic elastomers can be mentioned.
  • the resin material may contain other components other than the resin.
  • other components include various fillers (for example, silica, calcium carbonate, clay, etc.), antioxidants, oils, plasticizers, color formers, weathering agents, and the like.
  • the total content is preferably 10% by mass or less, and more preferably 5% by mass or less of the entire resin material.
  • the tensile modulus of elasticity defined in JIS K7113: 1995 of the resin material is preferably 50 MPa to 1000 MPa, more preferably 50 MPa to 800 MPa, and further preferably 50 MPa to 700 MPa.
  • the rim can be assembled efficiently while maintaining the shape of the tire frame.
  • the tensile strength specified in JIS K7113 (1995) of the resin material is usually about 15 MPa to 70 MPa, preferably 17 MPa to 60 MPa, and more preferably 20 MPa to 55 MPa.
  • the tensile yield strength specified in JIS K7113 (1995) of the resin material is preferably 5 MPa or more, more preferably 5 MPa to 20 MPa, and even more preferably 5 MPa to 17 MPa.
  • the resin material can withstand deformation against a load applied to the tire during traveling.
  • the tensile yield elongation specified in JIS K7113 (1995) of the resin material is preferably 10% or more, more preferably 10% to 70%, and further preferably 15% to 60%.
  • the tensile yield elongation of the resin material is 10% or more, the elastic region is large and the rim assembly property can be improved.
  • the tensile elongation at break specified in JIS K7113 (1995) of the resin material is preferably 50% or more, more preferably 100% or more, still more preferably 150% or more, and most preferably 200% or more.
  • the rim assemblability is good and it is difficult to break against a collision.
  • the deflection temperature under load (0.45 MPa load) specified in ISO 75-2 or ASTM D648 of the resin material is preferably 50 ° C. or higher, more preferably 50 ° C. to 150 ° C., and still more preferably 50 ° C. to 130 ° C.
  • the deflection temperature under load of the resin material is 50 ° C. or higher, deformation of the tire skeleton can be suppressed even when vulcanization is performed in the manufacture of the tire.
  • the Martens hardness (d1) of the tire frame body When the metal resin composite member has an adhesive layer between the metal cord and the resin layer, the Martens hardness (d1) of the tire frame body, the Martens hardness (d2) of the resin layer, and the Martens hardness (d3) of the adhesive layer, It is preferable to satisfy the relationship of d1 ⁇ d2 ⁇ d3.
  • the Martens hardness of the resin layer By setting the Martens hardness of the resin layer to be smaller than the Martens hardness of the adhesive layer and greater than or equal to the Martens hardness of the tire frame body, a rigidity step between the resin material constituting the tire frame body and the metal member Is effectively mitigated. As a result, the durability of the tire can be further improved.
  • FIG. 1A is a perspective view showing a cross section of a part of the tire 10 of the present embodiment.
  • FIG. 1B is a cross-sectional view of a bead portion when the tire 10 of the present embodiment is mounted on a rim.
  • the tire 10 has substantially the same cross-sectional shape as a conventional rubber pneumatic tire.
  • the tire 10 includes a pair of bead portions 12 that contact the bead seat 21 and the rim flange 22 of the rim 20 shown in FIG. 1B, and side portions 14 that extend outward from the bead portion 12 in the tire radial direction.
  • a tire case 17 is provided that includes a crown portion 16 (outer peripheral portion) that connects an outer end in the tire radial direction of one side portion 14 and an outer end in the tire radial direction of the other side portion 14.
  • the tire case 17 corresponds to the tire skeleton described above, and is formed from the resin material described above. In the present embodiment, the tire case 17 is entirely formed of the resin material described above. However, the present disclosure is not limited to this configuration, and the tire case 17 is similar to a conventional general rubber pneumatic tire. Different resin materials may be used for each portion (side portion 14, crown portion 16, bead portion 12, etc.). Further, in order to reinforce each part of the tire case 17, a reinforcing material (polymer material, metal fiber, cord, nonwoven fabric, woven fabric, or the like) may be embedded and disposed.
  • a reinforcing material polymer material, metal fiber, cord, nonwoven fabric, woven fabric, or the like
  • the tire case 17 is made of two tire case halves (tire frame pieces) having a shape in which the tread width is equally divided along the circumferential direction of the tire case 17, and these are joined at the equator portion of the tire. Formed.
  • the tire case 17 is not limited to the one formed by joining two members, and may be formed by joining three or more members.
  • the tire case half can be produced by a method such as vacuum forming, pressure forming, injection molding, melt casting, or the like. For this reason, it is not necessary to perform vulcanization compared to the case where the tire case is molded with rubber as in the prior art, the manufacturing process can be greatly simplified, and the molding time can be omitted.
  • an annular bead core 18 is embedded in the bead portion 12 shown in FIG. 1B in the same manner as a conventional general pneumatic tire.
  • a steel cord is used as the bead core 18, but an organic fiber cord, a resin layered organic fiber cord, a hard resin cord, or the like may be used.
  • the bead core 18 can be omitted if the rigidity of the bead portion 12 is ensured and there is no problem in fitting with the rim 20.
  • the portion of the bead portion 12 that comes into contact with the rim 20 and at least the portion that comes into contact with the rim flange 22 of the rim 20 are made of a circle made of a material having a better sealing property than the resin material constituting the tire case 17.
  • An annular seal layer 24 is formed.
  • the seal layer 24 may also be formed in a portion where the tire case 17 (bead portion 12) and the bead sheet 21 are in contact with each other. Note that the seal layer 24 may be omitted as long as the sealing property between the rim 20 and the resin material constituting the tire case 17 can be secured.
  • the material having better sealing performance than the resin material constituting the tire case 17 include softer materials than the resin material constituting the tire case 17, such as rubber, thermoplastic resin and thermoplastic elastomer softer than the resin material. Can be mentioned.
  • a reinforcing cord 26 corresponding to a metal resin composite member is wound around the crown portion 16 in the circumferential direction of the tire case 17.
  • the reinforcing cord 26 is wound spirally in a state in which at least a part thereof is embedded in the crown portion 16 in a cross-sectional view along the axial direction of the tire case 17, thereby forming a reinforcing cord layer 28.
  • the reinforcing cord 26 is in a state where a metal member 26A such as a steel cord is covered with a coating resin (resin mixture) 27 (covered cord member).
  • the reinforcing cord 26 is joined at a contact portion with the crown portion 16 by a method such as welding or bonding with an adhesive.
  • the reinforcing cord 26 has a substantially trapezoidal cross section.
  • the upper surface (surface on the outer side in the tire radial direction) of the reinforcing cord 26 is denoted by reference numeral 26U
  • the lower surface (surface on the inner side in the tire radial direction) is denoted by reference numeral 26D.
  • the cross-sectional shape of the reinforcing cord 26 is a substantially trapezoidal shape, but the present disclosure is not limited to this configuration, and the cross-sectional shape is from the lower surface 26D side (the tire radial direction inner side) to the upper surface 26U side. Any shape may be used as long as it is a shape excluding a shape that becomes wider toward the outer side in the tire radial direction.
  • the reinforcing cords 26 are arranged at intervals in the circumferential direction, a gap 28A is formed between adjacent reinforcing cords 26.
  • the outer peripheral surface of the reinforcing cord layer 28 has a shape with irregularities, and the outer peripheral surface 17S of the tire case 17 in which the reinforcing cord layer 28 constitutes the outer peripheral portion also has an irregular shape.
  • a fine roughened unevenness 96 is formed on the outer peripheral surface 17S (including the unevenness) of the tire case 17, and a cushion rubber 29 is bonded thereon via a bonding agent.
  • the cushion rubber 29 flows into the contact surface with the reinforcing cord 26 so as to fill the rough unevenness 96.
  • the above-mentioned tread 30 is joined on the cushion rubber 29 (the tire outer peripheral surface side).
  • the tread 30 is formed with a tread pattern (not shown) including a plurality of grooves on the ground contact surface with the road surface in the same manner as a conventional rubber pneumatic tire.
  • the tire manufacturing method of the present embodiment is not particularly limited. For example, you may manufacture by implementing the following tire case shaping
  • the joining portion of the tire case half is heated using the joining mold, but the present disclosure is not limited to this.
  • the joining portion may be heated by a separately provided high-frequency heater or the like.
  • the tire case halves may be joined by being softened or melted by irradiation with hot air, infrared rays, or the like, and pressurized by a joining mold.
  • FIG. 3 is an explanatory diagram for explaining the operation of embedding the reinforcing cord 26 in the crown portion of the tire case 17 using a cord heating device and rollers.
  • the cord supply device 56 is disposed on the reel 58 around which the reinforcing cord 26 is wound, the cord heating device 59 disposed on the downstream side of the reel 58 in the cord transport direction, and the downstream side of the reinforcing cord 26 in the transport direction.
  • the first roller 60, the first cylinder device 62 that moves the first roller 60 in the direction of contacting and separating from the outer peripheral surface of the tire, and the downstream side in the conveying direction of the reinforcing cord 26 of the first roller 60 A second roller 64, and a second cylinder device 66 that moves the second roller 64 in a direction in which the second roller 64 comes into contact with and separates from the tire outer peripheral surface.
  • the second roller 64 can be used as a metal cooling roller.
  • the surface of the first roller 60 or the second roller 64 is subjected to a treatment (for example, a fluororesin coating) for suppressing adhesion of the molten or softened coating resin 27.
  • a treatment for example, a fluororesin coating
  • the roller itself may be formed of a material to which the coating resin 27 is difficult to adhere.
  • the cord supply device 56 includes the two rollers of the first roller 60 or the second roller 64, but may include only one of the rollers.
  • the cord heating device 59 includes a heater 70 and a fan 72 that generate hot air. Further, the cord heating device 59 includes a heating box 74 through which the reinforcing cord 26 passes through an internal space in which hot air is supplied, and a discharge port 76 for discharging the heated reinforcing cord 26.
  • the temperature of the heater 70 of the cord heating device 59 is raised, and the ambient air heated by the heater 70 is sent to the heating box 74 by the wind generated by the rotation of the fan 72.
  • the reinforcing cord 26 unwound from the reel 58 is sent and heated into a heating box 74 in which the internal space is heated with hot air.
  • the heating temperature is set to a temperature at which the covering resin 27 of the reinforcing cord 26 is melted or softened.
  • the heated reinforcing cord 26 passes through the discharge port 76 and is wound spirally around the outer peripheral surface of the crown portion 16 of the tire case 17 rotating in the direction of arrow R in FIG. At this time, the lower surface 26 ⁇ / b> D of the reinforcing cord 26 contacts the outer peripheral surface of the crown portion 16. Then, the coating resin 27 melted or softened by heating spreads on the outer peripheral surface of the crown portion 16, and the reinforcing cord 26 is welded to the outer peripheral surface of the crown portion 16. Thereby, the joint strength between the crown portion 16 and the reinforcing cord 26 is improved.
  • the reinforcing cord 26 is joined to the outer peripheral surface of the crown portion 16 as described above, but joining may be performed by other methods. For example, joining may be performed so that a part or the whole of the reinforcing cord 26 is embedded in the crown portion 16.
  • a blasting device (not shown) emits a projection material at a high speed toward the outer peripheral surface 17S while rotating the tire case 17 side toward the outer peripheral surface 17S of the tire case 17.
  • the ejected projection material collides with the outer peripheral surface 17S, and fine roughening unevenness 96 having an arithmetic average roughness Ra of 0.05 mm or more is formed on the outer peripheral surface 17S.
  • the outer peripheral surface 17S becomes hydrophilic, and the wettability of the bonding agent described later is improved.
  • a bonding agent for bonding the cushion rubber 29 is applied to the outer peripheral surface 17S of the tire case 17 subjected to the roughening treatment.
  • the bonding agent is not particularly limited, and a triazine thiol adhesive, a chlorinated rubber adhesive, a phenolic resin adhesive, an isocyanate adhesive, a halogenated rubber adhesive, a rubber adhesive, and the like can be used. It is preferable that the cushion rubber 29 reacts at a vulcanizable temperature (90 ° C. to 140 ° C.).
  • the unvulcanized cushion rubber 29 is wound around the outer peripheral surface 17S to which the bonding agent has been applied for one round, and a bonding agent such as a rubber cement composition is applied onto the cushion rubber 29.
  • a bonding agent such as a rubber cement composition
  • the vulcanized or semi-cured tread rubber 30A is wound on the cushion rubber 29 to which the bonding agent has been applied for one round to form a raw tire case.
  • the raw tire case is accommodated in a vulcanizing can or mold and vulcanized.
  • the unvulcanized cushion rubber 29 flows into the roughened irregularities 96 formed on the outer peripheral surface 17S of the tire case 17 by the roughening treatment.
  • the anchor rubber is exerted by the cushion rubber 29 flowing into the roughened unevenness 96, and the bonding strength between the tire case 17 and the cushion rubber 29 is improved. That is, the bonding strength between the tire case 17 and the tread 30 is improved via the cushion rubber 29.
  • a resin comprising a metal cord and a resin layer, wherein the resin layer includes a polyester-based thermoplastic elastomer and an amorphous resin having an ester bond and a glass transition temperature (Tg) of 40 ° C. or higher.
  • a metal resin composite member for a tire formed from a mixture and having a content of the amorphous resin of 50% by mass or less of the resin mixture.
  • the amorphous resin is at least one selected from the group consisting of a polyester-based thermoplastic resin and a polycarbonate-based thermoplastic resin.
  • ⁇ 3> The metal resin composite member for tire according to ⁇ 1> or ⁇ 2>, wherein the elastic modulus of the resin layer is 400 MPa or more.
  • ⁇ 4> An annular tire skeleton, and the metal resin composite member for a tire according to any one of ⁇ 1> to ⁇ 3> disposed on an outer periphery of the tire skeleton, and the tire skeleton
  • the tire is formed of a resin material including a polyester-based thermoplastic resin.
  • ⁇ 5> The tire according to ⁇ 4>, wherein the difference between the melting point of the resin material and the melting point of the resin mixture is within 6 ° C.
  • ⁇ 6> The tire according to ⁇ 4> or ⁇ 5>, wherein the polyester-based thermoplastic resin includes a polyester-based thermoplastic elastomer.
  • ⁇ 7> The tire according to any one of ⁇ 4> to ⁇ 6>, wherein the tire metal-resin composite member is wound around an outer peripheral portion of the tire frame body.
  • tires of examples and comparative examples (tire size: 225 / 40R18) in which the metal resin composite member is arranged on the outer peripheral portion of the tire skeleton as shown in the above-described embodiment using the produced metal resin composite member.
  • the resin layer and the tire skeleton were formed using a resin having a blending ratio (parts by mass) shown in Table 1.
  • the details of the resin shown in Table 1 are as follows.
  • TPC1 Polyester thermoplastic elastomer whose hard segment is polybutylene terephthalate and soft segment is polytetramethylene glycol ("Hytrel 5557” manufactured by Toray DuPont Co., Ltd., HS ratio: 60.4 mol%)
  • TPC2 Polyester thermoplastic elastomer whose hard segment is polybutylene terephthalate and soft segment is PTMG ("Hytrel 6347" manufactured by Toray DuPont Co., Ltd., HS ratio: 75 mol%)
  • PBT1 Polybutylene terephthalate (Toraycon 1401X06 from Toray Industries, Inc.)
  • Amorphous resin 1 polyester-based thermoplastic resin (Toyobo Co., Ltd. “Byron 270”, glass transition temperature: 67 ° C.)
  • Amorphous resin 2 ... Polycarbonate thermoplastic resin ("Novalex 7020IR” from Mitsubishi Engineering Plastics, Tg: 120 ° C)
  • Amorphous resin 3 ... Styrenic thermoplastic elastomer (SEBS) ("Tuftec H1052" from Asahi Kasei Corporation, Tg: -47 ° C)
  • the resin layer contains a polyester-based thermoplastic elastomer and an amorphous resin having an ester bond with a Tg of 40 ° C. or higher, and the content of the amorphous resin is 50% by mass or less.
  • the tires of the examples both had good evaluations of bondability and cornering power.
  • the elastic modulus of the resin layer was lower than that of the example, and the evaluation of cornering power was lower than that of the example.
  • the polyester-based thermoplastic elastomer forming the resin layer was changed from TPC1 (Comparative Example 1) to TPC2 (Comparative Example 3) having a higher HS ratio and higher rigidity, the elastic modulus increased, but the melting point difference ⁇ Tm was 7 ° C. Expanded. As a result, the cornering power was improved, but the bondability with the tire frame was reduced.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Tires In General (AREA)
PCT/JP2018/013021 2017-06-16 2018-03-28 タイヤ用金属樹脂複合部材及びタイヤ Ceased WO2018230097A1 (ja)

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CN201880039791.5A CN110770037A (zh) 2017-06-16 2018-03-28 轮胎用金属-树脂复合构件和轮胎
EP18816962.7A EP3640045A4 (en) 2017-06-16 2018-03-28 METAL-RESIN COMPOSITE ELEMENT FOR TIRES AND TIRES
US16/699,067 US20200238763A1 (en) 2017-06-16 2019-11-28 Metal-resin composite member for tires, and tire

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JP2017118595A JP6770926B2 (ja) 2017-06-16 2017-06-16 タイヤ用金属樹脂複合部材及びタイヤ
JP2017-118595 2017-06-16

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JP6973562B2 (ja) * 2020-05-14 2021-12-01 住友ゴム工業株式会社 タイヤ用熱可塑性エラストマー組成物及びタイヤ

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JP2019001344A (ja) 2019-01-10
US20200238763A1 (en) 2020-07-30
CN110770037A (zh) 2020-02-07
EP3640045A1 (en) 2020-04-22
EP3640045A4 (en) 2021-03-17

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