WO2020080444A1 - Corps composite élastomère-câblé métallique et pneu utilisant celui-ci - Google Patents

Corps composite élastomère-câblé métallique et pneu utilisant celui-ci Download PDF

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Publication number
WO2020080444A1
WO2020080444A1 PCT/JP2019/040765 JP2019040765W WO2020080444A1 WO 2020080444 A1 WO2020080444 A1 WO 2020080444A1 JP 2019040765 W JP2019040765 W JP 2019040765W WO 2020080444 A1 WO2020080444 A1 WO 2020080444A1
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Prior art keywords
elastomer
metal
metal cord
rubber
cord composite
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PCT/JP2019/040765
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English (en)
Japanese (ja)
Inventor
一樹 上村
英幸 額賀
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株式会社ブリヂストン
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Priority to JP2020553266A priority Critical patent/JPWO2020080444A1/ja
Publication of WO2020080444A1 publication Critical patent/WO2020080444A1/fr

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    • 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
    • B60C9/00—Reinforcements or ply arrangement of pneumatic 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
    • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning 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
    • B60C9/18—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • the present invention relates to an elastomer-metal cord composite and a tire using the same, and more specifically, an elastomer-metal cord composite obtained by coating a metal cord composed of a bundle of metal filaments aligned without twisting with an elastomer, And a tire using the same.
  • a carcass including reinforcing cords embedded along the meridian direction of the ring-shaped tire body is arranged, and a belt layer is arranged on the tire radial outside of the carcass.
  • This belt layer is usually formed by using an elastomer-metal cord composite obtained by coating a metal cord such as steel with an elastomer, and imparts load resistance, traction resistance and the like to the tire.
  • the elastomer for coating the belt layer is required to have high durability, especially high crack growth resistance.
  • Patent Document 1 Although BES resistance is examined, steering stability, low loss, and crack growth resistance are not examined. Therefore, it has been required to realize a reinforcing material that can satisfy these required performances.
  • an object of the present invention is to coat a plurality of metal filaments without twisting the metal cords made of a bundle of metal cords covered with an elastomer, steering stability and crack growth resistance, low loss of tire and the like.
  • An object of the present invention is to provide an elastomer-metal cord composite capable of improving various performances, and a tire using the same.
  • the elastomer-metal cord composite of the present invention is an elastomer-metal cord composite in which a metal cord composed of a bundle in which a plurality of metal filaments are not twisted and aligned in a row is coated with an elastomer.
  • the metal filament is modeled, at least one pair of adjacent metal filaments having different phases is present in the metal cord, and the elastomer has 200% of 50% modulus value (M50).
  • the ratio M200 / M50 of the modulus value (M200) is 5.0 or less.
  • FIG. 1 is an explanatory diagram of the metal filament showing the definition of the metal filament forming amount h and the forming pitch p, and the forming amount h refers to the width of fluctuation that does not include the wire diameter of the metal filament 1.
  • the amount h of the metal filament 1 to be imprinted is measured by projecting the metal filament 1 after imprinting with a projector and projecting a projected image of the metal filament on a screen or the like.
  • the 50% modulus is the tensile stress at the elongation of the elastomer of 50%
  • the 200% modulus is the tensile stress of the elastomer at the elongation of 200%.
  • the metal filaments are molded with the same molding amount and the same pitch. Further, in the elastomer-metal cord composite of the present invention, the phase difference between the adjacent metal filaments is preferably ⁇ / 4 to 7 ⁇ / 4.
  • the adjacent metal filaments have an elastomer coverage of 10% or more per unit length on the side surface in the width direction of the metal cord.
  • the metal filament is two-dimensionally shaped, and the metal filament has an amount of 0.03 mm or more and 0.30 mm or less. It is preferable that the patterning pitch of is 2 mm or more and 30 mm or less.
  • the elastomer of the present invention is a rubber component, and carbon black DBP absorption is less than 50 cm 3/100 g or more 100 cm 3/100 g, a phenol resin, a methylene donor It is preferably composed of a rubber composition containing
  • the elastomer coverage means, for example, when rubber is used as the elastomer and steel cord is used as the metal cord, the rubber cord obtained by coating the steel cord with rubber and vulcanizing is obtained.
  • the steel cord is pulled out from the composite, and the length of the side surface of the steel filament in the width direction of the metal cord, which is covered with the rubber that has penetrated into the gap between the steel filaments that make up the steel cord, is measured and calculated based on the following formula It means the average of the values.
  • Elastomer coverage (rubber coating length / sample length) x 100 (%) The same calculation can be performed when an elastomer other than rubber is used as the elastomer and when a metal cord other than the steel cord is used as the metal cord.
  • the tire of the present invention is characterized by using the elastomer-metal cord composite of the present invention.
  • a metal cord made of a bundle in which a plurality of metal filaments are aligned without being twisted is coated with an elastomer, and various tire performances such as steering stability, crack growth resistance, and low loss property are provided. It was possible to provide an elastomer-metal cord composite capable of improving the above, and a tire using the same.
  • FIG. 3 is a partial cross-sectional view in the width direction of the elastomer-metal cord composite according to the preferred embodiment of the present invention.
  • FIG. 3 is a schematic plan view of a metal cord according to an elastomer-metal cord composite of a preferred embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view in the width direction of a metal cord according to an elastomer-metal cord composite of a preferred embodiment of the present invention.
  • FIG. 3 is a partial cross-sectional view in the width direction of the elastomer-metal cord composite according to the preferred embodiment of the present invention.
  • FIG. 3 is a schematic plan view of a metal cord according to an elastomer-metal cord composite of a preferred embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view in the width direction of a metal cord according to an elastomer-metal cord composite of a preferred embodiment of the present invention.
  • FIG. 5 is a schematic cross-sectional view in the width direction of a metal cord according to an elastomer-metal cord composite of another preferred embodiment of the present invention.
  • FIG. 7 is a schematic cross-sectional view in the width direction of the metal cord according to the elastomer-metal cord composite of yet another preferred embodiment of the present invention.
  • 1 is a schematic one-sided cross-sectional view of a tire according to a preferred embodiment of the present invention.
  • FIG. 2 is a partial cross-sectional view in the width direction of an elastomer-metal cord composite according to a preferred embodiment of the present invention
  • FIG. 3 is an elastomer-metal cord composite of a preferred embodiment of the present invention
  • FIG. 4 is a schematic plan view of the metal cord relating to the body
  • FIG. 4 is a schematic cross-sectional view in the width direction of the metal cord relating to the elastomer-metal cord composite of the preferred embodiment of the present invention.
  • the elastomer-metal cord composite 10 of the present invention has a plurality of metal filaments 1 covered with an elastomer 3 on a metal cord 2 formed of a bundle in which the metal filaments 1 are not twisted and aligned in a line.
  • the number of the metal filaments 1 is preferably 2 or more, more preferably 5 or more, preferably 20 or less, more preferably 18 or less, further preferably 15 or less, particularly preferably
  • the metal cord 2 is composed of a bundle of 12 or less. In the illustrated example, five metal filaments 1 are aligned without being twisted to form a metal cord 2.
  • the metal filaments are shaped, and at least one pair of metal filaments arranged in the metal cord 2 so as to have a phase different from that of the adjacent metal filaments.
  • the adjacent metal filaments of the metal filaments 1 are out of phase with each other, the continuous non-elastomer coating region between the metal filaments is eliminated and the adjacent metal filaments are adjacent to each other.
  • the elastomer can be sufficiently permeated between the metal filaments 1.
  • the adjacent metal filaments 1 are constrained by the elastomer, by using the elastomer-metal cord composite 10 of the present invention as a cord for a belt of a tire, the adjacent metal filaments are mutually protected even during rolling of the tire. As a result, the in-plane rigidity of the belt can be improved and steering stability can be improved.
  • the inventors of the present invention have conducted extensive studies on compatibility between low loss property and crack growth resistance property, and as a result, 200% modulus value (50% modulus value (M50)) of the elastomer 3 covering the metal cord 2 ( It was noted that the ratio M200 / M50 of M200) is highly related to the crack growth resistance. As a result of further study, the present inventors have made it possible to achieve both low loss property and crack propagation resistance at a higher level than in the prior art by setting the ratio M200 / M50 to a specific value or less. I found that. That is, in the elastomer-metal cord composite 10 of the present invention, the ratio M200 / M50 of the 200% modulus value to the 50% modulus value of the elastomer 3 covering the metal cord 2 is 5.0 or less.
  • the metal cord 2 including the pair of the predetermined metal filaments 1 and the elastomer 3 having the predetermined physical property values in combination a tire is obtained.
  • the metal cord 2 according to the present invention includes at least one pair of adjacent metal filaments having different phases.
  • adjacent metal filaments have different phases at least at one place in the metal cord 2, and the phase difference is ⁇ / 4 to 7 ⁇ / 4 is preferable.
  • the phase difference is more preferably ⁇ / 2 to 3 ⁇ / 2, and particularly preferably ⁇ / 2.
  • the effect of improving the in-plane rigidity of the belt by improving the in-plane rigidity of the belt by eliminating the existence of the continuous non-elastomer coating region between the adjacent metal filaments and ensuring the corrosion resistance is preferably 10% or more per unit length, and more preferably 20% or more.
  • the coating is more preferably 50% or more, and particularly preferably 80% or more. Most preferably, it is in a state of being covered by 90% or more.
  • the metal filament 1 may be shaped by two-dimensional wavy or zigzag as shown in the drawing or by three-dimensional shaping in a spiral shape. However, from the viewpoint of weight reduction, it is preferable that the metal filaments 1 do not overlap each other in the thickness direction of the metal cord 2.
  • the mold amount of the metal filament 1 is preferably 0.03 mm or more and 0.30 mm or less.
  • the imprinting amount is 0.30 mm or less, the strength of the elastomer-metal cord composite can be secured, and the effects of the present invention can be sufficiently obtained.
  • the molding amount is preferably 0.03 mm or more and 0.30 mm or less, and more preferably 0. It is 0.03 mm or more and 0.25 mm or less, and most preferably 0.03 mm or more and 0.20 mm or less.
  • the molding pitch of the metal filament 1 is preferably 2 mm or more and 30 mm or less, more preferably 2 mm or more and 20 mm or less, and most preferably 3 mm or more and 15 mm or less.
  • the molding amount of the metal filament 1 is preferably 0.10 mm or more and 0.50 mm or less, more preferably 0.20 mm or more and 0.30 mm or less. By setting the mold amount to 0.50 mm or less, it is possible to suppress the decrease in the strength of the elastomer-metal cord composite and obtain the effects of the present invention sufficiently.
  • the molding pitch of the metal filament 1 is preferably 5 mm or more, more preferably 8 mm or more and 20 mm or less.
  • the metal filaments 1 are molded with the same molding amount and the same pitch.
  • FIG. 5 is a schematic cross-sectional view in the width direction of the metal cord according to the elastomer-metal cord composite of another preferred embodiment of the present invention. Even with such a structure, rubber can be sufficiently permeated between the adjacent metal filaments 1, and the effect of the present invention can be obtained.
  • the elastomer-metal cord composite 10 of the present invention from the viewpoint of lightness, it is possible to make the elastomer-metal cord composite thinner when the molding directions of the adjacent metal filaments 1 are in the width direction of the metal cord 2. It is preferable because it is possible.
  • FIG. 6 is a schematic cross-sectional view in the width direction of the metal cord according to the elastomer-metal cord composite of still another preferred embodiment of the present invention.
  • the metal filament 1 is three-dimensionally spiral-shaped, and the five spiral-shaped metal filaments 1 are not twisted but aligned in a row to form the metal cord 2. ing.
  • the metal filament 1 is generally a steel, that is, a linear wire containing iron as a main component (the mass of iron is more than 50 mass% based on the total mass of the metal filament). It means a metal, and may be composed only of iron, or may contain a metal other than iron, such as zinc, copper, aluminum or tin.
  • the surface state of the metal filament 1 is not particularly limited, but for example, the following forms can be adopted. That is, as the metal filament 1, the N atom on the surface is 2 atom% or more and 60 atom% or less, and the Cu / Zn ratio on the surface is 1 or more and 4 or less. In addition, as the metal filament 1, the amount of phosphorus contained as an oxide in the outermost layer of the filament up to 5 nm inward in the radial direction of the filament from the filament surface is 7.0 atom% in the ratio of the total amount excluding the amount of C. The following cases may be mentioned.
  • the surface of the metal filament 1 may be plated.
  • the type of plating is not particularly limited, and examples thereof include zinc (Zn) plating, copper (Cu) plating, tin (Sn) plating, brass (copper-zinc (Cu-Zn)) plating, and bronze (copper-tin ( In addition to Cu-Sn)) plating and the like, there are ternary plating such as copper-zinc-tin (Cu-Zn-Sn) plating and copper-zinc-cobalt (Cu-Zn-Co) plating. Among these, brass plating and copper-zinc-cobalt plating are preferable.
  • the brass-plated metal filament has excellent adhesion to rubber.
  • the ratio of copper and zinc (copper: zinc) is usually 60 to 70:30 to 40 on a mass basis, and in copper-zinc-cobalt plating, copper is usually 60 to 75 mass%, Cobalt is 0.5 to 10 mass%.
  • the thickness of the plating layer is generally 100 nm or more and 300 nm or less.
  • the wire diameter, tensile strength, and cross-sectional shape of the metal filament 1 are not particularly limited.
  • the wire diameter of the metal filament 1 can be 0.15 mm or more and 0.40 mm or less.
  • the metal filament 1 one having a tensile strength of 2500 MPa (250 kg / mm 2 ) or more can be used.
  • the cross-sectional shape of the metal filament 1 in the width direction is not particularly limited, and may be an elliptical shape, a rectangular shape, a triangular shape, a polygonal shape, or the like, but a circular shape is preferable.
  • a wrapping filament spiral filament
  • the elastomer 3 used in the elastomer-metal cord composite 10 of the present invention may be one having a ratio M200 / M50 of 200% modulus value (M200) to 50% modulus value (M50) of 5.0 or less.
  • M200 modulus value
  • M50 50% modulus value
  • the above M50 is a parameter related to the elasticity of the elastomer in the low strain region. Therefore, M50 needs to be as high as possible in order to suppress the deformation of the belt portion of the tire.
  • M50 for example, in the rubber composition, it is considered that the phenol resin and the methylene donor described later are contained while adjusting the type and the content of carbon black described below.
  • the M200 is a parameter related to the elasticity of the elastomer in the high strain range. Therefore, from the viewpoint of suppressing crack growth, M200 needs to have a low value in order to reduce the concentration of stress at the crack tip. For this purpose, for example, in a rubber composition, it is possible to adjust the kind and content of carbon black described later.
  • the ratio of the size of the M200 to the size of the M50 is preferably 4.8 or less, and more preferably 4.5 or less.
  • M50 is 1.6 MPa or more and M200 is M200. Is preferably 10.5 MPa or less, more preferably M50 is 1.8 MPa or more and M200 is 9.0 MPa or less.
  • elastomer 3 specifically, a rubber composition or the like which has been conventionally used for coating a metal cord can be used.
  • main component of the elastomer 3 include natural rubber (NR), isoprene rubber (IR), epoxidized natural rubber, styrene butadiene rubber (SBR), butadiene rubber (BR, high cis BR and low cis BR), nitrile rubber.
  • NBR hydrogenated NBR
  • SBR hydrogenated SBR and other diene rubbers and hydrogenated products thereof
  • ethylene propylene rubber EPDM, EPM
  • maleic acid-modified ethylene propylene rubber M-EPM
  • butyl rubber IIR
  • isobutylene Aromatic vinyl or diene monomer copolymer acrylic rubber (ACM), olefin rubber such as ionomer, Br-IIR, CI-IIR, bromide of isobutylene paramethylstyrene copolymer (Br-IPMS), chloroprene rubber (CR), hydrin rubber (CHR), chlorosulfone Halogen-containing rubber such as polyethylene rubber (CSM), chlorinated polyethylene rubber (CM), maleic acid modified chlorinated polyethylene rubber (M-CM), silicone rubber such as methyl vinyl silicone rubber, dimethyl silicone rubber and methylphenyl vinyl silicone rubber.
  • CSM polyethylene rubber
  • CM chlorinated polyethylene rubber
  • M-CM maleic acid modified
  • Sulfur-containing rubber such as polysulfide rubber, vinylidene fluoride rubber, fluorine-containing vinyl ether rubber, tetrafluoroethylene-propylene rubber, fluorine-containing silicon rubber, fluorine-containing phosphazene rubber and other fluorine rubber, styrene-based elastomer, olefin-based rubber
  • Thermoplastic elastomers such as elastomers, ester elastomers, urethane elastomers and polyamide elastomers can be preferably used. These may be used alone or in combination of two or more.
  • the elastomer 3 contains, in addition to the above main components, sulfur, vulcanization accelerators, carbon black, antioxidants, zinc oxide, stearic acid, etc. which are commonly used in rubber products such as tires and conveyor belts. Can be appropriately mixed.
  • the rubber component Regarding the rubber component, from the viewpoint that excellent crack growth resistance and abrasion resistance can be obtained, natural rubber or a diene-based synthetic rubber is used alone, or a combination of a natural rubber and a diene-based synthetic rubber is used. Can be included. Further, the rubber component may be composed of only the above-mentioned diene rubber, but may also contain a rubber other than the diene rubber as long as the object of the present invention is not impaired. The content of the diene rubber in the rubber component is preferably 30% by mass or more, more preferably 40% by mass or more, and 50% by mass from the viewpoint that excellent crack growth resistance can be obtained. % Or more is more preferable.
  • the diene synthetic rubber polybutadiene rubber (BR), isoprene rubber (IR), styrene butadiene rubber (SBR), styrene isoprene butadiene rubber (SIBR), chloroprene rubber (CR), acrylonitrile butadiene rubber ( NBR) and the like.
  • the non-diene rubber include ethylene propylene diene rubber (EPDM), ethylene propylene rubber (EPM), butyl rubber (IIR) and the like.
  • EPDM ethylene propylene diene rubber
  • EPM ethylene propylene rubber
  • IIR butyl rubber
  • DBP dibutyl phthalate
  • DBP absorption amount can be used are as follows 50 cm 3/100 g or more 100 cm 3/100 g.
  • the DBP absorption is set to be lower than or equal 100 cm 3/100 g, by reducing the structure, moderately suppressed reinforcement of the rubber composition, to ensure flexibility, to obtain a sufficient resistance to crack growth resistance it can.
  • DBP absorption of carbon black is preferably 90cm 3/100 g or less, more preferably 80 cm 3/100 g or less.
  • the structure of carbon black is the size of the structure (aggregate of carbon black particles) formed as a result of fusion and connection of spherical carbon black particles.
  • the DBP absorption amount of carbon black is the amount of DBP (dibutyl phthalate) absorbed by 100 g of carbon black, and can be measured in accordance with JIS K 6217-4 (2008).
  • the carbon black has a nitrogen adsorption specific surface area (N 2 SA) of preferably 70 m 2 / g or more and 90 m 2 / g or less, more preferably 75 m 2 / g or more and 85 m 2 / g or less. .
  • N 2 SA nitrogen adsorption specific surface area
  • the nitrogen adsorption specific surface area can be measured by a single point method according to ISO 4652-1. For example, after degassed carbon black is immersed in liquid nitrogen, the surface of carbon black is equilibrated.
  • the specific surface area (m 2 / g) can be calculated from the measured value by measuring the amount of nitrogen adsorbed on.
  • the kind of the carbon black is not particularly limited except that it has the above DBP absorption amount.
  • any hard carbon manufactured by the oil furnace method can be used.
  • HAF grade carbon black from the viewpoint of realizing more excellent low loss property and crack growth resistance.
  • the content of carbon black is preferably 35 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the rubber component.
  • the content of carbon black is 35 parts by mass or more with respect to 100 parts by mass of the rubber component, high reinforcing property and crack growth resistance can be obtained, and when it is 45 parts by mass or less, low content can be obtained. It is possible to further improve the loss property.
  • the 50% modulus value (M50) can be improved by including the phenol resin together with the methylene donor described later. While maintaining the excellent low loss property, the reinforcing property of the rubber composition can be improved and the excellent crack propagation resistance can be realized.
  • the phenol resin is not particularly limited, and can be appropriately selected according to the required performance. Examples thereof include those produced by subjecting phenols such as phenol, cresol, resorcin, tert-butylphenol or a mixture thereof to formaldehyde and condensation reaction in the presence of an acid catalyst such as hydrochloric acid or oxalic acid.
  • phenol resin a modified one may be used, and for example, it may be modified with an oil such as rosin oil, tall oil, cashew oil, linoleic acid, oleic acid, linoleic acid.
  • 1 type can be used individually and 2 or more types can also be mixed and used.
  • the content of the phenol resin is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and 10 parts by mass or less with respect to 100 parts by mass of the rubber component. It is preferably 7 parts by mass or less.
  • the above 50% modulus value (M50) is improved by including a methylene donor as a curing agent for the phenol resin. It is possible to improve the reinforcing property of the rubber composition while maintaining excellent low loss property.
  • the methylene donor is not particularly limited and can be appropriately selected depending on the required performance.
  • these methylene donors from the group consisting of hexamethylenetetramine, hexamethoxymethylmelamine, hexamethoxymethylolmelamine and paraformaldehyde. Is-option, is preferably at least one. In addition, these methylene donors may be used alone, in combination can also be used.
  • the ratio of the content of the phenol resin to the content of the methylene donor is preferably 0.6 or more and 7 or less from the viewpoint of achieving both low loss property and crack growth resistance at a higher level. More preferably, it is 5 or less.
  • the rubber composition suitable as the elastomer 3 used for the elastomer-metal cord composite 10 of the present invention contains the above-mentioned rubber component, carbon black, phenol resin, and methylene donor, and other components, and the effects of the present invention can be obtained. It can be included to the extent that it is not damaged.
  • examples of other components include fillers other than the above carbon black, antioxidants, crosslinking accelerators, crosslinking agents, crosslinking accelerators, silane coupling agents, stearic acid, ozone deterioration inhibitors, and surfactants.
  • the additives commonly used in the rubber industry can be mentioned.
  • Examples of the above-mentioned filler include silica and other inorganic fillers, and among them, it is preferable to contain silica because excellent low loss property and crack growth resistance can be obtained.
  • silica examples include wet silica, colloidal silica, calcium silicate, aluminum silicate and the like. Among these, wet silica is preferably used, and precipitated silica is more preferably used. This is because these silicas have high dispersibility and can further improve the low loss property and abrasion resistance of the rubber composition. Precipitated silica is obtained by allowing the reaction solution to proceed at a relatively high temperature in a neutral to alkaline pH range at the early stage of production to grow silica primary particles, and then to control the acid to the acidic side. It refers to silica obtained as a result of aggregation.
  • the content of silica is not particularly limited, but from the viewpoint of realizing an excellent low loss property, it is preferably 1 part by mass or more, and 3 parts by mass or more with respect to 100 parts by mass of the rubber component. It is more preferable that the amount is 15 parts by mass or less, and it is more preferable that the amount is 10 parts by mass or less.
  • an inorganic compound represented by the following formula (I) can be used as the inorganic filler.
  • M is a metal selected from the group consisting of aluminum, magnesium, titanium, calcium and zirconium, oxides or hydroxides of these metals, and hydrates thereof, and carbonates of these metals.
  • n, x, y, and z are an integer of 1 to 5, an integer of 0 to 10, an integer of 2 to 5, and an integer of 0 to 10, respectively.
  • alumina such as ⁇ -alumina and ⁇ -alumina
  • alumina monohydrate such as boehmite and diaspore
  • gibbsite Aluminum hydroxide [Al (OH) 3 ] such as bayerite; aluminum carbonate [Al 2 (CO 3 ) 3 ], magnesium hydroxide [Mg (OH) 2 ], magnesium oxide (MgO), magnesium carbonate (MgCO 3 ).
  • talc (3MgO ⁇ 4SiO 2 ⁇ H 2 O), attapulgite (5MgO ⁇ 8SiO 2 ⁇ 9H 2 O), titanium white (TiO 2), titanium black (TiO 2n-1), calcium oxide (CaO), hydroxide calcium [Ca (OH) 2], magnesium aluminum oxide (MgO ⁇ Al 2 O 3) , clay (Al 2 O 3 ⁇ 2S O 2), kaolin (Al 2 O 3 ⁇ 2SiO 2 ⁇ 2H 2 O), pyrophyllite (Al 2 O 3 ⁇ 4SiO 2 ⁇ H 2 O), bentonite (Al 2 O 3 ⁇ 4SiO 2 ⁇ 2H 2 O) , Magnesium silicate (Mg 2 SiO 4 , MgSiO 3 etc.), aluminum aluminum silicate (Al 2 O 3 .CaO.2SiO 2 etc.), magnesium calcium silicate (CaMgSiO 4 ), calcium carbonate (Ca
  • antiaging agent known ones can be used and are not particularly limited.
  • a phenol anti-aging agent an imidazole anti-aging agent, an amine anti-aging agent, etc. can be mentioned.
  • These antioxidants can be used alone or in combination of two or more.
  • cross-linking accelerator known ones can be used and are not particularly limited.
  • thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole and dibenzothiazyl disulfide; N-cyclohexyl-2-benzothiazylsulfenamide, Nt-butyl-2-benzothiazylsulfenamide, etc.
  • Sulfenamide-based vulcanization accelerator Sulfenamide-based vulcanization accelerator; guanidine-based vulcanization accelerator such as diphenylguanidine; tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetradodecylthiuram disulfide, tetraoctylthiuram disulfide, tetrabenzylthiuram disulfide, di Examples include thiuram-based vulcanization accelerators such as pentamethylene thiuram tetrasulfide; dithiocarbamate-based vulcanization accelerators such as zinc dimethyldithiocarbamate; zinc dialkyldithiophosphate. .
  • the cross-linking agent is also not particularly limited, and examples thereof include sulfur and bismaleimide compounds.
  • the bismaleimide compound include N, N'-o-phenylene bismaleimide, N, N'-m-phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N '-(4,4 Examples include'-diphenylmethane) bismaleimide, 2,2-bis- [4- (4-maleimidophenoxy) phenyl] propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and the like.
  • N, N'-m-phenylene bismaleimide and N, N '-(4,4'-diphenylmethane) bismaleimide can be preferably used.
  • the crosslinking accelerator examples include zinc white (ZnO) and fatty acids.
  • the fatty acid may be saturated or unsaturated, linear or branched fatty acid, and the number of carbon atoms of the fatty acid is not particularly limited.
  • fatty acid having 1 to 30 carbon atoms, preferably 15 to 30 carbon atoms.
  • cyclohexanoic acid cyclohexanecarboxylic acid
  • naphthenic acid such as alkylcyclopentane having a side chain
  • hexanoic acid, octanoic acid decanoic acid (including branched carboxylic acid such as neodecanoic acid), dodecanoic acid
  • Saturated fatty acids such as tetradecanoic acid, hexadecanoic acid and octadecanoic acid (stearic acid); unsaturated fatty acids such as methacrylic acid, oleic acid, linoleic acid and linolenic acid; resin acids such as rosin, tall oil acid and abietic acid .
  • zinc white and stearic acid can be preferably used.
  • the rubber composition suitable as the elastomer 3 used for the elastomer-metal cord composite 10 of the present invention contains silica as the above-mentioned filler, it is preferable to further contain a silane coupling agent. This is because the effect of silica for reinforcement and low loss can be further improved.
  • Known silane coupling agents can be used as appropriate.
  • the preferred content of the silane coupling agent varies depending on the type of the silane coupling agent and the like, but is preferably 2% by mass or more, and particularly preferably 5% by mass or more, based on silica. It is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 18% by mass or less.
  • the content of the silane coupling agent is 2% by mass or more, the effect as the coupling agent can be sufficiently exerted, and when it is 25% by mass or less, gelation of the rubber component is prevented. it can.
  • the rubber composition suitable as the elastomer 3 used in the elastomer-metal cord composite 10 of the present invention is not particularly limited, and a rubber component as each component of the rubber composition, carbon black, a phenol resin, a methylene donor, and It can be prepared by blending other components and kneading. At this time, each of the above components may be kneaded at the same time, or any of the components may be kneaded in advance and then the remaining components may be kneaded. These conditions can be appropriately changed depending on the performance required of the rubber composition.
  • Phenolic resin has a strong interaction with carbon black, so if it is added at the same time, the reaction between the rubber component and carbon black may decrease. Therefore, by mixing and kneading the rubber component and carbon black prior to kneading with the phenol resin, the dispersibility and reinforcing properties of the carbon black are improved, and low loss and crack growth resistance can be further improved. Becomes
  • the elastomer-metal cord composite of the present invention can be manufactured by a known method.
  • a steel cord as a metal cord composed of a bundle of a plurality of metal filaments which are not twisted and twisted can be produced by coating in parallel with a rubber at a predetermined interval, and a sample for evaluation is then prepared. It can be produced by vulcanizing under general conditions.
  • the metal filament can be molded by a conventional molding machine according to a conventional method.
  • FIG. 7 shows a schematic one-side sectional view of a tire according to a preferred embodiment of the present invention.
  • the tire 100 of the present invention is formed by using the elastomer-metal cord composite 10 of the present invention, whereby the low loss property, the steering stability and the crack growth resistance can be improved.
  • the illustrated tire 100 includes a tread portion 101 forming a ground contact portion, a pair of sidewall portions 102 continuously extending inward in the tire radial direction on both side portions of the tread portion 101, and an inner circumference of each sidewall portion 102.
  • the pneumatic tire is provided with a bead portion 103 that is continuous on the side. Examples of the tire 100 of the present invention include tires for passenger cars and tires for trucks and buses.
  • the tread portion 101, the sidewall portion 102, and the bead portion 103 are reinforced by a carcass 104 formed of one carcass layer extending in a toroidal shape from one bead portion 103 to the other bead portion 103.
  • the tread portion 101 is reinforced by a belt 105 including at least two layers, which are two layers in the illustrated example, a first belt layer 105a and a second belt layer 105b, which are arranged outside the crown region of the carcass 104 in the tire radial direction. Has been done.
  • the carcass 104 may have a plurality of carcass layers, and an organic fiber cord extending in a direction substantially orthogonal to the tire circumferential direction, for example, an angle of 70 ° or more and 90 ° or less can be preferably used.
  • the elastomer-metal cord composite 10 of the present invention can be used for the first belt layer 105a and the second belt layer 105b.
  • the thickness of the first belt layer 105a and the second belt layer 105b can be reduced, and the weight of the tire can be reduced.
  • the elastomer-metal cord composite 10 of the present invention for a cord for a belt it is possible to simultaneously improve the durability, low loss, steering stability and crack growth resistance of the belt.
  • the cord angle of the belt 105 can be 30 ° or less with respect to the tire circumferential direction.
  • the tire 100 of the present invention may be any tire as long as it uses the elastomer-metal cord composite 10 of the present invention, and other specific tire structures are not particularly limited. Further, the application location of the elastomer-metal cord composite 10 of the present invention is not limited to the belt 105. For example, it may be used as a belt reinforcing layer arranged on the outer side in the tire radial direction of the belt 105, or as other reinforcing members. As the gas with which the tire 100 is filled, in addition to normal air or air whose oxygen partial pressure is adjusted, an inert gas such as nitrogen, argon, or helium can be used.
  • an inert gas such as nitrogen, argon, or helium
  • a metal cord for example, seven steel filaments having a wire diameter of 0.25 mm, which are wave-shaped (two-dimensionally molded) in the width direction of the cord, are arranged in a row without being twisted together.
  • a cord structure composed of bundles that are aligned and aligned is a steel cord of 0.25 mm ⁇ 7 bundles.
  • all steel filaments are two-dimensionally molded with the same molding amount and the same pitch. It is assumed that the steel filament has a mold amount of 0.1 mm and a mold pitch of 4 mm, and that all the adjacent steel filaments have a phase difference of ⁇ / 2.
  • the elastomer of an example of the present invention -A metal cord composite can be obtained.
  • a tire having a tire size of 205 / 55R16 shown in FIG. 7 can be obtained.
  • the cord angle in the belt layer can be, for example, ⁇ 28 ° with respect to the tire circumferential direction, and the number of driving can be 15.6 / 50 mm.
  • the thickness of the belt layer was 0.65 mm
  • the thickness of the rubber existing on the steel cord in the belt layer was 0.2 mm
  • the rubber existing between the steel cords in the belt layer was measured in a direction orthogonal to the cord longitudinal direction.
  • the thickness can be 0.6 mm.
  • the rubber compositions A and B in which the ratio M200 / M50 of the 200% modulus value (M200) to the 50% modulus value (M50) is changed are shown below.
  • the rubber composition B having a ratio M200 / M50 of 4.6 is an example of a rubber composition that can achieve the effects of the present invention.
  • Rubber compositions A and B were prepared by compounding and kneading according to a conventional method according to the compounds shown in the following table. The kneading of each component was performed using a Banbury mixer with a capacity of 3.0 L. Regarding the rubber composition B, the rubber component and carbon black were kneaded prior to the kneading with the phenol resin. The 50% modulus value (M50) and the 200% modulus value (M200) of each rubber composition are measured according to JIS K 6251 (2010) after vulcanizing each rubber composition at 145 ° C. for 40 minutes to obtain a vulcanized rubber. ).
  • the composition of the bundle of metal filaments is prescribed, and by using an elastomer that satisfies the prescribed physical properties, steering stability, crack propagation resistance, low loss, and other performances of the tire can be obtained. Improved elastomer-metal cord composites and tires can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ropes Or Cables (AREA)
  • Tires In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne : un corps composite élastomère-câblé métallique qui est susceptible d'améliorer diverses propriétés d'un pneu, notamment une stabilité directionnelle, une résistance à la croissance de fissures et des caractéristiques de faible perte ; et un pneu qui utilise ce corps composite élastomère-câblé métallique. Un mode de réalisation selon la présente invention est un corps composite élastomère-câblé métallique (10) qui est obtenu en recouvrant, avec un élastomère (3), un câblé métallique (2) qui est composé d'un faisceau d'une pluralité de filaments métalliques qui sont agencés en rang sans être torsadés. Les filaments métalliques forment un motif ; au moins deux filaments métalliques adjacents qui ont des phases différentes sont présents dans le câblé métallique ; et le rapport de la valeur de module à 200 % (M200) à la valeur de module à 50 % (M50) de l'élastomère, à savoir M200/M50, est inférieur ou égal à 5,0.
PCT/JP2019/040765 2018-10-17 2019-10-16 Corps composite élastomère-câblé métallique et pneu utilisant celui-ci WO2020080444A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116285026A (zh) * 2023-02-22 2023-06-23 宁波市骏凯橡胶工贸有限公司 一种耐腐蚀颗粒改性橡胶材料及其制备工艺和橡胶轮胎
CN116285026B (zh) * 2023-02-22 2024-06-07 宁波市骏凯橡胶工贸有限公司 一种耐腐蚀颗粒改性橡胶材料及其制备工艺和橡胶轮胎

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JPH07145578A (ja) * 1993-11-22 1995-06-06 Tokyo Seiko Co Ltd 形付け素線収束コード及び車両用タイヤ
JPH0913288A (ja) * 1995-06-22 1997-01-14 Bridgestone Corp ゴム物品補強用スチールコードおよび空気入りラジアルタイヤ
JP2000129583A (ja) * 1998-10-16 2000-05-09 Yokohama Rubber Co Ltd:The スチールコード及びこれを用いた空気入りラジアルタイヤ
JP2000198311A (ja) * 1999-01-06 2000-07-18 Toyo Tire & Rubber Co Ltd タイヤ用補強材および空気入りタイヤ
JP2002339276A (ja) * 2001-05-09 2002-11-27 Sumitomo Rubber Ind Ltd 金属コード及びそれを用いた空気入りタイヤ
JP2008156418A (ja) * 2006-12-21 2008-07-10 Sumitomo Rubber Ind Ltd スチールコード被覆用ゴム組成物、ならびにそれでスチールコードを被覆して得られるベルトまたはブレーカーを有するタイヤ
JP2009057535A (ja) * 2007-08-03 2009-03-19 Bridgestone Corp 空気入りタイヤ
JP2010070747A (ja) * 2008-08-19 2010-04-02 Bridgestone Corp ゴム組成物
JP2015205970A (ja) * 2014-04-18 2015-11-19 横浜ゴム株式会社 タイヤ金属コード被覆用ゴム組成物およびそれを用いた空気入りタイヤ
WO2016052449A1 (fr) * 2014-10-01 2016-04-07 株式会社ブリヂストン Corps composite à base de câblé métallique et de caoutchouc
WO2018190309A1 (fr) * 2017-04-11 2018-10-18 株式会社ブリヂストン Composite élastomère-câblé métallique et pneu faisant appel audit composite

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Publication number Priority date Publication date Assignee Title
JPS49134783A (fr) * 1973-04-26 1974-12-25
JPH07145578A (ja) * 1993-11-22 1995-06-06 Tokyo Seiko Co Ltd 形付け素線収束コード及び車両用タイヤ
JPH0913288A (ja) * 1995-06-22 1997-01-14 Bridgestone Corp ゴム物品補強用スチールコードおよび空気入りラジアルタイヤ
JP2000129583A (ja) * 1998-10-16 2000-05-09 Yokohama Rubber Co Ltd:The スチールコード及びこれを用いた空気入りラジアルタイヤ
JP2000198311A (ja) * 1999-01-06 2000-07-18 Toyo Tire & Rubber Co Ltd タイヤ用補強材および空気入りタイヤ
JP2002339276A (ja) * 2001-05-09 2002-11-27 Sumitomo Rubber Ind Ltd 金属コード及びそれを用いた空気入りタイヤ
JP2008156418A (ja) * 2006-12-21 2008-07-10 Sumitomo Rubber Ind Ltd スチールコード被覆用ゴム組成物、ならびにそれでスチールコードを被覆して得られるベルトまたはブレーカーを有するタイヤ
JP2009057535A (ja) * 2007-08-03 2009-03-19 Bridgestone Corp 空気入りタイヤ
JP2010070747A (ja) * 2008-08-19 2010-04-02 Bridgestone Corp ゴム組成物
JP2015205970A (ja) * 2014-04-18 2015-11-19 横浜ゴム株式会社 タイヤ金属コード被覆用ゴム組成物およびそれを用いた空気入りタイヤ
WO2016052449A1 (fr) * 2014-10-01 2016-04-07 株式会社ブリヂストン Corps composite à base de câblé métallique et de caoutchouc
WO2018190309A1 (fr) * 2017-04-11 2018-10-18 株式会社ブリヂストン Composite élastomère-câblé métallique et pneu faisant appel audit composite

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116285026A (zh) * 2023-02-22 2023-06-23 宁波市骏凯橡胶工贸有限公司 一种耐腐蚀颗粒改性橡胶材料及其制备工艺和橡胶轮胎
CN116285026B (zh) * 2023-02-22 2024-06-07 宁波市骏凯橡胶工贸有限公司 一种耐腐蚀颗粒改性橡胶材料及其制备工艺和橡胶轮胎

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