WO2021166904A1 - タイヤ - Google Patents

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Publication number
WO2021166904A1
WO2021166904A1 PCT/JP2021/005697 JP2021005697W WO2021166904A1 WO 2021166904 A1 WO2021166904 A1 WO 2021166904A1 JP 2021005697 W JP2021005697 W JP 2021005697W WO 2021166904 A1 WO2021166904 A1 WO 2021166904A1
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WO
WIPO (PCT)
Prior art keywords
mass
layer
parts
rubber
preferable
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/JP2021/005697
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English (en)
French (fr)
Japanese (ja)
Inventor
祐美 鈴木
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.)
Sumitomo Rubber Industries Ltd
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Sumitomo Rubber Industries Ltd
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 Sumitomo Rubber Industries Ltd filed Critical Sumitomo Rubber Industries Ltd
Priority to CN202180012439.4A priority Critical patent/CN115038595A/zh
Priority to JP2022501903A priority patent/JP7735993B2/ja
Priority to EP21757275.9A priority patent/EP4082774A4/en
Publication of WO2021166904A1 publication Critical patent/WO2021166904A1/ja
Anticipated expiration legal-status Critical
Priority to JP2025105876A priority patent/JP2025123505A/ja
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/18—Layered products comprising a layer of natural or synthetic rubber comprising butyl or halobutyl rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • 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
    • B60C1/0016—Compositions of the tread
    • 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
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/0041—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers
    • B60C11/005—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers with cap and base layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/248—All polymers belonging to those covered by group B32B25/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/744—Non-slip, anti-slip
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2413/00—Belts
    • 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
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
    • B60C2011/0016—Physical properties or dimensions
    • B60C2011/0033—Thickness of the tread

Definitions

  • the present invention relates to a tire having a well-balanced improvement in grip performance and durability performance.
  • thermoplastic elastomer The technology to improve the grip performance by blending a thermoplastic elastomer with the tread rubber is known.
  • Thermoplastic elastomers are softer at room temperature than resins, and when added to rubber, the increase in hardness of the rubber composition is suppressed, and when heat is applied, the intermolecular force between hard segments weakens, resulting in energy. It is considered that loss can be generated and the grip performance at the initial stage of running is improved.
  • thermoplastic elastomer when considering the vulcanization adhesiveness with other tire members composed of a rubber composition containing no thermoplastic elastomer, the thermoplastic elastomer is concentrated on the bonding interface due to the heat and concentration gradient during vulcanization. There is a concern that the durability performance may deteriorate due to the decrease in the adhesiveness between the rubber members.
  • An object of the present invention is to provide a tire having improved grip performance and durability performance in a well-balanced manner.
  • thermoplastic elastomer is blended in the first rubber layer (typically, a cap tread) constituting the tread surface, between the first layer and the belt layer.
  • first rubber layer typically, a cap tread
  • a tire with well-balanced grip performance and durability can be obtained by interposing a rubber layer containing a thermoplastic elastomer under predetermined conditions, and completed the present invention.
  • the present invention [1] A tire having a tread having a first layer constituting a tread surface and a second layer adjacent to the inside in the radial direction of the first layer, wherein the first layer and the second layer are rubber.
  • Tires composed of rubber compositions containing components and thermoplastic elastomers [2] The tire according to the above [1], wherein the rubber composition constituting the first layer contains 5 to 50 parts by mass of a thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the first layer.
  • the rubber composition constituting the second layer contains 3 to 30 parts by mass of a thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the second layer.
  • thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the first layer is larger than the value of the mass part of the thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the second layer.
  • thermoplastic elastomer has a styrene block at the end of the polymer.
  • thermoplastic elastomer when a thermoplastic elastomer is blended in a first rubber layer (typically a cap tread) constituting a tread surface, between the first layer and the belt layer under predetermined conditions.
  • a first rubber layer typically a cap tread
  • thermoplastic elastomer By interposing a rubber layer containing a thermoplastic elastomer, a tire having a well-balanced improvement in grip performance and durability is provided.
  • a tire according to an embodiment of the present disclosure has a tread including a first layer constituting a tread surface and a second layer adjacent to the inside in the radial direction of the first layer, and the first layer and the said.
  • the second layer is composed of a rubber composition containing a thermoplastic elastomer. Further, it is preferable that the content of the thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the first layer is larger than the content of the thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the second layer.
  • the tires of the present disclosure have a well-balanced improvement in grip performance and durability performance by the following mechanism.
  • a rubber layer containing a thermoplastic elastomer between the tread surface layer and the belt layer, vulcanization adhesion and the intermolecular force of the thermoplastic elastomer are provided between the tread surface layer and the second layer adjacent thereto.
  • the adhesiveness between the second layer and the belt topping rubber is ensured by vulcanization adhesion between the diene rubbers. Therefore, even if the content of the thermoplastic elastomer in the entire tread portion is increased, it is considered that the adhesiveness with the adjacent rubber member is ensured, the durability performance is maintained, and the grip performance is also improved.
  • the dimensions and angles of each member of the tire are measured in a state where the tire is incorporated into a regular rim and the tire is filled with air so as to have a regular internal pressure. At the time of measurement, no load is applied to the tire.
  • a "regular rim” is a rim defined for each tire in the standard system including the standard on which the tire is based. For example, “Measuring Rim”. In the case of a tire of a size not specified in the above standard system, the narrowest rim can be assembled to the tire and has the smallest diameter that does not cause air leakage between the rim and the tire. Shall refer to.
  • Regular internal pressure is the air pressure defined for each tire in the standard system including the standard on which the tire is based.
  • maximum air pressure for TRA, the table “TIRELOAD LIMITSAT” The maximum value described in "VARIOUS COLD INFLATION PRESSURES", and in the case of ETRTO, it is "INFLATION PRESSURE".
  • the normal internal pressure is 250 kPa.
  • FIG. 1 is an enlarged cross-sectional view showing a part of the tread of the tire according to the present disclosure.
  • FIG. 1 shows an enlarged portion of the tread according to the present disclosure in which a groove is not formed on the tread surface.
  • the vertical direction is the radial direction of the tire
  • the horizontal direction is the axial direction of the tire
  • the direction perpendicular to the paper surface is the circumferential direction of the tire.
  • the tread portion of the tire of the present disclosure includes a first layer and a second layer, the outer surface of the first layer constitutes the tread surface, and the second layer is adjacent to the inside in the radial direction of the first layer. ing.
  • the first layer typically corresponds to a cap tread.
  • one or more rubber layers may be further provided between the second layer and the belt layer as long as the object of the present disclosure is achieved.
  • a rubber layer for imparting adhesiveness at the time of molding may be provided between the innermost layer and the belt layer in the radial direction among the rubber layers constituting the tread portion.
  • double-headed arrow t1 is the thickness of the first layer
  • double-headed arrow t2 is the thickness of the second layer
  • double-headed arrow t3 is the thickness of the third layer.
  • any point on the tread surface where the groove is not formed is indicated by the symbol P.
  • the straight line represented by the symbol N is a straight line (normal line) that passes through the point P and is perpendicular to the tangent plane at this point P.
  • the thicknesses t1, t2 and t3 are the points P at the tire equatorial plane when there is no groove on the tire equatorial plane, and the land portion closest to the tire equatorial plane when there is a groove on the tire equatorial plane.
  • the central portion in the tire width direction of the tire is set as a point P, and the measurement is performed along the normal line N drawn from the point P.
  • the thickness t1 of the first layer is not particularly limited, but from the viewpoint of grip performance, 2.0 mm or more is preferable, 3.0 mm or more is more preferable, and 4.0 mm or more is further preferable. On the other hand, from the viewpoint of heat generation, 10.0 mm or less is preferable, 9.0 mm or less is more preferable, and 8.0 mm or less is further preferable.
  • the thickness t2 of the second layer is not particularly limited, but 1.0 mm or more is preferable, 1.5 mm or more is more preferable, and 2.0 mm or more is further preferable. Further, t2 is preferably 5.0 mm or less, more preferably 4.0 mm or less, and further preferably 3.0 mm or less.
  • the thickness t3 of the third layer is not particularly limited, but is preferably 0.5 mm or more, and more preferably 1.0 mm or more. Further, t3 is preferably 4.0 mm or less, more preferably 3.0 mm or less, and further preferably 2.0 mm or less.
  • the thickness t1 of the first layer with respect to the thickness of the entire tread portion is preferably 30 to 95%, more preferably 40 to 90%, further preferably 45 to 85%, and particularly preferably 50 to 80%.
  • the thickness of the entire tread portion in the present disclosure means the total thickness of the rubber layers constituting the tread portion, and is determined by the shortest distance from the tread surface to the belt layer.
  • the product of the content (parts by mass) of the thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the first layer and the thickness t1 (mm) of the first layer is preferably 120 or more, more preferably 130 or more, and 140 or more.
  • the above is more preferable, and 150 or more is particularly preferable.
  • the product of the content of the thermoplastic elastomer (parts by mass) and the thickness t1 (mm) of the first layer with respect to 100 parts by mass of the rubber component constituting the first layer is preferably 400 or less, more preferably 300 or less. , 250 or less is more preferable, and 200 or less is particularly preferable.
  • the product of the content (parts by mass) of the thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the second layer and the thickness t2 (mm) of the second layer is preferably 6 or more, more preferably 9 or more, and 12 or more.
  • the above is more preferable, and 15 or more is particularly preferable.
  • the product of the content of the thermoplastic elastomer (parts by mass) and the thickness t2 (mm) of the second layer with respect to 100 parts by mass of the rubber component constituting the second layer is preferably 150 or less, more preferably 100 or less. , 75 or less is more preferable, and 50 or less is particularly preferable.
  • the first tread layer is composed of a rubber composition containing a rubber component and a thermoplastic elastomer.
  • the rubber composition constituting the first layer preferably contains at least one selected from the group consisting of styrene-butadiene rubber (SBR), butadiene rubber (BR), and isoprene-based rubber as a rubber component, and preferably contains styrene-butadiene. It is more preferable to contain rubber (SBR). Further, the rubber component may be a rubber component composed of only SBR.
  • SBR solution polymerization SBR
  • E-SBR emulsion polymerization SBR
  • modified SBR modified SBR
  • modified SBR include modified SBRs (condensates, those having a branched structure, etc.) coupled with SBRs having modified terminals and / or main chains, tin, silicon compounds and the like. Of these, S-SBR and modified SBR are preferable. Further, hydrogenated additives of these SBRs (hydrogenated SBR) and the like can also be used. These SBRs may be used alone or in combination of two or more.
  • S-SBR manufactured and sold by JSR Co., Ltd., Sumitomo Chemical Co., Ltd., Ube Industries, Ltd., Asahi Kasei Co., Ltd., ZS Elastomer Co., Ltd., and the like. ..
  • the styrene content of SBR is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, from the viewpoint of grip performance and wear resistance performance. Further, from the viewpoint of temperature dependence of grip performance and blow resistance performance, 60% by mass or less is preferable, 55% by mass or less is more preferable, and 50% by mass or less is further preferable. In this specification, the styrene content of SBR is calculated by 1 1 H-NMR measurement.
  • the vinyl bond amount of SBR is preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol% or more, from the viewpoint of ensuring reactivity with silica, rubber strength and wear resistance performance.
  • the vinyl bond amount of SBR is preferably 70 mol% or less, more preferably 65 mol% or less, and more preferably 60 mol% or less from the viewpoints of preventing increase in temperature dependence, grip performance, elongation at break, and wear resistance. More preferred.
  • the vinyl bond amount (1,2-bonded butadiene unit amount) of SBR is measured by infrared absorption spectrum analysis.
  • the content of SBR in 100% by mass of the rubber component constituting the first layer is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 65% by mass or more, and 70% by mass. % Or more is particularly preferable. Further, the upper limit of the content of SBR in the rubber component is not particularly limited and may be 100% by mass.
  • the BR is not particularly limited, and for example, a BR having a cis content (cis-1,4 bond content) of less than 50% (low cis BR), a BR having a cis content of 90% or more (high cis BR), and a rare earth element.
  • Rare earth butadiene rubber (rare earth BR) synthesized using a system catalyst, BR containing syndiotactic polybutadiene crystals (SPB-containing BR), modified BR (Hisys modified BR, Rosis modified BR), etc. are common in the tire industry. Can be used.
  • BRs those commercially available from Ube Industries, Ltd., Sumitomo Chemical Co., Ltd., JSR Corporation, Lanxess Co., Ltd., etc. can be used. These BRs may be used alone or in combination of two or more.
  • Rare earth BR can be used that is generally used in the tire industry.
  • a known rare earth element catalyst can be used for the synthesis (polymerization) of the rare earth BR, and includes, for example, a lanthanum series rare earth element compound, an organoaluminum compound, an aluminoxane, a halogen-containing compound, and a Lewis base if necessary. Examples include catalysts. Of these, an Nd-based catalyst using a neodymium (Nd) -containing compound as the lanthanum-series rare earth element compound is preferable from the viewpoint of obtaining a BR having a high cis content and a low vinyl content.
  • Nd neodymium
  • the SPB-containing BR includes 1,2-syndiotactic polybutadiene crystals that are not simply dispersed in BR, but are dispersed after being chemically bonded to BR.
  • the modified BR is obtained by polymerizing 1,3-butadiene with a lithium initiator and then adding a tin compound, and further, the terminal of the modified BR molecule is bonded by a tin-carbon bond (tin).
  • Modified BR butadiene rubber having a condensed alkoxysilane compound at the active end of the butadiene rubber (modified BR for silica), and the like.
  • the content in 100% by mass of the rubber component is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and 20% by mass or less from the viewpoint of grip performance. Is particularly preferable.
  • the lower limit of the content when BR is contained is not particularly limited, but may be, for example, 1% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, and 15% by mass or more. ..
  • isoprene rubber As the isoprene-based rubber, for example, isoprene rubber (IR), natural rubber, and other rubbers commonly used in the tire industry can be used. Natural rubber includes non-modified natural rubber (NR), epoxidized natural rubber (ENR), hydrogenated natural rubber (HNR), deproteinized natural rubber (DPNR), high-purity natural rubber, and grafted natural rubber. Modified natural rubber and the like are also included. These isoprene-based rubbers may be used alone or in combination of two or more.
  • the NR is not particularly limited, and a tire that is common in the tire industry can be used, and examples thereof include SIR20, RSS # 3, and TSR20.
  • the content in 100% by mass of the rubber component is preferably 50% by mass or less from the viewpoint of grip performance. , 40% by mass or less is more preferable, 30% by mass or less is further preferable, and 20% by mass or less is particularly preferable.
  • the lower limit of the content when the isoprene-based rubber is contained is not particularly limited, but is, for example, 1% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, and 15% by mass or more. Can be done.
  • a rubber component other than the above-mentioned isoprene-based rubber, SBR and BR may be contained.
  • a crosslinkable rubber component generally used in the tire industry can be used, for example, a styrene-isoprene-butadiene copolymer rubber (SIBR), a styrene-isobutylene-styrene block copolymer ( SIBS), chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), hydride nitrile rubber (HNBR), butyl rubber (IIR), ethylene propylene rubber, polynorbornene rubber, silicone rubber, polyethylene chloride rubber, fluorine rubber (FKM) , Acrylic rubber (ACM), hydrin rubber and the like.
  • SIBR styrene-isoprene-butadiene copolymer rubber
  • SIBS styrene-isobutylene-styrene block cop
  • the rubber composition constituting the first layer contains a thermoplastic elastomer from the viewpoint of improving the grip performance.
  • thermoplastic elastomer is a polymer compound having elasticity, and constitutes a polymer which is crystalline and constitutes a hard segment having a high melting point, and a soft segment which is amorphous and has a low glass transition temperature. It means a thermoplastic resin material composed of a copolymer having a polymer.
  • the hard segment which is crystalline and has a high melting point, behaves as a pseudo cross-linking point and exhibits elasticity.
  • rubber has a double bond or the like in the molecular chain, and by adding sulfur or the like and cross-linking (vulcanizing), a three-dimensional network structure is generated and elasticity is exhibited.
  • thermoplastic elastomer when the thermoplastic elastomer is heated, the hard segment is melted and cooled, so that the pseudo cross-linking point can be regenerated and reused.
  • rubber when rubber is crosslinked (vulcanized), it forms a three-dimensional network structure, loses its fluidity, and is difficult to reuse even when heated.
  • the thermoplastic elastomer of the present disclosure does not contain the above-mentioned rubber component.
  • thermoplastic elastomer that can be used in the present disclosure is not particularly limited, and examples thereof include styrene-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, olefin-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyamide-based thermoplastic elastomers. Therefore, styrene-based thermoplastic elastomers and polyurethane-based thermoplastic elastomers are preferable. These thermoplastic elastomers may be used alone or in combination of two or more.
  • the styrene-based thermoplastic elastomer is a copolymer having at least one styrene block (hard segment) and at least one elastomer block (soft segment).
  • the molecular structure of the styrene-based thermoplastic elastomer is not particularly limited, but a molecular structure having a styrene block at one end or both ends and an elastomer block in the other end is preferable. Having a styrene block at least at one end tends to provide better grip performance.
  • the styrene-based thermoplastic elastomer preferably has a structure having no styrene block in the main chain portion other than the terminal. With such a structure, the hardness of the rubber in the normal temperature range does not become too high, better grip performance can be obtained, and better fracture characteristics and wear resistance tend to be obtained.
  • the elastomer block examples include vinyl-polydiene, polyisoprene, polybutadiene, polyethylene, polychloroprene, poly2,3-dimethylbutadiene and the like. Further, as the elastomer block, one obtained by hydrogenating the above-mentioned elastomer block can also be used.
  • styrene-based thermoplastic elastomer examples include styrene-isobutylene block copolymer (SIB), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-ethylene.
  • SIB styrene-isobutylene block copolymer
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • styrene-ethylene examples include styrene-ethylene block copolymer (SIB), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer
  • SEB styrene block copolymer
  • SEP styrene-ethylene / propylene block copolymer
  • SEBS styrene-ethylene / butylene-styrene block copolymer
  • SEBC hydrogenated styrene / butadiene copolymer
  • SEPS styrene-ethylene / propylene-styrene block copolymer
  • SEEPS styrene-ethylene / ethylene / propylene-styrene block copolymer
  • SEEPS styrene-ethylene / ethylene / propylene-styrene block copolymer
  • SEEPS styrene-butadiene -Butylene-styrene block copolymer
  • SBBS styrene-butadiene -Butylene-styrene block copolymer
  • the content of the styrene unit (styrene content) of the styrene-based thermoplastic elastomer is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of grip performance. Further, from the viewpoint of suppressing heat generation, 30% by mass or less is preferable, and 20% by mass or less is more preferable.
  • the polyurethane-based thermoplastic elastomer is not particularly limited, but for example, those prepared from polyols and diisocyanates can be preferably used.
  • the polyol include polyester-based polyols, polyester ether-based polyols, polycarbonate-based polyols, and polyether-based polyols.
  • the diisocyanate include tolylene diisocyanate (TDI) and 4,4'-diphenylmethane diisocyanate (MDI).
  • olefin-based thermoplastic elastomer examples include ethylene-propylene copolymer (EPR), ethylene-butene copolymer (EBR), ethylene-hexene copolymer (EHR), and ethylene-octene copolymer (EOR).
  • the content of the thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the first layer is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, further preferably 10 parts by mass or more, and 15 parts by mass. More than parts by mass is particularly preferable. From the viewpoint of wear resistance, 50 parts by mass or less is preferable, 45 parts by mass or less is more preferable, 40 parts by mass or less is further preferable, 35 parts by mass or less is further preferable, and 30 parts by mass or less is particularly preferable.
  • the rubber composition constituting the first layer preferably contains carbon black and / or silica as a filler.
  • the filler may be a filler containing carbon black, or may be a filler composed of only carbon black.
  • Carbon black As the carbon black, those commonly used in the tire industry can be appropriately used, and examples thereof include GPF, FEF, HAF, ISAF, and SAF. These carbon blacks may be used alone or in combination of two or more.
  • the nitrogen adsorption specific surface area (N 2 SA) of carbon black is preferably 50 m 2 / g or more, more preferably 70 m 2 / g or more, from the viewpoint of elongation at break. Further, from the viewpoint of fuel efficiency and workability, 200 m 2 / g or less is preferable, and 150 m 2 / g or less is more preferable.
  • the N 2 SA of carbon black is a value measured according to JIS K 6217-2 "Basic characteristics of carbon black for rubber-Part 2: How to obtain specific surface area-Nitrogen adsorption method-Single point method". ..
  • the amount of dibutyl phthalate (DBP) oil absorbed by carbon black is preferably 50 mL / 100 g or more, more preferably 70 mL / 100 g or more, and even more preferably 90 mL / 100 g or more from the viewpoint of reinforcing properties. Further, from the viewpoint of fuel efficiency and workability, 400 mL / 100 g or less is preferable, and 350 mL / 100 g or less is more preferable.
  • the DBP oil absorption amount of carbon black is a value measured according to JIS K 6221.
  • the content of carbon black with respect to 100 parts by mass of the rubber component constituting the first layer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 20 parts by mass or more, and 40 parts by mass. More than a portion is particularly preferable.
  • the upper limit of the carbon black content is not particularly limited, but from the viewpoint of fuel efficiency and wear resistance, 150 parts by mass or less is preferable, 130 parts by mass or less is more preferable, and 110 parts by mass or less is further preferable.
  • silica is not particularly limited, and for example, silica prepared by a dry method (anhydrous silica), silica prepared by a wet method (hydrous silica), and the like, which are common in the tire industry, can be used. Of these, hydrous silica prepared by a wet method is preferable because it has a large number of silanol groups. Silica may be used alone or in combination of two or more.
  • the nitrogen adsorption specific surface area (N 2 SA) of silica is preferably 140 m 2 / g or more, more preferably 170 m 2 / g or more, still more preferably 200 m 2 / g or more, from the viewpoint of fuel efficiency and wear resistance. From the viewpoint of fuel efficiency and workability, 350 m 2 / g or less is preferable, 300 m 2 / g or less is more preferable, and 250 m 2 / g or less is further preferable.
  • the N 2 SA of silica in the present specification is a value measured by the BET method according to ASTM D3037-93.
  • the average primary particle size of silica is preferably 20 nm or less, more preferably 18 nm or less, and even more preferably 16 nm or less.
  • the lower limit of the average primary particle size is not particularly limited, but is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more.
  • the average primary particle size of silica can be determined by observing with a transmission electron microscope or a scanning electron microscope, measuring 400 or more primary silica particles observed in the field of view, and averaging them.
  • the content of the rubber component with respect to 100 parts by mass is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass or more from the viewpoint of wet grip performance. From the viewpoint of wear resistance, 150 parts by mass or less is preferable, 130 parts by mass or less is more preferable, 110 parts by mass or less is further preferable, and 95 parts by mass or less is particularly preferable.
  • the total content of silica and carbon black with respect to 100 parts by mass of the rubber component constituting the first layer is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and further 60 parts by mass or more from the viewpoint of wear resistance performance. preferable. Further, from the viewpoint of fuel efficiency performance and elongation at break, 180 parts by mass or less is preferable, 160 parts by mass or less is more preferable, and 140 parts by mass or less is further preferable.
  • Silica is preferably used in combination with a silane coupling agent.
  • the silane coupling agent is not particularly limited, and any silane coupling agent conventionally used in combination with silica can be used in the tire industry.
  • Specific examples of the silane coupling agent include a silane coupling agent having a sulfide group such as bis (3-triethoxysilylpropyl) disulfide and bis (3-triethoxysilylpropyl) tetrasulfide ;; 3-mercaptopropyl.
  • Silane coupling agent having a thioester group a silane coupling agent having a vinyl group such as vinyltriethoxysilane and vinyltrimethoxysilane; 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2) -Aminoethyl)
  • a silane coupling agent having an amino group such as aminopropyltriethoxysilane
  • a silane coupling agent having a glycidoxy group such as ⁇ -glycidoxypropyltriethoxysilane and ⁇ -glycidoxypropyltrimethoxysilane
  • Silane coupling agent having a nitro group such as 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane
  • silane coupling having a chloro group such as 3-chloropropyltrimethoxysilane and 3-chloropropyltriethoxysilane.
  • Examples include agents. Among them, a silane coupling agent having a sulfide group, a silane coupling agent having a mercapto group, and a silane coupling agent having a thioester group are preferable, and a silane coupling agent having a mercapto group is more preferable. These silane coupling agents may be used alone or in combination of two or more.
  • the content of the rubber component with respect to 100 parts by mass is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and 2.0 parts by mass from the viewpoint of enhancing the dispersibility of silica. More than parts by mass is more preferable, and more than 4.0 parts by mass is particularly preferable. Further, from the viewpoint of preventing deterioration of wear resistance performance, 20 parts by mass or less is preferable, 12 parts by mass or less is more preferable, 10 parts by mass or less is further preferable, and 9.0 parts by mass or less is particularly preferable.
  • filler other fillers may be used in addition to carbon black and silica.
  • the filler is not particularly limited, and any filler generally used in this field such as aluminum hydroxide, alumina (aluminum oxide), calcium carbonate, magnesium sulfate, talc, and clay can be used. can. These fillers may be used alone or in combination of two or more.
  • the rubber composition constituting the first layer preferably contains a softening agent in order to improve grip performance.
  • a softening agent examples include resin components, oils, liquid rubbers and the like.
  • the rubber composition constituting the first layer may contain a resin component for the purpose of improving the adhesiveness with the adjacent rubber member.
  • the resin component is not particularly limited, and examples thereof include petroleum resin, terpene resin, rosin resin, and phenol resin commonly used in the tire industry. These resin components may be used alone or in combination of two or more.
  • C5 petroleum resin refers to a resin obtained by polymerizing a C5 fraction.
  • the C5 fraction include petroleum fractions having 4 to 5 carbon atoms such as cyclopentadiene, pentene, pentadiene, and isoprene.
  • a dicyclopentadiene resin DCPD resin
  • DCPD resin dicyclopentadiene resin
  • the "aromatic petroleum resin” refers to a resin obtained by polymerizing a C9 fraction, and may be hydrogenated or modified.
  • the C9 fraction include petroleum fractions having 8 to 10 carbon atoms such as vinyltoluene, alkylstyrene, indene, and methyl indene.
  • the aromatic petroleum resin for example, a kumaron inden resin, a kumaron resin, an inden resin, and an aromatic vinyl resin are preferably used.
  • aromatic vinyl resin a homopolymer of ⁇ -methylstyrene or styrene or a copolymer of ⁇ -methylstyrene and styrene is preferable because it is economical, easy to process, and has excellent heat generation. , A polymer of ⁇ -methylstyrene and styrene is more preferable.
  • aromatic vinyl-based resin for example, those commercially available from Clayton, Eastman Chemical, etc. can be used.
  • C5C9-based petroleum resin refers to a resin obtained by copolymerizing the C5 fraction and the C9 fraction, and may be hydrogenated or modified.
  • Examples of the C5 fraction and the C9 fraction include the above-mentioned petroleum fraction.
  • the C5C9-based petroleum resin for example, those commercially available from Tosoh Corporation, LUHUA, etc. can be used.
  • the terpene-based resin is a polyterpene resin consisting of at least one selected from terpene compounds such as ⁇ -pinene, ⁇ -pinene, limonene, and dipentene; an aromatic-modified terpene resin made from the terpene compound and an aromatic compound; Examples thereof include terpene phenol resins made from terpene compounds and phenolic compounds; and terpene resins obtained by subjecting these terpene resins to hydrogenation treatment (hydrogenated terpene resins).
  • Examples of the aromatic compound used as a raw material for the aromatic-modified terpene resin include styrene, ⁇ -methylstyrene, vinyltoluene, divinyltoluene and the like.
  • Examples of the phenolic compound used as a raw material for the terpenphenol resin include phenol, bisphenol A, cresol, xylenol and the like.
  • the rosin-based resin is not particularly limited, and examples thereof include natural resin rosin, and rosin-modified resin obtained by modifying it by hydrogenation, disproportionation, dimerization, esterification, or the like.
  • the phenol-based resin is not particularly limited, and examples thereof include phenol formaldehyde resin, alkylphenol formaldehyde resin, alkylphenol acetylene resin, and oil-modified phenol formaldehyde resin.
  • the softening point of the resin component is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, from the viewpoint of grip performance. Further, from the viewpoint of improving workability and dispersibility between the rubber component and the filler, 150 ° C. or lower is preferable, 140 ° C. or lower is more preferable, and 130 ° C. or lower is further preferable.
  • the softening point can be defined as the temperature at which the sphere has fallen by measuring the softening point defined in JIS K 6220-1: 2001 with a ring-ball type softening point measuring device.
  • the content of the rubber component with respect to 100 parts by mass is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and 12 parts by mass or more from the viewpoint of grip performance. Is particularly preferable. From the viewpoint of suppressing heat generation, 60 parts by mass or less is preferable, 50 parts by mass or less is more preferable, 40 parts by mass or less is further preferable, and 30 parts by mass or less is particularly preferable.
  • Examples of the oil include process oils, vegetable oils and fats, animal fats and oils, and the like.
  • Examples of the process oil include paraffin-based process oils, naphthenic-based process oils, aromatic-based process oils, and the like.
  • a process oil having a low content of a polycyclic aromatic compound (PCA) compound can also be used as an environmental measure.
  • Examples of the low PCA content process oil include a mild extraction solvate (MES), a treated distillate aromatic extract (TDAE), and a heavy naphthenic oil.
  • MES mild extraction solvate
  • TDAE treated distillate aromatic extract
  • heavy naphthenic oil a heavy naphthenic oil.
  • the content of the rubber component with respect to 100 parts by mass is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more from the viewpoint of processability. From the viewpoint of wear resistance, 120 parts by mass or less is preferable, 110 parts by mass or less is more preferable, and 100 parts by mass or less is further preferable.
  • the oil content also includes the amount of oil contained in the oil spread rubber.
  • the liquid rubber is not particularly limited as long as it is a polymer in a liquid state at room temperature (25 ° C.), and is, for example, liquid butadiene rubber (liquid BR), liquid styrene butadiene rubber (liquid SBR), liquid isoprene rubber (liquid IR), and liquid. Examples thereof include styrene isoprene rubber (liquid SIR) and liquid farnesene rubber. These liquid rubbers may be used alone or in combination of two or more.
  • the content of the rubber component with respect to 100 parts by mass is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more.
  • the content of the liquid rubber is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 20 parts by mass or less.
  • the content of the rubber component with respect to 100 parts by mass is preferably 20 parts by mass or more, preferably 30 parts by mass or more. More preferably, 40 parts by mass or more is further preferable, and 50 parts by mass or more is particularly preferable. From the viewpoint of workability, 130 parts by mass or less is preferable, 120 parts by mass or less is more preferable, 110 parts by mass or less is further preferable, and 100 parts by mass or less is particularly preferable.
  • the rubber composition constituting the first layer includes compounding agents generally used in the tire industry, such as wax, processing aid, stearic acid, zinc oxide, antiaging agent, and sulfur.
  • a vulcanizing agent, a vulcanization accelerator and the like can be appropriately contained.
  • the content of the rubber component with respect to 100 parts by mass is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, from the viewpoint of weather resistance of rubber. Further, from the viewpoint of preventing whitening of the tire by bloom, 10 parts by mass or less is preferable, and 5 parts by mass or less is more preferable.
  • processing aid examples include fatty acid metal salts, fatty acid amides, amide esters, silica surface activators, fatty acid esters, mixtures of fatty acid metal salts and amide esters, and mixtures of fatty acid metal salts and fatty acid amides. These processing aids may be used alone or in combination of two or more. As the processing aid, for example, those commercially available from Schill + Seilacher, Performance Additives and the like can be used.
  • the content of the rubber component with respect to 100 parts by mass is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, from the viewpoint of exerting the effect of improving processability. Further, from the viewpoint of wear resistance and breaking strength, 10 parts by mass or less is preferable, and 8 parts by mass or less is more preferable.
  • the anti-aging agent is not particularly limited, and examples thereof include amine-based, quinolin-based, quinone-based, phenol-based, and imidazole-based compounds, and anti-aging agents such as carbamate metal salts.
  • -(1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N' -Di-2-naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-bis (1,4-Dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3
  • the content of the rubber component with respect to 100 parts by mass is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, from the viewpoint of ozone crack resistance of the rubber. Further, from the viewpoint of wear resistance performance and wet grip performance, 10 parts by mass or less is preferable, and 5 parts by mass or less is more preferable.
  • the content of the rubber component with respect to 100 parts by mass is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more from the viewpoint of processability. Further, from the viewpoint of the vulcanization rate, 10 parts by mass or less is preferable, and 5 parts by mass or less is more preferable.
  • the content of the rubber component with respect to 100 parts by mass is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more from the viewpoint of processability. Further, from the viewpoint of wear resistance performance, 10 parts by mass or less is preferable, and 5 parts by mass or less is more preferable.
  • Sulfur is preferably used as the vulcanizing agent.
  • the sulfur powdered sulfur, oil-treated sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur and the like can be used.
  • the content of the rubber component with respect to 100 parts by mass is preferably 0.1 part by mass or more, more preferably 0.3 parts by mass or more, from the viewpoint of ensuring a sufficient vulcanization reaction. More preferably, it is 0.5 parts by mass or more. From the viewpoint of preventing deterioration, 5.0 parts by mass or less is preferable, 4.0 parts by mass or less is more preferable, and 3.0 parts by mass or less is further preferable.
  • the content of the vulcanizing agent is the total content of pure sulfur contained in the oil-containing sulfur.
  • vulcanizing agents other than sulfur examples include alkylphenol / sulfur chloride condensate, 1,6-hexamethylene-sodium dithiosulfate / dihydrate, and 1,6-bis (N, N'-dibenzylthiocarbamoyldithio). ) Hexane and the like can be mentioned.
  • vulcanizing agents other than sulfur those commercially available from Taoka Chemical Industry Co., Ltd., Lanxess Co., Ltd., Flexis Co., Ltd. and the like can be used.
  • the vulcanization accelerator is not particularly limited, but for example, sulfenamide-based, thiazole-based, thiuram-based, thiourea-based, guanidine-based, dithiocarbamate-based, aldehyde-amine-based or aldehyde-ammonia-based, Examples thereof include imidazoline-based and xanthate-based vulcanization accelerators, and among them, sulfenamide-based vulcanization accelerators and thiuram-based vulcanization accelerators are preferable from the viewpoint of more preferably obtaining desired effects.
  • the vulcanization reaction is likely to be inhibited by the thermoplastic elastomer.
  • a highly reactive thiuram-based vulcanization accelerator vulcanization adhesiveness is provided between adjacent rubber layers. It is thought that this can be easily obtained and the durability performance can be improved.
  • Examples of the sulfenamide-based vulcanization accelerator include (N-cyclohexyl-2-benzothiazolyl sulfenamide (CBS), N- (tert-butyl) -2-benzothiazolyl sulfenamide (TBBS), N- Examples thereof include oxyethylene-2-benzothiazolyl sulfenamide, N, N'-diisopropyl-2-benzothiazolyl sulfenamide, N, N-dicyclohexyl-2-benzothiazolyl sulfenamide and the like.
  • Examples of the sulfurization accelerator include 2-mercaptobenzothiazole and dibenzothiazolyl disulfide.
  • Examples of the thiuram-based vulcanization accelerator include tetramethylthium monosulfide, tetramethylthium disulfide, and tetrabenzylthiuram disulfide (TBzTD).
  • Examples of the guanidine-based vulcanization accelerator include diphenylguanidine (DPG), dioltotrilguanidine, orthotolylbiguanidine, and examples of the dithiocarbamate-based vulcanization accelerator include zinc dibutyldithiocarbamate and dibutyldithiocarbamate.
  • Examples thereof include zinc benzyl dithiocarbamate, sodium dibutyl dithiocarbamate, copper dimethyl dithiocarbamate, ferric dimethyl dithiocarbamate, telluryl diethyl dithiocarbamate, and the like. These vulcanization accelerators may be used alone or in combination of two. The above may be used together.
  • the content of the rubber component with respect to 100 parts by mass is preferably 1.0 part by mass or more, more preferably 1.5 parts by mass or more, still more preferably 2.0 parts by mass or more. 5 parts by mass or more is particularly preferable.
  • the content is preferably 8.0 parts by mass or less, more preferably 7.0 parts by mass or less, and further preferably 6.0 parts by mass or less.
  • At least one of the rubber composition constituting the first layer and the rubber composition constituting the second layer contains a thiuram-based vulcanization accelerator.
  • the content of the rubber component with respect to 100 parts by mass is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, and further preferably 1.5 parts by mass or more.
  • the content is preferably 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, and further preferably 2.0 parts by mass or less.
  • the second tread layer is composed of a rubber composition containing a rubber component and a thermoplastic elastomer.
  • the rubber composition constituting the second layer preferably contains at least one selected from the group consisting of styrene butadiene rubber (SBR), butadiene rubber (BR), and isoprene-based rubber as a rubber component, and styrene butadiene. It is more preferable to contain rubber (SBR). Further, the rubber component may be a rubber component containing SBR and isoprene-based rubber, a rubber component composed of only SBR, or a rubber component composed of only SBR and isoprene-based rubber.
  • SBR SBR
  • BR isoprene-based rubber
  • other rubber components those similar to the rubber composition constituting the first layer can be preferably used in the same manner.
  • the rubber composition constituting the second layer contains a thermoplastic elastomer.
  • the same thermoplastic elastomer as the rubber composition constituting the first layer can be preferably used in the same manner. From the viewpoint of grip performance, the content of the thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the first layer is larger than the content of the thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the second layer. Is preferable.
  • the content of the thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the second layer is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and 7 More than parts by mass is particularly preferable. From the viewpoint of wear resistance, 30 parts by mass or less is preferable, 25 parts by mass or less is more preferable, 20 parts by mass or less is further preferable, and 15 parts by mass or less is particularly preferable.
  • the rubber composition constituting the second layer preferably contains carbon black and / or silica as a filler, and more preferably contains carbon black.
  • silica when silica is contained, it is preferable to also contain a silane coupling agent.
  • the carbon black, silica, silane coupling agent, and other fillers those similar to the rubber composition constituting the first layer can be preferably used in the same manner.
  • the content of carbon black with respect to 100 parts by mass of the rubber component constituting the second layer is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, further preferably 50 parts by mass or more, and 60 parts by mass. More than a portion is particularly preferable.
  • the upper limit of the carbon black content is not particularly limited, but from the viewpoint of fuel efficiency and wear resistance, 150 parts by mass or less is preferable, 130 parts by mass or less is more preferable, and 110 parts by mass or less is further preferable.
  • the rubber composition constituting the second layer preferably contains a softening agent.
  • the softening agent include resin components, oils, liquid rubbers, and the like, and those similar to the rubber composition constituting the first layer can be preferably used in the same manner.
  • the rubber composition constituting the second layer contains a compounding agent generally used in the tire industry, for example, wax, processing aid, antiaging agent, stearic acid, zinc oxide, sulfur and the like.
  • a vulcanizing agent, a vulcanization accelerator and the like can be appropriately contained.
  • the same one as the rubber composition constituting the first layer can be preferably used in the same manner.
  • the tread portion of the tire of the present disclosure may further have one or more rubber layers between the second layer and the belt layer as long as the object of the present disclosure is achieved. ..
  • the tread portion preferably has a third layer composed of a rubber component and a rubber composition containing sulfur between the second layer and the belt layer.
  • the rubber composition constituting the rubber layer that can exist between the second layer and the belt layer consists of a group consisting of styrene-butadiene rubber (SBR), butadiene rubber (BR), and isoprene-based rubber as rubber components. It preferably contains at least one selected, and more preferably contains styrene-butadiene rubber (SBR). Further, the rubber component may be a rubber component containing SBR and isoprene-based rubber, a rubber component composed of only SBR, or a rubber component composed of only SBR and isoprene-based rubber.
  • SBR styrene-butadiene rubber
  • BR butadiene rubber
  • isoprene-based rubber as rubber components. It preferably contains at least one selected, and more preferably contains styrene-butadiene rubber (SBR).
  • the rubber component may be a rubber component containing SBR and isoprene-based rubber, a rubber component composed of only SBR,
  • SBR SBR
  • BR isoprene-based rubber
  • other rubber components those similar to the rubber composition constituting the first layer can be preferably used in the same manner.
  • the rubber composition constituting the rubber layer that can exist between the second layer and the belt layer may contain a thermoplastic elastomer.
  • the thermoplastic elastomer the same thermoplastic elastomer as the rubber composition constituting the first layer can be preferably used in the same manner.
  • the content of the thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the rubber layer (preferably the third layer) that can exist between the second layer and the belt layer is as described above. It is preferably less than the content of the thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the second layer.
  • the content of the thermoplastic elastomer with respect to 100 parts by mass of the rubber component constituting the rubber layer (preferably the third layer) that can exist between the second layer and the belt layer is preferably 1 part by mass or more and 2 parts by mass. More than 3 parts by mass is more preferable.
  • the content is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less.
  • the rubber composition constituting the rubber layer that can exist between the second layer and the belt layer preferably contains carbon black and / or silica as a filler.
  • silica when silica is contained, it is preferable to also contain a silane coupling agent.
  • the carbon black, silica, silane coupling agent, and other fillers those similar to the rubber composition constituting the first layer can be preferably used in the same manner.
  • the rubber composition constituting the rubber layer that can exist between the second layer and the belt layer preferably contains a softening agent.
  • the softening agent include resin components, oils, liquid rubbers, and the like, and those similar to the rubber composition constituting the first layer can be preferably used in the same manner.
  • the rubber composition constituting the rubber layer that can exist between the second layer and the belt layer includes a compounding agent generally used in the tire industry, such as wax and a processing aid.
  • a compounding agent generally used in the tire industry, such as wax and a processing aid.
  • Anti-aging agent, vulcanizing agent such as stearic acid, zinc oxide, sulfur, vulcanization accelerator and the like can be appropriately contained.
  • the same one as the rubber composition constituting the first layer can be preferably used in the same manner.
  • the sulfur content with respect to 100 parts by mass of the rubber component constituting the third layer is the same as that of the second layer from the viewpoint of further enhancing the adhesiveness with the adjacent belt topping rubber. It is preferably larger than the sulfur content with respect to 100 parts by mass of the constituent rubber component.
  • the sulfur content with respect to 100 parts by mass of the rubber component constituting the third layer is preferably 1.0 part by mass or more, more preferably 1.5 parts by mass or more, and further preferably 1.8 parts by mass or more. From the viewpoint of preventing deterioration, 5.0 parts by mass or less is preferable, 4.0 parts by mass or less is more preferable, and 3.0 parts by mass or less is further preferable.
  • the rubber composition according to the present disclosure can be produced by a known method.
  • a known kneader used in the general tire industry such as a Banbury mixer, a kneader, and an open roll is used to knead each of the above components other than the vulcanizing agent and the vulcanization accelerator, and then knead the components.
  • It can be produced by a method of adding a vulcanizing agent and a vulcanization accelerator to the tire, further kneading the tire, and then vulcanizing.
  • kneading is performed at 80 ° C. to 170 ° C. for 1 minute to 30 minutes
  • vulcanization is performed at 130 ° C. to 190 ° C. for 3 minutes to 20 minutes.
  • the tire according to the present disclosure includes a tread including the first layer and the second layer, and may be a pneumatic tire or a non-pneumatic tire.
  • pneumatic tires include passenger car tires, truck / bus tires, motorcycle tires, and high-performance tires.
  • the high-performance tire in the present specification is a tire having particularly excellent grip performance, and is a concept including a competition tire used for a competition vehicle.
  • a tire having a tread containing the first layer and the second layer can be manufactured by a usual method using the rubber composition. That is, an unvulcanized rubber composition in which each of the above components is blended with the rubber component as necessary is extruded according to the shape of the tread and bonded together with other tire members on a tire molding machine. An unvulcanized tire is formed by molding according to the above method, and the tire can be manufactured by heating and pressurizing the unvulcanized tire in a vulcanizer.
  • SBR1 Toughden 4850 manufactured by Asahi Kasei Corporation (unmodified S-SBR, styrene content: 40% by mass, vinyl bond amount: 46% by mass, oil content 50 parts by mass with respect to 100 parts by mass of rubber solid content)
  • SBR2 Toughden 3830 manufactured by Asahi Kasei Corporation (unmodified S-SBR, styrene content: 33% by mass, vinyl bond amount: 34%, oil content 37.5 parts by mass with respect to 100 parts by mass of rubber solid content)
  • NR TSR20 Carbon Black 1: Tokai Carbon Co., Ltd.
  • Seest 9SAF (N 2 SA: 142m 2 / g, DBP oil absorption: 115mL / 100g) Carbon Black 2: Show Black N330 manufactured by Cabot Japan Co., Ltd. (N 2 SA: 75m 2 / g, DBP refueling amount: 102mL / 100g) Silica: ULTRASIL (registered trademark) 9100GR (N 2 SA: 235 m 2 / g, average primary particle size: 15 nm) manufactured by Evonik Degussa. Thermoplastic Elastomer 1: Dynalon 4600P manufactured by JSR Co., Ltd.
  • Thermoplastic Elastomer 2 Hybler 5125 manufactured by Kuraray Co., Ltd.
  • Thermoplastic Elastomer 3 Miractran P22M (polyurethane-based thermoplastic elastomer) manufactured by Nippon Miractran Co., Ltd.
  • Resin component Petrotac 100V manufactured by Tosoh Corporation (C5C9 petroleum resin, softening point: 96 ° C., Mw: 3800, SP value: 8.3)
  • Oil VivaTech500 (TDAE oil) manufactured by H & R
  • Anti-aging agent Antigen 6C (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.
  • Wax Sunknock N manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
  • Stearic acid Stearic acid "Camellia” manufactured by NOF CORPORATION
  • Zinc oxide Zinc oxide type 2 manufactured by Mitsui Metal Mining Co., Ltd.
  • Sulfur Powdered sulfur vulcanization accelerator manufactured by Karuizawa Sulfur Co., Ltd .1: Noxeller CZ (N-cyclohexyl-2) manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd. -Benzothiazolyl sulfurenamide)
  • Vulcanization Accelerator 2 Sunseller TBZTD (Tetrabenzyl Thiram Disulfide) manufactured by Sanshin Chemical Industry Co., Ltd.
  • Vulcanization Accelerator 3 Sunseller NS-G (N- (tert-butyl) -2-benzothiazolysulfenamide) manufactured by Sanshin Chemical Industry Co., Ltd.
  • ⁇ Adhesion test> According to the structure shown in Table 4, the unvulcanized rubber compositions constituting the first layer, the second layer and the third layer of the tread are stacked, press vulcanized for 15 minutes under the condition of 170 ° C., and vulcanized and adhered. A rubber composition was obtained. At this time, vulcanization was carried out with cellophane sandwiched about 60 mm from the end in order to allow the testing machine to be gripped. The vulcanized and bonded rubber composition was subjected to an adhesive performance test according to JIS K 6256-1 "Vulcanized rubber and thermoplastic rubber-How to determine adhesiveness-Part 1: Peeling strength with cloth".
  • a rubber sheet of the vulcanized-bonded rubber composition was cut to a width of 25 mm to prepare a test piece, and the test piece was peeled off at a speed of 50 mm / min.
  • the adhesiveness between the first layer and the second layer is Comparative Example 3 and Comparative Example 11
  • the adhesiveness between the second layer and the third layer is Comparative Example 6 and Comparative Example 14
  • the adhesiveness between the innermost tread layer and the belt layer is Comparative Example.
  • the peel strength of 1 and Comparative Example 9 were expressed as 100, respectively, as an exponential notation. The larger the adhesive figure of merit, the better the adhesiveness.
  • the innermost layer of the tread is the first layer when the number of layers of the tread portion is 1, the second layer when the number of layers of the tread portion is 2, and the number of layers of the tread portion is 3. Refers to the third layer.
  • ⁇ Durability test> Using a drum tester, use a standard rim (6.0J), internal pressure (260kPa), load (4.56kN), and road surface temperature of 80 ° C. on a drum at a speed of 230km / h to make a tread rubber. The running time until peeling damage occurred was measured. The results were expressed exponentially with the reference comparative example (Comparative Example 7 in Table 4 and Comparative Example 15 in Table 5) as 100. The larger the index, the better the durability performance at high temperature and high speed running.
  • Tables 4 and 5 also show the overall figure of merit (the sum of the durability figure of merit, the initial grip figure of merit, and the grip stability figure of merit).
  • the tires of the present disclosure in which the first layer of the tread and the second layer are composed of a rubber composition containing a rubber component and a thermoplastic elastomer, have a well-balanced grip performance and durability performance. You can see that it has been improved.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024014499A (ja) * 2022-07-22 2024-02-01 住友ゴム工業株式会社 タイヤ

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1160810A (ja) * 1997-08-20 1999-03-05 Bridgestone Corp 重荷重用空気入りタイヤ
JP2004306730A (ja) * 2003-04-04 2004-11-04 Yokohama Rubber Co Ltd:The 空気入りタイヤ
JP2007119582A (ja) * 2005-10-27 2007-05-17 Toyo Tire & Rubber Co Ltd 空気入りタイヤ
JP2007326909A (ja) * 2006-06-06 2007-12-20 Toyo Tire & Rubber Co Ltd 空気入りタイヤ
WO2009093695A1 (ja) * 2008-01-23 2009-07-30 Ube Industries, Ltd. ゴム組成物、ベーストレッド用ゴム組成物、チェーファー用ゴム組成物、及びサイドウォール用ゴム組成物、並びにそれらを用いたタイヤ
JP2013159626A (ja) * 2012-02-01 2013-08-19 Bridgestone Corp 空気入りタイヤ
WO2013180257A1 (ja) * 2012-05-31 2013-12-05 横浜ゴム株式会社 空気入りタイヤ
JP2015514040A (ja) * 2012-04-02 2015-05-18 コンパニー ゼネラール デ エタブリッスマン ミシュラン クラウン領域が熱可塑性エラストマーを含むサブレイヤを備えたタイヤ
JP2016210937A (ja) 2015-05-12 2016-12-15 住友ゴム工業株式会社 ゴム組成物およびタイヤ
JP2017101199A (ja) * 2015-12-04 2017-06-08 住友ゴム工業株式会社 ゴム組成物およびタイヤ
JP2017210044A (ja) * 2016-05-24 2017-11-30 住友ゴム工業株式会社 空気入りタイヤ
JP2018083884A (ja) * 2016-11-22 2018-05-31 住友ゴム工業株式会社 空気入りタイヤ

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010031117A (ja) * 2008-07-28 2010-02-12 Yokohama Rubber Co Ltd:The トレッド用ゴム組成物
JP5486869B2 (ja) 2009-08-17 2014-05-07 住友ゴム工業株式会社 空気入りタイヤ
EP2415617B1 (en) * 2010-07-30 2014-05-14 Sumitomo Rubber Industries, Ltd. Polymer sheet for inner liner, polymer laminate for inner liner, and pneumatic tire
WO2014178336A1 (ja) * 2013-04-30 2014-11-06 住友ゴム工業株式会社 空気入りタイヤ
EP3390072B1 (en) * 2015-12-17 2020-07-01 Compagnie Générale des Etablissements Michelin A tire comprising a tread
JP6417064B1 (ja) 2018-04-09 2018-10-31 住友ゴム工業株式会社 タイヤ用ゴム組成物及びタイヤ
WO2021256123A1 (ja) * 2020-06-15 2021-12-23 住友ゴム工業株式会社 タイヤ

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1160810A (ja) * 1997-08-20 1999-03-05 Bridgestone Corp 重荷重用空気入りタイヤ
JP2004306730A (ja) * 2003-04-04 2004-11-04 Yokohama Rubber Co Ltd:The 空気入りタイヤ
JP2007119582A (ja) * 2005-10-27 2007-05-17 Toyo Tire & Rubber Co Ltd 空気入りタイヤ
JP2007326909A (ja) * 2006-06-06 2007-12-20 Toyo Tire & Rubber Co Ltd 空気入りタイヤ
WO2009093695A1 (ja) * 2008-01-23 2009-07-30 Ube Industries, Ltd. ゴム組成物、ベーストレッド用ゴム組成物、チェーファー用ゴム組成物、及びサイドウォール用ゴム組成物、並びにそれらを用いたタイヤ
JP2013159626A (ja) * 2012-02-01 2013-08-19 Bridgestone Corp 空気入りタイヤ
JP2015514040A (ja) * 2012-04-02 2015-05-18 コンパニー ゼネラール デ エタブリッスマン ミシュラン クラウン領域が熱可塑性エラストマーを含むサブレイヤを備えたタイヤ
WO2013180257A1 (ja) * 2012-05-31 2013-12-05 横浜ゴム株式会社 空気入りタイヤ
JP2016210937A (ja) 2015-05-12 2016-12-15 住友ゴム工業株式会社 ゴム組成物およびタイヤ
JP2017101199A (ja) * 2015-12-04 2017-06-08 住友ゴム工業株式会社 ゴム組成物およびタイヤ
JP2017210044A (ja) * 2016-05-24 2017-11-30 住友ゴム工業株式会社 空気入りタイヤ
JP2018083884A (ja) * 2016-11-22 2018-05-31 住友ゴム工業株式会社 空気入りタイヤ

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4082774A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024014499A (ja) * 2022-07-22 2024-02-01 住友ゴム工業株式会社 タイヤ

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JPWO2021166904A1 (https=) 2021-08-26
CN115038595A (zh) 2022-09-09

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