WO2025005129A1 - タイヤ用ゴム組成物及びタイヤ - Google Patents

タイヤ用ゴム組成物及びタイヤ Download PDF

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WO2025005129A1
WO2025005129A1 PCT/JP2024/023157 JP2024023157W WO2025005129A1 WO 2025005129 A1 WO2025005129 A1 WO 2025005129A1 JP 2024023157 W JP2024023157 W JP 2024023157W WO 2025005129 A1 WO2025005129 A1 WO 2025005129A1
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Prior art keywords
rubber
conjugated diene
mass
group
resins
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English (en)
French (fr)
Japanese (ja)
Inventor
前田　涼二
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Yokohama Rubber Co Ltd
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Yokohama Rubber Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/28—Reaction with compounds containing carbon-to-carbon unsaturated bonds
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/02—Copolymers of mineral oil hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the present invention relates to a rubber composition for tires and a tire.
  • Patent Document 1 Rubber compositions for tires that contain silica in order to improve performance have been known (for example, Patent Document 1).
  • the present invention aims to provide a rubber composition for tires that exhibits excellent processability and, when made into a tire, exhibits excellent rolling performance, wet performance, abrasion resistance, and chipping resistance, as well as a tire manufactured using the rubber composition for tires.
  • the present inventors discovered that the above-mentioned problems can be solved by using a specific modified conjugated diene rubber as the rubber component and a specific silane coupling agent, and thus arrived at the present invention. That is, the present inventors have found that the above problems can be solved by the following configuration.
  • a rubber composition comprising a rubber component (A) containing a modified conjugated diene rubber (A1), silica (B), and a silane coupling agent (C),
  • the modified conjugated diene rubber (A1) satisfies the following formulas (1) to (3) and has a modifying group containing a nitrogen atom, a silicon atom, and an oxygen atom adjacent thereto, The proportion of the modified conjugated diene rubber (A1) in the rubber component (A) is 25% by mass or more,
  • the modified conjugated diene rubber is subjected to gel permeation chromatography measurement using a differential refractive index detector and a viscosity detector as detectors.
  • the weight average intrinsic viscosity obtained using the high molecular weight side portion of the peak of the chromatogram obtained by the viscosity detector, which is 10% of the total peak area, is defined as IVw 10% .
  • the unit of weight average intrinsic viscosity is dL/g.
  • St represents the proportion (mass%) of repeating units derived from styrene to the entire modified conjugated diene rubber
  • Vn represents the proportion (mass%) of repeating units of 1,2-vinyl structure derived from conjugated diene to the entire modified conjugated diene rubber.
  • A a (B) b (C) c (D) d (R 1 ) e SiO (4-2a-b-c-de)/2
  • C2 In formula (C2), A represents a divalent organic group containing a sulfide group.
  • B represents a monovalent hydrocarbon group having 5 to 10 carbon atoms.
  • C represents a hydrolyzable group.
  • D represents an organic group containing a mercapto group.
  • R1 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms.
  • a to e satisfy the relational expressions 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 3, 0 ⁇ d ⁇ 1, 0 ⁇ e ⁇ 2, 0 ⁇ 2a+b+c+d+e ⁇ 4.
  • the modified conjugated diene rubber (A1) is a star structure having three or more branches, at least one branch of which has a moiety derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group;
  • the rubber composition for a tire according to the above (1) further comprising a main chain branched structure in the above portion.
  • the thermoplastic resin (D) comprises at least one selected from the group consisting of terpene resins, C5/C9 resins, C9 resins, DCPD resins, DCPD/C9 resins, hydrogenated C5/C9 resins, hydrogenated C9 resins, hydrogenated DCPD resins, and hydrogenated DCPD/C9 resins;
  • the thermoplastic resin (D) comprises at least two selected from the group consisting of terpene resins, C5/C9 resins, C9 resins, DCPD resins, DCPD/C9 resins, hydrogenated C5/C9 resins, hydrogenated C9 resins, hydrogenated DCPD resins, and hydrogenated DCPD/C9 resins;
  • the present invention can provide a rubber composition for tires that exhibits excellent processability and, when made into a tire, exhibits excellent rolling performance, wet performance, abrasion resistance, and chipping resistance, as well as a tire manufactured using the rubber composition for tires.
  • 1 is an example of a GPC chromatogram. 1 is a partial cross-sectional schematic view showing an example of an embodiment of a tire of the present invention.
  • a numerical range expressed using “to” means a range that includes the numerical values before and after “to” as the lower and upper limits.
  • each component may be used alone or in combination of two or more. When two or more components are used in combination, the content of the components refers to the total content unless otherwise specified.
  • the rolling performance, wet performance, wear resistance, and chipping resistance when made into a tire are also simply referred to as "rolling performance,””wetperformance,””wearresistance,” and “chipping resistance,” respectively.
  • a power of 10 may be represented as E.
  • E+5 represents 10 to the fifth power.
  • the rubber composition for tires of the present invention (hereinafter also referred to as the "composition of the present invention") is The rubber composition contains a rubber component (A) containing a modified conjugated diene rubber (A1), silica (B), and a silane coupling agent (C),
  • the modified conjugated diene rubber (A1) satisfies the formulas (1) to (3) described below and has a modifying group containing a nitrogen atom, a silicon atom, and an oxygen atom adjacent thereto,
  • the proportion of the modified conjugated diene rubber (A1) in the rubber component (A) is 25% by mass or more
  • the silane coupling agent (C) is 3-octanoylthio-1-propyltriethoxysilane or a polysiloxane represented by the average composition formula (C2) described below.
  • the composition of the present invention has the above-mentioned structure and is therefore believed to be able to solve the above-mentioned problems. Although the reason for this is not clear, it is speculated to be as follows.
  • the composition of the present invention contains, as a rubber component, a conjugated diene rubber (hereinafter also referred to as a "specific conjugated diene rubber”) that satisfies the formulas (1) to (3) described below and has a modifying group (hereinafter also referred to as a "specific modifying group”) that contains a nitrogen atom, a silicon atom, and an oxygen atom adjacent thereto.
  • Formula (1) specifies the relationship between the weight average intrinsic viscosity on the high molecular weight side and the weight average molecular weight on the high molecular weight side, and the inventors have found that rubber that satisfies formulas (1) and (3) has extremely excellent processability.
  • the specific modifying group possessed by the specific conjugated diene rubber interacts with silica.
  • the specific silane coupling agent contained in the composition of the present invention interacts with silica together with the specific modifying group, and further interacts with the skeleton of the specific conjugated diene rubber and other rubber components. Therefore, in the composition of the present invention, the dispersibility of silica is extremely high, which is believed to lead to excellent effects (rolling performance, wet performance, wear resistance, chipping resistance).
  • composition of the present invention contains a rubber component containing a specific conjugated diene rubber.
  • the composition of the present invention may contain a rubber component other than the specific conjugated diene rubber.
  • the specific conjugated diene rubber is a conjugated diene rubber that satisfies the formula (1) described below and the formula (2) described below and has a modifying group (specific modifying group) containing a nitrogen atom, a silicon atom, and an oxygen atom adjacent thereto.
  • the skeleton of the specific conjugated diene rubber is a polymer having repeating units derived from a conjugated diene.
  • conjugated diene examples include butadiene (particularly 1,3-butadiene), isoprene, chloroprene, etc.
  • the diene is preferably butadiene (particularly 1,3-butadiene) or isoprene, and more preferably butadiene (particularly 1,3-butadiene), because the effects of the present invention are more excellent.
  • the skeleton of the specific conjugated diene rubber may have a repeating unit other than the repeating unit derived from the conjugated diene.
  • the monomer (other monomer) that becomes such a repeating unit include vinyl monomers, alkenes (e.g., ethylene, propylene, butene), etc.
  • the vinyl monomer include aromatic vinyl (e.g., styrene), acrylonitrile, and the specific branching agent described later.
  • Specific examples of the skeleton include natural rubber (NR), butadiene rubber (BR), aromatic vinyl-conjugated diene copolymer rubber, isoprene rubber (IR), acrylonitrile-butadiene copolymer rubber (NBR), butyl rubber (IIR), halogenated butyl rubber (Br-IIR, Cl-IIR), chloroprene rubber (CR), etc.
  • the aromatic vinyl-conjugated diene copolymer rubber include styrene-butadiene rubber (SBR), styrene-isoprene copolymer rubber, etc.
  • the conjugated diene rubber is preferably SBR because the effects of the present invention are more excellent.
  • the specific conjugated diene rubber has a modifying group (specific modifying group) containing a nitrogen atom, a silicon atom, and an oxygen atom adjacent to the silicon atom.
  • the specific modifying group may be present at any one of the terminals, main chain, or side chain of the conjugated diene rubber.
  • the specific modifying group preferably contains a silicon atom and an oxygen atom adjacent thereto as an alkoxysilyl group.
  • the alkoxysilyl group is a group represented by -Si(OR1) n (R2) 3-n (wherein R1 is an alkyl group, R2 is a hydrogen atom or an alkyl group, and n is an integer of 1 to 3).
  • the specific modifying group preferably contains a nitrogen atom as an amino group (primary to tertiary amino group) because this provides better effects of the present invention.
  • the specific modifying group is preferably a group derived from a specific modifying agent described below, because the effects of the present invention are more excellent.
  • Formula (1) The specific conjugated diene rubber satisfies the following formula (1).
  • Formula (1) specifies the relationship between the weight-average intrinsic viscosity on the high molecular weight side and the weight-average molecular weight on the high molecular weight side, and polymers having a small molecular size relative to their molecular weight, such as those having branches, tend to satisfy formula (1).
  • the reason for limiting the molecular weight side is that it has a large effect on the physical properties of the entire polymer.
  • the Mw 10% and IVw 10% in formula (1) are determined as follows.
  • the modified conjugated diene rubber is subjected to gel permeation chromatography measurement using a differential refractive index detector (RI detector) and a viscosity detector as detectors.
  • the weight average molecular weight obtained using the high molecular weight side portion of the peak of the chromatogram obtained by the differential refractive index detector, which is 10% of the total peak area, is defined as Mw 10% .
  • the weight average intrinsic viscosity obtained using the high molecular weight side portion of the peak of the chromatogram obtained by the viscosity detector, which is 10% of the total peak area is defined as IVw 10% .
  • the unit of weight average intrinsic viscosity is dL/g.
  • the modified conjugated diene rubber is subjected to gel permeation chromatography (GPC) measurement using a differential refractive index detector and a viscosity detector as detectors.
  • GPC gel permeation chromatography
  • Toluene containing 5 mmol/L triethylamine is used as the eluent.
  • Three columns packed with polystyrene gel (product names "TSKgel G4000HXL”, “TSKgel G5000HXL”, and “TSKgel G6000HXL” manufactured by Tosoh Corporation) are connected together and used.
  • the measurement sample is dissolved in toluene to a concentration of 1 mg/mL to prepare the measurement solution, and 100 ⁇ L of the measurement solution is injected into the GPC measurement device and measured under conditions of an oven temperature of 40°C and a toluene flow rate of 1 mL/min.
  • the weight average molecular weight is determined using the portion on the high molecular weight side (the side with the shorter elution time) that accounts for 10% of the total peak area.
  • the weight average molecular weight obtained is designated as Mw 10% .
  • the weight-average intrinsic viscosity is calculated using the portion on the high molecular weight side (shorter elution time) which occupies 10% of the total area of the peaks.
  • the weight-average intrinsic viscosity thus obtained is designated as IVw10% .
  • the weight average intrinsic viscosity is defined as ( ⁇ ( ⁇ i ⁇ Mi ⁇ Ni))/( ⁇ (Mi ⁇ Ni)), where Ni is the number of molecules and ⁇ i is the intrinsic viscosity at molecular weight Mi.
  • GPC chromatogram horizontal axis: elution time, vertical axis: signal intensity
  • P1 a portion on the high molecular weight side (shorter elution time) that has an area of 10% of the area of P0, which is the entire peak.
  • Mw 10% is preferably from 100,000 to 10,000,000, and more preferably from 1,000,000 to 5,000,000, because the effects of the present invention are more excellent.
  • St represents the ratio (mass%) of repeating units derived from styrene to the entire specific conjugated diene rubber (hereinafter also referred to as the "styrene amount")
  • Vn represents the ratio (mass%) of repeating units of 1,2-vinyl structure derived from conjugated diene (e.g., butadiene) to the entire specific conjugated diene rubber (hereinafter also referred to as the "vinyl amount").
  • St+Vn is preferably 10 to 45, and more preferably 25 to 45, because this provides a better effect of the present invention.
  • St is preferably 5 to 40, more preferably 10 to 35, and even more preferably 15 to 30, because this provides a better effect of the present invention.
  • Vn is preferably 5 to 30, and more preferably 10 to 20, because this provides a better effect of the present invention.
  • the IVw 10% is preferably from 1 to 4.6, and more preferably from 2 to 4.4, because the effects of the present invention are more excellent.
  • the weight average molecular weight (Mw) of the specific conjugated diene rubber is preferably from 100,000 to 2,000,000, and more preferably from 200,000 to 1,300,000, because the effects of the present invention are more excellent.
  • the method for measuring the weight average molecular weight (Mw) of the specific conjugated diene rubber is the same as that for the above-mentioned Mw 10% , except that the entire peak is used.
  • the glass transition temperature (Tg) of the specific conjugated diene rubber is not particularly limited, but is preferably from -100°C to -30°C, and more preferably from -80°C to -45°C, for reasons of better effects of the present invention.
  • the glass transition temperature can be adjusted, for example, by the amount of styrene or vinyl.
  • the glass transition temperature (Tg) is measured using a differential scanning calorimeter (DSC) at a temperature rise rate of 10° C./min and calculated by the midpoint method.
  • the specific conjugated diene rubber preferably has a star structure having three or more branches, more preferably has a star structure having three or more branches with a specific modifying group as a branch point, and further preferably is a conjugated diene rubber represented by the following formula (A), because the effects of the present invention are more excellent.
  • X represents an n-valent group (specific modifying group) containing a nitrogen atom, a silicon atom, and an oxygen atom adjacent thereto
  • P represents a conjugated diene polymer chain
  • n represents an integer of 3 or more.
  • X represents an n-valent group (specific modifying group) containing a nitrogen atom, a silicon atom and an oxygen atom adjacent thereto.
  • X preferably contains a silicon atom and an oxygen atom adjacent thereto as an alkoxysilyl group, because this provides a better effect of the present invention.
  • X preferably contains a nitrogen atom as an amino group because the effect of the present invention is more excellent.
  • P represents a conjugated diene polymer chain.
  • a plurality of P's may be the same or different.
  • the definition, specific examples and preferred embodiments of the conjugated diene polymer chain are the same as those of the skeleton of the specific conjugated diene rubber described above.
  • n represents an integer of 3 or more. There is no particular upper limit to n, but it is preferably 30 or less because the effects of the present invention are superior.
  • the specific conjugated diene rubber has a star structure with three or more branches
  • at least one branched chain (conjugated diene polymer chain) of the star structure preferably has a portion derived from a specific branching agent described later, and the portion preferably has a further main chain branched structure, for reasons of better effects of the present invention.
  • the main chain branched structure refers to a structure in which a branched chain (conjugated diene polymer chain) forms a branch point at a portion derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group, and a polymer chain (e.g., another conjugated diene polymer chain) extends from the branch point.
  • the proportion of the specific conjugated diene rubber in the rubber component is 25% by mass or more.
  • the above ratio is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, because the effects of the present invention are more excellent.
  • the upper limit of the above proportion is not particularly limited, and is 100% by mass.
  • the method for producing the specific conjugated diene rubber is not particularly limited, but because the effects of the present invention are superior, a method including the following steps (1) and (2) (hereinafter also referred to as the "production method of the present invention") is preferred.
  • a polymerization step in which a monomer containing a conjugated diene is polymerized by anionic polymerization to obtain a conjugated diene polymer; (2) a modification step in which the conjugated diene polymer obtained in the polymerization step is reacted with a compound containing a nitrogen atom and an alkoxysilyl group (hereinafter also referred to as a "specific modifier") to obtain a conjugated diene rubber having a specific modifying group.
  • a modification step in which the conjugated diene polymer obtained in the polymerization step is reacted with a compound containing a nitrogen atom and an alkoxysilyl group (hereinafter also referred to as a "specific modifier") to obtain a conjugated diene rubber having a specific modifying group.
  • the polymerization step is a step of obtaining a conjugated diene-based polymer by polymerizing a monomer containing a conjugated diene by anionic polymerization.
  • the anionic polymerization is not particularly limited, but anionic polymerization using an organolithium compound as an initiator is preferred because the effects of the present invention are more excellent.
  • the organolithium compound is not particularly limited, but specific examples include mono-organolithium compounds such as n-butyllithium (n-BuLi), sec-butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium, and benzyllithium; and polyfunctional organolithium compounds such as 1,4-dilithiobutane, 1,5-dilithiopentane, 1,6-dilithiohexane, 1,10-dilithiodecane, 1,1-dilithiodiphenylene, dilithiopolybutadiene, dilithiopolyisoprene, 1,4-dilithiobenzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, and 1,3,5-trilithio-2,4,6-tri
  • mono-organolithium compounds such as n-butyllithium, sec-butyllithium, and tert-butyllithium are preferred because they provide better effects for the present invention, with n-butyllithium being more preferred.
  • the amount of the organolithium compound used is not particularly limited, but it is preferably 0.001 to 10 mol% relative to the monomer, because this provides a better effect of the present invention.
  • conjugated diene-containing monomer used in the polymerization step are the same as those of the conjugated diene and other monomers in the skeleton of the specific conjugated diene-based rubber described above.
  • the monomer preferably contains a vinyl monomer containing an alkoxysilyl group or a halosilyl group (hereinafter also referred to as a "specific branching agent") because this provides a superior effect of the present invention.
  • the specific branching agent is preferably an aromatic vinyl (particularly styrene) containing an alkoxysilyl group or a halosilyl group, more preferably an aromatic vinyl containing an alkoxysilyl group, and even more preferably an aromatic vinyl containing a trialkoxysilyl group, for reasons that the effects of the present invention are more excellent.
  • aromatic vinyls containing an alkoxysilyl group examples include 1-(trimethoxysilyl)-4-vinylbenzene, 1,1-bis(4-trimethoxysilylphenyl)ethylene, and the like.
  • aromatic vinyls containing a halosilyl group examples include trichloro(4-vinylphenyl)silane and 1,1-bis(4-trichlorosilylphenyl)ethylene.
  • the amount of the specific branching agent used is preferably 0.001 to 0.1% by mass, and more preferably 0.005 to 0.05% by mass, based on the conjugated diene, because this provides a better effect of the present invention.
  • a polar compound may be added. This allows the monomers to be randomly copolymerized.
  • polar compounds tend to be usable as vinylating agents for controlling the microstructure of conjugated dienes.
  • polar compounds tend to be effective in promoting polymerization reactions.
  • polar compound examples include ethers such as tetrahydrofuran, diethyl ether, dioxane, dimethoxybenzene, and 2,2-bis(2-oxolanyl)propane; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, and quinuclidine; alkali metal alkoxide compounds such as potassium tert-amylate and sodium tert-butylate; and phosphine compounds such as triphenylphosphine. These polar compounds may be used alone or in combination of two or more.
  • ethers such as tetrahydrofuran, diethyl ether, dioxane, dimethoxybenzene, and 2,2-bis(2-oxolanyl)propane
  • tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethan
  • the amount of the polar compound used is preferably 0.01 moles or more and 100 moles or less per mole of the initiator, because the effects of the present invention are more excellent.
  • the modification step is a step of obtaining a conjugated diene rubber having a specific modifying group by reacting the conjugated diene polymer obtained in the polymerization step with a modifier (specific modifier) containing a nitrogen atom, a silicon atom and an oxygen atom adjacent thereto.
  • the active terminal of the conjugated diene polymer obtained in the polymerization step is bonded to the silicon atom of the specific modifier.
  • the specific modifier contains an alkoxysilyl group
  • the active terminal is bonded to the silicon atom of the alkoxysilyl group, and the alkoxy group is eliminated.
  • the conjugated diene polymer obtained in the polymerization step has a portion derived from a specific branching agent, in addition to the above-mentioned active terminal, the alkoxysilyl group or halosilyl group of the above-mentioned portion is also considered to react with the specific modifying agent (e.g., alkoxysilyl group).
  • the alkoxysilyl group or halosilyl group of the above-mentioned portion is also considered to react with the active terminal of another conjugated diene polymer.
  • the conjugated diene polymer having a portion derived from a specific branching agent has a main chain branched structure (another conjugated diene polymer chain) in the above-mentioned portion.
  • the specific modifier is a compound containing a nitrogen atom, a silicon atom and an oxygen atom adjacent thereto.
  • the specific modifier preferably contains a silicon atom and an oxygen atom adjacent thereto as an alkoxysilyl group (particularly a trialkoxysilyl group) or a group containing a silazane structure (particularly a cyclic silazane structure) in which an alkoxy group is bonded to a silicon atom of the silazane structure.
  • the silazane structure refers to a structure in which a silicon atom and a nitrogen atom are directly bonded (a structure having a Si-N bond).
  • the specific modifying agent preferably contains a nitrogen atom as a group containing an amino group (primary to tertiary amino group) or a silazane structure (particularly a cyclic silazane structure) because the effects of the present invention are more excellent.
  • the specific modifying agent preferably has two or more (preferably three or more) sites capable of reacting with an active terminal such as an alkoxysilyl group. When the specific modifying agent has a plurality of such sites, the specific modifying agent functions as a coupling agent that connects conjugated diene polymers together.
  • Specific examples of the specific modifying agent include tertiary amines having an alkoxysilyl group, such as tris(3-trimethoxysilylpropyl)amine and tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine; cyclic silazanes having an alkoxysilyl group, such as 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane; tertiary amines having a group containing an alkoxysilyl group-containing cyclic silazane structure, such as tris[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]amine and tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine; bis(3-trimethoxysilyl group,
  • the amount of the specific modifier used is preferably 0.01 to 1% by mass, and more preferably 0.02 to 0.2% by mass, based on the conjugated diene, because this provides a better effect of the present invention.
  • the manufacturing method of the present invention may include steps (other steps) other than the steps described above.
  • Other steps include a polymerization terminating step in which a polymerization terminator (e.g., methanol) is added, and a solvent removal step in which the solvent is removed by steam stripping.
  • a polymerization terminator e.g., methanol
  • the rubber component may contain a rubber component (rubber component) other than the specific conjugated diene rubber.
  • rubber component rubber component
  • examples of such other rubber components include natural rubber (NR), butadiene rubber (BR), aromatic vinyl-conjugated diene copolymer rubber, isoprene rubber (IR), acrylonitrile-butadiene copolymer rubber (NBR), butyl rubber (IIR), halogenated butyl rubber (Br-IIR, Cl-IIR), chloroprene rubber (CR), etc.
  • the aromatic vinyl-conjugated diene copolymer rubber include styrene butadiene rubber (SBR), styrene isoprene copolymer rubber, etc.
  • the rubber component preferably contains SBR because the effects of the present invention are more excellent.
  • the proportion of SBR in the rubber component is preferably 1 to 30 mass%, and more preferably 5 to 20 mass%, because the effects of the present invention are more excellent.
  • the rubber component preferably contains BR because the effects of the present invention are more excellent.
  • the proportion of BR in the rubber component is preferably 1 to 30 mass%, and more preferably 5 to 20 mass%, because the effects of the present invention are more excellent.
  • the rubber component preferably contains natural rubber because the effects of the present invention are more excellent.
  • the proportion of natural rubber in the rubber component is preferably 1 to 30 mass%, and more preferably 5 to 20 mass%, because the effects of the present invention are more excellent.
  • the glass transition temperature (hereinafter also referred to as "average Tg") of the entire rubber component is preferably higher than -80°C and -45°C or lower, and more preferably -75°C or higher and -45°C or lower, for the reason that the effects of the present invention are more excellent.
  • the average Tg of the rubber components is the sum of the glass transition temperatures (Tg) of the individual rubber components multiplied by the mass fraction of each rubber component (weighted average value of the glass transition temperatures).
  • the preferred embodiment of the weight average molecular weight (Mw) of the rubber component is the same as that of the specific conjugated diene rubber described above.
  • silica The composition of the present invention contains silica.
  • the silica is not particularly limited, and any conventionally known silica can be used. Examples of silica include wet silica, dry silica, fumed silica, diatomaceous earth, etc. Silica derived from biomass such as rice husk may also be used. The above silica may be used alone or in combination of two or more kinds.
  • CTAB cetyltrimethylammonium bromide
  • CTAB adsorption specific surface area of silica
  • CTAB cetyltrimethylammonium bromide
  • the content of silica is preferably 30 to 150 parts by mass, and more preferably 50 to 100 parts by mass, per 100 parts by mass of the rubber component, because the effects of the present invention are more excellent.
  • composition of the present invention contains 3-octanoylthio-1-propyltriethoxysilane or a polysiloxane represented by the average composition formula (C2) described later (hereinafter, also collectively referred to as the "specific silane coupling agent").
  • 3-Octanoylthio-1-propyltriethoxysilane is a compound represented by the following structural formula.
  • the polysiloxane represented by the average composition formula (C2) (hereinafter, also referred to as the "specific polysiloxane") will be described below.
  • the specific polysiloxane is a polysiloxane represented by the average composition formula (C2) below.
  • A represents a divalent organic group containing a sulfide group.
  • B represents a monovalent hydrocarbon group having 5 to 10 carbon atoms.
  • C represents a hydrolyzable group.
  • D represents an organic group containing a mercapto group.
  • R1 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms.
  • Formula (C2) represents the average composition of the polysiloxane, i.e., the type of groups directly bonded to the Si atoms of the polysiloxane and the average number of each group.
  • Si represents a Si atom of the polysiloxane.
  • O in formula (C2) represents an O atom of the polysiloxane. Note that the O atom is a divalent group and is always bonded to two Si atoms (Si atoms of the polysiloxane). (4-2a-b-c-d-e)/2 in formula (C2) represents the average number of O atoms of the polysiloxane bonded to the Si atoms of the polysiloxane.
  • A, B, C, D, and R1 each represent a group bonded to a Si atom of the polysiloxane.
  • A is a divalent group and always bonds to two Si atoms (Si atoms of the polysiloxane).
  • a, b, c, d, and e each represent the average number of A, B, C, D, and R1 bonded to a Si atom of the polysiloxane.
  • the content of the specific silane coupling agent is not particularly limited. However, because the effects of the present invention are more excellent, the content is preferably 2 to 20 parts by mass, and more preferably 5 to 15 parts by mass, per 100 parts by mass of the rubber component described above.
  • the content of the specific silane coupling agent is preferably 1 to 20 mass % relative to the above-mentioned silica content, and more preferably 5 to 15 mass %, because this provides a better effect of the present invention.
  • the content of the specific silane coupling agent is preferably 10 to 30 mass % relative to the content of the specific conjugated diene rubber described above, because this provides a better effect of the present invention.
  • composition of the present invention may contain components (optional components) other than the above-mentioned components, as necessary.
  • components include various additives commonly used in rubber compositions, such as reinforcing fillers other than silica (preferably carbon black), silane coupling agents other than the specific silane coupling agent, thermally expandable microcapsules, zinc oxide (zinc white), stearic acid, antioxidants, wax, processing aids, liquid polymers, thermoplastic resins, thermosetting resins, vulcanizing agents (e.g., sulfur), vulcanization accelerators (accelerators), and vulcanization activators.
  • reinforcing fillers other than silica preferably carbon black
  • silane coupling agents other than the specific silane coupling agent
  • thermally expandable microcapsules such as zinc oxide (zinc white), stearic acid, antioxidants, wax, processing aids, liquid polymers, thermoplastic resins, thermosetting resins, vulcanizing agents (e.g., sulfur), vulcanization accelerators (acc
  • the composition of the present invention preferably contains a thermoplastic resin because the effects of the present invention are more excellent.
  • the composition of the present invention preferably contains two or more thermoplastic resins because the effects of the present invention are more excellent.
  • thermoplastic resin examples include coumarone resins (e.g., coumarone resin, coumarone-indene resin, coumarone-indene-styrene resin), phenol resins (e.g., phenol resin, phenol-acetylene resin, phenol-formaldehyde resin), xylene resins (e.g., xylene resin, xylene-acetylene resin, xylene-formaldehyde resin), rosin resins (e.g., rosin, rosin ester, hydrogenated rosin derivative), terpene resins (e.g., terpene resin, modified rosin ...
  • coumarone resins e.g., coumarone resin, coumarone-indene resin, coumarone-indene-styrene resin
  • phenol resins e.g., phenol resin, phenol-acetylene resin, phenol-formaldeh
  • the resins include aromatic terpene resins (such as aromatic modified terpene resins), terpene phenol resins, hydrogenated terpene resins, ⁇ -pinene resins, ⁇ -pinene resins, limonene resins, hydrogenated limonene resins, dipentene resins, and terpene styrene resins), styrene-based resins, petroleum-based resins (for example, C5/C9-based resins, C9-based resins, DCPD (dicyclopentadiene)-based resins, DCPD/C9-based resins, hydrogenated C5/C9-based resins, hydrogenated C9-based resins, hydrogenated DCPD-based resins, and hydrogenated DCPD/C9-based resins), and aliphatic saturated hydrocarbon-based resins.
  • aromatic terpene resins such as aromatic modified terpene resins
  • terpene phenol resins hydrogenated terpene resin
  • the thermoplastic resin preferably contains at least one type selected from the group consisting of terpene resins, C5/C9 resins, C9 resins, DCPD resins, DCPD/C9 resins, hydrogenated C5/C9 resins, hydrogenated C9 resins, hydrogenated DCPD resins, and hydrogenated DCPD/C9 resins, and more preferably contains at least two types selected from the above group, because this provides a better effect for the present invention.
  • the content of the thermoplastic resin is preferably 1 to 100 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the rubber component, because the effects of the present invention are more excellent.
  • the content of the thermoplastic resin is preferably 5 to 100% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 60% by mass, relative to the specific conjugated diene rubber described above, because this provides a better effect of the present invention.
  • the composition of the present invention preferably contains carbon black because the effects of the present invention are more excellent.
  • the carbon black may be used alone or in combination of two or more kinds.
  • the carbon black is not particularly limited, and various grades such as SAF-HS, SAF, ISAF-HS, ISAF, ISAF-LS, IISAF-HS, HAF-HS, HAF, HAF-LS, FEF, GPF, and SRF can be used.
  • the nitrogen adsorption specific surface area (N 2 SA) of the carbon black is not particularly limited, but in order to obtain a superior effect of the present invention, it is preferably 50 to 200 m 2 /g, and more preferably 70 to 150 m 2 /g.
  • the nitrogen adsorption specific surface area (N 2 SA) is the amount of nitrogen adsorbed on the surface of carbon black measured according to JIS K6217-2:2001 "Part 2: Determination of specific surface area - Nitrogen adsorption method - Single point method".
  • the content of carbon black is not particularly limited. However, in order to obtain better effects of the present invention, the content of carbon black is preferably 1 to 100 parts by mass, and more preferably 2 to 30 parts by mass, per 100 parts by mass of the rubber component described above.
  • the content of the reinforcing filler containing silica is preferably 50 parts by mass or more, more preferably 60 to 200 parts by mass, and even more preferably 70 to 150 parts by mass, per 100 parts by mass of the rubber component, because the effects of the present invention are more excellent.
  • the carbon black is included in the reinforcing filler.
  • composition of the present invention contains sulfur or a vulcanization accelerator
  • a high temperature preferably 100 to 160°C
  • cool the mixture preferably 100 to 160°C
  • the composition of the present invention can be vulcanized or crosslinked under conventionally known vulcanization or crosslinking conditions.
  • the tire of the present invention is a tire manufactured using the above-mentioned composition of the present invention.
  • the tire of the present invention is preferably a pneumatic tire, and can be filled with air, an inert gas such as nitrogen, or other gases.
  • FIG. 2 shows a schematic partial cross-sectional view of a tire that represents one example of an embodiment of a tire of the present invention.
  • the tire of the present invention is not limited to the embodiment shown in FIG. 2.
  • reference numeral 1 denotes a bead portion
  • reference numeral 2 denotes a sidewall portion
  • reference numeral 3 denotes a tire tread portion.
  • a carcass layer 4 having fiber cords embedded therein is installed, and the ends of this carcass layer 4 are folded back and wrapped around the bead cores 5 and bead fillers 6 from the inside to the outside of the tire.
  • a belt layer 7 is disposed on the outer side of the carcass layer 4 around one circumference of the tire.
  • a rim cushion 8 is disposed in the bead portion 1 at a portion that comes into contact with the rim.
  • At least one of the components 2, 3, 5, 6 and 8 (preferably the component 3) is made of the composition of the present invention.
  • the tire of the present invention can be manufactured, for example, according to a conventionally known method.
  • the gas to be filled into the tire can be normal air or air with an adjusted oxygen partial pressure, or an inert gas such as nitrogen, argon, or helium.
  • ⁇ Polymerization step> In a stirrer-equipped autoclave, cyclohexane 1000 g/h (hour), tetramethylethylenediamine 0.028 g/h, 1,3-butadiene 189.4 g/h, 1-butene 0.436 g/h, and styrene 10.6 g/h were charged under a nitrogen atmosphere, and n-butyllithium was continuously added at 1.43 mmol/h to initiate polymerization at 70° C. When the polymerization was sufficiently stabilized, 1-(trimethoxysilyl)-4-vinylbenzene (branching agent) was added at 0.07 g/h and reacted with stirring.
  • the branching agent corresponds to the specific branching agent described above.
  • conjugated diene rubber 1.14 parts by mass of Irganox 1520L (manufactured by BASF) was added as an anti-aging agent per 100 parts by mass of conjugated diene rubber, after which the solvent was removed by steam stripping and the mixture was vacuum dried at 60°C for 24 hours to obtain a solid conjugated diene rubber.
  • the resulting conjugated diene rubber is also referred to as conjugated diene rubber 1.
  • the conjugated diene rubber 1 is a reaction product of a conjugated diene polymer, which is a copolymer of butadiene, styrene, and a branching agent, with a modifier, and is a modified conjugated diene rubber having a modifying group (specific modifying group) derived from the modifier, which includes a nitrogen atom, a silicon atom, and an oxygen atom adjacent thereto.
  • a conjugated diene polymer which is a copolymer of butadiene, styrene, and a branching agent, with a modifier
  • a modified conjugated diene rubber having a modifying group (specific modifying group) derived from the modifier which includes a nitrogen atom, a silicon atom, and an oxygen atom adjacent thereto.
  • the conjugated diene rubber 1 has a star structure with three or more branches, with the modifying group as a branching point, and the branched chain bonded to the modifying group has a portion derived from a branching agent, and the portion derived from the branching agent has a further main chain branched structure (conjugated diene polymer chain).
  • conjugated diene rubbers 2 to 4 A solid conjugated diene rubber was obtained in the same manner as for conjugated diene rubber 1, except that the amount of each component was changed as shown in Table 1. The obtained conjugated diene rubbers are also referred to as conjugated diene rubbers 2 to 4.
  • Conjugated diene rubbers 2 to 4 are reaction products of a conjugated diene polymer, which is a copolymer of butadiene, styrene and a branching agent, with a modifier, and are modified conjugated diene rubbers having a modifying group (specific modifying group) containing a nitrogen atom, a silicon atom and an oxygen atom adjacent thereto, which is derived from the modifier.
  • a conjugated diene polymer which is a copolymer of butadiene, styrene and a branching agent
  • modified conjugated diene rubbers having a modifying group (specific modifying group) containing a nitrogen atom, a silicon atom and an oxygen atom adjacent thereto, which is derived from the modifier.
  • Conjugated diene rubbers 2 to 4 each have a star structure with three or more branches in which the modifying group is a branch point, and the branched chain bonded to the modifying group has a portion derived from a branching agent, and the portion derived from the branching agent has a further main chain branched structure (conjugated diene polymer chain).
  • cyclohexane (4000 g), 1,3-butadiene (474.0 g), and styrene (126.0 g) were charged into an autoclave equipped with a stirrer under a nitrogen atmosphere, and the entire amount of the polymer block (A) having active terminals obtained above was added, and polymerization was initiated at 50 ° C.
  • polyorganosiloxane represented by the following formula (11) was then added in the form of a xylene solution with a concentration of 20% by mass so that the content of epoxy groups was 1.42 mmol (equivalent to 0.33 times the molar amount of n-butyl lithium used), and reacted for 30 minutes. Thereafter, as a polymerization terminator, methanol in an amount equivalent to 2 times the molar amount of n-butyl lithium used was added to obtain a solution containing a conjugated diene rubber.
  • a small amount of an anti-aging agent (Irganox 1520, manufactured by BASF) was added to this solution, and solid rubber was collected by steam stripping. The obtained solid rubber was dehydrated with a roll and dried in a dryer to obtain a solid conjugated diene rubber, which was used as a comparative conjugated diene rubber.
  • X 1 , X 4 , R 1 to R 3 and R 5 to R 8 are methyl groups.
  • m is 80 and k is 120.
  • X 2 is a group represented by the following formula (12) (wherein * represents a bonding position).
  • Table 2 shows the Mw, Mw 10% , IVw, IVw 10% , St, Vn and glass transition temperature (Tg) of the conjugated diene rubbers synthesized as described above (conjugated diene rubbers 1 to 4, comparative conjugated diene rubbers).
  • the "right side” of formula (1) represents the value of the right side of formula (1), which is "3.1 ⁇ 10 -6 ⁇ Mw 10% -2.77".
  • "Suitable" of formula (1) indicates whether formula (1) is satisfied or not, and specifically, "A” indicates that formula (1) is satisfied, and “B” indicates that formula (1) is not satisfied.
  • St+Vn in formula (2) represents the above-mentioned St+Vn.
  • conjugated diene rubber 4 satisfies formulas (1) and (3) but does not satisfy formula (2), and therefore does not fall under the above-mentioned specific conjugated diene rubber. Also, the comparative conjugated diene rubber does not satisfy formulas (1) and (2), and therefore does not fall under the above-mentioned specific conjugated diene rubber.
  • Each rubber composition for tires was vulcanized at 170°C for 10 minutes using a mold of a predetermined shape (inner dimensions: length 150 mm, width 150 mm, thickness 2 mm) to prepare a vulcanized rubber test piece.
  • a dumbbell-shaped JIS No. 3 test piece was prepared in accordance with JIS K6251.
  • a tensile test was performed at room temperature (23°C) at a tensile speed of 500 mm/min to measure the tensile breaking strength.
  • the evaluation results are shown in the "wear resistance" column of Tables 3 to 5 as an index with the value of the standard example being 100. The larger this index, the higher the breaking strength and the more excellent the wear resistance.
  • an index value of "100" means that no improvement effect was obtained, and an index value of "102" or more means that excellent wear resistance was obtained.
  • Each rubber composition for tires was vulcanized at 170°C for 10 minutes using a mold of a given shape (inner dimensions: length 150 mm, width 150 mm, thickness 2 mm) to prepare a vulcanized rubber test piece.
  • a dumbbell-shaped JIS No. 3 test piece was prepared in accordance with JIS K6251.
  • a tensile test was performed at room temperature (23°C) at a tensile speed of 500 mm/min to measure the tensile breaking elongation.
  • the evaluation results are shown in the "chipping resistance" column as an index with the value of the standard example being 100. The larger this index, the higher the breaking elongation and the better the chipping resistance. In practical use, it is preferable that it is more than 100.
  • Carbon black Seast 3 manufactured by Tokai Carbon Co., Ltd. (HAF carbon black, nitrogen adsorption specific surface area (N 2 SA): 79 m 2 /g)
  • Silica ZEOSIL 1165MP manufactured by Solvay (CTAB adsorption specific surface area: 160 m 2 /g)
  • Terpene resin YS Resin TO125 manufactured by Yasuhara Chemical Co., Ltd.
  • Silane coupling agent 2 Polysiloxane synthesized as described above (corresponding to a specific silane coupling agent) Oil: Showa Shell Sekiyu Extract No. 4 S Anti-aging agent: Nocrac 6C (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) Wax: Sunnock (Ouchi Shinko Chemical Industry Co., Ltd.) Sulfur: Shikoku Chemical Industry Co., Ltd. Myucron OT-20 Vulcanization accelerator: Sancerer CM-G (sulfenamide type) manufactured by Sanshin Chemical Industry Co., Ltd.
  • Example 1 As can be seen from Tables 3 to 5, all of Examples 1 to 11, which contain a rubber component containing a specific amount of a specific conjugated diene rubber, silica, and a specific silane coupling agent, exhibited excellent rolling performance, wet performance, processability, abrasion resistance, and chipping resistance. Comparing Example 1 and Example 2 (comparison between embodiments in which only the type of specific conjugated diene rubber is different), Example 1, in which the specific conjugated diene rubber had a St+Vn of 40 or less, exhibited better rolling performance and abrasion resistance.
  • Example 1 comparing Example 1 and Example 2 (comparison between embodiments in which only the type of specific conjugated diene rubber is different), Example 2, in which the specific conjugated diene rubber had a St+Vn of 35 or more, exhibited better wet performance and chipping resistance.
  • Example 2 comparing Example 2 with Example 3 (comparison between embodiments having different proportions of specific conjugated diene rubber in the rubber component), Example 2, in which the proportion of the specific conjugated diene rubber in the rubber component is 50 mass% or more, exhibited superior rolling performance, wet performance, abrasion resistance and chipping resistance.
  • Example 1 a comparison between Example 1 and Examples 4 to 10 (a comparison between embodiments that differ only in the presence or absence of a thermoplastic resin) revealed that Examples 4 to 10, which contained a thermoplastic resin, exhibited superior abrasion resistance.
  • Examples 4 to 7 comparison between embodiments differing only in the content of thermoplastic resin
  • Examples 5 to 7 in which the content of thermoplastic resin per 100 parts by mass of the rubber component was 10 parts by mass or more, showed better wet performance, abrasion resistance, and chipping resistance.
  • Example 6 in which the content was 45 parts by mass or less, showed even better rolling performance, abrasion resistance, and chipping resistance.
  • Example 5 in which the amount of thermoplastic resin is 20 parts by mass
  • Examples 5 and 8 in which the thermoplastic resin contained a terpene resin showed better wet performance.
  • Example 8 in which the thermoplastic resin contained at least two selected from the group consisting of a terpene resin, a C5/C9 resin, a C9 resin, a DCPD resin, a DCPD/C9 resin, a hydrogenated C5/C9 resin, a hydrogenated C9 resin, a hydrogenated DCPD resin, and a hydrogenated DCPD/C9 resin showed even better wet performance.
  • Example 1 comparing Example 1 with Example 11 (comparison between embodiments in which only the type of specific silane coupling agent is different), Example 1, in which the specific silane coupling agent is 3-octanoylthio-1-propyltriethoxysilane, showed superior wet performance.

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WO2014129665A1 (ja) * 2013-02-25 2014-08-28 横浜ゴム株式会社 タイヤトレッド用ゴム組成物および空気入りタイヤ
WO2019221184A1 (ja) * 2018-05-16 2019-11-21 横浜ゴム株式会社 タイヤトレッド用ゴム組成物及び空気入りタイヤ
WO2021205932A1 (ja) * 2020-04-07 2021-10-14 Ｚｓエラストマー株式会社 共役ジエン系重合体、共役ジエン系重合体組成物、ゴム架橋物、およびタイヤ

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014129665A1 (ja) * 2013-02-25 2014-08-28 横浜ゴム株式会社 タイヤトレッド用ゴム組成物および空気入りタイヤ
WO2019221184A1 (ja) * 2018-05-16 2019-11-21 横浜ゴム株式会社 タイヤトレッド用ゴム組成物及び空気入りタイヤ
WO2021205932A1 (ja) * 2020-04-07 2021-10-14 Ｚｓエラストマー株式会社 共役ジエン系重合体、共役ジエン系重合体組成物、ゴム架橋物、およびタイヤ

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