WO2019117168A1 - Composition de caoutchouc et pneumatique - Google Patents

Composition de caoutchouc et pneumatique Download PDF

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Publication number
WO2019117168A1
WO2019117168A1 PCT/JP2018/045560 JP2018045560W WO2019117168A1 WO 2019117168 A1 WO2019117168 A1 WO 2019117168A1 JP 2018045560 W JP2018045560 W JP 2018045560W WO 2019117168 A1 WO2019117168 A1 WO 2019117168A1
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WO
WIPO (PCT)
Prior art keywords
styrene
mass
rubber composition
rubber
tire
Prior art date
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PCT/JP2018/045560
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English (en)
Japanese (ja)
Inventor
あかね 片山
Original Assignee
株式会社ブリヂストン
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Application filed by 株式会社ブリヂストン filed Critical 株式会社ブリヂストン
Priority to JP2019559672A priority Critical patent/JP7288861B2/ja
Publication of WO2019117168A1 publication Critical patent/WO2019117168A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a rubber composition and a tire.
  • Another object of the present invention is to provide a rubber composition capable of solving the above-mentioned problems of the prior art and highly balancing the low loss property of the tire, the wet performance and the dry handling property. Do. Another object of the present invention is to provide a tire that is highly balanced between low loss, wet performance, and dry handling.
  • the gist configuration of the present invention for solving the above problems is as follows.
  • the rubber composition of the present invention comprises a rubber component (A) and a styrene-alkylene block copolymer (B),
  • the styrene / alkylene block copolymer (B) has a total content of styrene units of 30% by mass or more, It is characterized in that the foaming ratio after vulcanization is 5 to 30%.
  • the rubber composition of the present invention by applying to the tread rubber of the tire, it is possible to highly balance the low loss property, the wet performance and the dry handling property of the tire.
  • the styrene / alkylene block copolymer (B) preferably has a glass transition temperature (Tg) of ⁇ 30 ° C. or less.
  • Tg glass transition temperature
  • the alkylene block of the styrene-alkylene block copolymer (B) comprises-[CH 2 -CH (C 2 H 5 )]-units (a) and-(-) And CH 2 -CH 2 ) -unit (b), and the content of the unit (a) is 50 mass to the total mass of all the alkylene blocks [unit (a) + unit (b)] % Or more.
  • the dry handling property of the tire can be further improved by applying the rubber composition to the tread rubber of the tire.
  • the styrene / alkylene block copolymer (B) preferably has a total content of styrene units of 50% by mass or more.
  • the dry handling property of the tire can be further improved by applying the rubber composition to the tread rubber of the tire.
  • the styrene-alkylene block copolymer (B) is a styrene-ethylene butylene-styrene block copolymer.
  • the dry handling property of the tire can be further improved by applying the rubber composition to the tread rubber of the tire.
  • the rubber composition of the present invention further comprises silica (C), and the silica (C) preferably has a BET surface area of 80 to 300 m 2 / g, more preferably 150 to 280 m 2 / g, still more preferably 220. ⁇ 270 meters was 2 / g, also cetyl trimethyl ammonium bromide adsorption specific surface area (CTAB) is preferably 80 ⁇ 260m 2 / g, more preferably 150 ⁇ 260m 2 / g, even more preferably 150 ⁇ 210m 2 / g And particularly preferably 176 to 206 m 2 / g.
  • CAB cetyl trimethyl ammonium bromide adsorption specific surface area
  • the silica (C) has a BET surface area of 220 to 270 m 2 / g and a cetyltrimethylammonium bromide adsorption specific surface area (CTAB) of 176 to 206 m 2 / g.
  • CTAB cetyltrimethylammonium bromide adsorption specific surface area
  • the rubber composition of the present invention further, C 5 resins, C 5 -C 9 resins, C 9 resins, terpene resins, terpene - aromatics-based resin, rosin resin, dicyclopentadiene resin and alkylphenols It is preferable to include at least one resin (D) selected from the group consisting of a system resin.
  • the wet performance of the tire can be further improved by applying the rubber composition to the tread rubber of the tire.
  • the tire according to the present invention is characterized in that the above rubber composition is used as a tread rubber.
  • the rubber composition is used for tread rubber, low loss, wet performance and dry handling are highly balanced.
  • the rubber composition which can make the low loss property of a tire, wet performance, and dry handling property highly balance can be provided. Further, according to the present invention, it is possible to provide a tire which is highly balanced between low loss, wet performance and dry handling.
  • the rubber composition of the present invention comprises a rubber component (A) and a styrene-alkylene block copolymer (B), and the styrene-alkylene block copolymer (B) has a total content of styrene units. It is characterized in that it is 30% by mass or more and the foaming ratio after vulcanization is 5 to 30%. Further, in other words, the vulcanized rubber obtained by vulcanizing the rubber composition of the present invention has a rubber component (A) and a styrene-alkylene block copolymer having a total content of styrene units of 30% by mass or more. It is characterized in that the rubber composition containing the united (B) is vulcanized and the foaming ratio is 5 to 30%.
  • the rubber composition of the present invention by setting the foaming ratio after vulcanization to 5 to 30%, it is possible to achieve both the low loss property and the wet performance of the tire to which the rubber composition is applied. Further, in the rubber composition of the present invention, while adding a styrene-alkylene block copolymer (B), by setting the foaming ratio after vulcanization to 30% or less, the tire composition to which the rubber composition is applied The modulus of elasticity can be improved, and dry handling can be improved. Although the effect is not desired to be bound by theory, the styrene block in the styrene-alkylene block copolymer (B) acts like a filler in the vulcanized rubber composition.
  • the rubber composition of the present invention has a foaming ratio after vulcanization of 5 to 30%, preferably 8 to 25%. If the foaming ratio is too large, the voids on the surface of the rubber composition will also be large, and there is a possibility that a sufficient ground contact area can not be secured, but if the foaming ratio is within the above range, air bubbles effectively functioning as drainage grooves. Since the amount of air bubbles can be appropriately maintained while ensuring the formation of the above, there is no risk of impairing the durability.
  • the foaming ratio after vulcanization of the rubber composition means the average foaming ratio Vs, and specifically means the value calculated by the following equation (1) .
  • Vs ( ⁇ 0 / ⁇ 1 -1) ⁇ 100 (%) (1)
  • ⁇ 1 represents the density (g / cm 3 ) of the rubber composition (foamed rubber) after vulcanization
  • ⁇ 0 represents the solid phase portion in the rubber composition (foamed rubber) after vulcanization
  • the density (g / cm 3 ) is shown.
  • the density of the rubber composition after vulcanization and the density of the solid phase portion of the rubber composition after vulcanization are calculated from the mass in ethanol and the mass in air.
  • the foaming ratio can be appropriately changed according to, for example, the type and amount of the foaming agent and the foaming aid.
  • the rubber component (A) is not particularly limited, and various rubbers can be used.
  • the rubber component (A) include natural rubber (NR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber (CR) And diene rubbers such as isoprene rubber (IR).
  • NR natural rubber
  • SBR styrene-butadiene copolymer rubber
  • BR butadiene rubber
  • NBR acrylonitrile-butadiene copolymer rubber
  • CR chloroprene rubber
  • IR chloroprene rubber
  • the rubber component (A) may be unmodified or modified.
  • the rubber component (A) may be used alone or in combination of two or more.
  • the rubber composition of the present invention preferably contains natural rubber (A1) as the rubber component (A).
  • the rubber composition contains a natural rubber (A1)
  • the low loss property of the tire can be further improved. 20 mass% or more is preferable, 30 mass% or more is still more preferable, 60 mass% or less is preferable, and, as for the content rate of the natural rubber (A1) in the said rubber component (A), 50 mass% or less is still more preferable. If the content of the natural rubber (A1) in the rubber component (A) is 20% by mass or more, the low loss property of the tire can be further improved.
  • the rubber composition of the present invention preferably contains butadiene rubber (BR) (A2) as the rubber component (A).
  • BR butadiene rubber
  • A2 the low loss property of the tire can be further improved. 20 mass% or more is preferable, 30 mass% or more is still more preferable, 60 mass% or less is preferable, and, as for the content rate of the butadiene rubber (A2) in the said rubber component (A), 50 mass% or less is still more preferable. If the content of butadiene rubber (A2) in the rubber component (A) is 20% by mass or more, the low loss property of the tire can be further improved.
  • natural rubber (A1) and butadiene rubber (A2) may be used in combination as the rubber component (A).
  • the natural rubber (A1) and the butadiene rubber (A2) are used in combination, the wet performance and the low loss performance of the tire can be highly compatible.
  • the rubber composition of the present invention preferably contains, as the rubber component (A), a rubber having a glass transition temperature (Tg) exceeding ⁇ 50 ° C. (hereinafter sometimes abbreviated as “high Tg rubber”). .
  • the high Tg rubber preferably has a glass transition temperature (Tg) of -45 ° C or more and -15 ° C or less.
  • Tg glass transition temperature
  • the low loss property of the tire can be further improved.
  • the glass transition temperature according to ISO 22768: 2006, a DSC curve is recorded while raising the temperature in a predetermined temperature range, and is taken as a peak top (Inflection point) of the DSC derivative curve.
  • the content of the high Tg rubber in the rubber component (A) is preferably 40 to 80% by mass, and more preferably 50 to 70% by mass.
  • the content of the high Tg rubber in the rubber component (A) is 40% by mass or more, the wet performance of the tire can be further improved when applied to the tire.
  • the content of the high Tg rubber in the rubber component (A) is 80% by mass or less, the processability of the rubber composition is improved.
  • the modified conjugated diene-based polymer (A3) has a weight average molecular weight of 20 ⁇ 10 4 to 300 ⁇ 10 4 , and a molecular weight of 200 ⁇ with respect to the total amount of the modified conjugated diene polymer (A3).
  • 10 4 or more 500 ⁇ 10 4 or less is modified conjugated diene polymer, comprising 0.25% by mass or more and 30% or less, shrinkage factor (g ') is less than 0.64.
  • shrinkage factor (g ') is less than 0.64.
  • branched polymers tend to be smaller in molecular size when compared with linear polymers having the same absolute molecular weight, and the shrinkage factors (g ′) are assumed to be identical. It is a measure of the ratio of the size occupied by the molecule to the linear polymer, which is an absolute molecular weight of That is, the shrinkage factor (g ') tends to decrease as the degree of branching of the polymer increases.
  • the intrinsic viscosity is used as an index of the molecular size
  • the shrinkage factor (g ') at each absolute molecular weight of the modified conjugated diene polymer is calculated, and the average value of the shrinkage factor (g') at an absolute molecular weight of 100 ⁇ 10 4 to 200 ⁇ 10 4 is calculated
  • a contraction factor (g ') of the modified conjugated diene polymer is calculated.
  • “branched” is formed by direct or indirect bonding of another polymer to one polymer.
  • the “degree of branching” is the number of polymers directly or indirectly bonded to each other for one branch. For example, the degree of branching is 5 when five conjugated diene polymer chains described later are linked to each other indirectly via a coupling residue described later.
  • the coupling residue is a constituent unit of a modified conjugated diene polymer which is bonded to a conjugated diene polymer chain, and for example, a conjugated diene polymer to be described later is reacted with a coupling agent.
  • a coupling agent Is a structural unit derived from a coupling agent.
  • the conjugated diene polymer chain is a constituent unit of a modified conjugated diene polymer, and is derived from, for example, a conjugated diene polymer which is produced by reacting a conjugated diene polymer described later with a coupling agent. It is a structural unit.
  • the contraction factor (g ′) is less than 0.64, preferably 0.63 or less, more preferably 0.60 or less, still more preferably 0.59 or less, still more preferably 0. It is less than .57.
  • the lower limit of the contraction factor (g ′) is not particularly limited, and may be below the detection limit, but is preferably 0.30 or more, more preferably 0.33 or more, and still more preferably 0. It is not less than .35 and more preferably not less than 0.45.
  • the processability of the rubber composition is improved by using the modified conjugated diene-based polymer (A3) in which the shrinkage factor (g ′) is in this range.
  • the contraction factor (g ′) tends to depend on the degree of branching, for example, the contraction factor (g ′) can be controlled using the degree of branching as an index. Specifically, when a modified conjugated diene polymer having a branching degree of 6 is used, the shrinkage factor (g ′) tends to be 0.59 or more and 0.63 or less, and the branching degree is 8 When a certain modified conjugated diene polymer is used, the shrinkage factor (g ′) tends to be 0.45 or more and 0.59 or less.
  • the modified conjugated diene-based polymer (A3) preferably has a branch, and the degree of branching is preferably 5 or more.
  • the modified conjugated diene polymer (A3) has one or more coupling residues, and a conjugated diene polymer chain bonded to the coupling residues, and the above-mentioned branching is 1 It is more preferable to include a branch in which five or more of the conjugated diene-based polymer chains are connected to the coupling residue of Structure of a modified conjugated diene-based polymer such that the degree of branching is 5 or more, and the branch includes a branch in which 5 or more conjugated diene-based polymer chains are bonded to one coupling residue
  • the contraction factor (g ′) can be more reliably made less than 0.64 by specifying
  • the number of conjugated diene-based polymer chains bound to one coupling residue can be confirmed from the value of shrinkage factor (g ').
  • the weight average molecular weight (Mw) of the modified conjugated diene polymer (A3) is 20 ⁇ 10 4 or more and 300 ⁇ 10 4 or less, preferably 50 ⁇ 10 4 or more, and more preferably 64 ⁇ 10 4 or more. More preferably, it is 80 ⁇ 10 4 or more.
  • the weight average molecular weight is preferably 250 ⁇ 10 4 or less, more preferably 180 ⁇ 10 4 or less, and more preferably 150 ⁇ 10 4 or less.
  • the weight average molecular weight is 20 ⁇ 10 4 or more, the low loss property and the wet performance of the tire can be further compatible with each other.
  • the weight average molecular weight is 300 ⁇ 10 4 or less, the processability of the rubber composition is improved.
  • the modified conjugated diene polymer (A3) is a modified conjugated diene polymer having a molecular weight of 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less based on the total amount (100% by mass) of the modified conjugated diene polymer (Hereinafter, it is also called "a specific high molecular weight component.") 0.25 mass% or more and 30 mass% or less. If the content of the specific high molecular weight component is 0.25% by mass or more and 30% by mass or less, the low loss property and the wet performance of the tire can be further highly compatible.
  • the modified conjugated diene polymer (A3) preferably contains 1.0% by mass or more, more preferably 1.4% by mass or more, and still more preferably 1.75% by mass or more of a specific high molecular weight component. Still more preferably, it contains 2.0% by mass or more, particularly preferably 2.15% by mass or more, and very preferably 2.5% by mass or more.
  • the modified conjugated diene polymer (A3) preferably contains a specific high molecular weight component in an amount of 28% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, still more preferably 18 mass% or less is included.
  • “molecular weight” is standard polystyrene conversion molecular weight obtained by GPC (gel permeation chromatography).
  • GPC gel permeation chromatography
  • the use amount of the organic monolithium compound described later as a polymerization initiator may be adjusted.
  • the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.6 or more and 3.0 or less. preferable. If the molecular weight distribution of the modified conjugated diene-based polymer (A3) is in this range, the processability of the rubber composition will be good.
  • the modified conjugated diene-based polymer (A3) is preferably represented by the following general formula (I).
  • D represents a conjugated diene polymer chain
  • R 1 , R 2 and R 3 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms
  • R 4 And R 7 each independently represent an alkyl group having 1 to 20 carbon atoms
  • R 5 , R 8 , and R 9 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
  • 6 and R 10 each independently represent an alkylene group having 1 to 20 carbon atoms
  • R 11 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
  • m and x each independently represent 1 to Represents an integer of 3, x ⁇ m, p represents 1 or 2, y represents an integer of 1 to 3, y ⁇ (p + 1), z represents an integer of
  • A is preferably represented by any of the following general formulas (II) to (V), and is represented by the following general formula (II) or (III) Is more preferred.
  • B 1 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms
  • a represents an integer of 1 to 10
  • B 2 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms
  • B 3 represents an alkyl group having 1 to 20 carbon atoms
  • a is an integer of 1 to 10
  • B 4 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms
  • a represents an integer of 1 to 10
  • B 5 represents a single bond or a hydrocarbon group having a carbon number of 1 ⁇ 20
  • a is an integer of 1 to 10, B 5 when there are a plurality, each independently ing.
  • examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkylene group having 1 to 20 carbon atoms.
  • the method for producing the modified conjugated diene polymer (A3) is not particularly limited, but at least the conjugated diene compound is polymerized using an organic monolithium compound as a polymerization initiator to obtain a conjugated diene polymer. It is preferable to have a polymerization step and a reaction step of reacting a penta- or higher functional reactive compound (hereinafter, also referred to as “coupling agent”) with respect to the active terminal of the conjugated diene polymer. As the coupling agent, it is preferable to react a pentafunctional or higher reactive compound having a nitrogen atom and a silicon atom.
  • the modified conjugated diene polymer (A3) is preferably formed by reacting a conjugated diene polymer with a coupling agent represented by the following general formula (VI).
  • a coupling agent represented by the following general formula (VI) represented by the following general formula (VI).
  • the dry handling property of the tire can be further improved by applying to a tire.
  • R 12 , R 13 and R 14 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms
  • R 15 , R 16 , R 17 , R 18 and R 20 Each independently represents an alkyl group having 1 to 20 carbon atoms
  • R 19 and R 22 each independently represent an alkylene group having 1 to 20 carbon atoms
  • R 21 has 1 to 20 carbon atoms
  • m represents an integer of 1 to 3
  • p represents 1 or 2
  • R 12 to R 22 , m and p each independently represent a plurality of alkyl groups or trialkylsilyl groups.
  • I, j and k each independently represent an integer of 0 to 6, provided that (i + j + k) is an integer of 3 to 10, and A is a hydrocarbon group having 1 to 20 carbon atoms, Or at least at least one selected from the group consisting of oxygen atom, nitrogen atom, silicon atom, sulfur atom and phosphorus atom It has a kind of atom, an organic group having no active hydrogen.
  • the modified conjugated diene-based polymer obtained by reacting the coupling agent represented by the general formula (VI) with the conjugated diene-based polymer is represented by, for example, the general formula (I).
  • A is preferably represented by any of the above general formulas (II) to (V).
  • A is one represented by any of the general formulas (II) to (V)
  • a modified conjugated diene polymer (A3) having more excellent performance can be obtained.
  • Examples of the coupling agent represented by the general formula (VI) include bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl].
  • the addition amount of the compound represented by the general formula (VI) as the coupling agent is adjusted so that the number of moles of the conjugated diene polymer to the number of moles of the coupling agent are reacted in a desired stoichiometric ratio. Can tend to achieve the desired degree of branching.
  • the specific number of moles of the polymerization initiator is preferably 5.0 or more moles, more preferably 6.0 or more moles, with respect to the number of moles of the coupling agent.
  • the number of functional groups of the coupling agent ((m-1) ⁇ i + p ⁇ j + k) is preferably an integer of 5 to 10, more preferably 6 to 10 preferable.
  • the conjugated diene-based polymer is obtained by polymerizing at least a conjugated diene compound, and is obtained by copolymerizing both a conjugated diene compound and a vinyl-substituted aromatic compound, if necessary.
  • the conjugated diene compound is preferably a conjugated diene compound having 4 to 12 carbon atoms, and more preferably a conjugated diene compound having 4 to 8 carbon atoms.
  • conjugated diene compounds for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3 Hexadiene and 1,3-heptadiene.
  • 1,3-butadiene and isoprene are preferable from the viewpoint of industrial availability.
  • These conjugated diene compounds may be used alone or in combination of two or more.
  • a monovinyl aromatic compound is preferable.
  • the monovinyl aromatic compound include styrene, p-methylstyrene, ⁇ -methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene and diphenylethylene.
  • styrene is preferable from the viewpoint of industrial availability.
  • These vinyl-substituted aromatic compounds may be used alone or in combination of two or more.
  • the organic monolithium compound is preferably an alkyllithium compound from the viewpoint of industrial availability and easiness of control of the polymerization reaction.
  • a conjugated diene polymer having an alkyl group at the polymerization initiation end is obtained.
  • the alkyllithium compound include n-butyllithium, sec-butyllithium, tert-butyllithium and n-hexyllithium.
  • n-butyllithium and sec-butyllithium are preferable from the viewpoint of industrial availability and easiness of control of polymerization reaction.
  • These organic monolithium compounds may be used alone or in combination of two or more.
  • the amount of conjugated conjugated diene in the conjugated diene polymer or the modified conjugated diene polymer (A3) is not particularly limited, but is preferably 40% by mass to 100% by mass, and is 55% by mass to 80% by mass. It is more preferable that The amount of bound aromatic vinyl in the conjugated diene polymer or the modified conjugated diene polymer (A3) is not particularly limited, but is preferably 0 mass% or more and 60 mass% or less, and is 20 mass% or more. It is more preferable that it is 45 mass% or less.
  • the amount of conjugated conjugated diene and the amount of conjugated aromatic vinyl is in the above range, the low loss property, the wet performance, and the dry handling property are further highly balanced. Is possible.
  • the amount of bound aromatic vinyl can be measured by the ultraviolet absorption of a phenyl group, and the amount of bound conjugated diene can also be determined from this.
  • the amount of vinyl bond in the conjugated diene bond unit is not particularly limited, but it is preferably 10 mol% or more and 75 mol% or less, and 20 mol % Or more and 65 mol% or less is more preferable.
  • the rubber composition is applied to the tire as the amount of vinyl bond is in the above range, it is possible to further balance the low loss property, the wet performance and the dry handling property.
  • the modified conjugated diene polymer (A3) is a copolymer of butadiene and styrene
  • the method of Hampton [R. R. Hampton, Analytical Chemistry, 21, 923 (1949)] can be used to determine the amount of vinyl bonds (1, 2-bonds) in butadiene bonding units.
  • the molecular weight distribution (Mw / Mn) of the conjugated diene polymer is preferably 1.5 or more and 2.5 or less, more preferably Preferably, it is set to 1.8 or more and 2.2 or less.
  • the modified conjugated diene polymer (A3) to be obtained is a polymer whose molecular weight curve by GPC has a peak detected.
  • the peak molecular weight (Mp 1 ) of the modified conjugated diene polymer (A3) by GPC is preferably 30 ⁇ 10 4 or more and 150 ⁇ 10 4 or less, and the peak molecular weight (Mp 2 ) of the conjugated diene polymer by GPC is 20 ⁇ 10 4 or more and 80 ⁇ 10 4 or less is preferable.
  • the rubber composition of the present invention is a styrene-butadiene copolymer rubber having a glass transition temperature (Tg) of ⁇ 50 ° C. or less (hereinafter sometimes abbreviated as “low Tg SBR”). It is preferable to contain (A4).
  • Tg glass transition temperature
  • the content of low Tg SBR (A4) in the rubber component (A) is preferably 5% by mass or more, preferably 10% by mass or more, preferably 20% by mass or more, and further preferably 40% by mass or more, and 80 % By mass or less is preferable, and 70% by mass or less is more preferable. If the content of the low Tg SBR (A4) in the rubber component (A) is 5% by mass or more, the heat generation of the tire can be further reduced.
  • the rubber composition of the present invention comprises a styrene-alkylene block copolymer (B) having a total content of styrene units of 30% by mass or more.
  • the styrene-alkylene block copolymer (B) is a copolymer having a block derived from a styrenic monomer and an alkylene block, and in the present invention, it is distinguished from the rubber component (A) described above.
  • the total content of styrene units in the styrene-alkylene block copolymer (B) is the total content of blocks derived from styrenic monomers relative to the total mass of the styrene-alkylene block copolymer (B).
  • the styrene / alkylene block copolymer (B) may be used alone or in combination of two or more.
  • the modulus of elasticity of the tire is not sufficiently improved when the rubber composition is applied to the tire, and the tire The dry handling properties of the above can not be sufficiently improved.
  • the styrene / alkylene block copolymer (B) preferably has a total content of styrene units of 50% by mass or more.
  • the total content of styrene units in the styrene-alkylene block copolymer (B) is 50% by mass or more, the dry handling properties of the tire can be further improved.
  • the styrene-alkylene block copolymer (B) is not particularly limited, but the total content of styrene units is preferably 60% by mass or less.
  • the (total) content of the styrene unit of the styrene-alkylene block copolymer (B) and the (total) content of the alkylene unit described later are determined by an integral ratio of 1 H-NMR.
  • the styrene / alkylene block copolymer (B) preferably has a glass transition temperature (Tg) of ⁇ 30 ° C. or less.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) of the styrene / alkylene block copolymer (B) is ⁇ 30 ° C. or less, the low loss property of the tire can be further improved.
  • Tg glass transition temperature
  • a DSC curve is recorded while raising the temperature in a predetermined temperature range, and this is taken as the peak top (Inflection point) of the DSC differential curve.
  • the styrene block of the styrene-alkylene block copolymer (B) has a unit derived from a styrenic monomer (polymerized styrenic monomer).
  • styrenic monomers include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyl toluene and the like. Among these, styrene is preferable as the styrene-based monomer.
  • the alkylene block of the styrene-alkylene block copolymer (B) has an alkylene (divalent saturated hydrocarbon group) unit.
  • an alkylene unit for example, an alkylene group having 1 to 20 carbon atoms can be mentioned.
  • the alkylene unit may be a linear structure, a branched structure, or a combination thereof.
  • Examples of the alkylene unit having a linear structure include, for example,-(CH 2 -CH 2 ) -unit (ethylene unit),-(CH 2 -CH 2 -CH 2 -CH 2 ) -unit (butylene unit), etc. .
  • alkylene unit having a branched structure examples include, for example,-[CH 2 -CH (C 2 H 5 )]-unit (butylene unit),-[CH 2 -CH (CH 3 )]-unit (propylene unit), etc. Be Among these, it is preferable to have an — [CH 2 —CH (C 2 H 5 )] — unit as the alkylene unit.
  • the total content of the alkylene units may be adjusted as appropriate, but it is preferably, for example, 40 to 70% by mass with respect to the total mass of the styrene-alkylene block copolymer (B).
  • the alkylene block of the styrene-alkylene block copolymer (B) is-[CH 2 -CH (C 2 H 5 )]-unit (a) and-(CH 2- CH 2) - units (b), it has a content of the unit (a) is, relative to the total mass of all alkylene block [unit (a) + units (b)], at 50 mass% or more Is preferable, and it is more preferable that the content is 65% by mass or more.
  • the content of the unit (a) is 50% by mass or more, the dry handling properties of the tire can be further improved.
  • styrene / alkylene block copolymer (B) examples include styrene / ethylene butylene / styrene block copolymer (SEBS), styrene / ethylene propylene / styrene block copolymer (SEPS), styrene / ethylene / ethylene propylene / styrene A block copolymer (SEEPS) etc. are mentioned, Among these, a styrene ethylene butylene styrene block copolymer is preferable.
  • the dry handling properties of the tire can be further improved.
  • the ethylene butylene block of the said styrene ethylene butylene styrene block copolymer is a block which has the ethylene unit and the butylene unit which were mentioned above.
  • the styrene-alkylene block copolymer (B) may contain other structural units other than the styrene block and the alkylene block.
  • Examples of such other structural units include structural units having unsaturated bonds such as — [CH 2 —CH (CH (CH 2 )] — units and the like.
  • the synthesis method of the styrene-alkylene block copolymer (B) is not particularly limited, and known methods can be used.
  • a precursor copolymer is obtained by copolymerizing a styrene-based monomer such as styrene and a conjugated diene compound such as 1,3-butadiene or an olefin such as butene, and hydrogenating this precursor copolymer
  • a styrene-alkylene block copolymer (B) can be obtained.
  • styrene / ethylene butylene / styrene block copolymer SEBS
  • SEBS styrene / ethylene butylene / styrene block copolymer
  • SBS styrene block copolymer
  • SEPS styrene isoprene styrene block copolymer
  • B styrene alkylene block copolymer
  • examples of such commercial products include JSR DYNARON (registered trademark) 8903P, 9901P, etc. manufactured by JSR Corporation.
  • the blending amount of the styrene-alkylene block copolymer (B) in the rubber composition of the present invention is not particularly limited, and may be appropriately adjusted.
  • the blending amount of the styrene-alkylene block copolymer (B) is preferably in the range of 5 to 20 parts by mass with respect to 100 parts by mass of the rubber component (A).
  • the blending amount of the styrene-alkylene block copolymer (B) is 5 parts by mass or more with respect to 100 parts by mass of the rubber component (A), the elastic modulus of the tire to which the rubber composition is applied is further improved, The dry handling property can be further improved, and if it is 20 parts by mass or less, the low loss property of the rubber composition is further improved.
  • the rubber composition of the present invention preferably further contains silica (C).
  • silica (C) is, BET surface area of preferably 80 ⁇ 300m 2 / g, more preferably 150 ⁇ 280m 2 / g, more preferably 200 ⁇ 270m 2 / g, more preferably 220 ⁇ 270m 2 / g
  • cetyltrimethylammonium bromide adsorption specific surface area (CTAB) is preferably 80 to 260 m 2 / g, more preferably 150 to 260 m 2 / g, still more preferably 150 to 210 m 2 / g, particularly preferably 176 to It is 206 m 2 / g.
  • the silica (C) has a BET surface area of 220 to 270 m 2 / g and a cetyltrimethylammonium bromide adsorption specific surface area (CTAB) of 176 to 206 m 2 / g.
  • CTAB cetyltrimethylammonium bromide adsorption specific surface area
  • the silica is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate and aluminum silicate. .
  • the blending amount of the silica (C) is particularly preferably in the range of 55 to 70 parts by mass with respect to 100 parts by mass of the rubber component (A). When the amount of silica (C) is in this range, low loss and wet performance can be further improved.
  • the rubber composition of the present invention may contain a filler other than the silica (C) as a filler.
  • a filler other than silica (C) include, for example, carbon black, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, Titanium oxide, potassium titanate, barium sulfate and the like can be mentioned. These fillers may be used alone or in combination of two or more.
  • the compounding amount of the filler is not particularly limited and may be appropriately adjusted. For example, it is 20 to 120 parts by mass with respect to 100 parts by mass of the rubber component (A).
  • the compounding amount of the filler is preferably 50 to 100 parts by mass with respect to 100 parts by mass of the rubber component (A) from the viewpoint of low loss property and wet performance.
  • the proportion of the silica (C) in the filler is not particularly limited and may be appropriately selected according to the purpose, but is preferably 50 to 100% by mass based on the total mass of the filler. 80 to 100% by mass is more preferable, and 90 to 100% by mass is particularly preferable.
  • the rubber composition of this invention contains a silane coupling agent with a silica (C).
  • the silane coupling agent is not particularly limited, and, for example, bis (3-triethoxysilylpropyl) tetrasulfide (for example, trade name “Si69” manufactured by Evonik Co., Ltd.), bis (3-triethoxy) Silylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide (for example, trade name “Si75” manufactured by Evonik Co., Ltd., etc.), bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilyl) Propyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysi
  • silane coupling agents may be used singly or in combination of two or more.
  • the amount of the silane coupling agent is preferably 1 part by mass or more, more preferably 4 parts by mass or more, with respect to 100 parts by mass of the silica (C), from the viewpoint of improving the dispersibility of the silica. 20 parts by mass or less is preferable, and 12 parts by mass or less is more preferable.
  • the rubber composition of the present invention further, C 5 resins, C 5 -C 9 resins, C 9 resins, terpene resins, terpene - aromatics-based resin, rosin resin, dicyclopentadiene resin and alkylphenols It is preferable to include at least one resin (D) selected from the group consisting of a system resin.
  • a resin (D) When the rubber composition contains a resin (D), the wet performance of the tire can be further improved.
  • the compounding amount of the resin (D) is preferably in the range of 5 to 40 parts by mass, and more preferably in the range of 10 to 20 parts by mass with respect to 100 parts by mass of the rubber component (A). When the compounding amount of the resin (D) is in this range, the wet performance of the tire can be further improved.
  • the C 5 -based resin refers to a C 5 -based synthetic petroleum resin, and means a resin obtained by polymerizing a C 5 fraction with a Friedel-Crafts-type catalyst such as AlCl 3 or BF 3 .
  • a Friedel-Crafts-type catalyst such as AlCl 3 or BF 3 .
  • copolymers containing isoprene, cyclopentadiene, 1,3-pentadiene and 1-pentene as main components
  • copolymers of 2-pentene and dicyclopentadiene and 1,3-pentadiene as main components. Polymers and the like.
  • the C 5 -C 9 resin refers to a C 5 -C 9 synthetic petroleum resin, and is obtained by polymerizing a C 5 -C 11 fraction using a Friedel-Crafts-type catalyst such as AlCl 3 or BF 3
  • a resin that For example, copolymers having styrene, vinyl toluene, ⁇ -methylstyrene, indene or the like as a main component can be mentioned.
  • a C 5 -C 9 based resin containing few components of C 9 or more is preferable because of its excellent compatibility with the rubber component.
  • a resin in which the proportion of the C 9 or more component in the C 5 -C 9 resin is less than 50% by mass is preferable, and the resin in which the proportion is 40% by mass or less is more preferable.
  • the C 9 -based resin refers to a C 9 -based synthetic petroleum resin, and means a resin obtained by polymerizing a C 9 fraction using a Friedel-Crafts-type catalyst such as AlCl 3 or BF 3 .
  • a Friedel-Crafts-type catalyst such as AlCl 3 or BF 3 .
  • copolymers having as main components indene, methyl indene, ⁇ -methyl styrene, vinyl toluene and the like can be mentioned.
  • the terpene resin can be obtained by blending turpentine oil obtained at the same time as obtaining rosin from pine tree trees or a polymerization component separated therefrom, and polymerizing using a Friedel-Crafts-type catalyst.
  • turpentine oil obtained at the same time as obtaining rosin from pine tree trees or a polymerization component separated therefrom, and polymerizing using a Friedel-Crafts-type catalyst.
  • ⁇ -pinene resin, ⁇ -pinene resin and the like can be mentioned.
  • the terpene-aromatic resin can be obtained by reacting terpenes with various phenols using a Friedel-Crafts-type catalyst, or by further condensing with formaldehyde.
  • terpene-phenol resin and the like can be mentioned.
  • resins in which the phenol component in the terpene-phenol resin is less than 50% by mass are preferable, and resins having 40% by mass or less are more preferable.
  • the terpene as the raw material is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include monoterpene hydrocarbons such as ⁇ -pinene and limonene. Among these, those containing ⁇ -pinene are preferable, and ⁇ -pinene is more preferable.
  • the rosin-based resin is not particularly limited and may be appropriately selected according to the purpose.
  • natural resin rosins such as gum rosin, tall oil resin and wood rosin contained in raw pine jani and tall oil; modified rosin; Modified rosin derivatives and the like can be mentioned.
  • the modified rosin derivative is, for example, polymerized rosin, partially hydrogenated rosin thereof, glycerin ester rosin, partially hydrogenated rosin or fully hydrogenated rosin thereof, pentaerythritol ester rosin, partially hydrogenated rosin or fully hydrogenated rosin Etc.
  • the dicyclopentadiene resin can be obtained by polymerizing dicyclopentadiene using a Friedel-Crafts-type catalyst such as AlCl 3 or BF 3 .
  • a Friedel-Crafts-type catalyst such as AlCl 3 or BF 3 .
  • Specific examples of commercially available products of dicyclopentadiene resin include Quinton 1920 (manufactured by Nippon Zeon Co., Ltd.), Quinton 1105 (manufactured by Nippon Zeon Co., Ltd.), Malcarez M-890A (manufactured by Maruzen Petrochemical Co., Ltd.), and the like.
  • alkylphenol-type resin there is no restriction
  • alkylphenol- acetylene resin such as p-tert- butylphenol- acetylene resin, the alkylphenol- formaldehyde resin of low polymerization degree, etc. It can be mentioned.
  • unsaturated bonds in the molecule may be partially or completely hydrogenated. If the unsaturated bonds in the molecule of the resin (D) are partially or completely hydrogenated, the wet performance of the tire can be further improved.
  • the hydrogenated resin include a hydrogenated resin of a petroleum-based hydrocarbon resin, and specific examples include Alcon (registered trademark) manufactured by Arakawa Chemical Industries, Ltd., and the like.
  • the hydrogenation is carried out, for example, by supporting a resin having an unsaturated bond in the molecule with an organic carboxylic acid nickel, an organic carboxylic acid cobalt, a hydrogenation catalyst of a group 1 to 3 organic metal compound; carbon, silica, diatomaceous earth, etc.
  • the hydrogenation can be carried out under hydrogen pressure of 1 to 100 atm, using one selected from nickel, platinum, palladium, ruthenium, rhodium metal catalyst, cobalt, nickel, rhodium, ruthenium complex and the like as a catalyst.
  • the resin (D) is preferably a partially or completely hydrogenated C 5 resin, C 5 -C 9 resin, or C 9 resin.
  • Resin (D) is, C 5 resins, if a C 5 -C 9 resins, partially or fully hydrogenated resin C 9 resin, it is possible to further improve the wet performance of the tire.
  • the rubber composition of the present invention preferably contains a foaming agent.
  • a foaming agent when the rubber composition contains a foaming agent, when the rubber composition is vulcanized to produce a vulcanized rubber, bubbles derived from the foaming agent are formed in the vulcanized rubber.
  • foaming agents examples include azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DNPT), dinitrosopentastyrenetetramine and benzenesulfonylhydrazide derivatives, p, p'-oxybisbenzenesulfonylhydrazide (OBSH), ammonium bicarbonate Sodium bicarbonate, ammonium carbonate, nitrososulfonylazo compound, N, N'-dimethyl-N, N'-dinitrosophthalamide, toluenesulfonylhydrazide, p-toluenesulfonyl semicarbazide, p, p'-oxybisbenzenesulfonyl semicarbazide Etc.
  • ADCA azodicarbonamide
  • DNPT dinitrosopentamethylenetetramine
  • OBSH dinitrosopentastyrenetetramine
  • OBSH benz
  • foaming agents dinitrosopentamethylenetetramine (DNPT) is preferred.
  • DNPT dinitrosopentamethylenetetramine
  • these foaming agents may be used alone or in combination of two or more.
  • the compounding amount of the foaming agent is not particularly limited, but is preferably in the range of 0.1 to 30 parts by mass, and in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the rubber component (A). Is more preferred.
  • foaming aid in combination with the above-mentioned foaming agent.
  • foaming assistants may be used alone or in combination of two or more.
  • the foaming aid in combination the foaming reaction can be promoted to increase the degree of completion of the reaction, and unnecessary deterioration can be suppressed with time.
  • the compounding amount of the foaming aid is not particularly limited, but is preferably in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the rubber component (A).
  • the rubber composition of the present invention preferably contains a vulcanizing agent.
  • Sulfur etc. are mentioned as this vulcanizing agent.
  • the amount of the vulcanizing agent is preferably in the range of 0.1 to 10 parts by mass as sulfur, more preferably 1 to 4 parts by mass, as 100 parts by mass of the rubber component (A). If the compounding amount of the vulcanizing agent is 0.1 parts by mass or more as sulfur content, the fracture strength, abrasion resistance and the like of the vulcanized rubber can be secured, and if it is 10 parts by mass or less, sufficient rubber elasticity can be obtained. Can be secured. In particular, the wet performance of the tire can be further improved by setting the blending amount of the vulcanizing agent to 4 parts by mass or less as sulfur content.
  • the rubber composition of the present invention preferably contains a vulcanization accelerator.
  • the vulcanization accelerator is not particularly limited.
  • thiazole-based vulcanization accelerators such as N- (tert-butyl) -2-benzothiazolylsulfenamide (NS) and guanidine-based vulcanization accelerators such as 1,3-diphenylguanidine (DPG).
  • the compounding amount of the vulcanization accelerator is preferably in the range of 0.1 to 7 parts by mass, and more preferably in the range of 0.2 to 5 parts by mass with respect to 100 parts by mass of the rubber component (A).
  • the rubber composition of the present invention can be used for various rubber products including tires.
  • the rubber composition of the present invention is suitable as a tread rubber of a tire.
  • the tire according to the present invention is characterized in that the above rubber composition is used for tread rubber.
  • the rubber composition is used for the tread rubber, the dry handling property is excellent while achieving both the low loss property and the wet performance.
  • the tire of this invention can be utilized as a tire for various vehicles, it is preferable as a tire for passenger cars.
  • the tire of the present invention may be obtained by molding and curing after molding using an unvulcanized rubber composition according to the type of tire to be applied, or by using a semi-vulcanized rubber which has undergone a pre-vulcanization process and the like. After molding, it may be obtained by further vulcanization.
  • the tire according to the present invention is preferably a pneumatic tire, and as a gas to be filled in the pneumatic tire, in addition to normal air having a controlled partial pressure of oxygen, an inert gas such as nitrogen, argon, or helium can be used. It can be used.
  • the rubber composition is manufactured by mixing in the order of the first kneading step and the second kneading step using a normal Banbury mixer. After the completion of the first kneading step, the mixture is once taken out of the Banbury mixer, and thereafter, the mixture is again introduced into the Banbury mixer to carry out the second kneading step. Further, the maximum temperature of the mixture in the first kneading step is 170 ° C., and the maximum temperature of the rubber composition in the second kneading step is 110 ° C.
  • the loss tangent (tan ⁇ ) and the storage elastic modulus (E ′) are measured for the obtained rubber composition by the following method. The prediction results are shown in Table 1.
  • Loss tangent (tan ⁇ ) and storage modulus (E ') A vulcanized rubber obtained by vulcanizing the rubber composition at 145 ° C. for 33 minutes is subjected to conditions of an initial strain of 2%, a dynamic strain of 1% and a frequency of 52 Hz using a spectrometer manufactured by Ueshima Seisakusho Co., Ltd. Measure the tan ⁇ (loss tangent) at 0 ° C. and 30 ° C., and the storage modulus (E ′) at 0 ° C.
  • ⁇ Method of synthesizing SBR1> Add a cyclohexane solution of 1,3-butadiene and a cyclohexane solution of styrene to a dry, nitrogen-substituted 800 mL pressure-resistant glass container so as to be 67.5 g of 1,3-butadiene and 7.5 g of styrene, 0.6 mmol of ditetrahydrofurylpropane was added, and 0.8 mmol of n-butyllithium was added, followed by polymerization at 50 ° C. for 1.5 hours.
  • the combined styrene content, microstructure of butadiene portion, molecular weight, shrinkage factor (g ') and glass transition temperature (Tg) of the synthesized modified styrene-butadiene copolymer rubber were analyzed by the following methods.
  • Amount of bound styrene The modified conjugated diene polymer was used as a sample, and 100 mg of the sample was measured to 100 mL with chloroform and dissolved to obtain a measurement sample. The amount of bound styrene (% by mass) relative to 100% by mass of the sample was measured by the amount of absorption of the ultraviolet absorption wavelength (around 254 nm) by the phenyl group of styrene (Spectrophotometer "UV-2450" manufactured by Shimadzu Corporation) .
  • Microstructure of butadiene moiety (1,2-vinyl bond content)
  • the modified conjugated diene polymer was used as a sample, and 50 mg of the sample was dissolved in 10 mL of carbon disulfide to obtain a measurement sample.
  • the infrared spectrum is measured in the range of 600 to 1000 cm -1 , and the method of Hampton according to the absorbance at a predetermined wave number (the method described in R. R. Hampton, Analytical Chemistry 21, 923 (1949))
  • the microstructure of the butadiene portion that is, the amount of 1,2-vinyl bond (mol%) was determined according to the calculation formula of (Fourier Transform Infrared Spectrophotometer “FT-IR230” manufactured by JASCO Corporation).
  • Molecular weight A GPC measuring apparatus (trade name "HLC-8320GPC” manufactured by Tosoh Corporation) in which three columns of polystyrene gel as a filler are linked using conjugated diene polymer or modified conjugated diene polymer as a sample
  • the chromatogram is measured using an RI detector (trade name "HLC 8020” manufactured by Tosoh Corporation) using a standard polystyrene, and the weight average molecular weight (Mw) and the number are measured based on a calibration curve obtained using standard polystyrene.
  • Mn average molecular weight of the molecular weight distribution (Mw / Mn), a peak top molecular weight of the modified conjugated diene polymer (Mp 1) and a peak top molecular weight of the conjugated diene polymer and (Mp 2), molecular weight 200 ⁇ 10 4
  • Mn average molecular weight of the molecular weight distribution
  • Mp 1 peak top molecular weight of the modified conjugated diene polymer
  • Mp 2 peak top molecular weight of the conjugated diene polymer and
  • the ratio of the molecular weight of 200 ⁇ 10 4 to 500 ⁇ 10 4 is calculated by subtracting the ratio of less than 200 ⁇ 10 4 in molecular weight from the ratio of 500 ⁇ 10 4 of molecular weight or less from the integral molecular weight distribution curve. did.
  • Contraction factor (g ') A light scattering detector using a GPC measurement apparatus (trade name "GPCmax VE-2001” manufactured by Malvern, Inc.) in which three columns of polystyrene-based gel as a packing material are connected using a modified conjugated diene polymer as a sample , RI detector, viscosity detector (trade name "TDA 305" manufactured by Malvern, Inc.) are measured using three detectors connected in order, and based on standard polystyrene, a light scattering detector and an RI detector The absolute molecular weight was determined from the results, and the intrinsic viscosity was determined from the results of the RI detector and the viscosity detector.
  • GPCmax VE-2001 manufactured by Malvern, Inc.
  • g ′ the shrinkage factor
  • 5 mmol / L of triethylamine with triethylamine was used as an eluent.
  • the columns were used by connecting Tosoh brand names “TSKgel G4000HXL”, “TSKgel G5000HXL”, and “TSKgel G6000HXL”.
  • a 20 mg sample for measurement was dissolved in 10 mL of THF to form a measurement solution, 100 ⁇ L of the measurement solution was injected into a GPC measurement apparatus, and measurement was performed under the conditions of an oven temperature of 40 ° C. and a THF flow rate of 1 mL / min.
  • Glass transition temperature (Tg) A modified conjugated diene-based polymer is used as a sample, using a differential scanning calorimeter “DSC 3200 S” manufactured by Mac Science Co., Ltd. in accordance with ISO 22768: 2006, under a flow of helium 50 mL / min, ⁇ 100 ° C. to 20 ° C./min The DSC curve was recorded while raising the temperature with and the peak top (Inflection point) of the DSC differential curve was taken as the glass transition temperature.
  • DSC 3200 S manufactured by Mac Science Co., Ltd. in accordance with ISO 22768: 2006
  • the internal volume is 10 L
  • the ratio (L / D) of the internal height (L) to the diameter (D) is 4.0
  • the inlet is at the bottom
  • the outlet is at the top
  • the tank reactor with stirrer is A tank-type pressure vessel having a stirrer and a jacket for temperature control was used as a polymerization reactor. 17.2 g / min of 1,3-butadiene, 10.5 g / min of styrene, and 145.3 g / min of n-hexane were mixed under the condition of water previously removed.
  • the temperature was controlled so that the temperature of the polymerization solution at the top of the reactor was 75 ° C.
  • a small amount of the polymer solution before addition of the coupling agent is withdrawn from the top outlet of the reactor, and after adding the antioxidant (BHT) to 0.2 g per 100 g of the polymer, the solvent is added It removed and measured various molecular weights.
  • BHT antioxidant
  • 0.0302 mmol / min of tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine diluted to 2.74 mmol / L as a coupling agent was added to the polymer solution flowing out from the outlet of the reactor.
  • the polymer solution to which the coupling agent was added was continuously added by passing through a static mixer at a rate of n-hexane solution (water containing 5.2 ppm), and the coupling reaction was carried out. At this time, the time until the coupling agent is added to the polymerization solution flowing out from the outlet of the reactor is 4.8 minutes and the temperature is 68 ° C., and the temperature in the polymerization step and the addition of the coupling agent are The difference from the temperature was 7 ° C.
  • Antioxidant (BHT) is continuously added at 0.055 g / min (n-hexane solution) to a concentration of 0.2 g per 100 g of the polymer to the polymer solution subjected to the coupling reaction to complete the coupling reaction. did.
  • the “degree of branching” corresponding to the number of branches assumed from the number of functional groups of the coupling agent and the addition amount is 8 (from the value of the shrinkage factor)
  • the “number of SiOR residues” corresponding to a value obtained by subtracting the number of SiORs reduced by the reaction from the total number of SiORs contained in one coupling agent molecule is 4).
  • the modified styrene-butadiene copolymer rubber (2) obtained contains 10.0 parts by mass of an oil component with respect to 100 parts by mass of a rubber component, and has a weight average molecular weight (Mw) of 85.2 ⁇ 10 4 , The ratio of molecular weight 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less is 4.6%, and the contraction factor (g ′) is 0.59.
  • Mw weight average molecular weight
  • g ′ the contraction factor
  • the neutralization reaction was carried out while maintaining the Na 2 O concentration in the reaction solution in the range of 0.005 to 0.035 mol / liter. During the reaction, the reaction solution became cloudy, and the viscosity increased at 46 minutes to form a gel-like solution. Further, the addition was continued to stop the reaction in 100 minutes. The concentration of silica in the resulting solution was 60 g / liter. Subsequently, the same sulfuric acid as above was added until the pH of the solution reached 3, to obtain a siliceous slurry. The obtained silica slurry was filtered by a filter press and washed with water to obtain a wet cake.
  • the wet cake was then dried as a slurry using an emulsifying device with a spray dryer to obtain silica.
  • the obtained silica had CTAB (cetyltrimethylammonium bromide adsorption specific surface area) of 191 (m 2 / g) and BET surface area of 245 (m 2 / g).
  • Silane coupling agent Ethoxy (3-mercaptopropyl) bis (3,6,9,12,15-pentaoxaoctacosan-1-yloxy) silane, manufactured by Evonik Degussa, trade name “Si 363” (registered trademark) Trademark) * 8 Wax: Micro crystal wax, manufactured by Nippon Seiwa Co., Ltd., trade name "Ozo Ace 0701” * 9
  • Anti-aging agent 6PPD N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine, manufactured by Ouchi Emerging Chemical Industry Co., Ltd., trade name "NOCLAK 6C” * 10
  • Anti-aging agent TMQ 2,2,4-trimethyl-1,2-dihydroquinoline polymer, manufactured by SEIKO CHEMICAL CO., LTD., Trade name "Nonflex RD-S” * 11
  • SEBS Styrene ⁇ ethylene butylene ⁇ st
  • the rubber composition of the present invention can be used as a tread rubber of a tire.
  • the tire of the present invention can be used as a tire for various vehicles.

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Abstract

La présente invention aborde le problème de la fourniture d'une composition de caoutchouc grâce à laquelle des propriétés de faible perte, des performances humides et une manipulation à sec d'un pneumatique peuvent être équilibrées à un degré élevé, la composition de caoutchouc en tant que solution à ce problème étant caractérisée en ce qu'elle comprend un composant de caoutchouc (A) et un copolymère séquencé styrène/alkylène (B), le copolymère séquencé styrène/alkylène (B) ayant une teneur totale en motifs styrène d'au moins 30 % en masse et un taux d'expansion après vulcanisation de 5 à 30 %.
PCT/JP2018/045560 2017-12-14 2018-12-11 Composition de caoutchouc et pneumatique WO2019117168A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021124640A1 (fr) * 2019-12-19 2021-06-24 株式会社ブリヂストン Pneu
EP3868823A3 (fr) * 2020-02-21 2021-09-29 Sumitomo Rubber Industries, Ltd. Composition de caoutchouc et pneumatique
WO2021200098A1 (fr) * 2020-04-03 2021-10-07 株式会社ブリヂストン Pneu
WO2022249763A1 (fr) * 2021-05-28 2022-12-01 株式会社ブリヂストン Composition de caoutchouc pour pneumatique, gomme de bande de roulement, et pneumatique
WO2022249765A1 (fr) * 2021-05-28 2022-12-01 株式会社ブリヂストン Composition de caoutchouc pour pneumatique, gomme de bande de roulement, et pneumatique
WO2022249764A1 (fr) * 2021-05-28 2022-12-01 株式会社ブリヂストン Composition de caoutchouc pour pneumatique, gomme de bande de roulement, et pneumatique
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CN114846068A (zh) * 2019-12-19 2022-08-02 株式会社普利司通 轮胎
JP7478754B2 (ja) 2019-12-19 2024-05-07 株式会社ブリヂストン タイヤ
EP3868823A3 (fr) * 2020-02-21 2021-09-29 Sumitomo Rubber Industries, Ltd. Composition de caoutchouc et pneumatique
WO2021200098A1 (fr) * 2020-04-03 2021-10-07 株式会社ブリヂストン Pneu
WO2022249763A1 (fr) * 2021-05-28 2022-12-01 株式会社ブリヂストン Composition de caoutchouc pour pneumatique, gomme de bande de roulement, et pneumatique
WO2022249765A1 (fr) * 2021-05-28 2022-12-01 株式会社ブリヂストン Composition de caoutchouc pour pneumatique, gomme de bande de roulement, et pneumatique
WO2022249764A1 (fr) * 2021-05-28 2022-12-01 株式会社ブリヂストン Composition de caoutchouc pour pneumatique, gomme de bande de roulement, et pneumatique
WO2022249637A1 (fr) * 2021-05-28 2022-12-01 株式会社ブリヂストン Composition de caoutchouc pour pneumatique, gomme de bande de roulement, et pneumatique
WO2022249636A1 (fr) * 2021-05-28 2022-12-01 株式会社ブリヂストン Composition de caoutchouc pour pneumatique, gomme de bande de roulement, et pneumatique
WO2022270122A1 (fr) * 2021-06-22 2022-12-29 株式会社ブリヂストン Composition de caoutchouc vulcanisé et pneu

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