WO2020075832A1 - Pneumatique - Google Patents

Pneumatique Download PDF

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Publication number
WO2020075832A1
WO2020075832A1 PCT/JP2019/040138 JP2019040138W WO2020075832A1 WO 2020075832 A1 WO2020075832 A1 WO 2020075832A1 JP 2019040138 W JP2019040138 W JP 2019040138W WO 2020075832 A1 WO2020075832 A1 WO 2020075832A1
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WIPO (PCT)
Prior art keywords
conjugated diene
rubber
group
mass
carbon atoms
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PCT/JP2019/040138
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English (en)
Japanese (ja)
Inventor
悟士 石川
健太郎 熊木
Original Assignee
株式会社ブリヂストン
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Priority to JP2020551241A priority Critical patent/JP7402812B2/ja
Publication of WO2020075832A1 publication Critical patent/WO2020075832A1/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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • 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
    • C08L21/00—Compositions of unspecified rubbers
    • 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 tire.
  • an object of the present invention is to provide a tire that has excellent grip performance on ice and snow road surfaces and wet road surfaces, and can reduce rolling resistance.
  • the gist of the present invention which solves the above problems is as follows.
  • the tire of the present invention is a tire including a tread portion having a base rubber and a cap rubber located on the tire radial direction outer side of the base rubber,
  • the base rubber has a storage elastic modulus E ′ of less than 6 MPa
  • the cap rubber includes a rubber component (A) containing a modified conjugated diene polymer (A1), a reinforcing filler (B) containing silica (B1) and carbon black (B2), and a low temperature softening agent (C).
  • the modified conjugated diene polymer (A1) has a weight average molecular weight of 20 ⁇ 10 4 or more and 300 ⁇ 10 4 or less, and has a molecular weight of 200 ⁇ with respect to the total amount of the modified conjugated diene polymer (A1).
  • the modified conjugated diene-based polymer of 10 4 or more and 500 ⁇ 10 4 or less is contained in an amount of 0.25% by mass or more and 30% by mass or less, and the shrinkage factor (g ′) is less than 0.64
  • the content of the silica (B1) is 65 to 155 parts by mass with respect to 100 parts by mass of the rubber component (A).
  • the rubber component (A) further contains at least one kind (A2) selected from the group consisting of natural rubber, polybutadiene rubber, styrene-butadiene rubber and isoprene rubber. This is because the grip performance of the tire on the snow and snowy road surface and the wet road surface and the reduction of rolling resistance can both be achieved at a higher level.
  • the low temperature softening agent (C) is octyl oleate. This is because the grip performance of the tire on the snowy and snowy road surface and the wet road surface can be further improved.
  • the cap rubber further contains a thermoplastic resin (D). This is because it is possible to achieve a higher level of both the grip performance on a snowy and snowy road surface and the reduction of rolling resistance of the tire.
  • the modified conjugated diene polymer (A1) has a branch and a branching degree of 5 or more. This is because the grip performance of the tire on the snowy and snowy road surface and the wet road surface can be further improved.
  • the modified conjugated diene polymer (A1) has one or more coupling residues and a conjugated diene polymer chain bonded to the coupling residues.
  • the branch preferably includes a branch in which 5 or more conjugated diene polymer chains are bonded to one coupling residue. This is because the grip performance of the tire on the snowy and snowy road surface and the wet road surface can be further improved.
  • the modified conjugated diene polymer (A1) has the following general formula (I):
  • D represents a conjugated diene-based 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 are 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
  • R 6 and R 10 Each independently represents 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 an integer of 1 to 3.
  • the modified conjugated diene-based polymer (A1) is a conjugated diene-based polymer represented by the following general formula (VI):
  • 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 are 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 represents an alkyl group having 1 to 20 carbon atoms or a trialkyl group.
  • m represents an integer of 1 to 3
  • p represents 1 or 2
  • R 12 to R 22 , m and p are independent when they exist
  • 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
  • A is a hydrocarbon group having 1 to 20 carbon atoms or an oxygen atom.
  • a nitrogen atom, a silicon atom, a sulfur atom and a phosphorus atom, Which is an organic group having at least one atom selected from the group and having no active hydrogen] is preferably reacted with a coupling agent represented by the formula (VI).
  • the agent is tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine. And at least one selected from the group consisting of tetrakis (3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane. This is because the rolling resistance of the tire can be further reduced.
  • the base rubber preferably has a tan ⁇ at 60 ° C. of 0.005 to 0.18. This is because at a higher level, it is possible to achieve both grip performance on ice and snow road surfaces and wet road surfaces of the tire and reduction of rolling resistance.
  • the base rubber has at least a natural rubber as a rubber component, and the content ratio of the natural rubber in the rubber component is 70 to 100% by mass. This is because the rolling resistance can be further reduced.
  • the present invention it is possible to provide a tire that has excellent grip performance on ice and snow road surfaces and wet road surfaces, and can reduce rolling resistance.
  • the tire of the present invention is a tire including a tread portion having a base rubber and a cap rubber located outside the base rubber in the tire radial direction. And the present invention is Regarding the base rubber, the storage elastic modulus E ′ is smaller than 6 MPa, Regarding the cap rubber, a rubber component (A) containing the modified conjugated diene polymer (A1), a reinforcing filler (B) containing silica (B1) and carbon black (B2), and a low temperature softening agent (C).
  • the modified conjugated diene polymer (A1) has a weight average molecular weight of 20 ⁇ 10 4 or more and 300 ⁇ 10 4 or less, and has a molecular weight of 200 ⁇ with respect to the total amount of the modified conjugated diene polymer (A1).
  • the modified conjugated diene-based polymer of 10 4 or more and 500 ⁇ 10 4 or less is contained in an amount of 0.25% by mass or more and 30% by mass or less, and the shrinkage factor (g ′) is less than 0.64,
  • the content of the silica (B1) is 65 to 155 parts by mass with respect to 100 parts by mass of the rubber component (A).
  • the modified conjugated diene polymer (A1) as the rubber component (A) of the cap rubber and the inclusion of a low temperature softening agent (C) to improve the loss tangent (tan ⁇ ) in the low temperature range.
  • the loss tangent (tan ⁇ ) in the low temperature range is related to the ice and snow performance and the wet performance of the tire. Therefore, the loss tangent (tan ⁇ ) in the low temperature range is improved, and The grip performance of can be improved.
  • the modified conjugated diene polymer (A1) as the rubber component (A) of the cap rubber, the dispersibility of silica (B1) contained in the cap rubber in a large amount is increased, and as a result, the rolling resistance is also increased.
  • the tire of the present invention includes the tread portion having the base rubber and the cap rubber, and the cap rubber includes the rubber component (A) containing the modified conjugated diene polymer (A1) and silica (B1). And a reinforcing filler (B) containing carbon black (B2), and a low temperature softening agent (C).
  • the rubber component (A) of the cap rubber contains the modified conjugated diene polymer (A1), and may contain other rubber components, if necessary.
  • the modified conjugated diene polymer (A1) has a weight average molecular weight (Mw) of 20 ⁇ 10 4 or more and 300 ⁇ 10 4 or less, based on the total amount of the modified conjugated diene polymer (A1).
  • the modified conjugated diene polymer having a molecular weight of 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less is contained in an amount of 0.25% by mass or more and 30% by mass or less, and a contraction factor (g ′) is less than 0.64. .
  • a polymer having a branch tends to have a smaller molecular size when compared with a linear polymer having the same absolute molecular weight, and the shrinkage factor (g ′) is assumed to be the same.
  • the intrinsic viscosity is used as an index of the size of the molecule
  • the contraction factor (g ') at each absolute molecular weight of the modified conjugated diene polymer was calculated, and the average value of the contraction factor (g') when the absolute molecular weight was 100 ⁇ 10 4 to 200 ⁇ 10 4 was calculated as The contraction factor (g ') of the modified conjugated diene polymer.
  • the "branch” is formed by directly or indirectly binding one polymer to another polymer.
  • the “branching degree” is the number of polymers directly or indirectly bonded to one branch. For example, when five conjugated diene-based polymer chains described below are indirectly bonded to each other via a coupling residue described later, the degree of branching is 5.
  • the coupling residue is a structural unit of a modified conjugated diene-based polymer that is bonded to a conjugated diene-based polymer chain, and is, for example, to react a conjugated diene-based polymer described below with a coupling agent. Is a structural unit derived from a coupling agent.
  • the conjugated diene-based polymer chain is a structural unit of the modified conjugated diene-based polymer, for example, generated by reacting a conjugated diene-based polymer and a coupling agent described below, derived from a conjugated diene-based polymer. 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, and even more preferably 0. It is less than or equal to .57.
  • the lower limit of the contraction factor (g ′) is not particularly limited and may be not more than the detection limit value, but is preferably 0.30 or more, more preferably 0.33 or more, and further preferably 0. It is 0.35 or more, and more preferably 0.45 or more.
  • a rubber composition that constitutes the cap rubber containing the modified conjugated diene polymer (A1)
  • the processability of a "rubber composition” may be improved. Since the contraction factor (g ′) tends to depend on the branching degree, for example, the contraction factor (g ′) can be controlled using the branching degree as an index.
  • the modified conjugated diene polymer (A1) preferably has a branch and a degree of branching of 5 or more.
  • the modified conjugated diene-based polymer (A1) has one or more coupling residues and a conjugated diene-based polymer chain bonded to the coupling residues, and further, the branch has 1 It is more preferable to include 5 or more branches in which the conjugated diene-based polymer chain is bonded to the coupling residue.
  • the structure of the modified conjugated diene-based polymer such that the degree of branching is 5 or more, and the branch contains a branch in which 5 or more conjugated diene-based polymer chains are bonded to one coupling residue.
  • the shrinkage factor (g ′) can be more reliably reduced to less than 0.64.
  • the number of conjugated diene-based polymer chains bonded to one coupling residue can be confirmed from the value of the shrinkage factor (g ').
  • the modified conjugated diene polymer (A1) preferably has a branch and a branching degree of 6 or more.
  • the modified conjugated diene-based polymer (A1) has one or more coupling residues and a conjugated diene-based polymer chain bonded to the coupling residues, and further, the branch has 1 It is more preferable to include a branch in which 6 or more of the conjugated diene-based polymer chains are bonded to the coupling residue of.
  • the structure of the modified conjugated diene-based polymer so that the degree of branching is 6 or more, and the branching includes a branch in which 6 or more conjugated diene-based polymer chains are bonded to one coupling residue.
  • the modified conjugated diene-based polymer (A1) has a branch, and the branching degree is more preferably 7 or more, and further preferably 8 or more.
  • the upper limit of the branching degree is not particularly limited, but is preferably 18 or less.
  • the modified conjugated diene-based polymer (A1) has one or more coupling residues and a conjugated diene-based polymer chain bonded to the coupling residues, and further, the branch has 1 It is even more preferred to include a branch in which 7 or more of the conjugated diene-based polymer chains are bonded to the coupling residue of, and 8 or more of the conjugated diene for 1 of the coupling residue.
  • the branch includes a branch in which 8 or more conjugated diene-based polymer chains are bonded to one coupling residue.
  • the contraction factor (g ′) can be reduced to 0.59 or less.
  • the modified conjugated diene polymer (A1) preferably has a nitrogen atom and a silicon atom.
  • the processability of the rubber composition containing the modified conjugated diene polymer (A1) is improved, and the rolling resistance is improved while improving the grip performance on the ice and snow road surface and the wet road surface of the tire, and the wear resistance. It can be further reduced.
  • the fact that the modified conjugated diene polymer (A1) has a nitrogen atom can be confirmed by the presence or absence of adsorption to a specific column by a method described in Examples described later. Further, the fact that the modified conjugated diene polymer (A1) has a silicon atom can be confirmed by metal analysis by the method described in Examples described later.
  • At least one end of the conjugated diene polymer chain is bonded to the silicon atom of the coupling residue.
  • the ends of a plurality of conjugated diene polymer chains may be bonded to one silicon atom.
  • the terminal of the conjugated diene polymer chain and the alkoxy group or hydroxyl group having 1 to 20 carbon atoms are bonded to one silicon atom, and as a result, the one silicon atom is converted to an alkoxysilyl group having 1 to 20 carbon atoms. Or a silanol group.
  • the modified conjugated diene-based copolymer (A1) can be an oil-extended polymer to which an extension oil is added.
  • the modified conjugated diene-based copolymer (A1) may be non-oil extended or oil extended, but from the viewpoint of abrasion resistance, the Mooney viscosity measured at 100 ° C. is 20 or more and 100 or more. It is preferably not more than 30 and more preferably not less than 30 and not more than 80.
  • the Mooney viscosity is measured by the method described in Examples below.
  • the modified conjugated diene polymer (A1) has a weight average molecular weight (Mw) of 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. And more preferably 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 further preferably 150 ⁇ 10 4 or less.
  • the weight average molecular weight is less than 20 ⁇ 10 4 , the grip performance on the ice / snow road surface and the wet road surface of the tire and the reduction of rolling resistance cannot both be achieved at a high level.
  • the processability of the rubber composition containing the modified conjugated diene-based copolymer (A1) deteriorates.
  • the weight average molecular weights of the modified conjugated diene polymer (A1) and the conjugated diene polymer described later are measured by the method described in Examples described later.
  • the modified conjugated diene polymer (A1) is a modified conjugated diene polymer having a molecular weight of 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less with respect to the total amount (100% by mass) of the modified conjugated diene polymer.
  • specific high molecular weight component is contained in an amount of 0.25% by mass or more and 30% by mass or less. Whether the content of the specific high molecular weight component is less than 0.25% by mass or more than 30% by mass, the grip performance on the ice and snow road surface and the wet road surface of the tire and the reduction of rolling resistance are compatible at a high level. I can't.
  • the modified conjugated diene polymer (A1) contains a specific high molecular weight component preferably in an amount of 1.0% by mass or more, more preferably 1.4% by mass or more, and further preferably 1.75% by mass or more. , More preferably 2.0% by mass or more, particularly preferably 2.15% by mass or more, and very preferably 2.5% by mass or more. Further, the modified conjugated diene polymer (A1) contains a specific high molecular weight component, preferably 28 mass% or less, more preferably 25 mass% or less, further preferably 20 mass% or less, and further preferably Contains 18 mass% or less.
  • molecular weight is a standard polystyrene conversion molecular weight obtained by GPC (gel permeation chromatography).
  • GPC gel permeation chromatography
  • 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.
  • the rubber composition containing the modified conjugated diene polymer (A1) has good processability.
  • the number average molecular weight, the weight average molecular weight, the molecular weight distribution, and the content of the specific high molecular weight component with respect to the modified conjugated diene polymer (A1) and the conjugated diene polymer described below are the methods described in Examples described later. To measure.
  • the method for producing the modified conjugated diene polymer (A1) 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 pentafunctional or higher-functional reactive compound (hereinafter, also referred to as “coupling agent”) 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 (A1) is preferably obtained by reacting the conjugated diene polymer with a coupling agent represented by the general formula (VI).
  • a coupling agent represented by the general formula (VI) By using the rubber composition containing the modified conjugated diene polymer (A1) which is reacted with the coupling agent for a tire, it is possible to improve the wear resistance of the tire and reduce the rolling resistance.
  • 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 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 represents an alkylene group having 1 to 20 carbon atoms.
  • m is an integer of 1 to 3
  • p is 1 or 2
  • R 11 to R 22 , m and p are independent of each other.
  • 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 oxygen atom, nitrogen atom, silicon atom, sulfur atom and phosphorus An organic group having at least one atom selected from the group consisting of atoms and having no active hydrogen is shown.
  • the hydrocarbon group represented by A includes saturated, unsaturated, aliphatic, and aromatic hydrocarbon groups.
  • organic group having no active hydrogen examples include active hydrogen such as a hydroxyl group (—OH), a secondary amino group (> NH), a primary amino group (—NH 2 ), and a sulfhydryl group (—SH).
  • active hydrogen such as a hydroxyl group (—OH), a secondary amino group (> NH), a primary amino group (—NH 2 ), and a sulfhydryl group (—SH).
  • the polymerization step is preferably a polymerization by a growth reaction by a living anion polymerization reaction, whereby a conjugated diene polymer having an active terminal can be obtained, and a modified diene polymer (A1) having a high modification rate is obtained.
  • the conjugated diene polymer is obtained by polymerizing at least a conjugated diene compound, and is optionally obtained by copolymerizing both a conjugated diene compound and a vinyl-substituted aromatic compound.
  • 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. Examples of such conjugated diene compounds include 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.
  • the vinyl-substituted aromatic compound is preferably a monovinyl aromatic compound.
  • 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 amount of the organic monolithium compound used as a polymerization initiator is preferably determined according to the molecular weight of the target conjugated diene polymer or modified conjugated diene polymer.
  • the amount of the monomer such as the conjugated diene compound used with respect to the amount of the polymerization initiator used is related to the degree of polymerization, that is, the number average molecular weight and / or the weight average molecular weight. Therefore, in order to increase the molecular weight, it is advisable to adjust the amount of the polymerization initiator to decrease, and to decrease the molecular weight, it is advisable to adjust the amount of the polymerization initiator to increase.
  • the organic monolithium compound is preferably an alkyllithium compound from the viewpoint of industrial availability and control of the polymerization reaction.
  • a conjugated diene-based polymer having an alkyl group at the polymerization start terminal is obtained.
  • the alkyl lithium compound include n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, and stilbene lithium.
  • n-butyllithium and sec-butyllithium are preferable from the viewpoint of industrial availability and easy control of the polymerization reaction.
  • These organic monolithium compounds may be used alone or in combination of two or more.
  • examples of the polymerization reaction mode include batch type and continuous type polymerization reaction modes.
  • the continuous mode one or two or more connected reactors can be used.
  • the continuous reactor for example, a tank type with a stirrer or a tubular type is used.
  • the monomer, the inert solvent, and the polymerization initiator are continuously fed to the reactor to obtain a polymer solution containing the polymer in the reactor, and the continuous polymerization is performed.
  • the coalescing solution is drained.
  • a tank type with a stirrer is used as the batch reactor.
  • the monomer, the inert solvent, and the polymerization initiator are fed, and the monomer is added continuously or intermittently during the polymerization as necessary, and the polymer is added in the reactor.
  • a polymer solution containing is obtained, and the polymer solution is discharged after completion of the polymerization.
  • a continuous system is preferable, which allows the polymer to be continuously discharged and subjected to the next reaction in a short time.
  • the polymerization step is preferably performed in an inert solvent.
  • the solvent include hydrocarbon-based solvents such as saturated hydrocarbons and aromatic hydrocarbons.
  • Specific hydrocarbon solvents are not limited to the following, for example, butane, pentane, hexane, heptane and other aliphatic hydrocarbons; cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane and other alicyclic hydrocarbons.
  • Hydrocarbons aromatic hydrocarbons such as benzene, toluene, xylene, and hydrocarbons composed of a mixture thereof.
  • a conjugated diene-based polymer having a high concentration of active terminals tends to be obtained, and a modification with a high modification rate is likely to occur. It is preferable because a conjugated diene polymer tends to be obtained.
  • a polar compound may be added in the polymerization step.
  • An aromatic vinyl compound can be randomly copolymerized with a conjugated diene compound by adding a polar compound, and the polar compound can also be used as a vinylating agent for controlling the microstructure of the conjugated diene part. Tends to be able to.
  • polar compound examples include ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, and 2,2-bis (2-oxolanyl) propane; Tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine and quinuclidine; alkali metal such as potassium-tert-amylate, potassium-tert-butyrate, sodium-tert-butyrate and sodium amylate Alkoxide compounds; phosphine compounds such as triphenylphosphine can be used. These polar compounds may be used alone or in combination of two or more.
  • the polymerization temperature is preferably 0 ° C or higher, more preferably 120 ° C or lower, and particularly preferably 50 ° C or higher and 100 ° C or lower, from the viewpoint of productivity. Within such a range, it tends to be possible to sufficiently secure the reaction amount of the coupling agent with respect to the active terminal after completion of the polymerization.
  • the amount of the bound conjugated diene in the conjugated diene polymer or the modified conjugated diene polymer (A1) is not particularly limited, but is preferably 40% by mass or more and 100% by mass or less, and 55% by mass or more and 80% by mass. The following is more preferable.
  • the amount of bound aromatic vinyl in the conjugated diene polymer or the modified conjugated diene polymer (A1) is not particularly limited, but is preferably 0% by mass or more and 60% by mass or less, and 20% by mass or more and 45% by mass.
  • the bound styrene content of the conjugated diene polymer is preferably 35% by mass or more, more preferably 37% by mass or more, further preferably 39% by mass or more, and 40% or more. Is particularly preferable.
  • the amount of bound aromatic vinyl and the amount of bound styrene can be measured by ultraviolet absorption of a phenyl group, and the amount of bound conjugated diene can also be obtained from this. Specifically, the measurement is performed according to the method described in Examples described later.
  • the modified conjugated diene polymer (A1) preferably has a glass transition temperature (Tg) of higher than ⁇ 50 ° C., more preferably ⁇ 30 ° C. or higher and ⁇ 20 ° C. or lower, and ⁇ 45 ° C. or higher and ⁇ 15 ° C. The following is more preferable.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) of the modified conjugated diene polymer (A1) is in the range of ⁇ 45 ° C. or higher and ⁇ 15 ° C. or lower, the grip performance and the rolling resistance reduction of the tire on the snow and snow road surface and the wet road surface are reduced. It can be compatible at a higher level.
  • the DSC curve is recorded while raising the temperature in a predetermined temperature range, and the peak top (Influence point) of the DSC differential curve is taken as the glass transition temperature. Specifically, it is measured by a method described in Examples described later.
  • the reactive compound (coupling agent) is preferably a pentafunctional or higher reactive compound having a nitrogen atom and a silicon atom, and has at least three silicon-containing functional groups.
  • a more preferable coupling agent is one in which at least one silicon atom constitutes an alkoxysilyl group having 1 to 20 carbon atoms or a silanol group, and more preferably a compound represented by the above general formula (VI).
  • the alkoxysilyl group contained in the coupling agent reacts with the active end of the conjugated diene-based polymer to dissociate the alkoxylithium, thereby binding the end of the conjugated diene-based polymer chain to the silicon of the coupling residue. Tend to form.
  • the value obtained by subtracting the SiOR number subtracted by the reaction from the total number of SiOR contained in one molecule of the coupling agent is the number of alkoxysilyl groups contained in the coupling residue.
  • the azasilacycle group of the coupling agent forms a> N-Li bond and a bond between the end of the conjugated diene polymer and the silicon of the coupling residue.
  • The> N-Li bond tends to easily become> NH and LiOH due to water or the like at the time of finishing.
  • the unreacted residual alkoxysilyl group tends to be easily converted to silanol (Si—OH group) by water or the like at the time of finishing.
  • the reaction temperature in the reaction step is preferably the same as the polymerization temperature of the conjugated diene polymer, more preferably 0 ° C or higher and 120 ° C or lower, and further preferably 50 ° C or higher and 100 ° C or lower.
  • the temperature change from the polymerization step to the addition of the coupling agent is preferably 10 ° C or lower, more preferably 5 ° C or lower.
  • the reaction time in the reaction step is preferably 10 seconds or longer, more preferably 30 seconds or longer.
  • the time from the end of the polymerization step to the start of the reaction step is preferably shorter from the viewpoint of the coupling rate, but more preferably 5 minutes or less.
  • the mixing in the reaction step may be mechanical stirring, stirring with a static mixer, or the like.
  • the reaction process is also preferably a continuous process.
  • the reactor in the reaction step for example, a tank type with a stirrer or a tubular type is used.
  • the coupling agent may be diluted with an inert solvent and continuously supplied to the reactor.
  • the reaction step may be carried out by a method of charging the coupling agent into the polymerization reactor or by transferring it to another reactor.
  • A is preferably represented by any of the general formulas (II) to (V).
  • A is represented by any one of formulas (II) to (V)
  • the modified conjugated diene polymer (A1) having more excellent performance can be obtained.
  • B 1 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 10. When a plurality of B 1's are present, each B 1 is independent.
  • 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 represents an integer of 1 to 10. Indicates. When a plurality of B 2 and B 3 are present, they are independent of each other.
  • B 4 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 10.
  • each B 4 is independent.
  • B 5 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 10.
  • each B 5 is independent.
  • examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkylene group having 1 to 20 carbon atoms.
  • A is represented by the general formula (II) or (III), and k represents 0. More preferably, in the general formula (VI), A is represented by the general formula (II) or (III), k represents 0, and in the general formula (II) or (III), a is Indicates an integer of 2 to 10. Even more preferably, in the general formula (VI), A is represented by the general formula (II), k is 0, and in the general formula (II), a is an integer of 2 to 10. Show.
  • Examples of such coupling agents include bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] amine, tris (3-trimethoxysilyl) Propyl) amine, tris (3-triethoxysilylpropyl) amine, tris (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1, 3-propanediamine, tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3- Propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane, Sus
  • tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] -1,3-propanediamine, Tetrakis (3-trimethoxysilylpropyl) -1,3-propanediamine and tetrakis (3-trimethoxysilylpropyl) -1,3-bisaminomethylcyclohexane are particularly preferable.
  • 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 and the number of moles of the coupling agent react in a desired stoichiometric ratio. Can be done, which tends to achieve the desired degree of branching.
  • the specific number of moles of the polymerization initiator is preferably 5.0 times or more, and more preferably 6.0 times or more the mole number of the coupling agent.
  • the number of functional groups ((m ⁇ 1) ⁇ i + p ⁇ j + k) of the coupling agent is preferably an integer of 5 to 10, and more preferably an integer of 6 to 10. preferable.
  • the molecular weight distribution (Mw / Mn) of the conjugated diene-based polymer is preferably 1.5 or more and 2.5 or less, It is preferably 1.8 or more and 2.2 or less.
  • the obtained modified conjugated diene polymer (A2) is preferably one in which a single peak is detected in the molecular weight curve by GPC.
  • the peak molecular weight by GPC of the modified conjugated diene polymer (A1) is Mp 1 and the peak molecular weight of the conjugated diene polymer is Mp 2 , the following formula is preferably satisfied.
  • Mp 1 / Mp 2 ⁇ 1.8 ⁇ 10 ⁇ 12 ⁇ (Mp 2 ⁇ 120 ⁇ 10 4 ) 2 +2 More preferably, Mp 2 is 20 ⁇ 10 4 or more and 80 ⁇ 10 4 or less, and Mp 1 is 30 ⁇ 10 4 or more and 150 ⁇ 10 4 or less. Mp 1 and Mp 2 are determined by the method described in Examples below.
  • the modification ratio of the modified conjugated diene polymer (A1) is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more.
  • the modification rate is measured by the method described in Examples below.
  • a deactivating agent, a neutralizing agent and the like may be added to the copolymer solution, if necessary.
  • the quenching agent include, but are not limited to, water; alcohols such as methanol, ethanol, and isopropanol.
  • the neutralizing agent is not limited to the following, and examples thereof include carboxylic acids such as stearic acid, oleic acid, and versatic acid (mixture of carboxylic acids having 9 to 11 carbon atoms and mainly 10 carbon atoms) with many branches. Acid; an aqueous solution of an inorganic acid, carbon dioxide gas and the like can be mentioned.
  • the modified conjugated diene-based polymer (A1) may be, for example, 2,6-di-tert-butyl-4-hydroxy from the viewpoint of preventing gel formation after polymerization and improving stability during processing.
  • extending oil can be added to the modified conjugated diene copolymer, if necessary.
  • the method of adding the extension oil to the modified conjugated diene polymer is not limited to the following, but the extension oil is added to the polymer solution and mixed to obtain an oil-extended copolymer solution as a desolvent. Is preferred.
  • the extending oil include aroma oil, naphthene oil, paraffin oil and the like.
  • an aromatic alternative oil having a polycyclic aromatic (PCA) component of 3% by mass or less according to the IP346 method is preferable from the viewpoints of environmental safety, oil bleed prevention and wet performance.
  • aroma substitute oils examples include TDAE (Treated Distilate Aromatic Extracts), MES (Mild Extraction, and others such as Mild Extract, Aerosert, Aerosol, etc.) described in Kautschuk ⁇ Gummi ⁇ Kunststoff 52 (12) 799 (1999).
  • the amount of extension oil added is not particularly limited, but is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and 12 parts by mass with respect to 100 parts by mass of the modified conjugated diene polymer (A1). It is particularly preferable that the content is not more than part.
  • the amount of the extender oil added is preferably 1% by mass or more, more preferably 3% by mass or more, and more preferably 5% by mass or more, with respect to 100 parts by mass of the modified conjugated diene polymer (A1). It is particularly preferable that
  • the modified conjugated diene polymer (A1) As a method of obtaining the modified conjugated diene polymer (A1) from the polymer solution, a known method can be used. As the method, for example, after separating the solvent by steam stripping, etc., the polymer is filtered off, further dehydration and drying to obtain the polymer, concentrated in a flushing tank, further vent extruder etc. And a method of directly devolatilizing with a drum dryer or the like.
  • the modified conjugated diene-based polymer (A1) 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).
  • D represents a conjugated diene polymer chain
  • the weight average molecular weight of the conjugated diene polymer chain is preferably 10 ⁇ 10 4 to 100 ⁇ 10 4 .
  • the conjugated diene-based polymer chain is a constituent unit of the modified conjugated diene-based polymer, and is, for example, a structural unit derived from a conjugated diene-based polymer generated by reacting a conjugated diene-based polymer with a coupling agent. is there.
  • 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
  • R 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 are integers of 1 to 3, x ⁇ m, p is 1 or 2
  • y is an integer of 1 to 3, y ⁇ (p + 1)
  • z is 1 Or, an integer of 2 is shown.
  • R 1 to R 11 , m, p, x, y, and z are respectively independent, they may be the same or different.
  • i represents an integer of 0 to 6
  • j represents an integer of 0 to 6
  • k represents an integer of 0 to 6
  • (i + j + k) is an integer of 3 to 10
  • ((x ⁇ i ) + (Y ⁇ j) + (z ⁇ k)) is an integer of 5 to 30.
  • A has a hydrocarbon group having 1 to 20 carbon atoms, or at least one atom selected from the group consisting of oxygen atom, nitrogen atom, silicon atom, sulfur atom, and phosphorus atom, and contains active hydrogen. An organic group which does not have is shown.
  • the hydrocarbon group represented by A includes saturated, unsaturated, aliphatic, and aromatic hydrocarbon groups.
  • Examples of the organic group having no active hydrogen include active hydrogen such as a hydroxyl group (—OH), a secondary amino group (> NH), a primary amino group (—NH 2 ), and a sulfhydryl group (—SH). And an organic group having no functional group.
  • A is preferably represented by any of the general formulas (II) to (V).
  • A is represented by any one of the general formulas (II) to (V)
  • the wear resistance can be highly balanced.
  • A is represented by the general formula (II) or (III), and k represents 0. More preferably, in the general formula (I), A is represented by the general formula (II) or (III), k is 0, and in the general formula (II) or (III), a is Indicates an integer of 2 to 10. Even more preferably, in the general formula (I), A is represented by the general formula (II), k is 0, and in the general formula (II), a is an integer of 2 to 10. Show.
  • the content of the modified conjugated diene polymer (A1) in the rubber component (A) of the cap rubber is preferably 20 to 70% by mass, more preferably 30 to 50% by mass.
  • the content of the modified conjugated diene polymer (A1) in the rubber component (A) is 20% by mass or more, when applied to a tire, the wet performance of the tire can be further improved. Further, when the content of the modified conjugated diene polymer (A1) in the rubber component (A) is 70% by mass or less, the processability of the rubber composition is improved.
  • the rubber component (A) of the cap rubber is, as the other rubber component, at least one (A2) selected from the group consisting of natural rubber, polybutadiene rubber, styrene-butadiene rubber and isoprene rubber (synthetic isoprene rubber), It is preferable to further include.
  • At least one type (A2) selected from the group consisting of natural rubber, polybutadiene rubber, styrene-butadiene rubber, and isoprene rubber (synthetic isoprene rubber) described above may be either unmodified rubber or modified rubber. May be
  • the cap rubber contains a reinforcing filler (B), and as the reinforcing filler, silica (B1) and carbon black (B2).
  • the content ratio of the silica (B1) in the reinforcing filler (B) is preferably 80 to 99% by mass, more preferably 92 to 98% by mass, further preferably 93 to 97% by mass. is there.
  • the proportion of silica (B1) in the reinforcing filler (B) is 80% by mass, the rubber composition containing the reinforcing filler (B) can be improved in low loss property (and eventually in rolling resistance). It is possible to contribute, and when the content is 99% by mass or less, it is possible to suppress deterioration of the processability of the rubber composition.
  • the content of the silica (B1) is 65 to 155 parts by mass, preferably 70 to 150 parts by mass, and more preferably 80 to 130 parts by mass with respect to 100 parts by mass of the rubber component (A). is there.
  • the content of the silica (B1) is 65 parts by mass or more with respect to 100 parts by mass of the rubber component (A)
  • the grip performance of the tire on snowy and snowy road surfaces and wet road surfaces can be improved, and 155 parts by mass or less. By doing so, it is possible to prevent deterioration of the processability of the rubber composition containing the reinforcing filler (B).
  • silica (B1) examples include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, and aluminum silicate. Among these, wet silica is preferable. These silicas may be used alone or in combination of two or more. Further, precipitated silica can be used as the wet silica. Precipitated silica means that at the initial stage of production, the reaction solution proceeds at a relatively high temperature in a neutral to alkaline pH range to grow silica primary particles, and then the primary particles are aggregated by controlling to acidic side. It is the silica obtained as a result.
  • the silica (B1) is cetyl trimethyl ammonium bromide adsorption specific surface area (CTAB) is preferably from 60 ⁇ 200m 2 / g, and more preferably 80 ⁇ 180m 2 / g. If the CTAB of the silica (B1) is 60 m 2 / g or more, the wear resistance of the tire can be further improved, and if the CTAB of the silica (B1) is 200 m 2 / g or less, rolling resistance and a rubber composition. It is possible to suppress deterioration of workability.
  • CTAB cetyl trimethyl ammonium bromide adsorption specific surface area
  • the cetyltrimethylammonium bromide adsorption specific surface area (CTAB) (m 2 / g) means a value measured according to ASTM D3765-92.
  • CTAB cetyltrimethylammonium bromide adsorption specific surface area
  • ASTM D3765-92 is a method for measuring CTAB of carbon black
  • CE-TRAB cetyl trimethyl ammonium bromide
  • silica OT sodium di-2-ethylhexyl sulfosuccinate
  • the specific surface area (m 2 / g) calculated from the amount of CE-TRAB adsorbed is taken as the value of CTAB. This is because carbon black and silica have different surfaces, and therefore it is considered that there is a difference in the amount of CE-TRAB adsorbed even with the same surface area.
  • the carbon black (B2) as the reinforcing filler (B) is not particularly limited, and examples thereof include GPF, FEF, HAF, ISAF, and SAF grade carbon black.
  • GPF GPF
  • FEF FEF
  • HAF HAF
  • ISAF SAF grade carbon black
  • SAF SAF grade carbon black
  • the content of carbon black (B2) in the cap rubber is not particularly limited, but is preferably in the range of 1 to 15 parts by mass and preferably in the range of 3 to 10 parts by mass with respect to 100 parts by mass of the rubber component (A). Is more preferable.
  • carbon black (B2) By blending 1 part by mass or more of carbon black, the wear resistance of the tire is further improved, and if the blending amount of carbon black is 15 parts by mass or less, deterioration of rolling resistance of the tire can be sufficiently suppressed.
  • the reinforcing filler (B) may be the above-mentioned silica (B1) and carbon black (B2), as well as the following general formula (XX): nM ⁇ xSiO y ⁇ zH 2 O (XX) [Wherein M is a metal selected from the group consisting of aluminum, magnesium, titanium, calcium and zirconium, oxides or hydroxides of these metals, and hydrates thereof, or carbonates of these metals. At least one selected; n, x, y, and z are each an integer of 1 to 5, an integer of 0 to 10, an integer of 2 to 5, and an integer of 0 to 10] Can also be included.
  • Aluminum hydroxide [Al (OH) 3 ] such as gibbsite and bayerite, aluminum carbonate [Al 2 (CO 3 ) 3 ], magnesium hydroxide [Mg (OH) 2 ], magnesium oxide (MgO), magnesium carbonate (MgCO 3), talc (3MgO ⁇ 4SiO 2 ⁇ H 2 O), attapulgite (5MgO ⁇ 8SiO 2 ⁇ 9H 2 O), titanium white (TiO 2), titanium black (TiO 2n-1), calcium oxide (CaO), water calcium oxide [Ca (OH) 2], magnesium aluminum oxide (MgO ⁇ Al 2 O 3) , clay (Al 2 O 3 ⁇ 2 iO 2), kaolin (Al
  • the average particle size of the inorganic compound represented by the general formula (XX) is preferably 0.01 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m, from the viewpoint of the balance between abrasion resistance and wet performance.
  • the compounding amount of the inorganic compound of the general formula (XX) is preferably 5 to 25 parts by mass, more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the rubber component (A).
  • the cap rubber may contain a silane coupling agent (E) in order to improve the compounding effect of the silica (B1).
  • the silane coupling agent (E) is represented by the following formula (VII): A m B 3-m Si- ( CH 2) a -S b - (CH 2) a -SiA m B 3-m ⁇ (VII) [In the formula (VII), A is C n H 2n + 1 O (n is an integer of 1 to 3) or a chlorine atom, B is an alkyl group having 1 to 3 carbon atoms, m is an integer of 1 to 3, a is an integer of 1 to 9 and b is an integer of 1 or more.
  • A is C n H 2n + 1 O (n is an integer of 1 to 3) or a chlorine atom
  • B is an alkyl group having 1 to 3 carbon atoms
  • Y is a mercapto group, a vinyl group
  • It is an amino group, a glycidoxy group or an epoxy group
  • m is an integer of 1 to 3
  • c is an integer of 0 to 9.
  • A is C n H 2n + 1 O (n is an integer of 1 to 3) or a chlorine atom
  • B is an alkyl group having 1 to 3 carbon atoms
  • Z is a benzothiazolyl group
  • N N A dimethylthiocarbamoyl group or a methacryloyl group
  • m may be an integer of 1 to 3
  • a may be an integer of 1 to 9
  • b may be an integer of 1 or more and may have a distribution.
  • R 32 is selected from hydrogen or an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an alkenyl group, a cycloalkenyl group and an aryl group;
  • R 33 is — [O (R 38 O) m ] 0.5 — (wherein R 38 is selected from an alkylene group and a cycloalkylene group, and has 1 to 18 carbon atoms, and m is 1 to 4).
  • R 34 is selected from an alkylene group, a cycloalkylene group, a cycloalkylalkylene group, an alkenylene group, an arylene group and an aralkylene group, and has 1 to 18 carbon atoms
  • R 35 is selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and an aralkyl group, and has 1 to 18 carbon atoms.
  • the compound represented by this is preferable.
  • These silane coupling agents (E) and (C) may be used alone or in combination of two or more.
  • Examples of the compound represented by the above formula (VII) include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (3-methyldimethoxysilylpropyl) tetrasulfide, and bis. Examples thereof include (3-triethoxysilylethyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) trisulfide and the like.
  • the alkyl group may be linear or branched, and the alkyl group Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group and the like.
  • the alkenyl group may be linear or branched, and examples of the alkenyl group include a vinyl group, an allyl group and a methanyl group.
  • examples of the cycloalkyl group include a cyclohexyl group and an ethylcyclohexyl group
  • examples of the cycloalkenyl group include a cyclohexenyl group and an ethylcyclohexenyl group
  • examples of the aryl group include a phenyl group and a tolyl group.
  • examples of the aralkyl group include a phenethyl group.
  • the alkylene group may be linear or branched, and examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group. Further, examples of the cycloalkylene group include a cyclohexylene group and the like. Furthermore, in R 34 , the alkenylene group may be linear or branched, and examples of the alkenylene group include a vinylene group and a propenylene group.
  • the cycloalkylalkylene group includes a cyclohexylmethylene group, the arylene group includes a phenylene group, and the aralkylene group includes a xylylene group.
  • a — [O (R 38 O) m ] 0.5 — group is a 1,2-ethanedioxy group, a 1,3-propanedioxy group, or a 1,4-butanedioxy group.
  • the compound represented by the above formula (X) can be synthesized in the same manner as in the method described in JP-A No. 2001-505225, and the product name “NXT” manufactured by Momentive Performance Materials Inc.
  • the amount of the silane coupling agent (E) to be blended is preferably 1 part by mass or more, and 4 parts by mass or more based on 100 parts by mass of the silica (B1) from the viewpoint of improving the dispersibility of the silica (B1). More preferably, it is preferably 20 parts by mass or less, and further preferably 12 parts by mass or less.
  • the cap rubber of the tire of the present invention contains a low temperature softening agent (C).
  • the rubber can be softened in a low temperature range (around 0 ° C.), and thus excellent grip performance on ice and snow road surfaces and wet road surfaces can be realized. It also has the effect of improving the workability and workability of the rubber composition containing the low temperature softening agent (C).
  • the low-temperature softening agent for example, mineral oil derived from minerals, aromatic oil derived from petroleum, paraffin oil, naphthene oil, palm oil derived from natural products, octyl oleate, and the like, but among these, It is preferable to use octyl oleate from the viewpoint of excellent softening performance in a low temperature range and further improving the grip performance of the tire on ice and snow road surfaces and wet road surfaces.
  • the content of the low temperature softening agent (C) is not particularly limited, but is preferably in the range of 1 to 5 parts by mass, and in the range of 1.5 to 3 parts by mass, relative to 100 parts by mass of the rubber component (A). Is more preferable.
  • 1 part by mass or more of the low-temperature softening agent (C) with 100 parts by mass of the rubber component (A) it becomes possible to improve grip performance on ice and snow road surfaces and wet road surfaces, and 5 parts by mass of the softening agent. By blending less than 1 part, it is possible to suppress the decrease in rigidity.
  • the cap rubber of the tire of the present invention preferably further contains a thermoplastic resin (D).
  • the cap rubber contains the thermoplastic resin (D)
  • the grip performance on the ice and snow road surface and the wet road surface of the tire and the reduction of rolling resistance can both be achieved at a higher level.
  • the content of the thermoplastic resin (D) is preferably 1 to 50 parts by mass and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the rubber component (A). If the content of the thermoplastic resin (D) is 1 part by mass or more relative to 100 parts by mass of the rubber component (A), the wet performance of the rubber composition is further improved, and if it is 50 parts by mass or less, It becomes easier to suppress the decrease in elastic modulus of the rubber composition. Therefore, when the content of the thermoplastic resin (D) is 1 to 50 parts by mass with respect to 100 parts by mass of the rubber component (A), the ice and snow road surface of the tire can be further improved.
  • thermoplastic resin (D) examples include C 5 resin, C 5 -C 9 resin, C 9 resin, dicyclopentadiene resin, terpene phenol resin, terpene resin, rosin resin, and alkylphenol resin. At least one selected from the group consisting of a C 5 resin, a C 5 -C 9 resin, a C 9 resin, a dicyclopentadiene resin, a rosin resin, and an alkylphenol resin is preferable.
  • thermoplastic resin (D) contains at least one of C 5 resin, C 5 -C 9 resin, C 9 resin, dicyclopentadiene resin, terpene phenol resin, terpene resin, rosin resin, and alkylphenol resin
  • the wet performance of the tire can be further improved.
  • C 5 resin, C 5 -C 9 resin and C 9 resin are particularly preferable.
  • the C 5 -C 9 type resin and the C 9 type resin have high compatibility with the natural rubber (A1), an effect of increasing the elastic modulus of the rubber composition in the low strain region, and a high strain region of the rubber composition. The effect of lowering the elastic modulus is further increased, and the wet performance of the tire can be further improved.
  • the said thermoplastic resin (D) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the C 5 type resin refers to a C 5 type synthetic petroleum resin, and examples of the C 5 type resin include C 5 fraction obtained by thermal decomposition of naphtha of petrochemical industry, AlCl 3 , BF 3, etc. And an aliphatic petroleum resin obtained by polymerization using the Friedel-Crafts type catalyst.
  • the C 5 fraction usually contains olefinic hydrocarbons such as 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene and 3-methyl-1-butene, 2- Diolefin hydrocarbons such as methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, and 3-methyl-1,2-butadiene are included.
  • a commercially available product can be used as the C 5 resin, for example, "ESCOLETS (registered trademark) 1000 series", which is an aliphatic petroleum resin manufactured by ExxonMobil Chemical Co., Ltd., an aliphatic manufactured by ZEON CORPORATION.
  • ESCOLETS (registered trademark) 1000 series which is an aliphatic petroleum resin manufactured by ExxonMobil Chemical Co., Ltd., an aliphatic manufactured by ZEON CORPORATION.
  • “Quinton (registered trademark) 100 series” which is a petroleum resin
  • the C 5 -C 9 series resin means a C 5 -C 9 series synthetic petroleum resin, and examples of the C 5 -C 9 series resin include a C 5 fraction and a C 9 fraction derived from petroleum. , AlCl 3 , BF 3 and other solid polymers obtained by polymerization using a Friedel-Crafts type catalyst. More specifically, styrene, vinyltoluene, ⁇ -methylstyrene, indene And the like. As the C 5 -C 9 resin, a resin having a small amount of C 9 or more components is preferable from the viewpoint of compatibility with the rubber component.
  • C 9 or more components in the total resin is less than 50 wt%, preferably shall refer to or less than 40 wt%.
  • the C 5 -C 9 resin a commercially available product can be used. Manufactured by Tonen Kagaku Co., Ltd. and the like.
  • the C 9 resin is, for example, vinyltoluene, alkylstyrene, and indene as main monomers, which are C 9 fractions that are by-produced together with petrochemical basic raw materials such as ethylene and propylene by thermal decomposition of naphtha in the petrochemical industry. It is a resin obtained by polymerizing an aromatic having 9 carbon atoms.
  • specific examples of the C 9 fraction obtained by thermal decomposition of naphtha include vinyltoluene, ⁇ -methylstyrene, ⁇ -methylstyrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, indene and the like. Is mentioned.
  • the C 9 -based resin includes C 9 fraction, C 8 fraction such as styrene, C 10 fraction such as methylindene and 1,3-dimethylstyrene, and further naphthalene, vinylnaphthalene, vinylanthracene, p It can also be obtained by using -tert-butylstyrene or the like as a raw material and copolymerizing the C 8 to C 10 fraction or the like as a mixture as it is, for example, with a Friedel-Crafts type catalyst. Further, the C 9 resin may be a modified petroleum resin modified with a compound having a hydroxyl group, an unsaturated carboxylic acid compound or the like.
  • C 9 resin commercially available products can be used.
  • trade names “Nisseki Neopolymer (registered trademark) L-90” and “Nisseki Examples include Neopolymer (registered trademark) 120, Nisseki Neopolymer (registered trademark) 130, Nisseki Neopolymer (registered trademark) 140 (manufactured by JX Nikko Nisseki Energy Co., Ltd.) and the like.
  • the above-mentioned dicyclopentadiene resin is a petroleum resin produced by using dicyclopentadiene obtained by dimerizing cyclopentadiene as a main raw material.
  • dicyclopentadiene resin commercially available products can be used. For example, “1105, 1325,” in the product name “Quinton (registered trademark) 1000 series”, which is an alicyclic petroleum resin manufactured by Nippon Zeon Co., Ltd. 1340 ”and the like.
  • the terpene phenol resin can be obtained, for example, by reacting a terpene with various phenols using a Friedel-Crafts type catalyst, or by further condensing with formalin.
  • a terpene used as a raw material, and monoterpene hydrocarbons such as ⁇ -pinene and limonene are preferable, those containing ⁇ -pinene are more preferable, and ⁇ -pinene is particularly preferable.
  • terpene phenolic resin commercially available products can be used, for example, trade names "Tamanor 803L”, “Tamanor 901” (manufactured by Arakawa Chemical Industry Co., Ltd.), trade names "YS Polystar (registered trademark) U” series.
  • the terpene resin is a solid resin obtained by terpine oil obtained at the same time as obtaining rosin from a pine tree, or by blending a polymerization component separated therefrom, and polymerizing using a Friedel-Crafts type catalyst. Examples thereof include ⁇ -pinene resin and ⁇ -pinene resin.
  • a commercially available product can be used as the terpene resin. 1570702233467_0 Product name "YS" 1570702233467_1 Series (PX-1250, TR-105, etc.), 1570702233467_2 Product name " 1570702233467_3 1570702233467_4 Examples include series (A115, S115, etc.).
  • the rosin resin is a residue remaining after distilling turpentine essential oil by collecting balsams such as pine resin (pine tar) that is sap of a Pinaceae plant.
  • They are a natural resin as a main component, a modified resin obtained by modifying them and processing them by hydrogenation, and a hydrogenated resin. Examples thereof include natural resin rosin, its polymerized rosin and partially hydrogenated rosin; glycerin ester rosin, its partially hydrogenated rosin, fully hydrogenated rosin and polymerized rosin; pentaerythritol ester rosin, its partially hydrogenated rosin and polymerized rosin. .
  • Examples of natural resin rosin include gum rosin contained in raw pine resin, tall oil, tall oil rosin, and wood rosin.
  • As the rosin resin a commercially available product can be used. For example, a product name “Neotol 105” (manufactured by Harima Kasei Co., Ltd.), a product name “SN Tuck 754” (manufactured by San Nopco Co., Ltd.), and a product name “Lime Resin” No.
  • the alkylphenol resin is obtained, for example, by a condensation reaction of an alkylphenol and formaldehyde under a catalyst.
  • alkylphenol resin commercially available products can be used, for example, trade name "Hitanol 1502P” (alkylphenol formaldehyde resin, manufactured by Hitachi Chemical Co., Ltd.), trade name "Takkyrol 201” (alkylphenol formaldehyde resin, Taoka Chemical Industry Co., Ltd.
  • a compounding agent usually used in the rubber industry for example, stearic acid, an antioxidant, zinc oxide (zinc white), a vulcanization accelerator, a vulcanizing agent, etc. is appropriately selected within a range not impairing the object of the present invention. Can be included.
  • the storage elastic modulus E'when measured at 15 Hz, 30 ° C. and 1% strain is preferably 4 to 8 MPa, more preferably 4.5 to 6.5 MPa. 5 to 6.2 is more preferable, 5.2 to 6.0 is particularly preferable, and 5.4 to 5.95 MPa is most preferable.
  • E ′ of the cap rubber and the base rubber at 30 ° C. E ′ of the cap / E ′ of the base rubber is preferably larger than 1, more preferably 1.2 or more, and 1.4 or more. Is more preferable. Further, E ′ of the cap / E ′ of the base rubber is preferably smaller than 2, more preferably 1.9 or less, and further preferably 1.85 or less.
  • the tire of the present invention includes the tread portion having the base rubber and the cap rubber, and the storage elastic modulus E ′ of the base rubber is smaller than 6 MPa.
  • the storage elastic modulus E ′ of the base rubber is an elastic modulus when measured at ⁇ 25 ° C. to 65 ° C. with a viscoelasticity measuring machine and measured at 15 Hz, 30 ° C. and strain 1%.
  • the storage elastic modulus E ′ of the base rubber is preferably 2 to 5 MPa, more preferably 2 to 4 MPa.
  • the storage elastic modulus E ′ of the base rubber is preferably 2.4 or more, more preferably 2.7 or more, and further preferably 2.9 or more.
  • the storage elastic modulus E ′ of the base rubber is preferably 3.9 or less, more preferably 3.75 or less, further preferably 3.6 or less, and particularly preferably 3.45 or less.
  • the base rubber has a tan ⁇ at 60 ° C. of 0.005 to 0. It is preferably 18, more preferably 0.005 to 0.10, and further preferably 0.005 to 0.08.
  • the tan ⁇ at 60 ° C. of the base rubber is 0.005 or more, it is possible to improve the grip performance on ice and snow road surfaces and wet road surfaces, and the tan ⁇ at 60 ° C. of the base rubber is 0.18 or less. As a result, deterioration of rolling resistance can be suppressed.
  • the base rubber may include a rubber component, a filler, and other contained components.
  • the rubber component contained in the base rubber is not particularly limited and can be appropriately changed according to the required performance.
  • the natural rubber or the diene-based synthetic rubber may be contained alone, or the natural rubber and the diene-based synthetic rubber may be used in combination.
  • the rubber component may be composed of 100% of the diene rubber, but may be a rubber other than the diene rubber as long as the object of the present invention is not impaired.
  • BR polybutadiene rubber
  • IR isoprene rubber
  • SBR styrene butadiene rubber
  • SIBR styrene isoprene butadiene rubber
  • CR chloroprene rubber
  • NBR acrylonitrile butadiene rubber
  • EPDM ethylene propylene diene rubber
  • EPM ethylene propylene rubber
  • IIR butyl rubber
  • the rubber component contained in the base rubber contains at least a natural rubber, from the viewpoint of improving grip performance on ice and snow road surfaces and wet road surfaces, and reducing rolling resistance at the same time.
  • the content ratio of the natural rubber therein is preferably 70 to 100% by mass.
  • the filler contained in the base rubber is not particularly limited and can be appropriately changed according to the required performance.
  • the filler may include carbon black, silica, other inorganic fillers, and the like.
  • the kind of the carbon black is not particularly limited and can be appropriately selected according to the required performance.
  • any hard carbon manufactured by the oil furnace method can be used.
  • the content of the carbon black contained in the base rubber is preferably 35 to 45 parts by mass with respect to 100 parts by mass of the rubber component.
  • the content of the carbon black contained in the base rubber is preferably 35 to 45 parts by mass with respect to 100 parts by mass of the rubber component.
  • silica examples include wet silica, colloidal silica, calcium silicate, aluminum silicate, and the like.
  • the silica is preferably wet silica, and more preferably precipitated silica.
  • These silicas have high dispersibility, can reduce rolling resistance of the tire, and can further improve wear resistance.
  • Precipitated silica means that at the initial stage of production, the reaction solution proceeds at a relatively high temperature in a neutral to alkaline pH range to grow silica primary particles, and then the primary particles are aggregated by controlling to acidic side. It is the silica obtained as a result.
  • the base rubber may include other components in addition to the rubber component and the filler described above to the extent that the effects of the invention are not impaired.
  • other components for example, silane coupling agents, softening agents, stearic acid, antioxidants, vulcanization accelerators, vulcanizing agents, and the like, which are commonly used in the rubber industry, can be appropriately contained. .
  • silica When silica is contained as the filler, it is preferable to further contain a silane coupling agent. This is because the effects of silica for reinforcement and low heat build-up can be further improved. Known silane coupling agents can be used as appropriate.
  • antiaging agent known ones can be used and are not particularly limited.
  • a phenol anti-aging agent an imidazole anti-aging agent, an amine anti-aging agent, etc. can be mentioned.
  • These antioxidants can be used alone or in combination of two or more.
  • vulcanization accelerator known ones can be used and are not particularly limited.
  • thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole and dibenzothiazyl disulfide; N-cyclohexyl-2-benzothiazylsulfenamide, Nt-butyl-2-benzothiazylsulfenamide, etc.
  • Sulfenamide-based vulcanization accelerators Sulfenamide-based vulcanization accelerators; guanidine-based vulcanization accelerators such as diphenylguanidine (1,3-diphenylguanidine); tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetradodecylthiuram disulfide, tetraoctyl Thiuram vulcanization accelerators such as thiuram disulfide, tetrabenzyl thiuram disulfide and dipentamethylene thiuram tetrasulfide; Dithiocarbamate vulcanization accelerators such as zinc dimethyldithiocarbamate; Kirujichiorin zinc, and the like.
  • guanidine-based vulcanization accelerators such as diphenylguanidine (1,3-diphenylguan
  • the vulcanization acceleration aid examples include zinc white (ZnO) and fatty acids.
  • the fatty acid may be saturated or unsaturated, linear or branched fatty acid, and the carbon number of the fatty acid is not particularly limited, but for example, a fatty acid having 1 to 30 carbon atoms, preferably 15 to 30 carbon atoms, More specifically, cyclohexanoic acid (cyclohexanecarboxylic acid), naphthenic acid such as alkylcyclopentane having a side chain; hexanoic acid, octanoic acid, decanoic acid (including branched carboxylic acid such as neodecanoic acid), dodecanoic acid, tetradecane Examples thereof include acids, saturated fatty acids such as hexadecanoic acid and octadecanoic acid (stearic acid); unsaturated fatty acids such as methacrylic acid, oleic acid, linoleic acid and
  • the tire of the present invention is not particularly limited except that the tread portion has the cap rubber and the base rubber described above. Further, the tire of the present invention may be vulcanized after molding using an unvulcanized rubber composition depending on the type of tire to be applied, and may be molded using a semi-vulcanized rubber that has undergone a preliminary vulcanization step or the like. After that, the main vulcanization may be further carried out for production. Furthermore, the tire of the present invention is preferably a pneumatic tire, and as the gas to be filled in the pneumatic tire, in addition to normal air or air whose oxygen partial pressure is adjusted, inert gas such as nitrogen, argon, helium, etc. Gas can be used.
  • the tire of the present invention can be used as a tire for various vehicles, it is preferably used as a tire for passenger cars. This is because it is possible to more effectively exhibit both the improvement of the grip performance on the icy and snowy road surface and the wet road surface and the reduction of the rolling resistance.
  • the amount of bound styrene, the microstructure of the butadiene portion, the molecular weight, the shrinkage factor (g '), the Mooney viscosity, the glass transition temperature (Tg), the modification rate, the presence or absence of nitrogen atoms, and the silicon atom of the synthesized modified conjugated diene polymer Existence is analyzed by the following method.
  • Amount of bound styrene Using a modified conjugated diene polymer as a sample, 100 mg of the sample is made up to 100 mL with chloroform and dissolved to obtain a measurement sample. The amount of bound styrene (% by mass) with respect to 100% by mass of the sample is measured by the amount of ultraviolet absorption wavelength (near 254 nm) absorbed by the phenyl group of styrene (Shimadzu Corporation's spectrophotometer "UV-2450"). .
  • 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 (Mp 2) and the ratio (Mp 1 / Mp 2 ) and the molecular weight of 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less are obtained.
  • Mp 1 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
  • TSKgel SuperMultipore HZ-H (trade name, manufactured by Tosoh Corporation) are connected, and a guard column is connected to a column (trade name, TSKguardcolumn SuperMP (HZ) -H, manufactured by Tosoh Corporation) connected as a guard column.
  • 10 mg of a sample for measurement is dissolved in 10 mL of THF to prepare a measurement solution, 10 ⁇ L of the measurement solution is poured into a GPC measuring device, and measurement is performed under the conditions of an oven temperature of 40 ° C. and a THF flow rate of 0.35 mL / min.
  • the above-mentioned peak top molecular weights (Mp 1 and Mp 2 ) are determined as follows.
  • a peak detected as a component having the highest molecular weight is selected.
  • the molecular weight corresponding to the maximum value of the peak is calculated and used as the peak top molecular weight.
  • the ratio of the above-mentioned molecular weight of 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less is calculated by subtracting the ratio of the molecular weight of less than 200 ⁇ 10 4 from the ratio of the molecular weight of 500 ⁇ 10 4 or less to the whole from the integrated molecular weight distribution curve. To do.
  • the eluent uses THF containing 5 mmol / L triethylamine.
  • the product names “TSKgel G4000HXL”, “TSKgel G5000HXL”, and “TSKgel G6000HXL” manufactured by Tosoh Corporation are connected and used.
  • Mooney viscosity Using a conjugated diene polymer or a modified conjugated diene polymer as a sample, a Mooney viscometer (trade name "VR1132" manufactured by Ueshima Seisakusho Co., Ltd.) is used, and an L-shaped rotor is used in accordance with JIS K6300. Measure Mooney viscosity. The measurement temperature is 110 ° C. when a conjugated diene-based polymer is used as a sample, and 100 ° C. when a modified conjugated diene-based polymer is used as a sample. First, after preheating the sample at the test temperature for 1 minute, the rotor is rotated at 2 rpm and the torque after 4 minutes is measured to obtain the Mooney viscosity (ML (1 + 4) ).
  • Glass transition temperature (Tg) Using the modified conjugated diene polymer as a sample and using a differential scanning calorimeter “DSC3200S” manufactured by Mac Science Co., Ltd., in accordance with ISO 22768: 2006, under flow of helium of 50 mL / min, from ⁇ 100 ° C. to 20 ° C./min. The DSC curve is recorded while the temperature is raised at, and the peak top (Infection point) of the DSC differential curve is taken as the glass transition temperature.
  • DSC3200S differential scanning calorimeter
  • the modified conjugated diene polymer is used as a sample, and the property that the modified basic polymer component is adsorbed is applied to a GPC column having a silica gel as a packing material.
  • the amount of adsorption of the sample and the sample solution containing the low-molecular-weight internal standard polystyrene on the silica-based column was determined from the difference between the chromatogram measured on the polystyrene-based column and the chromatogram measured on the silica-based column, and the denaturation rate was determined.
  • sample solution is prepared by dissolving 10 mg of a sample and 5 mg of standard polystyrene in 20 mL of THF.
  • a chromatogram was obtained using an RI detector under the conditions of a temperature of 40 ° C. and a THF flow rate of 0.35 mL / min.
  • TSKgel SuperMultipore HZ-H (trade name, manufactured by Tosoh Corporation) are connected, and a guard column is connected to a column (trade name, TSKguardcolumn SuperMP (HZ) -H, manufactured by Tosoh Corporation) connected as a guard column.
  • GPC measurement conditions using a silica-based column Tosoh's product name "HLC-8320GPC” was used, THF was used as an eluent, and 50 ⁇ L of the sample solution was injected into the apparatus, the column oven temperature was 40 ° C, and the THF flow rate was A chromatogram was obtained using an RI detector at 0.5 ml / min.
  • the column is used by connecting the trade names “Zorbax PSM-1000S”, “PSM-300S”, and “PSM-60S”, and the trade name “DIOL 4.6 ⁇ 12.5 mm 5micron” as a guard column at the front stage. Connect and use.
  • the internal volume is 10 L
  • the internal height (L) to diameter (D) ratio (L / D) is 4.0
  • the bottom has an inlet
  • the top has an outlet
  • a tank reactor with a stirrer A tank type pressure vessel having a stirrer and a temperature control jacket is used as a polymerization reactor.
  • a mixture of 1,3-butadiene (17.2 g / min), styrene (10.5 g / min), and n-hexane (145.3 g / min) mixed in advance with water removed therefrom is mixed.
  • n-butyllithium for inert treatment of residual impurities was added at 0.117 mmol / min, mixed, and then added to the bottom of the reaction group. Supply continuously. Further, polymerization is performed by vigorously mixing 2,2-bis (2-oxolanyl) propane as a polar compound at a rate of 0.019 g / min and n-butyllithium as a polymerization initiator at a rate of 0.242 mmol / min with a stirrer. It was supplied to the bottom of the reactor to continuously continue the polymerization reaction.
  • the temperature is controlled so that the temperature of the polymerization solution at the outlet at the top of the reactor is 75 ° C.
  • a small amount of the polymer solution before the addition of the coupling agent was withdrawn from the top outlet of the reactor, and an antioxidant (BHT) was added so that the amount became 0.2 g per 100 g of the polymer.
  • BHT antioxidant
  • 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 at 0.0302 mmol / min.
  • oil Simultaneously with the antioxidant, oil (JOMO process NC140 manufactured by JX Nikko Nisseki Energy Co., Ltd.) was continuously added to 10.0 g of the polymer, and mixed with a static mixer. The solvent is removed by steam stripping to obtain a modified conjugated diene polymer.
  • the modified conjugated diene-based polymer had a "branching degree" of 8 corresponding to the number of branches expected from the number of functional groups of the coupling agent and the amount added (which can also be confirmed from the value of the contraction 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 in one molecule is 4.
  • Rubber composition for base rubber According to the formulation shown in Table 1, a rubber composition for a base rubber was manufactured using a usual Banbury mixer. Table 1 also shows the storage elastic modulus E ′ (MPa) at 30 ° C. of the obtained vulcanized rubber under the conditions of 15 Hz and 1% strain.
  • Rubber composition for cap rubber With respect to Comparative Examples 1 to 3 and Example 1, rubber compositions for cap rubbers were produced according to the formulation shown in Table 2 by using a normal Banbury mixer. Table 2 also shows the storage elastic modulus E ′ (MPa) at 30 ° C. of the obtained vulcanized rubber under the conditions of 15 Hz and 1% strain. Further, for Examples 2 to 28 and Comparative Examples 4 to 112, rubber compositions for cap rubbers are manufactured according to the compounding recipes shown in Tables 3 to 6 using an ordinary Banbury mixer.
  • Examples 1-28, Comparative Examples 1-112> The obtained rubber composition for base rubber and rubber composition for cap rubber are used for a tread portion to prepare a sample of a pneumatic radial tire for passenger cars of size 195 / 65R15.
  • the tires thus obtained are evaluated for grip performance on ice and snow road surfaces, balance between wear resistance and rolling resistance, and balance between grip performance on wet road surfaces (WET grip) and rolling resistance by the following methods. The results are shown in Tables 2-5.
  • E ′ of the cap rubber and the base rubber at ⁇ 20 ° C. were measured.
  • E ′ is E ′ when measured at ⁇ 25 ° C. to 65 ° C. with a viscoelasticity measuring instrument and measured at 15 Hz, ⁇ 20 ° C. and strain 0.1%. Then, assuming that the contribution ratio was 1: 1, E ′ of the tread at ⁇ 20 ° C. was calculated and used as an index of grip performance on ice and snow road surfaces.
  • Comparative Example 1 is indexed as 100
  • Comparative Example 4 is indexed as 100
  • Comparative Example 29 is indexed as 100
  • Comparative Example 57 is indexed as 100
  • Comparative Example 85 is indexed and displayed as 100.
  • the Na 2 O concentration in the resulting solution is 0.015 mol / liter. While maintaining the temperature of this solution at 96 ° C., the same sodium silicate aqueous solution as above was added dropwise at a flow rate of 750 ml / min and sulfuric acid (18 mol / liter) at a flow rate of 33 ml / min at the same time.
  • the neutralization reaction is performed while adjusting the flow rate and 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 begins to become cloudy and the viscosity increases at 30 minutes to form a gel solution. Furthermore, the addition is continued and the reaction is stopped at 100 minutes.
  • the silica concentration in the resulting solution is 85 g / l.
  • sulfuric acid similar to the above is added until the pH of the solution becomes 3, to obtain a silicic acid slurry.
  • the obtained silicic acid slurry is filtered with a filter press and washed with water to obtain a wet cake.
  • the wet cake is dried as a slurry using an emulsifying apparatus with a spray dryer to obtain silica B.
  • the CTAB of the obtained silica B is 79 m 2 / g.
  • Silica C Tosoh Silica Co., Ltd., trade name "AQ-N" * 10 Silica D: Silica obtained by the following method In a 180-liter jacketed stainless steel reactor equipped with a stirrer, 89 liters of water and an aqueous sodium silicate solution (SiO 2 160 g / liter, SiO 2 / Na 2 O molar ratio) were used. 3.3) Add 1.70 liters and heat to 75 ° C. The Na 2 O concentration in the resulting solution is 0.015 mol / liter.
  • the same sodium silicate aqueous solution as above was added dropwise at a flow rate of 520 ml / min and sulfuric acid (18 mol / liter) at a flow rate of 23 ml / min at the same time.
  • the neutralization reaction is performed while adjusting the flow rate and maintaining the Na 2 O concentration in the reaction solution in the range of 0.005 to 0.035 mol / liter.
  • the reaction solution begins to become cloudy and the viscosity increases at 46 minutes to form a gel solution.
  • the addition is continued and the reaction is stopped at 100 minutes.
  • the silica concentration in the resulting solution is 60 g / l.
  • Silane coupling agent 3- [ethoxybis (3,6,9,12,15-pentaoxaoctacosano-1-yloxy) silyl] -1-propanethiol, a silane coupling agent manufactured by Evonik, trade name " Si363 "(registered trademark) * 12 low-temperature softening agents: octyl oleate, Kao Co., Ltd.
  • Example 1 has a higher score than Comparative Examples 1 to 3 and is an excellent effect. From the results of Tables 3 to 6, the samples of Examples have a better balance of grip performance on ice and snow road surfaces, abrasion resistance, grip performance on wet road surfaces, and rolling resistance than the samples of Comparative Examples. It can be seen that the excellent effect is exhibited. In addition, each sample of the comparative example shows a value inferior to the index value in at least one evaluation item.
  • the tire which can reduce rolling resistance can be provided, while having the outstanding grip performance on a snowy and snowy road surface and a wet road surface.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Tires In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention a pour objet de fournir un pneumatique qui tout en présentant d'excellentes performances d'adhérence sur chaussée enneigée ou verglacée et sur chaussé mouillée, permet de réduire la résistance au roulement. À cet effet, le pneumatique de l'invention est équipé d'une bande de roulement qui possède un caoutchouc de base, et un caoutchouc de capuchon positionné côté extérieur du caoutchouc de base dans la direction radiale du pneumatique. Le pneumatique de l'invention est caractéristique en ce que ledit caoutchouc de base présente un module d'élasticité de conservation (E') inférieur à 6MPa. En outre, ledit caoutchouc de capuchon contient un composant caoutchouc (A) contenant un polymère à base de diène conjugué modifié (A1), une charge de renforcement (B) contenant une silice (B1) et un noir de carbone (B2), et un plastifiant à basse température (C). Le polymère à base de diène conjugué modifié (A1) présente une masse moléculaire moyenne en poids supérieure ou égale à ２０×１０４ et inférieure ou égale à ３００×１０４. La masse totale de polymère à base de diène conjugué modifié (A1) comprend 0,25% en masse ou plus à 30% en masse ou moins d'un polymère à base de diène conjugué modifié de masse moléculaire supérieure ou égale à ２００×１０４ et inférieure ou égale à ５００×１０４. Le facteur de retrait (g') dudit caoutchouc de capuchon est inférieur à 0,64, et sa teneur en silice (B1) est comprise entre 65 et155 parties en masse pour 100 parties en masse dudit composant caoutchouc (A).
PCT/JP2019/040138 2018-10-10 2019-10-10 Pneumatique WO2020075832A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62268707A (ja) * 1986-05-19 1987-11-21 Bridgestone Corp 全天候で高運動性能を有する空気入りラジアルタイヤ
JPS63314255A (ja) * 1987-03-10 1988-12-22 Bridgestone Corp 全天候性能を有する改良された高運動性能タイヤ
JP2008013609A (ja) * 2006-07-03 2008-01-24 Toyo Tire & Rubber Co Ltd 重荷重用タイヤのベーストレッド用ゴム組成物
JP2014031405A (ja) * 2012-08-01 2014-02-20 Bridgestone Corp ゴム組成物及びそれを用いた空気入りタイヤ
JP2014189738A (ja) * 2013-03-28 2014-10-06 Bridgestone Corp トレッドベース用ゴム組成物及びそれを用いたタイヤ
JP2018028018A (ja) * 2016-08-17 2018-02-22 旭化成株式会社 変性共役ジエン系重合体組成物、トレッド用ゴム組成物、及びタイヤ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62268707A (ja) * 1986-05-19 1987-11-21 Bridgestone Corp 全天候で高運動性能を有する空気入りラジアルタイヤ
JPS63314255A (ja) * 1987-03-10 1988-12-22 Bridgestone Corp 全天候性能を有する改良された高運動性能タイヤ
JP2008013609A (ja) * 2006-07-03 2008-01-24 Toyo Tire & Rubber Co Ltd 重荷重用タイヤのベーストレッド用ゴム組成物
JP2014031405A (ja) * 2012-08-01 2014-02-20 Bridgestone Corp ゴム組成物及びそれを用いた空気入りタイヤ
JP2014189738A (ja) * 2013-03-28 2014-10-06 Bridgestone Corp トレッドベース用ゴム組成物及びそれを用いたタイヤ
JP2018028018A (ja) * 2016-08-17 2018-02-22 旭化成株式会社 変性共役ジエン系重合体組成物、トレッド用ゴム組成物、及びタイヤ

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