WO2019117266A1 - Composition de caoutchouc et pneumatique - Google Patents

Composition de caoutchouc et pneumatique Download PDF

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Publication number
WO2019117266A1
WO2019117266A1 PCT/JP2018/045983 JP2018045983W WO2019117266A1 WO 2019117266 A1 WO2019117266 A1 WO 2019117266A1 JP 2018045983 W JP2018045983 W JP 2018045983W WO 2019117266 A1 WO2019117266 A1 WO 2019117266A1
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Prior art keywords
styrene
rubber composition
mass
tire
rubber
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PCT/JP2018/045983
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English (en)
Japanese (ja)
Inventor
光彩 青木
孝典 辻
Original Assignee
株式会社ブリヂストン
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Priority to JP2019559211A priority Critical patent/JPWO2019117266A1/ja
Publication of WO2019117266A1 publication Critical patent/WO2019117266A1/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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • 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
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; 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
    • 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
    • C08L53/02—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 of vinyl-aromatic monomers and conjugated dienes
    • 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.
  • wet performance braking performance on wet road surfaces
  • SBR styrene-butadiene copolymer rubber
  • silica styrene-butadiene copolymer rubber
  • NR natural rubber
  • Another object of the present invention is to provide a rubber composition capable of solving the above-mentioned problems of the prior art and achieving a high balance between the low loss property of a tire, the wear resistance and the dry handling property. Do. Another object of the present invention is to provide a tire in which the low loss property, the wear resistance and the dry handling property are highly balanced.
  • 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), a styrene-alkylene block copolymer (B), silica (C) and a silane coupling agent (D),
  • the styrene / alkylene block copolymer (B) has a total content of styrene units of 30% by mass or more,
  • the silane coupling agent (D) is characterized by having a mercapto group.
  • the tire according to the present invention is characterized in that the above rubber composition is used for tread rubber.
  • the rubber composition which can make the low loss property of a tire, abrasion resistance, and dry handling property be highly balanced can be provided. Further, according to the present invention, it is possible to provide a tire in which low loss property, wear resistance and dry handling property are highly balanced.
  • the rubber composition of the present invention comprises a rubber component (A), a styrene-alkylene block copolymer (B), a silica (C) and a silane coupling agent (D), and the above-mentioned styrene-alkylene block co-polymer
  • the polymer (B) has a total content of styrene units of 30% by mass or more, and the silane coupling agent (D) has a mercapto group.
  • the rubber composition of the present invention can optionally contain a filler other than silica (C), a resin (E) and other components.
  • silane coupling agents having a mercapto group tend to deteriorate processability while having high activity.
  • the present inventors combined use of a styrene / alkylene block copolymer (B) containing a predetermined amount or more of styrene units with a silane coupling agent (D) having a mercapto group. It has been found that the above-mentioned deterioration can be suppressed and at the same time, low loss, dry handling and wear resistance of the tire can be made at a high level.
  • the styrene block in the styrene-alkylene block copolymer (B) acts like a filler in the vulcanized rubber composition.
  • an alkylene block is present between the polystyrene blocks, and the friction between the polystyrene blocks is reduced. Therefore, according to the rubber composition of the present invention, by applying to the tread rubber of a tire, it is possible to highly balance the low loss property of the tire, the wear resistance and the dry handling property.
  • 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).
  • 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 a natural rubber (A1) as the rubber component (A).
  • a natural rubber (A1) the low loss property of the tire can be further improved. 20 mass% or more is preferable, and, as for the content rate of the natural rubber (A1) in the said rubber component (A), 30 mass% or more is 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. Moreover, 60 mass% or less is preferable, and, as for the content rate of the natural rubber (A1) in a rubber component (A), 50 mass% or less is more preferable.
  • 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, may be abbreviated as “high Tg rubber”). .
  • the high Tg rubber more preferably has a glass transition temperature (Tg) of ⁇ 45 ° C. or more and ⁇ 15 ° C. or less.
  • Tg rubber a rubber having a glass transition temperature (Tg) of ⁇ 50 ° C. or less may be abbreviated as “low Tg rubber”.
  • the low Tg rubber preferably has a glass transition temperature (Tg) of -150 ° C. or more and -50 ° C.
  • Tg glass transition temperature
  • a glass transition temperature is recorded in accordance with ISO 22768: 2006, while a temperature is raised in a predetermined temperature range, and a DSC curve is recorded to be a peak top (Inflection point) of the DSC differential curve.
  • the content of the high Tg rubber in the rubber component (A) is preferably 20 to 50% by mass, and more preferably 25 to 40% by mass.
  • the content of the high Tg rubber in the rubber component (A) is 20% by mass or more, the wet performance of the tire can be improved when it is applied to the tire.
  • the content of the high Tg rubber in the rubber component (A) is 50% by mass or less, the processability of the rubber composition is improved.
  • the modified conjugated diene-based polymer (A2) has a weight average molecular weight of 20 ⁇ 10 4 or more and 300 ⁇ 10 4 or less, and a molecular weight of 200 ⁇ with respect to the total amount of the modified conjugated diene polymer (A2).
  • 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 to 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 (A2) 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 (A2) preferably has a branch and a degree of branching of 5 or more. Further, the modified conjugated diene polymer (A2) 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 (A2) 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 still more preferably 150 ⁇ 10 4 or less. If the weight average molecular weight is 20 ⁇ 10 4 or more, the low loss property and the wet performance of the tire can be more compatible. When the weight average molecular weight is 300 ⁇ 10 4 or less, the processability of the rubber composition is improved.
  • the modified conjugated diene polymer (A2) 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 more compatible.
  • the modified conjugated diene polymer (A2) 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. Even more preferably, it contains 2.0% by mass or more, particularly preferably 2.15% by mass or more, and most preferably 2.5% by mass or more. In addition, the modified conjugated diene polymer (A2) preferably contains 28% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less of the specific high molecular weight component, and 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 (A2) is in this range, the processability of the rubber composition will be good.
  • the modified conjugated diene polymer (A2) 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 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 each independently represent 1 Represents an integer of to 3, x ⁇ m
  • p represents 1 or 2
  • y represents an integer of 1 to 3
  • z represents an integer of 1 or 2
  • z represents an integer of 1 or 2
  • A is a hydrocarbon group having 1 to 20 carbon atoms, or Represents an organic group having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom, and a phosphorus atom, and having no active hydrogen preferable.
  • the hydrocarbon group represented by A includes saturated, unsaturated, aliphatic and aromatic hydrocarbon groups.
  • the organic group having no active hydrogen include active hydrogens such as hydroxyl group (-OH), secondary amino group (> NH), primary amino group (-NH 2 ) and sulfhydryl group (-SH). And an organic group having no functional group.
  • A is preferably one represented by any one of the following general formulas (II) to (V).
  • 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 a carbon number of 1 to 20
  • 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 and the like.
  • 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 , Represents 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 method for producing the modified conjugated diene polymer (A2) is not particularly limited, but at least a 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 (A2) is a conjugated diene 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 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 is an integer of 1 to 3
  • p is 1 or 2
  • R 12 to R 22 , m and p are each independently 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
  • A is a hydrocarbon group having 1 to 20 carbon atoms Or at least one selected from the group
  • 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 (A2) having more excellent performance can be obtained.
  • the coupling agent represented by the above general formula (VI) for example, bis (3-trimethoxysilylpropyl)-[3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl] Amine, tris (3-trimethoxysilylpropyl) 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-triamine) Methoxysilylpropyl) -1,3-propanediamine, tetrakis (3-trimethoxysilylpropyl) -1,3-bisamin
  • 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 can be reacted at 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 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 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.
  • benzyllithium, phenyllithium, and stilbene lithium can be mentioned as an organic monolithium compound other than the alkyllithium compound.
  • n-butyllithium and sec-butyllithium are preferable from the viewpoint of industrial availability and easiness of control of the 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 (A2) 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 (A2) is not particularly limited, but is preferably 0% by mass or more and 60% by mass or less, and is 20% by 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 abrasion resistance, and the dry handling property are further highly balanced. It becomes 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 low loss, wear resistance, and dry handling with a high degree.
  • the modified conjugated diene polymer (A2) 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, or more. Preferably, it is set to 1.8 or more and 2.2 or less. Moreover, it is preferable that the modified conjugated diene polymer (A2) 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 (A2) by GPC is preferably 30 ⁇ 10 4 or more and 150 ⁇ 10 4 or less
  • the peak molecular weight (Mp 2 ) of the conjugated diene polymer is 20 ⁇ 10 4 or more and 80 ⁇ 10 4 or less
  • (Mp 1 / Mp 2) ⁇ 1.8 ⁇ 10-12 ⁇ (Mp 2 -120 ⁇ 10 4) 2 +2 Mp 2 is more preferably 20 ⁇ 10 4 or more and 80 ⁇ 10 4 or less
  • Mp 1 is more preferably 30 ⁇ 10 4 or more and 150 ⁇ 10 4 or less.
  • the modification ratio of the modified conjugated diene polymer (A2) is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more.
  • a modification rate is 30 mass% or more, when a rubber composition is applied to a tire, rolling resistance can be further reduced, improving the abrasion resistance of a tire.
  • the modification ratio can be measured by applying the characteristic that the modified basic polymer component is adsorbed to a GPC column using a modified conjugated diene polymer as a sample and a silica gel as a filler. .
  • adsorption to a silica-based column from the difference between a chromatogram obtained by measuring a sample solution containing a sample and a low molecular weight internal standard polystyrene with a polystyrene-based column and a chromatogram obtained by measuring the sample solution with a silica-based column
  • the amount can be measured to determine the rate of denaturation.
  • 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). is there.
  • a styrene alkylene block copolymer (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the modulus of elasticity of the tire does not sufficiently improve when the rubber composition is applied to the tire, and at least The dry handling properties of the tire 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 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 said 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.
  • As the alkylene unit having a linear structure for example,-(CH 2 -CH 2 ) -unit (ethylene unit),-(CH 2 -CH 2 -CH 2 -CH 2 ) -unit (linear butylene unit), etc. It can be mentioned.
  • 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 content of the alkylene unit in the above-mentioned styrene / alkylene block copolymer (B) may be suitably adjusted, but for example, it is 40 to 70% by mass with respect to the total mass of the styrene / alkylene block copolymer (B) Is preferred.
  • the alkylene block of the styrene-alkylene block copolymer (B) is-[CH 2 -CH (C 2 H 5 )]-unit (butylene unit),-(CH 2) 2 -CH 2) - and a unit (ethylene units),
  • the content of the butylene units preferably has a total weight less than 50 wt% with respect to the oxybutylene units and the ethylene units, 65 wt% It is more preferable that it is more than.
  • the total amount is preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less.
  • the content is 50% by mass or more, the low loss property and the wear resistance can be further improved while further improving the dry handling property of the tire.
  • styrene / alkylene block copolymer (B) examples include styrene / ethylene butylene / styrene block copolymer (SEBS), styrene / ethylene propylene / styrene block copolymer (SEPS), styrene / ethylene / ethylene / styrene copolymer A polymer (SEEPS) etc. are mentioned, Among these, a styrene ethylene butylene styrene block copolymer is preferable.
  • SEEPS styrene ethylene butylene styrene block copolymer
  • 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 said styrene alkylene block copolymer (B) may contain the other structural units other than the said styrene block and an alkylene block.
  • other structural units for example, structural units having unsaturated bonds such as — [CH 2 —CH (CH (CH 2 )] — units and the like can be mentioned.
  • 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.
  • SEBS styrene / ethylene butylene / styrene block copolymer
  • SBS styrene / ethylene butylene / styrene block copolymer
  • SEPS styrene / ethylene propylene / styrene block copolymer
  • SBS styrene isoprene styrene block copolymer
  • B styrene alkylene block copolymer
  • JSR DYNARON registered trademark
  • 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 30 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 of the tire can be further improved, and if it is 30 parts by mass or less, the low loss property of the tire can be further improved.
  • the blending amount of the styrene-alkylene block copolymer (B) is more preferably 10 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the rubber component (A). .
  • the rubber composition of the present invention contains silica (C).
  • the low loss property of the rubber composition can be improved.
  • the silica (C) preferably has a BET specific surface area of 40 to 350 m 2 / g.
  • the low loss property of the tire can be further improved.
  • the BET specific surface area of the silica (C) is more preferably 80 m 2 / g or more, still more preferably 220 m 2 / g or more, and 300 m 2 / g or less. it is more preferable, and more preferably not more than 270m 2 / g.
  • the BET specific surface area is measured in accordance with JIS K6430.
  • the silica (C) preferably has a cetyltrimethylammonium bromide (CTAB) adsorption specific surface area of 150 to 260 m 2 / g.
  • CTAB cetyltrimethylammonium bromide
  • the low loss property of the tire can be further improved.
  • the CTAB adsorption specific surface area of the silica (C) is more preferably 176 to 206 m 2 / g.
  • cetyltrimethylammonium bromide (CTAB) adsorption specific surface area is measured by the method described in the examples.
  • silica examples include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate and the like, and among these, wet silica is preferable. These silicas may be used alone or in combination of two or more.
  • 40 mass parts or more are preferable with respect to 100 mass parts of said rubber components (A), as for the compounding quantity of the said silica, 45 mass parts or more are more preferable, and 120 mass parts or less are preferable, and 70 mass parts or less are more preferable .
  • the compounding amount of silica is 40 parts by mass or more with respect to 100 parts by mass of the rubber component (A)
  • tan ⁇ at around 60 ° C. of the rubber composition decreases, and the rolling resistance of the tire to which the rubber composition is applied
  • it is 120 parts by mass or less, the flexibility of the rubber composition is high, and by applying the rubber composition to the tread rubber of the tire, the deformation volume of the tread rubber becomes large, and the tire Wet performance can be improved.
  • the rubber composition of the present invention may contain a filler other than silica (C) (hereinafter simply referred to as "filler").
  • a filler other than silica (C) hereinafter simply referred to as "filler”
  • Such fillers include, for example, carbon black, aluminum oxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, magnesium oxide, titanium oxide, titanium Acid potassium, barium sulfate and the like. These fillers may be used alone or in combination of two or more.
  • the carbon black is not particularly limited, and examples thereof include carbon blacks such as high, middle or low structure SAF, ISAF, ISAF-HS, IISAF, N339, HAF, FEF, GPF, SRF grade and the like.
  • the compounding amount of the above-mentioned filler is not particularly limited and may be appropriately adjusted, and is, for example, 2 to 20 parts by mass with respect to 100 parts by mass of the rubber component (A).
  • the compounding amount of the filler is preferably 2 to 10 parts by mass with respect to 100 parts by mass of the rubber component (A) from the viewpoint of low loss and abrasion resistance.
  • the rubber composition of the present invention contains a silane coupling agent (D) having a mercapto group together with the silica (C) in order to improve the blending effect of the silica (C).
  • silane coupling agent for example, bis (3-triethoxysilylpropyl) tetrasulfide (for example, trade name “Si69” manufactured by Evonik Co., Ltd., etc.), bis (3-triethoxysilylpropyl) trisulfide, bis (3 -Triethoxysilylpropyl) disulfide (for example, trade name "Si75” manufactured by Evonik Co., Ltd.), bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2- Trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimeth
  • silane coupling agents (D) may be used alone or in combination of two or more.
  • the above-mentioned silane coupling agent (D) is 3-mercaptopropyltrimethoxysilane, and 3- [ethoxybis (3,6,9,12,15-pentaoxaoctacosan-1-yloxy) silyl]- It is preferably at least one selected from 1-propanethiol. In this case, the low loss property of the tire can be further improved.
  • the amount of the silane coupling agent (D) is preferably 1 part by mass or more, more preferably 4 parts by mass or more, based on 100 parts by mass of the silica (C), from the viewpoint of improving the dispersibility of the silica. Moreover, 20 mass parts or less are preferable, and 12 mass parts or less are 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 (E) selected from the group consisting of a system resin. When the rubber composition contains a resin (E), the wet performance of the tire can be improved.
  • the compounding quantity of the said resin (E) has the preferable range of 5 mass parts or more and 40 mass parts or less with respect to 100 mass parts of said rubber components (A). When the compounding quantity of resin (E) is this range, the wet performance of a tire can be improved effectively. From the same viewpoint, the compounding amount of the resin (E) is more preferably 10 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the rubber component (A).
  • the C 5 resin refers to C 5 type synthetic petroleum resins and C 5 fraction, it means a resin obtained by polymerization using a Friedel-Crafts catalyst such as AlCl 3 or BF 3. Specifically, 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 a 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, wood rosin and the like contained in raw pine jani and tall oil; modified rosin; And modified rosin derivatives.
  • 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 partially 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.), and Marcarets M-890A (manufactured by Maruzen Petrochemical Co., Ltd.).
  • alkyl phenol-type resin there is no restriction
  • unsaturated bonds in the molecule may be partially or completely hydrogenated.
  • the unsaturated bonds in the molecule of the resin (E) are partially or completely hydrogenated, the wet performance of the tire can be effectively improved.
  • a partially or completely hydrogenated C 5 resin, a partially or completely hydrogenated C 5 -C 9 resin, a partially or completely hydrogen Preferred is a C 9 -based resin added. In this case, the wet performance of the tire can be effectively improved.
  • the partially or completely hydrogenated resin commercially available products can be suitably used.
  • the hydrogenation may be carried out, for example, by using a resin having unsaturated bond in the molecule, a hydrogenation catalyst comprising nickel of organic carboxylic acid, cobalt of organic carboxylic acid, organic metal compound of groups 1 to 3; carbon, silica, diatomaceous earth, etc.
  • the hydrogenation can be carried out under a hydrogen pressure of 1 to 100 atm using a catalyst selected from nickel, platinum, palladium, ruthenium, rhodium metal catalyst, cobalt, nickel, rhodium, ruthenium complex and the like supported thereon.
  • the rubber composition of the present invention preferably contains a vulcanizing agent in addition to the components described above. 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, and more preferably in the range of 1 to 4 parts by mass with respect to 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 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 in addition to the components described above.
  • the vulcanization accelerator is, for example, at least one selected from guanidines, sulfenamides, thiazoles, thiourea and diethylthiourea. Each of these may be used alone or in combination of two or more.
  • the guanidines are not particularly limited and can be appropriately selected according to the purpose.
  • 1,3-diphenylguanidine, 1,3-di-o-tolyl guanidine and 1-o-tolylbiguanide are preferable in view of high reactivity, and 1,3-diphenyl guanidine is more preferable.
  • the sulfenamides are not particularly limited and may be appropriately selected depending on the purpose.
  • N- distearyl-2-benzothiazolyl sulfenamide and the like are preferable in terms of high reactivity.
  • the thiazoles are not particularly limited and may be appropriately selected depending on the purpose.
  • Thiourea is a compound represented by NH 2 CSNH 2 .
  • Diethyl thiourea is a compound represented by C 2 H 5 NHCSNHC 2 H 5 .
  • the compounding amount of the vulcanization accelerator is not particularly limited and may be appropriately adjusted according to the purpose.
  • it is 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.
  • the effect of the vulcanization is easily obtained when the amount is 0.1 parts by mass or more, and the excessive progress of the vulcanization can be suppressed when the amount is 20 parts by mass or less.
  • the rubber composition of the present invention more preferably contains at least one selected from guanidines, thiazoles and thioureas.
  • the method for preparing the rubber composition of the present invention is not particularly limited, and components such as a rubber component, a styrene / alkylene block copolymer, and a filler may be kneaded using a known kneading method.
  • the rubber composition of the present invention comprises a rubber component (A), a styrene-alkylene block copolymer (B), silica (C), a silane coupling agent (D), a vulcanization accelerator, and a vulcanizing agent.
  • Kneading step A in which at least part or all of rubber component (A), styrene / alkylene block copolymer (B), silica (C), silane coupling agent (D) and vulcanization accelerator are kneaded
  • a method including the kneading step B in which the kneaded material obtained by the kneading in the kneading step A and the vulcanizing agent are kneaded.
  • the rubber component (A), the styrene / alkylene block copolymer (B), the silica (C), the silane coupling agent (D), a part or all of the vulcanization accelerator, and optionalally, fillers other than silica (C), resin (E) are kneaded.
  • a kneaded material (preliminary composition) is obtained by this kneading.
  • the kneaded material (preliminary composition) prepared in the kneading step A does not contain a vulcanizing agent.
  • the maximum temperature of the mixture is preferably 120 to 190 ° C., preferably 130 to 175 ° C., from the viewpoint of enhancing the activity of the coupling function of the silane coupling agent (D) more suitably. Is more preferable, and the temperature is preferably 140 to 170.degree.
  • the rubber component (A), the styrene-alkylene block copolymer (B), the silica (C), the silane coupling agent (D), and optionally, other than the silica (C) It is preferable to mix
  • the kneading step B is a step of kneading the obtained kneaded product (preliminary composition) and the vulcanizing agent after the kneading step A or the kneading step C described later.
  • the rubber composition can be prepared by this kneading.
  • a vulcanization accelerator may be further added.
  • the maximum temperature of the mixture is preferably 60 to 140 ° C., more preferably 80 to 120 ° C., and still more preferably 100 to 120 ° C.
  • the above method may further include a step (kneading step C) of further kneading between the kneading step A and the kneading step B, if necessary, the kneaded material (preliminary composition) prepared in the kneading step A. Good.
  • the kneading step C may be performed multiple times. However, in the kneading step C, no vulcanizing agent is added.
  • the maximum temperature of the mixture is preferably 120 to 190 ° C., more preferably 130 to 175 ° C., from the viewpoint of more suitably enhancing the activity of the coupling function of the silane coupling agent.
  • the temperature is 140 to 170 ° C.
  • the kneading apparatus used for the kneading is not particularly limited and may be appropriately selected according to the purpose.
  • a single-screw kneading extruder a multi-screw kneading extruder (continuous kneader); Banbury mixer, intermix Kneaders having a meshing or non-meshing type rotary rotor such as a kneader; rolls (batch-type kneading apparatus) and the like.
  • Various conditions such as the rotational speed of the rotor, the ram pressure, the kneading temperature, the type of the kneading apparatus, and the like in the kneading can be appropriately selected.
  • 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 above rubber composition is used for the tread rubber, the dry handling property is excellent while achieving both the low loss property and the wear resistance.
  • 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.
  • ⁇ Preparation of Modified Conjugated Diene-Based Polymer 1> Add a cyclohexane solution of 1,3-butadiene and a cyclohexane solution of styrene to a dry, nitrogen-replaced 800 mL pressure-resistant glass container so that 67.5 g of 1,3-butadiene and 7.5 g of styrene are obtained. 0.6 mmol of ditetrahydrofurylpropane is added, and 0.8 mmol of n-butyllithium is added, followed by polymerization at 50 ° C. for 1.5 hours.
  • ⁇ Preparation of Modified Conjugated Diene-Based Polymer 2> Add a cyclohexane solution of 1,3-butadiene and a cyclohexane solution of styrene to 70.2 g of 1,3-butadiene and 39.5 g of styrene in an 800 mL pressure-resistant glass container which has been dried and replaced with nitrogen. 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 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 styrene-butadiene copolymer (conjugated diene polymer) obtained from the polymer solution before addition of the coupling agent was analyzed and found to have a weight average molecular weight (Mw) of 85.2 ⁇ 10 4 g / mol, and the molecular weight It was found that the ratio of 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less was 4.6%.
  • 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 (can also be confirmed from the value of 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 ring agent molecule is 4.
  • Amount of bound styrene 100 mg of a 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) .
  • Glass transition temperature (Tg) According to ISO 22768: 2006, using a differential scanning calorimeter “DSC3200S” manufactured by Mac Science, under the flow of helium 50 mL / min, record the DSC curve while raising the temperature from ⁇ 100 ° C. to 20 ° C./min. The peak point (Inflection point) of the DSC differential curve was taken as the glass transition temperature.
  • 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 45 minutes to form a gel-like solution. Furthermore, the addition was continued and the reaction was stopped 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 apparatus with a spray dryer to obtain silica 1. The BET specific surface area and the CTAB adsorption specific surface area of the obtained silica 1 were measured by the following method.
  • the OT (sodium di-2-ethylhexylsulfosuccinate) solution is standardized, and the adsorption cross section per molecule of CE-TRAB on the silica surface is 0.35 nm 2 and the adsorption amount of CE-TRAB is based on the specific surface area (m 2 / g ) Was calculated.
  • the CTAB adsorption specific surface area of silica 1 was 180 m 2 / g.
  • Green Strength A tensile test was conducted on the unvulcanized rubber composition in accordance with JIS K 6251: 2010. Specifically, a sheet of a rubber composition having a thickness of 4.00 ⁇ 0.40 mm is punched into a ring shape (JIS-5 type) to prepare a sample, and a speed of 100 ⁇ 5 mm / min at a temperature of 40 ° C. The tensile strength of the unvulcanized rubber composition was measured, and the stress was measured until the time of breakage. Assuming that the tensile strength of Comparative Example 1 is 100, the green strength is indicated as an index. The larger the index value, the better the processability.
  • Viscosity of Unvulcanized Rubber Composition Mooney viscosity was measured at 130 ° C. using an L-shaped rotor in accordance with JIS K 6300-1: 2001.
  • the viscosity of the unvulcanized rubber composition of Comparative Example 1 was indexed as 100. The larger the index value, the better the processability.
  • Storage elastic modulus (E ') and loss tangent (tan ⁇ ) of vulcanized rubber A vulcanized rubber obtained by vulcanizing the rubber composition at 145 ° C. for 33 minutes, using a spectrometer manufactured by Uejima Mfg. Co., Ltd., under conditions of initial strain 2%, dynamic strain 1%, frequency 52 Hz, The storage elastic modulus (E ′) at 30 ° C. and tan ⁇ (loss tangent) at 0 ° C., 30 ° C. and 50 ° C. were measured.
  • the rubber composition which can make the low loss property of a tire, abrasion resistance, and dry handling property be highly balanced can be provided. Further, according to the present invention, it is possible to provide a tire in which low loss property, wear resistance and dry handling property are highly balanced.

Abstract

L'invention concerne une composition de caoutchouc qui permet à un pneumatique d'obtenir un bon équilibre entre une faible tangente de perte, une résistance à l'usure et des propriétés de manipulation à sec. Cette composition de caoutchouc est caractérisée en ce qu'elle contient (A) un composant de caoutchouc, (B) un copolymère séquencé de styrène-alkylène, (C) une silice et (D) un agent de couplage au silane. Cette composition de caoutchouc est également caractérisée en ce que : le copolymère séquencé de styrène-alkylène (B) a une teneur totale en unités de styrène de 30 % en masse ou plus ; et l'agent de couplage de silane (D) a un groupe mercapto.
PCT/JP2018/045983 2017-12-14 2018-12-13 Composition de caoutchouc et pneumatique WO2019117266A1 (fr)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO2021125299A1 (fr) * 2019-12-19 2021-06-24 株式会社ブリヂストン Composition de caoutchouc et pneu
WO2021125300A1 (fr) * 2019-12-19 2021-06-24 株式会社ブリヂストン Composition de caoutchouc et pneu
JP2021130800A (ja) * 2020-02-21 2021-09-09 住友ゴム工業株式会社 ゴム組成物及びタイヤ
JP7345958B2 (ja) 2020-08-05 2023-09-19 エルジー・ケム・リミテッド 変性共役ジエン系重合体およびそれを含むゴム組成物

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