WO2019244850A1 - Composition de caoutchouc et pneu - Google Patents

Composition de caoutchouc et pneu Download PDF

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Publication number
WO2019244850A1
WO2019244850A1 PCT/JP2019/023945 JP2019023945W WO2019244850A1 WO 2019244850 A1 WO2019244850 A1 WO 2019244850A1 JP 2019023945 W JP2019023945 W JP 2019023945W WO 2019244850 A1 WO2019244850 A1 WO 2019244850A1
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Prior art keywords
mass
rubber
parts
styrene
component
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PCT/JP2019/023945
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English (en)
Japanese (ja)
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佑介 廣川
健太郎 熊木
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株式会社ブリヂストン
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Publication of WO2019244850A1 publication Critical patent/WO2019244850A1/fr

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    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • 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
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a rubber composition and a tire.
  • Another object of the present invention is to provide a rubber composition having a high level of both dry steering stability and low rolling resistance. Another object of the present invention is to provide a tire having a high level of both dry steering stability and low rolling resistance.
  • the rubber composition according to the present invention includes a rubber component (A), a filler (B), and a thermoplastic resin (C),
  • the rubber component (A) contains 70 to 100 parts by mass of the styrene butadiene rubber (A1) and 0 to 30 parts by mass of the rubber component (A2) based on 100 parts by mass of the rubber component (A).
  • the styrene-butadiene rubber (A1) has a glass transition temperature (Tg) higher than ⁇ 50 ° C.
  • the styrene butadiene rubber (A1) contains a modified styrene butadiene rubber (A1-1),
  • the modified styrene butadiene rubber (A1-1) has a weight average molecular weight of 20 ⁇ 10 4 to 300 ⁇ 10 4 , and has a molecular weight of 200 ⁇ 10 4 based on the total amount of the modified styrene butadiene rubber (A1-1).
  • the modified styrene-butadiene rubber is 500 ⁇ 10 4, containing from 0.25 to 30 wt%, shrinkage factor (g ') is less than 0.64,
  • the amount of extender oil added to the modified styrene butadiene rubber (A1-1) is 10 parts by mass or less based on 100 parts by mass of the modified styrene butadiene rubber (A1-1);
  • the rubber component (A2) has a glass transition temperature (Tg) of ⁇ 50 ° C.
  • the filler (B) contains 50 parts by mass or more of silica with respect to 100 parts by mass of the rubber component (A),
  • the thermoplastic resin (C) is a rubber composition containing 1 to 45 parts by mass of a styrene / alkylene block copolymer based on 100 parts by mass of the rubber component (A). This makes it possible to achieve a high degree of compatibility between dry steering stability and low rolling resistance.
  • a numerical range is intended to include the lower limit and the upper limit of the range, unless otherwise specified.
  • 0.25 to 30% by mass means 0.25% by mass or more and 30% by mass or less.
  • the rubber composition according to the present invention includes a rubber component (A), a filler (B), and a thermoplastic resin (C),
  • the rubber component (A) contains 70 to 100 parts by mass of the styrene butadiene rubber (A1) and 0 to 30 parts by mass of the rubber component (A2) based on 100 parts by mass of the rubber component (A).
  • the styrene-butadiene rubber (A1) has a glass transition temperature (Tg) higher than ⁇ 50 ° C.
  • the styrene butadiene rubber (A1) contains a modified styrene butadiene rubber (A1-1),
  • the modified styrene butadiene rubber (A1-1) has a weight average molecular weight of 20 ⁇ 10 4 to 300 ⁇ 10 4 , and has a molecular weight of 200 ⁇ 10 4 based on the total amount of the modified styrene butadiene rubber (A1-1).
  • the modified styrene-butadiene rubber is 500 ⁇ 10 4, containing from 0.25 to 30 wt%, shrinkage factor (g ') is less than 0.64,
  • the amount of extender oil added to the modified styrene butadiene rubber (A1-1) is 10 parts by mass or less based on 100 parts by mass of the modified styrene butadiene rubber (A1-1);
  • the rubber component (A2) has a glass transition temperature (Tg) of ⁇ 50 ° C.
  • the filler (B) contains 50 parts by mass or more of silica with respect to 100 parts by mass of the rubber component (A),
  • the thermoplastic resin (C) is a rubber composition containing 1 to 45 parts by mass of a styrene / alkylene block copolymer based on 100 parts by mass of the rubber component (A). This makes it possible to achieve a high degree of compatibility between dry steering stability and low rolling resistance.
  • the rubber component (A) of the rubber composition according to the present invention comprises 70 to 100 parts by mass of the styrene butadiene rubber (A1) and 0 to 30 parts by mass of the rubber component (A2) based on 100 parts by mass of the rubber component (A). Department included.
  • the content of the styrene-butadiene rubber (A1) is 80 parts by mass or more, or 90 parts by mass or more based on 100 parts by mass of the rubber component (A). In one example, the content of the styrene-butadiene rubber (A1) is 90 parts by mass or less, or 80 parts by mass or less based on 100 parts by mass of the rubber component (A).
  • the content of the rubber component (A2) is 5 parts by mass or more, 10 parts by mass or more, or 20 parts by mass or more based on 100 parts by mass of the rubber component (A). In one example, the content of the rubber component (A2) is 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less based on 100 parts by mass of the rubber component (A).
  • the styrene-butadiene rubber (A1) in the rubber composition according to the present invention has a Tg higher than ⁇ 50 ° C. and a bound styrene content of 35% by mass or more.
  • the styrene-butadiene rubber (hereinafter sometimes referred to as SBR) (A1) includes a modified styrene-butadiene rubber (A1-1).
  • the Tg of the component (A1) may be higher than ⁇ 50 ° C., for example, ⁇ 40 ° C. or higher, ⁇ 30 ° C. or higher, or ⁇ 20 ° C. or higher. Further, for example, the Tg of the component (A1) is -20 ° C or lower, -30 ° C or lower, or -40 ° C or lower.
  • the amount of bound styrene of component (A1) may be 35% by mass or more, for example, 35 to 60% by mass. From the viewpoint of achieving a balance between dry steering stability and low rolling resistance, the styrene content is more preferably 37% by mass or more, and still more preferably 39% by mass or more.
  • the vinyl bond amount of the component (A1) is, for example, preferably from 25 to 60% by mass, and more preferably from 35 to 45% by mass. More preferably, the vinyl bond amount is 37% by mass or more, further preferably 39% by mass or more, more preferably 44% by mass or less, and further preferably 43% by mass or less.
  • the glass transition temperature of the rubber composition becomes appropriately high, and it is easy to achieve both steering stability and fracture resistance.
  • the silane coupling agent is used.
  • the reactivity of the component (A1) is increased, which is preferable from the viewpoint of high compatibility between rolling resistance, wet gripping property, and fracture resistance. More preferably, both the amount of bound styrene and the amount of vinyl bond are 37% by mass or more.
  • the modified styrene-butadiene rubber (A1-1) in the rubber composition according to the present invention has a weight average molecular weight of 20 ⁇ 10 4 to 300 ⁇ 10 4 , based on the total amount of the modified styrene-butadiene rubber (A1-1).
  • the modified styrene-butadiene rubber having a molecular weight of 200 ⁇ 10 4 to 500 ⁇ 10 4 is contained in an amount of 0.25 to 30% by mass, and a shrinkage factor (g ′) is less than 0.64.
  • the weight average molecular weight (Mw) of the component (A1-1) is from 20 ⁇ 10 4 to 300 ⁇ 10 4 .
  • the above Mw is preferably 50 ⁇ 10 4 or more, 64 ⁇ 10 4 or more, or 80 ⁇ 10 4 or more. Further, the Mw is preferably 250 ⁇ 10 4 or less, 180 ⁇ 10 4 or less, or 150 ⁇ 10 4 or less.
  • Mw is at least 20 ⁇ 10 4 , both dry steering stability and low rolling resistance of the tire can be highly compatible.
  • Mw is at most 300 ⁇ 10 4 , the processability of the rubber composition will be improved.
  • the number average molecular weight, the weight average molecular weight, the molecular weight distribution, and the content of a specific high molecular weight component described below for the SBR and the component (A1-1) are measured as follows. Using SBR or denatured SBR as a sample, a GPC (gel permeation chromatography) measuring device (trade name “HLC-8320GPC” manufactured by Tosoh Corporation) in which three columns using polystyrene-based gel as a filler were connected, The chromatogram was measured using an RI detector (trade name “HLC-8020” manufactured by Tosoh Corporation), and the weight average molecular weight (Mw) and the number average molecular weight (Mw) were determined based on a calibration curve obtained using standard polystyrene.
  • GPC gel permeation chromatography
  • Mn molecular weight distribution
  • Mw / Mn molecular weight distribution
  • Mp 1 modified SBR peak top molecular weight
  • SBR peak top molecular weight SBR peak top molecular weight
  • Mp 2 modified SBR peak top molecular weight
  • Mp 1 / Mp 2 molecular weight 200 ⁇ 10 4 to The ratio of the modified SBR of 500 ⁇ 10 4 is determined.
  • THF tetrahydrofuran
  • 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 to the front stage.
  • 10 mg of a sample for measurement is dissolved in 10 mL of THF to form a measurement solution
  • 10 ⁇ L of the measurement solution is poured into a GPC measurement 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 peak top molecular weights (Mp 1 and Mp 2 ) are determined as follows. In the GPC curve obtained by the measurement, the peak detected as the component having the highest molecular weight is selected. With respect to the selected peak, the molecular weight corresponding to the maximum value of the peak is calculated, and is set as the peak top molecular weight.
  • the modified SBR (A1-1) is a modified SBR (A1-1) having a molecular weight of 200 ⁇ 10 4 to 500 ⁇ 10 4 based on the total amount (100% by mass) of the modified SBR (A1-1).
  • “Specific high molecular weight component” is contained in an amount of 0.25 to 30% by mass. When the content of the specific high molecular weight component is within this range, the dry steering stability of the tire and the low rolling resistance can both be highly compatible.
  • the ratio of the modified SBR having a molecular weight of 200 ⁇ 10 4 to 500 ⁇ 10 4 is calculated by subtracting the ratio of the molecular weight of less than 200 ⁇ 10 4 from the ratio of the total molecular weight of 500 ⁇ 10 4 or less from the integrated molecular weight distribution curve. I do.
  • the component (A1-1) is a component having a specific high molecular weight component of 1.0% by mass or more, 1.4% by mass or more, 1.75% by mass or more, 2.0% by mass or more, 2.15% by mass. % Or 2.5% or more. In one example, the component (A1-1) contains 28% by mass or less, 25% by mass or less, 20% by mass or less, or 18% by mass or less of a specific high molecular weight component.
  • the “molecular weight” is a standard polystyrene equivalent molecular weight obtained by GPC.
  • the amount of an organic monolithium compound to be described later used as a polymerization initiator may be adjusted.
  • a method having a residence time distribution may be used in any of the continuous and batch polymerization modes, that is, the time distribution of the growth reaction may be broadened.
  • the molecular weight distribution (Mw / Mn) of the component (A1-1) is 1.6 to 3.0.
  • the modified SBR (A1-1) has a shrinkage factor (g ′) of less than 0.64.
  • a polymer having a branch tends to have a smaller molecular size as 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 molecular size
  • the shrinkage factor (g ') of the modified SBR at each absolute molecular weight 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 as the shrinkage of the modified SBR.
  • the “branch” is formed by directly or indirectly bonding one polymer to another polymer.
  • the “degree of branching” is the number of polymers directly or indirectly bonded to one branch.
  • the coupling residue is a structural unit of a modified SBR that is bonded to a conjugated diene-based polymer chain, and is, for example, derived from a coupling agent generated by reacting an SBR described below with a coupling agent. It is a structural unit.
  • the conjugated diene-based polymer chain is a constituent unit of the modified SBR, and is, for example, a structural unit derived from a conjugated diene-based polymer, which is generated by reacting SBR described below with a coupling agent.
  • the 'shrinkage factor (g') is, for example, 0.63 or less, 0.60 or less, 0.59 or less, or 0.57 or less.
  • the lower limit of the shrinkage factor (g ′) is not particularly limited, and may be equal to or lower than the detection limit, for example, 0.30 or more, 0.33 or more, 0.35 or more, 0.45 or more, and .0. It is 57 or more, or 0.59 or more.
  • the shrinkage factor (g') tends to depend on the branching degree, for example, the shrinkage factor (g ') can be controlled using the branching degree as an index. Specifically, when the modified SBR having a branching degree of 6 is used, the shrinkage factor (g ′) tends to be 0.59 to 0.63, and the modified SBR having a branching degree of 8 is used. In such a case, the contraction factor (g ′) tends to be 0.45 to 0.59.
  • the method of measuring the contraction factor (g ′) is as follows. Using a denatured SBR as a sample, a light scattering detector and an RI detector using a GPC measuring device (trade name “GPCmax VE-2001” manufactured by Malvern) in which three columns each containing polystyrene-based gel as a filler are connected. Is measured using three detectors connected in order of a viscosity detector (trade name “TDA305” manufactured by Malvern), and based on the standard polystyrene, the absolute value is obtained from the results of the light scattering detector and the RI detector. The intrinsic viscosity of the molecular weight is determined from the results of the RI detector and the viscosity detector.
  • the eluent uses THF containing 5 mmol / L triethylamine.
  • the column is used by connecting “TSKgel G4000HXL”, “TSKgel G5000HXL”, and “TSKgel G6000HXL” manufactured by Tosoh Corporation.
  • the amount of extender oil added to component (A1-1) is 10 parts by mass or less based on 100 parts by mass of component (A1-1). Preferably, it is more than 0 parts by mass and 10 parts by mass or less. When the amount of the extension oil is 10 parts by mass or less, dry steering stability and low rolling resistance can be highly balanced.
  • Extension oils include, for example, aroma oil, naphthenic oil, paraffin oil, aroma substitute oil and the like. Among them, from the viewpoint of environmental safety, and from the viewpoints of preventing oil bleeding and wet braking, an aroma substitute oil having a polycyclic aromatic (PCA) component of 3% by mass or less according to the IP346 method is preferable.
  • aroma substitute oils include TDAE (Treated Distilate Aromatic Extracts), MES (Mil Extract Extract, and others such as Milt ExtractResert, Aerosol, and others) such as TDAE (Trusted Distillate Aromatic Extracts) shown in Kautschuk ⁇ Gummi ⁇ Kunststoff 52 (12) 799 (1999).
  • Component (A1-1) is an oil-extended polymer to which extender oil has been added if the amount of extender oil added is 10 parts by mass or less based on 100 parts by mass of component (A1-1). And may be a non-oil exhibition or an oil exhibition.
  • Component (A1-1) preferably has a branch and a degree of branching of 5 or more.
  • the component (A1-1) has one or more coupling residues and an SBR chain bonded to the coupling residues, and further, the branch has one or more coupling residues.
  • the degree of branching is 5 or more, and by specifying the structure of the modified SBR such that the branch contains a branch in which 5 or more SBR chains are bonded to one coupling residue, it is more reliable.
  • the shrinkage factor (g ') can be 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 ').
  • Component (A1-1) more preferably has a branch and a degree of branching of 6 or more.
  • the component (A1-1) has one or more coupling residues and an SBR chain bonded to the coupling residues, and further, the branch has one or more coupling residues. More preferably, it contains a branch to which 6 or more of the SBR chains are bonded.
  • (G ′) can be 0.63 or less.
  • the component (A1-1) has a branch, and the branching degree is more preferably 7 or more, and further preferably 8 or more.
  • the upper limit of the degree of branching is not particularly limited, but is preferably 18 or less.
  • the component (A1-1) has one or more coupling residues and an SBR chain bonded to the coupling residues, and further, the branch has one or more coupling residues. It is even more preferable to include a branch to which 7 or more of the SBR chains are bonded, and to include a branch to which 8 or more of the SBR chains are bonded to one coupling residue. Particularly preferred.
  • (G ′) can be set to 0.59 or less.
  • the rubber composition according to the present invention is characterized in that the modified styrene-butadiene rubber (A1-1) has a branch, one or more coupling residues, and a styrene-butadiene rubber bonded to the coupling residues. And a chain,
  • the branch preferably includes a branch in which five or more styrene-butadiene rubber chains are bonded to one coupling residue. This makes it possible to achieve both high levels of dry steering stability and low rolling resistance.
  • the modified styrene butadiene rubber (A1-1) has the following general formula (I):
  • D represents a styrene-butadiene rubber chain
  • R 1, R 2 and R 3 is independently a single bond or an alkylene group having a carbon number of 1 ⁇
  • R 4 and R 7 is independently 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 a carbon number of 1 to 20
  • 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 1 to 3 carbon atoms.
  • Represents an integer, x ⁇ m, p represents 1 or 2
  • y represents an integer of 1 to 3
  • z represents an integer of 1 or 2
  • D R 1 to R 11 , m, p, x, y, and z when there are a plurality of groups are each independently;
  • j represents an integer of 0 to 6
  • k represents an integer of 0 to 6
  • (i + j + k) represents an integer of 3 to 10
  • ((x ⁇ i) + (Y ⁇ j) + (z ⁇ k)) is an integer of 5 to 30, and
  • 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.
  • An organic group having at least one atom selected from the group consisting of atoms and having no active hydrogen]. This
  • the weight average molecular weight of the SBR chain represented by D in the general formula (I) is from 10 ⁇ 10 4 to 100 ⁇ 10 4 .
  • the SBR chain is a structural unit of the modified SBR, for example, a structural unit derived from SBR generated by reacting SBR with a coupling agent.
  • the hydrocarbon group represented by A includes saturated, unsaturated, aliphatic, and aromatic hydrocarbon groups.
  • 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 represents 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, and when a plurality of B 1 are present, B 1 is each independently ing;
  • 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, and a represents an integer of 1 to 10 And B 2 and B 3 when there are a plurality of each, are each independent;
  • B 4 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, a represents an integer of 1 to 10, and when a plurality of B 4 are present, B 4 is each independently There;
  • B 5 represents a single bond or a hydrocarbon group having a carbon number of 1 ⁇
  • A is represented by the general formula (II) or (III), and k represents 0.
  • A is represented by the general formula (II) or (III)
  • k represents 0, and in the general formula (II) or (III), Represents an integer of 2 to 10.
  • A is represented by the general formula (II)
  • k represents 0, and in the general formula (II)
  • a is an integer of 2 to 10. Is shown.
  • examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkylene group having 1 to 20 carbon atoms.
  • the component (A1-1) preferably has a nitrogen atom and a silicon atom.
  • the processability of the rubber composition is improved, and when applied to a tire, the dry steering stability and low rolling resistance of the tire can be both more highly compatible.
  • the component (A1) has a nitrogen atom
  • the fact that the component (A1-1) has a silicon atom is determined by the following method. Using 0.5 g of the modified SBR as a sample, it was measured using an ultraviolet-visible spectrophotometer (trade name “UV-1800” manufactured by Shimadzu Corporation) in accordance with JIS K 0101 44.3.1, and the molybdenum blue absorbance was measured. Quantify by method. Thus, when a silicon atom is detected (detection lower limit: 10 mass ppm), it is determined that the silicon atom is present.
  • UV-1800 ultraviolet-visible spectrophotometer
  • the SBR chain has at least one end bonded to a silicon atom of a coupling residue.
  • the terminals of the plurality of SBR chains may be bonded to one silicon atom.
  • the terminal of the SBR chain and an alkoxy group or a 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 or a silanol group having 1 to 20 carbon atoms. May be configured.
  • the amount of the conjugated diene in the SBR or the component (A1-1) is, for example, 40 to 100% by mass, or 55 to 80% by mass.
  • the amount of the bond conjugated diene is within the above range, when the rubber composition is applied to a tire, it is possible to achieve both high dry steering stability and low rolling resistance.
  • the amount of bound styrene in the component (A1-1) is 35% by mass or more.
  • the amount of the bound aromatic vinyl is 35% by mass or more, when the rubber composition is applied to a tire, it is possible to achieve both high dry steering stability and low rolling resistance.
  • the amount of bound aromatic vinyl can be measured by ultraviolet absorption of the phenyl group, and the amount of bound conjugated diene can be determined therefrom. Specifically, it is measured according to the following. Using the denatured SBR as a sample, 100 mg of the sample is made up to 100 mL with chloroform and dissolved to prepare a measurement sample. The amount (% by mass) of bound styrene with respect to 100% by mass of the sample is measured based on the amount of absorption at an ultraviolet absorption wavelength (around 254 nm) by the phenyl group of styrene (Spectrophotometer “UV-2450” manufactured by Shimadzu Corporation). .
  • the vinyl bond amount in the conjugated diene bond unit is, for example, 10 to 75 mol% or 20 to 65 mol%.
  • the vinyl bond amount (1,2-bond amount) in the butadiene bond unit can be determined. Specifically, it is as follows. Using the modified SBR as a sample, 50 mg of the sample is dissolved in 10 mL of carbon disulfide to obtain a measurement sample. Using a solution cell, an infrared spectrum was measured in the range of 600 to 1000 cm -1 , and the microstructure of the butadiene portion, that is, 1,2-vinyl bond, was calculated from the absorbance at a predetermined wave number according to the above-described Hampton formula. The amount (mol%) is determined (Fourier transform infrared spectrophotometer “FT-IR230” manufactured by JASCO Corporation).
  • Component (A1-1) preferably has a Tg higher than -50 ° C, more preferably -45 to -15 ° C.
  • Tg of the component (A1-1) is in the range of ⁇ 45 to ⁇ 15 ° C.
  • the dry steering stability and the low rolling resistance are both more highly compatible. Can be.
  • Tg a DSC curve is recorded while the temperature is raised within a predetermined temperature range, and the peak top (Inflection point) of the DSC differential curve is defined as Tg. Specifically, it is as follows. Using denatured SBR as a sample, the temperature was raised from ⁇ 100 ° C. to 20 ° C./min under a flow of 50 mL / min of helium using a differential scanning calorimeter “DSC3200S” manufactured by Mac Science in accordance with ISO # 22768: 2006. While the DSC curve is recorded, the peak top (Inflection @ point) of the DSC differential curve is defined as Tg.
  • the component (A1-1) has a Mooney viscosity measured at 100 ° C. of, for example, 20 to 100 or 30 to 80.
  • the method for measuring the Mooney viscosity is as follows. Using SBR or modified SBR as a sample, Mooney viscosity is measured using a Mooney viscometer (trade name “VR1132” manufactured by Ueshima Seisakusho Co., Ltd.) using an L-shaped rotor according to JIS K6300. The measurement temperature is 110 ° C. when SBR is used as a sample, and 100 ° C. when denatured SBR 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) ).
  • the method for synthesizing component (A1-1) is not particularly limited.
  • styrene is obtained by polymerizing at least butadiene using an organic monolithium compound as a polymerization initiator.
  • a synthesis method including a polymerization step of obtaining a butadiene rubber, and a reaction step of reacting a reactive compound having five or more functional groups (hereinafter, also referred to as a “coupling agent”) with an active terminal of the styrene-butadiene rubber. Is mentioned.
  • the polymerization step includes, for example, polymerization by a growth reaction by a living anionic polymerization reaction. Thereby, a styrene-butadiene rubber having an active terminal can be obtained, and a component (A1-1) having a high modification rate can be obtained.
  • the amount of the organic monolithium compound used as the polymerization initiator can be adjusted according to the target molecular weight of SBR or modified SBR. Decreasing the polymerization initiator increases the molecular weight, while increasing the polymerization initiator decreases the molecular weight.
  • the organic monolithium compound is preferably an alkyl lithium compound from the viewpoint of industrial availability and easy control of the polymerization reaction.
  • SBR having an alkyl group at the polymerization initiation terminal is obtained.
  • alkyl lithium compound examples include n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, and stilbene lithium. These organic monolithium compounds may be used alone or in a combination of two or more.
  • a batch type or continuous type polymerization reaction mode can be appropriately selected and used.
  • an inert solvent may be used.
  • the inert solvent examples include aliphatic hydrocarbons such as butane, pentane, hexane and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; aromatics such as benzene, toluene and xylene Hydrocarbons and the like.
  • the inert solvent may be used alone or in combination of two or more.
  • treatment with an organometallic compound may be performed to remove allenes and acetylenes as impurities in the inert solvent.
  • a polar compound may be used.
  • styrene can be randomly copolymerized with butadiene.
  • the polar compound can also be used as a vinylating agent for controlling the microstructure of the conjugated diene part.
  • the 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 methylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine and quinuclidine; alkali metal alkoxides such as potassium-tert-amylate, potassium-tert-butyrate, sodium-tert-butyrate and sodium amylate Compounds; phosphine compounds such as triphenylphosphine and the like can be mentioned.
  • the polar compounds may be used alone or in combination of two or more.
  • the polymerization temperature in the polymerization step may be appropriately adjusted, and is, for example, 0 to 120 ° C. or 50 to 100 ° C. from the viewpoint of ensuring a sufficient reaction amount of the coupling agent with respect to the active terminal after completion of the polymerization.
  • the coupling agent includes, for example, a pentafunctional or more reactive compound having a nitrogen atom and a silicon atom.
  • the reactive compound has at least three silicon-containing functional groups.
  • the coupling agent is preferably one in which at least one silicon atom forms an alkoxysilyl group or a silanol group having 1 to 20 carbon atoms, and more preferably a compound represented by the following general formula (VI) It is.
  • One type of coupling agent may be used alone, or two or more types may be used in combination.
  • the alkoxysilyl group of the coupling agent tends to react with the active terminal of the SBR to dissociate the alkoxylithium and form a bond between the terminal of the SBR chain and silicon of the coupling residue.
  • the value obtained by subtracting the number of SiORs reduced by the reaction from the total number of SiORs in one molecule of the coupling agent is the number of alkoxysilyl groups in the coupling residue.
  • the azasilacycle group of the coupling agent forms a> N—Li bond and a bond between the SBR terminal and silicon of the coupling residue. Note that the> N—Li bond tends to easily become> NH and LiOH due to water or the like at the time of finishing. Further, in the coupling agent, the unreacted remaining alkoxysilyl group can easily become silanol (Si—OH group) by water or the like at the time of finishing.
  • the modified styrene-butadiene rubber (A1-1) is a styrene-butadiene rubber 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 Is independently an alkyl group having 1 to 20 carbon atoms
  • R 19 and R 22 are each independently an alkylene group having 1 to 20 carbon atoms
  • R 21 is an alkyl group having 1 to 20 carbon atoms.
  • m represents an integer of 1 to 3
  • p represents 1 or 2
  • R 12 to R 22 , m and p are plural, they are each independently
  • 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 consisting of oxygen, nitrogen, silicon, sulfur and phosphorus atoms
  • the hydrocarbon group represented by A includes saturated, unsaturated, aliphatic, and aromatic hydrocarbon groups.
  • 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 represented by the general formula (II) or (III), and k represents 0.
  • A is represented by the general formula (II) or (III)
  • k represents 0, and in the general formula (II) or (III)
  • a represents an integer of 2 to 10.
  • Examples of such a coupling agent include 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, 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-propanedia
  • the addition amount of the compound represented by the general formula (VI) as a coupling agent can be adjusted so that the number of moles of SBR to the number of moles of the coupling agent is reacted at a desired stoichiometric ratio, This tends to achieve a desired degree of branching.
  • the specific number of moles of the polymerization initiator is, for example, 5.0 times or more, or 6.0 times or more the number of moles of the coupling agent.
  • the number of functional groups ((m ⁇ 1) ⁇ i + p ⁇ j + k) of the coupling agent is an integer of 5 to 10, or an integer of 6 to 10.
  • the reaction temperature in the reaction step may be appropriately adjusted, and is, for example, 0 to 120 ° C or 50 to 100 ° C. Further, the temperature change after the polymerization step until the coupling agent is added is, for example, 10 ° C. or less, or 5 ° C. or less.
  • the reaction time in the reaction step may be appropriately adjusted, for example, 10 seconds or more, or 30 seconds or more.
  • 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 ratio, and is, for example, within 5 minutes.
  • ⁇ Mixing in the reaction step may be any of mechanical stirring, stirring with a static mixer, and the like.
  • the molecular weight distribution (Mw / Mn) of the SBR is preferably 1.5 to 2.5, or 1.8 to 2.2. Further, as for the obtained component (A1), it is preferable that a peak having a single peak in a molecular weight curve by GPC is detected.
  • Mp 2 is between 20 ⁇ 10 4 and 80 ⁇ 10 4 and Mp 1 is between 30 ⁇ 10 4 and 150 ⁇ 10 4 .
  • the modification rate of the component (A1-1) is, for example, 30% by mass or more, 50% by mass or more, or 70% by mass or more.
  • the modification ratio is 30% by mass or more, when the rubber composition is applied to a tire, the low rolling resistance can be further improved while the wear resistance of the tire is improved.
  • the method for measuring the denaturation rate is as follows. Using a modified SBR as a sample, the measurement is performed by applying the property of adsorbing the modified basic polymer component to a GPC column using a silica gel as a filler. 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. Ask. Specifically, it is as shown below.
  • sample solution 10 mg of a sample and 5 mg of standard polystyrene are dissolved in 20 mL of THF to prepare a sample solution.
  • GPC measurement conditions using a polystyrene column using “HLC-8320GPC” (trade name, manufactured by Tosoh Corporation), 10 ⁇ L of a sample solution was injected into the apparatus using 5 mmol / L of THF containing triethylamine as an eluent, and a column oven was used.
  • a chromatogram is obtained using an RI detector.
  • 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 to the front stage.
  • GPC measurement conditions using silica column using HLS-8320GPC (trade name, manufactured by Tosoh Corporation), using THF as an eluent, injecting 50 ⁇ L of a sample solution into the apparatus, column oven temperature 40 ° C., THF flow rate At 0.5 ml / min, a chromatogram is obtained using an RI detector.
  • the column is used by connecting the trade names “Zorbax PSM-1000S”, “PSM-300S” and “PSM-60S”, and the trade name “DIOL 4.6 ⁇ 12.5mm 5micron” is used as a guard column in the preceding stage. Connect and use.
  • Calculation method of denaturation ratio The peak area of a sample is P1, the peak area of a standard polystyrene is P2, and the peak area of a chromatogram using a silica column is 100, where the total peak area of a chromatogram using a polystyrene column is 100.
  • a deactivator, a neutralizing agent and the like may be added to the copolymer solution as needed.
  • the quencher include water; alcohols such as methanol, ethanol, and isopropanol.
  • the neutralizing agent include carboxylic acids such as stearic acid, oleic acid, and versatic acid (a mixture of carboxylic acids having 9 to 11 carbon atoms and having mainly 10 branches); an aqueous solution of an inorganic acid, Gas and the like.
  • Component (A1-1) is, for example, 2,6-di-tert-butyl-4-hydroxytoluene (BHT), from the viewpoint of preventing gel formation after polymerization and improving stability during processing.
  • BHT 2,6-di-tert-butyl-4-hydroxytoluene
  • An antioxidant such as n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-tert-butylphenol) propionate or 2-methyl-4,6-bis [(octylthio) methyl] phenol is added. Is preferred.
  • an extender oil may be added to the modified styrene-butadiene rubber, if necessary.
  • a method of adding the extender oil to the modified styrene-butadiene rubber for example, a method of adding the extender oil to the polymer solution, mixing the resulting mixture, and removing the solvent from the oil-extended copolymer solution can be used.
  • a known method can be used as a method for obtaining the component (A1-1) from the polymer solution.
  • the method for example, after separating the solvent by steam stripping or the like, the polymer is separated by filtration, further dehydration and drying to obtain a polymer, concentrated in a flushing tank, further vented extruder, etc. And a method of devolatilizing directly with a drum dryer or the like.
  • the content of the component (A1-1) in the component (A1) is, for example, 18% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, based on the total amount of the component (A1). It is 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.
  • the content of the component (A1-1) in the component (A1) is, for example, 100% by mass or less, 90% by mass or less, 80% by mass or less, and 70% by mass based on the total amount of the component (A1). Or less, or 60% by mass or less.
  • Component (A1) may contain, in addition to Component (A1-1), Component (A1-2) having a Tg higher than ⁇ 50 ° C. and a bound styrene content of 35% by mass or more.
  • the component (A1-2) may be unmodified SBR or modified SBR.
  • the component (A1-2) is a modified SBR, the component (A1-2) is composed of the component (A1-1) and Tg, the amount of bound styrene, Mw, the ratio of a specific high molecular weight component, a shrinkage factor, Alternatively, either the amount of extender oil added may be different.
  • component (A1-2) for example, a modified (co) polymer as the polymer component P2 of WO2017 / 077712 and a modified polymer E described in Examples are mentioned.
  • the rubber component (A2) has a Tg of ⁇ 50 ° C. or less.
  • the component (A2) in combination in addition to the component (A1-1) and the component (C), it is possible to achieve a high level of compatibility between dry steering stability and low rolling resistance. it can.
  • the component (A2) may have a Tg of ⁇ 50 ° C. or lower, and a known rubber component can be used.
  • a known rubber component can be used.
  • Examples of the component (A1-2) include a natural rubber (NR), a modified (co) polymer as the polymer component P2 of WO2017 / 077772, a modified polymer C described in Examples, and a modified polymer. D and the like.
  • the rubber component (A2) preferably contains at least one selected from the group consisting of natural rubber, synthetic isoprene rubber, butadiene rubber, and styrene-butadiene rubber. Thereby, low rolling resistance is further increased.
  • the styrene-butadiene rubber (A1) when used in combination with the styrene-butadiene rubber (A1), it is possible to achieve both wet performance and dry steering stability.
  • the rubber composition according to the present invention contains a filler (B).
  • the filler (B) contains 50 parts by mass or more of silica with respect to 100 parts by mass of the rubber component (A).
  • Silica can be appropriately selected according to the purpose, and examples thereof include wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, and aluminum silicate. Silica may be used alone or in combination of two or more.
  • Silica is, for example, a hydrated silicic acid described in JP-A-2013-245306, that is, cetyltrimethylammonium bromide adsorption specific surface area (CTAB) (m 2 / g) and ink bottle-like pore index (IB). And hydrous silicic acid satisfying the formula (Y) described in JP-A-2013-245306.
  • CTAB cetyltrimethylammonium bromide adsorption specific surface area
  • IB ink bottle-like pore index
  • Y hydrous silicic acid satisfying the formula (Y) described in JP-A-2013-245306.
  • Silica has a cetyltrimethylammonium bromide adsorption specific surface area (CTAB) (m 2 / g) and an ink bottle-like pore index (IB) represented by the following formula (1): IB ⁇ ⁇ 0.36 ⁇ CTAB + 86.8 (1)
  • CTAB cetyltrimethylammonium bromide adsorption specific surface area
  • IB ink bottle-like pore index
  • IB M2-M1
  • the low rolling resistance and the wear resistance of the rubber composition can be further improved.
  • CAB cetyltrimethylammonium bromide adsorption specific surface area
  • IB ink bottle-like pore
  • M2 is the mercury when the pressure is decreased from 32000 PSI to 1 PSI in the measurement. It is the diameter (nm) of the opening that shows the maximum value of the discharge amount]
  • the loss on ignition the mass loss when heated at 750 ° C. for 3 hours
  • the mass loss when heated for 2 hours (% by mass) is expressed by the following formula (5): Loss on burning-Loss on heating ⁇ 2.5 (% by mass) (5) It is also preferable to satisfy the following. Also in this case, the low rolling resistance and the wear resistance of the rubber composition can be further improved.
  • the amount of the component (B) is, for example, 50 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, 90 parts by mass or more, 100 parts by mass or more, and 110 parts by mass with respect to 100 parts by mass of the rubber component (A). Or more, or 120 parts by mass or more. Further, for example, the compounding amount of the component (B) is 150 parts by mass or less, 140 parts by mass or less, 130 parts by mass or less, 120 parts by mass or less, 110 parts by mass or less with respect to 100 parts by mass of the rubber component (A). 100 parts by mass or less, 90 parts by mass or less, or 80 parts by mass or less.
  • the amount of silica may be 50 parts by mass or more with respect to 100 parts by mass of the rubber component (A), and is, for example, 70 parts by mass or more, 80 parts by mass or more, 90 parts by mass or more, 100 parts by mass or more, 110 parts by mass. Parts or more, or 120 parts by mass or more. Further, for example, the compounding amount of silica is 150 parts by mass or less, 140 parts by mass or less, 130 parts by mass or less, 120 parts by mass or less, 110 parts by mass or less, and 100 parts by mass with respect to 100 parts by mass of the rubber component (A). Hereinafter, it is 90 parts by mass or less, or 80 parts by mass or less.
  • the rubber composition may or may not contain other fillers as component (B) in addition to silica.
  • fillers include, for example, carbon black, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, titanium oxide, titanium oxide And potassium barium sulfate and the like.
  • the ratio of the silica in the component (B) may be appropriately adjusted, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more. % Or more, or 100% by mass. Further, for example, the proportion of silica in the component (B) is 100% by mass or less, less than 100% by mass, 95% by mass or less, 90% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, or It is 60% by mass or less.
  • the component (B) may be used alone or in combination of two or more.
  • thermoplastic resin (C) contains a styrene-alkylene block copolymer, and the thermoplastic resin (C) contains 1 to 45 parts by mass of the styrene-alkylene block copolymer based on 100 parts by mass of the rubber component (A). Department included.
  • a styrene-alkylene block copolymer is a copolymer having a block derived from a styrene-based monomer and an alkylene block.
  • the styrene-alkylene block copolymer may be used alone or in combination of two or more.
  • the total styrene content of the styrene-alkylene block copolymer is, for example, 30% by mass or more, or 30 to 60% by mass. When the total styrene content is 30% by mass or more, dry steering stability is enhanced.
  • the total styrene content is preferably 40% by mass or more, or 50% by mass or more. Thereby, dry steering stability can be further enhanced.
  • the styrene content of the styrene-alkylene block copolymer and the content of the alkylene unit described later are determined by 1 H-NMR integration ratio.
  • the styrene block of the styrene-alkylene block copolymer has a unit derived from a styrene monomer (polymerized styrene monomer).
  • a styrene-based monomer include styrene, ⁇ -methylstyrene, p-methylstyrene, and vinyl toluene. Among them, styrene is preferable as the styrene monomer.
  • the alkylene block of the styrene-alkylene block copolymer has an alkylene (divalent saturated hydrocarbon group) unit.
  • alkylene unit examples include an alkylene group having 1 to 20 carbon atoms.
  • the alkylene unit may have a linear structure, a branched structure, or a combination thereof.
  • alkylene unit having a linear structure examples include a — (CH 2 —CH 2 ) —unit (ethylene unit) and a — (CH 2 —CH 2 —CH 2 —CH 2 ) —unit (butylene unit). .
  • alkylene unit having a branched structure examples include a — (CH 2 —CH (C 2 H 5 )) — unit (butylene unit).
  • the alkylene unit preferably has a — (CH 2 —CH (C 2 H 5 )) — unit.
  • the total content of the alkylene units may be appropriately adjusted, and is, for example, 40 to 70% by mass based on the total mass of the styrene-alkylene block copolymer.
  • the alkylene block of the styrene-alkylene block copolymer has-(CH 2 -CH (C 2 H 5 ))-units (C A ) and-(CH 2 -CH 2 ).
  • - has units (C B)
  • the total content of the units (C a) is, relative to the total weight of the unit (C a) + units (C B), 40 wt% or more, 45 wt% or more, 50 wt % Or more, 55% by mass or more, 60% by mass or more, or 65% by mass or more.
  • the total content of the units (C A) is, relative to the total weight of the unit (C A) + units (C B), 90 wt% or less, preferably not more than 85 wt%, or 80 wt%. Thereby, good dry steering stability can be ensured without deteriorating low rolling resistance.
  • the styrene / alkylene block copolymer is styrene / ethylene / butylene / styrene block copolymer (SEBS), styrene / ethylene propylene / styrene block copolymer (SEPS), and styrene.
  • SEBS styrene / ethylene / butylene / styrene block copolymer
  • SEPS styrene / ethylene propylene / styrene block copolymer
  • SEEPS ethylene-ethylene propylene-styrene block copolymer
  • the styrene-alkylene block copolymer is preferably a styrene-ethylenebutylene-styrene block copolymer. This makes it possible to achieve both high levels of dry steering stability and low rolling resistance.
  • the ethylene butylene block of the styrene / ethylene butylene / styrene block copolymer is a block having the above-mentioned ethylene unit and butylene unit.
  • the styrene-alkylene block copolymer may contain other structural units other than the styrene block and the alkylene block.
  • the method for preparing the styrene-alkylene block copolymer is not particularly limited, and a known method can be used.
  • a styrene-based monomer such as styrene and a conjugated diene compound such as 1,3-butadiene or an olefin such as butene are copolymerized to obtain a precursor copolymer, and the precursor copolymer is hydrogenated.
  • a styrene-alkylene block copolymer is not particularly limited, and a known method can be used.
  • a styrene-based monomer such as styrene and a conjugated diene compound such as 1,3-butadiene or an olefin such as butene are copolymerized to obtain a precursor copolymer, and the precursor copolymer is hydrogenated.
  • a styrene-alkylene block copolymer is not particularly limited, and a known
  • styrene-alkylene block copolymer may be used.
  • examples of such commercially available products include JSR @ DYNARON (registered trademark) 8903P and 9901P manufactured by JSR Corporation.
  • the amount of the component (C) is, for example, 1 part by mass or more, 2 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, and 20 parts by mass with respect to 100 parts by mass of the rubber component (A). As mentioned above, it is 30 parts by mass or more, 40 parts by mass or more, or 50 parts by mass or more.
  • the amount of the component (C) is 50 parts by mass or less, 45 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, and 100 parts by mass of the rubber component (A). It is at most 5 parts by mass, or at most 1 part by mass.
  • the amount of the styrene-alkylene block copolymer is 1 part by mass or more, for example, 2 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass with respect to 100 parts by mass of the rubber component (A). As mentioned above, it is 20 parts by mass or more, 30 parts by mass or more, or 40 parts by mass or more. Further, for example, the amount of the styrene-alkylene block copolymer is 45 parts by mass or less, for example, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less based on 100 parts by mass of the rubber component (A). , 10 parts by mass or less, or 5 parts by mass or less.
  • the rubber composition according to the present invention includes, in addition to the components described above, components commonly used in the rubber industry, for example, a softening agent, a vulcanization accelerator, a silane coupling agent, a vulcanizing agent, a glycerin fatty acid ester, and an antiaging agent.
  • a softening agent for example, a silicone rubber, a silicone rubber, a silicone rubber, a silicone rubber, and a silane coupling agent, a vulcanizing agent, a glycerin fatty acid ester, and an antiaging agent.
  • An agent, a vulcanization accelerator, an organic acid compound and the like can be appropriately selected and contained within a range not contrary to the gist of the present invention.
  • the method for preparing the rubber composition according to the present invention is not particularly limited, and components such as component (A), component (B), and component (C) may be kneaded using a known kneading method.
  • the rubber composition according to the present invention is preferably for a tire, and more preferably for a tread of a tire.
  • the tire according to the present invention is a tire using any one of the above rubber compositions for a tread rubber. This makes it possible to achieve a high degree of compatibility between dry steering stability and low rolling resistance.
  • Modified SBR (A1-1) Modified SBR (1): synthesized by the method described later.
  • Modified SBR (2) synthesized by a method described later.
  • Silica (1) trade name “Nipsil (registered trademark) AQ” manufactured by Tosoh Silica Corporation
  • Silica (2) synthesized by the method described below
  • Component (C) Styrene-alkylene block copolymer (total styrene content 53 wt%), SEBS: JSR Corp. DYNARON (registered trademark) 9901P, relative to the total weight of the unit (C A) units (C A) + units (C B) 70% by mass
  • Anti-aging agent N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, trade name "Nocrack 6C” manufactured by Ouchi Shinko Chemical Co., Ltd.
  • Anti-aging agent (TMDQ) 2,2,4-trimethyl-1,2-dihydroquinoline polymer, trade name “Nocrack 224” manufactured by Ouchi Shinko Chemical Co., Ltd.
  • WAX Microcrystalline wax, trade name “OZOACE 0701” manufactured by Nippon Seiro Co., Ltd.
  • Silane coupling agent ethoxy (3-mercaptopropyl) bis (3,6,9,12,15-pentaoxaoctacosan-1-yloxy) silane, trade name “Si363” (registered trademark) manufactured by Evonik Degussa Vulcanization accelerator (DPG): 1,3-diphenylguanidine, trade name “Socinol (registered trademark) DG” manufactured by Sumitomo Chemical Co., Ltd.
  • Vulcanization accelerator (MBTS) di (2-benzothiazolyl) persulfide, trade name “NOXELLER (registered trademark) DM-P” manufactured by Ouchi Shinko Chemical Co., Ltd.
  • 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 presence or absence of silicon atoms of the modified SBR (A1-1) Is analyzed by the following method.
  • Amount of bound styrene Using modified SBR as a sample, 100 mg of the sample is made up to 100 mL with chloroform and dissolved to prepare a measurement sample. The amount (% by mass) of bound styrene with respect to 100% by mass of the sample is measured based on the amount of absorption at an ultraviolet absorption wavelength (around 254 nm) by the phenyl group of styrene (Spectrophotometer “UV-2450” manufactured by Shimadzu Corporation). .
  • Mw / Mn modified SBR peak top molecular weight (Mp 1 ), SBR peak top molecular weight (Mp 2 ) and its ratio (Mp 1 / Mp 2 ), molecular weight 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less And the ratio of.
  • THF tetrahydrofuran
  • Mp 2 modified SBR peak top molecular weight
  • Mp 1 / Mp 2 molecular weight 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less
  • Mp 1 / Mp 2 molecular weight 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less
  • Mp 1 / Mp 2 molecular weight 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less
  • Mp 1 / Mp 2 molecular weight 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less
  • Mp 1 / Mp 2 molecular weight 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less
  • Mp 1 / Mp 2
  • the ratio of the 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 total molecular weight of 500 ⁇ 10 4 or less from the integrated molecular weight distribution curve. I do.
  • the eluent uses THF containing 5 mmol / L triethylamine.
  • the column is used by connecting “TSKgel G4000HXL”, “TSKgel G5000HXL”, and “TSKgel G6000HXL” manufactured by Tosoh Corporation.
  • Mooney Viscosity Using SBR or modified SBR as a sample, Mooney viscosity is measured using a Mooney viscometer (trade name “VR1132” manufactured by Ueshima Seisakusho Co., Ltd.) using an L-shaped rotor according to JIS K6300. The measurement temperature is 110 ° C. when SBR is used as a sample, and 100 ° C. when denatured SBR 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) ).
  • Modification rate is measured by applying the property of adsorbing the modified basic polymer component to a GPC column using silica gel as a filler, using the modified SBR as a sample.
  • 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.
  • 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 to the front stage.
  • GPC measurement conditions using silica column using HLS-8320GPC (trade name, manufactured by Tosoh Corporation), using THF as an eluent, injecting 50 ⁇ L of a sample solution into the apparatus, column oven temperature 40 ° C., THF flow rate At 0.5 ml / min, a chromatogram is obtained using an RI detector.
  • the column is used by connecting the trade names “Zorbax PSM-1000S”, “PSM-300S” and “PSM-60S”, and the trade name “DIOL 4.6 ⁇ 12.5mm 5micron” is used as a guard column in the preceding stage. Connect and use.
  • Calculation method of denaturation ratio The peak area of a sample is P1, the peak area of a standard polystyrene is P2, and the peak area of a chromatogram using a silica column is 100, where the total peak area of a chromatogram using a polystyrene column is 100.
  • 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.
  • 2,2-bis (2-oxolanyl) propane as a polar substance is mixed vigorously with a stirrer at a rate of 0.019 g / min and n-butyllithium as a polymerization initiator at a rate of 0.242 mmol / min. It is fed to the bottom of the polymerization reactor to continuously continue the polymerization reaction.
  • the temperature is controlled so that the temperature of the polymerization solution at the top outlet 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 as to be 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.
  • the modified SBR (1) has a nitrogen atom and a silicon atom.
  • the “branching degree” corresponding to the number of branches assumed from the number of functional groups and the amount of addition of the coupling agent is 8 (also confirmed from the value of the shrinkage factor).
  • the “number of SiOR residues”, which corresponds to a value obtained by subtracting the number of SiORs reduced by the reaction from the total number of SiORs, is 4.
  • the neutralization reaction is performed while maintaining the Na 2 O concentration in the reaction solution in the range of 0.005 to 0.035 mol / L.
  • the reaction solution starts to become cloudy, and the viscosity increases at the 46th minute to become a gel-like solution.
  • the addition is continued and the reaction is stopped after 100 minutes.
  • the silica concentration in the resulting solution is 60 g / L.
  • the same sulfuric acid as 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 formed into a slurry using an emulsifying device and dried with a spray dryer to obtain silica (2).
  • silica (1) and silica (2) are evaluated by the following methods and are as follows.
  • IB Ink Bottle Pore Index
  • a rubber composition is produced using an ordinary Banbury mixer.
  • a pneumatic radial tire for a passenger car having a size of 195 / 65R15 is manufactured by using the rubber composition as a tread rubber.
  • the rubber composition or the tire is evaluated for low rolling resistance and dry steering stability by the following method. Table 1 shows the results.
  • ⁇ Dry steering stability> The test tire is mounted on a test vehicle, and in an actual vehicle test on a dry road surface, the driving stability is represented by a driver's feeling score, and the feeling score of the tire of Comparative Example 1 is indicated as 5.5. The higher the rating value, the better the dry steering stability.
  • Dry steering stability and low rolling resistance were comprehensively evaluated according to the following criteria. :: The index value of the low rolling resistance is improved by 5 points or more compared to Comparative Example 1, and the dry steering stability is also improved. :: The dry steering stability and the low rolling resistance are each Comparative Example 1. ⁇ : Any of dry steering stability and low rolling resistance is lower than Comparative Example 1.
  • the rubber composition according to the present invention makes it possible to achieve a high balance between dry steering stability and low rolling resistance.

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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)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Tires In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de caoutchouc qui combine une stabilité de conduite à sec avec des caractéristiques de faible résistance au roulement à un degré élevé. La composition de caoutchouc comprend un ingrédient de caoutchouc (A), une charge (B) et une résine thermoplastique (C), l'ingrédient (A) comprenant un caoutchouc styrène-butadiène (SBR) (A1) et un ingrédient de caoutchouc (A2) dans des quantités de 70 à 100 parties en masse et de 0 à 30 parties en masse, respectivement, pour 100 parties en masse de l'ingrédient (A). Le SBR (A1) présente une Tg supérieure à -50 °C et une teneur en St combinée de 35 % en masse ou plus. Le SBR (A1) comprend un SBR modifié (A1-1), qui a un poids moléculaire moyen en poids spécifique et un facteur de retrait spécifique (g'). Le SBR modifié (A1-1) contient une huile d'extension en une quantité de 10 parties en masse ou moins pour 100 parties en masse du SBR modifié (A1-1). L'ingrédient de caoutchouc (A2) présente une Tg de -50 °C ou moins. La charge (B) comprend 50 parties en masse ou plus de silice pour 100 parties en masse de l'ingrédient (A). La résine (C) comprend de 1 à 45 parties en masse d'un copolymère séquencé styrène/alkylène pour 100 parties en masse de l'ingrédient (A).
PCT/JP2019/023945 2018-06-18 2019-06-17 Composition de caoutchouc et pneu WO2019244850A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210284827A1 (en) * 2020-03-10 2021-09-16 Asahi Kasei Kabushiki Kaisha Conjugated diene-based polymer composition and tire

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JP2009280808A (ja) * 2008-04-25 2009-12-03 Bridgestone Corp タイヤ用ゴム組成物及びタイヤ
WO2015186755A1 (fr) * 2014-06-04 2015-12-10 横浜ゴム株式会社 Composition de caoutchouc pour bande de roulement
WO2016133154A1 (fr) * 2015-02-19 2016-08-25 旭化成株式会社 Polymère de diène conjugué modifié et son procédé de production, composition de caoutchouc, et pneu
JP2018002986A (ja) * 2016-07-08 2018-01-11 旭化成株式会社 変性共役ジエン系重合体組成物、サイドウォール用ゴム組成物、及びタイヤ
WO2018034217A1 (fr) * 2016-08-19 2018-02-22 旭化成株式会社 Polymère à base de diène conjugué modifié ainsi que procédé de fabrication de celui-ci, composition de caoutchouc, et pneumatique
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
JP2018083884A (ja) * 2016-11-22 2018-05-31 住友ゴム工業株式会社 空気入りタイヤ

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Publication number Priority date Publication date Assignee Title
JP2009280808A (ja) * 2008-04-25 2009-12-03 Bridgestone Corp タイヤ用ゴム組成物及びタイヤ
WO2015186755A1 (fr) * 2014-06-04 2015-12-10 横浜ゴム株式会社 Composition de caoutchouc pour bande de roulement
WO2016133154A1 (fr) * 2015-02-19 2016-08-25 旭化成株式会社 Polymère de diène conjugué modifié et son procédé de production, composition de caoutchouc, et pneu
JP2018002986A (ja) * 2016-07-08 2018-01-11 旭化成株式会社 変性共役ジエン系重合体組成物、サイドウォール用ゴム組成物、及びタイヤ
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
WO2018034217A1 (fr) * 2016-08-19 2018-02-22 旭化成株式会社 Polymère à base de diène conjugué modifié ainsi que procédé de fabrication de celui-ci, composition de caoutchouc, et pneumatique
JP2018083884A (ja) * 2016-11-22 2018-05-31 住友ゴム工業株式会社 空気入りタイヤ

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210284827A1 (en) * 2020-03-10 2021-09-16 Asahi Kasei Kabushiki Kaisha Conjugated diene-based polymer composition and tire

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