WO2013077017A1 - Composition de caoutchouc et pneu - Google Patents

Composition de caoutchouc et pneu Download PDF

Info

Publication number
WO2013077017A1
WO2013077017A1 PCT/JP2012/066208 JP2012066208W WO2013077017A1 WO 2013077017 A1 WO2013077017 A1 WO 2013077017A1 JP 2012066208 W JP2012066208 W JP 2012066208W WO 2013077017 A1 WO2013077017 A1 WO 2013077017A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
mass
silica
carbon atoms
parts
Prior art date
Application number
PCT/JP2012/066208
Other languages
English (en)
Japanese (ja)
Inventor
智史 川崎
隆一 時宗
Original Assignee
住友ゴム工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友ゴム工業株式会社 filed Critical 住友ゴム工業株式会社
Publication of WO2013077017A1 publication Critical patent/WO2013077017A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0025—Compositions of the sidewalls
    • 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
    • C08C19/22—Incorporating nitrogen atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
    • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—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
    • 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
    • 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
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • 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
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area

Definitions

  • the present invention relates to a rubber composition and a pneumatic tire produced using the rubber composition.
  • Patent Documents 1 to 3 in a compound containing silica, a specific polar group is added to the rubber so as to have an affinity for silica, thereby improving the dispersibility of the silica and improving the fuel efficiency.
  • a method for obtaining a composition is described, when this method is used, Mooney viscosity becomes high and processability deteriorates, or the bond between silica and rubber becomes too dense and the rubber strength decreases. There is. Therefore, a method for improving the fuel economy, rubber strength, cut resistance and processability in a well-balanced manner is required.
  • An object of the present invention is to solve the above-mentioned problems and to provide a rubber composition that can improve fuel economy, rubber strength, cut resistance and processability in a well-balanced manner, and a pneumatic tire using the same.
  • R 11 represents a hydrocarbylene group having 1 to 100 carbon atoms
  • R 12 and R 13 are hydrocarbyl groups which may have a substituent, Alternatively, it represents a trihydrocarbylsilyl group, or R 12 and R 13 are bonded to each other and have at least one atom selected from the atomic group consisting of a silicon atom, a nitrogen atom and an oxygen atom as a hetero atom.
  • An optionally substituted hydrocarbylene group, and M represents an alkali metal atom.
  • R 11 in the above formula (I) is preferably a group represented by the following formula (Ia).
  • R 14 represents a hydrocarbylene group composed of a structural unit derived from a conjugated diene compound and / or a structural unit derived from an aromatic vinyl compound, and n represents an integer of 1 to 10.
  • R 14 in the above formula (Ia) is preferably a hydrocarbylene group composed of 1 to 10 structural units derived from isoprene.
  • the silicon-containing vinyl compound is preferably a compound represented by the following formula (II).
  • m is 0 or 1
  • R 21 represents a hydrocarbylene group
  • X 1 , X 2 and X 3 have a substituted amino group, a hydrocarbyloxy group, or a substituent. Represents a good hydrocarbyl group.
  • the conjugated diene polymer preferably has a structural unit derived from an aromatic vinyl compound.
  • the silica preferably contains silica (1) having a nitrogen adsorption specific surface area of 150 m 2 / g or more and silica (2) having a nitrogen adsorption specific surface area of 100 m 2 / g or less.
  • the rubber composition preferably contains 2 to 30 parts by mass of conductive carbon black with respect to 100 parts by mass of the rubber component.
  • the silica includes silica (1) having a nitrogen adsorption specific surface area of 150 m 2 / g or more and silica (2) having a nitrogen adsorption specific surface area of 100 m 2 / g or less, and the rubber composition contains the rubber component 100. It is preferable to contain 2 to 30 parts by mass of conductive carbon black with respect to parts by mass.
  • the rubber composition preferably contains 0.5 to 20 parts by mass of a silane coupling agent having a mercapto group with respect to 100 parts by mass of the silica.
  • the rubber composition contains 0.5 to 20 parts by mass of a silane coupling agent having a mercapto group with respect to 100 parts by mass of the silica, and the silica has a nitrogen adsorption specific surface area of 150 m 2 / g or more ( 1) and silica (2) having a nitrogen adsorption specific surface area of 100 m 2 / g or less are preferable.
  • the rubber composition includes 0.5 to 20 parts by mass of a silane coupling agent having a mercapto group with respect to 100 parts by mass of the silica, and 2 to 2 parts of conductive carbon black with respect to 100 parts by mass of the rubber component. It is preferable to include 30 parts by mass.
  • the rubber composition contains 0.5 to 20 parts by mass of a silane coupling agent having a mercapto group with respect to 100 parts by mass of the silica, and the silica has a nitrogen adsorption specific surface area of 150 m 2 / g or more ( 1) and silica (2) having a nitrogen adsorption specific surface area of 100 m 2 / g or less, and the rubber composition contains 2 to 30 parts by mass of conductive carbon black with respect to 100 parts by mass of the rubber component. Is preferred.
  • the rubber composition contains 0.5 to 20 parts by mass of a silane coupling agent having a mercapto group with respect to 100 parts by mass of the silica, and the silane coupling agent is a compound represented by the following formula (1): And / or a compound containing a binding unit A represented by the following formula (2) and a binding unit B represented by the following formula (3).
  • R 101 to R 103 are each a branched or unbranched alkyl group having 1 to 12 carbon atoms, a branched or unbranched alkoxy group having 1 to 12 carbon atoms, or —O— (R 111 — O) z —R 112
  • z R 111 represents a branched or unbranched divalent hydrocarbon group having 1 to 30 carbon atoms.
  • the z R 111 may be the same or different.
  • R 112 is a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms.
  • Z represents an integer of 1 to 30.
  • R 101 to R 103 may be the same or different, and R 104 represents a branched or unbranched carbon atom having 1 to 6 carbon atoms.
  • R 201 is hydrogen, halogen, branched or unbranched alkyl group having 1 to 30 carbon atoms, branched or unbranched alkenyl group having 2 to 30 carbon atoms, branched or unbranched.
  • R 202 represents a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or non-branched alkynyl group having 2 to 30 carbon atoms, or a group in which the terminal hydrogen of the alkyl group is substituted with a hydroxyl group or a carboxyl group.
  • R 201 and R 202 may form a ring structure.
  • the silica includes a silica (1) having a nitrogen adsorption specific surface area of 150 m 2 / g or more and a silica (2) having a nitrogen adsorption specific surface area of 100 m 2 / g or less, and the silicas (1) and (2) It is preferable that the content satisfies the following formula. (Content of silica (2)) ⁇ 0.2 ⁇ (content of silica (1)) ⁇ (content of silica (2)) ⁇ 6.5
  • the rubber composition preferably contains 2 to 30 parts by mass of conductive carbon black, and the conductive carbon black preferably has a nitrogen adsorption specific surface area of 40 to 80 m 2 / g.
  • the rubber composition is preferably used for a sidewall.
  • the present invention also relates to a pneumatic tire produced using the rubber composition.
  • the present invention since it is a rubber composition containing a specific amount of a specific conjugated diene polymer and silica, the fuel efficiency, rubber strength, cut resistance and processability are improved in a well-balanced manner. Tires can be provided.
  • the hydrocarbyl group represents a monovalent group obtained by removing one hydrogen atom from a hydrocarbon.
  • the hydrocarbylene group represents a divalent group obtained by removing two hydrogen atoms from a hydrocarbon.
  • the hydrocarbyloxy group represents a monovalent group having a structure in which a hydrogen atom of a hydroxy group is replaced with a hydrocarbyl group.
  • a substituted amino group is a group having a structure in which at least one hydrogen atom of an amino group is replaced by a monovalent atom other than a hydrogen atom or a monovalent group, or two hydrogen atoms of an amino group are divalent groups
  • the hydrocarbyl group having a substituent hereinafter sometimes referred to as a substituted hydrocarbyl group
  • a hydrocarbylene group having a heteroatom is a carbon atom and / or hydrogen other than the carbon atom from which the hydrogen atom of the hydrocarbylene group is removed.
  • a divalent group having a structure in which an atom is replaced with a group having a hetero atom is represented.
  • the conjugated diene polymer according to the present invention is a copolymer obtained by polymerizing a monomer component containing a conjugated diene compound and a silicon-containing vinyl compound using a polymerization initiator represented by the following formula (I). It is obtained by reacting a compound containing a nitrogen atom and / or a silicon atom with the active terminal.
  • R 11 represents a hydrocarbylene group having 1 to 100 carbon atoms
  • R 12 and R 13 are hydrocarbyl groups which may have a substituent, Alternatively, it represents a trihydrocarbylsilyl group, or R 12 and R 13 are bonded to each other and have at least one atom selected from the atomic group consisting of a silicon atom, a nitrogen atom and an oxygen atom as a hetero atom.
  • An optionally substituted hydrocarbylene group, and M represents an alkali metal atom.
  • “modify” means that a compound other than these is bonded to a diene compound or a copolymer having a diene compound and an aromatic vinyl compound.
  • the polymer initiation terminal is modified by the polymerization initiator represented by the above formula (I)
  • the main chain is modified by copolymerizing the silicon-containing vinyl compound, the nitrogen atom and / or Alternatively, it has a structure in which the terminating end is modified with a silicon-containing vinyl compound.
  • I in the formula (I) is 0 or 1, preferably 1.
  • R 11 in the formula (I) is a hydrocarbylene group having 1 to 100 carbon atoms, preferably a hydrocarbylene group having 6 to 100 carbon atoms, more preferably 7 to 80 carbon atoms. It is a hydrocarbylene group.
  • the number of carbon atoms in R 11 exceeds 100, the molecular weight of the polymerization initiator increases, and the economy and operability during polymerization may be reduced.
  • the polymerization initiator represented by formula (I) the number of carbon atoms of R 11 may be used in combination plural kinds of different compounds.
  • R 11 in the formula (I) is preferably a group represented by the following formula (Ia).
  • R 14 represents a hydrocarbylene group composed of a structural unit derived from a conjugated diene compound and / or a structural unit derived from an aromatic vinyl compound, and n represents an integer of 1 to 10.
  • R 14 represents a hydrocarbylene group composed of a structural unit derived from a conjugated diene compound and / or a structural unit derived from an aromatic vinyl compound, preferably a hydrocarbylene group composed of a structural unit derived from isoprene. More preferably, it is a hydrocarbylene group consisting of 1 to 10 structural units derived from isoprene.
  • the number of structural units derived from a conjugated diene compound and / or an aromatic vinyl compound in R 14 is preferably 1 to 10 units, and more preferably 1 to 5 units.
  • n is an integer of 1 to 10, preferably an integer of 2 to 4.
  • R 11 includes a group in which 1 to 10 structural units derived from isoprene and a methylene group are bonded, a group in which 1 to 10 structural units derived from isoprene and an ethylene group are bonded, and a structural unit 1 to 1 derived from isoprene. Examples thereof include a group in which 10 units and a trimethylene group are bonded, and a group in which 1 to 10 structural units derived from isoprene and a trimethylene group are bonded is preferable.
  • R 12 and R 13 in formula (I) represent a hydrocarbyl group or trihydrocarbylsilyl group which may have a substituent, or R 12 and R 13 are bonded to each other to form a silicon atom,
  • the hydrocarbylene group which may have as a hetero atom the atom selected from the group which consists of a nitrogen atom and an oxygen atom is represented.
  • the hydrocarbyl group which may have a substituent is a hydrocarbyl group or a substituted hydrocarbyl group.
  • substituent in the substituted hydrocarbyl group include a substituted amino group and a hydrocarbyloxy group.
  • Hydrocarbyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and n-octyl.
  • a chain alkyl group such as n-dodecyl group
  • a cyclic alkyl group such as cyclopentyl group and cyclohexyl group
  • an aryl group such as phenyl group and benzyl group, preferably a chain alkyl group, more preferably Is a chain alkyl group having 1 to 4 carbon atoms.
  • the substituted hydrocarbyl group in which the substituent is a substituted amino group include an N, N-dimethylaminomethyl group, a 2-N, N-dimethylaminoethyl group, and a 3-N, N-dimethylaminopropyl group.
  • Examples of the substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group include a methoxymethyl group, a methoxyethyl group, and an ethoxymethyl group.
  • a hydrocarbyl group is preferable, a chain alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is further preferable.
  • trihydrocarbylsilyl group examples include a trimethylsilyl group and a tert-butyl-dimethylsilyl group, and a trimethylsilyl group is preferable.
  • the hydrocarbylene group which may have at least one atom selected from the atomic group consisting of a silicon atom, a nitrogen atom and an oxygen atom as a heteroatom is a hydrocarbylene group, or a heteroatom is a silicon atom, nitrogen It is a heteroatom-containing hydrocarbylene group which is at least one atom selected from an atomic group consisting of an atom and an oxygen atom.
  • hydrocarbylene group examples include a tetramethylene group, a pentamethylene group, a hexamethylene group, a pentane-2-ene-1,5-diyl group, and a 2,2,4-trimethylhexane-1,6-diyl group.
  • Alkylene group Alkenediyl group such as pentane-2-ene-1,5-diyl group can be mentioned, preferably an alkylene group, more preferably an alkylene group having 4 to 7 carbon atoms.
  • heteroatom-containing hydrocarbylene group in which the heteroatom is a silicon atom examples include a group represented by —Si (CH 3 ) 2 —CH 2 —CH 2 —Si (CH 3 ) 2 —.
  • heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom examples include a group represented by —CH ⁇ N—CH ⁇ CH— and a group represented by —CH ⁇ N—CH 2 —CH 2 —. be able to.
  • heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom examples include a group represented by —CH 2 —CH 2 —O—CH 2 —CH 2 —.
  • a hydrocarbylene group is preferable, an alkylene group having 4 to 7 carbon atoms is more preferable, and a tetramethylene group, a pentamethylene group, and a hexamethylene group are further preferable.
  • R 12 and R 13 are preferably hydrocarbyl groups, or R 12 and R 13 are preferably bonded to form a hydrocarbylene group, which is a chain alkyl group having 1 to 4 carbon atoms, or a bond An alkylene group having 4 to 7 carbon atoms is more preferable, and a methyl group or an ethyl group is further preferable.
  • M represents an alkali metal atom.
  • alkali metal atom examples include Li, Na, K, and Cs, and Li is preferable.
  • examples of the compound in which i is 1 include compounds obtained by polymerizing 1 to 5 structural units derived from isoprene on an aminoalkyl lithium compound.
  • the aminoalkyl lithium compounds include 3- (N, N-dimethylamino) -1-propyllithium, 3- (N, N-diethylamino) -1-propyllithium, 3- (N, N-di-n- Butylamino) -1-propyllithium, 4- (N, N-dimethylamino) -1-butyllithium, 4- (N, N-diethylamino) -1-butyllithium, 4- (N, N-di-n N, N-dialkylaminoalkyllithium such as -propylamino) -1-butyllithium, 3- (N, N-di-n-butylamino) -1-butyllithium; 3- (1-pyrrolidino)
  • Heteroatom-containing cyclic aminoalkyllithium compounds can be mentioned, N, N-dialkylaminoalkyllithium is preferred, 3- (N, N-dimethylamino) -1-propyllithium or 3- (N, N-diethylamino) More preferred is 1-propyllithium.
  • compounds in which i is 0 include lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, and lithium dimethylamide.
  • a compound in which i is 0 may be preliminarily prepared from a secondary amine and a hydrocarbyl lithium compound and used for the polymerization reaction, or generated in a polymerization system. Also good.
  • examples of the secondary amine include dimethylamine, diethylamine, dibutylamine, dioctylamine, dicyclohexylamine, diisobutylamine and the like, azacycloheptane (ie, hexamethyleneimine), 2- (2-ethylhexyl) pyrrolidine, 3 -(2-propyl) pyrrolidine, 3,5-bis (2-ethylhexyl) piperidine, 4-phenylpiperidine, 7-decyl-1-azacyclotridecane, 3,3-dimethyl-1-azacyclotetradecane, 4- Dodecyl-1-azacyclooctane, 4- (2-phenylbutyl) -1-azacyclooctane, 3-ethyl-5-cyclohexyl-1-azacycloheptane, 4-hexyl-1-azacycloheptane, 9-isoamyl -1-Azacycloh
  • the polymerization initiator represented by the formula (I) is preferably a compound in which i is 1, more preferably a compound obtained by polymerizing 1 to 5 structural units derived from isoprene on N, N-aminoalkyllithium. More preferred is a compound obtained by polymerizing 1 to 5 structural units derived from isoprene to-(N, N-dimethylamino) -1-propyllithium or 3- (N, N-diethylamino) -1-propyllithium.
  • the amount of the polymerization initiator represented by the formula (I) is preferably 0.01 to 15 mmol, more preferably 0.1 to 10 mmol, per 100 g of monomer components used in the polymerization.
  • n-butyl lithium may be used in combination.
  • conjugated diene compound examples include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, and myrcene. These may be one kind, Two or more kinds may be used. From the viewpoint of availability, 1,3-butadiene and isoprene are preferable.
  • the silicon-containing vinyl compound is preferably a compound represented by the following formula (II).
  • m is 0 or 1
  • R 21 represents a hydrocarbylene group
  • X 1 , X 2 and X 3 have a substituted amino group, a hydrocarbyloxy group, or a substituent. Represents a good hydrocarbyl group.
  • M in the formula (II) is 0 or 1, preferably 0.
  • Examples of the hydrocarbylene group in the formula (II) include an alkylene group, an alkenediyl group, an arylene group, and a group in which an arylene group and an alkylene group are bonded.
  • Examples of the alkylene group include a methylene group, an ethylene group, and a trimethylene group.
  • Examples of the alkenediyl group include a vinylene group and an ethylene-1,1-diyl group.
  • Examples of the arylene group include a phenylene group, a naphthylene group, and a biphenylene group.
  • Examples of the group in which an arylene group and an alkylene group are bonded include a group in which a phenylene group and a methylene group are bonded, and a group in which a phenylene group and an ethylene group are bonded.
  • R 21 is preferably an arylene group, more preferably a phenylene group.
  • X 1 , X 2 and X 3 represent a substituted amino group, a hydrocarbyloxy group, or a hydrocarbyl group which may have a substituent.
  • at least one of X 1 , X 2 and X 3 is a substituted amino group, more preferably two of X 1 , X 2 and X 3 are substituted amino groups.
  • the substituted amino group in formula (II) is preferably a group represented by the following formula (IIa).
  • R 22 and R 23 represent a hydrocarbyl group or trihydrocarbylsilyl group which may have a substituent, or R 22 and R 23 are bonded to form a nitrogen atom.
  • R 22 and R 23 are bonded to form a nitrogen atom.
  • / or a hydrocarbylene group which may have an oxygen atom as a hetero atom.
  • the hydrocarbyl group which may have a substituent in formula (IIa) is a hydrocarbyl group or a substituted hydrocarbyl group.
  • the substituted hydrocarbyl group include a substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group.
  • Hydrocarbyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and n-octyl.
  • a chain alkyl group such as a group; a cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group; and an aryl group such as a phenyl group, a benzyl group, and a naphthyl group.
  • a chain alkyl group is preferred, and a methyl group or an ethyl group is preferred. More preferred.
  • Examples of the substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group include alkoxyalkyl groups such as a methoxymethyl group, ethoxymethyl group, and methoxyethyl group; aryloxyalkyl groups such as a phenoxymethyl group.
  • trihydrocarbylsilyl group in the formula (IIa) examples include trialkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group.
  • the hydrocarbylene group which may have a nitrogen atom and / or an oxygen atom in formula (IIa) as a heteroatom is a heteroatom-containing hydrocarbyl group in which the hydrocarbylene group or heteroatom is a nitrogen atom and / or an oxygen atom. It is a len group.
  • the heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom and / or an oxygen atom includes a heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom, and a heteroatom-containing hydrocarbylene in which the heteroatom is an oxygen atom You can raise a group.
  • hydrocarbylene group examples include trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, decamethylene group, dodecamethylene group, 2,2,4-trimethylhexane-1,6.
  • An alkylene group such as a diyl group; and an alkenediyl group such as a pentane-2-ene-1,5-diyl group.
  • heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom include a group represented by —CH ⁇ N—CH ⁇ CH— and a group represented by —CH ⁇ N—CH 2 —CH 2 —. be able to.
  • heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom examples include a group represented by —CH 2 —CH 2 —O—CH 2 —CH 2 —.
  • R 22 and R 23 are alkyl groups, or R 22 and R 23 are preferably bonded to form an alkylene group, more preferably an alkyl group, and a methyl group or an ethyl group. Is more preferable.
  • R 22 and R 23 are hydrocarbyl groups
  • R 22 and R 23 are hydrocarbyl groups
  • R 22 and R 23 are hydrocarbyl groups
  • Dialkylamino groups such as di-n-butylamino group, diisobutylamino group, di-sec-butylamino group and di-tert-butylamino group
  • diarylamino groups such as diphenylamino group.
  • Group is preferred, and dimethylamino group, diethylamino group, and di-n-butylamino group are more preferred.
  • Examples of the substituted hydrocarbyl group in which R 22 and R 23 have a hydrocarbyloxy group as a substituent include di (alkoxyalkyl) amino groups such as di (methoxymethyl) amino group and di (ethoxymethyl) amino group.
  • R 22 and R 23 are trihydrocarbylsilyl groups containing trialkylsilyl groups such as bis (trimethylsilyl) amino group, bis (tert-butyldimethylsilyl) amino group, N-trimethylsilyl-N-methylamino group An amino group can be mentioned.
  • substituted amino groups represented by the formula (IIa) include 1-trimethyleneimino group, 1-pyrrolidino group, 1- Examples include 1-alkyleneimino groups such as piperidino group, 1-hexamethyleneimino group, 1-heptamethyleneimino group, 1-octamethyleneimino group, 1-decamethyleneimino group, 1-dodecamethyleneimino group.
  • Examples of the hetero atom-containing hydrocarbylene group in which the hetero atom is a nitrogen atom include a 1-imidazolyl group and a 4,5-dihydro-1-imidazolyl group.
  • the hetero atom-containing hydrocarbylene group in which the hetero atom is an oxygen atom include a morpholino group.
  • the substituted amino group represented by the formula (IIa) is preferably a dialkylamino group or a 1-alkyleneimino group, more preferably a dialkylamino group, and further preferably a dimethylamino group, a diethylamino group, or a di-n-butylamino group. .
  • hydrocarbyloxy group in the formula (II) examples include alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group; phenoxy group, benzyloxy And aryloxy groups such as a group.
  • the hydrocarbyl group which may have a substituent in formula (II) is a hydrocarbyl group or a substituted hydrocarbyl group.
  • the substituted hydrocarbyl group include a substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group.
  • the hydrocarbyl group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group; a phenyl group, a 4-methyl-1-phenyl group, An aryl group such as a benzyl group can be mentioned.
  • the substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group include alkoxyalkyl groups such as a methoxymethyl group, an ethoxymethyl group, and an ethoxyethyl group.
  • one of X 1 , X 2 and X 3 is a substituted amino group, and m is 0.
  • one of X 1 , X 2 and X 3 is a substituted amino group, and m is 1, (Dimethylamino) dimethyl-4-vinylphenylsilane, (dimethylamino) dimethyl-3-vinylphenylsilane, (diethylamino) dimethyl-4-vinylphenylsilane, (diethylamino) dimethyl-3-vinylphenylsilane, (di-n -Propylamino) dimethyl-4-vinylphenylsilane, (di-n-propylamino) dimethyl-3-vinylphenylsilane, (di-n-butylamino) dimethyl-4-vinylphenylsilane, (di-n-butyl) Amino) dimethyl-3-vinylphenylsilane, (dimethylamino) diethyl-4-vinylsilane, (dimethylamino) dieth
  • X 1 , X 2 and X 3 are substituted amino groups, and m is 0.
  • X 1 , X 2 and X 3 are substituted amino groups, and m is 1, Bis (dimethylamino) methyl-4-vinylphenylsilane, bis (dimethylamino) methyl-3-vinylphenylsilane, bis (diethylamino) methyl-4-vinylphenylsilane, bis (diethylamino) methyl-3-vinylphenylsilane, Bis (di-n-propylamino) methyl-4-vinylphenylsilane, bis (di-n-propylamino) methyl-3-vinylphenylsilane, bis (di-n-butylamino) methyl-4-vinylphenylsilane Bis (di-n-butylamino) methyl-3-vinylphenylsilane, bis (dimethylamino) ethyl-4
  • silicon-containing vinyl compounds represented by the formula (II) three of X 1 , X 2 and X 3 are substituted amino groups, and m is 0.
  • examples thereof include tris (dialkylamino) vinylsilane such as tris (dimethylamino) vinylsilane, tris (diethylamino) vinylsilane, tris (di-n-propylamino) vinylsilane, and tris (di-n-butylamino) vinylsilane.
  • X 1 , X 2 and X 3 are substituted amino groups and m is 1, Tris (dimethylamino) -4-vinylphenylsilane, Tris (dimethylamino) -3-vinylphenylsilane, Tris (diethylamino) -4-vinylphenylsilane, Tris (diethylamino) -3-vinylphenylsilane, Tris (di- n-propylamino) -4-vinylphenylsilane, tris (di-n-propylamino) -3-vinylphenylsilane, tris (di-n-butylamino) -4-vinylphenylsilane, tris (di-n- And tris (dialkylamino) vinylphenylsilane such as butylamino) -3-vinylpheny
  • Trialkoxyvinylsilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxyvinylsilane; dialkoxyalkylvinylsilanes such as methyldimethoxyvinylsilane and methyldiethoxyvinylsilane; di (tert-pentoxy) phenylvinylsilane, di (tert-butoxy) phenylvinylsilane, etc.
  • Dialkoxyaryl vinyl silanes monoalkoxy dialkyl vinyl silanes such as dimethylmethoxy vinyl silane; monoalkoxy diaryl vinyl silanes such as tert-butoxy diphenyl vinyl silane; tert-pentoxy diphenyl vinyl silane; tert-butoxymethyl phenyl vinyl silane; Monoalkoxyalkylary Vinylsilane; tris (beta-methoxyethoxy) substitution such as vinyl silane alkoxy vinyl silane compounds can be mentioned.
  • examples of the silicon-containing vinyl compound include bis (trialkylsilyl) aminostyrene such as 4-N, N-bis (trimethylsilyl) aminostyrene and 3-N, N-bis (trimethylsilyl) aminostyrene; 4-bis (trimethylsilyl) Bis (trialkylsilyl) aminoalkylstyrene such as aminomethylstyrene, 3-bis (trimethylsilyl) aminomethylstyrene, 4-bis (trimethylsilyl) aminoethylstyrene, 3-bis (trimethylsilyl) aminoethylstyrene .
  • the silicon-containing vinyl compound is preferably a compound represented by formula (II), more preferably a compound in which m in formula (II) is 0, and among X 1 , X 2 and X 3 in formula (II) More preferred are compounds in which two are dialkylamino groups.
  • Particularly preferred compounds as the silicon-containing vinyl compound are bis (dimethylamino) methylvinylsilane, bis (diethylamino) methylvinylsilane, and bis (di-n-butylamino) methylvinylsilane.
  • the amount of silicon-containing vinyl compound used is 100% by mass based on the total amount of monomer components used in the polymerization, resulting in low fuel consumption, rubber strength, cut resistance and processability. Is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and still more preferably 0.05% by mass or more. In order to increase the economic efficiency and to increase the tensile strength at break and increase the rubber strength, it is preferably 20% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less. It is.
  • a polymerizable monomer may be used as the monomer component in addition to the conjugated diene compound and the silicon-containing vinyl compound.
  • the monomer include aromatic vinyl compounds, vinyl nitriles and unsaturated carboxylic acid esters.
  • the aromatic vinyl compound include styrene, ⁇ -methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, and divinyl naphthalene.
  • Examples of the vinyl nitrile include acrylonitrile, and examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. In these, an aromatic vinyl compound is preferable and styrene is more preferable.
  • the amount of the aromatic vinyl compound used is preferably 10% by mass, with the total amount of the conjugated diene compound and the aromatic vinyl compound being 100% by mass. It is at least mass% (the amount of conjugated diene compound used is 90% by mass or less), more preferably at least 15% by mass (the amount of conjugated diene compound used is 85% by mass or less). From the viewpoint of low fuel consumption, the amount of aromatic vinyl compound used is preferably 50% by mass or less (the amount of conjugated diene compound used is 50% by mass or more), more preferably 45% by mass or less (conjugated diene). The amount of the compound used is 55% by mass or more).
  • the polymerization is preferably performed in a hydrocarbon solvent.
  • the hydrocarbon solvent is a solvent that does not deactivate the polymerization initiator of formula (I), and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons.
  • examples of the aliphatic hydrocarbon include propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, n-heptane, and n-octane.
  • the aromatic hydrocarbon include benzene, toluene, xylene, and ethylbenzene.
  • the alicyclic hydrocarbon examples include cyclopentane and cyclohexane.
  • the hydrocarbon solvent may be a mixture of various components such as industrial hexane. Preferably, it is a hydrocarbon having 2 to 12 carbon atoms.
  • Polymerization reaction is an agent that adjusts the amount of vinyl bonds of conjugated diene units, an agent that adjusts the distribution of monomer units based on monomers other than conjugated diene units and conjugated dienes in the conjugated diene polymer chain , And collectively referred to as “regulators”).
  • agents include ether compounds, tertiary amine compounds, and phosphine compounds.
  • ether compounds include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; aliphatic monoethers such as diethyl ether and dibutyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and diethylene glycol diethyl ether. And aliphatic diethers such as diethylene glycol dibutyl ether; aromatic ethers such as diphenyl ether and anisole.
  • cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane
  • aliphatic monoethers such as diethyl ether and dibutyl ether
  • ethylene glycol dimethyl ether ethylene glycol diethyl ether
  • ethylene glycol dibutyl ether ethylene glycol dibutyl ether
  • Examples of the tertiary amine compound include triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N-diethylaniline, pyridine, quinoline and the like.
  • Examples of the phosphine compound include trimethylphosphine, triethylphosphine, triphenylphosphine, and the like. One or more of these are used.
  • a polymerization initiator may be supplied to the polymerization reactor before supplying the monomer component to the polymerization reactor.
  • the polymerization initiator may be supplied to the polymerization reactor after being supplied to the reactor, or a part of the monomer components used for the polymerization may be supplied to the polymerization reactor and then supplied to the polymerization reactor. Good.
  • a polymerization initiator may be supplied to a polymerization reactor at a time, and may be supplied continuously.
  • the monomer component may be supplied to the polymerization reactor at a time, may be supplied continuously, or may be supplied intermittently. Moreover, each monomer may be supplied separately to the polymerization reactor or may be supplied simultaneously.
  • the polymerization temperature in the production of the conjugated diene polymer is usually 25 to 100 ° C., preferably 35 to 90 ° C. More preferably, it is 50 to 80 ° C.
  • the polymerization time is usually 10 minutes to 5 hours.
  • the conjugated diene polymer is prepared by polymerizing a monomer component containing a conjugated diene compound and a silicon-containing vinyl compound using a polymerization initiator represented by the formula (I) (active terminal (copolymer)). It can be obtained by reacting a compound containing a nitrogen atom and / or a silicon atom with the active terminal of the polymer (which is considered to have an alkali metal derived from the polymerization initiator) (terminal modification reaction). Specifically, a compound containing a nitrogen atom and / or a silicon atom is added to the polymerization solution and mixed.
  • a polymerization initiator represented by the formula (I) (active terminal (copolymer)
  • the amount of the compound containing nitrogen atoms and / or silicon atoms added to the polymerization solution is usually 0.1 to 3 mol per 1 mol of the alkali metal derived from the polymerization initiator represented by the formula (I) used.
  • the amount is preferably 0.5 to 2 mol, and more preferably 0.7 to 1.5 mol.
  • the reaction temperature of the terminal modification reaction is usually 25 to 100 ° C., preferably 35 to 90 ° C., more preferably 50 to 80 ° C.
  • the reaction time for the terminal reaction is usually 60 seconds to 5 hours, preferably 5 minutes to 1 hour, more preferably 15 minutes to 1 hour.
  • the compounds containing a nitrogen atom and / or a silicon atom preferred are compounds containing a nitrogen atom and a carbonyl group.
  • R 31 is a hydrocarbyl group which may have a substituent, a hydrocarbylene group which may be bonded to R 32 and have a nitrogen atom and / or an oxygen atom as a hetero atom, or
  • R 34 represents a divalent group
  • R 32 has a hydrocarbyl group which may have a substituent
  • R 31 has a nitrogen atom and / or an oxygen atom as a hetero atom
  • R 34 may be a hydrocarbyl group which may have a substituent, a hydrogen atom, or a divalent group bonded to R 31.
  • R 33 represents a divalent group.
  • K represents 0 or 1.
  • the hydrocarbyl group which may have a substituent of R 31 , R 32 and R 34 is a hydrocarbyl group or a substituted hydrocarbyl group.
  • the substituted hydrocarbyl group include a substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group, and a substituted hydrocarbyl group in which the substituent is a substituted amino group.
  • the hydrocarbyl group include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group; alkenyl groups such as vinyl group, allyl group and isopropenyl group; and aryl groups such as phenyl group.
  • Examples of the substituted hydrocarbyl group in which the substituent is a hydrocarbyloxy group include alkoxyalkyl groups such as a methoxymethyl group, an ethoxymethyl group, and an ethoxyethyl group.
  • the substituted hydrocarbyl group in which the substituent is a substituted amino group includes 2- (N, N-dimethylamino) ethyl group, 2- (N, N-diethylamino) ethyl group, 3- (N, N-dimethylamino) propyl Groups, (N, N-dialkylamino) alkyl groups such as 3- (N, N-diethylamino) propyl group; 4- (N, N-dimethylamino) phenyl group, 3- (N, N-dimethylamino) phenyl Groups, (N, N-dialkylamino) aryl groups such as 4- (N, N-diethylamino) phenyl group, 3- (N, N-diethylamino) phenyl group; 4- (N, N-dimethylamino) methylphenyl Groups, (N, N-dialkylamino) alkylaryl groups such as 4- (N, N-
  • the hydrocarbylene group optionally having a nitrogen atom and / or an oxygen atom to which R 31 and R 32 are bonded as a hetero atom is a hydrocarbylene group, or a hetero atom is a nitrogen atom and And / or a heteroatom-containing hydrocarbylene group which is an oxygen atom.
  • the heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom and / or an oxygen atom includes a heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom, and a heteroatom-containing hydrocarbylene in which the heteroatom is an oxygen atom You can raise a group.
  • the hydrocarbylene group includes trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, pentane-2-ene-1,5-diyl group, 2,2,4-trimethylhexane-1,6-diyl
  • An alkylene group such as a group
  • an arylene group such as a 1,4-phenylene group.
  • heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom include a group represented by —CH ⁇ N—CH ⁇ CH— and a group represented by —CH ⁇ N—CH 2 —CH 2 —. be able to.
  • heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom examples include groups represented by — (CH 2 ) s —O— (CH 2 ) t — (s and t are integers of 1 or more). Can do.
  • the divalent group in which R 31 and R 34 are bonded and the divalent group of R 33 include a hydrocarbylene group, a heteroatom-containing hydrocarbylene group in which the hetero atom is a nitrogen atom, hetero A heteroatom-containing hydrocarbylene group in which the atom is an oxygen atom, a group in which a hydrocarbylene group and an oxygen atom are bonded, a group represented by a hydrocarbylene group and —NR 35 — (R 35 is a hydrocarbyl group or a hydrogen atom And a group bonded to each other.
  • the hydrocarbylene group includes trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, pentane-2-ene-1,5-diyl group, 2,2,4-trimethylhexane-1,6-diyl
  • An alkylene group such as a group
  • an arylene group such as a 1,4-phenylene group.
  • heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom include a group represented by —CH ⁇ N—CH ⁇ CH— and a group represented by —CH ⁇ N—CH 2 —CH 2 —. be able to.
  • heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom examples include groups represented by — (CH 2 ) s —O— (CH 2 ) t — (s and t are integers of 1 or more). Can do.
  • R 35 represents a hydrocarbyl group or a hydrogen atom
  • a group represented by — (CH 2 ) p —NR 35 — R 35 represents a hydrocarbyl group (preferably a hydrocarbyl group having 1 to 6 carbon atoms) or a hydrogen atom
  • p represents an integer of 1 or more.
  • Preferred examples of the compound represented by the formula (III) include a compound represented by the following formula (IIIa) in which k is 0 and R 34 is a hydrocarbyl group or a hydrogen atom which may have a substituent. it can.
  • R 31 represents a hydrocarbyl group which may have a substituent, or a hydrocarbylene which may be bonded to R 32 and have a nitrogen atom and / or an oxygen atom as a hetero atom
  • R 32 represents a hydrocarbyl group which may have a substituent or a hydrocarbylene group which may be bonded to R 31 and have a nitrogen atom and / or an oxygen atom as a hetero atom
  • R 34 represents a hydrocarbyl group or a hydrogen atom which may have a substituent.
  • a hydrocarbyl group which may have a substituent of R 31 , R 32 and R 34 , a nitrogen atom and / or an oxygen atom to which R 31 and R 32 are bonded have a hetero atom.
  • the description and examples of the preferred hydrocarbylene group are the same as those described in the description of formula (III).
  • R 31 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbylene group having 3 to 10 carbon atoms bonded to R 32 or a hetero atom is a nitrogen atom. It is a heteroatom-containing hydrocarbylene group having 3 to 10 carbon atoms. More preferably, it is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or an alkylene group having 3 to 10 carbon atoms bonded to R 32 , —CH ⁇ N—CH ⁇ A group represented by CH— or a group represented by —CH ⁇ N—CH 2 —CH 2 —. More preferably, it is an alkyl group having 1 to 6 carbon atoms. Particularly preferred is a methyl group or an ethyl group.
  • R 32 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbylene group having 3 to 10 carbon atoms bonded to R 31 or a hetero atom is a nitrogen atom. It is a heteroatom-containing hydrocarbylene group having 3 to 10 carbon atoms. More preferably, it is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or an alkylene group having 3 to 10 carbon atoms bonded to R 31 , —CH ⁇ N—CH ⁇ A group represented by CH— or a group represented by —CH ⁇ N—CH 2 —CH 2 —. More preferably, it is an alkyl group having 1 to 6 carbon atoms. Particularly preferred is a methyl group or an ethyl group.
  • R 34 is preferably a hydrocarbyl group or a hydrogen atom, more preferably a hydrocarbyl group or a hydrogen atom having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms or A hydrogen atom, particularly preferably a hydrogen atom, a methyl group, or an ethyl group.
  • R 34 is a hydrocarbyl group
  • those in which R 34 is a hydrocarbyl group include N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-N-ethylacetamide and the like.
  • those in which R 34 is a hydrogen atom include N, N-dimethylformamide, N, N-dimethylformamide, N-methyl-N-ethylformamide and the like N, N Mention may be made of dihydrocarbylformamide.
  • Preferable compounds represented by the formula (III) include compounds represented by the following formula (IIIb) in which k is 0 and R 34 is bonded to R 31 to form a divalent group.
  • R 32 represents an optionally substituted hydrocarbyl group
  • R 36 is a hydrocarbylene group or a group obtained by bonding a hydrocarbylene group to a group represented by —NR 35 —.
  • R 35 represents a hydrocarbyl group or a hydrogen atom.
  • hydrocarbylene group for R 36 trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, pentane-2-ene-1,5-diyl group, 2,2,4- Examples thereof include alkylene groups such as trimethylhexane-1,6-diyl group; and arylene groups such as 1,4-phenylene group.
  • R 36 As the group of R 36 to which a hydrocarbylene group and a group represented by —NR 35 — (R 35 represents a hydrocarbyl group or a hydrogen atom) is bonded, — (CH 2 ) p —NR 35 — And a group represented by the formula (R 35 represents a hydrocarbyl group or a hydrogen atom, and p represents an integer of 1 or more).
  • R 32 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and further preferably Is an alkyl group having 1 to 6 carbon atoms or a phenyl group, particularly preferably a methyl group, an ethyl group or a phenyl group.
  • R 36 is preferably a hydrocarbylene group having 1 to 10 carbon atoms, or a group represented by —NR 35 — and a hydrocarbylene group having 1 to 10 carbon atoms
  • R 35 is A hydrocarbyl group (preferably a hydrocarbyl group having 1 to 10 carbon atoms) or a hydrogen atom), and more preferably an alkylene group having 3 to 6 carbon atoms or — (CH 2 ) p —.
  • a group represented by NR 35 — R 35 represents a hydrocarbyl group (preferably a hydrocarbyl group having 1 to 10 carbon atoms), and p represents an integer of 1 or more (preferably an integer of 2 to 5)).
  • p represents an integer of 1 or more (preferably an integer of 2 to 5)
  • p represents an integer of 1 or more (preferably an integer of 2 to 5)
  • R 36 is a hydrocarbylene group
  • R 36 is a hydrocarbylene group
  • R 36 is a hydrocarbylene group
  • N-methyl-2-pyrrolidone N-vinyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, N-tert-butyl-2-pyrrolidone, N-methyl-5-methyl-2- N-hydrocarbyl-2-pyrrolidone such as pyrrolidone
  • N-hydrocarbyl-2-piperidone such as N-methyl-2-piperidone, N-vinyl-2-piperidone, N-phenyl-2-piperidone
  • N-methyl- ⁇ - N-hydrocarbyl- ⁇ -caprolactam such as caprolactam, N-phenyl- ⁇ -caprolactam
  • R 36 is a group in which a hydrocarbylene group and a group represented by —NR 35 — (R 35 represents a hydrocarbyl group or a hydrogen atom) are combined.
  • Examples include 1,3-dihydrocarbyl-2-imidazolidinone such as non-one, among which 1,3-dimethyl-2-imidazolidinone is preferable.
  • Preferable compounds represented by the formula (III) include compounds represented by the following formula (IIIc) in which k is 1 and R 33 is a hydrocarbylene group.
  • R 31 represents a hydrocarbyl group which may have a substituent, or a hydrocarbyl which may be bonded to R 32 and have a nitrogen atom and / or an oxygen atom as a hetero atom.
  • R 32 represents a hydrocarbyl group which may have a substituent, or R 32 may be bonded to R 31 and may have a nitrogen atom and / or an oxygen atom as a hetero atom
  • R 33 represents a hydrocarbylene group
  • R 34 represents a hydrocarbyl group or a hydrogen atom which may have a substituent.
  • a hydrocarbyl group which may have a substituent of R 31 , R 32 and R 34 , a nitrogen atom and / or an oxygen atom to which R 31 and R 32 are bonded have a hetero atom.
  • the description and illustration of the preferred hydrocarbylene group, the hydrocarbylene group of R 33 are the same as those described in the description of formula (III).
  • R 33 is preferably a hydrocarbylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms, An alkylene group having 1 to 6 carbon atoms or a phenylene group is more preferable, and an ethylene group, trimethylene group, or 1,4-phenylene group is particularly preferable.
  • R 34 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a substituted hydrocarbyl group having 1 to 10 carbon atoms in which the substituent is a dialkylamino group, more preferably 1 carbon atom.
  • R 31 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, a hydrocarbylene group having 3 to 10 carbon atoms bonded to R 32 , or a hetero atom having a nitrogen atom or oxygen atom
  • a heteroatom-containing hydrocarbylene group having 3 to 10 carbon atoms more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or a bond to R 32
  • CH N—CH ⁇ CH—
  • R 32 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbylene group having 3 to 10 carbon atoms bonded to R 31 , or a hetero atom having a nitrogen atom or oxygen atom
  • a C3-C10 heteroatom-containing hydrocarbylene group more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or a bond to R 31
  • CH N—CH ⁇ CH— A group represented by —CH ⁇ N—CH 2
  • 4-N, N-dihydrocarbylaminoacetophenone such as 4- (N, N-dimethylamino) acetophenone, 4-N-methyl-N-ethylaminoacetophenone, 4-N, N-diethylaminoacetophenone; 4 ′-(imidazole Examples include 4-cyclic aminoacetophenone compounds such as -1-yl) acetophenone and 4-pyrazolylacetophenone, among which 4-cyclic aminoacetophenone compounds are preferable, and 4 ′-(imidazol-1-yl) acetophenone is more preferable. .
  • k is 1, and R 33 is a group in which a hydrocarbylene group and an oxygen atom are bonded, or a group represented by a hydrocarbylene group and —NR 35 — ( R 35 represents a compound represented by the following formula (IIId) which is a group bonded to a hydrocarbyl group or a hydrogen atom.
  • R 31 represents a hydrocarbyl group which may have a substituent, or a hydrocarbyl which may be bonded to R 32 and have a nitrogen atom and / or an oxygen atom as a hetero atom.
  • R 32 represents a hydrocarbyl group which may have a substituent, or R 32 may be bonded to R 31 and may have a nitrogen atom and / or an oxygen atom as a hetero atom
  • R 37 represents a hydrocarbylene group
  • A represents an oxygen atom or —NR 35 —
  • R 35 represents a hydrocarbyl group or a hydrogen atom
  • R 34 represents a hydrocarbyl group which may have a substituent or Represents a hydrogen atom.
  • a hydrocarbyl group which may have a substituent of R 31 , R 32 and R 34 , a nitrogen atom and / or an oxygen atom to which R 31 and R 32 are bonded have a hetero atom.
  • the description and examples of the preferred hydrocarbylene group are the same as those described in the description of formula (III).
  • the hydrocarbyl group of R 35 is the same as that described for the hydrocarbyl group of R 31 , R 32 , and R 34 .
  • A is preferably an oxygen atom or a group represented by —NR 35 — (R 35 is a hydrocarbyl group (preferably a hydrocarbyl group having 1 to 5 carbon atoms) or a hydrogen atom). More preferred is an oxygen atom or a group represented by —NH—, and still more preferred is a group represented by —NH—.
  • the hydrocarbylene group represented by R 37 includes trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, pentane-2-ene-1,5-diyl group, 2,2,4- Examples thereof include alkylene groups such as trimethylhexane-1,6-diyl group; and arylene groups such as 1,4-phenylene group.
  • R 34 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, more preferably an alkenyl group having 2 to 5 carbon atoms, and further preferably a vinyl group.
  • R 37 is preferably a hydrocarbylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, still more preferably an ethylene group or a trimethylene group. Particularly preferred is a trimethylene group.
  • R 31 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, a hydrocarbylene group having 3 to 10 carbon atoms bonded to R 32 , or a hetero atom having a nitrogen atom or oxygen atom
  • R 32 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, a hydrocarbylene group having 3 to 10 carbon atoms bonded to R 31 , or a hetero atom having a nitrogen atom or oxygen
  • a C3-C10 heteroatom-containing hydrocarbylene group more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or a bond to R 31
  • N N-dihydrocarbylaminoethylacrylamide, such as N, N-dimethylaminoethylacrylamide, N, N-diethylaminoethylacrylamide; N, N-, such as N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide Dihydrocarbylaminopropylacrylamide; N, N-dihydrocarbylaminobutylacrylamide such as N, N-dimethylaminobutylacrylamide, N, N-diethylaminobutylacrylamide; N, N-dimethylaminoethylmethacrylamide, N, N-diethylaminoethyl N, N-dihydrocarbylaminoe
  • a preferred compound represented by the formula (III) is a compound represented by the formula (IIId), among which N, N-dihydrocarbylaminopropylacrylamide is particularly preferred, and N, N-dimethylaminopropylacrylamide is most preferred. .
  • a compound containing an alkoxysilyl group can also be mentioned as a preferable compound containing a nitrogen atom and / or a silicon atom.
  • R 41 represents a hydrocarbyl group
  • R 42 and R 43 represent a hydrocarbyl group or a hydrocarbyloxy group
  • R 44 represents a hydrocarbyl group or trihydrocarbylsilyl group which may have a substituent.
  • R 45 represents a silicon atom, a nitrogen atom and hydrocarbylene group optionally having at least one atom as a hetero atom selected from the group of atoms consisting of oxygen atoms
  • R 45 is substituted represent a hydrocarbyl group or a trihydrocarbylsilyl group which may have a group, or combined with R 44, at least one atom selected from the group of atoms of silicon atoms, nitrogen atoms and oxygen atoms as a hetero atom (It represents a hydrocarbylene group which may be present, and j represents an integer of 1 to 5.)
  • the hydrocarbyl group which may have a substituent is a hydrocarbyl group or a substituted hydrocarbyl group.
  • hydrocarbyl groups include alkyl groups such as methyl, ethyl, n-propyl, isopropyl and n-butyl groups; alkenyl groups such as vinyl, allyl and isopropenyl groups; and aryl groups such as phenyl groups. It is preferably an alkyl group, more preferably a methyl group or an ethyl group.
  • the substituted hydrocarbyl group include oxacycloalkyl groups such as an oxiranyl group and a tetrahydrofuranyl group, and a tetrahydrofuranyl group is preferable.
  • the oxacycloalkyl group represents a group in which CH 2 on the alicyclic ring of the cycloalkyl group is replaced with an oxygen atom.
  • Hydrocarbyloxy groups include alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy; aryloxy such as phenoxy and benzyloxy Group, and preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
  • trihydrocarbylsilyl group examples include a trimethylsilyl group and a tert-butyl-dimethylsilyl group, and a trimethylsilyl group is preferable.
  • the hydrocarbylene group which may have at least one atom selected from the atomic group consisting of a silicon atom, a nitrogen atom and an oxygen atom as a heteroatom is a hydrocarbylene group, or the heteroatom is a silicon atom or a nitrogen atom And a heteroatom-containing hydrocarbylene group that is at least one atom selected from the group consisting of oxygen atoms.
  • hydrocarbylene group examples include a tetramethylene group, a pentamethylene group, a hexamethylene group, a pentane-2-ene-1,5-diyl group, and a 2,2,4-trimethylhexane-1,6-diyl group.
  • An alkylene group can be mentioned. Among them, an alkylene group having 4 to 7 carbon atoms is preferable, and a pentamethylene group or a hexamethylene group is particularly preferable.
  • heteroatom-containing hydrocarbylene group in which the heteroatom is a silicon atom include a group represented by —Si (CH 3 ) 2 —CH 2 —CH 2 —Si (CH 3 ) 2 —.
  • the heteroatom-containing hydrocarbylene group in which the heteroatom is a nitrogen atom includes a group represented by —CH ⁇ N—CH ⁇ CH— or a group represented by —CH ⁇ N—CH 2 —CH 2 —.
  • I can give you. Examples thereof include a heteroatom-containing hydrocarbylene group in which the heteroatom is an oxygen atom, and a group represented by —CH 2 —CH 2 —O—CH 2 —CH 2 —.
  • R 41 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.
  • R 42 and R 43 are preferably a hydrocarbyloxy group, more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group.
  • R 44 and R 45 are preferably a hydrocarbyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group.
  • J is preferably an integer of 2 to 4.
  • Examples of the compound represented by the formula (IV) include 3-dimethylaminopropyltriethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 3-diethylaminopropyltriethoxysilane, 3-diethylaminopropyltrimethoxysilane, and 3-dimethyl.
  • [(Dialkylamino) alkyl] alkoxysilane compounds such as aminopropylmethyldiethoxysilane, 2-dimethylaminoethyltriethoxysilane, 2-dimethylaminoethyltrimethoxysilane; hexamethyleneiminomethyltrimethoxysilane, 3-hexamethyleneimino Cyclic amino such as propyltriethoxysilane, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-trimethoxysilylpropyl) -4,5-imidazole [Di (tetrahydrofuranyl) amino] alkylalkoxysilane compounds such as 3- [di (tetrahydrofuranyl) amino] propyltrimethoxysilane and 3- [di (tetrahydrofuranyl) amino] propyltriethoxysilane; N N, N-bis (t
  • Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane; trialkoxyhydrocarbylsilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane; trimethoxychlorosilane, Trialkoxyhalosilanes such as triethoxychlorosilane and tri-n-propoxychlorosilane; dialkoxydihydrocarbylsilanes such as dimethoxydimethylsilane, diethoxydimethylsilane and dimethoxydiethylsilane; dimethoxydichlorosilane, diethoxydichloro
  • the compound containing an alkoxysilyl group may contain a nitrogen atom and a carbonyl group.
  • tris [3- (trimethoxysilyl) propyl] isocyanurate tris [3- (triethoxysilyl) propyl] isocyanurate
  • tris [3 Examples include tris [(alkoxysilyl) alkyl] isocyanurate compounds such as-(tripropoxysilyl) propyl] isocyanurate and tris [3- (tributoxysilyl) propyl] isocyanurate, among which tris [3- (tri Methoxysilyl) propyl] isocyanurate is preferred.
  • examples of the compound containing a nitrogen atom and / or a silicon atom include N, N-dialkyl-substituted carboxylic acid amide dialkyl acetal compounds.
  • Examples of N, N-dialkyl-substituted carboxylic acid amide dialkyl acetal compounds include N, N-dimethylformamide dimethyl acetal, N, N-diethylformamide dimethyl acetal and the like; N, N-dialkylformamide dialkyl acetal; N, N-dialkylacetamido dialkyl acetals such as acetal and N, N-diethylacetamidodimethylacetal; N, N-dialkylpropionamide dialkyl such as N, N-dimethylpropionamide dimethylacetal and N, N-diethylpropionamide dimethylacetal Acetal and the like.
  • N, N-dialkylformamide dialkylacetal is preferable, and N, N-dimethylformamide dimethyl
  • a coupling agent may be added to the hydrocarbon solution of the conjugated diene polymer from the start of polymerization of the monomer to the recovery of the polymer described later.
  • An example of the coupling agent is a compound represented by the following formula (V).
  • R 51 a ML 4-a (V) (In the formula (V), R 51 represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aryl group, M represents a silicon atom or a tin atom, L represents a halogen atom or a hydrocarbyloxy group, and a represents 0 to Represents an integer of 2.)
  • silicon tetrachloride methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, tin tetrachloride, methyltrichlorotin, dimethyldichlorotin, trimethylchlorotin, tetramethoxysilane
  • examples thereof include methyltrimethoxysilane, dimethoxydimethylsilane, methyltriethoxysilane, ethyltrimethoxysilane, dimethoxydiethylsilane, diethoxydimethylsilane, tetraethoxysilane, ethyltriethoxysilane, and diethoxydiethylsilane.
  • the addition amount of the coupling agent is preferably 0.03 mol or more, more preferably 0.05 mol or more, per 1 mol of alkali metal derived from the alkali metal catalyst in order to improve the processability of the conjugated diene polymer. Moreover, in order to improve low-fuel-consumption property, Preferably it is 0.4 mol or less, More preferably, it is 0.3 mol or less.
  • an unreacted active terminal may be treated with an alcohol such as methanol or isopropyl alcohol before recovering the polymer described later.
  • a known method can be used as a method for recovering the conjugated diene polymer from the conjugated diene polymer hydrocarbon solution.
  • a known method can be used. For example, (A) a method of adding a coagulant to the conjugated diene polymer hydrocarbon solution. (B) A method of adding steam to the hydrocarbon solution of the conjugated diene polymer (steam stripping treatment) can be mentioned.
  • the recovered conjugated diene polymer may be dried by a known dryer such as a band dryer or an extrusion dryer.
  • the content of the structural unit derived from the polymerization initiator represented by the formula (I) is a polymer from the viewpoint of improving fuel economy, rubber strength, cut resistance and processability in a balanced manner.
  • Per unit mass preferably 0.0001 mmol / g polymer or more, more preferably 0.001 mmol / g polymer or more, preferably 0.15 mmol / g polymer or less, more preferably 0.1 mmol / g. Below the polymer.
  • the content of the structural unit derived from the silicon-containing vinyl compound is preferably from the viewpoint of improving the fuel economy, rubber strength, cut resistance and processability in a balanced manner, per polymer unit mass, 0.01 mmol / g polymer or more, more preferably 0.02 mmol / g polymer or more, preferably 0.4 mmol / g polymer or less, more preferably 0.2 mmol / g polymer or less.
  • the conjugated diene polymer preferably has a structural unit derived from the compound represented by the formula (II).
  • the structural unit derived from the compound represented by the formula (II) in the conjugated diene polymer means a structural unit represented by the following formula (IIb). (In the formula (IIb), m, R 21 , X 1 , X 2 and X 3 are the same as those in the formula (II).)
  • the conjugated diene polymer according to the present invention in the structural unit derived from the compound represented by formula (II) in the conjugated diene polymer, at least one of X 1 , X 2 and X 3 is substituted with a hydroxyl group. It is preferable that two or more are substituted with a hydroxyl group, and it is more preferable that two are substituted with a hydroxyl group. Thereby, the improvement effect of low fuel consumption, rubber strength, cut resistance, and workability can be enhanced.
  • the method for substituting X 1 , X 2 and X 3 with a hydroxyl group is not particularly limited, and an example is a method by steam stripping treatment.
  • the conjugated diene polymer preferably has a structural unit (aromatic vinyl unit) derived from an aromatic vinyl compound.
  • the content of the aromatic vinyl unit in the conjugated diene polymer is such that the structural unit derived from the conjugated diene compound (conjugated diene unit) and the aromatic vinyl unit.
  • the total amount is preferably 10% by mass or more (content of the conjugated diene unit content compound is 90% by mass or less), more preferably 15% by mass or more (content of the conjugated diene unit is 85% by mass or less).
  • the content of the aromatic vinyl unit is preferably 50% by mass or less (the content of the conjugated diene unit is 50% by mass or more), more preferably 45% by mass or less (conjugated diene).
  • the unit content is 55% by mass or more).
  • the vinyl bond content (vinyl content) of the conjugated diene polymer is low fuel consumption, with the conjugated diene unit content being 100 mol%. From this viewpoint, it is preferably 80 mol% or less, more preferably 70 mol% or less.
  • the conjugated diene polymer preferably has no structural unit of an aromatic vinyl compound.
  • the vinyl bond content (vinyl content) of the conjugated diene polymer ) is 100 mol%, preferably 20 mol% or less, more preferably 15 mol% or less.
  • the vinyl bond amount of the said conjugated diene type polymer can be measured by the method as described in the Example mentioned later.
  • the molecular weight distribution of the conjugated diene polymer is preferably 1 to 5 and more preferably 1 to 2 in order to improve fuel efficiency.
  • the molecular weight distribution is obtained by measuring the number average molecular weight (Mn) and the weight average molecular weight (Mw) by gel permeation chromatography (GPC) method and dividing Mw by Mn.
  • the conjugated diene polymer can be used in the rubber composition of the present invention as a rubber component.
  • the content of the conjugated diene polymer in 100% by mass of the rubber component is 90% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less. If it exceeds 90% by mass, the rubber strength and cut resistance tend to decrease and the cost tends to increase. Moreover, content of the said conjugated diene type polymer is 1 mass% or more, Preferably it is 5 mass% or more, More preferably, it is 10 mass% or more, More preferably, it is 20 mass% or more. If it is less than 1% by mass, the effect of improving fuel economy tends to be difficult to obtain.
  • polyisoprene rubber can be preferably used as another rubber component used in combination with the conjugated diene polymer.
  • polyisoprene rubber By blending the polyisoprene-based rubber, the rubber strength is improved, and the rubber grouping at the time of kneading is improved, so that productivity can be improved.
  • polyisoprene rubber examples include natural rubber (NR) and polyisoprene rubber (IR).
  • NR is not particularly limited.
  • SIR20, RSS # 3, TSR20, deproteinized natural rubber (DPNR), high purity natural rubber (HPNR), epoxidized natural rubber (ENR), etc. which are common in the tire industry Can be used.
  • DPNR deproteinized natural rubber
  • HPNR high purity natural rubber
  • EMR epoxidized natural rubber
  • the content of the polyisoprene rubber in 100% by mass of the rubber component is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably. It is 50 mass% or more. If it is less than 30% by mass, the rubber strength may be reduced, or the rubber may not be tightly kneaded at the time of kneading, so that productivity may be deteriorated.
  • the content of the polyisoprene rubber is 70% by mass or less, preferably 65% by mass or less, and more preferably 60% by mass or less. When it exceeds 70 mass%, there exists a possibility that cut resistance may deteriorate.
  • Examples of rubber components that can be used in addition to the polyisoprene-based rubber include conventional styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), butadiene-isoprene copolymer rubber, and butyl rubber.
  • SBR styrene-butadiene copolymer rubber
  • BR polybutadiene rubber
  • butadiene-isoprene copolymer rubber and butyl rubber.
  • an ethylene-propylene copolymer, an ethylene-octene copolymer, and the like can be given.
  • Two or more of these rubber components may be used in combination. Among them, from the viewpoint that fuel economy, rubber strength, cut resistance and processability can be improved in a well-balanced manner, those containing 50 mass% or more of a structural unit derived from a conjugated diene compound can be preferably used. Is preferably BR or SBR.
  • the BR is not particularly limited.
  • BR1220 manufactured by Nippon Zeon Co., Ltd., BR130B manufactured by Ube Industries, Ltd., BR150B having high cis content such as BR150B, VCR412 manufactured by Ube Industries, Ltd., VCR617, etc.
  • Commonly used in the tire industry such as BR containing syndiotactic polybutadiene crystals can be used.
  • the content of BR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more. . If it is less than 5% by mass, the cut resistance tends to decrease.
  • the BR content is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less. If it exceeds 60% by mass, the rubber strength tends to decrease.
  • the SBR is not particularly limited, and for example, those commonly used in the tire industry such as Nipol NS116R manufactured by Nippon Zeon Co., Ltd. can be used.
  • the content of SBR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 15% by mass or more. If it is less than 5% by mass, the cut resistance tends to decrease.
  • the SBR content is preferably 50% by mass or less, and more preferably 30% by mass or less. If it exceeds 50% by mass, fuel efficiency tends to deteriorate.
  • the rubber composition of the present invention contains silica having a nitrogen adsorption specific surface area (N 2 SA) of 40 to 400 m 2 / g.
  • the silica is not particularly limited, and examples thereof include dry process silica (anhydrous silica), wet process silica (hydrous silica), and wet process silica is preferred because of its large number of silanol groups.
  • Silica may be used alone or in combination of two or more.
  • the nitrogen adsorption specific surface area (N 2 SA) of silica is 40 m 2 / g or more, preferably 50 m 2 / g or more, more preferably 60 m 2 / g or more. If it is less than 40 m ⁇ 2 > / g, a reinforcement effect is small and there exists a tendency for cut resistance and rubber strength to fall.
  • the N 2 SA of the silica 400 meters 2 / g or less, preferably 360 m 2 / g or less, and more preferably not more than 300m 2 / g. When it exceeds 400 m 2 / g, silica is difficult to disperse, and the fuel economy and processability tend to deteriorate.
  • N 2 SA of silica is a value measured by the BET method according to ASTM D3037-93.
  • the content of silica (when using two or more types of silica, the total amount) is 10 parts by mass or more, preferably 15 parts by mass or more, more preferably 20 parts by mass or more, relative to 100 parts by mass of the rubber component. It is. When the amount is less than 10 parts by mass, the effect of blending silica cannot be sufficiently obtained, and the cut resistance and rubber strength tend to decrease.
  • the silica content is 70 parts by mass or less, preferably 65 parts by mass or less, and more preferably 60 parts by mass or less. When it exceeds 70 mass parts, there exists a tendency for workability to deteriorate.
  • Silica may be used alone or in combination of two or more.
  • Silica (1) having a nitrogen adsorption specific surface area of 150 m 2 / g or more and a nitrogen adsorption specific surface area of 100 m 2 / g
  • silica (2) it is more preferable to use the following silica (2) in combination.
  • silica (1) and (2) can be dispersed well, and both reduction of rolling resistance and improvement of rubber strength can be achieved. it can.
  • the improvement effect of each performance can further be heightened by using together the silane coupling agent which has a mercapto group mentioned later, and electroconductive carbon with silica (1) and (2).
  • the nitrogen adsorption specific surface area (N 2 SA) of silica (1) is 150 m 2 / g or more, preferably 160 m 2 / g or more, more preferably 165 m 2 / g or more. If it is less than 150 m ⁇ 2 > / g, there exists a possibility that the effect by blending with a silica (2) may not fully be acquired.
  • N 2 SA of the silica (1) is preferably 400 meters 2 / g, more preferably at most 360 m 2 / g. When it exceeds 400 m 2 / g, not only the workability is deteriorated, but also the rolling resistance tends not to be sufficiently reduced.
  • Silica (1) is not particularly limited as long as N 2 SA is 150 m 2 / g or more, and can be obtained as, for example, Zeosyl 1205MP manufactured by Rhodia. Silica (1) may be used alone or in combination of two or more.
  • the content of silica (1) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 5 parts by mass, sufficient rubber strength tends not to be obtained. Further, the content of silica (1) is preferably 70 parts by mass or less, more preferably 65 parts by mass or less. If it exceeds 70 parts by mass, the workability tends to deteriorate even if the rubber strength is improved.
  • N 2 SA of silica (2) is 100 m 2 / g or less, preferably 80 m 2 / g or less, more preferably 60 m 2 / g or less. If it exceeds 100 m 2 / g, the effect of blending with silica (1) may not be sufficiently obtained. Further, N 2 SA of silica (2) is preferably 20 m 2 / g or more, more preferably 30 m 2 / g or more. When N 2 SA is less than 20 m 2 / g, the rubber strength of the resulting rubber composition tends to decrease.
  • Silica (2) is not particularly limited as long as N 2 SA is 100 m 2 / g or less.
  • silica (2) only 1 type may be used and it may be used in combination of 2 or more type.
  • the content of silica (2) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 5 parts by mass, the rolling resistance tends not to be sufficiently reduced. Further, the content of silica (2) is preferably 70 parts by mass or less, more preferably 65 parts by mass or less. If it exceeds 70 parts by mass, the rubber strength tends to decrease even though the rolling resistance can be reduced.
  • the total content of silica (1) and (2) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, particularly preferably 30 parts per 100 parts by mass of the rubber component. More than part by mass. If it is less than 10 mass parts, there exists a possibility that the sufficient reinforcement effect by blending silica (1) and (2) may not be acquired.
  • the total content of silica (1) and (2) is preferably 70 parts by mass or less, more preferably 65 parts by mass or less. When it exceeds 70 parts by mass, it is difficult for silica to be uniformly dispersed in the rubber composition, and not only the processability of the rubber composition is deteriorated but also the rolling resistance tends to increase.
  • silica (1) and (2) preferably satisfy the following formula. Thereby, silica (1) and (2) can be disperse
  • the content of silica (1) is preferably 0.2 times or more, more preferably 0.5 times or more of the content of silica (2). If the content of silica (1) is less than 0.2 times the content of silica (2), the rubber strength tends to decrease.
  • the content of silica (1) is preferably 6.5 times or less, more preferably 4 times or less, and still more preferably 1 time (1 time) or less of the content of silica (2). When the content of silica (1) exceeds 6.5 times the content of silica (2), the rolling resistance tends to increase.
  • the rubber composition of the present invention preferably contains a silane coupling agent having a mercapto group.
  • a silane coupling agent having a mercapto group can be improved synergistically by blending a silane coupling agent having a mercapto group together with the conjugated diene polymer and silica.
  • the improvement effect of each performance can further be heightened by using together the above-mentioned silica (1) and (2) and the electroconductive carbon black mentioned later with the silane coupling agent which has a mercapto group.
  • Examples of the silane coupling agent having a mercapto group include a compound represented by the following formula (1) and / or a binding unit A represented by the following formula (2) and a binding unit B represented by the following formula (3).
  • the compound containing can be used conveniently.
  • R 101 to R 103 are each a branched or unbranched alkyl group having 1 to 12 carbon atoms, a branched or unbranched alkoxy group having 1 to 12 carbon atoms, or —O— (R 111 — O) z —R 112
  • z R 111 represents a branched or unbranched divalent hydrocarbon group having 1 to 30 carbon atoms.
  • the z R 111 may be the same or different.
  • R 112 is a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms.
  • Z represents an integer of 1 to 30.
  • R 101 to R 103 may be the same or different, and R 104 represents a branched or unbranched carbon atom having 1 to 6 carbon atoms.
  • R 201 is hydrogen, halogen, branched or unbranched alkyl group having 1 to 30 carbon atoms, branched or unbranched alkenyl group having 2 to 30 carbon atoms, branched or unbranched.
  • R 202 represents a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or non-branched alkynyl group having 2 to 30 carbon atoms, or a group in which the terminal hydrogen of the alkyl group is substituted with a hydroxyl group or a carboxyl group.
  • R 201 and R 202 may form a ring structure.
  • silica is dispersed well, and the effects of the present invention are obtained well.
  • R 101 to R 103 are each a branched or unbranched alkyl group having 1 to 12 carbon atoms, a branched or unbranched alkoxy group having 1 to 12 carbon atoms, or —O— (R 111 —O) z —R 112 . Represents the group represented.
  • At least one of R 101 to R 103 is preferably a group represented by —O— (R 111 —O) z —R 112 , and two of them are — More preferably, it is a group represented by O— (R 111 —O) z —R 112 , and one is a branched or unbranched C 1-12 alkoxy group.
  • Examples of the branched or unbranched alkyl group having 1 to 12 carbon atoms (preferably 1 to 5 carbon atoms) of R 101 to R 103 include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, iso-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group and the like.
  • Examples of the branched or unbranched alkoxy group having 1 to 12 carbon atoms (preferably 1 to 5 carbon atoms) of R 101 to R 103 include, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n- Examples include butoxy, iso-butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy and the like.
  • R 111 is a branched or unbranched carbon number of 1 to 30 (preferably having a carbon number of 1 to 15, more preferably a carbon number of 1).
  • a divalent hydrocarbon group examples include a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or unbranched alkenylene group having 2 to 30 carbon atoms, and a branched or unbranched alkynylene group having 2 to 30 carbon atoms. And an arylene group having 6 to 30 carbon atoms. Of these, branched or unbranched alkylene groups having 1 to 30 carbon atoms are preferred.
  • Examples of the branched or unbranched alkylene group having 1 to 30 carbon atoms (preferably 1 to 15 carbon atoms, more preferably 1 to 3 carbon atoms) of R 111 include, for example, a methylene group, an ethylene group, a propylene group, and a butylene group. Pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group and the like.
  • the branched or unbranched 2 carbon atoms to 30 (preferably 2 to 15 carbon atoms, more preferably having 2 to 3 carbon atoms) alkenylene group of R 111, for example, vinylene group, propenylene group, 2-propenylene Group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2-pentenylene group, 1-hexenylene group, 2-hexenylene group, 1-octenylene group and the like.
  • Examples of the branched or unbranched alkynylene group having 2 to 30 carbon atoms (preferably 2 to 15 carbon atoms, more preferably 2 to 3 carbon atoms) of R 111 include, for example, an ethynylene group, a propynylene group, a butynylene group, and a pentynylene group. Hexynylene group, heptynylene group, octynylene group, noninylene group, decynylene group, undecynylene group, dodecynylene group and the like.
  • Examples of the arylene group having 6 to 30 carbon atoms (preferably 6 to 15 carbon atoms) of R 111 include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group.
  • z represents an integer of 1 to 30 (preferably 2 to 20, more preferably 3 to 7, even more preferably 5 to 6).
  • R 112 represents a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. To express. Of these, branched or unbranched alkyl groups having 1 to 30 carbon atoms are preferred.
  • Examples of the branched or unbranched alkyl group having 1 to 30 carbon atoms (preferably 3 to 25 carbon atoms, more preferably 10 to 15 carbon atoms) of R 112 include, for example, a methyl group, an ethyl group, an n-propyl group, Isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group and the like.
  • Examples of the branched or unbranched alkenyl group having 2 to 30 carbon atoms (preferably 3 to 25 carbon atoms, more preferably 10 to 15 carbon atoms) for R 112 include, for example, vinyl group, 1-propenyl group, 2-propenyl group. Group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-octenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group Group, pentadecenyl group, octadecenyl group and the like.
  • Examples of the aryl group having 6 to 30 carbon atoms (preferably 10 to 20 carbon atoms) of R 112 include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group.
  • Examples of the aralkyl group having 7 to 30 carbon atoms (preferably 10 to 20 carbon atoms) of R 112 include a benzyl group and a phenethyl group.
  • —O— (R 111 —O) z —R 112 include, for example, —O— (C 2 H 4 —O) 5 —C 11 H 23 , —O— (C 2 H 4 —O) 5 —C 12 H 25 , —O— (C 2 H 4 —O) 5 —C 13 H 27 , —O— (C 2 H 4 —O) 5 —C 14 H 29 , —O -(C 2 H 4 -O) 5 -C 15 H 31 , -O- (C 2 H 4 -O) 3 -C 13 H 27 , -O- (C 2 H 4 -O) 4 -C 13 H 27 , —O— (C 2 H 4 —O) 6 —C 13 H 27 , —O— (C 2 H 4 —O) 7 —C 13 H 27, and the like.
  • —O— (C 2 H 4 —O) 5 —C 11 H 23 , —O— (C 2 H 4 —O) 5 —C 13 H 27 , —O— (C 2 H 4 —O) 5 —C 15 H 31 , —O— (C 2 H 4 —O) 6 —C 13 H 27 are preferred.
  • Examples of the branched or unbranched alkylene group having 1 to 6 carbon atoms (preferably 1 to 5 carbon atoms) of R 104 include the same groups as the branched or unbranched alkylene group having 1 to 30 carbon atoms of R 111. Can give.
  • Examples of the compound represented by the above formula (1) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane,
  • the compound represented by the following formula (Si363 manufactured by Evonik Degussa) and the like can be mentioned, and the compound represented by the following formula can be preferably used. These may be used alone or in combination of two or more.
  • the compound containing the bond unit A represented by the formula (2) and the bond unit B represented by the formula (3) is more viscous during processing than the polysulfide silane such as bis- (3-triethoxysilylpropyl) tetrasulfide.
  • the rise is suppressed. This is presumably because the increase in Mooney viscosity is small because the sulfide portion of the bond unit A is a C—S—C bond and is thermally stable compared to tetrasulfide and disulfide.
  • the shortening of the scorch time is suppressed as compared with mercaptosilane such as 3-mercaptopropyltrimethoxysilane.
  • the bonding unit B has a mercaptosilane structure, but the —C 7 H 15 portion of the bonding unit A covers the —SH group of the bonding unit B, so that it does not easily react with the polymer and scorch is less likely to occur. This is probably because of this.
  • the content of the bond unit A is preferably 30 from the viewpoint that the effect of suppressing the increase in viscosity during processing and the effect of suppressing the shortening of the scorch time can be enhanced. It is at least mol%, more preferably at least 50 mol%, preferably at most 99 mol%, more preferably at most 90 mol%. Further, the content of the bond unit B is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, preferably 70 mol% or less, more preferably 65 mol% or less, More preferably, it is 55 mol% or less.
  • the total content of the binding units A and B is preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol%.
  • the content of the bond units A and B is an amount including the case where the bond units A and B are located at the terminal of the silane coupling agent.
  • the form in which the bonding units A and B are located at the end of the silane coupling agent is not particularly limited, as long as the units corresponding to the formulas (2) and (3) indicating the bonding units A and B are formed. .
  • halogen for R 201 examples include chlorine, bromine, and fluorine.
  • Examples of the branched or unbranched alkyl group having 1 to 30 carbon atoms of R 201 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group. Examples thereof include a butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group and a decyl group.
  • the alkyl group preferably has 1 to 12 carbon atoms.
  • Examples of the branched or unbranched alkenyl group having 2 to 30 carbon atoms of R 201 include a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, and 2-pentenyl group. Group, 1-hexenyl group, 2-hexenyl group, 1-octenyl group and the like.
  • the alkenyl group preferably has 2 to 12 carbon atoms.
  • Examples of the branched or unbranched alkynyl group having 2 to 30 carbon atoms of R 201 include ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, undecynyl group, And dodecynyl group.
  • the alkynyl group preferably has 2 to 12 carbon atoms.
  • Examples of the branched or unbranched alkylene group having 1 to 30 carbon atoms of R 202 include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, Examples include dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group and the like.
  • the alkylene group preferably has 1 to 12 carbon atoms.
  • Examples of the branched or unbranched C 2-30 alkenylene group of R 202 include vinylene group, 1-propenylene group, 2-propenylene group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2-pentenylene. Group, 1-hexenylene group, 2-hexenylene group, 1-octenylene group and the like.
  • the alkenylene group preferably has 2 to 12 carbon atoms.
  • Examples of the branched or unbranched C 2-30 alkynylene group of R 202 include ethynylene group, propynylene group, butynylene group, pentynylene group, hexynylene group, heptynylene group, octynylene group, noninylene group, decynylene group, undecynylene group, And dodecynylene group.
  • the alkynylene group preferably has 2 to 12 carbon atoms.
  • the repetition of the total of the repeating number (x) of the bonding unit A and the repeating number (y) of the bonding unit B is preferably in the range of 3 to 300. Within this range, the mercaptosilane of the bond unit B is covered with —C 7 H 15 of the bond unit A, so that it is possible to suppress the scorch time from being shortened and to have good reactivity with silica and rubber components. Can be secured.
  • NXT-Z30, NXT-Z45, NXT-Z60, etc. manufactured by Momentive are used as the compound containing the binding unit A represented by the formula (2) and the coupling unit B represented by the formula (3). Can do. These may be used alone or in combination of two or more.
  • the content of the silane coupling agent having a mercapto group is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the total content of silica (total of silica (1) and (2) and other silica). More preferably, it is 3 parts by mass or more. If the amount is less than 0.5 parts by mass, the dispersibility of silica tends not to be sufficiently improved. Moreover, content of the silane coupling agent which has a mercapto group becomes like this. Preferably it is 20 mass parts or less, More preferably, it is 10 mass parts or less. When it exceeds 20 parts by mass, the rubber strength and the cut resistance tend to decrease.
  • the rubber composition of the present invention preferably uses another silane coupling agent in combination with the silane coupling agent having a mercapto group.
  • silane coupling agents include bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (4-triethoxysilylbutyl) tetrasulfide, and bis (3 -Trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, bis (4-trimethoxysilylbutyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (2-tri Ethoxysilylethyl) trisulfide, bis (4-triethoxysilylbutyl) trisulf
  • the content of the other silane coupling agent is preferably 0.5 parts by mass or more, more preferably 1.5 parts by mass or more with respect to 100 parts by mass of the total content of silica. If the amount is less than 0.5 parts by mass, the dispersibility of silica tends not to be sufficiently improved. Moreover, content of another silane coupling agent becomes like this. Preferably it is 10 mass parts or less, More preferably, it is 5 mass parts or less. If it exceeds 10 parts by mass, bleeding tends to occur.
  • the total content of the silane coupling agent is preferably 1 part by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of the total content of silica. If it is less than 1 part by mass, there is a tendency that the dispersibility of silica cannot be sufficiently improved. Moreover, the total content of the silane coupling agent is preferably 30 parts by mass or less, more preferably 15 parts by mass or less. If it exceeds 30 parts by mass, bleeding tends to occur.
  • the rubber composition of the present invention preferably contains conductive carbon black.
  • Conductive carbon black has a highly developed structure in colloidal characteristics as compared with normal carbon black. That is, in the present invention, the conductive carbon black means a high-structure carbon black, which can be distinguished from normal carbon black based on observation with an electron microscope or a difference in DBP oil absorption.
  • the conductive carbon black include those exhibiting excellent conductivity such as acetylene black, ketjen black, and graphitized carbon black, and acetylene black can be suitably used. These may be used alone or in combination of two or more.
  • Acetylene which is a raw material of acetylene black, is produced from carbides obtained from natural gas, synthetic petroleum waste gas, coke oven gas, petroleum oil cracking, quicklime and coke.
  • the nitrogen adsorption specific surface area (N 2 SA) of the conductive carbon black is preferably 40 m 2 / g or more, more preferably 60 m 2 / g or more, and further preferably 65 m 2 / g or more. If it is less than 40 m ⁇ 2 > / g, there exists a tendency for favorable electroconductivity not to be obtained. Also, N 2 SA of the conductive carbon black is preferably 80 m 2 / g or less, and more preferably not more than 70m 2 / g. If N 2 SA of the conductive carbon black exceeds 80 m 2 / g, sufficient dispersion cannot be obtained, and good performance tends not to be exhibited. The nitrogen adsorption specific surface area is measured according to ASTM D4820-93.
  • the dibutyl phthalate oil absorption (DBP oil absorption) of the conductive carbon black is preferably 100 ml / 100 g or more, more preferably 150 ml / 100 g or more, and further preferably 170 ml / 100 g or more. If it is less than 100 ml / 100 g, sufficient conductivity tends not to be obtained. Further, the DBP oil absorption amount of the conductive carbon black is preferably 230 ml / 100 g or less, more preferably 220 ml / 100 g or less. When it exceeds 230 ml / 100 g, there is a tendency that sufficient dispersion cannot be obtained as in the case of N 2 SA. The DBP oil absorption is measured according to ASTM D2414-93.
  • the content of the conductive carbon black is preferably 2 parts by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of the rubber component. There exists a tendency for sufficient electroconductivity not to be acquired as it is less than 2 mass parts.
  • the conductive carbon black content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less. When it exceeds 30 parts by mass, there is a tendency that an effect of reducing rolling resistance and an effect of improving rubber strength and cut resistance are difficult to obtain.
  • additives can be used, such as sulfur vulcanizing agents; thiazole vulcanization accelerators, thiuram vulcanization accelerators, sulfenamide vulcanization accelerators, guanidine vulcanization accelerators.
  • Vulcanization accelerators such as stearic acid and zinc oxide; organic peroxides; ordinary carbon black (carbon black other than conductive carbon black), calcium carbonate, talc, alumina, clay, water Examples thereof include fillers such as aluminum oxide and mica; processing aids such as extender oil and lubricant; and anti-aging agents.
  • normal carbon black examples include channel black (channel carbon black) such as EPC, MPC, and CC. These can be used alone or in combination of two or more.
  • the normal carbon black content is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 5 parts by mass, sufficient reinforcement may not be obtained.
  • the normal carbon black content is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 60 parts by mass or less. If it exceeds 80 parts by mass, the fuel economy tends to deteriorate.
  • the content of normal carbon black is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 2 parts by mass or less. If it exceeds 10 parts by mass, the fuel efficiency tends to deteriorate.
  • the lower limit of the normal carbon black content is not particularly limited, but may be about 0.5 parts by mass.
  • the nitrogen adsorption specific surface area (N 2 SA) of ordinary carbon black is usually 5 to 200 m 2 / g, the lower limit is preferably 50 m 2 / g, and the upper limit is preferably 150 m 2 / g, and the lower limit is 90 m 2. / G is more preferable.
  • Carbon black has a dibutyl phthalate (DBP) absorption of usually 5 to 140 ml / 100 g, preferably a lower limit of 80 ml / 100 g and an upper limit of 130 ml / 100 g.
  • DBP dibutyl phthalate
  • N 2 SA or DBP oil absorption amount of normal carbon black is less than the lower limit of the above range, the reinforcing effect is small and the cut resistance and rubber strength tend to decrease, and when the upper limit of the above range is exceeded, dispersibility is poor, Hysteresis loss increases and fuel efficiency tends to decrease.
  • the nitrogen adsorption specific surface area is measured according to ASTM D4820-93, and the DBP oil absorption is measured according to ASTM D2414-93.
  • Tokai Carbon Co., Ltd. product name Siest 6 and Sieist 7HM, Sieist KH, Evonik Degussa Co., Ltd. product name CK3, Special Black 4A, etc. can be used.
  • the extending oil examples include aromatic mineral oil (viscosity specific gravity constant (VGC value) 0.900 to 1.049), naphthenic mineral oil (VGC value 0.850 to 0.899), paraffinic mineral oil (VG value 0.790 to 0.849), and the like.
  • the polycyclic aromatic content of the extender oil is preferably less than 3% by mass, more preferably less than 1% by mass.
  • the polycyclic aromatic content is measured according to the British Petroleum Institute 346/92 method.
  • the aromatic compound content (CA) of the extending oil is preferably 20% by mass or more.
  • These extending oils may be used in combination of two or more.
  • vulcanization accelerator examples include thiazole vulcanization accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram monosulfide, tetramethylthiuram Thiuram vulcanization accelerators such as disulfides; N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N -Sulfenamide vulcanization accelerators such as oxyethylene-2-benzothiazole sulfenamide and N, N'-diisopropyl-2-benzothiazole sulfenamide; diphenylguanidine, diortolylguanidine, orthotolylbiguanidine What guanidine-based
  • a known method for example, using a known mixer such as a roll or a banbury for each component.
  • a kneading method can be used.
  • the kneading temperature is usually 50 to 200 ° C., preferably 80 to 190 ° C.
  • the kneading time is usually 30 seconds. -30 minutes, and preferably 1-30 minutes.
  • the kneading temperature is usually 100 ° C. or lower, preferably room temperature to 80 ° C.
  • a composition containing a vulcanizing agent and a vulcanization accelerator is usually used after vulcanization treatment such as press vulcanization.
  • the vulcanization temperature is usually 120 to 200 ° C, preferably 140 to 180 ° C.
  • the rubber composition of the present invention is excellent in the balance of low fuel consumption, rubber strength, cut resistance and processability, and can achieve a remarkable improvement effect of these performances.
  • the carbon ratio of the rubber composition of the present invention is preferably 90 or less, more preferably 80 or less. If it exceeds 90, fuel economy may be deteriorated. Moreover, the carbon ratio of the rubber composition of the present invention is preferably 5 or more, more preferably 7 or more. If it is less than 5, sufficient reinforcing properties may not be obtained. The carbon ratio is a value obtained by the measurement method described in Examples described later.
  • the rubber composition of the present invention can be used for each member of a tire and can be suitably used for a sidewall.
  • the pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, if necessary, a rubber composition containing various additives is extruded in accordance with the shape of the tire sidewall, etc. at an unvulcanized stage, and molded on a tire molding machine by a normal method. Then, they are bonded together with other tire members to form an unvulcanized tire. This unvulcanized tire can be heated and pressurized in a vulcanizer to produce the pneumatic tire of the present invention.
  • the pneumatic tire of the present invention can be suitably used as a tire for passenger cars.
  • THF anhydrous tetrahydrofuran hydride manufactured by Kanto Chemical Co., Ltd .: diethylamine manufactured by Kanto Chemical Co., Ltd .: methyl vinyl dichlorosilane manufactured by Kanto Chemical Co., Ltd .: anhydrous hexane manufactured by Shin-Etsu Chemical Co., Ltd .: styrene manufactured by Kanto Chemical Co., Ltd. : Kanto Chemical Co., Ltd. Butadiene: Tokyo Chemical Industry Co., Ltd. 1,3-Butadiene TMEDA: Kanto Chemical Co., Ltd.
  • tetramethylethylenediamine n-butyllithium solution 1.6M n- from Kanto Chemical Co., Ltd.
  • Butyllithium hexane solution initiator (1) Compound in which two units of structural units derived from isoprene are bonded to AI-200CE2 (3- (N, N-dimethylamino) -1-propyllithium manufactured by FMC (represented by the following formula) Compound)) (0.9M) Piperidine: Diamylamine manufactured by Tokyo Chemical Industry Co., Ltd .: 2,6-di-tert-butyl-p-cresol manufactured by Tokyo Chemical Industry Co., Ltd. Nocrack 200 manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • Bis (dimethylamino) methylvinylsilane N, N-dimethylaminopropyl acrylamide manufactured by Shin-Etsu Chemical Co., Ltd .: 3-diethylaminopropyltriethoxysilane manufactured by Tokyo Chemical Industry Co., Ltd .: 1,3-dimethyl- manufactured by Amax Co., Ltd.
  • 2-Imidazolidinone N-phenyl-2-pyrrolidone manufactured by Tokyo Chemical Industry Co., Ltd .: N-methyl- ⁇ -caprolactam manufactured by Tokyo Chemical Industry Co., Ltd .: Tris [3- (trimethoxy manufactured by Tokyo Chemical Industry Co., Ltd.
  • ⁇ Preparation of modifier (3) (main chain modifier)> 1000 mL of THF and 13 g of sodium hydride were added to a 2 L three-necked flask sufficiently purged with nitrogen, and 36.5 g of diethylamine was slowly added dropwise with stirring on an ice-water bath. After stirring for 30 minutes, 36 g of methylvinyldichlorosilane was added dropwise over 30 minutes and stirred for 2 hours. The resulting solution was concentrated, filtered, and purified by distillation under reduced pressure to synthesize bis (diethylamino) methylvinylsilane.
  • ⁇ Preparation of initiator (4) (bifunctional initiator)> 550 ml of cyclohexane, 27 ml of TMEDA and 200 ml of sec-butyllithium solution were added to a 1 L eggplant flask which had been thoroughly dried and purged with nitrogen, and 17 ml of 1,3-diisopropenylbenzene was slowly added over 30 minutes while stirring at 45 ° C. Furthermore, after stirring for 1 hour, it was made to cool to normal temperature and created.
  • the weight average molecular weight Mw and number average molecular weight Mn of the copolymer were determined by gel permeation chromatography (GPC) (GPC-8000 series, manufactured by Tosoh Corporation, detector: differential refractometer, column: TSKGEL manufactured by Tosoh Corporation) It was determined as a standard polystyrene equivalent value based on the measured value by SUPERMULTIPORE HZ-M). From the measurement results, the molecular weight distribution Mw / Mn was calculated.
  • GPC gel permeation chromatography
  • Copolymer (1) was obtained.
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (2)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (2)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (2) was obtained by the same formulation as the synthesis of the copolymer (1) except that 34 mL of the initiator (2) was changed to 34 mL of the initiator (3).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (3)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (2)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (3) was obtained by the same formulation as the synthesis of the copolymer (1) except that the amount of styrene was changed to 900 g and the amount of butadiene was changed to 1100 g.
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (2)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (2)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (4) was obtained by the same formulation as the synthesis of the copolymer (1) except that 34 mL of the initiator (2) was changed to 19 ml of the initiator (1).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component. Further, the polymerization initiator (initiator (1)) charged was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (2)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (7) was obtained by the same formulation as the synthesis of the copolymer (4) except that 40 mL of the modifier (1) was changed to 40 mL of the modifier (3).
  • the silicon-containing vinyl compound (modifier (3)) added was 0.43 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (2)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (8) was obtained by the same formulation as the synthesis of the copolymer (7) except that 19 mL of the initiator (1) was changed to 10.6 mL of n-butyllithium solution.
  • the silicon-containing vinyl compound (modifier (3)) added was 0.43 g per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (2)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (9) was obtained by the same formulation as the synthesis of the copolymer (6) except that 23 mL of the initiator (1) was changed to 13 mL of n-butyllithium solution.
  • the silicon-containing vinyl compound (modifier (1)) added was 0.43 g per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (2)) added was 0.95 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (10) was obtained by the same formulation as the synthesis of the copolymer (1) except that 40 mL of the modifier (1) was changed to 0 mL.
  • the charged polymerization initiator (initiator (2)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (2)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (11) was obtained by the same formulation as the synthesis of the copolymer (1) except that 20 mL of the modifier (2) was changed to 0 mL.
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (2)) was 0.85 mmol per 100 g of the monomer component.
  • a copolymer (14) was obtained by the same formulation as the synthesis of the copolymer (7) except that 40 mL of the modifier (3) was changed to 0 mL and 20 mL of the modifier (2) was changed to 0 mL.
  • the charged polymerization initiator (initiator (1)) was 8.5 mmol per 100 g of the monomer component.
  • the copolymer (15) was prepared in the same formulation as the copolymer (7) except that 19 mL of the initiator (1) was changed to 6.8 mL of n-butyllithium solution and 20 mL of the modifier (2) was changed to 0 mL. Got. In addition, the silicon-containing vinyl compound (modifier (3)) added was 0.43 g per 100 g of the monomer component.
  • the copolymer (16) was prepared in the same formulation as the copolymer (7) except that 19 mL of the initiator (1) was changed to 6.8 mL of n-butyllithium solution and 40 mL of the modifier (3) was changed to 0 mL. Got. The amount of the nitrogen atom and / or silicon atom-containing compound (modifier (2)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (19) was obtained by the same formulation as the synthesis of the copolymer (8) except that the amount of styrene was changed to 0 g, the amount of butadiene was changed to 2000 g, and TMEDA 10 mmol was changed to THF 5 mmol.
  • the silicon-containing vinyl compound (modifier (3)) added was 0.43 g per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (2)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (22) was obtained by the same formulation as the synthesis of the copolymer (1) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (4).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (2)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (4)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (23) was obtained by the same formulation as the synthesis of the copolymer (2) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (4).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (3)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (4)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (24) was obtained by the same formulation as the synthesis of the copolymer (3) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (4).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (2)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (4)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (25) was obtained by the same formulation as the synthesis of the copolymer (4) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (4).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (4)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (26) was obtained by the same formulation as the synthesis of the copolymer (5) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (4).
  • the silicon-containing vinyl compound (modifier (1)) added was 1.19 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (4)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (27) was obtained by the same formulation as the synthesis of the copolymer (6) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (4).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 1.05 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (4)) added was 0.95 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (28) was obtained by the same formulation as the synthesis of the copolymer (7) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (4).
  • the silicon-containing vinyl compound (modifier (3)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (4)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • Copolymer (30) was prepared in the same manner as the synthesis of copolymer (28) except that 19 mL of initiator (1) was changed to 10.6 mL of n-butyllithium solution and 40 mL of modifier (3) was changed to 0 mL. Got. The amount of the nitrogen atom and / or silicon atom-containing compound (modifier (4)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (31) was obtained by the same formulation as the synthesis of the copolymer (18) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (4).
  • the silicon-containing vinyl compound (modifier (3)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (4)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (33) was obtained by the same formulation as the synthesis of the copolymer (1) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (5).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (2)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (5)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (34) was obtained by the same formulation as the synthesis of the copolymer (2) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (5).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (3)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (5)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (35) was obtained by the same formulation as the synthesis of the copolymer (3) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (5).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (2)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (5)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (36) was obtained by the same formulation as the synthesis of the copolymer (4) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (5).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (5)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (37) was obtained by the same formulation as the synthesis of the copolymer (5) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (5).
  • the silicon-containing vinyl compound (modifier (1)) added was 1.19 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (5)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (38) was obtained by the same formulation as the synthesis of the copolymer (6) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (5).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 1.05 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (5)) added was 0.95 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (39) was obtained by the same formulation as the synthesis of the copolymer (7) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (5).
  • the silicon-containing vinyl compound (modifier (3)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (5)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (41) was obtained by the same formulation as the synthesis of the copolymer (7) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (6).
  • the silicon-containing vinyl compound (modifier (3)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the compound containing nitrogen atom and / or silicon atom (modifier (6)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (42) was obtained by the same formulation as the synthesis of the copolymer (7) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (7).
  • the silicon-containing vinyl compound (modifier (3)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (7)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (43) is obtained by the same formulation as the synthesis of the copolymer (39) except that 19 mL of the initiator (1) is changed to 10.6 mL of the butyllithium solution and 40 mL of the modifier (3) is changed to 0 mL. It was. The amount of the compound containing nitrogen atom and / or silicon atom (modifier (5)) added was 1.18 mol per 1 mol of alkali metal derived from the added polymerization initiator.
  • a copolymer (31) was obtained by the same formulation as the synthesis of the copolymer (18) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (5).
  • the silicon-containing vinyl compound (modifier (3)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (5)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (46) was obtained by the same formulation as the synthesis of the copolymer (1) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (8).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (2)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (8)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (47) was obtained by the same formulation as the synthesis of the copolymer (2) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (8).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (3)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (8)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (48) was obtained by the same formulation as the synthesis of the copolymer (3) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (8).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (2)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (8)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (49) was obtained by the same formulation as the synthesis of the copolymer (4) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (8).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (8)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (50) was obtained by the same formulation as the synthesis of the copolymer (5) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (8).
  • the silicon-containing vinyl compound (modifier (1)) added was 1.19 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (8)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (51) was obtained by the same formulation as the synthesis of the copolymer (6) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (8).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 1.05 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (8)) added was 0.95 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (52) was obtained by the same formulation as the synthesis of the copolymer (7) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (8).
  • the silicon-containing vinyl compound (modifier (3)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (8)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (54) is obtained by the same formulation as the synthesis of the copolymer (52) except that 19 mL of the initiator (1) is changed to 10.6 mL of the butyllithium solution and 40 mL of the modifier (3) is changed to 0 mL. It was. In addition, the compound (modifying agent (8)) containing the nitrogen atom and / or silicon atom added was 1.18 mol per 1 mol of the alkali metal derived from the polymerization initiator added.
  • a copolymer (55) was obtained by the same formulation as the synthesis of the copolymer (18) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (8).
  • the silicon-containing vinyl compound (modifier (3)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (8)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (57) was obtained by the same formulation as the synthesis of the copolymer (1) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (9).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (2)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (9)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (58) was obtained by the same formulation as the synthesis of the copolymer (2) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (9).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (3)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (9)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (59) was obtained by the same formulation as the synthesis of the copolymer (3) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (9).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (2)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (9)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (60) was obtained by the same formulation as the synthesis of the copolymer (4) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (9).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (9)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (61) was obtained by the same formulation as the synthesis of the copolymer (5) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (9).
  • the silicon-containing vinyl compound (modifier (1)) added was 1.19 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (9)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (62) was obtained by the same formulation as the synthesis of the copolymer (6) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (9).
  • the silicon-containing vinyl compound (modifier (1)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 1.05 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (9)) added was 0.95 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (63) was obtained by the same formulation as the synthesis of the copolymer (7) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (9).
  • the silicon-containing vinyl compound (modifier (3)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (9)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • a copolymer (65) is obtained by the same formulation as the synthesis of the copolymer (63) except that 19 mL of the initiator (1) is changed to 10.6 mL of the butyllithium solution and 40 mL of the modifier (3) is changed to 0 mL. It was. The amount of the compound containing nitrogen atom and / or silicon atom (modifier (9)) added was 1.18 mol per 1 mol of alkali metal derived from the added polymerization initiator.
  • a copolymer (66) was obtained by the same formulation as the synthesis of the copolymer (18) except that 20 mL of the modifier (2) was changed to 20 mL of the modifier (9).
  • the silicon-containing vinyl compound (modifier (3)) added was 0.32 g per 100 g of the monomer component.
  • the charged polymerization initiator (initiator (1)) was 0.85 mmol per 100 g of the monomer component.
  • the amount of the nitrogen atom and / or silicon atom-containing compound (modifier (9)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
  • the monomer components of the copolymers (1) to (67) are summarized in Tables 1 to 5.
  • Copolymers (1) to (67) Synthetic natural rubber by the above method: TSR20 Butadiene rubber: Ubepol BR150B manufactured by Ube Industries, Ltd.
  • Silica 1 Ultrasil VN3-G (N 2 SA: 175 m 2 / g) manufactured by Evonik Degussa
  • Silica 2 Ultrasil 360 (N 2 SA: 50 m 2 / g) manufactured by Evonik Degussa Silane coupling agent A: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Evonik Degussa Silane coupling agent B: Si363 manufactured by Evonik Degussa Silane coupling agent C: NXT-Z45 manufactured by Momentive (compound containing bonding unit A and bonding unit B (bonding unit A: 55 mol%, bonding unit B: 45 mol%))
  • Conductive carbon black 1 Seast
  • Conductive carbon black 2 Acetylene black (N 2 SA: 68 m 2 / g, DBP oil absorption: 175 ml / 100 g) manufactured by Denki Kagaku Kogyo Co., Ltd.
  • Oil X-140 of JX Nippon Oil & Energy Corporation
  • Anti-aging agent Antigen 3C manufactured by Sumitomo Chemical Co., Ltd.
  • Stearic acid Beads manufactured by NOF Corporation
  • Zinc stearate zinc oxide Zinc flower No. 1 manufactured by Mitsui Kinzoku Mining Co., Ltd.
  • Wax Sunnock N manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • Sulfur Powder sulfur vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd. 1: Soxinol CZ manufactured by Sumitomo Chemical Co., Ltd.
  • Vulcanization accelerator 2 Soxinol D manufactured by Sumitomo Chemical Co., Ltd.
  • the obtained unvulcanized rubber composition was molded into a sidewall shape, and bonded together with other tire members on a tire molding machine to form an unvulcanized tire, and vulcanized at 170 ° C. for 12 minutes, A test tire (size: 195 / 65R15) was produced.
  • tan ⁇ of the vulcanized rubber composition was measured at a dynamic strain amplitude of 1%, a frequency of 10 Hz, and a temperature of 50 ° C.
  • the reciprocal value of tan ⁇ was expressed as an index with the reference comparative example being 100. The larger the value, the smaller the rolling resistance (less heat generation) and the better the fuel efficiency.
  • Carbon ratio A / (A + B) ⁇ 100
  • ⁇ Cut resistance index> Using a pendulum impact cutting tester, a steel blade having a width of 20 mm was struck against the sidewall of the test tire, and the depth of the scratches generated was indexed with reference reference example 100. The larger the index, the better the cut resistance.
  • the examples have a specific amine structure at the initiation terminal, a structural unit derived from a silicon-containing compound in the main chain portion, and a nitrogen atom and / or a silicon atom at the termination terminal.
  • the above conjugated diene polymer having a structure in which three sites of the start terminal, main chain, and stop terminal are modified with a specific compound, and a copolymer in which only the start terminal, only the main chain, and only the stop terminal are modified.
  • the conjugated diene polymer has a structural unit derived from a silicon-containing compound in the main chain portion and a structural unit derived from a compound containing a nitrogen atom and / or a silicon atom at the terminal end.
  • Comparative Examples 8, 27 and 45 containing a copolymer (17) having no amine structure at the starting terminal had lower performance than the Examples, and the cut resistance and workability were higher than those of the Reference Comparative Example. Was also inferior.

Landscapes

  • 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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de caoutchouc permettant d'améliorer de façon équilibrée la consommation de carburant, la résistance du caoutchouc, la résistance aux coupures et l'aptitude au façonnage ; et un pneu à base de celle-ci. La présente invention concerne, donc, une composition de caoutchouc contenant un polymère de diène conjugué obtenu en faisant réagir un composé contenant un atome d'azote et/ou un atome de silicium avec l'extrémité terminale active d'un copolymère obtenu par polymérisation d'un composant monomère comprenant un composé diène conjugué et un composé vinylique contenant du silicium au moyen d'un initiateur de polymérisation représenté par la formule (I) ; et de la silice présentant une surface spécifique d'absorption de l'azote variant de 40 à 400 m²/g. Dans 100 % en poids du composant de type caoutchouc, la teneur en polymère de diène conjugué varie de 1 à 90 % en poids et la teneur en caoutchouc de polyisoprène de 0 à 70 % en poids, tandis que la teneur en silice représente de 10 à 70 parties en poids pour 100 parties en poids du composant de type caoutchouc.
PCT/JP2012/066208 2011-11-24 2012-06-26 Composition de caoutchouc et pneu WO2013077017A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2011256611 2011-11-24
JP2011256610 2011-11-24
JP2011-256610 2011-11-24
JP2011-256611 2011-11-24
JP2011-256612 2011-11-24
JP2011256612 2011-11-24

Publications (1)

Publication Number Publication Date
WO2013077017A1 true WO2013077017A1 (fr) 2013-05-30

Family

ID=48469479

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/066208 WO2013077017A1 (fr) 2011-11-24 2012-06-26 Composition de caoutchouc et pneu

Country Status (1)

Country Link
WO (1) WO2013077017A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015054957A (ja) * 2013-09-13 2015-03-23 住友ゴム工業株式会社 空気入りタイヤ
JP2015054902A (ja) * 2013-09-11 2015-03-23 住友ゴム工業株式会社 空気入りタイヤ
JP2015054901A (ja) * 2013-09-11 2015-03-23 住友ゴム工業株式会社 空気入りタイヤ
JP2015054903A (ja) * 2013-09-11 2015-03-23 住友ゴム工業株式会社 空気入りタイヤ
JP2015101658A (ja) * 2013-11-26 2015-06-04 住友ゴム工業株式会社 空気入りタイヤ
JP2015101657A (ja) * 2013-11-26 2015-06-04 住友ゴム工業株式会社 空気入りタイヤ
JP2015101663A (ja) * 2013-11-26 2015-06-04 住友ゴム工業株式会社 空気入りタイヤ
JP2015101662A (ja) * 2013-11-26 2015-06-04 住友ゴム工業株式会社 空気入りタイヤ
JP2015140430A (ja) * 2014-01-30 2015-08-03 住友ゴム工業株式会社 トラック・バスタイヤ
JP2015140431A (ja) * 2014-01-30 2015-08-03 住友ゴム工業株式会社 トラック・バスタイヤ
JP2017128713A (ja) * 2016-01-21 2017-07-27 ハンファ トータル ペトロケミカル カンパニー リミテッド 変性共役ジエン系重合体の製造方法及びこの方法により製造された重合体を用いたゴム組成物

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4817674B1 (fr) * 1970-03-23 1973-05-31
JPH08253520A (ja) * 1995-02-01 1996-10-01 Bridgestone Corp 環状アミン含有アミノアルキルリチウム化合物およびそれらを用いて得られるポリマー類
JP2000239444A (ja) * 1999-02-19 2000-09-05 Bridgestone Corp ゴム組成物及びそれを用いた重荷重用空気入りタイヤ
JP2006233177A (ja) * 2005-01-28 2006-09-07 Sumitomo Rubber Ind Ltd ゴム組成物およびそれを用いたトレッドを有するタイヤ
JP2010077413A (ja) * 2008-08-27 2010-04-08 Sumitomo Chemical Co Ltd 共役ジエン系重合体、共役ジエン系重合体組成物及び共役ジエン系重合体の製造方法
JP2011079913A (ja) * 2009-10-05 2011-04-21 Sumitomo Rubber Ind Ltd 重合体、タイヤ用ゴム組成物及び空気入りタイヤ
WO2011087004A1 (fr) * 2010-01-13 2011-07-21 住友ゴム工業株式会社 Composition de gomme pour pneus, et pneu ainsi obtenu
WO2012011571A1 (fr) * 2010-07-23 2012-01-26 住友ゴム工業株式会社 Mélange caoutchouté et pneumatique
JP2012167257A (ja) * 2011-01-24 2012-09-06 Sumitomo Chemical Co Ltd 共役ジエン系重合体の製造方法、共役ジエン系重合体、及び、共役ジエン系重合体組成物

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4817674B1 (fr) * 1970-03-23 1973-05-31
JPH08253520A (ja) * 1995-02-01 1996-10-01 Bridgestone Corp 環状アミン含有アミノアルキルリチウム化合物およびそれらを用いて得られるポリマー類
JP2000239444A (ja) * 1999-02-19 2000-09-05 Bridgestone Corp ゴム組成物及びそれを用いた重荷重用空気入りタイヤ
JP2006233177A (ja) * 2005-01-28 2006-09-07 Sumitomo Rubber Ind Ltd ゴム組成物およびそれを用いたトレッドを有するタイヤ
JP2010077413A (ja) * 2008-08-27 2010-04-08 Sumitomo Chemical Co Ltd 共役ジエン系重合体、共役ジエン系重合体組成物及び共役ジエン系重合体の製造方法
JP2011079913A (ja) * 2009-10-05 2011-04-21 Sumitomo Rubber Ind Ltd 重合体、タイヤ用ゴム組成物及び空気入りタイヤ
WO2011087004A1 (fr) * 2010-01-13 2011-07-21 住友ゴム工業株式会社 Composition de gomme pour pneus, et pneu ainsi obtenu
WO2012011571A1 (fr) * 2010-07-23 2012-01-26 住友ゴム工業株式会社 Mélange caoutchouté et pneumatique
JP2012167257A (ja) * 2011-01-24 2012-09-06 Sumitomo Chemical Co Ltd 共役ジエン系重合体の製造方法、共役ジエン系重合体、及び、共役ジエン系重合体組成物

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015054902A (ja) * 2013-09-11 2015-03-23 住友ゴム工業株式会社 空気入りタイヤ
JP2015054901A (ja) * 2013-09-11 2015-03-23 住友ゴム工業株式会社 空気入りタイヤ
JP2015054903A (ja) * 2013-09-11 2015-03-23 住友ゴム工業株式会社 空気入りタイヤ
JP2015054957A (ja) * 2013-09-13 2015-03-23 住友ゴム工業株式会社 空気入りタイヤ
JP2015101658A (ja) * 2013-11-26 2015-06-04 住友ゴム工業株式会社 空気入りタイヤ
JP2015101657A (ja) * 2013-11-26 2015-06-04 住友ゴム工業株式会社 空気入りタイヤ
JP2015101663A (ja) * 2013-11-26 2015-06-04 住友ゴム工業株式会社 空気入りタイヤ
JP2015101662A (ja) * 2013-11-26 2015-06-04 住友ゴム工業株式会社 空気入りタイヤ
JP2015140430A (ja) * 2014-01-30 2015-08-03 住友ゴム工業株式会社 トラック・バスタイヤ
JP2015140431A (ja) * 2014-01-30 2015-08-03 住友ゴム工業株式会社 トラック・バスタイヤ
JP2017128713A (ja) * 2016-01-21 2017-07-27 ハンファ トータル ペトロケミカル カンパニー リミテッド 変性共役ジエン系重合体の製造方法及びこの方法により製造された重合体を用いたゴム組成物
CN106987039A (zh) * 2016-01-21 2017-07-28 韩华道达尔有限公司 改性共轭二烯系聚合物的制造方法及使用了通过该方法制造的聚合物的橡胶组合物

Similar Documents

Publication Publication Date Title
JP5918261B2 (ja) ゴム組成物及び空気入りタイヤ
JP5918263B2 (ja) ゴム組成物及び空気入りタイヤ
JP5723009B2 (ja) ゴム組成物及び空気入りタイヤ
JP5918259B2 (ja) ゴム組成物及び空気入りタイヤ
JP5918262B2 (ja) ゴム組成物及びスタッドレスタイヤ
JP5902447B2 (ja) ゴム組成物及び空気入りタイヤ
WO2013077021A1 (fr) Composition de caoutchouc et pneu
JP6050254B2 (ja) ゴム組成物及び空気入りタイヤ
JP5918260B2 (ja) ゴム組成物及び空気入りタイヤ
WO2013077017A1 (fr) Composition de caoutchouc et pneu
JPWO2013099324A1 (ja) ゴム組成物及び空気入りタイヤ
JP5798457B2 (ja) ゴム組成物及び空気入りタイヤ
JP2013108035A (ja) ゴム組成物及び空気入りタイヤ
JP2013133387A (ja) ゴム組成物及び空気入りタイヤ
JP5917895B2 (ja) ゴム組成物及び空気入りタイヤ
JP5902446B2 (ja) ゴム組成物及び空気入りタイヤ
JP5886610B2 (ja) ゴム組成物及び空気入りタイヤ
JP5967907B2 (ja) ゴム組成物及び空気入りタイヤ
JP5902445B2 (ja) ゴム組成物及び空気入りタイヤ
JP5917894B2 (ja) ゴム組成物及び空気入りタイヤ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12851752

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12851752

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP