WO2013077016A1 - ゴム組成物及び空気入りタイヤ - Google Patents
ゴム組成物及び空気入りタイヤ Download PDFInfo
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- WO2013077016A1 WO2013077016A1 PCT/JP2012/066206 JP2012066206W WO2013077016A1 WO 2013077016 A1 WO2013077016 A1 WO 2013077016A1 JP 2012066206 W JP2012066206 W JP 2012066206W WO 2013077016 A1 WO2013077016 A1 WO 2013077016A1
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- 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
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- 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
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—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
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- 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
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- 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
Definitions
- the present invention relates to a rubber composition and a pneumatic tire produced using the rubber composition.
- a rubber composition for an automobile tire a rubber composition containing a conjugated diene polymer such as polybutadiene or butadiene-styrene copolymer and a filler such as carbon black or silica is used.
- Patent Document 1 proposes a method using a diene rubber (modified rubber) modified with an organosilicon compound containing an amino group and an alkoxy group.
- the modified rubber when used, the fuel efficiency is improved, while the Mooney viscosity is increased and the processability tends to be deteriorated.
- the strength required for the rubber composition for automobile tires also includes breaking strength, but the breaking strength is generally in contradiction to low fuel consumption, and each performance can be obtained in a high level with a good balance. It was difficult.
- An object of the present invention is to solve the above-mentioned problems and to provide a rubber composition that can improve fuel economy, breaking strength, and processability in a well-balanced manner, and a pneumatic tire using the rubber composition.
- the present invention provides a nitrogen atom and an active terminal of 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). And / or a conjugated diene polymer obtained by reacting a compound containing a silicon atom and silica, and in 100% by mass of the rubber component, the content of the conjugated diene polymer is 10% by mass or more,
- the present invention relates to a rubber composition having a silica content of 10 to 70 parts by mass with respect to 100 parts by mass of the rubber component.
- 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 nitrogen adsorption specific surface area of the silica is preferably 40 to 400 m 2 / g.
- the silica preferably contains silica (1) having a nitrogen adsorption specific surface area of 40 m 2 / g or more and less than 120 m 2 / g and silica (2) having a nitrogen adsorption specific surface area of 120 m 2 / g or more.
- the rubber composition preferably contains 1 to 10 parts by mass of a liquid resin having a softening point of ⁇ 20 to 20 ° C. with respect to 100 parts by mass of the rubber component.
- the rubber composition comprises a silica (1) having a nitrogen adsorption specific surface area of 40 m 2 / g or more and less than 120 m 2 / g, and a silica (2) having a nitrogen adsorption specific surface area of 120 m 2 / g or more, Preferably contains 1 to 10 parts by mass of a liquid resin having a softening point of ⁇ 20 to 20 ° C. with respect to 100 parts by mass of the rubber component.
- the rubber composition preferably contains 1 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 1 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 40 m 2 / g or more and 120 m 2 / g. It is preferable that less than silica (1) and silica (2) having a nitrogen adsorption specific surface area of 120 m 2 / g or more are included.
- the rubber composition contains 1 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 has a softening point of ⁇ 20 to 20 ° C. with respect to 100 parts by mass of the rubber component. It is preferable to contain 1 to 10 parts by mass of a liquid resin.
- the rubber composition contains 1 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 40 m 2 / g or more and 120 m 2 / g. Less than silica (1) and silica (2) having a nitrogen adsorption specific surface area of 120 m 2 / g or more.
- the rubber composition has a softening point of ⁇ 20 to 20 with respect to 100 parts by mass of the rubber component. It is preferable to contain 1 to 10 parts by mass of a liquid resin at 0 ° C.
- the rubber composition contains 1 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): It is preferable that the compound includes 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 from each other, and R 104 is 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 C 1-30 alkylene group, branched or non-branched alkynyl group having 2 to 30 carbon atoms, or a hydrogen atom 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 40 m 2 / g or more and less than 120 m 2 / g, and a silica (2) having a nitrogen adsorption specific surface area of 120 m 2 / g or more, and the silica (1 It is preferable that the nitrogen adsorption specific surface area and the content of (2) and (2) satisfy the following formula. (Nitrogen adsorption specific surface area of silica (2)) / (Nitrogen adsorption specific surface area of silica (1)) ⁇ 1.4 (Content of silica (1)) ⁇ 0.06 ⁇ (content of silica (2)) ⁇ (content of silica (1)) ⁇ 15
- the present invention also relates to a pneumatic tire produced using the rubber composition.
- a pneumatic tire having improved fuel economy, breaking strength and processability in a well-balanced manner is provided. it can.
- 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
- the hydrocarbylene group having a heteroatom (hereinafter sometimes referred to as a heteroatom-containing hydrocarbylene group) is a carbon atom and / or a hydrogen atom other than the carbon atom from which the hydrogen atom of the hydrocarbylene group is removed. Represents a divalent group having a structure in which a group having a hetero atom (an atom other than a carbon atom or a hydrogen atom) is substituted.
- 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, and may be a chain alkyl group having 1 to 4 carbon atoms or bonded to each other.
- 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.
- 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 group 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, 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 the silicon-containing vinyl compound used is 100% by mass based on the total amount of monomer components used in the polymerization, and the fuel economy, breaking strength and processability are improved in a well-balanced manner. Therefore, Preferably it is 0.01 mass% or more, More preferably, it is 0.02 mass% or more, More preferably, it is 0.05 mass% or more.
- the content is preferably 20% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less.
- 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 , Generally 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 is 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 represents divalent group bonded to R 34
- R 32 are have an optionally substituted hydrocarbyl group, or a nitrogen atom and / or oxygen atom bonded to R 31 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 combine with R 31 and have a nitrogen atom and / or an oxygen atom as a hetero atom.
- R 34 represents an optionally substituted hydrocarbyl group or 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).
- 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
- 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.
- 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 is represented by — (CH 2 ) p —NR 35 —.
- Group (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 group bonded to a hydrocarbyl group (preferably a hydrocarbyl group having 1 to 10 carbon atoms) or a hydrogen atom, more preferably an alkylene group having 3 to 6 carbon atoms or — (CH 2 ) p —NR 35 - group represented by (R 35 is a hydrocarbyl group (preferably an hydrocarbyl group) of 1 to 10 carbon atoms, p is an integer of 1 or more (preferably an integer) of 2 to 5), and More preferred is a trimethylene group, a tetramethylene group, a pentamethylene group, or a group represented by — (CH 2 ) 2 —N (CH 3 ) —.
- 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 even 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
- 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 from the viewpoint of improving the fuel efficiency, breaking strength and processability in a balanced manner, Preferably, it is 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 polymer or less. is there.
- the content of the structural unit derived from the silicon-containing vinyl compound is preferably 0.01 mmol / per polymer unit mass from the viewpoint of improving the fuel efficiency, breaking strength and processability in a balanced manner.
- 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 property, breaking strength, and workability can be heightened.
- 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 derived from an aromatic vinyl compound (aromatic vinyl unit) from the viewpoint of improving fuel economy, breaking strength and processability in a balanced manner.
- aromatic vinyl unit 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 does not have an aromatic vinyl compound structural unit.
- 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 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more. If the amount is less than 10% by mass, the effect of improving fuel economy tends to be difficult to obtain. Further, the content of the conjugated diene polymer is preferably 90% by mass or less, more preferably 85% by mass or less. If it exceeds 90 mass%, the fracture strength tends to decrease and the cost tends to increase.
- the conjugated diene polymer is preferably used in combination with other rubber components.
- a polyisoprene rubber can be preferably used. By blending the polyisoprene-based rubber, the breaking strength is improved, and the rubber is better packed at the time of kneading, 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 5% by mass or more, more preferably 15% by mass or more. If it is less than 5% by mass, the effect of improving the breaking strength may not be sufficiently obtained.
- the content of the polyisoprene rubber is preferably 50% by mass or less, more preferably 30% by mass or less. When the content of the polyisoprene rubber exceeds 50% by mass, processability tends to 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, adhesiveness and processability can be improved in a balanced manner, those containing 50% by mass or more of a structural unit derived from a conjugated diene compound can be preferably used. , BR and SBR are preferable.
- 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 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 rubber composition of the present invention contains silica.
- 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 preferable because of its large number of silanol groups.
- the nitrogen adsorption specific surface area (N 2 SA) of silica is preferably 40 m 2 / g or more, more preferably 50 m 2 / g or more. If it is less than 40 m 2 / g, the reinforcing effect is small, and the fracture strength tends to decrease. Further, N 2 SA of silica is preferably 400 m 2 / g or less, more preferably 360 m 2 / g or less, and further preferably 300 m 2 / g or less. When it exceeds 400 m 2 / g, silica is difficult to disperse, and the fuel economy and processability tend to deteriorate. Note that N 2 SA of silica is a value measured by the BET method according to ASTM D3037-93.
- the content of silica (when two or more types of silica are used, the total amount) is 10 parts by mass or more, preferably 15 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 10 parts by mass, the effect of blending silica cannot be sufficiently obtained, and the fracture strength tends to decrease.
- the content of silica is 70 parts by mass or less, preferably 65 parts by mass or less. When it exceeds 70 mass parts, there exists a tendency for workability to deteriorate.
- Silica one kind may be used alone, it is preferable to use a combination of two or more, N 2 SA is 40 m 2 / g or more, 120 m and 2 / g less than the silica (1), N 2 SA is More preferably, 120 m 2 / g or more of silica (2) is used in combination.
- silica (1) and (2) can be dispersed well, and the improvement effect of each performance can be enhanced synergistically. It can greatly improve fuel efficiency and breaking strength.
- the improvement effect of each performance can further be heightened by using silica (1) and (2), the silane coupling agent which has a mercapto group mentioned later, and a specific liquid resin together.
- Silica (1) is not particularly limited, and can be obtained as, for example, Ultrasil 360 manufactured by EVONIK-DEGUSSA, Z40 manufactured by Rhodia, RP80 manufactured by Rhodia, or the like.
- silica (2) is not particularly limited, and can be obtained as, for example, Zeosyl 1205MP manufactured by Rhodia. These may be used alone or in combination of two or more.
- Silica (1) and (2) it is preferable to satisfy the ⁇ 1.4 relationship (N 2 SA of the silica (1)) N 2 SA is (silica (2) N 2 SA) of /, (silica ( it is more preferable to satisfy the N 2 SA) / (N 2 SA) ⁇ 2.0 relationship silica (1) 2). If it is less than 1.4, the difference in particle diameter between silica (1) and (2) is small, and the dispersion improving effect by blending two types of silica tends to be insufficient.
- N 2 SA of silica (1) is 40 m 2 / g or more, preferably 50 m 2 / g or more. If it is less than 40 m 2 / g, sufficient reinforcing properties cannot be obtained, and the fracture strength may be reduced. Also, N 2 SA of the silica (1) is less than 120 m 2 / g, preferably 100 m 2 / g, more preferably at most 80 m 2 / g. If it is 120 m 2 / g or more, there is a possibility that the effect of the combined use of silica (1) and (2) cannot be obtained sufficiently.
- N 2 SA of silica (2) is 120 m 2 / g or more, preferably 150 m 2 / g or more. If it is less than 120 m 2 / g, the effect of the combined use of silica (1) and (2) may not be sufficiently obtained. Further, N 2 SA of silica (2) is preferably 250 m 2 / g or less, more preferably 220 m 2 / g or less. When it exceeds 250 m 2 / g, fuel economy and processability tend to deteriorate.
- the contents of silica (1) and (2) preferably satisfy the following formula. (Content of silica (1)) ⁇ 0.06 ⁇ (content of silica (2)) ⁇ (content of silica (1)) ⁇ 15
- content of silica (2) is less than 0.06 times the content of silica (1), there is a tendency that sufficient rubber strength cannot be obtained.
- content of a silica (2) exceeds 15 times of content of a silica (1), there exists a tendency for rolling resistance to increase.
- the content of silica (2) is more preferably 0.3 times or more and more preferably 0.5 times or more of the content of silica (1). Further, the content of silica (2) is more preferably 7 times or less of the content of silica (1), and further preferably 4 times or less.
- 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 it is less than 5 parts by mass, the fuel economy may not be sufficiently improved. 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 fuel efficiency is good, but the breaking strength tends to decrease.
- 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, sufficient fracture strength may not be obtained. Further, the content of silica (2) is preferably 70 parts by mass or less, more preferably 65 parts by mass or less. When it exceeds 70 mass parts, although fracture strength is favorable, there exists a tendency for workability to deteriorate.
- the total content of silica (1) and (2) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 10 parts by mass, there is a possibility that a sufficient reinforcing effect by the blend of silica (1) and (2) cannot be obtained.
- the total content of silica (1) and (2) is preferably 70 parts by mass or less, more preferably 65 parts by mass or less. If it exceeds 70 parts by mass, it will be difficult for silica to be uniformly dispersed in the rubber composition, and not only the processability of the rubber composition will deteriorate but also the rolling resistance may increase.
- the rubber composition of the present invention preferably contains a silane coupling agent having a mercapto group.
- silica can be dispersed well and each performance can be improved synergistically. Moreover, the improvement effect of each performance can further be heightened by using together the above-mentioned silica (1) and (2) and the specific liquid resin mentioned later with the silane coupling agent which has a mercapto group.
- 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 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.
- Z represents an integer of 1 to 30.
- R 101 to R 103 may be the same or different, and R 104 is 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 C 1-30 alkylene group, branched or non-branched alkynyl group having 2 to 30 carbon atoms, or a hydrogen atom 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. In particular, the fuel efficiency can be greatly improved.
- 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) of 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 benzyl group and 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 suitably 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 1 part by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of silica. If it is less than 1 part by mass, the viscosity of the unvulcanized rubber composition is high, and good processability may not be ensured. 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. If it exceeds 20 parts by mass, the rubber strength tends to decrease.
- silane coupling agents may be used in combination with the silane coupling agent having a mercapto group.
- examples of other silane coupling agents include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, and bis (2-triethoxysilylpropyl) tetrasulfide. These can be used alone or in any combination. Of these, bis (3-triethoxysilylpropyl) tetrasulfide is preferably used from the viewpoint that the effect of improving the reinforcement and workability is great.
- the content of the other silane coupling agent is preferably 0.5 parts by mass or more, more preferably 3 parts by mass or more, preferably 100 parts by mass or more with respect to 100 parts by mass of silica, from the viewpoint of ensuring good processability. Is 10 parts by mass or less. From the same viewpoint, the content of other silane coupling agents is preferably less than the content of silane coupling agents having a mercapto group.
- the rubber composition of the present invention preferably contains a liquid resin having a softening point of ⁇ 20 to 20 ° C.
- a liquid resin having a softening point of ⁇ 20 to 20 ° C By blending the liquid resin together with the conjugated diene polymer, the effect of improving each performance can be increased synergistically, and particularly, the fuel efficiency and processability can be greatly improved. Moreover, the improvement effect of each performance can further be heightened by using together the said liquid resin, the above-mentioned silane coupling agent which has a mercapto group, and silica (1) and (2).
- the liquid resin has a softening point lower than that of the solid resin, and is liquid at 70 ° C., which is considered to have a correlation in rolling resistance characteristics. Therefore, it is considered that when a liquid resin is blended, the polymer becomes easy to move, energy loss is reduced, and fuel efficiency is improved.
- liquid resin examples include liquid petroleum-based or coal-based resins such as liquid coumarone indene resin, liquid indene resin, liquid ⁇ -methylstyrene resin, liquid vinyltoluene resin, and liquid polyisopentane resin.
- liquid coumarone indene resin is preferable because it has a large effect of improving fuel economy.
- the softening point of the liquid resin is ⁇ 20 ° C. or higher, preferably ⁇ 5 ° C. or higher, more preferably 0 ° C. or higher. If it is lower than -20 ° C, the viscosity of the liquid resin tends to be too low and the kneadability with the rubber component tends to deteriorate.
- the softening point of the liquid resin is 20 ° C. or lower, preferably 19 ° C. or lower, more preferably 17 ° C. or lower. When it exceeds 20 ° C., energy loss increases and fuel efficiency tends to deteriorate.
- the softening point is the temperature at which the sphere descends when the softening point specified in JIS K 6220-1: 2001 is measured with a ring and ball softening point measuring apparatus.
- the content of the liquid resin is preferably 1 part by mass or more, more preferably 2 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 1 part by mass, fuel economy may not be sufficiently improved. Further, the content of the liquid resin is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. If it exceeds 10 parts by mass, good processability can be obtained, while low fuel consumption tends to deteriorate.
- 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; fillers such as carbon black, calcium carbonate, talc, alumina, clay, aluminum hydroxide and mica; Examples include processing aids such as lubricants; anti-aging agents.
- the carbon black examples include furnace black (furness carbon black) such as SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF and ECF; acetylene black (acetylene carbon black); FT and Examples thereof include thermal black (thermal carbon black) such as MT; channel black (channel carbon black) such as EPC, MPC and CC; graphite and the like. These can be used alone or in combination of two or more.
- the content of carbon black 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 rubber component. If the amount is less than 1 part by mass, sufficient reinforcement may not be obtained.
- the carbon black content is preferably 90 parts by mass or less, more preferably 85 parts by mass or less. If it exceeds 90 parts by mass, the fuel efficiency tends to deteriorate.
- Nitrogen adsorption specific surface area (N 2 SA) of carbon black is usually 5 ⁇ 200m 2 / g, the lower limit is preferably 50 m 2 / g, the upper limit is 150 meters 2 / g.
- Carbon black has a dibutyl phthalate (DBP) absorption of usually 5 to 300 ml / 100 g, preferably a lower limit of 80 ml / 100 g and an upper limit of 180 ml / 100 g. If the N 2 SA or DBP absorption amount of carbon black is less than the lower limit of the above range, the reinforcing effect tends to be small and the fracture strength tends to decrease. There is a tendency for fuel efficiency to decrease.
- DBP dibutyl phthalate
- the nitrogen adsorption specific surface area is measured according to ASTM D4820-93, and the DBP absorption is measured according to ASTM D2414-93.
- ASTM D4820-93 The nitrogen adsorption specific surface area is measured according to ASTM D4820-93
- DBP absorption is measured according to ASTM D2414-93.
- SHIEST 6 and SEAST 7HM SEAST KH
- Special Black 4A etc.
- 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 has an excellent balance of low fuel consumption, breaking strength and processability, and can achieve a remarkable improvement effect of these performances.
- the rubber composition of the present invention can be used for each member of a tire and can be suitably used for a base tread.
- the pneumatic tire of the present invention is manufactured by a usual method. That is, the rubber composition is kneaded using a normal tire tread processing method, for example, a roll, a Banbury mixer, a kneader, etc., and the resulting unvulcanized rubber composition is composed of a base tread and a cap tread.
- a normal tire tread processing method for example, a roll, a Banbury mixer, a kneader, etc.
- An unvulcanized tire is formed by extruding into the shape of a tread of the layer and bonding together with other members by a normal method on a tire molding machine.
- the unvulcanized tire can be heated and pressurized in a vulcanizer to obtain 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 Tris [3- (trimethoxysilyl) propyl] isocyanurate manufactured by Tokyo Chemical Industry Co., Ltd .: N, N-dimethylformamide dimethyl acetal manufactured by Shin-Etsu Chemical Co., Ltd .: manufactured by Tokyo Chemical Industry Co., Ltd.
- 1,3-diisopropenylbenzene manufactured by Tokyo Chemical Industry Co., Ltd. sec-butyllithium solution: manufactured by Kanto Chemical Co., Inc. (1.0 mol / L) Cyclohexane: manufactured by Kanto Chemical Co., Inc.
- ⁇ Preparation of modifier (2) (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.
- weight average molecular weight Mw and number average molecular weight Mn The weight average molecular weight Mw and the number average molecular weight Mn of the copolymer were determined by gel permeation chromatography (GPC) (GPC-8000 series, manufactured by Tosoh Corp., detector: differential refractometer, column: TSKGEL SUPERMULTIPORE, manufactured by Tosoh Corp.). Based on the measured value by HZ-M), it was determined as a standard polystyrene equivalent value. 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 (2)) 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 (1)) 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 19 mL of the initiator (1) was changed to 10.6 mL of n-butyllithium solution.
- the silicon-containing vinyl compound (modifier (2)) 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 (1)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
- a copolymer (5) was obtained by the same formulation as the synthesis of the copolymer (1) except that 40 mL of the modifier (2) was changed to 0 mL and 20 mL of the modifier (1) was changed to 0 mL.
- the charged polymerization initiator (initiator (1)) was 8.5 mmol per 100 g of the monomer component.
- Copolymer (6) was prepared in the same formulation as the synthesis of copolymer (1) except that 19 mL of initiator (1) was changed to 6.8 mL of n-butyllithium solution and 20 mL of modifier (1) was changed to 0 mL. Got. The silicon-containing vinyl compound (modifier (2)) added was 0.43 g per 100 g of the monomer component.
- a copolymer (7) was obtained by the same formulation as the synthesis of the copolymer (1) except that 20 mL of the modifier (1) was changed to 20 mL of the modifier (3).
- the silicon-containing vinyl compound (modifier (2)) 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 (3)) added was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
- the copolymer (9) was prepared in 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 and 40 mL of the modifier (2) was changed to 0 mL. Got.
- the compound (modifier (3)) containing the introduced nitrogen atom and / or silicon atom was 1.18 mol per 1 mol of the alkali metal derived from the added polymerization initiator.
- a copolymer (12) was obtained by the same formulation as the synthesis of the copolymer (1) except that 20 mL of the modifier (1) was changed to 20 mL of the modifier (4).
- the silicon-containing vinyl compound (modifier (2)) 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.
- the copolymer (14) was prepared in the same formulation as the synthesis of the copolymer (12) except that 19 mL of the initiator (1) was changed to 10.6 mL of n-butyllithium solution and 40 mL of the modifier (2) 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 (15) was obtained by the same formulation as the synthesis of the copolymer (1) except that 20 mL of the modifier (1) was changed to 20 mL of the modifier (5).
- the silicon-containing vinyl compound (modifier (2)) 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.
- the copolymer (17) was prepared by the same formulation as the copolymer (15) except that 19 mL of the initiator (1) was changed to 10.6 mL of n-butyllithium solution and 40 mL of the modifier (2) was changed to 0 mL. Got. 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 (18) was obtained by the same formulation as the synthesis of the copolymer (1) except that 20 mL of the modifier (1) was changed to 20 mL of the modifier (6).
- the silicon-containing vinyl compound (modifier (2)) 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.
- the copolymer (20) was prepared by the same formulation as the synthesis of the copolymer (18) except that 19 mL of the initiator (1) was changed to 10.6 mL of n-butyllithium solution and 40 mL of the modifier (2) was changed to 0 mL. Got.
- the compound (modifier (6)) containing the nitrogen atom and / or silicon atom that was added was 1.18 mol per 1 mol of the alkali metal derived from the polymerization initiator that was added.
- Natural rubber TSR20 Copolymers (1) to (20): Synthetic butadiene rubber by the above method: Ubepol BR150B manufactured by Ube Industries, Ltd.
- Silica 1 Ultrasil 360 manufactured by EVONIK-DEGUSSA (N 2 SA: 50 m 2 / g)
- Silica 2 Zeosyl 1205MP (N 2 SA: 200 m 2 / g) manufactured by Rhodia Silane coupling agent 1: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by EVONIK-DEGUSSA
- Silane coupling agent 2 NXT-Z45 manufactured by Momentive (compound containing bonding unit A and bonding unit B (bonding unit A: 55 mol%, bonding unit B: 45 mol%))
- Silane coupling agent 3 Si363 manufactured by EVONIK-DEGUSSA Carbon black: Dia Black N339 manufactured by Mitsubishi Chemical Corporation (N 2 SA
- Anti-aging agent Antigen 6C 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 .: Soxinol CZ manufactured by Sumitomo Chemical Co., Ltd.
- the obtained unvulcanized rubber composition is molded into a base tread 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. Larger values indicate lower rolling resistance and better fuel efficiency.
- the unvulcanized rubber composition was extruded and formed into a rubber sheet having a thickness of 1.0 mm with a roll, and the state of the resulting rubber sheet was confirmed.
- the case where the ears were not cut off and there was no problem in the skin of the fabric was indicated by ⁇ , and the case where it was not indicated by ⁇ .
- the Examples have specific amine structures at the starting ends, have structural units derived from silicon-containing compounds in the main chain portion, and nitrogen atoms and / or silicon atoms at the terminating ends. Containing a specific amount of a conjugated diene copolymer having a structural unit derived from the compound to be contained, silica, and a silane coupling agent having a mercapto group, so that it has low fuel consumption compared to the rubber composition of the comparative example The fracture strength and workability were improved in a well-balanced manner.
- Examples 5 to 5 in which at least one of a silane coupling agent having a mercapto group, two types of silica having a specific nitrogen adsorption specific surface area, and a liquid resin having a specific softening point is blended with the conjugated diene polymer.
- the performances of Nos. 14 and 21 to 74 were greatly improved. Among them, Examples 43 to 46 using all of them showed particularly good performance.
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Abstract
Description
(シリカ(2)の窒素吸着比表面積)/(シリカ(1)の窒素吸着比表面積)≧1.4
(シリカ(1)の含有量)×0.06≦(シリカ(2)の含有量)≦(シリカ(1)の含有量)×15
なお、式(I)で表される重合開始剤としては、R11の炭素原子数が異なる化合物を複数種併用してもよい。
(ジメチルアミノ)ジメチルビニルシラン、(エチルメチルアミノ)ジメチルビニルシラン、(ジ-n-プロピルアミノ)ジメチルビニルシラン、(ジイソプロピルアミノ)ジメチルビニルシラン、(ジメチルアミノ)ジエチルビニルシラン、(エチルメチルアミノ)ジエチルビニルシラン、(ジ-n-プロピルアミノ)ジエチルビニルシラン、(ジイソプロピルアミノ)ジエチルビニルシランなどの(ジアルキルアミノ)ジアルキルビニルシラン;[ビス(トリメチルシリル)アミノ]ジメチルビニルシラン、[ビス(t-ブチルジメチルシリル)アミノ]ジメチルビニルシラン、[ビス(トリメチルシリル)アミノ]ジエチルビニルシラン、[ビス(t-ブチルジメチルシリル)アミノ]ジエチルビニルシランなどの[ビス(トリアルキルシリル)アミノ]ジアルキルビニルシラン;(ジメチルアミノ)ジ(メトキシメチル)ビニルシラン、(ジメチルアミノ)ジ(メトキシエチル)ビニルシラン、(ジメチルアミノ)ジ(エトキシメチル)ビニルシラン、(ジメチルアミノ)ジ(エトキシエチル)ビニルシラン、(ジエチルアミノ)ジ(メトキシメチル)ビニルシラン、(ジエチルアミノ)ジ(メトキシエチル)ビニルシラン、(ジエチルアミノ)ジ(エトキシメチル)ビニルシラン、(ジエチルアミノ)ジ(エトキシエチル)ビニルシランなどの(ジアルキルアミノ)ジ(アルコキシアルキル)ビニルシラン;ピロリジノジメチルビニルシラン、ピペリジノジメチルビニルシラン、ヘキサメチレンイミノジメチルビニルシラン、4,5-ジヒドロイミダゾリルジメチルビニルシラン、モルホリノジメチルビニルシランなどの環状アミノジアルキルビニルシラン化合物をあげることができる。
(ジメチルアミノ)ジメチル-4-ビニルフェニルシラン、(ジメチルアミノ)ジメチル-3-ビニルフェニルシラン、(ジエチルアミノ)ジメチル-4-ビニルフェニルシラン、(ジエチルアミノ)ジメチル-3-ビニルフェニルシラン、(ジ-n-プロピルアミノ)ジメチル-4-ビニルフェニルシラン、(ジ-n-プロピルアミノ)ジメチル-3-ビニルフェニルシラン、(ジ-n-ブチルアミノ)ジメチル-4-ビニルフェニルシラン、(ジ-n-ブチルアミノ)ジメチル-3-ビニルフェニルシラン、(ジメチルアミノ)ジエチル-4-ビニルフェニルシラン、(ジメチルアミノ)ジエチル-3-ビニルフェニルシラン、(ジエチルアミノ)ジエチル-4-ビニルフェニルシラン、(ジエチルアミノ)ジエチル-3-ビニルフェニルシラン、(ジ-n-プロピルアミノ)ジエチル-4-ビニルフェニルシラン、(ジ-n-プロピルアミノ)ジエチル-3-ビニルフェニルシラン、(ジ-n-ブチルアミノ)ジエチル-4-ビニルフェニルシラン、(ジ-n-ブチルアミノ)ジエチル-3-ビニルフェニルシランなどの(ジアルキルアミノ)ジアルキルビニルフェニルシランをあげることができる。
ビス(ジメチルアミノ)メチルビニルシラン、ビス(ジエチルアミノ)メチルビニルシラン、ビス(ジ-n-プロピルアミノ)メチルビニルシラン、ビス(ジ-n-ブチルアミノ)メチルビニルシラン、ビス(ジメチルアミノ)エチルビニルシラン、ビス(ジエチルアミノ)エチルビニルシラン、ビス(ジ-n-プロピルアミノ)エチルビニルシラン、ビス(ジ-n-ブチルアミノ)エチルビニルシランなどのビス(ジアルキルアミノ)アルキルビニルシラン;ビス[ビス(トリメチルシリル)アミノ]メチルビニルシラン、ビス[ビス(tert-ブチルジメチルシリル)アミノ]メチルビニルシラン、ビス[ビス(トリメチルシリル)アミノ]エチルビニルシラン、ビス[ビス(tert-ブチルジメチルシリル)アミノ]エチルビニルシランなどのビス[ビス(トリアルキルシリル)アミノ]アルキルビニルシラン;ビス(ジメチルアミノ)メトキシメチルビニルシラン、ビス(ジメチルアミノ)メトキシエチルビニルシラン、ビス(ジメチルアミノ)エトキシメチルビニルシラン、ビス(ジメチルアミノ)エトキシエチルビニルシラン、ビス(ジエチルアミノ)メトキシメチルビニルシラン、ビス(ジエチルアミノ)メトキシエチルビニルシラン、ビス(ジエチルアミノ)エトキシメチルビニルシラン、ビス(ジメチルアミノ)エトキシエチルビニルシランなどのビス(ジアルキルアミノ)アルコキシアルキルシラン;ビス(ピロリジノ)メチルビニルシラン、ビス(ピペリジノ)メチルビニルシラン、ビス(ヘキサメチレンイミノ)メチルビニルシラン、ビス(4,5-ジヒドロイミダゾリル)メチルビニルシラン、ビス(モルホリノ)メチルビニルシランなどのビス(環状アミノ)アルキルビニルシラン化合物をあげることができる。
ビス(ジメチルアミノ)メチル-4-ビニルフェニルシラン、ビス(ジメチルアミノ)メチル-3-ビニルフェニルシラン、ビス(ジエチルアミノ)メチル-4-ビニルフェニルシラン、ビス(ジエチルアミノ)メチル-3-ビニルフェニルシラン、ビス(ジ-n-プロピルアミノ)メチル-4-ビニルフェニルシラン、ビス(ジ-n-プロピルアミノ)メチル-3-ビニルフェニルシラン、ビス(ジ-n-ブチルアミノ)メチル-4-ビニルフェニルシラン、ビス(ジ-n-ブチルアミノ)メチル-3-ビニルフェニルシラン、ビス(ジメチルアミノ)エチル-4-ビニルフェニルシラン、ビス(ジメチルアミノ)エチル-3-ビニルフェニルシラン、ビス(ジエチルアミノ)エチル-4-ビニルフェニルシラン、ビス(ジエチルアミノ)エチル-3-ビニルフェニルシラン、ビス(ジ-n-プロピルアミノ)エチル-4-ビニルフェニルシラン、ビス(ジ-n-プロピルアミノ)エチル-3-ビニルフェニルシラン、ビス(ジ-n-ブチルアミノ)エチル-4-ビニルフェニルシラン、ビス(ジ-n-ブチルアミノ)エチル-3-ビニルフェニルシランなどのビス(ジアルキルアミノ)アルキルビニルフェニルシランをあげることができる。
トリス(ジメチルアミノ)ビニルシラン、トリス(ジエチルアミノ)ビニルシラン、トリス(ジ-n-プロピルアミノ)ビニルシラン、トリス(ジ-n-ブチルアミノ)ビニルシランなどのトリス(ジアルキルアミノ)ビニルシランをあげることができる。
トリス(ジメチルアミノ)-4-ビニルフェニルシラン、トリス(ジメチルアミノ)-3-ビニルフェニルシラン、トリス(ジエチルアミノ)-4-ビニルフェニルシラン、トリス(ジエチルアミノ)-3-ビニルフェニルシラン、トリス(ジ-n-プロピルアミノ)-4-ビニルフェニルシラン、トリス(ジ-n-プロピルアミノ)-3-ビニルフェニルシラン、トリス(ジ-n-ブチルアミノ)-4-ビニルフェニルシラン、トリス(ジ-n-ブチルアミノ)-3-ビニルフェニルシランなどのトリス(ジアルキルアミノ)ビニルフェニルシランをあげることができる。
トリメトキシビニルシラン、トリエトキシビニルシラン、トリプロポキシビニルシランなどのトリアルコキシビニルシラン;メチルジメトキシビニルシラン、メチルジエトキシビニルシランなどのジアルコキシアルキルビニルシラン;ジ(tert-ペントキシ)フェニルビニルシラン、ジ(tert-ブトキシ)フェニルビニルシランなどのジアルコキシアリールビニルシラン;ジメチルメトキシビニルシランなどのモノアルコキシジアルキルビニルシラン;tert-ブトキシジフェニルビニルシラン、tert-ペントキシジフェニルビニルシランなどのモノアルコキシジアリールビニルシラン;tert-ブトキシメチルフェニルビニルシラン、tert-ブトキシエチルフェニルビニルシランなどのモノアルコキシアルキルアリールビニルシラン;トリス(β-メトキシエトキシ)ビニルシランなどの置換アルコキシビニルシラン化合物をあげることができる。
4-(N,N-ジメチルアミノ)アセトフェノン、4-N-メチル-N-エチルアミノアセトフェノン、4-N,N-ジエチルアミノアセトフェノンなどの4-N,N-ジヒドロカルビルアミノアセトフェノン;4’-(イミダゾール-1-イル)アセトフェノン、4-ピラゾリルアセトフェノンなどの4-環状アミノアセトフェノン化合物などをあげることができ、中でも4-環状アミノアセトフェノン化合物が好ましく、4’-(イミダゾール-1-イル)アセトフェノンがより好ましい。
1,7-ビス(メチルエチルアミノ)-4-ヘプタノン、1,3-ビス(ジフェニルアミノ)-2-プロパノンなどのビス(ジヒドロカルビルアミノアルキル)ケトン;4-N,N-ジメチルアミノベンゾフェノン、4-N,N-ジ-t-ブチルアミノベンゾフェノン、4-N,N-ジフェニルアミノベンゾフェノンなどの4-(ジヒドロカルビルアミノ)ベンゾフェノン;4,4’-ビス(ジメチルアミノ)ベンゾフェノン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、4,4’-ビス(ジフェニルアミノ)ベンゾフェノンなどの4,4’-ビス(ジヒドロカルビルアミノ)ベンゾフェノンをあげることができ、中でも4,4’-ビス(ジヒドロカルビルアミノ)ベンゾフェノンが好ましく、4,4’-ビス(ジエチルアミノ)ベンゾフェノンがより好ましい。
2-N,N-ジメチルアミノエチルアクリレート、2-N,N-ジエチルアミノエチルアクリレートなどの2-N,N-ジヒドロカルビルアミノエチルアクリレート;3-N,N-ジメチルアミノプロピルアクリレートなどの3-N,N-ジヒドロカルビルアミノプロピルアクリレート;2-N,N-ジメチルアミノエチルメタクリレート、2-N,N-ジエチルアミノエチルメタクリレートなどの2-N,N-ジヒドロカルビルアミノエチルメタクリレート;3-N,N-ジメチルアミノプロピルメタクリレートなどの3-N,N-ジヒドロカルビルアミノプロピルメタクリレートをあげることができ、3-N,N-ジヒドロカルビルアミノプロピルアクリレートが好ましく、3-N,N-ジメチルアミノプロピルアクリレートがより好ましい。
N,N-ジメチルアミノエチルアクリルアミド、N,N-ジエチルアミノエチルアクリルアミドなどのN、N-ジヒドロカルビルアミノエチルアクリルアミド;N,N-ジメチルアミノプロピルアクリルアミド、N,N-ジエチルアミノプロピルアクリルアミドなどのN,N-ジヒドロカルビルアミノプロピルアクリルアミド;N,N-ジメチルアミノブチルアクリルアミド、N,N-ジエチルアミノブチルアクリルアミドなどのN,N-ジヒドロカルビルアミノブチルアクリルアミド;N,N-ジメチルアミノエチルメタクリルアミド、N,N-ジエチルアミノエチルメタクリルアミドなどのN、N-ジヒドロカルビルアミノエチルメタクリルアミド;N,N-ジメチルアミノプロピルメタクリルアミド、N,N-ジエチルアミノプロピルメタクリルアミドなどのN,N-ジヒドロカルビルアミノプロピルメタクリルアミド;N,N-ジメチルアミノブチルメタクリルアミド、N,N-ジエチルアミノブチルメタクリルアミドなどのN,N-ジヒドロカルビルアミノブチルメタクリルアミドをあげることができ、N,N-ジヒドロカルビルアミノプロピルアクリルアミドが好ましく、N,N-ジメチルアミノプロピルアクリルアミドがより好ましい。
テトラメトキシシラン、テトラエトキシシラン、テトラ-n-プロポキシシランなどのテトラアルコキシシラン;メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、フェニルトリメトキシシランなどのトリアルコキシヒドロカルビルシラン;トリメトキシクロロシラン、トリエトキシクロロシラン、トリ-n-プロポキシクロロシランなどのトリアルコキシハロシラン;ジメトキシジメチルシラン、ジエトキシジメチルシラン、ジメトキシジエチルシランなどのジアルコキシジヒドロカルビルシラン;ジメトキシジクロロシラン、ジエトキシジクロロシラン、ジ-n-プロポキシジクロロシランなどのジアルコキシジハロシラン;メトキシトリメチルシランなどのモノアルコキシトリヒドロカルビルシラン;メトキシトリクロロシラン、エトキシトリクロロシランなどのモノアルコキシトリハロシラン;2-グリシドキシエチルトリメトキシシラン、2-グリシドキシエチルトリエトキシシラン、(2-グリシドキシエチル)メチルジメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、(3-グリシドキシプロピル)メチルジメトキシシランなどの(グリシドキシアルキル)アルコキシシラン化合物;2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチル(メチル)ジメトキシシランなどの(3,4-エポキシシクロヘキシル)アルキルアルコキシシラン化合物;3-トリメトキシシリルプロピルコハク酸無水物、3-トリエトキシシリルプロピルコハク酸無水物などのアルコキシシリルアルキルコハク酸無水物;3-メタクリロイロキシプロピルトリメトキシシラン、3-メタクリロイロキシプロピルトリエトキシシランなどの(メタクリロイロキシアルキル)アルコキシシラン化合物をあげることができる。
R51 aML4-a (V)
(式(V)中、R51はアルキル基、アルケニル基、シクロアルケニル基又はアリール基を表し、Mはケイ素原子又はスズ原子を表し、Lはハロゲン原子又はヒドロカルビルオキシ基を表し、aは0~2の整数を表す)
なお、シリカのN2SAは、ASTM D3037-93に準じてBET法で測定される値である。
(シリカ(1)の含有量)×0.06≦(シリカ(2)の含有量)≦(シリカ(1)の含有量)×15
シリカ(2)の含有量がシリカ(1)の含有量の0.06倍未満では、充分なゴム強度が得られない傾向がある。また、シリカ(2)の含有量がシリカ(1)の含有量の15倍を超えると、転がり抵抗が増大する傾向がある。なお、シリカ(2)の含有量は、シリカ(1)の含有量の0.3倍以上がより好ましく、0.5倍以上がさらに好ましい。また、シリカ(2)の含有量は、シリカ(1)の含有量の7倍以下がより好ましく、4倍以下がさらに好ましい。
該炭化水素基としては、例えば、分岐若しくは非分岐の炭素数1~30のアルキレン基、分岐若しくは非分岐の炭素数2~30のアルケニレン基、分岐若しくは非分岐の炭素数2~30のアルキニレン基、炭素数6~30のアリーレン基などがあげられる。中でも、分岐若しくは非分岐の炭素数1~30のアルキレン基が好ましい。
なお、結合単位A、Bの含有量は、結合単位A、Bがシランカップリング剤の末端に位置する場合も含む量である。結合単位A、Bがシランカップリング剤の末端に位置する場合の形態は特に限定されず、結合単位A、Bを示す式(2)、(3)と対応するユニットを形成していればよい。
なお、本明細書において、軟化点とは、JIS K 6220-1:2001に規定される軟化点を環球式軟化点測定装置で測定し、球が降下した温度である。
THF:関東化学(株)製無水テトラヒドロフラン
水素化ナトリウム:関東化学(株)製
ジエチルアミン:関東化学(株)製
メチルビニルジクロロシラン:信越化学工業(株)製
無水ヘキサン:関東化学(株)製
スチレン:関東化学(株)製
ブタジエン:東京化成工業(株)製1,3-ブタジエン
TMEDA:関東化学(株)製テトラメチルエチレンジアミン
n-ブチルリチウム溶液:関東化学(株)製の1.6M n-ブチルリチウムヘキサン溶液
開始剤(1):FMC社製AI-200CE2(3-(N,N-ジメチルアミノ)-1-プロピルリチウムにイソプレン由来の構造単位が2単位結合した化合物(下記式で表される化合物))(0.9M)
ジアミルアミン:東京化成工業(株)製
2,6-ジ-tert-ブチル-p-クレゾール:大内新興化学工業(株)製のノクラック200
ビス(ジメチルアミノ)メチルビニルシラン:信越化学工業(株)製
N,N-ジメチルアミノプロピルアクリルアミド:東京化成工業(株)製
3-ジエチルアミノプロピルトリエトキシシラン:アヅマックス(株)製
1,3-ジメチル-2-イミダゾリジノン:東京化成工業(株)製
トリス[3-(トリメトキシシリル)プロピル]イソシアヌレート:信越化学工業(株)製
N,N-ジメチルホルムアミドジメチルアセタール:東京化成工業(株)製
1,3-ジイソプロペニルベンゼン:東京化成工業(株)製
sec-ブチルリチウム溶液:関東化学(株)製(1.0mol/L)
シクロヘキサン:関東化学(株)製
窒素雰囲気下、100mlメスフラスコにN-(3-ジメチルアミノプロピル)アクリルアミドを15.6g入れ、さらに無水ヘキサンを加え全量を100mlにして作成した。
充分に窒素置換した2L三つ口フラスコにTHF1000mL、水素化ナトリウム13gを加え、氷水バス上で撹拌しながらジエチルアミン36.5gをゆっくり滴下した。30分撹拌後、メチルビニルジクロロシラン36gを30分かけて滴下し、2時間撹拌させた。得られた溶液を濃縮し、ろ過後、減圧蒸留精製を行い、ビス(ジエチルアミノ)メチルビニルシランを合成した。得られたビス(ジエチルアミノ)メチルビニルシラン21.4gを窒素雰囲気下で100mlメスフラスコに入れ、さらに無水ヘキサンを加え全量を100mlにした。
窒素雰囲気下、100mlメスフラスコに3-ジエチルアミノプロピルトリエトキシシランを27.7g入れ、さらに無水ヘキサンを加え全量を100mlにして作製した。
窒素雰囲気下、100mlメスフラスコに1,3-ジメチル-2-イミダゾリジノンを11.4g入れ、さらに無水ヘキサンを加え全量を100mlにして作製した。
窒素雰囲気下、100mlメスフラスコにトリス[3-(トリメトキシシリル)プロピル]イソシアヌレートを30.7g入れ、さらに無水ヘキサンを加え全量を200mlにして作製した。
窒素雰囲気下、100mlメスフラスコにN,N-ジメチルホルムアミドジメチルアセタールを11.9g入れ、さらに無水ヘキサンを加え全量を200mlにして作製した。
下記により得られた共重合体(共役ジエン系重合体)の分析は以下の方法で行った。
共重合体の重量平均分子量Mw及び数平均分子量Mnは、ゲルパーミエーションクロマトグラフ(GPC)(東ソー(株)製GPC-8000シリーズ、検出器:示差屈折計、カラム:東ソー(株)製TSKGEL SUPERMULTIPORE HZ-M)による測定値を基に標準ポリスチレン換算値として求めた。測定結果から、分子量分布Mw/Mnを算出した。
共重合体の構造同定(スチレン含有量、ビニル含有量)は、日本電子(株)製JNM-ECAシリーズの装置を用いて行った。測定は、重合体0.1gを15mlのトルエンに溶解させ、30mlのメタノール中にゆっくり注ぎ込んで再沈殿させたものを、減圧乾燥後に測定した。
充分に窒素置換した30L耐圧容器にn-ヘキサンを18L、スチレンを600g、ブタジエンを1400g、変性剤(2)を40mL、TMEDAを10mmol加え、40℃に昇温した。次に、開始剤(1)を19mL加えた後、50℃に昇温させ3時間撹拌した。次に、変性剤(1)を20mL追加し30分間撹拌を行った。反応溶液にメタノール15mL及び2,6-tert-ブチル-p-クレゾール0.1gを添加後、スチームストリッピング処理によって重合体溶液から凝集体を回収し、得られた凝集体を24時間減圧乾燥させ、共重合体(1)を得た。なお、投入したケイ素含有ビニル化合物(変性剤(2))は、単量体成分100gあたり0.43gであった。投入した重合開始剤(開始剤(1))は、単量体成分100gあたり0.85mmolであった。投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(1))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
開始剤(1)19mLをn-ブチルリチウム溶液10.6mLに変えた以外は、共重合体(1)の合成と同じ処方により、共重合体(2)を得た。なお、投入したケイ素含有ビニル化合物(変性剤(2))は、単量体成分100gあたり0.43gであった。投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(1))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
充分に窒素置換した30L耐圧容器にn-ヘキサンを18L、スチレンを600g、ブタジエンを1400g、TMEDAを10mmol加え、40℃に昇温した。次に、n-ブチルリチウム溶液を11mL加えた後、50℃に昇温させ3時間撹拌した。次に、反応溶液にメタノール1mL及び2,6-tert-ブチル-p-クレゾール0.1gを添加後、スチームストリッピング処理によって重合体溶液から凝集体を回収し、得られた凝集体を24時間減圧乾燥させ、共重合体(3)を得た。
重合体溶液から凝集体を回収する際、スチームストリッピング処理の代わりに、重合体溶液を常温で24時間蒸発させ、その後減圧乾燥をさせることで凝集体を回収した以外は、共重合体(1)の合成と同じ処方により、共重合体(4)を得た。なお、投入したケイ素含有ビニル化合物(変性剤(2))は、単量体成分100gあたり0.43gであった。投入した重合開始剤(開始剤(1))は、単量体成分100gあたり0.85mmolであった。投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(1))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
変性剤(2)40mLを0mLに、変性剤(1)20mLを0mLに変えた以外は、共重合体(1)の合成と同じ処方により、共重合体(5)を得た。なお、投入した重合開始剤(開始剤(1))は、単量体成分100gあたり8.5mmolであった。
開始剤(1)19mLをn-ブチルリチウム溶液6.8mLに、変性剤(1)20mLを0mLに変えた以外は、共重合体(1)の合成と同じ処方により、共重合体(6)を得た。なお、投入したケイ素含有ビニル化合物(変性剤(2))は、単量体成分100gあたり0.43gであった。
変性剤(1)20mLを変性剤(3)20mLに変えた以外は、共重合体(1)の合成と同じ処方により、共重合体(7)を得た。なお、投入したケイ素含有ビニル化合物(変性剤(2))は、単量体成分100gあたり0.32gであった。投入した重合開始剤(開始剤(1))は、単量体成分100gあたり0.85mmolであった。投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(3))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
重合体溶液から凝集体を回収する際、スチームストリッピング処理の代わりに、重合体溶液を常温で24時間蒸発させ、その後減圧乾燥をさせることで凝集体を回収した以外は、共重合体(7)の合成と同じ処方により、共重合体(8)を得た。なお、投入したケイ素含有ビニル化合物(変性剤(2))は、単量体成分100gあたり0.32gであった。投入した重合開始剤(開始剤(1))は、単量体成分100gあたり0.85mmolであった。投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(3))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
開始剤(1)19mLをn-ブチルリチウム溶液10.6mLに、変性剤(2)40mLを0mLに変えた以外は、共重合体(7)の合成と同じ処方により、共重合体(9)を得た。なお、投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(3))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
スチレンの量を0gに、ブタジエンの量を2000gに、TMEDA10mmoLをTHF5mmoLに、開始剤(1)19mLを開始剤(1)23mLに変えた以外は、共重合体(1)の合成と同じ処方により、共重合体(10)を得た。なお、投入したケイ素含有ビニル化合物(変性剤(2))は、単量体成分100gあたり0.43gであった。投入した重合開始剤(開始剤(1))は、単量体成分100gあたり0.85mmolであった。
投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(1))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
重合体溶液から凝集体を回収する際、スチームストリッピング処理の代わりに、重合体溶液を常温で24時間蒸発させ、その後減圧乾燥をさせることで凝集体を回収した以外は、共重合体(10)の合成と同じ処方により、共重合体(11)を得た。なお、投入したケイ素含有ビニル化合物(変性剤(2))は、単量体成分100gあたり0.43gであった。投入した重合開始剤(開始剤(1))は、単量体成分100gあたり0.85mmolであった。投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(1))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
変性剤(1)20mLを変性剤(4)20mLに変えた以外は、共重合体(1)の合成と同じ処方により、共重合体(12)を得た。なお、投入したケイ素含有ビニル化合物(変性剤(2))は、単量体成分100gあたり0.32gであった。投入した重合開始剤(開始剤(1))は、単量体成分100gあたり0.85mmolであった。投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(4))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
重合体溶液から凝集体を回収する際、スチームストリッピング処理の代わりに、重合体溶液を常温で24時間蒸発させ、その後減圧乾燥をさせることで凝集体を回収した以外は、共重合体(12)の合成と同じ処方により、共重合体(13)を得た。なお、投入したケイ素含有ビニル化合物(変性剤(2))は、単量体成分100gあたり0.32gであった。投入した重合開始剤(開始剤(1))は、単量体成分100gあたり0.85mmolであった。投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(4))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
開始剤(1)19mLをn-ブチルリチウム溶液10.6mLに、変性剤(2)40mLを0mLに変えた以外は、共重合体(12)の合成と同じ処方により、共重合体(14)を得た。なお、投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(4))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
変性剤(1)20mLを変性剤(5)20mLに変えた以外は、共重合体(1)の合成と同じ処方により、共重合体(15)を得た。なお、投入したケイ素含有ビニル化合物(変性剤(2))は、単量体成分100gあたり0.32gであった。投入した重合開始剤(開始剤(1))は、単量体成分100gあたり0.85mmolであった。投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(5))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
重合体溶液から凝集体を回収する際、スチームストリッピング処理の代わりに、重合体溶液を常温で24時間蒸発させ、その後減圧乾燥をさせることで凝集体を回収した以外は、共重合体(15)の合成と同じ処方により、共重合体(16)を得た。なお、投入したケイ素含有ビニル化合物(変性剤(2))は、単量体成分100gあたり0.32gであった。投入した重合開始剤(開始剤(1))は、単量体成分100gあたり0.85mmolであった。投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(5))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
開始剤(1)19mLをn-ブチルリチウム溶液10.6mLに、変性剤(2)40mLを0mLに変えた以外は、共重合体(15)の合成と同じ処方により、共重合体(17)を得た。なお、投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(5))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
変性剤(1)20mLを変性剤(6)20mLに変えた以外は、共重合体(1)の合成と同じ処方により、共重合体(18)を得た。なお、投入したケイ素含有ビニル化合物(変性剤(2))は、単量体成分100gあたり0.32gであった。投入した重合開始剤(開始剤(1))は、単量体成分100gあたり0.85mmolであった。投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(6))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
重合体溶液から凝集体を回収する際、スチームストリッピング処理の代わりに、重合体溶液を常温で24時間蒸発させ、その後減圧乾燥をさせることで凝集体を回収した以外は、共重合体(18)の合成と同じ処方により、共重合体(19)を得た。なお、投入したケイ素含有ビニル化合物(変性剤(2))は、単量体成分100gあたり0.32gであった。投入した重合開始剤(開始剤(1))は、単量体成分100gあたり0.85mmolであった。投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(6))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
開始剤(1)19mLをn-ブチルリチウム溶液10.6mLに、変性剤(2)40mLを0mLに変えた以外は、共重合体(18)の合成と同じ処方により、共重合体(20)を得た。なお、投入した窒素原子及び/又はケイ素原子を含有する化合物(変性剤(6))は、投入した重合開始剤に由来するアルカリ金属1molあたり、1.18molであった。
天然ゴム:TSR20
共重合体(1)~(20):上記方法で合成
ブタジエンゴム:宇部興産(株)製のウベポールBR150B
シリカ1:EVONIK-DEGUSSA社製のウルトラジル360(N2SA:50m2/g)
シリカ2:ローディア社製のゼオシル1205MP(N2SA:200m2/g)
シランカップリング剤1:EVONIK-DEGUSSA社製のSi69(ビス(3-トリエトキシシリルプロピル)テトラスルフィド)
シランカップリング剤2:Momentive社製のNXT-Z45(結合単位A及び結合単位Bを含む化合物(結合単位A:55モル%、結合単位B:45モル%))
シランカップリング剤3:EVONIK-DEGUSSA社製のSi363
カーボンブラック:三菱化学(株)製のダイアブラックN339(N2SA:96m2/g、DBP吸収量:124ml/100g)
オイル:JX日鉱日石エネルギー(株)製のX-140
固体レジン:エクソンモービル社製のエスコレッツ1102
液状レジン:ルトカーズケミカル社製のNOVARES C10(液状クマロンインデン樹脂、軟化点:5~15℃)
老化防止剤:住友化学(株)製のアンチゲン6C
ステアリン酸:日油(株)製のビーズステアリン酸つばき
酸化亜鉛:三井金属鉱業(株)製の亜鉛華1号
ワックス:大内新興化学工業(株)製のサンノックN
硫黄:鶴見化学工業(株)製の粉末硫黄
加硫促進剤:住友化学(株)製のソクシノールCZ
表2~11に示す配合内容に従い、(株)神戸製鋼所製の1.7Lバンバリーミキサーを用いて、硫黄及び加硫促進剤以外の材料を150℃の条件下で5分間混練りし、混練り物を得た。次に、得られた混練り物に硫黄及び加硫促進剤を添加し、オープンロールを用いて、80℃の条件下で5分間練り込み、未加硫ゴム組成物を得た。得られた未加硫ゴム組成物を170℃で20分間、0.5mm厚の金型でプレス加硫し、加硫ゴム組成物を得た。
また、得られた未加硫ゴム組成物をベーストレッドの形状に成形し、タイヤ成型機上で他のタイヤ部材とともに貼り合わせて未加硫タイヤを形成し、170℃で12分間加硫し、試験用タイヤ(サイズ:195/65R15)を製造した。
なお、以下の評価項目において、表2、4、5、6、8、9、11における基準比較例を比較例1、表3、7、10における基準比較例を比較例9とした。
(株)上島製作所製スペクトロメーターを用いて、動的歪振幅1%、周波数10Hz、温度50℃で加硫ゴム組成物のtanδを測定した。tanδの逆数の値について基準比較例を100として指数表示した。数値が大きいほど転がり抵抗が小さく、低燃費性に優れることを示している。
転がり抵抗試験機を用い、試験用タイヤを、リム(15×6JJ)、内圧(230kPa)、荷重(3.43kN)、速度(80km/h)で走行させたときの転がり抵抗を測定し、基準比較例を100とした時の指数で表示した。数値が大きいほど転がり抵抗が小さく、低燃費性に優れることを示している。
上記加硫ゴム組成物からなる3号ダンベルを用いて、JIS K 6251:2010「加硫ゴム及び熱可塑性ゴム― 引張特性の求め方」に準じて引張試験を行い、破断強度(TB)及び破断時伸び(EB)を測定して、破壊エネルギー(TB×EB/2)を算出した。そして、基準比較例の破壊エネルギーを100とし、下記計算式により、各配合の破壊エネルギーを指数表示した。数値が大きいほど、破壊強度が高いことを示す。
(破壊エネルギー指数) =(各配合の破壊エネルギー)/(基準比較例の破壊エネルギー)×100
JIS K 6300-1:2001「未加硫ゴム-物理特性-第1部:ムーニー粘度計による粘度及びスコーチタイムの求め方」に準じて、ムーニー粘度試験機を用いて、1分間の予熱によって熱せられた130℃の温度条件にて、小ローターを回転させ、4分間経過した時点での上記未加硫ゴム組成物のムーニー粘度(ML1+4/130℃)を測定した。結果は指数で表し、数値が大きいほどムーニー粘度が低く、加工性(混練加工性)が良好である。指数は次の式で求めた。
(ムーニー粘度指数)=(基準比較例のムーニー粘度)/(各配合のムーニー粘度)×100
上記未加硫ゴム組成物をロールにて1.0mm厚さのゴムシートに押出し成形し、得られたゴムシートの生地の状態を確認した。耳切れが発生しておらず、さらに生地肌に問題がないものを○、そうでないものを×で表記した。
Claims (16)
- 下記式(I)で表される重合開始剤を用いて共役ジエン化合物及びケイ素含有ビニル化合物を含む単量体成分を重合させて得られる共重合体の活性末端に、窒素原子及び/又はケイ素原子を含有する化合物を反応させて得られる共役ジエン系重合体と、
シリカとを含み、
ゴム成分100質量%中、前記共役ジエン系重合体の含有量が10質量%以上であり、
前記ゴム成分100質量部に対する前記シリカの含有量が10~70質量部であるゴム組成物。
- 前記式(Ia)のR14がイソプレン由来の構造単位1~10単位からなるヒドロカルビレン基である請求項2記載のゴム組成物。
- 前記共役ジエン系重合体が芳香族ビニル化合物由来の構造単位を有する請求項1~4のいずれかに記載のゴム組成物。
- 前記シリカの窒素吸着比表面積が40~400m2/gである請求項1~5のいずれかに記載のゴム組成物。
- 前記シリカが、窒素吸着比表面積が40m2/g以上、120m2/g未満のシリカ(1)と、窒素吸着比表面積が120m2/g以上のシリカ(2)とを含む請求項1~6のいずれかに記載のゴム組成物。
- 前記ゴム成分100質量部に対して、軟化点が-20~20℃の液状レジンを1~10質量部含む請求項1~7のいずれかに記載のゴム組成物。
- 前記シリカが、窒素吸着比表面積が40m2/g以上、120m2/g未満のシリカ(1)と、窒素吸着比表面積が120m2/g以上のシリカ(2)とを含み、
前記ゴム成分100質量部に対して、軟化点が-20~20℃の液状レジンを1~10質量部含む請求項1~8のいずれかに記載のゴム組成物。 - 前記シリカ100質量部に対して、メルカプト基を有するシランカップリング剤を1~20質量部含む請求項1~9のいずれかに記載のゴム組成物。
- 前記シリカ100質量部に対して、メルカプト基を有するシランカップリング剤を1~20質量部含み、
前記シリカが、窒素吸着比表面積が40m2/g以上、120m2/g未満のシリカ(1)と、窒素吸着比表面積が120m2/g以上のシリカ(2)とを含む請求項1~10のいずれかに記載のゴム組成物。 - 前記シリカ100質量部に対して、メルカプト基を有するシランカップリング剤を1~20質量部含み、
前記ゴム成分100質量部に対して、軟化点が-20~20℃の液状レジンを1~10質量部含む請求項1~11のいずれかに記載のゴム組成物。 - 前記シリカ100質量部に対して、メルカプト基を有するシランカップリング剤を1~20質量部含み、
前記シリカが、窒素吸着比表面積が40m2/g以上、120m2/g未満のシリカ(1)と、窒素吸着比表面積が120m2/g以上のシリカ(2)とを含み、
前記ゴム成分100質量部に対して、軟化点が-20~20℃の液状レジンを1~10質量部含む請求項1~12のいずれかに記載のゴム組成物。 - 前記シリカ100質量部に対して、メルカプト基を有するシランカップリング剤を1~20質量部含み、
前記シランカップリング剤が、下記式(1)で表される化合物、及び/又は下記式(2)で示される結合単位Aと下記式(3)で示される結合単位Bとを含む化合物である請求項1~13のいずれかに記載のゴム組成物。
- 前記シリカが、窒素吸着比表面積が40m2/g以上、120m2/g未満のシリカ(1)と、窒素吸着比表面積が120m2/g以上のシリカ(2)とを含み、
前記シリカ(1)及び(2)の窒素吸着比表面積及び含有量が以下の式を満たす請求項1~14のいずれかに記載のゴム組成物。
(シリカ(2)の窒素吸着比表面積)/(シリカ(1)の窒素吸着比表面積)≧1.4
(シリカ(1)の含有量)×0.06≦(シリカ(2)の含有量)≦(シリカ(1)の含有量)×15 - 請求項1~15のいずれかに記載のゴム組成物を用いて作製した空気入りタイヤ。
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CN201280055150.1A CN103917589B (zh) | 2011-11-24 | 2012-06-26 | 橡胶组合物以及充气轮胎 |
US14/347,290 US9006326B2 (en) | 2011-11-24 | 2012-06-26 | Rubber composition and pneumatic tire |
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JP5918261B2 (ja) * | 2011-11-24 | 2016-05-18 | 住友ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
WO2013077021A1 (ja) | 2011-11-24 | 2013-05-30 | 住友ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
WO2013077020A1 (ja) | 2011-11-24 | 2013-05-30 | 住友ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
EP2787031B1 (en) | 2011-12-26 | 2016-12-14 | Sumitomo Rubber Industries, Ltd. | Rubber composition and pneumatic tire |
JP6050254B2 (ja) | 2011-12-26 | 2016-12-21 | 住友ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
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CN105670051A (zh) * | 2016-04-06 | 2016-06-15 | 山东玲珑轮胎股份有限公司 | 一种夏季超高性能半钢胎胎面胶料及其制法和应用 |
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CN103917589A (zh) | 2014-07-09 |
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US20140228501A1 (en) | 2014-08-14 |
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