WO2016039005A1 - 空気入りタイヤ - Google Patents
空気入りタイヤ Download PDFInfo
- Publication number
- WO2016039005A1 WO2016039005A1 PCT/JP2015/069823 JP2015069823W WO2016039005A1 WO 2016039005 A1 WO2016039005 A1 WO 2016039005A1 JP 2015069823 W JP2015069823 W JP 2015069823W WO 2016039005 A1 WO2016039005 A1 WO 2016039005A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- copolymer
- parts
- hydrogenated
- pneumatic tire
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
-
- 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
-
- 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
- C08C19/02—Hydrogenation
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
Definitions
- the present invention relates to a pneumatic tire manufactured using a predetermined rubber composition.
- a rubber composition for automobile tires a rubber composition containing a conjugated diene polymer such as polybutadiene and a butadiene-styrene copolymer, and a filler such as carbon black and silica is used. Further, in a truck / bus tire, a rubber composition containing an isoprene-based rubber together with these components 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 fuel efficiency is improved by such conventional techniques, it is also important to sufficiently secure the wear resistance and the fracture characteristics (rubber fracture strength) from the viewpoint of economy and safety.
- the wear resistance which is contrary to the fuel economy is not sufficient, and there is a problem of causing a rubber chipping, and the rubber breaking strength and the wear resistance are improved. There is room.
- An object of the present invention is to solve the above-mentioned problems and to provide a pneumatic tire in which the rubber breaking strength and the abrasion resistance are well improved while the good fuel economy is maintained or improved.
- the present invention is a pneumatic tire produced using a rubber composition, wherein the rubber composition has a hydrogenation ratio of a conjugated diene portion obtained by copolymerizing an aromatic vinyl compound and a conjugated diene compound.
- the present invention relates to a pneumatic tire having a carbon black content of 3 parts by mass or more and a silica content of 1 to 200 parts by mass with respect to parts.
- the weight average molecular weight of the hydrogenated copolymer is preferably 200,000 to 2,000,000.
- the hydrogenation rate of the said hydrogenated copolymer is 90 mol% or more.
- the said hydrogenated copolymer is a hydrogenated styrene butadiene copolymer.
- the hydrogenated styrene butadiene copolymer is preferably a hydrogenated modified styrene butadiene copolymer.
- the styrene content of the hydrogenated styrene butadiene copolymer is preferably 5 to 40% by mass.
- the content of the hydrogenated styrene-butadiene copolymer in 100% by mass of the rubber component is preferably 90 to 100% by mass.
- the content of the silica is 10 to 80 parts by mass and the content of carbon black in 100% by mass of the filler is 50% by mass or more with respect to 100 parts by mass of the rubber component.
- the tan ⁇ peak temperature of the rubber composition may be less than -16 ° C or may be -16 ° C or more. It is advantageous when making the pneumatic tire of the present invention into a studless tire or an all season tire that the temperature is less than -16 ° C, and when the pneumatic tire of the present invention is a summer tire when the temperature is -16 ° C or higher. It is advantageous to
- the pneumatic tire according to the present invention is preferably a truck / bus tire, a studless tire, an all-season tire or a summer tire having a tread manufactured using the rubber composition.
- the specific hydrogenated copolymer having a hydrogenation rate of 75% by mol or more is contained in 100% by mass of the rubber component, and 3 carbon blacks with respect to 100 parts by mass of the rubber component Since it is a pneumatic tire produced using a rubber composition containing 1 to 200 parts by mass of silica or more, it has good fuel economy, rubber breaking strength and wear resistance.
- the pneumatic tire of the present invention is a conjugated diene of a copolymer obtained by copolymerizing an aromatic vinyl compound and a conjugated diene compound (hereinafter also referred to as a copolymer of an aromatic vinyl compound and a conjugated diene compound). 100% by mass of a hydrogenated copolymer containing 75% by mass or more of a hydrogenated copolymer having a hydrogenation rate of 75% by mass or more and 3 parts by mass of carbon black based on 100 parts by mass of the rubber component It is produced using a rubber composition containing 1 to 200 parts by mass of silica or more.
- a rubber component is a hydrogenated copolymer in which a conjugated diene portion of a copolymer of an aromatic vinyl compound and a conjugated diene compound is hydrogenated and the hydrogenation rate is 75 mol% or more.
- % Contains 75% by mass or more, and 3 parts by mass or more of carbon black and 1 to 200 parts by mass of silica with respect to 100 parts by mass of the rubber component.
- the rubber composition according to the present invention is characterized in that it contains, as a rubber component, a hydrogenated copolymer in which a conjugated diene portion of a copolymer of an aromatic vinyl compound and a conjugated diene compound is hydrogenated.
- a hydrogenated copolymer in which a conjugated diene portion of a copolymer of an aromatic vinyl compound and a conjugated diene compound is hydrogenated.
- aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, 2,4,6-trimethylstyrene and the like. These may be used alone or in combination of two or more. Among them, practical aspects such as availability of monomers and the reason for the effects of the present invention to be obtained more suitably. Particularly preferred is styrene.
- conjugated diene compounds include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene. These may be used alone or in combination of two or more. Among them, practical aspects such as availability of monomers and the reason for the effects of the present invention to be obtained more suitably. 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is more preferable.
- a copolymer of an aromatic vinyl compound and a conjugated diene compound a copolymer of styrene and 1,3-butadiene (styrene-butadiene copolymer) is preferable. Therefore, as a hydrogenated copolymer, a hydrogenated styrene butadiene copolymer is preferable. Furthermore, the hydrogenated styrene butadiene copolymer is preferably a hydrogenated modified styrene butadiene copolymer modified by the method described later.
- the order of copolymerization is not particularly limited as long as the above-mentioned styrene butadiene copolymer copolymerizes styrene and 1,3-butadiene, and may be random copolymerization or block copolymerization, but random copolymerization is preferable. .
- copolymers of an aromatic vinyl compound other than a styrene butadiene copolymer and a conjugated diene compound are examples of an aromatic vinyl compound other than a styrene butadiene copolymer and a conjugated diene compound.
- the hydrogenation rate of the hydrogenated copolymer is 75 mol% or more, preferably 80 mol% or more, More preferably, it is 90 mol% or more, still more preferably 93 mol% or more. If the hydrogenation rate is less than 75 mol%, it is difficult to improve the rubber fracture strength and the wear resistance.
- the hydrogenation rate of the hydrogenated copolymer is preferably 99 mol% or less, more preferably 98 mol% or less. If the degree of hydrogenation exceeds 99 mol%, the rubber composition may become hard.
- the hydrogenation rate can be calculated from the spectrum reduction rate of the unsaturated bond part of the spectrum obtained by measuring H 1 -NMR.
- the weight average molecular weight (Mw) of the hydrogenated copolymer is preferably 200,000 or more, more preferably 400,000 or more. If Mw is less than 200,000, there is a possibility that good rubber fracture strength and abrasion resistance can not be obtained.
- the Mw of the hydrogenated copolymer is preferably 2,000,000 or less, more preferably 1,000,000 or less, and still more preferably 700,000 or less. If the Mw exceeds 2,000,000, the processability tends to decrease.
- weight average molecular weight (Mw) and number average molecular weight (Mn) are gel permeation chromatograph (GPC) (GPC-8000 series manufactured by Tosoh Corp., detector: differential refractometer, column: It can obtain
- GPC gel permeation chromatograph
- the glass transition temperature (Tg) of the hydrogenated copolymer is preferably ⁇ 50 ° C. or higher, more preferably ⁇ 45 ° C. or higher, still more preferably ⁇ 40 ° C. or higher, and particularly preferably ⁇ 35 ° C. or higher. If the Tg is less than ⁇ 50 ° C., the wet grip performance may be deteriorated.
- the Tg of the hydrogenated copolymer is preferably less than -15 ° C, more preferably less than -17.5 ° C, and still more preferably less than -20 ° C. If the Tg is -15 ° C or higher, the fuel economy may be deteriorated.
- the Tg of the hydrogenated copolymer is preferably ⁇ 50 ° C. or higher, and more preferably ⁇ 43 ° C. or higher.
- the Tg of the hydrogenated copolymer is preferably less than -25.degree. C., more preferably less than -30.degree. C., and still more preferably less than -38.degree.
- the Tg of the hydrogenated copolymer is preferably -40 ° C or higher, and more preferably -36 ° C or higher for the glass transition temperature (Tg) of the hydrogenated copolymer.
- the Tg of the hydrogenated copolymer is preferably less than -15 ° C, more preferably less than -19 ° C, and still more preferably less than -23 ° C.
- the glass transition temperature (Tg) of a hydrogenated copolymer is measured by the method of the statement of the below-mentioned Example.
- the styrene content of the hydrogenated styrene butadiene copolymer is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass. % Or more, particularly preferably 20% by mass or more, and most preferably 25% by mass or more. If the styrene content is less than 5% by mass, sufficient grip performance may not be obtained. Further, the styrene content of the hydrogenated styrene butadiene copolymer is preferably 40% by mass or less, more preferably 35% by mass or less.
- the styrene content of the hydrogenated styrene butadiene copolymer is preferably 5% by mass or more, more preferably 8% by mass or more. And preferably 30% by mass or less, more preferably 20% by mass or less.
- styrene content is measured by the method as described in the Example mentioned later.
- the hydrogenated copolymer can be synthesized, for example, by subjecting a polymer obtained by polymerizing an aromatic vinyl compound and a conjugated diene compound to a hydrogenation treatment, and specifically, it can be synthesized by the following method.
- Polymerization method There is no restriction
- the polymerization type may be either batch type or continuous type.
- the monomer concentration in the solvent (the total of styrene and 1,3-butadiene in the case of a styrene butadiene copolymer) is preferably 5% by mass or more, and more preferably 10% by mass or more . If the monomer concentration in the solution is less than 5% by mass, the amount of the copolymer obtained is small, and the cost tends to be high. Moreover, 50 mass% or less is preferable, and, as for the monomer concentration in a solvent, 30 mass% or less is more preferable. If the monomer concentration in the solvent exceeds 50% by mass, the solution viscosity becomes too high, which makes stirring difficult and tends to make polymerization difficult.
- the polymerization initiator is not particularly limited, but an organic lithium compound is preferably used.
- the organic lithium compound is preferably one having an alkyl group having a carbon number of 2 to 20, and examples thereof include ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, tert- Octyllithium, n-decyllithium, phenyllithium, 2-naphthyllithium, 2-butyl-phenyllithium, 4-phenyl-butyllithium, cyclohexyllithium, cyclopentyllithium, reaction product of diisopropenylbenzene with butyllithium, etc.
- n-butyllithium or sec-butyllithium is preferable from the viewpoint of availability
- the polymerization reaction may be carried out in the presence of a compound (R) obtained by mixing at least one of the above-mentioned organic lithium compounds and a compound (B1) having a functional group that interacts with silica.
- a functional group having an interaction with silica can be introduced at the polymerization initiation terminal of the copolymer. This gives a copolymer having a modified starting end.
- reaction refers to an intermolecular force which forms a covalent bond between molecules or which is weaker than the covalent bond (eg, ion-dipole interaction, dipole-dipole interaction, It means to form an electromagnetic force acting between molecules such as hydrogen bond, van der Waals force, etc.
- the “functional group that interacts with silica” refers to a group having at least one atom that interacts with silica, such as a nitrogen atom, a sulfur atom, a phosphorus atom, or an oxygen atom.
- a reaction product of an organic lithium compound and a nitrogen-containing compound such as a secondary amine compound preferred is a reaction product of an organic lithium compound and a nitrogen-containing compound such as a secondary amine compound.
- the nitrogen-containing compound include, for example, dimethylamine, diethylamine, dipropylamine, dibutylamine, dodecamethyleneimine, N, N'-dimethyl-N'-trimethylsilyl-1,6-diaminohexane, piperidine, pyrrolidine, Hexamethyleneimine, heptamethyleneimine, dicyclohexylamine, N-methylbenzylamine, di- (2-ethylhexyl) amine, diallylamine, morpholine, N- (trimethylsilyl) piperazine, N- (tert-butyldimethylsilyl) piperazine, 1,1 3-ditrimethylsilyl-1,3,5-triazinan and the like.
- the compound (R) is prepared by mixing the organic lithium compound and the compound (B1) in advance, and the prepared compound (R) is added to the polymerization system
- the polymerization may be carried out by adding it to Alternatively, the organic lithium compound and the compound (B1) may be added to the polymerization system, and the two may be mixed in the polymerization system to prepare the compound (R) for polymerization.
- Method of anionic polymerization There is no restriction
- the target copolymer such as a styrene butadiene copolymer can be obtained by anionically polymerizing styrene, 1,3-butadiene and the like in the presence of
- the hydrocarbon-based solvent is preferably one having 3 to 8 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, trans-2 -Butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. These may be used alone or in combination of two or more.
- the randomizer refers to the control of the microstructure of the conjugated diene moiety in the copolymer, for example, the 1,2-bond in butadiene, the increase in 3,4-bond in isoprene, etc., or the composition of monomer units in the copolymer It is a compound having an action such as control of distribution, for example, randomization of styrene unit and butadiene unit in a styrene butadiene copolymer.
- the randomizer is not particularly limited, and any one of known compounds generally used conventionally as randomizers can be used.
- potassium salts such as potassium-t-amylate and potassium-t-butoxide, and sodium salts such as sodium-t-amylate can be used.
- One of these randomizers may be used alone, or two or more thereof may be used in combination.
- 0.01 molar equivalent or more is preferable with respect to 1 mol of organic lithium compounds, and, as for the usage-amount of a randomizer, 0.05 molar equivalent or more is more preferable. If the amount of randomizer used is less than 0.01 molar equivalent, the effect of addition is small and it tends to be difficult to randomize. Moreover, 1000 molar equivalent or less is preferable with respect to 1 mol of organic lithium compounds, and, as for the usage-amount of a randomizer, 500 molar equivalent or less is more preferable. When the amount of randomizer used exceeds 1000 molar equivalents, the reaction rate of the monomers changes significantly, and on the contrary, it tends to be difficult to randomize.
- the Tg of the copolymer can be adjusted by adjusting the type and amount of the randomizer. For example, decreasing the amount of tetrahydrofuran can lower the Tg of the copolymer.
- reaction temperature The reaction temperature in the anionic polymerization is not particularly limited as long as the reaction proceeds suitably, but it is preferably -10 ° C to 100 ° C, and more preferably 25 ° C to 70 ° C.
- the polymerization end of the copolymer interacts with the silica.
- Functional groups can be introduced. Thereby, a copolymer in which the polymerization termination end is modified is obtained.
- end means a moiety other than a structure derived from a monomer having a carbon-carbon double bond, which is present at the end of a molecular chain.
- the polymerization initiation end may be unmodified or may be modified.
- the compound (B2) is not particularly limited as long as it is a compound having a functional group capable of interacting with silica and capable of reacting with the polymerization active terminal.
- Preferred specific examples of the compound (B2) include, for example, (I) a compound (B2-1) represented by the following formula (1):
- a 1 has at least one atom selected from the group consisting of a nitrogen atom, a phosphorus atom and a sulfur atom, has no active hydrogen and is a nitrogen atom with respect to R 5 , R 3 and R 4 are hydrocarbyl groups, R 5 is a hydrocarbylene group, and n is an integer of 0 to 2, provided that R 3 and R 4 are hydrocarbyl groups.
- the plurality of R 3 and R 4 may be the same or different.
- the (thio) carbonyl group indicates a carbonyl group and a thiocarbonyl group
- the iso (thio) cyanate group indicates an isocyanate group and an isothiocyanate group.
- a linear or branched alkyl group having 1 to 20 carbon atoms a cycloalkyl group having 3 to 20 carbon atoms, or a 6 to 20 carbon atoms It is preferable that it is an aryl group.
- R 5 is preferably a linear or branched alkanediyl group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.
- n is preferably 0 or 1 from the viewpoint of enhancing the reactivity with the copolymer.
- a 1 has at least one atom selected from the group consisting of a nitrogen atom, a phosphorus atom and a sulfur atom (hereinafter also referred to as a specific atom), and is bonded to R 5 at these specific atoms.
- the specific atom is not bonded to active hydrogen and may be protected by, for example, a trisubstituted hydrocarbylsilyl group.
- active hydrogen refers to a hydrogen atom bonded to an atom other than a carbon atom, preferably to one having a lower bonding energy than the carbon-hydrogen bond of polymethylene.
- a 1 is preferably a group which can be an onium ion by an onium salt generator.
- a 1 for example, a nitrogen-containing group in which two hydrogen atoms of a primary amino group are substituted by two protecting groups, and one hydrogen atom of a secondary amino group is substituted by one protecting group
- a hydrogen-containing group, a tertiary amino group, an imino group, a pyridyl group, a primary phosphino group and two hydrogen atoms are substituted by two protecting groups, and a hydrogen atom of one secondary phosphino group is 1
- Examples include a phosphorus-containing group which is substituted by one protecting group, a tertiary phosphino group, and a sulfur-containing group which is obtained by substituting one hydrogen atom of a thiol group by one protecting group.
- the “protecting group” is a functional group which converts A 1 into a functional group inactive to the polymerization active terminal, and examples thereof include a trisubstituted hydrocarbyl silyl group and the like.
- N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyl for example, as a compound having a nitrogen-containing group or a tertiary amino group, and an alkoxysilyl group.
- Phosphorus-containing group in which two hydrogen atoms of primary phosphino group are substituted by two protecting groups phosphorus-containing group in which one hydrogen atom of secondary phosphino group is substituted by one protecting group, tertiary phosphino group
- Examples of compounds having a sulfur-containing group in which one hydrogen atom of a thiol group is substituted by one protecting group and an alkoxysilyl group include P, P-bis (trimethylsilyl) phosphinopropylmethyldimethoxysilane, P , P-Bis (trimethylsilyl) phosphinopropyltrimethoxysilane, 3-Dimethylphosphinopropyltrimethoxysilane, 3-Dimethylphosphinopropylmethyldimethoxysilane, 3-Diphenylphosphinopropyltrimethoxysilane, 3-Diphenylphosphinopropyl Triethoxysilane, 3- Phen
- the compound (B2-2) is preferably a group in which the group (x2) contains a nitrogen atom which is not bonded to active hydrogen, and as a specific example thereof, a compound having a cyclic ether group is, for example, tetra Epoxyamine compounds such as glycidyl-1,3-bisaminomethylcyclohexane;
- a compound having a (thio) carbonyl group for example, 4-aminoacetophenone such as 4-N, N-dimethylaminobenzophenone; and bis (dihydrocarbylaminoalkyl) such as 1,7-bis (methylethylamino) -4-heptanone Ketones; dihydrocarbylaminoalkyl (meth) acrylates such as 2-dimethylaminoethyl acrylate; hydrocarbyl imidazolidinones such as 1,3-dimethyl-2-imidazolidinone; N-hydrocarbyl pyrrolidone
- Examples of the compound (B2-3) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and p-phenylene di-isocyanate.
- Isocyanate, tris (isocyanatophenyl) thiophosphate, xylene diisocyanate, benzene-1,2,4-triisocyanate, naphthalene-1,2,5,7-tetraisocyanate, 1,4-phenylene diisocyanate Ocyanato etc. can be mentioned.
- the compound (B2) in particular, the compound (B2-1) is preferably used in that the affinity with silica is strong.
- a silane compound (B2-1) in order to adjust the Mooney viscosity of a modified copolymer, a silicon tetrachloride, an epoxy containing compound (for example, tetraglycidyl 1, and a) with a silane compound (B2-1) 3-bisaminomethylcyclohexane etc. may be used.
- the compounds (B2) exemplified above all have the same action in that it is possible to obtain a modified copolymer in which the polymerization termination end is modified. Thus, even those not described in the following examples can be used in the present invention.
- R 6 is a hydrogen atom or a hydrocarbyl group, and a plurality of R 6 may be the same or different.
- a 4 , R 3 , R 5 and n are as described above It is synonymous with A ⁇ 1 >, R ⁇ 3 >, R ⁇ 5 > and n of Formula (1).
- the above-mentioned terminal modification reaction can be performed, for example, as a solution reaction.
- This solution reaction may be carried out using a solution containing unreacted monomers after the completion of the polymerization reaction in the above polymerization step, and the copolymer contained in the solution is isolated and dissolved in a suitable solvent such as cyclohexane. You may go above.
- the terminal modification reaction may be carried out using either a batch system or a continuous system.
- the addition method of the compound (B2) is not particularly limited, and examples thereof include a method of adding all at once, a method of adding dividedly, and a method of adding continuously.
- the amount of the compound (B2) to be used for the terminal modification reaction may be appropriately set according to the type of the compound to be used for the reaction, but is preferably 0. to the metal atom involved in the polymerization reaction of the polymerization initiator. It is 1 molar equivalent or more, more preferably 0.3 molar equivalent or more. By setting the amount to 0.1 molar equivalent or more, the modification reaction can be sufficiently advanced, and the dispersibility of the silica can be suitably improved.
- the temperature of the terminal modification reaction is usually the same as the temperature of the above-mentioned polymerization reaction, preferably -20 to 150 ° C, more preferably 0 to 120 ° C, particularly preferably 20 to 100 ° C. preferable.
- the reaction time of the denaturation reaction is preferably 1 minute to 5 hours, more preferably 2 minutes to 1 hour.
- reaction terminator for example, polar solvents having active protons such as alcohols such as methanol, ethanol and isopropanol or acetic acid, and mixtures thereof, or polar solvents thereof and nonpolar solvents such as hexane and cyclohexane A mixed solution is mentioned.
- the addition amount of the reaction terminator is usually sufficient in the same molar amount or about 2 times the molar amount with respect to the anionic polymerization initiator.
- a coupling agent may be added to the hydrocarbon solution of the copolymer from the initiation of polymerization of the monomer to the recovery of the polymer described later.
- the coupling agent include compounds represented by the following formula (2-1).
- R 1 a ML 4-a (2-1) (In formula (2-1), R 1 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, a represents Represents an integer of 0 to 2)
- silicon tetrachloride methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, tin tetrachloride, methyl trichlorotin, dimethyldichlorotin, trimethylchlorotin, tetramethoxy
- Examples include silane, methyltrimethoxysilane, dimethoxydimethylsilane, methyltriethoxysilane, ethyltrimethoxysilane, dimethoxydiethylsilane, diethoxydimethylsilane, tetraethoxysilane, ethyltriethoxysilane, diethoxydiethylsilane and the like.
- the amount of the coupling agent added is preferably 0.03 mol or more, more preferably 0.05 mol or more, per mol of alkali metal derived from the alkali metal catalyst in order to enhance the processability of the polymer. Moreover, in order to improve low fuel consumption, it is preferably 0.4 mol or less, more preferably 0.3 mol or less.
- Hydrogenation method In the method for producing a hydrogenated copolymer, the above-described copolymer is hydrogenated to obtain a hydrogenated copolymer having a hydrogenation rate of 75 mol% or more.
- the heat resistance is improved.
- the degree of hydrogenation is low, the effect of improving the rubber fracture strength and the wear resistance can not be sufficiently obtained.
- the method of hydrogenation and the reaction conditions there is no particular limitation on the method of hydrogenation and the reaction conditions, and known methods and conditions may be used for the hydrogenation. It is usually carried out in the presence of a hydrogenation catalyst under hydrogen pressure of 20 to 150 ° C. and 0.1 to 10 MPa.
- the hydrogenation rate can be arbitrarily selected by changing the amount of hydrogenation catalyst, hydrogen pressure at the time of hydrogenation reaction, reaction time and the like.
- a hydrogenation catalyst usually, a compound containing any of Group 4-11 metals of the periodic table of the elements can be used.
- a compound containing Ti, V, Co, Ni, Zr, Ru, Rh, Pd, Hf, Re, and Pt atoms can be used as a hydrogenation catalyst.
- More specific hydrogenation catalysts include metallocene compounds such as Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh and Re; carbons such as Pd, Ni, Pt, Rh and Ru; A supported heterogeneous catalyst supported on a carrier such as silica, alumina or diatomaceous earth; a homogeneous Ziegler catalyst in which an organic salt of a metal element such as Ni or Co or an acetylacetone salt is combined with a reducing agent such as organoaluminum; Examples thereof include organic metal compounds or complexes such as Ru and Rh; fullerenes having absorbed hydrogen; and carbon nanotubes.
- metallocene compounds such as Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh and Re
- carbons such as Pd, Ni, Pt, Rh and Ru
- a supported heterogeneous catalyst supported on a carrier such as silica, alumina or diatomaceous earth
- metallocene compounds containing any of Ti, Zr, Hf, Co and Ni are preferable in that they can be hydrogenated in a homogeneous system in an inert organic solvent. Furthermore, metallocene compounds containing any of Ti, Zr and Hf are preferable.
- a hydrogenation catalyst in which a titanocene compound and an alkyllithium are reacted is preferable because it is an inexpensive and industrially particularly useful catalyst.
- these hydrogenation catalysts can be used individually by 1 type or in combination of 2 or more types.
- the content of the hydrogenated copolymer in 100% by mass of the rubber component is 75% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass. is there.
- the content of the hydrogenated copolymer is less than 75% by mass, it is difficult to obtain the effect of improving the rubber fracture strength and the wear resistance (particularly, the rubber fracture strength).
- the hydrogenated copolymer is a hydrogenated styrene butadiene copolymer
- the content of the hydrogenated styrene butadiene copolymer in 100 mass% of the rubber component is preferably 90 mass% or more, more preferably Is at least 95% by mass, more preferably 100% by mass.
- NR is not particularly limited, and, for example, SIR20, RSS # 3, TSR20, etc., which are common in the tire industry, can be used.
- the content of NR in 100% by mass of the rubber component is preferably 5% by mass or more.
- the content of the NR is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.
- BR When BR is contained as a rubber component, it is not particularly limited as BR, for example, BR with high cis content BR such as BR1220 manufactured by Nippon Zeon Co., Ltd., BR130B manufactured by Ube Industries, Ltd., BR150B, Ube Industries, Ltd. And BR containing syndiotactic polybutadiene crystals such as VCR412 and VCR617 manufactured by Among them, the cis content of BR is preferably 90% by mass or more because abrasion resistance is good.
- the content of BR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less.
- the total content of NR and BR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less.
- the rubber composition in the present invention is characterized by containing carbon black and silica as fillers.
- the carbon black contained in the rubber composition in the present invention includes carbon black such as SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF and ECF (furnace carbon (furnace carbon) Black); acetylene black (acetylene carbon black); thermal blacks such as FT and MT (thermal carbon black); channel blacks such as EPC, MPC and CC (channel carbon black); graphite and the like. These can be used alone or in combination of two or more.
- the nitrogen adsorption specific surface area (N 2 SA) of carbon black is usually 5 to 200 m 2 / g.
- the lower limit is preferably 50 m 2 / g, and more preferably 80 m 2 / g.
- the upper limit is preferably 150 m 2 / g, more preferably 120 m 2 / g.
- the dibutyl phthalate (DBP) absorption amount of carbon black is usually 5 to 300 ml / 100 g, and the lower limit is preferably 80 ml / 100 g and the upper limit is preferably 180 ml / 100 g.
- the amount of N 2 SA or DBP absorbed by carbon black is less than the lower limit of the above range, the reinforcing effect tends to be small and the abrasion resistance tends to decrease, and if it exceeds the upper limit of the above range, the dispersibility is poor and hysteresis loss increases. There is a tendency for fuel economy to decrease.
- the nitrogen adsorption specific surface area (N 2 SA) of carbon black is usually 5 to 200 m 2 / g.
- the lower limit is preferably 50 m 2 / g, more preferably 70 m 2 / g, and still more preferably 90 m 2 / g.
- the upper limit is 150 meters 2 / g, and more preferably 130m 2 / g.
- the dibutyl phthalate (DBP) absorption amount of carbon black is usually 5 to 300 ml / 100 g, and the lower limit is preferably 80 ml / 100 g and the upper limit is preferably 180 ml / 100 g.
- the nitrogen adsorption specific surface area is measured according to ASTM D 4820-93, and the DBP absorption is measured according to ASTM D 2414-93.
- the content of carbon black is 3 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 3 parts by mass, sufficient reinforcement may not be obtained.
- the content of carbon black is preferably 60 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 15 parts by mass or less. If the amount is more than 60 parts by mass, fuel economy tends to deteriorate.
- the content of carbon black is preferably 5 parts by mass or more, more preferably 10 parts by mass with respect to 100 parts by mass of the rubber component. It is at least a part by mass, more preferably at least 20 parts by mass, particularly preferably at least 30 parts by mass.
- the content of carbon black is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 40 parts by mass or less.
- the silica is not particularly limited, and examples thereof include dry method silica (anhydrous silica), wet method silica (hydrous silica) and the like, and wet method silica is preferable because it has many silanol groups.
- the nitrogen adsorption specific surface area (N 2 SA) of the silica is preferably 40 m 2 / g or more, more preferably 45 m 2 / g or more, still more preferably 55 m 2 / g or more, particularly preferably 60 m 2 / g or more, more particularly Preferably it is 100 m 2 / g or more, most preferably 150 m 2 / g or more. If it is less than 40 m 2 / g, the abrasion resistance and the rubber breaking strength may be deteriorated.
- the N 2 SA of the silica is preferably 400 meters 2 / g or less, more preferably 350 meters 2 / g or less, more preferably 300 meters 2 / g or less, particularly preferably 270 meters 2 / g or less, and most preferably 220 m 2 / g or less. If it exceeds 400 m 2 / g, it is difficult to disperse the silica, and the fuel economy may be deteriorated.
- the nitrogen adsorption specific surface area of silica is a value measured by the BET method according to ASTM D3037-81.
- the content of silica is 1 part by mass or more, preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 45 parts by mass or more with respect to 100 parts by mass of the rubber component.
- the content of the silica is 200 parts by mass or less, preferably 150 parts by mass or less, more preferably 120 parts by mass or less, still more preferably 100 parts by mass or less, particularly preferably 80 parts by mass or less.
- the content of silica is preferably 10 parts by mass or more, more preferably 20 parts by mass with respect to 100 parts by mass of the rubber component. Part or more. Further, the content of silica is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, particularly preferably 40 parts by mass or less, and most preferably 30 parts by mass or less.
- the total content of silica and carbon black in the rubber composition is preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component,
- the amount is more preferably 20 parts by mass or more, still more preferably 40 parts by mass or more, and particularly preferably 50 parts by mass or more. If the amount is less than 10 parts by mass, sufficient reinforcing properties may not be obtained.
- the total content is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less. If it exceeds 150 parts by mass, sufficient fuel economy may not be obtained.
- the content (carbon ratio) of carbon black in 100% by mass of the filler of the rubber composition is preferably 50% by mass or more, more preferably It is 55 mass% or more, More preferably, it is 57 mass% or more.
- the effect of the present invention is acquired more suitably as carbon ratio is 50 mass% or more, and not only rubber fracture strength and abrasion resistance but also low fuel consumption can be improved favorably.
- the carbon ratio is less than 50% by mass, the fuel consumption tends to deteriorate.
- the carbon ratio is preferably 70% by mass or less, more preferably 67% by mass or less, and still more preferably 65% by mass or less. If the carbon ratio exceeds 70% by mass, fuel economy may be deteriorated.
- the rubber composition in the present invention may further contain fillers other than carbon black and silica.
- the filler is added to the rubber composition for the purpose of reinforcing the rubber, and for example, calcium carbonate, mica such as sericite, aluminum hydroxide, magnesium oxide, magnesium hydroxide, clay, Examples thereof include white fillers such as talc, alumina, titanium oxide and mica. These fillers may be used in combination of two or more.
- the total content of silica and carbon black in 100% by mass of the filler is preferably 80% by mass or more, and more preferably 90% by mass or more, because the effects of the present invention are more suitably obtained. 100 mass% may be sufficient.
- the rubber composition in the present invention preferably uses a silane coupling agent in combination with silica.
- silane coupling agent conventionally known ones can be used.
- silane coupling agents may be used alone or in combination of two or more.
- sulfide-based silane coupling agents are preferable from the viewpoint of coupling effect by a silane coupling agent, processability, and cost, and bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) Disulfide is more preferred.
- 3 mass parts or more are preferable with respect to 100 mass parts of silicas, and, as for content of a silane coupling agent, 5 mass parts or more are more preferable. If the amount is less than 3 parts by mass, the coupling effect is insufficient, high silica dispersion can not be obtained, and the effect of the present invention tends not to be sufficiently obtained. Therefore, there is a possibility that fuel economy and rubber destructive strength may fall. Moreover, 15 mass parts or less are preferable with respect to 100 mass parts of silicas, and, as for content of a silane coupling agent, 10 mass parts or less are more preferable. If it exceeds 15 parts by mass, excess silane coupling agent may remain, which may lead to deterioration of the processability and the fracture characteristics of the obtained rubber composition.
- the content of the silane coupling agent is preferably 1 part by mass or more, and 2 parts by mass with respect to 100 parts by mass of silica.
- the above is more preferable, 6 parts by mass or more is further preferable, and 10 parts by mass or more is particularly preferable.
- 20 mass parts or less are preferable with respect to 100 mass parts of silicas, and, as for content of a silane coupling agent, 15 mass parts or less are more preferable.
- a vulcanizing agent such as sulfur, etc .
- thiazole-based vulcanization accelerator such as sulfur, etc .
- thiuram-based vulcanization accelerator such as thiuram-based vulcanization accelerator
- sulfenamide-based vulcanization accelerator such as guanidine-based vulcanization acceleration Accelerators
- thickeners such as thickeners
- vulcanization activators such as stearic acid and zinc oxide
- organic peroxides such as extender oils (oils) and lubricants
- processing aids such as extender oils (oils) and lubricants
- additive can be used.
- the extender oil oil
- aromatic mineral oil viscosity specific gravity constant (VGC value) 0.900 to 1.049
- naphthenic mineral oil VG. C. value 0. 850 to 0.899
- paraffinic mineral oil V.G.C. value 0.790 to 0.849
- 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 extender oil is preferably 20% by mass or more.
- thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole, dibenzothiazyldisulfide, N-cyclohexyl-2-benzothiazylsulfenamide, etc .; tetramethylthiuram monosulfide, tetramethylthiuram disulfide N-cyclohexyl-2-benzothiazolesulfenamide, N-t-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N- Sulfenamide-based vulcanization accelerators such as oxyethylene-2-benzothiazole sulfenamide, N, N'-diisopropyl-2-benzothiazole sulfenamide, etc .; such as diphenyl guanidine, diorto tolyl guanidine, ortho tolyl biguanidine and the like Guani It can be
- sulfenamide-based vulcanization accelerators are preferable, and N-cyclohexyl-2-benzothiazolesulfenamide is more preferable, because the effects of the present invention are more suitably obtained. Furthermore, it is also preferable to use a guanidine-based vulcanization accelerator in combination.
- the amount of the vulcanization accelerator used is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass with respect to 100 parts by mass of the rubber component.
- the vulcanizing agent is not particularly limited, but sulfur can be suitably used.
- the content of sulfur is preferably 0.5 to 5 parts by mass, more preferably 1 to 3 parts by mass with respect to 100 parts by mass of the rubber component. Thereby, the effect of the present invention is more suitably acquired.
- the rubber composition in the present invention is produced by a general method. That is, it can manufacture by the method etc. which knead
- the tan ⁇ peak temperature (Tg) of the rubber composition (after vulcanization) in the present invention to less than -16 ° C (preferably less than -18 ° C, more preferably less than -20 ° C), good performance on snow and ice is obtained. Since it is possible to maintain low fuel consumption, the effects of the present invention can be suitably obtained, and a tire used on a road surface on snow and ice, particularly a studless tire that can be used in winter as well without replacing the tire in summer It can be suitably used as a rubber composition for producing an all-season tire.
- Tg tan ⁇ peak temperature
- the lower limit of the tan ⁇ peak temperature (Tg) of the rubber composition (after vulcanization) in the present invention is not particularly limited, but is preferably -35 ° C or more, more preferably -30 ° C or more. If it is less than -35 ° C., the wet grip performance may be deteriorated.
- tan-delta peak temperature (Tg) is a value obtained by the measuring method as described in the Example mentioned later.
- the tan ⁇ peak temperature (Tg) of the rubber composition can be adjusted to less than ⁇ 16 ° C. by adjusting the type of the hydrogenated copolymer and the compounding ratio of the rubber composition.
- the rubber composition has a low tan ⁇ peak temperature (Tg) by (1) reducing the styrene content of the hydrogenated copolymer, (2) increasing the NR content, (3) increasing the BR content, etc. can do.
- the tan ⁇ peak temperature (Tg) of the rubber composition (after vulcanization) in the present invention is not particularly limited, but is preferably less than -4 ° C, more preferably less than -8 ° C, still more preferably -10. It is less than ° C. If the temperature is -4 ° C or higher, fuel economy and wear resistance may be deteriorated.
- the tan ⁇ peak temperature (Tg) of the rubber composition can be adjusted to ⁇ 16 ° C. or more by adjusting the kind of the hydrogenated copolymer and the compounding ratio of the rubber composition.
- the tan ⁇ peak temperature (Tg) of the rubber composition can be increased by (1) increasing the styrene content of the hydrogenated copolymer, (2) reducing the blending amount of BR, or the like.
- the rubber composition in the present invention can be used for each component (tread, sidewall, carcass, belt, bead, etc.) of a tire, and is suitably used as a tread of a tire among others.
- a tread of a tire In the case of a two-layer tread, it is composed of a surface layer (cap tread) and an inner layer (base tread).
- the tread of the multilayer structure is manufactured by a method of bonding sheet-like ones in a predetermined shape, or a method of charging two or more extruders and forming two or more layers at the outlet of the extruder. Can.
- the pneumatic tire of the present invention is manufactured by the usual method using the above rubber composition. That is, a rubber composition containing a hydrogenated copolymer and, if necessary, a rubber composition blended with the above-mentioned various compounding agents is extruded at the unvulcanized stage according to the shape of each tire member such as a tread, and the like
- An unvulcanized tire is formed by molding the tire member of the present invention on a tire molding machine according to a conventional method. By heating and pressing this unvulcanized tire in a vulcanizer, the pneumatic tire of the present invention is obtained.
- the pneumatic tire of the present invention is suitably used as a passenger car tire, a truck / bus tire, a motorcycle tire, a competition tire, etc.
- a passenger car tire more specifically, a studless tire, an all season tire, summer
- Tires and truck and bus tires.
- THF anhydrous tetrahydrofuran n-hexane manufactured by Kanto Chemical Co., Ltd .: styrene manufactured by Kanto Chemical Co., Ltd .: butadiene manufactured by Kanto Chemical Co., Ltd. butadiene: 1,3-butadiene
- TMEDA manufactured by Tokyo Chemical Industry Co., Ltd .: Kanto Chemical Co., Ltd.
- N, N, N ', N'- tetramethylethylenediamine n-butyllithium solution 1.6 M n-butyllithium hexane solution manufactured by Kanto Chemical Co., Ltd.
- the H 1 -NMR was measured at 25 ° C. using a JEOL JNM-A 400 NMR apparatus, and the phenyl proton and 4.9 to 5.4 ppm butadiene based on 6.5 to 7.2 ppm of styrene units determined from the spectrum
- the styrene content was determined from the ratio of vinyl protons based on units.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) of the copolymer were determined by gel permeation chromatography (GPC) (GPC-8000 series manufactured by Tosoh Corp., detector: differential refractometer, column: Tosoh (stock It calculated
- GPC gel permeation chromatography
- Mw and Mn were measured before carrying out the modifying treatment. This is because when the copolymer having a modifying group is measured, the modifying group and the silica gel of the column interact with each other and accurate Mw and Mn can not be obtained.
- the glass transition temperature (Tg) should be measured according to JIS K 7121, using a differential scanning calorimeter (Q200) manufactured by TA Instruments Japan, while raising the temperature at a heating rate of 10 ° C./min. It calculated
- copolymer (A-1) had a weight average molecular weight (Mw) of 490,000 and a styrene content of 30% by mass.
- Synthesis Example A-2 (Synthesis of copolymer (A-2): hydrogenation rate 60 mol%, hydrogenated SBR)
- a copolymer (A-2) was obtained in the same manner as the copolymer (A-1) except that the obtained polymer was hydrogenated. That is, after the polymerization conversion reaction in the copolymer (A-1), the alcohol is not added to stop the polymerization reaction, and then it is stirred for 20 minutes while supplying hydrogen gas at a pressure of 0.4 MPa-gauge, The reaction was carried out with the polymer terminal lithium of to give lithium hydride.
- the hydrogen gas supply pressure was 0.7 MPa-gauge, the reaction temperature was 90 ° C., and hydrogenation was performed using a catalyst consisting mainly of titanocene dichloride.
- the reaction temperature is brought to normal temperature when hydrogen absorption reaches the target hydrogen addition rate, hydrogen pressure is returned to normal pressure, hydrogen pressure is removed from the reaction vessel, the reaction solution is stirred into water, and the solvent is steamed. Removal by stripping gave a copolymer (A-2).
- the hydrogenation rate of the obtained copolymer (A-2) was 60 mol%, and the weight average molecular weight (Mw) was 450,000.
- Synthesis Example A-3 (Synthesis of copolymer (A-3): hydrogenation ratio 80 mol%, hydrogenated SBR)
- a copolymer (A-3) was obtained by the same formulation as the copolymer (A-2), except that the cumulative amount of hydrogen suction was adjusted so as to obtain a target hydrogenation rate.
- the hydrogenation rate of the resulting copolymer (A-3) was 80 mol%, and the weight average molecular weight (Mw) was 480,000.
- Synthesis Example A-4 (Synthesis of copolymer (A-4): hydrogenation ratio 95 mol%, hydrogenated SBR)
- a copolymer (A-4) was obtained by the same formulation as the copolymer (A-2), except that the cumulative amount of hydrogen suction was adjusted so as to obtain a target hydrogenation rate.
- the hydrogenation rate of the resulting copolymer (A-4) was 95 mol%, and the weight average molecular weight (Mw) was 450,000.
- Synthesis Example A-5 (Synthesis of Copolymer (A-5): Hydrogenation ratio 95 mol%, Hydrogenated modified SBR) Add 2000 ml of n-hexane, 60 g of styrene, 140 g of 1,3-butadiene, 0.93 g of TMEDA, and 0.45 mmol of n-butyllithium to a heat-resistant reaction vessel fully purged with nitrogen, and stir at 50 ° C for 5 hours to carry out the polymerization reaction went. Thereafter, 0.15 mol of an amine modifier was added, and the mixture was stirred at 0 ° C. for 1 hour.
- a copolymer (A-5) was obtained in the same manner as the copolymer (A-2) except that the cumulative amount of hydrogen suction was adjusted.
- the hydrogenation rate of the obtained copolymer (A-5) was 95 mol%, and the weight average molecular weight (Mw) before modification was 440,000.
- Synthesis Example B-1 (Synthesis of Copolymer (B-1): Hydrogen Addition Rate 0 mol%, SBR) 2000 ml of n-hexane, 60 g of styrene, 140 g of butadiene, 1.75 g of THF, and 0.45 mmol of n-butyllithium were added to a heat-resistant reaction vessel sufficiently substituted with nitrogen, and stirred at 50 ° C. for 5 hours to carry out a polymerization reaction. Thereafter, alcohol was added to stop the reaction, and 1 g of 2,6-di-tert-butyl-p-cresol was added to the reaction solution, followed by reprecipitation purification to obtain a copolymer (B-1).
- the obtained copolymer (B-1) had a weight average molecular weight (Mw) of 490,000 and a styrene content of 30% by mass.
- Synthesis Example B-2 (Synthesis of copolymer (B-2): hydrogenation rate 60 mol%, hydrogenated SBR)
- a copolymer (B-2) was obtained in the same manner as the copolymer (B-1) except that the obtained polymer was hydrogenated. That is, after the polymerization conversion reaction in the copolymer (B-1), the alcohol is not added to stop the polymerization reaction, and then it is stirred for 20 minutes while supplying hydrogen gas at a pressure of 0.4 MPa-gauge, The reaction was carried out with the polymer terminal lithium of to give lithium hydride.
- the hydrogen gas supply pressure was 0.7 MPa-gauge, the reaction temperature was 90 ° C., and hydrogenation was performed using a catalyst consisting mainly of titanocene dichloride.
- the reaction temperature is brought to normal temperature when hydrogen absorption reaches the target hydrogen addition rate, hydrogen pressure is returned to normal pressure, hydrogen pressure is removed from the reaction vessel, the reaction solution is stirred into water, and the solvent is steamed. Removal by stripping gave a copolymer (B-2).
- the hydrogenation rate of the obtained copolymer (B-2) was 60 mol%, and the weight average molecular weight (Mw) was 450,000.
- Synthesis Example B-3 (Synthesis of copolymer (B-3): hydrogenation ratio 80 mol%, hydrogenated SBR)
- a copolymer (B-3) was obtained by the same formulation as the copolymer (B-2) except that the cumulative amount of hydrogen suction was adjusted so as to obtain a target hydrogenation rate.
- the hydrogenation rate of the obtained copolymer (B-3) was 80 mol%, and the weight average molecular weight (Mw) was 480,000.
- Synthesis Example B-4 (Synthesis of Copolymer (B-4): Hydrogenation rate 95 mol%, Hydrogenated SBR)
- a copolymer (B-4) was obtained by the same formulation as the copolymer (B-2) except that the cumulative amount of hydrogen suction was adjusted so as to obtain a target hydrogenation rate.
- the hydrogenation rate of the obtained copolymer (B-4) was 95 mol%, and the weight average molecular weight (Mw) was 450,000.
- Synthesis Example B-5 (Synthesis of Copolymer (B-5): Hydrogenation ratio 95 mol%, Hydrogenated modified SBR) Add 2000 ml of n-hexane, 60 g of styrene, 140 g of 1,3-butadiene, 0.93 g of TMEDA, and 0.45 mmol of n-butyllithium to a heat-resistant reaction vessel fully purged with nitrogen, and stir at 50 ° C for 5 hours to carry out the polymerization reaction went. Thereafter, 0.15 mol of an amine modifier was added, and the mixture was stirred at 0 ° C. for 1 hour.
- a copolymer (B-5) was obtained by the same formulation as the copolymer (B-2) except that the cumulative amount of hydrogen suction was adjusted.
- the hydrogenation rate of the obtained copolymer (5) was 95 mol%, and the weight average molecular weight (Mw) before modification was 440,000.
- Synthesis Example C-1 (Synthesis of Copolymer (C-1): Hydrogen Addition Rate 0 mol%, SBR) Add 2000 ml of n-hexane, 20 g of styrene, 180 g of 1,3-butadiene, 15.0 g of THF and 0.45 mmol of n-butyllithium to a heat-resistant reaction vessel fully purged with nitrogen, and stir at 50 ° C for 5 hours to carry out the polymerization reaction went. Thereafter, alcohol was added to stop the reaction, and 1 g of 2,6-di-tert-butyl-p-cresol was added to the reaction solution, followed by reprecipitation purification to obtain a copolymer (C-1).
- the obtained copolymer (C-1) had a weight average molecular weight (Mw) of 480,000 and a styrene content of 10% by mass.
- Synthesis Example C-2 (Synthesis of Copolymer (C-2): Hydrogenation rate 0 mol%, Hydrogenated SBR) Add 2000 ml of n-hexane, 20 g of styrene, 180 g of 1,3-butadiene, 1.75 g of THF and 0.45 mmol of n-butyllithium to a heat-resistant reaction vessel fully purged with nitrogen, and stir at 50 ° C for 5 hours to carry out the polymerization reaction went. Thereafter, alcohol was added to stop the reaction, and 1 g of 2,6-di-tert-butyl-p-cresol was added to the reaction solution, followed by reprecipitation purification to obtain a copolymer (C-2).
- the obtained copolymer (C-2) had a weight average molecular weight (Mw) of 490,000 and a styrene content of 10% by mass.
- Synthesis Example C-3 (Synthesis of copolymer (C-3): hydrogenation rate 60 mol%, hydrogenated SBR)
- a copolymer (C-3) was obtained in the same manner as the copolymer (C-2) except that the obtained polymer was hydrogenated. That is, after the polymerization conversion reaction in the copolymer (C-2), the alcohol is not added to stop the polymerization reaction, and then it is stirred for 20 minutes while supplying hydrogen gas at a pressure of 0.4 MPa-gauge, The reaction was carried out with the polymer terminal lithium of to give lithium hydride.
- the hydrogen gas supply pressure was 0.7 MPa-gauge, the reaction temperature was 90 ° C., and hydrogenation was performed using a catalyst consisting mainly of titanocene dichloride.
- the reaction temperature is brought to normal temperature when hydrogen absorption reaches the target hydrogen addition rate, hydrogen pressure is returned to normal pressure, hydrogen pressure is removed from the reaction vessel, the reaction solution is stirred into water, and the solvent is steamed. By removing by stripping, a hydrogenated copolymer was obtained.
- the hydrogenation rate of the obtained copolymer (C-3) was 60 mol%, and the weight average molecular weight (Mw) was 450,000.
- Synthesis Example C-4 (Synthesis of copolymer (C-4): hydrogenation rate 80 mol%, hydrogenated SBR)
- a copolymer (C-4) was obtained by the same formulation as the copolymer (C-3), except that the cumulative amount of suction of hydrogen was adjusted so as to obtain a target hydrogenation rate.
- the hydrogenation rate of the obtained copolymer (C-4) was 80 mol%, and the weight average molecular weight (Mw) was 480,000.
- Synthesis Example C-5 (Synthesis of Copolymer (C-5): Hydrogenation rate 95 mol%, Hydrogenated SBR)
- a copolymer (C-5) was obtained by the same formulation as the copolymer (C-3), except that the cumulative amount of hydrogen suction was adjusted so as to obtain a target hydrogenation rate.
- the hydrogenation rate of the obtained copolymer (C-5) was 95 mol%, and the weight average molecular weight (Mw) was 450,000.
- Synthesis Example C-6 (Synthesis of Copolymer (C-6): Hydrogenation ratio 95 mol%, Hydrogenated modified SBR) Add 2000 ml of n-hexane, 20 g of styrene, 180 g of 1,3-butadiene, 0.93 g of TMEDA, and 0.45 mmol of n-butyllithium to a heat-resistant reaction vessel fully purged with nitrogen, and stir at 50 ° C for 5 hours to carry out the polymerization reaction went. Thereafter, 0.15 mol of an amine modifier was added, and the mixture was stirred at 0 ° C. for 1 hour.
- a copolymer (C-6) was obtained by the same formulation as the copolymer (C-2) except that the cumulative amount of hydrogen suction was adjusted.
- the hydrogenation rate of the obtained copolymer (C-6) was 95 mol%, and the weight average molecular weight (Mw) before modification was 440,000.
- Synthesis Example D-1 (Synthesis of copolymer (D-1): Hydrogenation ratio 0 mol%, SBR) Add 2000 ml of n-hexane, 70 g of styrene, 130 g of 1,3-butadiene, 12.5 g of THF and 0.45 mmol of n-butyllithium to a heat-resistant reaction vessel fully purged with nitrogen, and stir at 50 ° C for 5 hours for polymerization reaction went. Thereafter, alcohol was added to stop the reaction, and 1 g of 2,6-di-tert-butyl-p-cresol was added to the reaction solution, followed by reprecipitation purification to obtain a copolymer (D-1). The obtained copolymer (D-1) had a weight average molecular weight (Mw) of 490,000 and a styrene content of 35% by mass.
- Mw weight average molecular weight
- Synthesis Example D-2 (Synthesis of Copolymer (D-2): Hydrogenation rate 60 mol%, SBR)
- a copolymer (D-2) was obtained in the same manner as the copolymer (D-1) except that the obtained polymer was hydrogenated. That is, after the polymerization conversion reaction in the copolymer (D-1), the alcohol is not added to stop the polymerization reaction, and then it is stirred for 20 minutes while supplying hydrogen gas at a pressure of 0.4 MPa-gauge, The reaction was carried out with the polymer terminal lithium of to give lithium hydride.
- the hydrogen gas supply pressure was 0.7 MPa-gauge, the reaction temperature was 90 ° C., and hydrogenation was performed using a catalyst consisting mainly of titanocene dichloride.
- the reaction temperature is brought to normal temperature when hydrogen absorption reaches the target hydrogen addition rate, hydrogen pressure is returned to normal pressure, hydrogen pressure is removed from the reaction vessel, the reaction solution is stirred into water, and the solvent is steamed. Removal by stripping gave a copolymer (D-2).
- the hydrogenation rate of the obtained copolymer (D-2) was 60 mol%, and the weight average molecular weight (Mw) was 450,000.
- Synthesis Example D-3 (Synthesis of copolymer (D-3): hydrogenation ratio 80 mol%, hydrogenated SBR)
- a copolymer (D-3) was obtained by the same formulation as the copolymer (D-2), except that the cumulative amount of hydrogen suction was adjusted so as to obtain a target hydrogenation rate.
- the hydrogenation rate of the resulting copolymer (D-3) was 80 mol%, and the weight average molecular weight (Mw) was 480,000.
- Synthesis Example D-4 (Synthesis of copolymer (D-4): hydrogenation rate 95 mol%, hydrogenated SBR)
- a copolymer (D-4) was obtained by the same formulation as the copolymer (D-2), except that the cumulative amount of suction of hydrogen was adjusted so as to obtain a target hydrogenation rate.
- the hydrogenation rate of the obtained copolymer (D-4) was 95 mol%, and the weight average molecular weight (Mw) was 450,000.
- Synthesis Example D-5 (Synthesis of Copolymer (D-5): Hydrogenation ratio 95 mol%, Hydrogenated modified SBR) Add 2000 ml of n-hexane, 70 g of styrene, 130 g of 1,3-butadiene, 0.93 g of TMEDA, and 0.45 mmol of n-butyllithium to a heat-resistant reaction vessel fully purged with nitrogen, and stir at 50 ° C for 5 hours to carry out the polymerization reaction went. Thereafter, 0.15 mol of an amine modifier was added, and the mixture was stirred at 0 ° C. for 1 hour.
- copolymer (D-5) was obtained in the same manner as copolymer (D-2) except that the cumulative amount of hydrogen suction was adjusted.
- the hydrogenation rate of the obtained copolymer (D-5) was 95 mol%.
- the weight average molecular weight (Mw) was 440,000.
- Copolymers (A-1) to (A-5), (B-1) to (B-5), (C-1) to (C-6), (D-1) to (D-5) Synthetic natural rubber by the above method: TSR20 Butadiene rubber: Ubepol BR150B (cis content: 97% by mass) manufactured by Ube Industries, Ltd.
- Stearic acid Beads manufactured by NOF Corporation, Ltd. beads stearic acid zinc oxide, manufactured by NOF Corporation, and zinc oxide No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd.
- Sulfur Powdered sulfur vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd. (1): Succinol CZ (N-cyclohexyl-2-benzothiazolylsulfenamide) manufactured by Sumitomo Chemical Co., Ltd.
- Vulcanization accelerator (2) Succinol D (1,3-diphenylguanidine) manufactured by Sumitomo Chemical Co., Ltd.
- Example and Comparative Example Materials other than sulfur and a vulcanization accelerator are kneaded at 150 ° C. for 5 minutes using a 1.7 L Banbury mixer manufactured by Kobe Steel, Ltd. according to the contents of the formulations shown in Tables 5 to 8 and mixed. I got a paste. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product, and kneaded using an open roll for 5 minutes at 80 ° C. to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was press vulcanized with a 0.5 mm-thick mold at 170 ° C. for 20 minutes to obtain a vulcanized rubber composition.
- Tables 5-8 The 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. using a spectrometer manufactured by Uejima Mfg.
- the standard composition was indexed as 100 for the value of the reciprocal of tan ⁇ . The larger the value, the smaller the rolling resistance and the better the fuel economy. In addition, when the index was 98 or more, it was judged to be good.
- Test ⁇ peak temperature Tables 7, 8 From the obtained vulcanized rubber composition, a test piece of a predetermined size is prepared, and an initial strain of 10%, a dynamic strain of 0.5%, a frequency of 10 Hz and the like using a visco-elastic spectrometer VES manufactured by Iwamoto Manufacturing Co., Ltd. Measure the temperature dispersion curve of tan ⁇ at a temperature of ⁇ 100 to 100 ° C. under the condition of amplitude ⁇ 0.25% and heating rate 2 ° C./min, and the temperature corresponding to the largest tan ⁇ value in the temperature distribution curve is tan ⁇ peak temperature And
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Tires In General (AREA)
Abstract
Description
なお、水素添加率は、H1-NMRを測定して得られたスペクトルの不飽和結合部のスペクトル減少率から計算することができる。
同様の理由から、本発明の空気入りタイヤをスタッドレスタイヤ又はオールシーズンタイヤとする場合、水添共重合体のTgは、-50℃以上が好ましく、-43℃以上がより好ましい。また、水添共重合体のTgは、-25℃未満が好ましく、-30℃未満がより好ましく、-38℃未満が更に好ましい。
本発明の空気入りタイヤを夏用タイヤとする場合、水添共重合体のTgは、水添共重合体のガラス転移温度(Tg)は、-40℃以上が好ましく、-36℃以上がより好ましく、-33℃以上が更に好ましく、-29℃以上が特に好ましい。また、水添共重合体のTgは、-15℃未満が好ましく、-19℃未満がより好ましく、-23℃未満が更に好ましい。
なお、水添共重合体のガラス転移温度(Tg)は、後述の実施例の記載の方法により測定される。
同様の理由から、本発明の空気入りタイヤをスタッドレスタイヤ又はオールシーズンタイヤとする場合、水添スチレンブタジエン共重合体のスチレン含有量は、好ましくは5質量%以上、より好ましくは8質量%以上であり、また、好ましくは30質量%以下、より好ましくは20質量%以下である。
なお、スチレン含有量は、後述する実施例に記載の方法により測定される。
(重合方法)
芳香族ビニル化合物及び共役ジエン化合物の共重合体の重合方法については特に制限はなく、溶液重合法、気相重合法、バルク重合法のいずれも用いることができるが、特に溶液重合法が好ましい。また、重合形式は、回分式及び連続式のいずれであってもよい。
アニオン重合を行う場合、重合開始剤としては特に制限はないが、有機リチウム化合物が好ましく用いられる。前記有機リチウム化合物としては、炭素数2~20のアルキル基を有するものが好ましく、例えばエチルリチウム、n-プロピルリチウム、イソプロピルリチウム、n-ブチルリチウム、sec-ブチルリチウム、tert-ブチルリチウム、tert-オクチルリチウム、n-デシルリチウム、フェニルリチウム、2-ナフチルリチウム、2-ブチルーフェニルリチウム、4-フェニル-ブチルリチウム、シクロヘキシルリチウム、シクロペンチルリチウム、ジイソプロペニルベンゼンとブチルリチウムとの反応生成物などが挙げられるが、これらの中で、入手容易性、安全性等の観点からn-ブチルリチウムまたはsec-ブチルリチウムが好ましい。
前記重合開始剤を用いてアニオン重合し、共重合体を製造する方法としては、特に制限はなく、従来公知の方法を用いることができる。
具体的には、反応に不活性な有機溶剤、例えば脂肪族、脂環族、芳香族炭化水素化合物などの炭化水素系溶剤中において、例えばブチルリチウムを重合開始剤とし、必要に応じてランダマイザーの存在下でスチレン及び1,3-ブタジエン等をアニオン重合させることにより、スチレンブタジエン共重合体等の目的の共重合体を得ることができる。
前記炭化水素系溶剤としては、炭素数3~8のものが好ましく、例えばプロパン、n-ブタン、イソブタン、n-ペンタン、イソペンタン、n-ヘキサン、シクロヘキサン、プロペン、1-ブテン、イソブテン、トランス-2-ブテン、シス-2-ブテン、1-ペンテン、2-ペンテン、1-ヘキセン、2-ヘキセン、ベンゼン、トルエン、キシレン、エチルベンゼンなどを挙げることができる。これらは単独で用いてもよく、2種以上を混合して用いてもよい。
また、前記ランダマイザーとは、共重合体中の共役ジエン部分のミクロ構造制御、例えばブタジエンにおける1,2-結合、イソプレンにおける3,4-結合の増加など、あるいは共重合体におけるモノマー単位の組成分布の制御、例えばスチレンブタジエン共重合体におけるスチレン単位、ブタジエン単位のランダム化などの作用を有する化合物のことである。このランダマイザーとしては、特に制限はなく、従来ランダマイザーとして一般に使用されている公知の化合物の中から任意のものを用いることができる。例えば、ジメトキシベンゼン、テトラヒドロフラン、ジメトキシエタン、ジエチレングリコールジブチルエーテル、ジエチレングリコールジメチルエーテル、ビステトラヒドロフリルプロパン、トリエチルアミン、ピリジン、N-メチルモルホリン、N,N,N’,N’-テトラメチルエチレンジアミン、1,2-ジピペリジノエタンなどのエーテル類及び第三級アミン類などを挙げることができる。また、カリウム-t-アミレート、カリウム-t-ブトキシドなどのカリウム塩類、ナトリウム-t-アミレートなどのナトリウム塩類も用いることができる。これらのランダマイザーは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。また、ランダマイザーの使用量は、有機リチウム化合物1モル当たり、0.01モル当量以上が好ましく、0.05モル当量以上がより好ましい。ランダマイザーの使用量が0.01モル当量未満では、添加効果が小さく、ランダム化しにくい傾向がある。また、ランダマイザーの使用量は、有機リチウム化合物1モル当たり1000モル当量以下が好ましく、500モル当量以下がより好ましい。ランダマイザーの使用量が1000モル当量を超えると、モノマーの反応速度が大きく変化してしまい、逆にランダム化しにくくなる傾向がある。
アニオン重合の際の反応温度は、好適に反応が進行する限り特に限定はないが、通常-10℃~100℃であることが好ましく、25℃~70℃であることがより好ましい。
上記重合の工程により得られた共重合体の活性末端と、シリカと相互作用する官能基を有する化合物(B2)とを反応させる工程により、共重合体の重合終了末端に、シリカと相互作用する官能基を導入することができる。これにより、重合終了末端が変性された共重合体が得られる。なお、本発明において末端とは、分子鎖の端に存在する、炭素-炭素二重結合を有するモノマーに由来する構造以外の部分を意味する。
(I)下記式(1)で表される化合物(B2-1);
(II)分子中に、環状エーテル基、(チオ)カルボニル基及びイソ(チオ)シアナート基からなる群より選択される少なくとも1種の官能基(x1)と、窒素原子、リン原子、酸素原子及び硫黄原子からなる群より選択される少なくとも一種の原子(但し、窒素原子、リン原子及び硫黄原子は、少なくともいずれかが3置換のヒドロカルビルシリル基で保護されていてもよい。)を有し、かつ活性水素を有していない、前記官能基(x1)とは異なる基(x2)と、を各々1つ以上有する化合物(B2-2);
(III)分子中に、イソ(チオ)シアナート基を2つ以上有する化合物(B2-3);
等が挙げられる。化合物(B2)としては、これらを一種単独で又は二種以上を組み合わせて使用することができる。なお、本明細書において、(チオ)カルボニル基は、カルボニル基及びチオカルボニル基を示し、イソ(チオ)シアナート基は、イソシアナート基及びイソチオシアナート基を示す。
R5は、炭素数1~20の直鎖状若しくは分岐状のアルカンジイル基、炭素数3~20のシクロアルキレン基又は炭素数6~20のアリーレン基であることが好ましい。
nは、共重合体との反応性を高める観点から、0又は1が好ましい。
A1は、窒素原子、リン原子及び硫黄原子からなる群より選択される少なくとも一種の原子(以下、特定原子ともいう。)を有し、これら特定原子でR5に結合する。特定原子は活性水素に結合しておらず、例えば3置換のヒドロカルビルシリル基等で保護されていてもよい。なお、ここでいう「活性水素」とは、炭素原子以外の原子に結合した水素原子をいい、好ましくはポリメチレンの炭素-水素結合よりも結合エネルギが低いものを指す。
A1の具体例としては、例えば1級アミノ基の2つの水素原子が2つの保護基によって置換されてなる窒素含有基、2級アミノ基の1つの水素原子が1つの保護基によって置換されてなる窒素含有基、3級アミノ基、イミノ基、ピリジル基、1級ホスフィノ基の2つの水素原子が2つの保護基によって置換されてなるリン含有基、2級ホスフィノ基の1つの水素原子が1つの保護基によって置換されてなるリン含有基、3級ホスフィノ基、及び、チオール基の1つの水素原子が1つの保護基によって置換されてなる硫黄含有基等が挙げられる。これらの中でも、シリカとの親和性が良好である観点から、窒素原子を有する基であることが好ましい。なお、「保護基」とは、A1を重合活性末端に対して不活性な官能基に変換しておく官能基であり、例えば3置換のヒドロカルビルシリル基等が挙げられる。
(チオ)カルボニル基を有する化合物として、例えば4-N,N-ジメチルアミノベンゾフェノン等の4-アミノアセトフェノン;1,7-ビス(メチルエチルアミノ)-4-ヘプタノン等のビス(ジヒドロカルビルアミノアルキル)ケトン;2-ジメチルアミノエチルアクリレート等のジヒドロカルビルアミノアルキル(メタ)アクリレート;1,3-ジメチル-2-イミダゾリジノン等のヒドロカルビルイミダゾリジノン;1-フェニル-2-ピロリドン等のN-ヒドロカルビルピロリドン;N-メチル-ε-カプロラクタム等のN-ヒロドカルビルカプトラクタム;N,N-ジエチルホルムアミド等のN-ジヒドロカルビルホルムアミド;N,N-ジメチルアセトアミド等のN,N-ジヒドロカルビルアセトアミド;N,N-ジメチルアクリルアミド等の(メタ)アクリルアミド;などを;
イソ(チオ)シアナート基を有する化合物として、例えば3-イソシアナトプロピルトリメトキシシランなどを;挙げることができる。
末端変性反応の温度は、通常、上記重合反応の温度と同じであり、-20~150℃であることが好ましく、0~120℃であることがより好ましく、20~100℃であることが特に好ましい。変性反応の温度が低いと、変性共重合体の粘度が上昇する傾向がある。一方、変性反応の温度が高いと、重合活性末端が失活しやすくなる。変性反応の反応時間は、好ましくは1分~5時間であり、より好ましくは2分~1時間である。
上記アニオン重合は、この分野で通常使用する反応停止剤の添加により、停止させることができる。そのような反応停止剤としては、例えば、メタノール、エタノール、イソプロパノールなどのアルコールまたは酢酸などの活性プロトンを有する極性溶媒およびこれらの混液、またはそれらの極性溶媒とヘキサン、シクロヘキサンなどの無極性溶媒との混液が挙げられる。反応停止剤の添加量は、通常、アニオン重合開始剤に対し、同モル量もしくは2倍モル量程度で充分である。
上記共重合体の製造方法においては、単量体の重合開始から、後述する重合体の回収までに、共重合体の炭化水素溶液にカップリング剤を添加してもよい。カップリング剤としては、下記式(2-1)で表される化合物を挙げることができる。
R1 aML4-a (2-1)
(式(2-1)中、R1はアルキル基、アルケニル基、シクロアルケニル基またはアリール基を表し、Mはケイ素原子またはスズ原子を表し、Lはハロゲン原子また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。)
水添共重合体の製造方法においては、これまでに説明した共重合体を水素添加して、水素添加率が75モル%以上の水添共重合体を得る。共重合体を水素添加することによって、耐熱性が向上するという利点がある。また、水素添加率が低いと、ゴム破壊強度及び耐摩耗性の改善効果が充分に得られない。
同様の理由から、本発明におけるゴム組成物をトラック・バス用タイヤのトレッドとして用いる場合、カーボンブラックの窒素吸着比表面積(N2SA)は、通常5~200m2/gである。下限は50m2/gであることが好ましく、70m2/gであることがより好ましく、90m2/gであることが更に好ましい。また、上限は150m2/gであることが好ましく、130m2/gであることがより好ましい。また、カーボンブラックのジブチルフタレート(DBP)吸収量は、通常5~300ml/100gであり、下限は80ml/100g、上限は180ml/100gであることが好ましい。
該窒素吸着比表面積は、ASTM D4820-93に従って測定され、該DBP吸収量は、ASTM D2414-93に従って測定される。
同様の理由から、本発明におけるゴム組成物をトラック・バス用タイヤのトレッドとして用いる場合、カーボンブラックの含有量は、ゴム成分100質量部に対して、好ましくは5質量部以上、より好ましくは10質量部以上、更に好ましくは20質量部以上、特に好ましくは30質量部以上である。また、カーボンブラックの含有量は、好ましくは60質量部以下、より好ましくは50質量部以下、更に好ましくは40質量部以下である。
なお、シリカの窒素吸着比表面積は、ASTM D3037-81に準じてBET法で測定される値である。
同様の理由から、本発明におけるゴム組成物をトラック・バス用タイヤのトレッドとして用いる場合、シリカの含有量は、ゴム成分100質量部に対して、好ましくは10質量部以上、より好ましくは20質量部以上である。また、シリカの含有量は、好ましくは80質量部以下、より好ましくは60質量部以下、更に好ましくは50質量部以下、特に好ましくは40質量部以下、最も好ましくは30質量部以下である。
同様の理由から、本発明におけるゴム組成物をトラック・バス用タイヤのトレッドとして用いる場合、シランカップリング剤の含有量は、シリカ100質量部に対して、1質量部以上が好ましく、2質量部以上がより好ましく、6質量部以上が更に好ましく、10質量部以上が特に好ましい。また、シランカップリング剤の含有量は、シリカ100質量部に対して、20質量部以下が好ましく、15質量部以下がより好ましい。
なお、tanδピーク温度(Tg)は、後述する実施例に記載の測定方法により得られる値である。
THF:関東化学(株)製の無水テトラヒドロフラン
n-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)製の1,3-ブタジエン
TMEDA:関東化学(株)製のN,N,N’,N’-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
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
アミン系変性剤:N,N-ビス(トリメチルシリル)アミノプロピルメチルジエトキシシラン
アルコール:東京化成工業(株)製のメタノール
四塩化炭素を溶媒として用いて15質量%濃度の溶液を調製して、100MHzのH1-NMRの不飽和結合部のスペクトル減少率から算出した。
25℃にてJEOL JNM-A 400NMR装置を用いてH1-NMRを測定し、そのスペクトルより求めた6.5~7.2ppmのスチレン単位に基づくフェニルプロトンと4.9~5.4ppmのブタジエン単位に基づくビニルプロトンの比からスチレン含有量を決定した。
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)製のTSKGEL SUPERMULTIPORE HZ-M)による測定値を基に標準ポリスチレン換算により求めた。また、共重合体が変性基を有する場合、変性処理を実施する前にMw、Mnを測定した。これは、変性基を有する共重合体を測定した場合、変性基とカラムのシリカゲルとが相互作用を起こし、正確なMw、Mnが得られないためである。
ガラス転移温度(Tg)は、JIS K 7121に従い、ティー・エイ・インスツルメント・ジャパン社製の示差走査熱量計(Q200)を用いて昇温速度10℃/分で昇温しながら測定することにより、ガラス転移開始温度として求めた。
合成例A-1(共重合体(A-1)の合成:水素添加率0モル%、SBR)
十分に窒素置換した耐熱反応容器にn-ヘキサン2000ml、スチレン60g、1,3-ブタジエン140g、TMEDA0.93g、n-ブチルリチウム0.45mmolを加えて、50℃で5時間攪拌し、重合反応を行った。その後、アルコールを加えて反応を止め、反応溶液に2,6-ジ-tert-ブチル-p-クレゾール1gを添加後、再沈殿精製により共重合体(A-1)を得た。得られた共重合体(A-1)は重量平均分子量(Mw)490,000、スチレン含有量30質量%であった。
得られた重合体を水素添加する以外は、共重合体(A-1)と同様の処方にて共重合体(A-2)を得た。すなわち、共重合体(A-1)において重合転化反応後、アルコールを加えて重合反応を停止させず、次いで、水素ガスを0.4MPa-Gaugeの圧力で供給しながら20分間撹拌し、未反応のポリマー末端リチウムと反応させ、水素化リチウムとした。水素ガス供給圧力を0.7MPa-Gauge、反応温度を90℃とし、チタノセンジクロリドを主体とする触媒を用いて水素添加を行った。水素の吸収が目的の水素添加率となる積算量に達した時点で、反応温度を常温とし、水素圧を常圧に戻して反応容器より抜き出し、反応溶液を水中に撹拌投入して溶媒をスチームストリッピングにより除去することによって、共重合体(A-2)を得た。得られた共重合体(A-2)の水素添加率は60モル%であり、重量平均分子量(Mw)は450,000であった。
目的の水素添加率となるように、水素の吸引の積算量を調整した以外は、共重合体(A-2)と同様の処方により、共重合体(A-3)を得た。得られた共重合体(A-3)の水素添加率は80モル%であり、重量平均分子量(Mw)は480,000であった。
目的の水素添加率となるように、水素の吸引の積算量を調整した以外は、共重合体(A-2)と同様の処方により、共重合体(A-4)を得た。得られた共重合体(A-4)の水素添加率は95モル%であり、重量平均分子量(Mw)は450,000であった。
十分に窒素置換した耐熱反応容器にn-ヘキサン2000ml、スチレン60g、1,3-ブタジエン140g、TMEDA0.93g、n-ブチルリチウム0.45mmolを加えて、50℃で5時間攪拌し、重合反応を行った。その後アミン系変性剤を0.15mol加えて、0℃で1時間撹拌した。その後の工程については、水素の吸引の積算量を調整した以外は、共重合体(A-2)と同様の処方により、共重合体(A-5)を得た。得られた共重合体(A-5)の水素添加率は95モル%であり、変性前の重量平均分子量(Mw)は440,000であった。
十分に窒素置換した耐熱反応容器にn-ヘキサン2000ml、スチレン60g、ブタジエン140g、THF1.75g、n-ブチルリチウム0.45mmolを加えて、50℃で5時間攪拌し、重合反応を行った。その後、アルコールを加えて反応を止め、反応溶液に2,6-ジ-tert-ブチル-p-クレゾール1gを添加後、再沈殿精製により共重合体(B-1)を得た。得られた共重合体(B-1)は重量平均分子量(Mw)490,000、スチレン含有量30質量%であった。
得られた重合体を水素添加する以外は、共重合体(B-1)と同様の処方にて共重合体(B-2)を得た。すなわち、共重合体(B-1)において重合転化反応後、アルコールを加えて重合反応を停止させず、次いで、水素ガスを0.4MPa-Gaugeの圧力で供給しながら20分間撹拌し、未反応のポリマー末端リチウムと反応させ、水素化リチウムとした。水素ガス供給圧力を0.7MPa-Gauge、反応温度を90℃とし、チタノセンジクロリドを主体とする触媒を用いて水素添加を行った。水素の吸収が目的の水素添加率となる積算量に達した時点で、反応温度を常温とし、水素圧を常圧に戻して反応容器より抜き出し、反応溶液を水中に撹拌投入して溶媒をスチームストリッピングにより除去することによって、共重合体(B-2)を得た。得られた共重合体(B-2)の水素添加率は60モル%であり、重量平均分子量(Mw)は450,000であった。
目的の水素添加率となるように、水素の吸引の積算量を調整した以外は、共重合体(B-2)と同様の処方により、共重合体(B-3)を得た。得られた共重合体(B-3)の水素添加率は80モル%であり、重量平均分子量(Mw)は480,000であった。
目的の水素添加率となるように、水素の吸引の積算量を調整した以外は、共重合体(B-2)と同様の処方により、共重合体(B-4)を得た。得られた共重合体(B-4)の水素添加率は95モル%であり、重量平均分子量(Mw)は450,000であった。
十分に窒素置換した耐熱反応容器にn-ヘキサン2000ml、スチレン60g、1,3-ブタジエン140g、TMEDA0.93g、n-ブチルリチウム0.45mmolを加えて、50℃で5時間攪拌し、重合反応を行った。その後アミン系変性剤を0.15mol加えて、0℃で1時間撹拌した。その後の工程については、水素の吸引の積算量を調整した以外は、共重合体(B-2)と同様の処方により、共重合体(B-5)を得た。得られた共重合体(5)の水素添加率は95モル%であり、変性前の重量平均分子量(Mw)は440,000であった。
十分に窒素置換した耐熱反応容器にn-ヘキサン2000ml、スチレン20g、1,3-ブタジエン180g、THF15.0g、n-ブチルリチウム0.45mmolを加えて、50℃で5時間攪拌し、重合反応を行った。その後、アルコールを加えて反応を止め、反応溶液に2,6-ジ-tert-ブチル-p-クレゾール1gを添加後、再沈殿精製により共重合体(C-1)を得た。得られた共重合体(C-1)は重量平均分子量(Mw)480,000、スチレン含有量10質量%であった。
十分に窒素置換した耐熱反応容器にn-ヘキサン2000ml、スチレン20g、1,3-ブタジエン180g、THF1.75g、n-ブチルリチウム0.45mmolを加えて、50℃で5時間攪拌し、重合反応を行った。その後、アルコールを加えて反応を止め、反応溶液に2,6-ジ-tert-ブチル-p-クレゾール1gを添加後、再沈殿精製により共重合体(C-2)を得た。得られた共重合体(C-2)は重量平均分子量(Mw)490,000、スチレン含有量10質量%であった。
得られた重合体を水素添加する以外は、共重合体(C-2)と同様の処方にて共重合体(C-3)を得た。すなわち、共重合体(C-2)において重合転化反応後、アルコールを加えて重合反応を停止させず、次いで、水素ガスを0.4MPa-Gaugeの圧力で供給しながら20分間撹拌し、未反応のポリマー末端リチウムと反応させ、水素化リチウムとした。水素ガス供給圧力を0.7MPa-Gauge、反応温度を90℃とし、チタノセンジクロリドを主体とする触媒を用いて水素添加を行った。水素の吸収が目的の水素添加率となる積算量に達した時点で、反応温度を常温とし、水素圧を常圧に戻して反応容器より抜き出し、反応溶液を水中に撹拌投入して溶媒をスチームストリッピングにより除去することによって、水添共重合体を得た。得られた共重合体(C-3)の水素添加率は60モル%であり、重量平均分子量(Mw)は450,000であった。
目的の水素添加率となるように、水素の吸引の積算量を調整した以外は、共重合体(C-3)と同様の処方により、共重合体(C-4)を得た。得られた共重合体(C-4)の水素添加率は80モル%であり、重量平均分子量(Mw)は480,000であった。
目的の水素添加率となるように、水素の吸引の積算量を調整した以外は、共重合体(C-3)と同様の処方により、共重合体(C-5)を得た。得られた共重合体(C-5)の水素添加率は95モル%であり、重量平均分子量(Mw)は450,000であった。
十分に窒素置換した耐熱反応容器にn-ヘキサン2000ml、スチレン20g、1,3-ブタジエン180g、TMEDA0.93g、n-ブチルリチウム0.45mmolを加えて、50℃で5時間攪拌し、重合反応を行った。その後アミン系変性剤を0.15mol加えて、0℃で1時間撹拌した。その後の工程については、水素の吸引の積算量を調整した以外は、共重合体(C-2)と同様の処方により、共重合体(C-6)を得た。得られた共重合体(C-6)の水素添加率は95モル%であり、変性前の重量平均分子量(Mw)は440,000であった。
十分に窒素置換した耐熱反応容器にn-ヘキサン2000ml、スチレン70g、1,3-ブタジエン130g、THF12.5g、n-ブチルリチウム0.45mmolを加えて、50℃で5時間攪拌し、重合反応を行った。その後、アルコールを加えて反応を止め、反応溶液に2,6-ジ-tert-ブチル-p-クレゾール1gを添加後、再沈殿精製により共重合体(D-1)を得た。得られた共重合体(D-1)は重量平均分子量(Mw)490,000、スチレン含有量35質量%であった。
得られた重合体を水素添加する以外は、共重合体(D-1)と同様の処方にて共重合体(D-2)を得た。すなわち、共重合体(D-1)において重合転化反応後、アルコールを加えて重合反応を停止させず、次いで、水素ガスを0.4MPa-Gaugeの圧力で供給しながら20分間撹拌し、未反応のポリマー末端リチウムと反応させ、水素化リチウムとした。水素ガス供給圧力を0.7MPa-Gauge、反応温度を90℃とし、チタノセンジクロリドを主体とする触媒を用いて水素添加を行った。水素の吸収が目的の水素添加率となる積算量に達した時点で、反応温度を常温とし、水素圧を常圧に戻して反応容器より抜き出し、反応溶液を水中に撹拌投入して溶媒をスチームストリッピングにより除去することによって、共重合体(D-2)を得た。得られた共重合体(D-2)の水素添加率は60モル%であり、重量平均分子量(Mw)は450,000であった。
目的の水素添加率となるように、水素の吸引の積算量を調整した以外は、共重合体(D-2)と同様の処方により、共重合体(D-3)を得た。得られた共重合体(D-3)の水素添加率は80モル%であり、重量平均分子量(Mw)は480,000であった。
目的の水素添加率となるように、水素の吸引の積算量を調整した以外は、共重合体(D-2)と同様の処方により、共重合体(D-4)を得た。得られた共重合体(D-4)の水素添加率は95モル%であり、重量平均分子量(Mw)は450,000であった。
十分に窒素置換した耐熱反応容器にn-ヘキサン2000ml、スチレン70g、1,3-ブタジエン130g、TMEDA0.93g、n-ブチルリチウム0.45mmolを加えて、50℃で5時間攪拌し、重合反応を行った。その後アミン系変性剤を0.15mol加えて、0℃で1時間撹拌した。その後の工程については、水素の吸引の積算量を調整した以外は、共重合体(D-2)と同様の処方により、共重合体(D-5)を得た。得られた共重合体(D-5)の水素添加率は95モル%であった。重量平均分子量(Mw)は440,000であった。
共重合体(A-1)~(A-5)、(B-1)~(B-5)、(C-1)~(C-6)、(D-1)~(D-5):上記方法で合成
天然ゴム:TSR20
ブタジエンゴム:宇部興産(株)製のウベポールBR150B(シス含量:97質量%)
カーボンブラック(1):三菱化学(株)製のダイアブラックN339(N2SA:96m2/g、DBP吸収量:124ml/100g)
カーボンブラック(2):三菱化学(株)製のダイアブラックN220(N2SA:111m2/g、DBP吸収量:115ml/100g)
オイル:(株)ジャパンエナジー製のX-140
シリカ:EVONIK社製のULTRASIL VN3(N2SA:180m2/g)
シランカップリング剤:デグッサ社製の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)
老化防止剤:住友化学(株)製のアンチゲン3C
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(1):住友化学(株)製のソクシノールCZ(N-シクロヘキシル-2-ベンゾチアゾリルスルフェンアミド)
加硫促進剤(2):住友化学(株)製のソクシノールD(1,3-ジフェニルグアニジン)
表5~8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。
得られた加硫ゴム組成物について、下記の評価を行った。結果を表5~8に示す。なお、各表における基準配合は以下のとおりである。
表5:比較例A-2
表6:比較例B-1
表7:比較例C-2
表8:比較例D-2
上記加硫ゴム組成物について、JIS K 6251に準じて引張試験を行い、破断伸びを測定した。測定結果を、基準配合を100とした指数で示した。指数が大きいほどゴム破壊強度が大きいことを示している。
(ゴム破壊強度指数)=(各配合のゴム破壊強度)/(基準配合のゴム破壊強度)×100
LAT試験機(Laboratory Abration and Skid Tester)を用い、荷重50N、速度20km/h、スリップアングル5°の条件にて、各加硫ゴム組成物の容積損失量を測定した。基準配合の容積損失量を100として指数表示した。数値が大きいほど耐摩耗性に優れることを示している。
(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配合を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。なお、指数が98以上の場合に、良好と判断した。
JIS K 6259「加硫ゴム及び熱可塑性ゴム-耐オゾン性の求め方」に基づき、オゾン濃度50±5pphm、温度25℃、伸張歪20±2%の条件下で、48時間試験した後の亀裂の状態を観察することで、耐オゾン性を評価した。評価方法は、JISに記載の方式に従い、亀裂の数と大きさを表した。アルファベット(A、B及びC)は、Aが亀裂の数が少なく、Cが亀裂の数が大きいことを示し、数字(1~5)は、大きいほど、亀裂の大きさが大きいことを示し、「なし」は、クラックが発生しなかったことを示す。なお、クラックが発生しないもののみ良好と判断した。
得られた加硫ゴム組成物を用いて、厚み2mm、15cm四方の試験片を作成した。そして、ADVANTEST社製の電気抵抗測定器R8340Aを用いて、この試験片の電気抵抗(体積固有抵抗値(Ω・cm))を測定した。測定条件は、電圧500V、気温25℃、湿度50%とした。基準配合の体積固有抵抗値を100とし、下記計算式により、各配合の体積固有抵抗値を指数表示した。指数が大きいほど、体積固有抵抗値が低く(電気抵抗が低く)、導電性に優れることを示す。なお、指数が100以上の場合に、良好と判断した。
(導電性指数)=(基準配合の体積固有抵抗値)/(各配合の体積固有抵抗値)×100
得られた加硫ゴム組成物から、所定サイズの試験片を作製し、(株)岩本製作所製の粘弾性スペクトロメータVESを用いて、初期歪10%、動歪0.5%、周波数10Hz及び振幅±0.25%、昇温速度2℃/分の条件下で温度-100~100℃のtanδの温度分散曲線を測定し、温度分布曲線における最も大きいtanδ値に対応する温度をtanδピーク温度とした。
Claims (14)
- ゴム組成物を用いて作製した空気入りタイヤであって、
前記ゴム組成物は、芳香族ビニル化合物及び共役ジエン化合物を共重合して得られた、共役ジエン部の水素添加率が75モル%以上である水添共重合体と、カーボンブラックと、シリカとを含み、
ゴム成分100質量%中の前記水添共重合体の含有量が75質量%以上であり、
ゴム成分100質量部に対する前記カーボンブラックの含有量が3質量部以上、前記シリカの含有量が1~200質量部である空気入りタイヤ。 - 前記水添共重合体の重量平均分子量が200,000~2,000,000である請求項1に記載の空気入りタイヤ。
- 前記水添共重合体の水素添加率が90モル%以上である請求項1又は2に記載の空気入りタイヤ。
- 前記水添共重合体が水添スチレンブタジエン共重合体である請求項1~3のいずれかに記載の空気入りタイヤ。
- 前記水添スチレンブタジエン共重合体が水添変性スチレンブタジエン共重合体である請求項4に記載の空気入りタイヤ。
- 前記水添スチレンブタジエン共重合体のスチレン含有量が5~40質量%である請求項4又は5に記載の空気入りタイヤ。
- ゴム成分100質量%中の前記水添スチレンブタジエン共重合体の含有量が90~100質量%である請求項4~6のいずれかに記載の空気入りタイヤ。
- ゴム成分100質量部に対して、前記シリカの含有量が10~80質量部であり、
充填剤100質量%中のカーボンブラックの含有量が50質量%以上である請求項1~7のいずれかに記載の空気入りタイヤ。 - 前記ゴム組成物のtanδピーク温度が-16℃未満である請求項1~8のいずれかに記載の空気入りタイヤ。
- 前記ゴム組成物のtanδピーク温度が-16℃以上である請求項1~8のいずれかに記載の空気入りタイヤ。
- 前記ゴム組成物を用いて作製されたトレッドを有するトラック・バス用タイヤである請求項8に記載の空気入りタイヤ。
- 前記ゴム組成物を用いて作製されたトレッドを有するスタッドレスタイヤである請求項9に記載の空気入りタイヤ。
- 前記ゴム組成物を用いて作製されたトレッドを有するオールシーズンタイヤである請求項9に記載の空気入りタイヤ。
- 前記ゴム組成物を用いて作製されたトレッドを有する夏用タイヤである請求項10に記載の空気入りタイヤ。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/503,111 US20170226233A1 (en) | 2014-09-08 | 2015-07-10 | Pneumatic tire |
EP15840313.9A EP3178878B1 (en) | 2014-09-08 | 2015-07-10 | Pneumatic tire |
CN201580043384.8A CN106574079A (zh) | 2014-09-08 | 2015-07-10 | 充气轮胎 |
JP2015562972A JP6627512B2 (ja) | 2014-09-08 | 2015-07-10 | 空気入りタイヤ |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-182388 | 2014-09-08 | ||
JP2014182388 | 2014-09-08 | ||
JP2014182385 | 2014-09-08 | ||
JP2014-182389 | 2014-09-08 | ||
JP2014-182392 | 2014-09-08 | ||
JP2014182392 | 2014-09-08 | ||
JP2014182389 | 2014-09-08 | ||
JP2014-182385 | 2014-09-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016039005A1 true WO2016039005A1 (ja) | 2016-03-17 |
Family
ID=55458767
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/069823 WO2016039005A1 (ja) | 2014-09-08 | 2015-07-10 | 空気入りタイヤ |
Country Status (5)
Country | Link |
---|---|
US (1) | US20170226233A1 (ja) |
EP (1) | EP3178878B1 (ja) |
JP (1) | JP6627512B2 (ja) |
CN (1) | CN106574079A (ja) |
WO (1) | WO2016039005A1 (ja) |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016056349A (ja) * | 2014-09-08 | 2016-04-21 | 住友ゴム工業株式会社 | 空気入りタイヤ |
JP2016056350A (ja) * | 2014-09-08 | 2016-04-21 | 住友ゴム工業株式会社 | 空気入りタイヤ |
JP2016056351A (ja) * | 2014-09-08 | 2016-04-21 | 住友ゴム工業株式会社 | 空気入りタイヤ |
JP2016069628A (ja) * | 2014-09-30 | 2016-05-09 | 住友ゴム工業株式会社 | 空気入りタイヤ |
JPWO2017014282A1 (ja) * | 2015-07-22 | 2018-05-24 | Jsr株式会社 | 水添共役ジエン系重合体及びその製造方法、重合体組成物、架橋重合体、並びにタイヤ |
CN108084532A (zh) * | 2016-11-22 | 2018-05-29 | 住友橡胶工业株式会社 | 充气轮胎 |
WO2018119168A1 (en) * | 2016-12-21 | 2018-06-28 | Bridgestone Corporation | High strength hydrogenated polymers, and rubber compositions incorporating same |
JP2019014796A (ja) * | 2017-07-05 | 2019-01-31 | 住友ゴム工業株式会社 | 空気入りタイヤ |
CN109790302A (zh) * | 2016-09-30 | 2019-05-21 | Jsr株式会社 | 橡胶组合物的制造方法和轮胎 |
CN110088191A (zh) * | 2016-12-15 | 2019-08-02 | 通伊欧轮胎株式会社 | 轮胎用橡胶组合物及使用了该轮胎用橡胶组合物的充气轮胎 |
WO2019216110A1 (ja) * | 2018-05-08 | 2019-11-14 | 株式会社ブリヂストン | 加硫ゴム組成物、タイヤトレッド及びタイヤ |
EP3650472A1 (en) | 2018-11-12 | 2020-05-13 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire |
JP2020105379A (ja) * | 2018-12-27 | 2020-07-09 | Toyo Tire株式会社 | タイヤ用ゴム組成物の製造方法、及び空気入りタイヤの製造方法 |
JP2020143289A (ja) * | 2018-11-12 | 2020-09-10 | 住友ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JPWO2020203984A1 (ja) * | 2019-04-01 | 2020-10-08 | ||
WO2020261618A1 (ja) | 2019-06-26 | 2020-12-30 | 住友ゴム工業株式会社 | 空気入りタイヤ |
WO2021079564A1 (ja) | 2019-10-23 | 2021-04-29 | 住友ゴム工業株式会社 | タイヤ |
WO2021079676A1 (ja) | 2019-10-23 | 2021-04-29 | 住友ゴム工業株式会社 | ゴム組成物及びタイヤ |
WO2021102202A3 (en) * | 2019-11-19 | 2021-07-01 | Bridgestone Corporation | Hydrogenated polymers and rubber compositions incorporating the same |
JP2021107500A (ja) * | 2019-12-27 | 2021-07-29 | Toyo Tire株式会社 | タイヤトレッド用ゴム組成物、及びそれを用いた空気入りタイヤ |
WO2022091982A1 (ja) * | 2020-10-30 | 2022-05-05 | 旭化成株式会社 | ゴム組成物、及びタイヤ |
WO2022102456A1 (ja) | 2020-11-11 | 2022-05-19 | 住友ゴム工業株式会社 | 可塑剤、組成物及びタイヤ |
WO2022102453A1 (ja) | 2020-11-11 | 2022-05-19 | 住友ゴム工業株式会社 | タイヤ |
EP4230438A1 (en) | 2022-02-22 | 2023-08-23 | Sumitomo Rubber Industries, Ltd. | Tire |
US12054614B2 (en) | 2018-11-12 | 2024-08-06 | Sumitomo Rubber Industries, Ltd. | Rubber composition and pneumatic tire |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106661282A (zh) | 2014-09-08 | 2017-05-10 | 住友橡胶工业株式会社 | 充气轮胎 |
JP6716942B2 (ja) * | 2016-02-18 | 2020-07-01 | 住友ゴム工業株式会社 | 空気入りタイヤ及び空気入りタイヤの製造方法 |
JP6972534B2 (ja) | 2016-10-31 | 2021-11-24 | 住友ゴム工業株式会社 | 混練機投入用ポリマー |
JP7371631B2 (ja) * | 2018-08-06 | 2023-10-31 | 住友ゴム工業株式会社 | 空気入りタイヤ |
KR102150277B1 (ko) * | 2018-11-12 | 2020-09-02 | 금호석유화학 주식회사 | 경주용 타이어 고무 조성물 및 그 제조방법 |
JP7305674B2 (ja) * | 2018-11-16 | 2023-07-10 | 株式会社ブリヂストン | ゴム組成物、加硫ゴム及びタイヤ |
JP7500440B2 (ja) * | 2019-01-30 | 2024-06-17 | 株式会社Eneosマテリアル | ゴム組成物、架橋体及びタイヤ |
WO2021246128A1 (ja) * | 2020-06-03 | 2021-12-09 | 住友ゴム工業株式会社 | タイヤ |
US12006436B2 (en) * | 2020-11-13 | 2024-06-11 | The Goodyear Tire & Rubber Company | Rubber composition and a tire |
DE102021206278A1 (de) * | 2021-06-18 | 2022-12-22 | Continental Reifen Deutschland Gmbh | Kautschukmischung und Reifen |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003277560A (ja) * | 2002-03-25 | 2003-10-02 | Asahi Kasei Corp | 水添共重合体組成物 |
JP2008184517A (ja) * | 2007-01-29 | 2008-08-14 | Bridgestone Corp | ゴム組成物及びそれを用いた空気入りタイヤ |
WO2014126184A1 (ja) * | 2013-02-14 | 2014-08-21 | Jsr株式会社 | 水添共役ジエン重合体の製造方法 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6248739A (ja) * | 1985-08-27 | 1987-03-03 | Bridgestone Corp | 高速走行に適した高グリツプトレツドゴム組成物 |
US5191003A (en) * | 1990-08-08 | 1993-03-02 | Sumitomo Chemical Company, Limited | Rubber composition |
US5804644A (en) * | 1994-08-08 | 1998-09-08 | Asahi Kasei Kabushiki Kaisha | Hydrogenerated rubber composition |
JP2000119445A (ja) * | 1998-10-14 | 2000-04-25 | Sumitomo Rubber Ind Ltd | タイヤトレッド用ゴム組成物 |
US20010016629A1 (en) * | 2000-01-27 | 2001-08-23 | Makio Mori | Rubber composition for tire and method of manufacturing same |
JP4881563B2 (ja) * | 2005-02-03 | 2012-02-22 | 株式会社ブリヂストン | ゴム組成物及びそれを用いた空気入りタイヤ |
CN102115554B (zh) * | 2010-01-04 | 2014-09-10 | 住友橡胶工业株式会社 | 轮胎用橡胶组合物以及无钉防滑轮胎 |
JP5616073B2 (ja) * | 2010-01-27 | 2014-10-29 | 住友ゴム工業株式会社 | タイヤ用ゴム組成物及び空気入りタイヤ |
JP5518515B2 (ja) * | 2010-02-09 | 2014-06-11 | 住友ゴム工業株式会社 | タイヤ用ゴム組成物及び空気入りタイヤ |
JP5508148B2 (ja) * | 2010-06-03 | 2014-05-28 | 住友ゴム工業株式会社 | ベーストレッド用ゴム組成物及び空気入りタイヤ |
JP2012102239A (ja) * | 2010-11-10 | 2012-05-31 | Sumitomo Rubber Ind Ltd | ウェットマスターバッチ、タイヤ用ゴム組成物及び空気入りタイヤ |
JP5687658B2 (ja) * | 2012-06-01 | 2015-03-18 | 住友ゴム工業株式会社 | 空気入りタイヤ |
JP5745491B2 (ja) * | 2012-11-08 | 2015-07-08 | 住友ゴム工業株式会社 | ベーストレッド用ゴム組成物及び空気入りタイヤ |
JP6057683B2 (ja) * | 2012-11-28 | 2017-01-11 | 住友ゴム工業株式会社 | ベーストレッド用ゴム組成物、その製造方法及び空気入りタイヤ |
KR102225993B1 (ko) * | 2013-02-28 | 2021-03-09 | 제이에스알 가부시끼가이샤 | 타이어용 부재 및 중합체 조성물 |
JP6627513B2 (ja) * | 2014-09-08 | 2020-01-08 | 住友ゴム工業株式会社 | 空気入りタイヤ |
-
2015
- 2015-07-10 CN CN201580043384.8A patent/CN106574079A/zh active Pending
- 2015-07-10 WO PCT/JP2015/069823 patent/WO2016039005A1/ja active Application Filing
- 2015-07-10 US US15/503,111 patent/US20170226233A1/en not_active Abandoned
- 2015-07-10 JP JP2015562972A patent/JP6627512B2/ja active Active
- 2015-07-10 EP EP15840313.9A patent/EP3178878B1/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003277560A (ja) * | 2002-03-25 | 2003-10-02 | Asahi Kasei Corp | 水添共重合体組成物 |
JP2008184517A (ja) * | 2007-01-29 | 2008-08-14 | Bridgestone Corp | ゴム組成物及びそれを用いた空気入りタイヤ |
WO2014126184A1 (ja) * | 2013-02-14 | 2014-08-21 | Jsr株式会社 | 水添共役ジエン重合体の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3178878A4 * |
Cited By (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016056350A (ja) * | 2014-09-08 | 2016-04-21 | 住友ゴム工業株式会社 | 空気入りタイヤ |
JP2016056351A (ja) * | 2014-09-08 | 2016-04-21 | 住友ゴム工業株式会社 | 空気入りタイヤ |
JP2016056349A (ja) * | 2014-09-08 | 2016-04-21 | 住友ゴム工業株式会社 | 空気入りタイヤ |
JP2016069628A (ja) * | 2014-09-30 | 2016-05-09 | 住友ゴム工業株式会社 | 空気入りタイヤ |
JPWO2017014282A1 (ja) * | 2015-07-22 | 2018-05-24 | Jsr株式会社 | 水添共役ジエン系重合体及びその製造方法、重合体組成物、架橋重合体、並びにタイヤ |
EP3521341A4 (en) * | 2016-09-30 | 2020-04-08 | JSR Corporation | PROCESS FOR PRODUCING GUM COMPOSITION, AND TIRE |
CN109790302A (zh) * | 2016-09-30 | 2019-05-21 | Jsr株式会社 | 橡胶组合物的制造方法和轮胎 |
CN108084532A (zh) * | 2016-11-22 | 2018-05-29 | 住友橡胶工业株式会社 | 充气轮胎 |
EP3326838A1 (en) * | 2016-11-22 | 2018-05-30 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire |
JP2018083884A (ja) * | 2016-11-22 | 2018-05-31 | 住友ゴム工業株式会社 | 空気入りタイヤ |
CN108084532B (zh) * | 2016-11-22 | 2021-09-14 | 住友橡胶工业株式会社 | 充气轮胎 |
CN110088191A (zh) * | 2016-12-15 | 2019-08-02 | 通伊欧轮胎株式会社 | 轮胎用橡胶组合物及使用了该轮胎用橡胶组合物的充气轮胎 |
JP2021138967A (ja) * | 2016-12-21 | 2021-09-16 | 株式会社ブリヂストン | 高強度水素化ポリマー、及びこれを組み込んだゴム組成物 |
JP7337879B2 (ja) | 2016-12-21 | 2023-09-04 | 株式会社ブリヂストン | 高強度水素化ポリマー、及びこれを組み込んだゴム組成物 |
CN110099937A (zh) * | 2016-12-21 | 2019-08-06 | 株式会社普利司通 | 高强度氢化聚合物和含有高强度氢化聚合物的橡胶组合物 |
WO2018119168A1 (en) * | 2016-12-21 | 2018-06-28 | Bridgestone Corporation | High strength hydrogenated polymers, and rubber compositions incorporating same |
JP2020514446A (ja) * | 2016-12-21 | 2020-05-21 | 株式会社ブリヂストン | 高強度水素化ポリマー、及びこれを組み込んだゴム組成物 |
US20230134110A1 (en) * | 2016-12-21 | 2023-05-04 | Bridgestone Corporation | High Strength Hydrogenated Polymers, And Rubber Compositions Incorporating Same |
JP2019014796A (ja) * | 2017-07-05 | 2019-01-31 | 住友ゴム工業株式会社 | 空気入りタイヤ |
JPWO2019216110A1 (ja) * | 2018-05-08 | 2021-06-10 | 株式会社ブリヂストン | 加硫ゴム組成物、タイヤトレッド及びタイヤ |
JP7217744B2 (ja) | 2018-05-08 | 2023-02-03 | 株式会社ブリヂストン | 加硫ゴム組成物、タイヤトレッド及びタイヤ |
WO2019216110A1 (ja) * | 2018-05-08 | 2019-11-14 | 株式会社ブリヂストン | 加硫ゴム組成物、タイヤトレッド及びタイヤ |
CN112105688A (zh) * | 2018-05-08 | 2020-12-18 | 株式会社普利司通 | 硫化橡胶组合物、轮胎胎面和轮胎 |
JP2020078967A (ja) * | 2018-11-12 | 2020-05-28 | 住友ゴム工業株式会社 | 空気入りタイヤ |
US12054614B2 (en) | 2018-11-12 | 2024-08-06 | Sumitomo Rubber Industries, Ltd. | Rubber composition and pneumatic tire |
JP2020143289A (ja) * | 2018-11-12 | 2020-09-10 | 住友ゴム工業株式会社 | ゴム組成物及び空気入りタイヤ |
JP7159799B2 (ja) | 2018-11-12 | 2022-10-25 | 住友ゴム工業株式会社 | 空気入りタイヤ |
EP3650472A1 (en) | 2018-11-12 | 2020-05-13 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire |
JP2020105379A (ja) * | 2018-12-27 | 2020-07-09 | Toyo Tire株式会社 | タイヤ用ゴム組成物の製造方法、及び空気入りタイヤの製造方法 |
JPWO2020203984A1 (ja) * | 2019-04-01 | 2020-10-08 | ||
JP7516355B2 (ja) | 2019-04-01 | 2024-07-16 | 株式会社Eneosマテリアル | 架橋物及びタイヤ |
WO2020203984A1 (ja) * | 2019-04-01 | 2020-10-08 | Jsr株式会社 | 架橋物及びタイヤ |
WO2020261618A1 (ja) | 2019-06-26 | 2020-12-30 | 住友ゴム工業株式会社 | 空気入りタイヤ |
WO2021079676A1 (ja) | 2019-10-23 | 2021-04-29 | 住友ゴム工業株式会社 | ゴム組成物及びタイヤ |
WO2021079564A1 (ja) | 2019-10-23 | 2021-04-29 | 住友ゴム工業株式会社 | タイヤ |
WO2021102202A3 (en) * | 2019-11-19 | 2021-07-01 | Bridgestone Corporation | Hydrogenated polymers and rubber compositions incorporating the same |
JP2021107500A (ja) * | 2019-12-27 | 2021-07-29 | Toyo Tire株式会社 | タイヤトレッド用ゴム組成物、及びそれを用いた空気入りタイヤ |
JP7396893B2 (ja) | 2019-12-27 | 2023-12-12 | Toyo Tire株式会社 | タイヤトレッド用ゴム組成物、及びそれを用いた空気入りタイヤ |
WO2022091982A1 (ja) * | 2020-10-30 | 2022-05-05 | 旭化成株式会社 | ゴム組成物、及びタイヤ |
WO2022102456A1 (ja) | 2020-11-11 | 2022-05-19 | 住友ゴム工業株式会社 | 可塑剤、組成物及びタイヤ |
WO2022102453A1 (ja) | 2020-11-11 | 2022-05-19 | 住友ゴム工業株式会社 | タイヤ |
EP4230438A1 (en) | 2022-02-22 | 2023-08-23 | Sumitomo Rubber Industries, Ltd. | Tire |
Also Published As
Publication number | Publication date |
---|---|
CN106574079A (zh) | 2017-04-19 |
US20170226233A1 (en) | 2017-08-10 |
EP3178878A4 (en) | 2018-01-24 |
EP3178878A1 (en) | 2017-06-14 |
EP3178878B1 (en) | 2019-06-05 |
JPWO2016039005A1 (ja) | 2017-06-15 |
JP6627512B2 (ja) | 2020-01-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6627512B2 (ja) | 空気入りタイヤ | |
CN108084532B (zh) | 充气轮胎 | |
CN109206691B (zh) | 充气轮胎 | |
JP6631254B2 (ja) | 空気入りタイヤ | |
JP6627513B2 (ja) | 空気入りタイヤ | |
JP6627294B2 (ja) | 空気入りタイヤ | |
CN107090111B (zh) | 充气轮胎 | |
JP6627293B2 (ja) | 空気入りタイヤ | |
JP6716942B2 (ja) | 空気入りタイヤ及び空気入りタイヤの製造方法 | |
JP6801183B2 (ja) | 空気入りタイヤ | |
JP6627511B2 (ja) | 空気入りタイヤ | |
JP6631059B2 (ja) | 空気入りタイヤ | |
JP7159799B2 (ja) | 空気入りタイヤ | |
JPWO2020031904A1 (ja) | 空気入りタイヤ | |
US20240132706A1 (en) | Rubber composition for tires and tire | |
JP2021004309A (ja) | 空気入りタイヤ |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2015562972 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15840313 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2015840313 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015840313 Country of ref document: EP |