WO2013122237A1 - タイヤトレッド用ゴム組成物 - Google Patents
タイヤトレッド用ゴム組成物 Download PDFInfo
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- WO2013122237A1 WO2013122237A1 PCT/JP2013/053770 JP2013053770W WO2013122237A1 WO 2013122237 A1 WO2013122237 A1 WO 2013122237A1 JP 2013053770 W JP2013053770 W JP 2013053770W WO 2013122237 A1 WO2013122237 A1 WO 2013122237A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the present invention relates to a rubber composition for a tire tread, and more particularly to a rubber composition for a tire tread in which low rolling resistance, wet performance, and wear resistance are improved to a conventional level or more.
- the required performance of pneumatic tires for high-performance vehicles is not only excellent in handling stability and braking performance when driving on wet roads, but also in terms of fuel efficiency as interest in global environmental issues increases. ing.
- the dynamic viscoelastic properties such as loss tangent (tan ⁇ ) of the tread rubber are improved, heat generation is suppressed, rolling resistance is reduced, and fuel efficiency performance is improved.
- tan ⁇ loss tangent
- silica has poor affinity with diene rubber and tends to be poorly dispersed, especially when the particle size of silica is reduced, the dispersibility deteriorates, so the effect of improving low heat build-up and wet performance cannot be obtained sufficiently. It was. Further, the reinforcing property is small as compared with carbon black, and the wear resistance cannot always be sufficiently ensured.
- Patent Document 1 improves the dispersibility of silica with a rubber composition in which silica is blended with a terminal-modified solution-polymerized styrene butadiene rubber whose terminal is modified with polyorganosiloxane or the like, and the exothermic property (tan ⁇ at 60 ° C.) is improved. It has been proposed to reduce the wet grip property (tan ⁇ at 0 ° C.) and improve the wear resistance.
- Patent Document 2 discloses a rubber composition in which 80 to 180 parts by weight of a filler containing 50 parts by weight or more of silica and 5 to 60 parts by weight of a resin having a softening point of 100 to 150 ° C. are blended with 100 parts by weight of a styrene butadiene copolymer rubber. Proposing things.
- An object of the present invention is to provide a rubber composition for a tire tread in which the low rolling resistance and the wet performance are improved to the conventional level or more.
- the rubber composition for a tire tread of the present invention that achieves the above object is an aromatic composition based on 100 parts by weight of a diene rubber containing 35 to 89% by weight of a modified conjugated diene polymer rubber and 11 to 40% by weight of a butadiene rubber. 3-60 parts by weight of modified terpene resin, 100-150 parts by weight of filler, and 70% by weight or more of silica in the filler, blending amount of aromatic modified terpene resin with respect to blending amount Wbr of butadiene rubber Wte ratio Wte / Wbr is 0.5 to 1.3, and the modified conjugated diene polymer rubber is conjugated diene monomer using an organic active metal compound as an initiator in a hydrocarbon solvent.
- the terminal modified group includes a functional group that interacts with silica, and the modified conjugated diene polymer rubber has an aromatic vinyl unit content of 38 to 48% by weight, vinyl.
- the unit content is 20 to 35% by weight, the weight average molecular weight is 600,000 to 1,000,000, and the softening point of the aromatic modified terpene resin is 100 to 150 ° C.
- the rubber composition for a tire tread of the present invention has at least one functional group having a reactive group at the active end of an active conjugated diene polymer chain obtained by copolymerizing a conjugated diene monomer and an aromatic vinyl monomer. It has a terminal-modified group obtained by reacting various types of compounds, and this terminal-modified group includes a functional group having an interaction with silica, and has an aromatic vinyl unit content of 38 to 48% by weight and a vinyl unit content of 20 Softening point with respect to 100 parts by weight of diene rubber containing 35 to 89% by weight of modified conjugated diene polymer rubber having a weight average molecular weight of 600,000 to 1,000,000, and 11 to 40% by weight of butadiene rubber.
- the modified conjugated diene polymer rubber forms a fine phase separation form and is capable of reacting with the active end of the active conjugated diene polymer chain.
- the terminal modified group generated by the reaction with at least one compound having a group contains a functional group that interacts with silica, and the weight average molecular weight is set to 600,000 to 1,000,000 to optimize the concentration of the terminal modified group.
- the end-modifying group acts efficiently on the silica to further improve the dispersibility of the silica, thereby greatly reducing the low rolling resistance of the pneumatic tire and further improving the wet performance.
- Silica has a DBP absorption of 185 to 250 ml / 100 g and a ratio of nitrogen adsorption specific surface area (N 2 SA) to CTAB specific surface area (CTAB) (N 2 SA / CTAB) of 0.90 to 1.25. It is preferable that 70% by weight or more of silica is included in the total silica. By blending silica in this way, even if the blending amount of the filler is large, it is possible to achieve both good rolling resistance and wear resistance.
- Carbon black preferably has a nitrogen adsorption specific surface area of 70 to 165 m 2 / g, and can maintain and maintain both wet performance and rolling resistance without impairing wear resistance.
- the compound having a functional group capable of reacting with the active end of the active conjugated diene polymer chain described above preferably includes at least one polyorganosiloxane compound selected from the following general formulas (I) to (III).
- R 1 to R 8 are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and these may be the same or different from each other.
- X 1 and X 4 is an aryl group of the active conjugated diene polymer chain groups having a functional group capable of reacting with the active terminal of an alkyl group or having 6 to 12 carbon atoms having 1 to 6 carbon atoms,, X 1 and X 4 may be the same as or different from each other,
- X 2 is a group having a functional group that reacts with the active end of the active conjugated diene polymer chain,
- X 3 is a group of 2 to 20 alkylene glycols A group containing repeating units, and a part of X 3 may be a group derived from a group containing repeating units of 2 to 20 alkylene glycol, m is an integer of 3 to 200, and n is 0 to 200 is an integer, and k is an integer from a
- R 9 to R 16 are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and these may be the same or different from each other.
- X 5 to X 8 are groups having a functional group that reacts with the active terminal of the active conjugated diene polymer chain.
- R 17 to R 19 are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and these may be the same or different from each other.
- 9 to X 11 are groups having a functional group that reacts with the active end of the active conjugated diene polymer chain, and S is an integer of 1 to 18.
- ⁇ Pneumatic tires using this rubber composition in the tread part can improve the low rolling resistance, wet performance and wear resistance to the conventional level or higher.
- the rubber component is a diene rubber
- the diene rubber necessarily includes a modified conjugated diene polymer rubber and a butadiene rubber.
- the modified conjugated diene polymer rubber is a conjugated diene polymer rubber produced by solution polymerization that has functional groups at both ends of a molecular chain. Incorporating the modified conjugated diene polymer rubber increases the affinity with silica and improves dispersibility, further improving the action and effect of silica, thus improving low rolling resistance and wet performance, Increase wear resistance.
- the skeleton of the modified conjugated diene polymer is composed of a copolymer obtained by copolymerizing a conjugated diene monomer and an aromatic vinyl monomer.
- the conjugated diene monomer include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and 2-chloro-1,3-butadiene. 1,3-pentadiene and the like.
- aromatic vinyl monomer examples include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, ⁇ -methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert -Butylstyrene, divinylbenzene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl) dimethylaminoethyl ether, N, N-dimethylaminoethylstyrene, vinylpyridine and the like.
- the terminal of the conjugated diene polymer serving as a skeleton is constituted by an isoprene unit block. Since the terminal is composed of isoprene unit blocks, when the terminal is modified and silica is blended, the affinity between the modified conjugated diene polymer and silica is improved, and low heat build-up, wet performance, wear resistance Good.
- the conjugated diene monomer unit constituting the polymer contains a conjugated diene other than the isoprene unit, before adding the compound having a functional group capable of reacting with the active end of the active conjugated diene polymer chain, Alternatively, as will be described later, when the compound is reacted in multiple stages, or when the same or different compounds are sequentially reacted, a polymer having an active terminal is contained during the addition of these compounds separately. It is preferable to introduce isoprene unit blocks at the ends of the polymer by adding isoprene to the solution.
- the conjugated diene polymer is prepared by copolymerizing the above conjugated diene monomer and aromatic vinyl monomer in a hydrocarbon solvent using an organic active metal compound as an initiator.
- the hydrocarbon solvent may be any commonly used solvent, and examples thereof include cyclohexane, n-hexane, benzene, toluene and the like.
- an organic alkali metal compound is preferably used.
- organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stilbenelithium; dilithiomethane
- Organic polyvalent lithium compounds such as 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene
- organic sodium compounds such as sodium naphthalene
- organic potassium compounds such as potassium naphthalene Is mentioned.
- 3,3- (N, N-dimethylamino) -1-propyllithium, 3- (N, N-diethylamino) -1-propyllithium, 3- (N, N-dipropylamino) -1- Propyllithium, 3-morpholino-1-propyllithium, 3-imidazole-1-propyllithium and organolithium compounds in which these are chain-extended with 1 to 10 units of butadiene, isoprene or styrene can also be used.
- diethyl ether diethylene glycol dimethyl ether, tetrahydrofuran, 2,2-bis (2-oxolanyl) propane, etc. for the purpose of randomly copolymerizing aromatic vinyl monomers with conjugated diene monomers.
- aprotic polar compounds such as amines such as ethers, triethylamine and tetramethylethylenediamine.
- At least one compound having a reactive functional group is bonded to the active terminal of an active conjugated diene polymer chain obtained by copolymerizing a conjugated diene monomer and an aromatic vinyl monomer.
- the compound having a functional group capable of reacting with the active terminal of the active conjugated diene polymer chain may be bonded to at least one active conjugated diene polymer chain, and one or more active conjugates may be bonded to one compound. Diene polymer chains can be bonded.
- the modified conjugated diene polymer rubber used in the present invention is a modified rubber having modified groups at both ends of the conjugated diene polymer, and optionally other conjugated diene polymers having one or more modified groups. Bonded modified rubbers and mixtures of these modified rubbers can be included.
- the reaction between the active terminal of the active conjugated diene polymer chain and the compound having a functional group capable of reacting with this active terminal can be reacted in one stage or multiple stages. The same or different compounds can be reacted sequentially.
- examples of the compound having a functional group capable of reacting with the active terminal of the active conjugated diene polymer chain include tin compounds, silicon compounds, silane compounds, amide compounds and / or imide compounds, isocyanates and / or isothiocyanates.
- examples of compounds having compounds, ketone compounds, ester compounds, vinyl compounds, oxirane compounds, thiirane compounds, oxetane compounds, polysulfide compounds, polysiloxane compounds, polyorganosiloxane compounds, polyether compounds, polyene compounds, halogen compounds, fullerenes, etc. be able to. Of these, polyorganosiloxane compounds are preferred. These compounds can be bonded to a polymer by combining one type of compound or a plurality of compounds.
- the compound having a functional group capable of reacting with the active terminal of the active conjugated diene polymer chain include polyglycidyl ethers of polyhydric alcohols such as ethylene glycol diglycidyl ether and glycerin triglycidyl ether, and diglycidylated bisphenol A.
- Polyepoxy compounds of aromatic compounds having two or more phenol groups such as polyglycidyl ether, 1,4-diglycidylbenzene, 1,3,5-triglycidylbenzene, polyepoxidized liquid polybutadiene, etc.
- Epoxy group-containing tertiary amines such as' -diglycidyl-diphenylmethylamine, 4,4'-diglycidyl-dibenzylmethylamine, diglycidylaniline, diglycidylorthotoluidine, tetraglycidylmetaxylenediamine, tetraglycidylaminodi Enirumetan, tetraglycidyl -p- phenylenediamine, diglycidyl aminomethyl cyclohexane, diglycidyl amino compounds such as tetraglycidyl-1,3-bis-aminomethyl cyclohexane, and the like.
- silicon compound examples include tetrachlorosilicon, tetrabromosilicon, methyltrichlorosilicon, butyltrichlorosilicon, dichlorosilicon, bistrichlorosilylsilicon, and the like.
- tin compound examples include tetrachlorotin, tetrabromotin, methyltrichlorotin, butyltrichlorotin, dichlorotin, bistrichlorosilyltin, and bistrichlorosilyltin.
- silane compound examples include a silane compound containing at least one selected from an alkoxy group, a phenoxy group, and a halogen.
- silane compounds include dimethoxydimethylsilane, diphenoxydimethylsilane, diethoxydiethylsilane, triphenoxymethylsilane, triphenoxyvinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tri (2-methylbutoxy) ethylsilane, tri (2-methylbutoxy) vinylsilane, triphenoxyphenylsilane, tetraphenoxysilane, tetraethoxysilane, tetramethoxysilane, tetrakis (2-ethylhexyloxy) silane, phenoxydivinylchlorosilane, methoxybiethylchlorosilane, diphenoxymethylchlorosilane, diphenoxy Phenyl
- the silane compound can have a glycidyl group, an epoxy group, a methacryloxy group, or the like as a functional group other than the above.
- silane compounds include ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxybutyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -Glycidoxypropyltripropoxysilane, ⁇ -glycidoxypropyltributoxysilane, ⁇ -glycidoxypropyltriphenoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -glycidoxypropylethyldimethoxysilane, ⁇ -Glycidoxypropylethyldiethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane,
- Examples of the isocyanate compound or isothiocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, triphenylmethane triisocyanate, p-phenylene diisocyanate, tris (isocyanatophenyl) thiophosphate, xylylene diisocyanate, benzene-1,2,4-triisocyanate, naphthalene-1,2,5,7-tetraisocyanate, naphthalene-1 , 3,7-triisocyanate, phenyl isocyanate, hexamethylene diisocyanate, methylcyclohexane diisocyanate, phenyl-1,4-diisothiocyanate, 2,4-tolylene diisocyanate
- aromatic polyisocyanate compounds such
- a compound represented by the following general formula (IV) is preferable, and a plurality of active conjugated diene polymer chains can be easily bonded to one molecule of the compound.
- X 1 and X 2 are a halogen atom or an alkoxy group having 1 to 20 carbon atoms.
- P and q are each independently an integer of 0 to 3, and represented by Formula (IV).
- the total number of halogen atoms and alkoxy groups having 1 to 20 carbon atoms in the compound is at least 5.
- R 1 and R 2 are each a monovalent hydrocarbon group having 1 to 20 carbon atoms, n is 0 And A 1 and A 2 are each independently a single bond or a divalent hydrocarbon having 1 to 20 carbon atoms, A 3 is represented by the formula — (SiX 3 r R 3 2-r ) m-, or -NR 4 -, or -N (-A 4 -SiX 4 S R 5 3-S) -.
- X 3 is a halogen atom or is .R 3
- R 5 is an alkoxy group having a carbon number of 1 to 20
- .R 4 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, hydrogen atoms
- .A 4 is a monovalent hydrocarbon group having 1 to 20 carbon atoms
- .r is a divalent hydrocarbon group of a single bond or a C 1-20 is an integer of 0 ⁇ 2
- m is (It is an integer from 0 to 20.
- s is an integer from 0 to 3.)
- Examples of the compound represented by the general formula (IV) include hexachlorodisilane, bis (trichlorosilyl) methane, 1,2-bis (trichlorosilyl) ethane, 1,3-bis (trichlorosilyl) propane, 1,4 -Silicon halide compounds such as bis (trichlorosilyl) butane, 1,5-bis (trichlorosilyl) pentane, 1,6-bis (trichlorosilyl) hexane; hexamethoxydisilane, hexaethoxydisilane, bis (trimethoxysilyl) Methane, bis (triethoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (trimethoxysilyl) propane, bis (triethoxysilyl) propane, bis (trimethoxysilyl) butane,
- the polyorganosiloxane compound compounds represented by the following general formulas (I) to (III) are preferable. That is, the compound having a functional group capable of reacting with the active terminal of the active conjugated diene polymer chain may contain at least one selected from these polyorganosiloxane compounds, and a plurality of types may be combined. Moreover, you may combine these polyorganosiloxane compounds and the other compound which has a functional group which can react with an active terminal, for example, the compound represented by Formula (IV) mentioned above.
- R 1 to R 8 are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and these may be the same or different from each other.
- X 1 and X 4 is an aryl group of the active conjugated diene polymer chain groups having a functional group capable of reacting with the active terminal of an alkyl group or having 6 to 12 carbon atoms having 1 to 6 carbon atoms, X 1 and X 4 may be the same as or different from each other,
- X 2 is a group having a functional group that reacts with the active end of the active conjugated diene polymer chain,
- X 3 is a group of 2 to 20 alkylene glycols A group containing repeating units, and a part of X 3 may be a group derived from a group containing repeating units of 2 to 20 alkylene glycol, m is an integer of 3 to 200, and n is 0 to 200 is an integer, and k is
- R 9 to R 16 are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and these may be the same or different from each other.
- X 5 to X 8 are groups having a functional group that reacts with the active terminal of the active conjugated diene polymer chain.
- R 17 to R 19 are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and these may be the same or different from each other.
- 9 to X 11 are groups having a functional group that reacts with the active end of the active conjugated diene polymer chain, and S is an integer of 1 to 18.
- examples of the alkyl group having 1 to 6 carbon atoms constituting R 1 to R 8 , X 1 and X 4 include, for example, methyl group, ethyl group, n- Examples include propyl group, isopropyl group, butyl group, pentyl group, hexyl group, cyclohexyl group and the like.
- examples of the aryl group having 6 to 12 carbon atoms include a phenyl group and a methylphenyl group. Among these alkyl groups and aryl groups, a methyl group is particularly preferable.
- the group having a functional group that reacts with the active terminal of the polymer chain constituting X 1 , X 2 and X 4 includes an alkoxyl group having 1 to 5 carbon atoms, 2- A hydrocarbon group containing a pyrrolidonyl group and a group having 4 to 12 carbon atoms containing an epoxy group are preferred.
- Examples of the alkoxyl group having 1 to 5 carbon atoms constituting X 1 , X 2 and X 4 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. Of these, a methoxy group is preferable.
- X 1 , X 2 and X 4 are alkoxyl group having 1 to 5 carbon atoms
- a polyorganosiloxane having an alkoxyl group at the active end of the active conjugated diene polymer chain is reacted, a silicon atom and an alkoxyl
- the bond with the oxygen atom of the group is cleaved, and the active conjugated diene polymer chain is directly bonded to the silicon atom to form a single bond.
- Preferred examples of the hydrocarbon group containing a 2-pyrrolidonyl group constituting X 1 , X 2 and X 4 include groups represented by the following general formula (V).
- j is an integer of 2 to 10. In particular, j is preferably 2.
- polyorganosiloxane containing a hydrocarbon group in which at least one of X 1 , X 2 and X 4 contains a 2-pyrrolidonyl group is reacted with the active end of the active conjugated diene polymer chain, 2-pyrrolidonyl
- the carbon-oxygen bond of the carbonyl group constituting the group is cleaved to form a structure in which the polymer chain is bonded to the carbon atom.
- Preferred examples of the group having 4 to 12 carbon atoms and having an epoxy group constituting X 1 , X 2 and X 4 include groups represented by the following general formula (VI).
- Z is an alkylene group or alkylarylene group having 1 to 10 carbon atoms
- Y is a methylene group, sulfur atom or oxygen atom
- E is a carbon atom having 2 to 10 carbon atoms having an epoxy group. It is a hydrogen group.
- Y is preferably an oxygen atom, more preferably Y is an oxygen atom and E is a glycidyl group, Z is an alkylene group having 3 carbon atoms, Y is an oxygen atom, and E is a glycidyl group. Those are particularly preferred.
- the activity of the active conjugated diene polymer chain when a polyorganosiloxane is reacted at the terminal, the carbon-oxygen bond constituting the epoxy ring is cleaved to form a structure in which a polymer chain is bonded to the carbon atom.
- X 1 and X 4 among the above, a group having 4 to 12 carbon atoms or an alkyl group having 1 to 6 carbon atoms containing an epoxy group is preferable, X 2 is preferably a group having 4 to 12 carbon atoms containing an epoxy group.
- X 3 is a group containing 2 to 20 alkylene glycol repeating units.
- the group containing 2 to 20 alkylene glycol repeating units is preferably a group represented by the following general formula (VII).
- t is an integer of 2 to 20
- R 1 is an alkylene group or alkylarylene group having 2 to 10 carbon atoms
- R 3 is a hydrogen atom or a methyl group
- R 2 is a carbon number 1 to 10 alkoxyl groups or aryloxy groups.
- t is an integer of 2 to 8
- R 1 is an alkylene group having 3 carbon atoms
- R 3 is a hydrogen atom
- R 2 is a methoxy group
- R 9 to R 16 are alkyl groups having 1 to 6 carbon atoms or aryl groups having 6 to 12 carbon atoms, and these may be the same or different from each other. You may do it.
- X 5 to X 8 are groups having a functional group that reacts with the active end of the polymer chain.
- R 17 to R 19 are alkyl groups having 1 to 6 carbon atoms or aryl groups having 6 to 12 carbon atoms, and these may be the same or different from each other. You may do it.
- X 9 to X 11 are groups having a functional group that reacts with the active end of the polymer chain. s is an integer of 1 to 18.
- polyorganosiloxane represented by the general formula (II) and the general formula (III) it reacts with an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an active end of a polymer chain.
- the group having a functional group is the same as that described for the polyorganosiloxane of the general formula (I).
- generated by the said reaction has a functional group which has an interaction with a silica.
- the functional group having an interaction with silica may be a functional group included in the structure of the compound described above.
- the functional group which could be produced by reaction with the said compound and active terminal may be sufficient.
- the functional group having an interaction with silica is not particularly limited. For example, alkoxysilyl group, hydroxyl group (including organosiloxane structure), aldehyde group, carboxyl group, amino group, imino group, epoxy group Amide group, thiol group, ether group and the like. Of these, a hydroxyl group (including an organosiloxane structure) is preferable.
- affinity with a silica can be made higher and a dispersibility can be improved significantly.
- the concentration of the terminal modified group in the modified conjugated diene polymer rubber is determined in relation to the weight average molecular weight (Mw) of the modified conjugated diene polymer rubber.
- the weight average molecular weight of the modified conjugated diene polymer rubber is 600,000 to 1,000,000, preferably 650,000 to 850,000. For example, 650,000-750,000 and 750,000-850,000.
- the weight average molecular weight of the modified conjugated diene polymer rubber is less than 600,000, the modified group concentration at the end of the modified conjugated diene polymer rubber is increased, and the dispersibility of silica in the rubber composition is improved.
- the weight average molecular weight of the modified conjugated diene polymer rubber exceeds 1,000,000, the modified group concentration at the end of the modified conjugated diene polymer rubber will be low, the affinity with silica will be insufficient, and the dispersibility will deteriorate. The effect of reducing the resistance is insufficient, or the wet performance is insufficient. At the same time, the rigidity and strength of the rubber composition are lowered.
- the weight average molecular weight (Mw) of the modified conjugated diene polymer rubber is measured by gel permeation chromatography (GPC) in terms of standard polystyrene.
- the modified conjugated diene polymer rubber used in the present invention has an aromatic vinyl unit content of 38 to 48% by weight, preferably 40 to 45% by weight. For example, they are 40 to 41% by weight, 41 to 42% by weight, and 42 to 45% by weight.
- aromatic vinyl unit content of the modified conjugated diene polymer rubber within such a range, it is possible to achieve both wet performance and wear resistance when making a pneumatic tire.
- the modified conjugated diene polymer rubber forms a fine phase separation form with respect to the other diene rubber.
- the modified conjugated diene polymer rubber is localized near the silica particles, and the affinity of the terminal modified group is increased due to the effective action of the terminal modified group on the silica, thereby dispersing the silica.
- Property can be improved.
- the aromatic vinyl unit content of the modified conjugated diene polymer rubber is less than 38% by weight, the effect of forming a fine phase separation form with respect to other diene rubbers cannot be sufficiently obtained. Further, the effect of increasing the rigidity and strength of the rubber composition cannot be sufficiently obtained.
- the aromatic vinyl unit content of the modified conjugated diene polymer rubber exceeds 48% by weight, the glass transition temperature (Tg) of the conjugated diene polymer rubber rises, the balance of viscoelastic properties becomes worse, and heat is generated. It becomes difficult to obtain the effect of reducing the property.
- Tg glass transition temperature
- the aromatic vinyl unit content of the modified conjugated diene polymer rubber is measured by infrared spectroscopic analysis (Hampton method).
- the vinyl unit content of the modified conjugated diene polymer rubber is 20 to 35% by weight, preferably 26 to 34% by weight. For example, it is 26 to 32% by weight and 32 to 34% by weight.
- the term “vinyl unit” means a conjugated diene unit.
- the vinyl unit content of the modified conjugated diene polymer rubber is less than 20% by weight, the Tg of the modified conjugated diene polymer rubber becomes low, and the loss of dynamic viscoelastic properties at 0 ° C., which is an index of wet performance.
- the tangent (tan ⁇ ) decreases.
- the fine phase separation form of the modified conjugated diene polymer rubber cannot be stabilized.
- the vinyl unit content of the modified conjugated diene polymer rubber exceeds 35% by weight, the vulcanization rate may decrease, and the strength and rigidity may decrease.
- the vinyl unit content of the modified conjugated diene polymer rubber is measured by infrared spectroscopic analysis (Hampton method).
- the modified conjugated diene polymer rubber can improve the molding processability of the rubber composition by oil-extended.
- the amount of oil extended is not particularly limited, but is preferably 25 parts by weight or less with respect to 100 parts by weight of the modified conjugated diene polymer rubber.
- the oil extended amount of the modified conjugated diene polymer rubber exceeds 25 parts by weight, the degree of freedom in composition design is reduced when an oil, a softener, a tackifier or the like is added to the rubber composition.
- the glass transition temperature (Tg) of the modified conjugated diene polymer rubber is not particularly limited, but is preferably ⁇ 30 to ⁇ 15 ° C. By setting the Tg of the modified conjugated diene polymer rubber within such a range, it is possible to ensure steering stability and reduce rolling resistance. Moreover, wet grip performance is securable by making Tg into such a range.
- the glass transition temperature (Tg) of the modified conjugated diene polymer rubber is measured by a differential scanning calorimetry (DSC) under a temperature increase rate condition of 20 ° C./min, and is defined as the temperature at the midpoint of the transition region. When the modified conjugated diene polymer rubber is an oil-extended product, the glass transition temperature of the modified conjugated diene polymer rubber in a state not containing an oil-extended component (oil) is used.
- DSC differential scanning calorimetry
- the content of the modified conjugated diene polymer rubber is 35 to 89% by weight, preferably 40 to 85% by weight, in 100% by weight of the diene rubber.
- they are 40 to 45% by weight, 45 to 75% by weight, and 75 to 85% by weight.
- the content of the modified conjugated diene polymer rubber is less than 35% by weight in the diene rubber, the affinity with silica is deteriorated and the dispersibility of silica cannot be improved.
- the content of the modified conjugated diene polymer rubber exceeds 89% by weight, the glass transition temperature of the rubber composition becomes high, so that the wear resistance is lowered.
- the rubber composition for a tire tread of the present invention can improve the wear resistance while maintaining low rolling resistance and wet performance at a high level by containing butadiene rubber.
- the blending amount of butadiene rubber is 11 to 40% by weight, preferably 15 to 35% by weight, in 100% by weight of diene rubber. For example, the content is 15 to 30% by weight and 30 to 35% by weight. If the amount of butadiene rubber is less than 11% by weight, good wear resistance cannot be achieved. Moreover, when the compounding quantity of butadiene rubber exceeds 40 weight%, wet grip performance will deteriorate.
- the butadiene rubber those usually used in rubber compositions for tires may be used.
- diene rubbers other than modified conjugated diene polymer rubber (first modified conjugated diene polymer rubber) and butadiene rubber can be blended as a rubber component.
- diene rubbers include natural rubber, isoprene rubber, solution polymerized styrene butadiene rubber (S-SBR), emulsion polymerized styrene butadiene rubber (E-SBR), butyl rubber, and halogenated butyl rubber. Natural rubber, isoprene rubber, solution polymerized styrene butadiene rubber, and emulsion polymerized styrene butadiene rubber are preferred.
- the solution-polymerized styrene-butadiene rubber is a solution-polymerized styrene-butadiene rubber that is not terminal-modified, or a terminal-modified solution-polymerized styrene-butadiene rubber other than the modified conjugated diene-based polymer rubber of the present invention (second modified conjugated diene-based polymer rubber). ).
- Such diene rubbers can be used alone or as a plurality of blends.
- the content of the other diene rubber is 54% by weight or less, preferably 40% by weight or less, in 100% by weight of the diene rubber. For example, they are 1 to 25% by weight and 25 to 40% by weight.
- the upper limit of the content of other diene rubbers is not particularly limited, but is, for example, 1% by weight.
- the rubber composition for a tire tread of the present invention can further improve wet performance, particularly handling stability on a wet road surface while maintaining low rolling resistance by blending an aromatic modified terpene resin.
- an aromatic modified terpene resin one having a softening point of 100 to 150 ° C., preferably 110 to 140 ° C. may be used. For example, it is good to use what is 110-125 degreeC and 125-140 degreeC. When the softening point of the aromatic modified terpene resin is less than 100 ° C., the effect of improving the wet performance cannot be sufficiently obtained.
- the softening point of aromatic modified terpene resin exceeds 150 degreeC, the dispersibility with respect to diene type rubber will deteriorate, the grip performance on wet road surface will fall, and rubber strength will fall.
- the softening point of the aromatic modified terpene resin is measured according to JIS K6220-1 (ring and ball method).
- the blending amount of the aromatic modified terpene resin is 3 to 60 parts by weight with respect to 100 parts by weight of the diene rubber, and the ratio Wte / Wbr of the blending amount Wte of the aromatic modified terpene resin to the blending amount Wbr of the butadiene rubber is 0.00. 5 to 1.3, preferably 0.8 to 1.1. For example, 0.5 to 0.8, 0.8 to 1.3.
- the ratio Wte / Wbr is less than 0.5, the glass transition temperature of the rubber composition is lowered, and thus the effect of improving the wet grip performance cannot be sufficiently obtained.
- the blend amount of the aromatic modified terpene resin is, for example, 3 to 12 parts by weight, 12 to 40 parts by weight, or 40 to 60 parts by weight with respect to 100 parts by weight of the diene rubber.
- the aromatic modified terpene resin is obtained by polymerizing a terpene and an aromatic compound.
- terpenes include ⁇ -pinene, ⁇ -pinene, dipentene, limonene and the like.
- the aromatic compound include styrene, ⁇ -methylstyrene, vinyl toluene, indene and the like.
- a styrene-modified terpene resin is preferable as the aromatic-modified terpene resin.
- Such an aromatic modified terpene resin has good compatibility with the diene rubber, so that the tan ⁇ at 0 ° C. of the rubber composition is increased and the wet grip performance is improved.
- the hydroxyl value of the aromatic modified terpene resin is preferably 30 KOHmg / g or less, more preferably 0 to 25 KOHmg / g.
- the hydroxyl value of the aromatic modified terpene resin is measured according to JIS K1557-1.
- a filler containing 70 to 95% by weight of silica is blended in an amount of 100 to 150 parts by weight, for example, 100 to 120 parts by weight, 120 to 130 parts by weight, 130 to 150 parts by weight, based on 100 parts by weight of the diene rubber. .
- the compounding quantity of a filler into such a range, the low rolling resistance and wet performance of a rubber composition can be balanced at a higher level.
- the blending amount of the filler is less than 100 parts by weight, the wet performance is lowered.
- the blending amount of the filler exceeds 150 parts by weight, the heat generation becomes large and the low rolling resistance deteriorates.
- the content of silica in 100% by weight of the filler is 70% by weight or more, preferably 80 to 100% by weight. For example, it is 80 to 92% by weight and 92 to 100% by weight.
- the content of silica in the filler in such a range, the low rolling resistance and wet performance of the rubber composition can be balanced at a higher level.
- the affinity with a silica is made high and a dispersibility is improved by mix
- specific silica 1 can be used alone as silica, or specific silica 1 can be used together with other silicas.
- This specific silica 1 has a DBP absorption of 185 to 250 ml / 100 g, and a ratio of nitrogen adsorption specific surface area (N 2 SA) to CTAB specific surface area (CTAB) (N 2 SA / CTAB) of 0.9 to 1. 25 is preferably satisfied.
- the amount of silica 1 is preferably 70 to 100% by weight based on the total silica.
- the rubber composition for a tire tread of the present invention increases the blending amount of the filler to 100 to 150 parts by weight by blending only silica 1 or at least two types of silica containing silica 1 and 100 wt. While the silica content is 70% by weight or more, the low rolling resistance and wet performance and the wear resistance can be balanced at a high level.
- the blending amount of silica 1 is preferably 70% by weight or more, more preferably 80 to 100% by weight in the total silica. For example, they are 70 to 75% by weight, 75 to 83% by weight, and 83 to 100% by weight. When the blending amount of silica 1 is less than 70% by weight, the wear resistance is lowered due to a decrease in strength of the rubber.
- the DBP absorption amount of silica 1 is preferably 185 to 250 ml / 100 g. For example, they are 185 to 200 ml / 100 g and 200 to 250 ml / 100 g.
- the DBP absorption is less than 185 ml / 100 g, the abrasion resistance deteriorates because the breaking strength decreases.
- the DBP absorption exceeds 250 ml / 100 g, heat generation is deteriorated and rolling resistance is deteriorated.
- the DBP absorption amount of silica is determined in accordance with JIS K6217-4 oil absorption amount A method.
- the ratio of N 2 SA to CTAB (N 2 SA / CTAB) of silica 1 is preferably 0.90 to 1.25, more preferably 0.95 to 1.20. For example, 0.95 to 1.01 and 1.01 to 1.20.
- N 2 SA / CTAB characteristic ratio of silica
- the characteristic ratio of silica (N 2 SA / CTAB) is less than 0.90, the reinforcing property is lowered.
- the silica characteristic ratio (N 2 SA / CTAB) exceeds 1.25, the dispersibility of the silica is lowered, and the rolling resistance and wet performance are deteriorated.
- N 2 SA of silica is determined in accordance with JIS K6217-2.
- the CTAB of silica is determined according to JIS K6217-3.
- silica usually used in rubber compositions for tire treads, for example, wet method silica, dry method silica, or surface-treated silica can be used.
- the rubber composition of the present invention it is preferable to blend a silane coupling agent together with silica, so that the dispersibility of silica can be improved and the reinforcing property with the diene rubber can be further increased.
- the silane coupling agent is preferably added in an amount of 3 to 20% by weight, more preferably 5 to 15% by weight, based on the amount of silica. For example, 5 to 10% by weight and 10 to 15% by weight.
- the compounding amount of the silane coupling agent is less than 3% by weight of the silica weight, the effect of improving the dispersibility of the silica cannot be sufficiently obtained.
- the silane coupling agent exceeds 20% by weight, the silane coupling agents are polymerized with each other, and a desired effect cannot be obtained.
- the silane coupling agent is not particularly limited, but a sulfur-containing silane coupling agent is preferable.
- a sulfur-containing silane coupling agent is preferable.
- the carbon black preferably has a nitrogen adsorption specific surface area of 70 to 165 m 2 / g.
- they are 70 to 77 m 2 / g, 77 to 123 m 2 / g, 123 to 165 m 2 / g.
- the nitrogen adsorption specific surface area of the carbon black is less than 70 m 2 / g, the abrasion resistance deteriorates due to a decrease in reinforcement.
- N 2 SA of carbon black is obtained in accordance with JIS K6217-2.
- the blending amount of carbon black is not particularly limited, and is, for example, 10 to 15 parts by weight, 15 to 20 parts by weight, or 20 to 60 parts by weight with respect to 100 parts by weight of the diene rubber.
- the rubber composition for a tire tread of the present invention can contain other fillers other than silica.
- fillers other than silica include carbon black, clay, mica, talc, calcium carbonate, aluminum hydroxide, aluminum oxide, and titanium oxide. Of these, carbon black is preferred. By adding carbon black, the rubber strength can be increased.
- the tire tread rubber composition generally includes a vulcanization or crosslinking agent, a vulcanization accelerator, an anti-aging agent, a plasticizer, a processing aid, a liquid polymer, a thermosetting resin, and the like.
- Various compounding agents used can be blended.
- Such a compounding agent can be kneaded by a general method to form a rubber composition, which can be used for vulcanization or crosslinking.
- the compounding amounts of these compounding agents can be the conventional general compounding amounts as long as they do not contradict the purpose of the present invention.
- the rubber composition for a tire tread can be produced by mixing each of the above components using a known rubber kneading machine such as a Banbury mixer, a kneader, or a roll.
- the rubber composition for a tire tread of the present invention can be suitably used for a pneumatic tire.
- a pneumatic tire using this rubber composition in the tread portion can improve low rolling resistance, wet performance, and wear resistance to a level higher than the conventional level.
- the description of the total of the filler is the total of silica and carbon black (parts by weight)
- the description of the silica ratio in the filler is the description of the content of silica in 100% by weight (wt%)
- the ratio of silica 1 in silica Indicates the content (wt%) of silica 1 in 100 wt% of the total silica, and the ratio Wte / Wbr of the butadiene rubber blending amount Wbr and the aromatic modified terpene resin blending amount Wte, respectively.
- the amounts of the common compounding components shown in FIG. 4 mean that they were blended in parts by weight with respect to 100 parts by weight of the diene rubber described in FIGS.
- 38 types of the obtained rubber compositions for tire treads were press vulcanized at 160 ° C. for 20 minutes in a mold having a predetermined shape to prepare a vulcanized rubber sample, and rolling resistance (60 ° C. tan ⁇ ) and abrasion resistance were measured.
- Abrasion resistance Lambone wear of the obtained vulcanized rubber sample was measured in accordance with JIS K6264-2 using a lambone wear tester manufactured by Iwamoto Seisakusho under the conditions of a temperature of 20 ° C., a load of 15 N and a slip ratio of 50%. It was measured. The obtained results are shown in FIGS. 1 to 3 with the index of Comparative Example 1 as 100. The larger the index, the more excellent the abrasion resistance, especially when the index is 102 or more.
- the obtained pneumatic tire is assembled to a wheel with a rim size of 18 x 8 JJ, mounted on a domestic 2.5 liter class test vehicle, and a test course of 2.6 km per lap consisting of a wet road surface under the condition of air pressure 230 kPa.
- the vehicle was run, and the handling stability at that time was scored by a sensitive evaluation by three expert panelists.
- the obtained results are shown in FIGS. 1 to 3 with the index of Comparative Example 1 being 100. It means that the wet steering stability on a wet road surface is excellent when the index is larger, particularly when the index is 102 or more. 1 to 3 show the types of raw materials used.
- Modified S-SBR1 modified conjugated diene polymer rubber comprising a polyorganosiloxane having the structure of the above general formula (I), aromatic vinyl unit content 42% by weight, vinyl unit content 32%, weight average An oil-extended product having a molecular weight (Mw) of 750,000, Tg of ⁇ 25 ° C., 100 parts by weight of a rubber component and 25 parts by weight of oil, and a terminal-modified solution-polymerized styrene butadiene rubber prepared by the following production method.
- Mw molecular weight
- a small amount of an anti-aging agent (Irganox 1520, manufactured by BASF) is added to the obtained polymer solution, and 25 parts of Fukkoreramic 30 (manufactured by Nippon Oil Co., Ltd.) is added as an extending oil, and then solidified by a steam stripping method. Rubber was recovered. The obtained solid rubber was dehydrated with a roll and dried in a drier to obtain modified S-SBR1.
- an anti-aging agent Irganox 1520, manufactured by BASF
- Fukkoreramic 30 manufactured by Nippon Oil Co., Ltd.
- Modified S-SBR2 Modified conjugated diene polymer rubber comprising a polyorganosiloxane having the structure of the above general formula (II), aromatic vinyl unit content 42% by weight, vinyl unit content 32%, weight average An oil-extended product having a molecular weight (Mw) of 750,000, Tg of ⁇ 25 ° C., 100 parts by weight of a rubber component and 25 parts by weight of oil, and a terminal-modified solution-polymerized styrene butadiene rubber prepared by the following production method.
- Mw molecular weight
- a small amount of an anti-aging agent (Irganox 1520, manufactured by BASF) is added to the obtained polymer solution, and 25 parts of Fukkoreramic 30 (manufactured by Nippon Oil Co., Ltd.) is added as an extending oil, and then solidified by a steam stripping method. Rubber was recovered. The obtained solid rubber was dehydrated with a roll and dried in a drier to obtain modified S-SBR2.
- an anti-aging agent Irganox 1520, manufactured by BASF
- Fukkoreramic 30 manufactured by Nippon Oil Co., Ltd.
- Polyorganosiloxane B a polyorganosiloxane having the structure of the general formula (II), wherein R 9 to R 16 are each a methyl group (—CH 3 ), and X 5 to X 8 are each a formula (VIII).
- Modified S-SBR3 Modified conjugated diene polymer rubber composed of polyorganosiloxane having the structure of the above general formula (III), aromatic vinyl unit content 41% by weight, vinyl unit content 32%, weight average An oil-extended product having a molecular weight (Mw) of 750,000, Tg of ⁇ 25 ° C., 100 parts by weight of a rubber component and 25 parts by weight of oil, and a terminal-modified solution-polymerized styrene butadiene rubber prepared by the following production method.
- Mw molecular weight
- a small amount of an anti-aging agent (Irganox 1520, manufactured by BASF) is added to the obtained polymer solution, and 25 parts of Fukkoreramic 30 (manufactured by Nippon Oil Co., Ltd.) is added as an extending oil, and then solidified by a steam stripping method. Rubber was recovered. The obtained solid rubber was dehydrated with a roll and dried in a dryer to obtain modified S-SBR3.
- an anti-aging agent Irganox 1520, manufactured by BASF
- Fukkoreramic 30 manufactured by Nippon Oil Co., Ltd.
- Modified S-SBR4 terminal modified solution polymerized styrene butadiene rubber, aromatic vinyl unit content 30% by weight, vinyl unit content 61% by weight, weight average molecular weight (Mw) 590,000, Tg ⁇ 25 ° C., Nipol NS530, manufactured by ZEON Corporation
- -Modified S-SBR5 terminal modified solution polymerized styrene butadiene rubber, aromatic vinyl unit content 16% by weight, vinyl unit content 32%, weight average molecular weight (Mw) 610,000, Tg -60 ° C, Japan ZEON Nipol NS612, non-oil exhibition
- Modified S-SBR6 Modified conjugated diene polymer rubber composed of polyorganosiloxane having the structure of the general formula (I), aromatic vinyl unit content 34% by weight, vinyl unit content 34%, weight average An oil-extended product having a molecular weight (Mw) of 760,000, Tg of ⁇ 33 ° C., 25 parts by weight of oil per 100 parts by weight of the rubber component, and a terminal-modified solution-polymerized styrene butadiene rubber prepared by the following production method.
- Mw molecular weight
- a small amount of an anti-aging agent (Irganox 1520, manufactured by BASF) is added to the obtained polymer solution, and 25 parts of Fukkoreramic 30 (manufactured by Nippon Oil Co., Ltd.) is added as an extending oil, and then solidified by a steam stripping method. Rubber was recovered. The obtained solid rubber was dehydrated with a roll and dried in a drier to obtain modified S-SBR6.
- an anti-aging agent Irganox 1520, manufactured by BASF
- Fukkoreramic 30 manufactured by Nippon Oil Co., Ltd.
- Modified S-SBR7 Modified conjugated diene polymer rubber composed of polyorganosiloxane having the structure of the general formula (I), aromatic vinyl unit content 49% by weight, vinyl unit content 28%, weight average An oil-extended product having a molecular weight (Mw) of 710,000, Tg of ⁇ 17 ° C., 100 parts by weight of a rubber component and 25 parts by weight of oil, and a terminal-modified solution-polymerized styrene butadiene rubber prepared by the following production method.
- Mw molecular weight
- a small amount of an anti-aging agent (Irganox 1520, manufactured by BASF) is added to the obtained polymer solution, and 25 parts of Fukkoreramic 30 (manufactured by Nippon Oil Co., Ltd.) is added as an extending oil, and then solidified by a steam stripping method. Rubber was recovered. The obtained solid rubber was dehydrated with a roll and dried in a drier to obtain modified S-SBR7.
- an anti-aging agent Irganox 1520, manufactured by BASF
- Fukkoreramic 30 manufactured by Nippon Oil Co., Ltd.
- Modified S-SBR8 Modified conjugated diene polymer rubber composed of polyorganosiloxane having the structure of the above general formula (I), aromatic vinyl unit content 41% by weight, vinyl unit content 17%, weight average An oil-extended product having a molecular weight (Mw) of 740,000, Tg of ⁇ 37 ° C., 25 parts by weight of oil per 100 parts by weight of a rubber component, and a terminal-modified solution-polymerized styrene butadiene rubber prepared by the following production method.
- Mw molecular weight
- a small amount of anti-aging agent (Irganox 1520, manufactured by BASF) is added to the obtained polymer solution, and 25 parts of FUCKOL ERAMIC 30 (manufactured by Nippon Oil Co., Ltd.) is added as an extension oil, followed by steam stripping.
- the solid rubber was recovered.
- the obtained solid rubber was dehydrated with a roll and dried in a drier to obtain modified S-SBR8.
- Modified S-SBR9 Modified conjugated diene polymer rubber comprising polyorganosiloxane having the structure of the general formula (I), aromatic vinyl unit content 39% by weight, vinyl unit content 40%, weight average An oil-extended product having a molecular weight (Mw) of 750,000, Tg of -21 ° C., 100 parts by weight of a rubber component and 25 parts by weight of oil, and a terminal-modified solution-polymerized styrene butadiene rubber prepared by the following production method.
- Mw molecular weight
- a small amount of an anti-aging agent (Irganox 1520, manufactured by BASF) is added to the obtained polymer solution, and 25 parts of Fukkoreramic 30 (manufactured by Nippon Oil Co., Ltd.) is added as an extending oil, and then solidified by a steam stripping method. Rubber was recovered. The obtained solid rubber was dehydrated with a roll and dried in a drier to obtain modified S-SBR9.
- an anti-aging agent Irganox 1520, manufactured by BASF
- Fukkoreramic 30 manufactured by Nippon Oil Co., Ltd.
- Modified S-SBR10 terminal modified solution polymerized styrene butadiene rubber, aromatic vinyl unit content 37% by weight, vinyl unit content 43% by weight, weight average molecular weight (Mw) 1.2 million, Tg ⁇ 27 ° C.
- S-SBR unmodified solution-polymerized styrene butadiene rubber, aromatic vinyl unit content 41% by weight, vinyl unit content 25%, weight average molecular weight (Mw) 1,010,000, Tg -30 ° C, Dow Chemical SLR6430, an oil-extended product containing 37.5 parts by weight of oil with respect to 100 parts by weight of the rubber component
- BR butadiene rubber
- Silica-b Rhodia Zeosil 115GR, DBP absorption 160 ml / 100 g, nitrogen adsorption specific surface area (N 2 SA) 115 m 2 / g,
- Terpene resin 1 aromatic modified terpene resin having a softening point of 125 ° C., YS resin TO-125 manufactured by Yasuhara Chemical Co., Ltd.
- Terpene resin 2 Aromatic modified terpene resin having a softening point of 85 ° C., YS resin TO-85 manufactured by Yashara Chemical Co., Ltd.
- Terpene resin 3 Aromatic modified terpene resin having a softening point of 105 ° C., YS resin TO-105 manufactured by Yashara Chemical Co., Ltd.
- Coupling agent Si69 manufactured by Evonik Degussa ⁇ Oil: Showa Shell Sekiyu Extract 4 S
- ⁇ Stearic acid NOF beads stearic acid YR Anti-aging agent: Santoflex 6PPD manufactured by Flexis ⁇ Wax: Sunnock manufactured by Ouchi Shinsei Chemical Co., Ltd. ⁇ Zinc flower: Zinc oxide 3 types manufactured by Shodo Chemical Industry Co., Ltd. ⁇ Sulfur: Fine powder sulfur containing Jinhua seal oil manufactured by Tsurumi Chemical Industry Co., Ltd. , Nouchira CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd. ⁇ Vulcanization accelerator 2: Vulcanization accelerator DPG, Noxeller D manufactured by Ouchi Shinsei Chemical Co., Ltd.
- the rubber composition of Comparative Example 2 has a modified S-SBR4 having an aromatic vinyl unit content of less than 38% by weight, a vinyl unit content of more than 35% by weight, and a weight average molecular weight of 600,000. Therefore, the low rolling resistance (tan ⁇ at 60 ° C.), the wet performance and the wear resistance cannot be improved.
- the rubber composition of Comparative Example 3 was blended with unmodified S-SBR instead of the modified conjugated diene polymer rubber, so that the dispersibility of the silica was poor, so that the rolling resistance was deteriorated, and the wear resistance was sufficiently improved. Can not do it.
- the rubber composition of Comparative Example 4 has a wet performance because the modified S-SBR5 has an aromatic vinyl unit content of less than 38% by weight, a vinyl unit content of more than 35% by weight, and a weight average molecular weight of less than 600,000. Gets worse.
- the aromatic vinyl unit content of the modified S-SBR6 is less than 38% by weight, the wet performance is deteriorated.
- the aromatic vinyl unit content of the modified S-SBR7 exceeds 48% by weight, rolling resistance and wear resistance are deteriorated.
- the rubber composition of Comparative Example 7 cannot improve the wet performance because the vinyl unit content of the modified S-SBR8 is less than 20% by weight.
- the vinyl unit content of the modified S-SBR9 exceeds 35% by weight, the rolling resistance is deteriorated.
- the wet performance cannot be improved because the compounding amount of butadiene rubber exceeds 40% by weight.
- the compounding amount of butadiene rubber is less than 11% by weight, so the wear resistance is deteriorated and sufficient rolling resistance cannot be improved.
- the rubber composition of Comparative Example 11 has a modified S-SBR1 content of less than 35% by weight, so the rolling resistance deteriorates and the wear resistance cannot be improved.
- the rubber composition of Comparative Example 12 since the blending amount of the modified S-SBR1 exceeds 89% by weight and the blending amount of the butadiene rubber is less than 11% by weight, the wear resistance is deteriorated and the rolling resistance is sufficiently improved. Not done.
- the total amount of the filler is less than 100 parts by weight, the wet performance is deteriorated and the wear resistance cannot be sufficiently improved.
- the silica ratio in 100% by weight of the total filler is less than 70% by weight, so that the rolling resistance is deteriorated and the wet performance cannot be improved.
- the total compounding amount of the filler exceeds 150 parts by weight, so that the rolling resistance is deteriorated. Since the weight ratio Wte / Wbr of the terpene resin and butadiene rubber is less than 0.5, the rubber composition of Comparative Example 16 cannot improve the wet performance. Since the ratio Wte / Wbr of the rubber composition of Comparative Example 17 exceeds 1.3, rolling resistance and wear resistance are deteriorated.
- the softening point of the terpene resin 2 is less than 100 ° C., the wet performance is deteriorated. Also, the rolling resistance cannot be improved sufficiently.
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Abstract
Description
(上記式(I)において、R1~R8は、炭素数1~6のアルキル基または炭素数6~12のアリール基であり、これらは互いに同一であっても相違してもよい。X1およびX4は、活性共役ジエン系重合体鎖の活性末端と反応する官能基を有する基、または炭素数1~6のアルキル基もしくは炭素数6~12のアリール基であり、X1およびX4は互いに同一であっても相違してもよい。X2は、活性共役ジエン系重合体鎖の活性末端と反応する官能基を有する基である。X3は、2~20のアルキレングリコールの繰返し単位を含有する基であり、X3の一部は2~20のアルキレングリコールの繰返し単位を含有する基から導かれる基であってもよい。mは3~200の整数、nは0~200の整数、kは0~200の整数である。)
(上記式(II)において、R9~R16は、炭素数1~6のアルキル基または炭素数6~12のアリール基であり、これらは互いに同一であっても相違してもよい。X5~X8は、活性共役ジエン系重合体鎖の活性末端と反応する官能基を有する基である。)
(上記式(III)において、R17~R19は、炭素数1~6のアルキル基または炭素数6~12のアリール基であり、これらは互いに同一であっても相違してもよい。X9~X11は、活性共役ジエン系重合体鎖の活性末端と反応する官能基を有する基である。Sは1~18の整数である。)
(式(IV)において、X1及びX2はハロゲン原子又は炭素数1~20のアルコキシ基である。p及びqは、それぞれ独立に0~3の整数であり、式(IV)で表わされる化合物におけるハロゲン原子及び炭素数1~20のアルコキシ基の数の合計は5以上である。R1及びR2は、それぞれ炭素数1~20の1価の炭化水素基である。nは、0~20の整数であり、A1及びA2は、それぞれ独立に、単結合又は炭素数1~20の2価の炭化水素である。A3は、式-(SiX3 rR3 2-r)m-、又は-NR4-、又は-N(-A4-SiX4 SR5 3-S)-で表わされる2価の基である。なお、X3,X4は、ハロゲン原子または炭素数1~20のアルコキシ基である。R3,R5は、炭素数1~20の1価の炭化水素基である。R4は、水素原子または炭素数1~20の1価の炭化水素基である。A4は、単結合または炭素数1~20の2価の炭化水素基である。rは0~2の整数であり、mは0~20の整数である。sは、0~3の整数である。)
(上記式(I)において、R1~R8は、炭素数1~6のアルキル基または炭素数6~12のアリール基であり、これらは互いに同一であっても相違してもよい。X1およびX4は、活性共役ジエン系重合体鎖の活性末端と反応する官能基を有する基、または炭素数1~6のアルキル基もしくは炭素数6~12のアリール基であり、X1およびX4は互いに同一であっても相違してもよい。X2は、活性共役ジエン系重合体鎖の活性末端と反応する官能基を有する基である。X3は、2~20のアルキレングリコールの繰返し単位を含有する基であり、X3の一部は2~20のアルキレングリコールの繰返し単位を含有する基から導かれる基であってもよい。mは3~200の整数、nは0~200の整数、kは0~200の整数である。)
(上記式(II)において、R9~R16は、炭素数1~6のアルキル基または炭素数6~12のアリール基であり、これらは互いに同一であっても相違してもよい。X5~X8は、活性共役ジエン系重合体鎖の活性末端と反応する官能基を有する基である。)
(上記式(III)において、R17~R19は、炭素数1~6のアルキル基または炭素数6~12のアリール基であり、これらは互いに同一であっても相違してもよい。X9~X11は、活性共役ジエン系重合体鎖の活性末端と反応する官能基を有する基である。Sは1~18の整数である。)
(式(V)中、jは2~10の整数である。特にjは2であることが好ましい。)
このようにX1,X2及びX4の少なくとも一つが2-ピロリドニル基を含有する炭化水素基を含むポリオルガノシロキサンを、活性共役ジエン系重合体鎖の活性末端に反応させると、2-ピロリドニル基を構成するカルボニル基の炭素-酸素結合が開裂して、その炭素原子に重合体鎖が結合した構造を形成する。
一般式(VI): ZYE
上記式(VI)中、Zは炭素数1~10のアルキレン基またはアルキルアリーレン基であり、Yはメチレン基、硫黄原子または酸素原子であり、Eはエポキシ基を有する炭素数2~10の炭化水素基である。これらの中でも、Yが酸素原子であるものが好ましく、Yが酸素原子かつEがグリシジル基であるものがより好ましく、Zが炭素数3のアルキレン基、Yが酸素原子かつEがグリシジル基であるものが特に好ましい。
式(VII)中、tは2~20の整数であり、R1は炭素数2~10のアルキレン基またはアルキルアリーレン基であり、R3は水素原子またはメチル基であり、R2は炭素数1~10のアルコキシル基またはアリーロキシ基である。これらの中でも、tが2~8の整数であり、R1が炭素数3のアルキレン基であり、R3が水素原子であり、かつR2がメトキシ基であるものが好ましい。
得られた加硫ゴムサンプルの転がり抵抗を、転がり抵抗の指標であることが知られている損失正接tanδ(60℃)により評価した。tanδ(60℃)は、東洋精機製作所社製粘弾性スペクトロメーターを用いて、初期歪み10%、振幅±2%、周波数20Hz、温度60℃の条件下で測定した。得られた結果は比較例1を100とする指数として、図1~3に示した。この指数が小さいほど、特に指数が98以下であると、tanδ(60℃)が小さく低発熱であり、空気入りタイヤにしたとき転がり抵抗が小さく燃費性能が優れることを意味する。
得られた加硫ゴムサンプルのランボーン摩耗を、JIS K6264-2に準拠して、岩本製作所社製ランボーン摩耗試験機を使用し、温度20℃、荷重15N、スリップ率50%の条件で測定した。得られた結果は、比較例1を100とする指数として、図1~3に示した。この指数が大きいほど、特に指数が102以上であると、耐摩耗性が優れることを意味する。
得られた空気入りタイヤをリムサイズ18×8JJのホイールに組付け、国産2.5リットルクラスの試験車両に装着し、空気圧230kPaの条件で湿潤路面からなる1周2.6kmのテストコースを実車走行させ、そのときの操縦安定性を専門パネラー3名による感応評価により採点した。得られた結果は比較例1を100とする指数として、図1~3に示した。この指数が大きいほど、特に指数が102以上であると、湿潤路面におけるウェット操縦安定性が優れていることを意味する。
なお、図1~3において使用した原材料の種類を示す。
窒素置換された内容量10Lのオートクレーブ反応器に、シクロヘキサン4533g、スチレン338.9g(3.254mol)、ブタジエン468.0g(8.652mol)、イソプレン20.0g(0.294mol)およびN,N,N′,N′-テトラメチルエチレンジアミン0.189mL(1.271mmol)を仕込み、攪拌を開始した。反応容器内の内容物の温度を50℃にした後、n-ブチルリチウム5.061mL(7.945mmol)を添加した。重合転化率がほぼ100%に到達した後、さらにイソプレン12.0gを添加して5分間反応させた後、1,6-ビス(トリクロロシリル)ヘキサンの40wt%トルエン溶液0.281g(0.318mmol)を添加し、30分間反応させた。さらに、下記に示すポリオルガノシロキサンAの40wt%キシレン溶液18.3g(0.318mmol)を添加し、30分間反応させた。メタノール0.5mLを添加して30分間攪拌した。得られたポリマー溶液に老化防止剤(イルガノックス1520、BASF社製)を少量添加し、伸展油としてフッコールエラミック30(新日本石油社製)を25部添加した後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、変性S-SBR1を得た。
窒素置換された内容量10Lのオートクレーブ反応器に、シクロヘキサン4550g、スチレン341.1g(3.275mol)、ブタジエン459.9g(8.502mol)、イソプレン20.0g(0.294mol)およびN,N,N′,N′―テトラメチルエチレンジアミン0.190mL(1.277mmol)を仕込み、攪拌を開始した。反応容器内の内容物の温度を50℃にした後、n-ブチルリチウム5.062mL(7.946mmol)を添加した。重合転化率がほぼ100%に到達した後、さらにイソプレン12.0gを添加して5分間反応させた後、1,6-ビス(トリクロロシリル)ヘキサンの40wt%トルエン溶液0.283g(0.320mmol)を添加し、30分間反応させた。さらに下記に示すポリオルガノシロキサンBの40wt%キシレン溶液19.0g(0.330mmol)を添加し、30分間反応させた。メタノール0.5mLを添加して30分間攪拌した。得られたポリマー溶液に老化防止剤(イルガノックス1520、BASF社製)を少量添加し、伸展油としてフッコールエラミック30(新日本石油社製)を25部添加した後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、変性S-SBR2を得た。
窒素置換された内容量10Lのオートクレーブ反応器に、シクロヘキサン4542g、スチレン339.2g(3.257mol)、ブタジエン462.8g(8.556mol)、イソプレン20.0g(0.294mol)およびN,N,N′,N′―テトラメチルエチレンジアミン0.188mL(1.264mmol)を仕込み、攪拌を開始した。反応容器内の内容物の温度を50℃にした後、n-ブチルリチウム5.059mL(7.942mmol)を添加した。重合転化率がほぼ100%に到達した後、さらにイソプレン12.0gを添加して5分間反応させた後、1,6-ビス(トリクロロシリル)ヘキサンの40wt%トルエン溶液0.283g(0.320mmol)を添加し、30分間反応させた。さらに下記に示すポリオルガノシロキサンCの40wt%キシレン溶液19.2g(0.333mmol)を添加し、30分間反応させた。メタノール0.5mLを添加して30分間攪拌した。得られたポリマー溶液に老化防止剤(イルガノックス1520、BASF社製)を少量添加し、伸展油としてフッコールエラミック30(新日本石油社製)を25部添加した後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、変性S-SBR3を得た。
窒素置換された内容量10Lのオートクレーブ反応器に、シクロヘキサン4541g、スチレン277.6g(2.665mol)、ブタジエン523.1g(9.671mol)、イソプレン20.0g(0.294mol)およびN,N,N′,N′―テトラメチルエチレンジアミン0.175mL(1.178mmol)を仕込み、攪拌を開始した。反応容器内の内容物の温度を50℃にした後、n-ブチルリチウム4.984mL(7.824mmol)を添加した。重合転化率がほぼ100%に到達した後、さらにイソプレン12.0gを添加して5分間反応させた後、1,6-ビス(トリクロロシリル)ヘキサンの40wt%トルエン溶液0.273g(0.327mmol)を添加し、30分間反応させた。さらに、上述したポリオルガノシロキサンAの40wt%キシレン溶液18.1g(0.314mmol)を添加し、30分間反応させた。メタノール0.5mLを添加して30分間攪拌した。得られたポリマー溶液に老化防止剤(イルガノックス1520、BASF社製)を少量添加し、伸展油としてフッコールエラミック30(新日本石油社製)を25部添加した後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、変性S-SBR6を得た。
窒素置換された内容量10Lのオートクレーブ反応器に、シクロヘキサン4536g、スチレン401.0g(3.850mol)、ブタジエン392.0g(7.247mol)、イソプレン20.0g(0.294mol)およびN,N,N′,N′―テトラメチルエチレンジアミン0.201mL(1.352mmol)を仕込み、攪拌を開始した。反応容器内の内容物の温度を50℃にした後、n-ブチルリチウム5.141mL(8.071mmol)を添加した。重合転化率がほぼ100%に到達した後、さらにイソプレン12.0gを添加して5分間反応させた後、1,6-ビス(トリクロロシリル)ヘキサンの40wt%トルエン溶液0.279g(0.320mmol)を添加し、30分間反応させた。さらに、上述したポリオルガノシロキサンAの40wt%キシレン溶液18.6g(0.323mmol)を添加し、30分間反応させた。メタノール0.5mLを添加して30分間攪拌した。得られたポリマー溶液に老化防止剤(イルガノックス1520、BASF社製)を少量添加し、伸展油としてフッコールエラミック30(新日本石油社製)を25部添加した後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、変性S-SBR7を得た。
窒素置換された内容量10Lのオートクレーブ反応器に、シクロヘキサン4542g、スチレン339.2g(3.257mol)、ブタジエン462.8g(8.556mol)、イソプレン20.0g(0.294mol)およびN,N,N′,N′―テトラメチルエチレンジアミン0.0376mL(0.253mmol)を仕込み、攪拌を開始した。反応容器内の内容物の温度を50℃にした後、n-ブチルリチウム5.059mL(7.942mmol)を添加した。重合転化率がほぼ100%に到達した後、さらにイソプレン12.0gを添加して5分間反応させた後、1,6-ビス(トリクロロシリル)ヘキサンの40wt%トルエン溶液0.280g(0.331mmol)を添加し、30分間反応させた。さらに、上述したポリオルガノシロキサンAの40wt%キシレン溶液18.8g(0.326mmol)を添加し、30分間反応させた。メタノール0.5mLを添加して30分間攪拌した。得られたポリマー溶液に老化防止剤(イルガノックス1520、BASF社製)を少量添加し、伸展油としてフッコールエラミック30(新日本石油株式化社製)を25部添加した後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、変性S-SBR8を得た。
窒素置換された内容量10Lのオートクレーブ反応器に、シクロヘキサン4543g、スチレン319.8g(3.071mol)、ブタジエン480.1g(8.876mol)、イソプレン20.0g(0.294mol)およびN,N,N′,N′―テトラメチルエチレンジアミン0.217mL(1.462mmol)を仕込み、攪拌を開始した。反応容器内の内容物の温度を50℃にした後、n-ブチルリチウム5.141mL(8.0714mmol)を添加した。重合転化率がほぼ100%に到達した後、さらにイソプレン12.0gを添加して5分間反応させた後、1,6-ビス(トリクロロシリル)ヘキサンの40wt%トルエン溶液0.279g(0.320mmol)を添加し、30分間反応させた。さらに、上述したポリオルガノシロキサンAの40wt%キシレン溶液18.6g(0.323mmol)を添加し、30分間反応させた。メタノール0.5mLを添加して30分間攪拌した。得られたポリマー溶液に老化防止剤(イルガノックス1520、BASF社製)を少量添加し、伸展油としてフッコールエラミック30(新日本石油社製)を25部添加した後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、変性S-SBR9を得た。
・BR:ブタジエンゴム、日本ゼオン社製Nipol BR1220
・シリカ-a(シリカ1):ローディア社製Zeosil 1165MP、DBP吸収量が200ml/100g、窒素吸着比表面積(N2SA)が160m2/g、CTAB比表面積(CTAB)が159m2/g、N2SA/CTABが1.01
・シリカ-b:ローディア社製Zeosil 115GR、DBP吸収量が160ml/100g、窒素吸着比表面積(N2SA)が115m2/g、CTAB比表面積(CTAB)が110m2/g、N2SA/CTABが1.06
・CB1:カーボンブラック、東海カーボン社製シースト7HM、N2SA=123m2/g
・CB2:カーボンブラック、東海カーボン社製シーストKHA、N2SA=77m2/g
・テルペン樹脂1:軟化点が125℃の芳香族変性テルペン樹脂、ヤスハラケミカル社製YSレジンTO-125
・テルペン樹脂2:軟化点が85℃の芳香族変性テルペン樹脂、ヤスハラケミカル社製YSレジンTO-85
・テルペン樹脂3:軟化点が105℃の芳香族変性テルペン樹脂、ヤスハラケミカル社製YSレジンTO-105
・カップリング剤:エボニックデグサ社製Si69
・オイル:昭和シェル石油社製エキストラクト 4号S
・ステアリン酸:日油社製ビーズステアリン酸YR
・老化防止剤:フレキシス社製サントフレックス6PPD
・ワックス:大内新興化学工業社製サンノック
・亜鉛華:正同化学工業社製酸化亜鉛3種
・硫黄:鶴見化学工業社製金華印油入微粉硫黄
・加硫促進剤1:加硫促進剤CBS、大内新興化学工業社製ノクセラーCZ-G
・加硫促進剤2:加硫促進剤DPG、大内新興化学工業社製ノクセラーD
Claims (6)
- 変性共役ジエン系重合体ゴムを35~89重量%、ブタジエンゴムを11~40重量%含むジエン系ゴム100重量部に対し、
芳香族変性テルペン樹脂を3~60重量部、
充填剤を100~150重量部配合すると共に、
前記充填剤中シリカを70重量%以上含み、
前記ブタジエンゴムの配合量Wbrに対する芳香族変性テルペン樹脂の配合量Wteの比Wte/Wbrが0.5~1.3であり、かつ
前記変性共役ジエン系重合体ゴムが、炭化水素溶媒中、有機活性金属化合物を開始剤として用いて共役ジエン系単量体と芳香族ビニル単量体とを共重合させた活性共役ジエン系重合体鎖に、その重合体鎖の活性末端と反応可能な官能基を有する少なくとも1種類の化合物を反応させた末端変性基を有し、該末端変性基がシリカとの相互作用を有する官能基を含むと共に、
この変性共役ジエン系重合体ゴムの芳香族ビニル単位含有量が38~48重量%、ビニル単位含有量が20~35重量%、重量平均分子量が60万~100万であり、
前記芳香族変性テルペン樹脂の軟化点が100~150℃である
ことを特徴とするタイヤトレッド用ゴム組成物。 - 前記シリカ中の70重量%以上が、DBP吸収量が185~250ml/100g、かつ窒素吸着比表面積(N2SA)とCTAB比表面積(CTAB)の比(N2SA/CTAB)が0.90~1.25を満たすことを特徴とする請求項1に記載のタイヤトレッド用ゴム組成物。
- 前記活性共役ジエン系重合体鎖の活性末端と反応可能な官能基を有する化合物が、下記一般式(I)~(III)から選ばれる少なくとも1種類のポリオルガノシロキサン化合物を含むことを特徴とする請求項1又は2に記載のタイヤトレッド用ゴム組成物。
(上記式(I)において、R1~R8は、炭素数1~6のアルキル基または炭素数6~12のアリール基であり、これらは互いに同一であっても相違してもよい。X1およびX4は、活性共役ジエン系重合体鎖の活性末端と反応する官能基を有する基、または炭素数1~6のアルキル基もしくは炭素数6~12のアリール基であり、X1およびX4は互いに同一であっても相違してもよい。X2は、活性共役ジエン系重合体鎖の活性末端と反応する官能基を有する基である。X3は、2~20のアルキレングリコールの繰返し単位を含有する基であり、X3の一部は2~20のアルキレングリコールの繰返し単位を含有する基から導かれる基であってもよい。mは3~200の整数、nは0~200の整数、kは0~200の整数である。)
(上記式(II)において、R9~R16は、炭素数1~6のアルキル基または炭素数6~12のアリール基であり、これらは互いに同一であっても相違してもよい。X5~X8は、活性共役ジエン系重合体鎖の活性末端と反応する官能基を有する基である。)
(上記式(III)において、R17~R19は、炭素数1~6のアルキル基または炭素数6~12のアリール基であり、これらは互いに同一であっても相違してもよい。X9~X11は、活性共役ジエン系重合体鎖の活性末端と反応する官能基を有する基である。Sは1~18の整数である。) - 窒素吸着比表面積が70~165m2/gのカーボンブラックを含むことを特徴とする請求項1~3のいずれかに記載のタイヤトレッド用ゴム組成物。
- さらに、前記変性共役ジエン系重合体ゴムである第1の変性共役ジエン系重合体ゴム以外に、第2の変性共役ジエン系重合体ゴムを、前記ジエン系ゴム中54重量%以下含むことを特徴とする請求項1~4のいずれかに記載のタイヤトレッド用ゴム組成物。
- 請求項1~5のいずれかに記載のタイヤトレッド用ゴム組成物を使用した空気入りタイヤ。
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US14/379,271 US9139721B2 (en) | 2012-02-15 | 2013-02-15 | Rubber composition for tire treads |
CN201380019931.XA CN104220510B (zh) | 2012-02-15 | 2013-02-15 | 轮胎胎面用橡胶组合物 |
KR1020147025488A KR101523627B1 (ko) | 2012-02-15 | 2013-02-15 | 타이어 트레드용 고무 조성물 |
DE112013000983.8T DE112013000983B9 (de) | 2012-02-15 | 2013-02-15 | Kautschukzusammensetzung zur Verwendung in Reifenlaufflächen, vulkanisiertes Produkt und dessen Verwendung |
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CN104220510A (zh) | 2014-12-17 |
JP2013166864A (ja) | 2013-08-29 |
US9139721B2 (en) | 2015-09-22 |
KR101523627B1 (ko) | 2015-05-28 |
DE112013000983B4 (de) | 2016-03-10 |
KR20140117693A (ko) | 2014-10-07 |
DE112013000983B9 (de) | 2016-06-30 |
CN104220510B (zh) | 2016-04-13 |
JP5316660B2 (ja) | 2013-10-16 |
US20150031791A1 (en) | 2015-01-29 |
DE112013000983T5 (de) | 2014-12-04 |
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