WO2015194549A1 - タイヤ用ゴム組成物および空気入りタイヤ - Google Patents
タイヤ用ゴム組成物および空気入りタイヤ Download PDFInfo
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- WO2015194549A1 WO2015194549A1 PCT/JP2015/067299 JP2015067299W WO2015194549A1 WO 2015194549 A1 WO2015194549 A1 WO 2015194549A1 JP 2015067299 W JP2015067299 W JP 2015067299W WO 2015194549 A1 WO2015194549 A1 WO 2015194549A1
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/45—Friedel-Crafts-type
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- 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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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three 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
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- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the present invention relates to a rubber composition for a tire and a pneumatic tire.
- Patent Document 1 discloses a rubber composition containing a conjugated diene rubber having an isoprene block. According to Patent Document 1, it is described that by using the above composition, the affinity between silica and rubber is improved, and the low heat build-up (low rolling resistance) and wet grip properties of the tire can be improved. ing.
- the present invention provides a tire rubber composition excellent in wear resistance, wet performance, dry performance and low rolling resistance when made into a tire, and the tire rubber composition in the tread portion.
- An object is to provide a used pneumatic tire.
- the present inventor determined that a natural rubber, a diene blend rubber comprising a predetermined solution polymerization SBR and a predetermined emulsion polymerization SBR, an aromatic modified terpene resin, silica, and carbon black are predetermined. It was found that by blending at a ratio of, it showed excellent wear resistance, wet performance, dry performance and low rolling resistance when made into a tire, and the present invention was achieved. That is, the present inventor has found that the above problem can be solved by the following configuration.
- the solution polymerization SBR contains a specific solution polymerization SBR having a block containing an isoprene unit at one end and a modified end for silica at the other end,
- the styrene unit content of the emulsion polymerization SBR is 35 to 50% by mass
- the content of the natural rubber in the diene blend rubber is 10 to 30% by mass
- the total content of the solution polymerization SBR and the emulsion polymerization SBR in the diene blend rubber is 70 to 90% by mass
- the content of the aromatic modified terpene resin is 1 to 25 parts by mass with respect to 100 parts by mass of the diene blend rubber
- the silica content is 80 to 150 parts by mass with respect to 100 parts by mass of the diene blend rubber.
- a tire rubber composition wherein the content of the carbon black is 15 to 50 parts by mass with respect to 100 parts by mass of the diene blend rubber.
- the used pneumatic tire can be provided.
- the tire rubber composition of the present invention (hereinafter also simply referred to as the composition of the present invention) is a diene blend rubber comprising natural rubber, solution-polymerized SBR and emulsion-polymerized SBR, an aromatic-modified terpene resin, silica, Carbon black.
- the solution polymerization SBR contains a specific solution polymerization SBR having a block containing an isoprene unit at one end and a modified terminal for silica at the other end.
- the emulsion polymerization SBR has a styrene unit content of 35 to 50% by mass (hereinafter, the emulsion polymerization SBR is also referred to as a specific emulsion polymerization SBR).
- the content of the natural rubber in the diene blend rubber is 10 to 30% by mass.
- the total content of the solution polymerization SBR and the emulsion polymerization SBR in the diene blend rubber is 70 to 90% by mass.
- the content of the aromatic modified terpene resin is 1 to 25 parts by mass with respect to 100 parts by mass of the diene blend rubber.
- the silica content is 80 to 150 parts by mass with respect to 100 parts by mass of the diene blend rubber.
- the carbon black content is 15 to 50 parts by mass with respect to 100 parts by mass of the diene blend rubber.
- the composition of this invention takes such a structure, it is thought that a desired effect is acquired. The reason is not clear, but it is presumed that it is as follows.
- the specific solution polymerization SBR contained in the composition of the present invention has a block containing an isoprene unit at one end and a modified end for silica at the other end. Therefore, it is considered that these terminals interact with silica and a good dispersion state is formed, and as a result, excellent low rolling resistance is exhibited.
- a flexible and strong three-dimensional network structure is obtained by using natural rubber, emulsion polymerization SBR having a specific microstructure (specifically, styrene unit content), aromatic modified terpene resin and carbon black in a predetermined ratio.
- a specific microstructure specifically, styrene unit content
- aromatic modified terpene resin and carbon black
- the wear resistance, wet performance and dry performance are also excellent.
- the diene blend rubber contained in the composition of the present invention comprises natural rubber, a solution polymerization SBR containing a specific solution polymerization SBR, and a specific emulsion polymerization SBR.
- the diene blend rubber contains natural rubber.
- the content of natural rubber in the diene blend rubber is 10 to 30% by mass. In particular, the content is preferably 15 to 25% by mass. If the content of the natural rubber in the diene blend rubber is less than 10% by mass, the resulting tire has insufficient wear resistance and dry performance. On the other hand, if the content of the natural rubber in the diene blend rubber exceeds 30% by mass, the wear resistance, wet performance and dry performance become insufficient.
- the solution polymerization SBR contained in the diene-based blend rubber contains a specific solution polymerization SBR described later.
- the content of the specific solution polymerization SBR in the solution polymerization SBR is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 50% by mass or more.
- the specific solution polymerization SBR is not particularly limited as long as it is a solution polymerization SBR having a block containing an isoprene unit at one end and a modified end for silica at the other end.
- the block containing the isoprene unit is not particularly limited as long as it is a homopolymer of isoprene or a copolymer of isoprene and another monomer (monomer).
- the content of the isoprene unit is not particularly limited, but is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and 100% by mass. Particularly preferred.
- the specific solution polymerization SBR has a modified end for silica at the other end. That is, the specific solution polymerized SBR is modified at the other end to an end capable of interacting with silica (preferably an end capable of reacting with a silanol group on the silica surface).
- the modified terminal for silica is not particularly limited as long as it is a terminal capable of interacting with silica, and examples thereof include a terminal having a polyorganosiloxane structure.
- the modified terminal for silica preferably has at least one group selected from the group consisting of an epoxy group and a hydrocarbyloxysilyl group.
- solution polymerization SBR for example, three or more SBR polymer chains (p1) obtained by a reaction between an SBR polymer chain (p1) described later and a modifier (p2) described later are included.
- SBR solution polymerization SBR
- P solution polymerization SBR
- P2 solution polymerization SBR
- SBR polymer chain (p1) used to form the structure (p) contained in the solution polymerization SBR (P) is a polymer comprising a butadiene monomer unit and a styrene monomer.
- the chain is not particularly limited as long as it has an isoprene block at one end and an active end (polymerization active end or living growth end) at the other end.
- the SBR polymer chain (p1) is obtained by, for example, subjecting an isoprene or isoprene mixture containing a predetermined amount of isoprene in an inert solvent by living polymerization using a polymerization initiator (active end (polymerization active end)). Or isoprene block having a living growth terminal), and then a monomer mixture comprising a butadiene monomer and a styrene monomer is bonded to the isoprene block having an active terminal, followed by living polymerization. Can be obtained.
- the isoprene block is a homopolymer of isoprene or a copolymer of isoprene and another monomer (monomer), and is a polyisoprene having a content of isoprene units of 70% by mass or more.
- the content of isoprene units in the isoprene block is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass.
- the SBR polymer chain (p1) has the isoprene block at one end.
- An isoprene block may be further included in the chain of the SBR polymer chain (p1). It has an isoprene block at both ends, and an isoprene block at one end of them may have an active end, but it is preferable from the viewpoint of productivity to have an isoprene block only at the end that is not the active end. .
- the weight average molecular weight of the isoprene block is not particularly limited, but is preferably 500 to 25,000, more preferably 1,000 to 15,000, and particularly preferably 1,500 to 10,000 from the viewpoint of strength. is there.
- the molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the isoprene block is not particularly limited, but from the viewpoint of productivity, it is preferably 1.0 to 1. 5, more preferably 1.0 to 1.4, particularly preferably 1.0 to 1.3.
- isoprene block Other monomers that can be copolymerized with isoprene used for obtaining the isoprene block are not particularly limited as long as they are copolymerizable with isoprene, and examples thereof include 1,3-butadiene, styrene, ⁇ -methylstyrene. Etc. can be used. Among these, styrene is preferable.
- the content of other monomer units is less than 30% by mass, preferably less than 20% by mass, more preferably less than 10% by mass, and monomers other than isoprene units. It is particularly preferred not to contain.
- any solvent that is usually used in solution polymerization and does not inhibit the polymerization reaction can be used without particular limitation.
- Specific examples thereof include, for example, chain aliphatic hydrocarbons such as butane, pentane, hexane, heptane and 2-butene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclohexene; aromatics such as benzene, toluene and xylene. Group hydrocarbons; and the like.
- the amount of the inert solvent used is not particularly limited, but is usually an amount such that the concentration of all monomers (isoprene and other monomers) is 1 to 50% by mass, preferably 10 to 40% by mass. It is the quantity which becomes.
- the polymerization initiator for synthesizing the isoprene block is not particularly limited as long as it is capable of living polymerizing isoprene (or an isoprene mixture) to give a polymer chain having an active end.
- a polymerization initiator mainly comprising an alkali metal compound, an organic alkaline earth metal compound, a lanthanum series metal compound, or the like is preferably used.
- organic alkali metal compound examples include, for example, organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenelithium; dilithiomethane, 1,4-dilithiobutane Organic polyvalent lithium compounds such as 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, and 1,3,5-tris (lithiomethyl) benzene; organic sodium compounds such as sodium naphthalene; Organic potassium compounds such as potassium naphthalene; and the like.
- organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenelithium
- dilithiomethane 1,4-dilithiobutane
- Organic polyvalent lithium compounds such
- organic alkaline earth metal compounds include di-n-butylmagnesium, di-n-hexylmagnesium, diethoxycalcium, calcium distearate, di-t-butoxystrontium, diethoxybarium, diisopropoxybarium, diethyl Examples include mercaptobarium, di-t-butoxybarium, diphenoxybarium, diethylaminobarium, barium distearate, and diketylbarium.
- a polymerization initiator having a lanthanum series metal compound as a main catalyst a lanthanum series metal salt comprising a lanthanum series metal such as lanthanum, cerium, praseodymium, neodymium, samarium and gadolinium, a carboxylic acid, and a phosphorus-containing organic acid
- a polymerization initiator comprising this and a co-catalyst such as an alkylaluminum compound, an organoaluminum hydride compound, and an organoaluminum halide compound.
- organic monolithium compounds and organic polyvalent lithium compounds are preferably used, organic monolithium compounds are more preferably used, and n-butyllithium is particularly preferably used.
- the organic alkali metal compound is a secondary compound such as dibutylamine, dihexylamine, dibenzylamine, pyrrolidine, hexamethyleneimine, and heptamethyleneimine (preferably pyrrolidine, hexamethyleneimine, and heptamethyleneimine). You may make it react with an amine and use it as an organic alkali metal amide compound.
- These polymerization initiators can be used alone or in combination of two or more.
- the amount of the polymerization initiator used may be determined according to the target molecular weight, but is preferably 4 to 250 mmol, more preferably 30 to 200 mmol, and particularly preferably 40 to 100 mmol per 100 g of isoprene (or isoprene mixture). It is a range.
- the polymerization temperature is usually in the range of ⁇ 80 to 150 ° C., preferably 0 to 100 ° C., more preferably 20 to 90 ° C.
- a polar compound to the inert organic solvent during the polymerization.
- the polar compound include ether compounds such as dibutyl ether, tetrahydrofuran and 2,2-di (tetrahydrofuryl) propane; tertiary amines such as tetramethylethylenediamine; alkali metal alkoxides; phosphine compounds; Among these, ether compounds and tertiary amines are preferable, and among them, those capable of forming a chelate structure with the metal of the polymerization initiator are more preferable, and 2,2-di (tetrahydrofuryl) propane and tetramethylethylenediamine are particularly preferable.
- the amount of the polar compound used may be determined according to the target vinyl bond content, and is preferably adjusted in the range of 0.1 to 30 mol, more preferably 0.5 to 10 mol with respect to 1 mol of the polymerization initiator. do it. When the amount of the polar compound used is within this range, the vinyl bond content can be easily adjusted, and problems due to the deactivation of the polymerization initiator hardly occur.
- the content of vinyl bonds derived from isoprene units in the isoprene block is preferably 5 to 85% by mass, more preferably 21 to 85% by mass, still more preferably 50 to 80% by mass, and particularly preferably 70 to 80% by mass.
- the isoprene unit-derived vinyl bond content is the ratio of the total of 1,2-vinyl bond units derived from isoprene units and 3,4-vinyl bond units derived from isoprene units (mass). %).
- the portion other than the isoprene block in the SBR polymer chain (p1) is a copolymer chain of a butadiene monomer and a styrene monomer.
- the mass ratio of the butadiene monomer unit and the styrene monomer unit in the portion other than the isoprene block (butadiene monomer unit: styrene monomer unit) is preferably 100: 0 to 50:50, 90:10 to 70:30 is more preferable.
- Examples of the butadiene monomer used for obtaining a portion other than the isoprene block in the SBR polymer chain (p1) include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2, Examples include 3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, and the like. Among these, 1,3-butadiene or isoprene is preferably used, and 1,3-butadiene is more preferably used. These butadiene monomers can be used alone or in combination of two or more.
- the styrene monomer used for obtaining a portion other than the isoprene block in the SBR polymer chain (p1) is not particularly limited.
- styrene, ⁇ -methylstyrene, and 4-methylstyrene are preferable, and styrene is more preferable.
- These styrenic monomers can be used alone or in combination of two or more.
- a butadiene type monomer and a styrene type monomer are optionally added within a range not impairing the essential characteristics of the present invention.
- Other monomers other than the body can be used.
- Other monomers include, for example, ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated carboxylic acids or acid anhydrides such as acrylic acid, methacrylic acid, and maleic anhydride; methyl methacrylate Unsaturated carboxylic acid esters such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene Non-conjugated dienes can be mentioned.
- the amount of these monomers used is preferably 10% by mass or less, preferably 5% by mass or less, based on all monomers used for obtaining a portion other than the isoprene block in the SBR polymer chain (p1). More preferably.
- the inert solvent used for the polymerization of a portion other than the isoprene block in the SBR polymer chain (p1) is the same as the inert solvent used for the synthesis of the isoprene block described above.
- the polymerization initiator used for the synthesis of a portion other than the isoprene block in the SBR polymer chain (p1) the above-described isoprene block having an active end is used as it is.
- the amount of the polymerization initiator used may be determined according to the target molecular weight, but is usually 0.1 to 5 mmol, preferably 0.2 to 2 mmol, more preferably 0 per 100 g of the monomer (mixture). The range is from 3 to 1.5 mmol.
- the polymerization temperature is usually in the range of ⁇ 80 to 150 ° C., preferably 0 to 100 ° C., more preferably 20 to 90 ° C. .
- the polymerization mode any mode such as batch mode or continuous mode can be adopted, but batch mode is preferable.
- the bonding mode of the portion other than the isoprene block in the SBR polymer chain (p1) can be various bonding modes such as block, taper, or random. Among these, a random shape is preferable.
- the bonding mode of butadiene monomer and styrene monomer is random, the ratio of styrene monomer to the total amount of butadiene monomer and styrene monomer in the polymerization system It is preferable to polymerize by supplying a butadiene monomer or a butadiene monomer and a styrene monomer continuously or intermittently into the polymerization system so that the temperature does not become too high.
- an inert organic solvent is used during the polymerization. It is preferable to add a polar compound to. However, when an isoprene block is synthesized, if an amount of polar compound sufficient to adjust the vinyl bond content in the portion other than the isoprene block of the SBR polymer chain is added to the inert organic solvent, It is not necessary to add a polar compound.
- the specific example about the polar compound used in order to adjust vinyl bond content in parts other than an isoprene block is the same as the polar compound used for the synthesis
- the amount of the polar compound used may be determined according to the target vinyl bond content, and is preferably adjusted in the range of 0.01 to 100 mol, more preferably 0.1 to 30 mol with respect to 1 mol of the polymerization initiator. do it. When the amount of the polar compound used is within this range, the vinyl bond content in the portion other than the isoprene block can be easily adjusted, and problems due to the deactivation of the polymerization initiator hardly occur.
- the vinyl bond content in the part other than the isoprene block of the SBR polymer chain (p1) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, from the viewpoint of the balance between viscoelastic properties and strength. is there.
- the vinyl bond content in the portion other than the isoprene block is the ratio (% by mass) of vinyl bond units in the portion other than the isoprene block of the SBR polymer chain (p1).
- the weight average molecular weight of the SBR polymer chain (p1) is not particularly limited, but is preferably 1,000 to 2,000,000, more preferably 10,000 to 1,500,000, and 100,000 to 1, 000,000 is particularly preferred.
- the molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the SBR polymer chain (p1) is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, particularly preferably 1.0 to 2.2.
- Mw / Mn molecular weight distribution value
- P solution polymerization SBR
- the SBR polymer chain (p1) forms an isoprene block having an active end by, for example, living polymerizing isoprene (or a mixture of isoprene) in an inert solvent using a polymerization initiator first. Then, using this isoprene block as a new polymerization initiator, it can be obtained by living polymerizing a butadiene monomer and a styrene monomer. At this time, the isoprene block may be added to the monomer solution, or the monomer may be added to the isoprene block solution, but it is preferable to add the isoprene block to the monomer solution.
- isoprene block is also added to the active terminal side of the SBR polymer chain (p1) by newly adding isoprene (or isoprene mixture). Can be formed.
- the amount of isoprene (or isoprene mixture) used is preferably 10 to 100 mol, more preferably 15 to 70 mol, and particularly preferably 20 to 35 mol with respect to 1 mol of the polymerization initiator used in the initial polymerization reaction.
- the preferred range of the mass ratio of the butadiene monomer unit to the styrene monomer unit (butadiene monomer unit: styrene monomer unit) in the SBR polymer chain (p1) is the above-described isoprene block. It is the same as other parts.
- the preferable range of the vinyl bond content in the SBR polymer chain (p1) is also the same as the portion other than the above-described isoprene block.
- the vinyl bond content in the SBR polymer chain (p1) is the proportion (mass%) of vinyl bond units in the SBR polymer chain (p1).
- the solution-polymerized SBR (P) has an active end of the SBR polymer chain (p1) obtained as described above, an epoxy group and / or a hydrocarbyloxysilyl group, the epoxy group, and the hydrocarbyloxysilyl group. It is formed by reaction with a modifier (p2) having a total number of 3 or more with a hydrocarbyloxy group (—OR: where R is a hydrocarbon group or an aryl group) contained in the group.
- the “modifier” is a compound having a functional group that reacts with the active end of the SBR polymer chain (p1) in one molecule.
- the functional group to be contained is limited to those having an affinity for silica.
- the functional group is an epoxy group or a hydrocarbyloxy group contained in a hydrocarbyloxysilyl group.
- the modifier (p2) used to form the structure (p) contained in the solution-polymerized SBR (P) has an epoxy group and / or a hydrocarbyloxysilyl group, and the epoxy group and the hydrocarbyloxysilyl group If it is a modifier
- Those having 3 or more in the molecule can be used, and in addition, both the epoxy group and the hydrocarbyloxysilyl group are included in the molecule, and in one molecule, in the epoxy group and the hydrocarbyloxysilyl group Those having a total number of 3 or more of hydrocarbyloxy groups bonded to silicon atoms can also be used.
- the silicon atom having one hydrocarbyloxy group Includes two or more, those having two or more hydrocarbyloxy groups on the same silicon atom, and combinations thereof.
- the organic group is not particularly limited.
- the epoxy group is opened by opening at least a part of the epoxy group in the modifier (p2). It is considered that a bond is formed between the carbon atom of the ring portion and the active end of the SBR polymer chain (p1).
- the SBR polymer chain (p1) reacts with the modifier (p2) having a hydrocarbyloxysilyl group
- at least a part of the hydrocarbyloxysilyl group in the hydrocarbyloxysilyl group of the modifier (p2) is eliminated. By doing so, it is considered that a bond between the silicon atom contained in the modifier (p2) and the active end of the SBR polymer chain (p1) is formed.
- the 3 or more SBR polymer chains (p1) are converted into the modifying agent (p1).
- a solution-polymerized SBR (P) having a structure (p) bonded through p2) can be obtained.
- hydrocarbyloxysilyl group contained in the modifier (p2) examples include alkoxysilyl groups such as methoxysilyl group, ethoxysilyl group, propoxysilyl group, butoxysilyl group, and aryloxysilyl groups such as phenoxysilyl group. Can be mentioned. Among these, an alkoxysilyl group is preferable and an ethoxysilyl group is more preferable.
- Examples of the hydrocarbyloxy group contained in the hydrocarbyloxysilyl group contained in the modifier (p2) include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and an aryloxy group such as a phenoxy group. Can be mentioned. Among these, an alkoxy group is preferable and an ethoxy group is more preferable.
- the modifying agent (p2) is preferably a polyorganosiloxane.
- the polyorganosiloxane represented by following formula (A1), the polyorganosiloxane represented by following formula (A2), and the polyorganosiloxane represented by following formula (A3) examples thereof include siloxane and hydrocarbyloxysilane represented by the following formula (A4).
- a polyorganosiloxane represented by the following formula (A1), a polyorganosiloxane represented by the following formula (A2), and a polyorganosiloxane represented by the following formula (A3) are preferable.
- the polyorganosiloxane represented by (A1) is more preferable.
- 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 are each an alkoxy group having 1 to 5 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, or a group having 4 to 12 carbon atoms containing an epoxy group, or carbon
- An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and X 1 and X 4 may be the same or different.
- X 2 is an alkoxy group having 1 to 5 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, or 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.
- m is an integer of 3 to 200
- n is an integer of 0 to 200
- k is an integer of 0 to 200.
- R 9 to R 16 are each 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 as or different from each other.
- X 5 to X 8 are an alkoxy group having 1 to 5 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, or a group having 4 to 12 carbon atoms containing an epoxy group. May be the same or different.
- R 17 to R 19 are each 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 as or different from each other.
- X 9 to X 11 are an alkoxy group having 1 to 5 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, or a group having 4 to 12 carbon atoms containing an epoxy group. May be the same or different.
- s is an integer of 1 to 18.
- R 20 is an alkylene group having 1 to 12 carbon atoms.
- R 21 to R 29 are each 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 as or different from each other.
- r is an integer of 1 to 10.
- examples of the alkyl group having 1 to 6 carbon atoms represented by 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, and cyclohexyl group.
- examples of the aryl group having 6 to 12 carbon atoms include a phenyl group and a methylphenyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of production of the polyorganosiloxane itself.
- examples of the alkoxy group having 1 to 5 carbon atoms represented by X 1 , X 2 and X 4 include a methoxy group, an ethoxy group, a propoxy group, A propoxy group, a butoxy group, etc. are mentioned. Especially, a methoxy group and an ethoxy group are preferable from a reactive viewpoint with the active terminal of a SBR type polymer chain (p1).
- examples of the aryloxy group having 6 to 14 carbon atoms represented by X 1 , X 2 , and X 4 include a phenoxy group and a tolyloxy group. It is done.
- Z 1 is an alkylene group or alkylarylene group having 1 to 10 carbon atoms
- Z 2 is a methylene group, a sulfur atom, or an oxygen atom
- E is a carbon number 2 having an epoxy group. ⁇ 10 hydrocarbyl groups (hydrocarbon groups).
- * represents a bonding position.
- Z 2 is an oxygen atom
- Z 2 is an oxygen atom
- E is a glycidyl group
- Z 1 is 3 carbon atoms
- Z 2 is an oxygen atom
- E is a glycidyl group
- X 1 and X 4 are preferably a group having 4 to 12 carbon atoms containing an epoxy group or an alkyl group having 1 to 6 carbon atoms.
- X 2 is preferably a group having 4 to 12 carbon atoms containing an epoxy group, X 1 and X 4 are alkyl groups having 1 to 6 carbon atoms, and X 2 is an epoxy group. It is more preferably a group having 4 to 12 carbon atoms containing a group.
- the group represented by the following formula (A6) is preferred as the group containing X 3 , that is, a repeating unit of 2 to 20 alkylene glycol.
- t is an integer of 2 to 20
- P is an alkylene group or alkylarylene group having 2 to 10 carbon atoms
- R is a hydrogen atom or a methyl group
- Q is 1 to carbon atoms. 10 alkoxy groups or aryloxy groups.
- * represents a bonding position.
- P is an alkylene group having 3 carbon atoms
- R is a hydrogen atom
- Q is a methoxy group
- m is preferably an integer of 20 to 150, more preferably 30 to 120, for the reason that low rolling resistance and mechanical strength are more excellent.
- n is preferably an integer of 0 to 150, more preferably an integer of 0 to 120.
- k is preferably an integer of 0 to 150, more preferably an integer of 0 to 120.
- the total number of m, n, and k is preferably 400 or less, more preferably 300 or less, and particularly preferably 250 or less. .
- the total number of m, n, and k is 400 or less, the production of the polyorganosiloxane itself is facilitated, the viscosity is not excessively increased, and the handling is facilitated.
- examples of the alkylene group having 1 to 12 carbon atoms represented by R 20 include a methylene group, an ethylene group, and a propylene group. Among these, a propylene group is preferable.
- specific examples and preferred embodiments of R 21 to R 29 are the same as R 1 to R 8 in the above formula (A1).
- hydrocarbyloxysilane represented by the above formula (A4) include N, N-bis (trimethylsilyl) -3-aminopropyltrimethoxysilane and N, N-bis (trimethylsilyl) -3-aminopropyltriethoxy.
- examples include silane, N, N-bis (trimethylsilyl) aminoethyltrimethoxysilane, and N, N-bis (trimethylsilyl) aminoethyltriethoxysilane.
- N, N-bis (trimethylsilyl) -3-aminopropyltrimethoxysilane and N, N-bis (trimethylsilyl) -3-aminopropyltriethoxysilane are preferably used.
- modifier (p2) examples include tetraalkoxysilane compounds such as tetramethoxysilane; hexaalkoxysilane compounds such as bis (trimethoxysilyl) methane; alkylalkoxysilane compounds such as methyltriethoxysilane; vinyltrimethoxy Alkenyl alkoxysilane compounds such as Silane; arylalkoxysilane compounds such as phenyltrimethoxysilane; halogenoalkoxysilane compounds such as triethoxychlorosilane; 3-glycidoxyethyltrimethoxysilane, 3-glycidoxybutylpropyltri Epoxy group-containing alkoxysilane compounds such as methoxysilane and bis (3-glycidoxypropyl) dimethoxysilane; sulfur-containing compounds such as bis (3- (triethoxysilyl) propyl) disulfide Lucoxysilane compound; amino
- one type may be used alone, or two or more types may be used in combination.
- modifier denaturant (p2)
- the ratio of the total number of moles of the epoxy group and the hydrocarbyloxy group contained in the hydrocarbyloxysilyl group is usually from 0.1 to 5, and the reason why the rolling resistance and mechanical strength are more excellent is 0. 5 to 3 is preferable.
- the SBR polymer chain (p1) is a polymerization terminator other than the polymerization terminator and the modifier (p2), as long as the effect of the present invention is not inhibited before reacting the above modifier (p2), and A coupling agent or the like may be added to the polymerization system to inactivate a part of the active terminal of the SBR polymer chain (p1).
- polymerization terminal modifier and coupling agent used at this time examples include N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, and N-methyl- ⁇ -caprolactam.
- N-substituted cyclic amides N-substituted cyclic ureas such as 1,3-dimethylethyleneurea and 1,3-diethyl-2-imidazolidinone; 4,4′-bis (dimethylamino) benzophenone, and N-substituted amino ketones such as 4,4′-bis (diethylamino) benzophenone; aromatic isocyanates such as diphenylmethane diisocyanate and 2,4-tolylene diisocyanate; N, N-dimethylaminopropyl methacrylamide and the like N, N-disubstituted aminoalkylmethacrylamides; 4-N, N- N-substituted aminoaldehydes such as methylaminobenzaldehyde; N-substituted carbodiimides such as dicyclohexylcarbodiimide; Schiff bases such as N-ethylethylideneimine and
- a metal halide compound is preferably used as a coupling agent for the reason that the coupling efficiency is more excellent, and a silicon halide compound having 5 or more silicon-halogen atom bonds in one molecule is used as a coupling agent. More preferably, 1,6-bis (trichlorosilyl) hexane is particularly preferably used.
- the amount of coupling agent used is not particularly limited as long as it does not impair the effects of the present invention.
- the amount used is as follows.
- the ratio of the number of moles of silicon-halogen atom bonds of the silicon halide compound to the number of moles of the polymerization initiator used in the polymerization reaction is 0.001 to It is preferably 0.25, more preferably 0.01 to 0.2.
- the above coupling agents may be used alone or in combination of two or more.
- the modifier (p2) and the coupling agent When adding the modifier (p2) and the coupling agent to the solution containing the SBR polymer chain (p1), they are dissolved in an inert solvent and polymerized from the viewpoint of controlling the reaction well. It is preferable to add in the system.
- the solution concentration is preferably in the range of 1 to 50% by mass.
- the solution polymerization SBR (P) is a solution polymerization SBR obtained by reacting the SBR polymer chain (p1) with the modifier (p2), specifically, three or more SBR polymer chains.
- the structure (p) formed by bonding (p1) through the modifier (p2) contains 5% by mass or more.
- the reaction between the SBR polymer chain (p1) and the modifier (p2) can be performed, for example, by adding the modifier (p2) to a solution containing the SBR polymer chain (p1).
- the timing for adding the modifier (p2), the coupling agent, etc. is not particularly limited, but the polymerization reaction in the SBR polymer chain (p1) is not completed and the solution contains the SBR polymer chain (p1). More specifically, a solution containing a monomer such as isoprene, more specifically, a solution containing an SBR polymer chain (p1) is preferably 100 ppm or more, more preferably 300 to 50,000 ppm. It is desirable to add a denaturing agent (p2), a coupling agent, and the like to this solution while containing the body. By adding a modifier (p2), a coupling agent, etc., side reactions between the SBR polymer chain (p1) and impurities contained in the polymerization system can be suppressed, and the reaction can be controlled well. It becomes possible.
- solution polymerization SBR when two or more modifiers (p2) and coupling agents are used in combination, the order of adding them to the polymerization system is not particularly limited. Even when the modifier (p2) and a silicon halide compound as a coupling agent having 5 or more silicon-halogen atom bonds in one molecule are used in combination, the order of addition is not particularly limited. It is preferable to add the agent prior to the addition of the modifier (p2). By adding in such an order, it becomes easy to obtain a highly branched solution polymerization SBR obtained via a coupling agent, and a tire obtained using the highly branched solution polymerization SBR is more excellent in driving stability. .
- the temperature is usually in the range of 0 to 100 ° C., preferably 30 to 90 ° C., and each reaction time is usually 1 to 1 ° C. The range is 120 minutes, preferably 2 to 60 minutes.
- an anti-aging agent such as a phenol-based stabilizer, a phosphorus-based stabilizer, a sulfur-based stabilizer, a crumbing agent, a scale inhibitor, etc. Is added to the polymerization solution, and then the polymerization solvent is separated from the polymerization solution by direct drying and steam stripping to recover solution-polymerized SBR (P).
- an extension oil may be mixed into the polymerization solution, and the solution polymerization SBR (P) may be recovered as an oil-extended rubber.
- Examples of the extending oil (oil-extended oil) used when recovering the solution-polymerized SBR (P) as an oil-extended rubber include, for example, paraffinic, aromatic and naphthenic petroleum softeners, plant softeners, and fatty acids. Etc.
- the polycyclic aromatic content is preferably less than 3%. This content is measured by the method of IP346 (the inspection method of THE INSTITUTE PETROLEUM, UK).
- the amount used is usually 5 to 100 parts by weight, preferably 10 to 60 parts by weight, more preferably 20 to 50 parts by weight with respect to 100 parts by weight of the solution polymerization SBR (P). is there.
- the solution-polymerized SBR (P) contains 5% by mass or more of a structure (p) in which three or more SBR polymer chains (p1) are bonded via a modifier (p2), more preferably 5 It is contained in an amount of ⁇ 40% by mass, particularly preferably 10-30% by mass.
- the ratio of the structure (p) in which three or more SBR polymer chains (p1) are bonded via the modifier (p2) to the total amount of the solution-polymerized SBR (P) finally obtained is expressed as “three branches.
- the above coupling rate (mass%) "(hereinafter also simply referred to as coupling rate) is used. This can be measured by gel permeation chromatography (polystyrene conversion).
- the ratio (s2 / s1) is a coupling rate of three or more branches.
- a coupling agent other than the modifying agent (p2) is added before the modification, a sample is taken before the modifying agent (p2) is added, and the coupling agent is measured by measuring GPC. It is possible to correct the proportion of the SBR polymer chain bonded only to the.
- the weight average molecular weight of the solution polymerization SBR (P) is not particularly limited, but is usually 1,000 to 3,000,000, preferably 100,000 to 2 as a value measured by gel permeation chromatography in terms of polystyrene. In the range of 300,000 to 1,500,000. When the weight average molecular weight is 3,000,000 or less, it becomes easy to add silica to the solution-polymerized SBR (P), and the scorch resistance of the tire rubber composition becomes more excellent. Further, when the weight average molecular weight is 1,000 or more, the low rolling resistance of the obtained tire becomes more excellent.
- the molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the solution polymerization SBR (P) is not particularly limited, but preferably 1.1 to 3.0, More preferably, it is 1.2 to 2.5, and particularly preferably 1.3 to 2.2. When the molecular weight distribution value (Mw / Mn) is 3.0 or less, the resulting tire has more excellent low rolling resistance.
- the Mooney viscosity (ML 1 + 4 (100 ° C.)) of the solution-polymerized SBR (P) is not particularly limited, but is usually in the range of 20 to 100, preferably 30 to 90, more preferably 40 to 85.
- the Mooney viscosity of the oil-extended rubber is preferably set in the above range.
- the emulsion polymerization SBR (specific emulsion polymerization SBR) contained in the diene blend rubber is not particularly limited as long as the styrene unit content is 35 to 50% by mass.
- the total content of the solution polymerization SBR and the emulsion polymerization SBR in the diene blend rubber is 70 to 90% by mass.
- the total content in the diene blend rubber exceeds 90% by mass, the resulting tire has insufficient wear resistance and dry performance. Further, if the total content in the diene blend rubber is less than 70% by mass, the wear resistance, wet performance and dry performance become insufficient.
- the aromatic modified terpene resin contained in the composition of the present invention is not particularly limited.
- the softening point of the aromatic modified terpene resin is not particularly limited, but is preferably 100 to 160 ° C, and more preferably 100 to 130 ° C.
- the softening point is a Vicat softening point measured according to JIS K6220-17206: 1999.
- the content of the aromatic modified terpene resin is 1 to 25 parts by mass with respect to 100 parts by mass of the diene blend rubber. In particular, the amount is preferably 5 to 20 parts by mass.
- the silica contained in the composition of the present invention is not particularly limited, and any conventionally known silica that is blended in a rubber composition for applications such as tires can be used.
- Examples of the silica include wet silica, dry silica, fumed silica, diatomaceous earth, and the like.
- the silica one type of silica may be used alone, or two or more types of silica may be used in combination.
- the nitrogen adsorption specific surface area (N 2 SA) of the silica is not particularly limited, but is preferably from 130 to 260 m 2 / g because the wear resistance, wet performance and dry performance of the obtained tire are more excellent. More preferably, it is ⁇ 260 m 2 / g.
- N 2 SA is a surrogate property of the surface area that silica can use for adsorption with rubber molecules, and the amount of nitrogen adsorbed on the silica surface is determined according to JIS K6217-2: 2001 “Part 2: Determination of specific surface area— It is a value measured according to the “nitrogen adsorption method—single point method”.
- the content of the silica is 80 to 150 parts by mass with respect to 100 parts by mass of the diene blend rubber.
- the carbon black contained in the composition of the present invention is not particularly limited.
- SAF-HS, SAF, ISAF-HS, ISAF, ISAF-LS, IISAF-HS, HAF-HS, HAF, HAF-LS, FEF Various grades such as can be used.
- the nitrogen adsorption specific surface area (N 2 SA) of the carbon black is not particularly limited, but is preferably 100 to 160 m 2 / g, and more preferably 120 to 150 m 2 / g.
- the nitrogen adsorption specific surface area (N 2 SA) is determined according to JIS K6217-2: 2001 “Part 2: Determination of specific surface area—nitrogen adsorption method—single point method”. It is a measured value.
- the content of the carbon black is 15 to 50 parts by mass with respect to 100 parts by mass of the diene blend rubber. In particular, it is preferably 20 to 50 parts by mass.
- the composition of this invention can contain another component (arbitrary component) in the range which does not impair the effect and the objective as needed.
- the optional components include fillers, silane coupling agents, zinc oxide (zinc white), stearic acid, anti-aging agents, waxes, processing aids, process oils, liquid polymers, thermosetting resins, and vulcanizing agents.
- fillers silane coupling agents, zinc oxide (zinc white), stearic acid, anti-aging agents, waxes, processing aids, process oils, liquid polymers, thermosetting resins, and vulcanizing agents.
- zinc oxide zinc oxide
- stearic acid stearic acid
- anti-aging agents waxes
- processing aids processing aids
- process oils liquid polymers
- thermosetting resins thermosetting resins
- vulcanizing agents for example, sulfur
- various additives generally used in rubber compositions such as vulcanization accelerators, rubber components other than the above-mentioned natural rubber, solution polymerization SBR and emulsion polymer
- the production method of the composition of the present invention is not particularly limited, and specific examples thereof include, for example, kneading the above-described components using a known method and apparatus (for example, a Banbury mixer, a kneader, a roll, etc.). The method etc. are mentioned.
- a known method and apparatus for example, a Banbury mixer, a kneader, a roll, etc.
- the method etc. are mentioned.
- the composition of the present invention contains sulfur or a vulcanization accelerator, it is preferable to mix components other than sulfur and the vulcanization accelerator first, cool the mixture, and then mix the sulfur or vulcanization accelerator. .
- the composition of the present invention can be vulcanized or crosslinked under conventionally known vulcanization or crosslinking conditions.
- the pneumatic tire of the present invention is a pneumatic tire manufactured using the composition of the present invention described above. Especially, it is preferable that it is a pneumatic tire which used the composition of this invention for the tread part (tire tread).
- FIG. 1 shows a schematic partial sectional view of a tire representing an example of an embodiment of the pneumatic tire of the present invention, but the pneumatic tire of the present invention is not limited to the embodiment shown in FIG.
- reference numeral 1 represents a bead portion
- reference numeral 2 represents a sidewall portion
- reference numeral 3 represents a tire tread portion
- a carcass layer 4 in which fiber cords are embedded is mounted between the pair of left and right bead portions 1, and the end of the carcass layer 4 extends from the inside of the tire to the outside around the bead core 5 and the bead filler 6. Wrapped and rolled up.
- a belt layer 7 is disposed over the circumference of the tire on the outside of the carcass layer 4.
- the rim cushion 8 is arrange
- the pneumatic tire of the present invention can be manufactured, for example, according to a conventionally known method. Moreover, as gas with which a tire is filled, inert gas, such as nitrogen, argon, helium other than the air which adjusted normal or oxygen partial pressure, can be used.
- inert gas such as nitrogen, argon, helium other than the air which adjusted normal or oxygen partial pressure
- 1,6-bis (trichlorosilyl) hexane 0.08 mmol was then obtained.
- 0.027 mmol of polyorganosiloxane A represented by the following formula (9) was added in the form of a 20% by mass xylene solution and reacted for 30 minutes.
- an amount of methanol corresponding to twice the mole of n-butyllithium used was added to obtain a solution containing solution-polymerized SBR.
- the obtained solution-polymerized SBR corresponds to the above-described solution-polymerized SBR (P), has a block containing an isoprene unit at one end, and has a polyorganosiloxane structure as a modified end for silica at the other end. Contains a specific solution polymerized SBR having a terminal end.
- X 1 , X 4 , R 1 to R 3 and R 5 to R 8 are methyl groups.
- m is 80 and k is 120.
- X 2 is a group represented by the following formula (10) (here, * represents a bonding position).
- the obtained solution-polymerized SBR was measured for weight average molecular weight, molecular weight distribution, coupling rate, styrene unit content in portions other than the isoprene block, vinyl bond content in portions other than the isoprene block, and Mooney viscosity.
- the measurement results are shown in Table 2.
- the measurement method is as follows.
- Weight average molecular weight, molecular weight distribution and coupling rate About weight average molecular weight, molecular weight distribution, and coupling rate (ratio (mass%) of structure (p) to solution polymerization SBR (P)), a chart based on molecular weight in terms of polystyrene was obtained by gel permeation chromatography. It calculated
- the specific measurement conditions for gel permeation chromatography are as follows.
- HLC-8020 manufactured by Tosoh Corporation
- Column: GMH-HR-H manufactured by Tosoh Company
- Detector Differential refractometer RI-8020 (manufactured by Tosoh Company)
- Elution night Tetrahydrofuran-Column temperature: 40 ° C
- the coupling rate is the ratio of the area (s2) of the peak portion having a peak top molecular weight of 2.8 times or more of the peak top molecular weight indicated by the smallest peak of molecular weight to the total elution area (s1) (s2 / s1).
- Mooney viscosity The Mooney viscosity (ML 1 + 4 (100 ° C.)) was measured according to JIS K6300-1: 2001.
- ⁇ Preparation of tire rubber composition The components shown in Table 3 below were blended in the proportions (parts by mass) shown in Table 3 below. Specifically, first, the components excluding sulfur and the vulcanization accelerator among the components shown in Table 3 below were raised to around 150 ° C. using a 1.7 liter closed Banbury mixer, and then 5 After mixing for a minute, it was discharged and cooled to room temperature to obtain a masterbatch. Furthermore, using the Banbury mixer, sulfur and a vulcanization accelerator were mixed into the obtained master batch to obtain a tire rubber composition.
- vulcanized rubber sheet for evaluation The prepared tire rubber composition (unvulcanized) was press-vulcanized at 160 ° C. for 20 minutes in a mold (15 cm ⁇ 15 cm ⁇ 0.2 cm) to produce a vulcanized rubber sheet.
- a pneumatic tire was manufactured using the obtained tire rubber composition (tire size: 225 / 50R17).
- the obtained pneumatic tire is assembled to a wheel of rim size 7 ⁇ J and mounted on a domestic 2.5 liter class vehicle.
- Wet grip performance was measured based on this.
- the obtained results are shown in the column of “Wet performance” in Table 3 as an index with the value of Comparative Example 1 being 100. The larger the wet performance index, the better the wet grip performance.
- a pneumatic tire was manufactured using the obtained tire rubber composition (tire size: 225 / 50R17).
- the obtained pneumatic tire was assembled to a wheel with a rim size of 7 ⁇ J and mounted on a domestic 2.5-liter class vehicle to obtain an evaluation vehicle.
- the braking distance was measured when sudden braking was applied from a speed of 100 km / h on a dry road surface.
- the reciprocal of the braking distance is shown in Table 3 (dry performance).
- the result was expressed as an index with the reciprocal of the braking distance of Comparative Example 1 as 100. The larger the index, the shorter the braking distance on the dry road surface and the better the dry performance.
- SBR The net content of SBR in SBR is 72.7% by mass), styrene unit content: 37 masses %, Vinyl bond content: 43%, manufactured by Asahi Kasei Corporation)
- Emulsion polymerization SBR Nipol 9548 (oil-extended product (including 37.5 parts by mass of oil-extended oil with respect to 100 parts by mass of SBR.
- the net content of SBR in SBR is 72.7% by mass), styrene unit content: 37% by mass , Vinyl bond content: 13%, manufactured by Nippon Zeon Co., Ltd.) (emulsion polymerization SBR corresponding to the above-mentioned specific emulsion polymerization SBR)
- emulsion polymerization SBR corresponding to the above-mentioned specific emulsion polymerization SBR
- Comparative emulsion polymerization SBR Nipol 1723 (oil-extended product (including 37.5 parts by mass of oil-extended oil with respect to 100 parts by mass of SBR.
- Zinc flower 3 types of zinc oxide (manufactured by Shodo Chemical Industry Co., Ltd.)
- Stearic acid Industrial stearic acid N (Chiba Fatty Acid Co., Ltd.)
- Anti-aging agent Ozonon 6C (manufactured by Seiko Chemical Co., Ltd.)
- Sulfur Fine sulfur with Jinhua stamp oil (manufactured by Tsurumi Chemical Co., Ltd.)
- Vulcanization accelerator 1 Noxeller CZ-G (manufactured by Ouchi Shinsei Chemical Co., Ltd.)
- Vulcanization accelerator 2 PERKACIT DPG (manufactured by Flexis)
- Table 3 it contains a natural rubber, a diene blend rubber comprising a solution polymerization SBR containing a specific solution polymerization SBR and a specific emulsion polymerization SBR, an aromatic modified terpene resin, silica, and carbon black. All of the examples of the present application exhibited excellent wear resistance, wet performance, dry performance, and low rolling resistance. Among them, the N 2 SA of silica is, 200 meters 2 / g or more in which Example 4 showed better wear resistance, wet performance and dry performance. From the comparison of Examples 1 to 3, Examples 1 and 3 in which the content of the solution-polymerized SBR in the diene-based blend rubber was 30% by mass or more showed better wear resistance and wet performance.
- Example 3 in which the content of the solution-polymerized SBR in the diene-based blend rubber was 50% by mass or more showed further excellent wear resistance and wet performance.
- Example 5 in which the content of carbon black was 30 parts by mass or more with respect to 100 parts by mass of the diene-based blend rubber showed more excellent wear resistance and dry performance.
- Comparative Example 1 containing solution-polymerized SBR but not containing specific solution-polymerized SBR had insufficient wear resistance, wet performance, and dry performance.
- Comparative Example 2 containing emulsion polymerization SBR but not containing specific emulsion polymerization SBR had insufficient wet performance and dry performance.
- it contains a diene blend rubber comprising natural rubber, a solution polymerization SBR containing a specific solution polymerization SBR and a specific emulsion polymerization SBR, an aromatic modified terpene resin, silica, and carbon black.
- Comparative Example 3 in which the content of the natural rubber was less than 10% by mass, the wear resistance and the dry performance were insufficient.
- Comparative Example 4 in which the content of the natural rubber in the diene blend rubber exceeded 30% by mass was insufficient in wear resistance, wet performance and dry performance.
- Comparative Example 5 containing no emulsion polymerization SBR had insufficient wear resistance and dry performance.
- the comparative example 6 which does not contain an aromatic modified terpene resin had insufficient wet performance and dry performance.
- Comparative Example 7 in which the content of carbon black was less than 15 parts by mass with respect to 100 parts by mass of the diene blend rubber was insufficient in dry performance.
- Comparative Example 8 in which the content of silica was less than 80 parts by mass with respect to 100 parts by mass of the diene blend rubber was insufficient in wet performance and low rolling resistance.
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Abstract
Description
しかし、シリカはゴム成分との親和性が低く、また、シリカ同士の凝集性が高いため、ゴム成分に単にシリカを配合してもシリカが分散せず、これらの性能を向上させる効果が十分に得られないという問題がある。
このようななか、本発明者が特許文献1に記載のゴム組成物について検討したところ、耐摩耗性、ウェット性能およびドライ性能は昨今求められているレベルを必ずしも満たしていないことが明らかになった。
すなわち、本発明者は、以下の構成により上記課題が解決できることを見出した。
上記溶液重合SBRが、一方の端にイソプレン単位を含有するブロックを有し、他方の端にシリカ用変性末端を有する、特定溶液重合SBRを含有し、
上記乳化重合SBRのスチレン単位含有量が、35~50質量%であり、
上記ジエン系ブレンドゴム中の上記天然ゴムの含有量が、10~30質量%であり、
上記ジエン系ブレンドゴム中の上記溶液重合SBRおよび上記乳化重合SBRの合計の含有量が、70~90質量%であり、
上記芳香族変性テルペン樹脂の含有量が、上記ジエン系ブレンドゴム100質量部に対して、1~25質量部であり、
上記シリカの含有量が、上記ジエン系ブレンドゴム100質量部に対して、80~150質量部であり、
上記カーボンブラックの含有量が、上記ジエン系ブレンドゴム100質量部に対して、15~50質量部である、タイヤ用ゴム組成物。
(2) 上記シリカ用変性末端が、エポキシ基およびヒドロカルビルオキシシリル基からなる群より選択される少なくとも1種の基を有する、上記(1)に記載のタイヤ用ゴム組成物。
(3) 上記シリカの窒素吸着比表面積(N2SA)が、130~260m2/gである、上記(1)または(2)に記載のタイヤ用ゴム組成物。
(4) 上記シリカの窒素吸着比表面積(N2SA)が、200~260m2/gである、上記(1)~(3)のいずれかに記載のタイヤ用ゴム組成物。
(5) 上記(1)~(4)のいずれかに記載のタイヤ用ゴム組成物をトレッド部に用いた空気入りタイヤ。
ここで、上記溶液重合SBRは、一方の端にイソプレン単位を含有するブロックを有し、他方の端にシリカ用変性末端を有する、特定溶液重合SBRを含有する。
また、上記乳化重合SBRのスチレン単位含有量は、35~50質量%である(以下、上記乳化重合SBRを特定乳化重合SBRとも言う)。
また、上記ジエン系ブレンドゴム中の上記天然ゴムの含有量は、10~30質量%である。
また、上記ジエン系ブレンドゴム中の上記溶液重合SBRおよび上記乳化重合SBRの合計の含有量は、70~90質量%である。
また、上記芳香族変性テルペン樹脂の含有量は、上記ジエン系ブレンドゴム100質量部に対して、1~25質量部である。
また、上記シリカの含有量は、上記ジエン系ブレンドゴム100質量部に対して、80~150質量部である。
また、上記カーボンブラックの含有量は、上記ジエン系ブレンドゴム100質量部に対して、15~50質量部である。
上述のとおり、本発明の組成物に含有される特定溶液重合SBRは、一方の端にイソプレン単位を含有するブロックを有し、他方の端にシリカ用変性末端を有する。そのため、これらの末端がシリカと相互作用し、良好な分散状態が形成され、結果として優れた低転がり抵抗性を示すものと考えられる。さらに、天然ゴム、特定のミクロ構造(具体的にはスチレン単位含有量)を有する乳化重合SBR、芳香族変性テルペン樹脂およびカーボンブラックを所定の割合で併用することにより柔軟かつ強固な三次元網目構造が形成され、結果として、耐摩耗性、ウェット性能およびドライ性能にも優れるものと考えられる。
これらのことは、後述する比較例が示すように、特定溶液重合SBRを含有しない場合には耐摩耗性、ウェット性能およびドライ性能が不十分となること(比較例1)、特定溶液重合SBRを含有しても特定乳化重合SBRを含有しない場合にはウェット性能およびドライ性能が不十分となること(比較例2)、各成分を含有しても所定の割合を満たさない場合にはいずれかの性能が不十分となること(比較例3、4、7および8)、からも推測される。
[ジエン系ブレンドゴム]
本発明の組成物に含有されるジエン系ブレンドゴムは、天然ゴム、特定溶液重合SBRを含有する溶液重合SBR、および、特定乳化重合SBRからなる。
上述のとおり、ジエン系ブレンドゴムは天然ゴムを含有する。
ジエン系ブレンドゴム中の天然ゴムの含有量は10~30質量%である。なかでも、15~25質量%であることが好ましい。
ジエン系ブレンドゴム中の天然ゴムの含有量が10質量%未満であると得られるタイヤの耐摩耗性およびドライ性能が不十分となる。また、ジエン系ブレンドゴム中の天然ゴムの含有量が30質量%を超えると耐摩耗性、ウェット性能およびドライ性能が不十分となる。
ジエン系ブレンドゴムに含有される溶液重合SBRは、後述する特定溶液重合SBRを含有する。溶液重合SBR中の特定溶液重合SBRの含有量は特に制限されないが、10質量%以上であることが好ましく、20質量%以上であることがより好ましく、50質量%以上であることが特に好ましい。
上記イソプレン単位を含有するブロックは、イソプレンの単独重合体、または、イソプレンと他の単量体(モノマー)との共重合体であれば特に制限されない。イソプレン単位の含有量は特に制限されないが、70質量%以上であることが好ましく、80質量%以上であることがより好ましく、90質量%以上であることがさらに好ましく、100質量%であることが特に好ましい。
シリカ用変性末端はシリカと相互作用が可能な末端であれば特に制限されないが、例えば、ポリオルガノシロキサン構造を有する末端などが挙げられる。
上記シリカ用変性末端はエポキシ基およびヒドロカルビルオキシシリル基からなる群より選択される少なくとも1種の基を有するのが好ましい。
溶液重合SBR(P)に含まれる構造体(p)を形成するのに使用されるSBR系重合体鎖(p1)は、ブタジエン系単量体単位およびスチレン系単量体を含んでなる重合体鎖であって、一方の端にイソプレンブロックを有し、他方の端に活性末端(重合活性末端またはリビング成長末端)を有するものであれば、特に限定されない。
イソプレンブロックは、イソプレンの単独重合体、または、イソプレンと他の単量体(モノマー)との共重合体であり、イソプレン単位の含有量が70質量%以上のポリイソプレンである。イソプレンブロック中のイソプレン単位の含有量は、80質量%以上であることが好ましく、90質量%以上であることがより好ましく、100質量%であることが特に好ましい。
SBR系重合体鎖(p1)におけるイソプレンブロック以外の部分は、ブタジエン系単量体とスチレン系単量体との共重合体鎖である。イソプレンブロック以外の部分におけるブタジエン系単量体単位とスチレン系単量体単位との質量比(ブタジエン系単量体単位:スチレン系単量体単位)は、100:0~50:50が好ましく、90:10~70:30がより好ましい。
なお、イソプレンブロック以外の部分におけるビニル結合含有量とは、SBR系重合体鎖(p1)のイソプレンブロック以外の部分における、ビニル結合単位の割合(質量%)である。
SBR系重合体鎖(p1)の重量平均分子量は、特に限定されないが、1,000~2,000,000が好ましく、10,000~1,500,000がより好ましく、100,000~1,000,000が特に好ましい。
SBR系重合体鎖(p1)は、上述したように、例えば、不活性溶媒中、まず重合開始剤を用いてイソプレン(またはイソプレン混合物)をリビング重合させることにより、活性末端を有するイソプレンブロックを形成し、次いで、このイソプレンブロックを新たな重合開始剤として用いて、ブタジエン系単量体およびスチレン系単量体をリビング重合させることにより得ることができる。この際、単量体の溶液中にイソプレンブロックを加えてもよいし、イソプレンブロックの溶液中に単量体を加えてもよいが、単量体の溶液中にイソプレンブロックを加えることが好ましい。また、単量体の重合転化率が通常95%以上になった時点で、新たにイソプレン(またはイソプレン混合物)を添加することにより、SBR系重合体鎖(p1)の活性末端側にもイソプレンブロックを形成させることができる。このイソプレン(またはイソプレン混合物)の使用量は、初めの重合反応に使用した重合開始剤1molに対して、好ましくは10~100mol、より好ましくは15~70mol、特に好ましくは20~35molである。
SBR系重合体鎖(p1)におけるブタジエン系単量体単位とスチレン系単量体単位との質量比(ブタジエン系単量体単位:スチレン系単量体単位)の好ましい範囲は、上述のイソプレンブロック以外の部分と同じである。また、SBR系重合体鎖(p1)におけるビニル結合含有量の好ましい範囲も、上述のイソプレンブロック以外の部分と同じである。なお、SBR系重合体鎖(p1)におけるビニル結合含有量とは、SBR系重合体鎖(p1)におけるビニル結合単位の割合(質量%)である。
溶液重合SBR(P)は、以上のようにして得られるSBR系重合体鎖(p1)の活性末端と、エポキシ基および/またはヒドロカルビルオキシシリル基を有し、上記エポキシ基と、上記ヒドロカルビルオキシシリル基に含まれるヒドロカルビルオキシ基(-OR:ここでRは炭化水素基またはアリール基)との合計数が3以上である変性剤(p2)とが反応してなるものである。
上記式(A4)で表されるヒドロカルビルオキシシランにおいて、R21~R29の具体例および好適な態様は、上記式(A1)中のR1~R8と同様である。
溶液重合SBR(P)は、SBR系重合体鎖(p1)と、変性剤(p2)とが反応することにより得られる溶液重合SBRであり、具体的には、3以上のSBR系重合体鎖(p1)が変性剤(p2)を介して結合してなる構造体(p)を5質量%以上含有するものである。
最終的に得られた溶液重合SBR(P)の全量に対する、3以上のSBR系重合体鎖(p1)が変性剤(p2)を介して結合された構造体(p)の割合を「3分岐以上のカップリング率(質量%)」(以下、単にカップリング率ともいう)として表す。これは、ゲルパーミエーションクロマトグラフィ(ポリスチレン換算)により測定することができる。ゲルパーミエーションクロマトグラフィ測定により得られたチャートより、全溶出面積(s1)に対する、分子量の最も小さいピークが示すピークトップ分子量の2.8倍以上のピークトップ分子量を有するピーク部分の面積(s2)の比(s2/s1)を3分岐以上のカップリング率とする。なお、変性剤(p2)以外のカップリング剤などを変性前に添加した場合には、変性剤(p2)を添加する前にサンプルを採取し、GPCを測定しておくことで、カップリング剤のみと結合したSBR系重合体鎖の割合の補正を行うことができる。
ジエン系ブレンドゴムに含有される乳化重合SBR(特定乳化重合SBR)は、スチレン単位含有量が35~50質量%であれば、特に制限されない。
ジエン系ブレンドゴム中の上記合計の含有量が90質量%を超えると得られるタイヤの耐摩耗性およびドライ性能が不十分となる。また、ジエン系ブレンドゴム中の上記合計の含有量が70質量%未満であると耐摩耗性、ウェット性能およびドライ性能が不十分となる。
本発明の組成物に含有される芳香族変性テルペン樹脂は特に制限されない。
芳香族変性テルペン樹脂の軟化点は特に制限されないが、100~160℃であることが好ましく、100~130℃であることがより好ましい。
ここで、軟化点は、JIS K6220-17206:1999に準拠して測定されたビカット軟化点である。
本発明の組成物において、上記芳香族変性テルペン樹脂の含有量は、上記ジエン系ブレンドゴム100質量部に対して、1~25質量部である。なかでも、5~20質量部であることが好ましい。
本発明の組成物に含有されるシリカは特に限定されず、タイヤ等の用途でゴム組成物に配合されている従来公知の任意のシリカを用いることができる。
上記シリカとしては、例えば、湿式シリカ、乾式シリカ、ヒュームドシリカ、珪藻土などが挙げられる。上記シリカは、1種のシリカを単独で用いても、2種以上のシリカを併用してもよい。
上記シリカの窒素吸着比表面積(N2SA)は特に制限されないが、得られるタイヤの耐摩耗性、ウェット性能およびドライ性能がより優れる理由から、130~260m2/gであることが好ましく、200~260m2/gであることがより好ましい。
ここで、N2SAは、シリカがゴム分子との吸着に利用できる表面積の代用特性であり、シリカ表面への窒素吸着量をJIS K6217-2:2001「第2部:比表面積の求め方-窒素吸着法-単点法」にしたがって測定した値である。
本発明の組成物において、上記シリカの含有量は、上記ジエン系ブレンドゴム100質量部に対して80~150質量部である。
本発明の組成物に含有されるカーボンブラックは特に限定されず、例えば、SAF-HS、SAF、ISAF-HS、ISAF、ISAF-LS、IISAF-HS、HAF-HS、HAF、HAF-LS、FEF等の各種グレードのものを使用することができる。
上記カーボンブラックの窒素吸着比表面積(N2SA)は特に制限されないが、100~160m2/gであることが好ましく、120~150m2/gであることがより好ましい。
ここで、窒素吸着比表面積(N2SA)は、カーボンブラック表面への窒素吸着量をJIS K6217-2:2001「第2部:比表面積の求め方-窒素吸着法-単点法」にしたがって測定した値である。
本発明の組成物において、上記カーボンブラックの含有量は、上記ジエン系ブレンドゴム100質量部に対して15~50質量部である。なかでも、20~50質量部であることが好ましい。
本発明の組成物は、必要に応じて、その効果や目的を損なわない範囲でさらに他の成分(任意成分)を含有することができる。
上記任意成分としては、例えば、充填剤、シランカップリング剤、酸化亜鉛(亜鉛華)、ステアリン酸、老化防止剤、ワックス、加工助剤、プロセスオイル、液状ポリマー、熱硬化性樹脂、加硫剤(例えば、硫黄)、加硫促進剤などのゴム組成物に一般的に使用される各種添加剤、上述した天然ゴム、溶液重合SBRおよび乳化重合SBR以外のゴム成分(ブタジエンゴムなど)などが挙げられる。
本発明の組成物の製造方法は特に限定されず、その具体例としては、例えば、上述した各成分を、公知の方法、装置(例えば、バンバリーミキサー、ニーダー、ロールなど)を用いて、混練する方法などが挙げられる。本発明の組成物が硫黄または加硫促進剤を含有する場合は、硫黄および加硫促進剤以外の成分を先に混合し、冷却してから、硫黄または加硫促進剤を混合するのが好ましい。
また、本発明の組成物は、従来公知の加硫または架橋条件で加硫または架橋することができる。
本発明の空気入りタイヤは、上述した本発明の組成物を用いて製造した空気入りタイヤである。なかでも、本発明の組成物をトレッド部(タイヤトレッド)に用いた空気入りタイヤであることが好ましい。
図1に、本発明の空気入りタイヤの実施態様の一例を表すタイヤの部分断面概略図を示すが、本発明の空気入りタイヤは図1に示す態様に限定されるものではない。
また、左右一対のビード部1間においては、繊維コードが埋設されたカーカス層4が装架されており、このカーカス層4の端部はビードコア5およびビードフィラー6の廻りにタイヤ内側から外側に折り返されて巻き上げられている。
また、タイヤトレッド3においては、カーカス層4の外側に、ベルト層7がタイヤ1周に亘って配置されている。
また、ビード部1においては、リムに接する部分にリムクッション8が配置されている。
窒素置換された100mlアンプル瓶に、シクロヘキサン28gおよびテトラメチルエチレンジアミン8.6mmolを添加し、さらに、n-ブチルリチウム6.1mmolを添加した。次いで、イソプレン8.0gをゆっくりと添加し、60℃のアンプル瓶内で120分反応させることにより、イソプレンブロック(開始剤1とする)を得た。この開始剤1について、重量平均分子量、分子量分布、およびイソプレン単位由来のビニル結合含有量を測定した。測定結果を第1表に示す。
なお、得られた溶液重合SBRは、上述した溶液重合SBR(P)に該当し、一方の端にイソプレン単位を含有するブロックを有し、他方の端にシリカ用変性末端としてポリオルガノシロキサン構造を有する末端を有する特定溶液重合SBRを含有する。
重量平均分子量、分子量分布およびカップリング率(溶液重合SBR(P)に対する構造体(p)の割合(質量%))については、ゲルパーミエーションクロマトグラフィにより、ポリスチレン換算の分子量に基づくチャートを得て、そのチャートに基づいて求めた。なお、ゲルパーミエーションクロマトグラフィの具体的な測定条件は、以下のとおりである。
・カラム:GMH-HR-H(東ソ一社製)2本を直列に連結した
・検出器:示差屈折計RI-8020(東ソ一社製)
・溶離夜:テトラヒドロフラン
・カラム温度:40℃
スチレン単位含有量およびビニル結合含有量については、1H-NMRにより測定した。
ムーニー粘度(ML1+4(100℃))については、JIS K6300-1:2001に準じて測定した。
下記第3表に示す成分を、下記第3表に示す割合(質量部)で配合した。
具体的には、まず、下記第3表に示す成分のうち硫黄および加硫促進剤を除く成分を、1.7リットルの密閉式バンバリーミキサーを用いて150℃付近に温度を上げてから、5分間混合した後に放出し、室温まで冷却してマスターバッチを得た。さらに、上記バンバリーミキサーを用いて、得られたマスターバッチに硫黄および加硫促進剤を混合し、タイヤ用ゴム組成物を得た。
調製したタイヤ用ゴム組成物(未加硫)を、金型(15cm×15cm×0.2cm)中、160℃で20分間プレス加硫して、加硫ゴムシートを作製した。
上述のとおり作製した加硫ゴムシートについて、JIS K6264-1、2:2005に準拠し、ランボーン摩耗試験機(岩本製作所社製)を用いて、温度20℃、スリップ率50%の条件で摩耗減量を測定した。
結果を第3表に示す(耐摩耗性)。結果は比較例1の摩耗量を100として、次式により指数化したものを表した。指数が大きいほど摩耗量が小さく、タイヤにしたときに耐摩耗性に優れる。
耐摩耗性=(比較例1の摩耗量/試料の摩耗量)×100
得られたタイヤ用ゴム組成物を用いて空気入りタイヤを製造した(タイヤサイズ:225/50R17)。そして、得られた空気入りタイヤをリムサイズ7×Jのホイールに組み付け、国産2.5リットルクラスの車輌に装着し、EU規則 ウェットグリップ グレーディング試験法(TEST METHOD FOR TYRE WET GRIP GRADING (C1 TYPES))に基づきウェットグリップ性能を測定した。得られた結果は、比較例1の値を100とする指数として、第3表の「ウェット性能」の欄に示した。ウェット性能の指数が大きいほどウェットグリップ性が優れていることを意味する。
得られたタイヤ用ゴム組成物を用いて空気入りタイヤを製造した(タイヤサイズ:225/50R17)。そして、得られた空気入りタイヤをリムサイズ7×Jのホイールに組み付け、国産2.5リットルクラスの車輌に装着して、評価用車輌とした。
ドライ路面上で100km/hの速度から急ブレーキをかけたときの制動距離を測定した。制動距離の逆数を第3表に示す(ドライ性能)。結果は比較例1の制動距離の逆数を100とする指数で表した。指数が大きいほどドライ路面における制動距離が小さく、ドライ性能に優れる。
上述のとおり作製した加硫ゴムシートについて、JIS K6394:2007に準じて、粘弾性スペクトロメーター(岩本製作所社製)を用いて、伸張変形歪率10%±2%、振動数20Hz、温度60℃の条件で、tanδ(60℃)を測定した。
tanδ(60℃)の逆数を第3表に示す(低転がり抵抗性)。結果は比較例1のtanδ(60℃)の逆数を100とする指数で表した。指数が大きいほどtanδ(60℃)が小さく、タイヤにしたときに低転がり抵抗性に優れる。
・天然ゴム:SIR-20
・溶液重合SBR:上述のとおり製造された溶液重合SBR(上述した溶液重合SBR(P)に該当し、一方の端にイソプレン単位を含有するブロックを有し、他方の端にシリカ用変性末端としてポリオルガノシロキサン構造を有する末端を有する特定溶液重合SBRを含有する溶液重合SBR)
・比較溶液重合SBR:E581(油展品(SBR100質量部に対して油展オイル37.5質量部を含む。SBR中のSBRの正味は72.7質量%。)、スチレン単位含有量:37質量%、ビニル結合含有量:43%、旭化成社製)
・乳化重合SBR:Nipol9548(油展品(SBR100質量部に対して油展オイル37.5質量部を含む。SBR中のSBRの正味は72.7質量%。)、スチレン単位含有量:37質量%、ビニル結合含有量:13%、日本ゼオン社製)(上述した特定乳化重合SBRに該当する乳化重合SBR)
・比較乳化重合SBR:Nipol1723(油展品(SBR100質量部に対して油展オイル37.5質量部を含む。SBR中のSBRの正味は72.7質量%。)、スチレン単位含有量:25質量%、ビニル結合含有量:15%、日本ゼオン社製)
・シリカ1:Zeosil 1165MP(N2SA:160m2/g、ローディア社製)
・シリカ2:Zeosil Premium 200MP(N2SA:210m2/g、ローディア社製)
・カーボンブラック:ショウブラックN234(キャボットジャパン社製)
・シランカップリング剤: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、エボニックデグッサ社製)
・芳香族変性テルペン樹脂:YSレジンTO-125(芳香族変性テルペン樹脂、軟化点:125℃、ヤスハラケミカル社製)
・オイル:エキストラクト4号S(昭和シェル石油社製)
・亜鉛華:酸化亜鉛3種(正同化学工業社製)
・ステアリン酸:工業用ステアリン酸N(千葉脂肪酸社製)
・老化防止剤:オゾノン6C(精工化学社製)
・硫黄:金華印油入微粉硫黄(鶴見化学工業社製)
・加硫促進剤1:ノクセラーCZ-G(大内新興化学工業社製)
・加硫促進剤2:PERKACIT DPG(フレキシス社製)
実施例1~3の対比から、ジエン系ブレンドゴム中の溶液重合SBRの含有量が30質量%以上である実施例1および3はより優れた耐摩耗性およびウェット性能を示した。なかでも、ジエン系ブレンドゴム中の溶液重合SBRの含有量が50質量%以上である実施例3はさらに優れた耐摩耗性およびウェット性能を示した。
実施例1~5の対比から、カーボンブラックの含有量が、ジエン系ブレンドゴム100質量部に対して30質量部以上である実施例5はより優れた耐摩耗性およびドライ性能を示した。
また、天然ゴム、特定溶液重合SBRを含有する溶液重合SBRおよび特定乳化重合SBRからなるジエン系ブレンドゴムと、芳香族変性テルペン樹脂と、シリカと、カーボンブラックとを含有するが、ジエン系ブレンドゴム中の天然ゴムの含有量が10質量%未満である比較例3は耐摩耗性およびドライ性能が不十分であった。同様に各成分を含有するが、ジエン系ブレンドゴム中の天然ゴムの含有量が30質量%を超える比較例4は耐摩耗性、ウェット性能およびドライ性能が不十分であった。
また、乳化重合SBRを含有しない比較例5は耐摩耗性およびドライ性能が不十分であった。
また、芳香族変性テルペン樹脂を含有しない比較例6はウェット性能およびドライ性能が不十分であった。
また、カーボンブラックの含有量がジエン系ブレンドゴム100質量部に対して15質量部未満である比較例7はドライ性能が不十分であった。
また、シリカの含有量がジエン系ブレンドゴム100質量部に対して80質量部未満である比較例8はウェット性能および低転がり抵抗性が不十分であった。
2 サイドウォール部
3 タイヤトレッド部
4 カーカス層
5 ビードコア
6 ビードフィラー
7 ベルト層
8 リムクッション
Claims (5)
- 天然ゴム、溶液重合SBRおよび乳化重合SBRからなるジエン系ブレンドゴムと、芳香族変性テルペン樹脂と、シリカと、カーボンブラックとを含有し、
前記溶液重合SBRが、一方の端にイソプレン単位を含有するブロックを有し、他方の端にシリカ用変性末端を有する、特定溶液重合SBRを含有し、
前記乳化重合SBRのスチレン単位含有量が、35~50質量%であり、
前記ジエン系ブレンドゴム中の前記天然ゴムの含有量が、10~30質量%であり、
前記ジエン系ブレンドゴム中の前記溶液重合SBRおよび前記乳化重合SBRの合計の含有量が、70~90質量%であり、
前記芳香族変性テルペン樹脂の含有量が、前記ジエン系ブレンドゴム100質量部に対して、1~25質量部であり、
前記シリカの含有量が、前記ジエン系ブレンドゴム100質量部に対して、80~150質量部であり、
前記カーボンブラックの含有量が、前記ジエン系ブレンドゴム100質量部に対して、15~50質量部である、タイヤ用ゴム組成物。 - 前記シリカ用変性末端が、エポキシ基およびヒドロカルビルオキシシリル基からなる群より選択される少なくとも1種の基を有する、請求項1に記載のタイヤ用ゴム組成物。
- 前記シリカの窒素吸着比表面積(N2SA)が、130~260m2/gである、請求項1または2に記載のタイヤ用ゴム組成物。
- 前記シリカの窒素吸着比表面積(N2SA)が、200~260m2/gである、請求項1~3のいずれか1項に記載のタイヤ用ゴム組成物。
- 請求項1~4のいずれか1項に記載のタイヤ用ゴム組成物をトレッド部に用いた空気入りタイヤ。
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US10919989B2 (en) | 2017-10-20 | 2021-02-16 | Iowa State University Research Foundation, Inc. | End group functionalization agents for polydiene |
CN107759860B (zh) * | 2017-10-31 | 2020-09-04 | 肇庆骏鸿实业有限公司 | 一种中大型汽车轮胎胎面用橡胶组合物 |
JP7416771B2 (ja) * | 2018-05-18 | 2024-01-17 | コンパニー ゼネラール デ エタブリッスマン ミシュラン | タイヤトレッド用組成物 |
JP6838587B2 (ja) * | 2018-08-22 | 2021-03-03 | 住友ゴム工業株式会社 | トレッド用ゴム組成物及び空気入りタイヤ |
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