WO2014021002A1 - トレッド用ゴム組成物及び空気入りタイヤ - Google Patents
トレッド用ゴム組成物及び空気入りタイヤ Download PDFInfo
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- WO2014021002A1 WO2014021002A1 PCT/JP2013/066330 JP2013066330W WO2014021002A1 WO 2014021002 A1 WO2014021002 A1 WO 2014021002A1 JP 2013066330 W JP2013066330 W JP 2013066330W WO 2014021002 A1 WO2014021002 A1 WO 2014021002A1
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- 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
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- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
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- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
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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
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- C08K3/36—Silica
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- C08K5/00—Use of organic ingredients
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- C08K5/00—Use of organic ingredients
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- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
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- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
- C08L45/02—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers of coumarone-indene polymers
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- C08L7/00—Compositions of natural rubber
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- C08L9/06—Copolymers with styrene
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- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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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 tread and a pneumatic tire using the same.
- the silica manufacturer adjusts the surface activity and particle distribution of the silica to improve the dispersibility of the silica in the rubber composition.
- the modified polymer and silica are bonded to each other to prevent the dispersion of silica.
- a technique for improving wear resistance by utilizing the characteristics of butadiene rubber itself by using about 10 to 35% by mass of 100% by mass of a high-cis butadiene rubber synthesized using an Nd catalyst is also known.
- a tire for a passenger car or a tire tread for a multi-purpose sports car with a low contact pressure with the road surface per unit volume there is a possibility that the wet grip performance may be greatly reduced, and the amount used is 35% by mass of 100% by mass of the rubber component.
- the degree is the limit.
- the present invention provides a rubber composition for a tread that solves the above-described problems, has excellent wear resistance, has good wet grip performance, and also has good fuel economy and elongation at break, and the same.
- An object of the present invention is to provide pneumatic tires using tires (particularly, tires for passenger cars, tires for multipurpose sports cars).
- the content of the modified butadiene rubber for silica having a cis content of 50% by mass or less in 100% by mass of the rubber component is 8 to 40% by mass, and the content of the styrene butadiene rubber is 25 to 75% by mass.
- the present invention relates to a rubber composition for a tread containing 40 to 120 parts by mass of silica having a nitrogen adsorption specific surface area of 160 to 270 m 2 / g with respect to 100 parts by mass.
- the modified butadiene rubber for silica includes a modified butadiene rubber modified with a compound represented by the following formula (1), a modified butadiene rubber modified with a low molecular compound containing a glycidylamino group in the molecule, and a glycidyl in the molecule. It is preferably at least one selected from the group consisting of a modified butadiene rubber modified with a mixture of a low molecular compound containing an amino group and an oligomer of a dimer or higher of the low molecular compound.
- R 1 , R 2 and R 3 are the same or different and each represents an alkyl group, an alkoxy group, a silyloxy group, an acetal group, a carboxyl group, a mercapto group, or a derivative thereof.
- R 4 and R And 5 are the same or different and each represents a hydrogen atom or an alkyl group, R 4 and R 5 may combine to form a ring structure with a nitrogen atom, and n represents an integer.
- the low molecular compound containing a glycidylamino group in the molecule is preferably a compound represented by the following formula.
- R 11 and R 12 are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group is at least one selected from the group consisting of ethers and tertiary amines
- R 13 and R 14 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group includes an ether and a tertiary amine.
- R 15 represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is an ether, a tertiary amine, an epoxy, a carbonyl, And at least one group selected from the group consisting of halogen and m represents an integer of 1 to 6.
- the styrene butadiene rubber preferably contains a modified styrene butadiene rubber for silica.
- R 101 to R 103 each represents a branched or unbranched alkyl group having 1 to 12 carbon atoms, a branched or unbranched alkoxy group having 1 to 12 carbon atoms, or —O— (R 111 — O) z —R 112
- z R 111 represents a branched or unbranched divalent hydrocarbon group having 1 to 30 carbon atoms.
- the z R 111 may be the same or different.
- R 112 is a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms.
- Z represents an integer of 1 to 30.
- R 101 to R 103 may be the same or different, and R 104 represents a branched or unbranched carbon atom having 1 to 6 carbon atoms.
- R 201 is hydrogen, halogen, branched or unbranched alkyl group having 1 to 30 carbon atoms, branched or unbranched alkenyl group having 2 to 30 carbon atoms, branched or unbranched.
- R 202 represents a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or non-branched alkynyl group having 2 to 30 carbon atoms, or a group in which the terminal hydrogen of the alkyl group is substituted with a hydroxyl group or a carboxyl group.
- a compound represented by the following formula It is preferable that 1 to 15 parts by mass of at least one silane coupling agent selected from the group consisting of:
- the content of butadiene rubber synthesized using a rare earth element-based catalyst in 100% by mass of the rubber component is preferably 40% by mass or less.
- a liquid resin having a softening point of ⁇ 20 to 45 ° C. is preferable, and the liquid resin is preferably a liquid coumarone indene resin and / or a liquid terpene resin.
- the liquid resin is preferably a liquid coumarone indene resin and / or a liquid terpene resin.
- a terpene resin having a softening point of 46 to 160 ° C a rosin resin having a softening point of 46 to 140 ° C, a C5 petroleum resin having a softening point of 46 to 140 ° C, and an aromatic resin having a softening point of 46 to 140 ° C. It is preferable to include at least one selected resin.
- the present invention relates to a pneumatic tire produced using the rubber composition.
- the pneumatic tire is preferably a passenger tire or a multipurpose sports vehicle tire.
- the content of the modified butadiene rubber for silica having a cis content of 50% by mass or less is 8 to 40% by mass, and the content of the styrene butadiene rubber is 25 to 75% by mass.
- the rubber composition for a tread includes 40 to 120 parts by mass of silica having a nitrogen adsorption specific surface area of 160 to 270 m 2 / g with respect to 100 parts by mass of the rubber component, the rubber composition should be used for a tire tread.
- the rubber composition for a tread of the present invention is a modified butadiene rubber for silica (modified low cis BR for silica), styrene butadiene rubber (SBR) having a cis content of 50% by mass or less, silica having a nitrogen adsorption specific surface area of 160 to 270 m 2 / g ( Each contains a specific amount of particulate silica). As a result, it has excellent wear resistance, good wet grip performance, good fuel economy, and elongation at break.
- modified low cis BR for silica modified low cis BR for silica
- SBR styrene butadiene rubber
- silica having a nitrogen adsorption specific surface area of 160 to 270 m 2 / g
- Fine particle silica has a strong cohesive force and is generally difficult to disperse uniformly.
- SBR silica modified low cis BR
- silica modified SBR preferably silica modified SBR as a rubber component
- the fine particle silica is made uniform.
- excellent wear resistance, wet grip performance, low fuel consumption and elongation at break can be obtained at the same time, and the performance balance can be remarkably improved.
- the rubber composition of the present invention contains a modified Rhosis BR for silica as a rubber component.
- a modified Rhosis BR for silica as a rubber component.
- the modified low-cis BR for silica has a reactive vinyl group inside, and even when used with a silane coupling agent such as Si266 having low reactivity, a coupling bond is easily formed, and the effect of the present invention is efficient. Is obtained.
- a functional group that interacts with silica preferably, a group consisting of nitrogen, oxygen, and silicon.
- the BR is not particularly limited as long as it is a low cis-content BR modified by a compound having a functional group containing at least one selected atom.
- at least one terminal of BR is modified with a terminal-modified low-cis BR modified with a compound having a functional group (modifier), a main-chain modified low-cis BR having the functional group in the main chain, or a main chain and a terminal.
- Main chain terminal modified low-cis BR having the above functional group for example, main chain terminal modified low molecular BR having the above functional group in the main chain and at least one terminal modified with the above modifier
- Modified low-sis BR is preferred.
- Examples of the functional group include amino group, amide group, alkoxysilyl group, isocyanate group, imino group, imidazole group, urea group, ether group, carbonyl group, oxycarbonyl group, sulfide group, disulfide group, sulfonyl group, sulfinyl group. Thiocarbonyl group, ammonium group, imide group, hydrazo group, azo group, diazo group, carboxyl group, nitrile group, pyridyl group, alkoxy group, hydroxyl group, oxy group, epoxy group and the like. These functional groups may have a substituent.
- 1, 2 and tertiary amino groups are preferred because of their high fuel economy and wet grip performance.
- An alkoxysilyl group preferably an alkoxysilyl group having 1 to 6 carbon atoms.
- the terminal-modified low-cis BR is preferably a low-cis-modified low-cis butadiene rubber (S-modified low-cis BR) modified with a compound represented by the following formula (1).
- R 1 , R 2 and R 3 are the same or different and are alkyl group, alkoxy group, silyloxy group, acetal group, carboxyl group (—COOH), mercapto group (—SH) or these R 4 and R 5 are the same or different and each represents a hydrogen atom or an alkyl group, R 4 and R 5 may be bonded to form a ring structure with a nitrogen atom, and n represents an integer. .
- S-modified BR examples include those described in JP 2010-111753 A and the like.
- an alkoxy group is preferable as R 1 , R 2 and R 3 from the viewpoint that excellent fuel economy and breaking resistance can be obtained (preferably having 1 to 8 carbon atoms, more preferably carbon atoms).
- R 4 and R 5 are preferably an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms).
- n is preferably 1 to 5, more preferably 2 to 4, and still more preferably 3.
- R 4 and R 5 are bonded to form a ring structure with a nitrogen atom, a 4- to 8-membered ring is preferable.
- the alkoxy group also includes a cycloalkoxy group (such as cyclohexyloxy group) and an aryloxy group (such as phenoxy group and benzyloxy group).
- a cycloalkoxy group such as cyclohexyloxy group
- an aryloxy group such as phenoxy group and benzyloxy group
- Specific examples of the compound represented by the formula (1) include 2-dimethylaminoethyltrimethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 2-dimethylaminoethyltriethoxysilane, and 3-dimethylaminopropyltriethoxysilane.
- 3-dimethylaminopropyltrimethoxysilane, 3-dimethylaminopropyltriethoxysilane, and 3-diethylaminopropyltrimethoxysilane are preferable from the viewpoint that the above-described performance can be improved satisfactorily. These may be used alone or in combination of two or more.
- Methods for modifying butadiene rubber with the compound represented by formula (1) include conventionally known methods such as the methods described in JP-B-6-53768 and JP-B-6-57767. Can be used. For example, it can be modified by bringing the butadiene rubber into contact with the compound. Specifically, after the preparation of the butadiene rubber by anionic polymerization, a predetermined amount of the compound is added to the rubber solution, and the polymerization terminal of the butadiene rubber (active And the like, and the like.
- the terminal-modified low-cis BR is preferably a modified butadiene rubber having a low cis content modified with a low-molecular compound containing a glycidylamino group in the molecule.
- a modified butadiene rubber having a low cis content modified with a low molecular compound represented by the following formula can be preferably used.
- R 11 and R 12 are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group is at least one selected from the group consisting of ethers and tertiary amines
- R 13 and R 14 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group includes an ether and a tertiary amine.
- R 15 represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is an ether, a tertiary amine, an epoxy, a carbonyl, And at least one group selected from the group consisting of halogen and m represents an integer of 1 to 6.
- R 11 and R 12 are preferably an alkylene group having 1 to 10 carbon atoms (preferably having 1 to 3 carbon atoms).
- R 13 and R 14 are preferably a hydrogen atom.
- R 15 includes a hydrocarbon group having 3 to 20 carbon atoms (preferably 6 to 10 carbon atoms, more preferably 8 carbon atoms), and is preferably a cycloalkyl group or a cycloalkylene group represented by the following formula, A cycloalkylene group is more preferable.
- m is preferably 2 to 3.
- the compound represented by the above formula include tetraglycidylmetaxylenediamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane, tetraglycidyl-1,3-bisaminomethylcyclohexane and the like. Preferably used.
- the modified butadiene rubber having a low cis content modified with a low molecular compound containing a glycidylamino group in the molecule includes a low molecular compound containing a glycidylamino group in the molecule, and an oligomer of a dimer or higher of the low molecular compound. More preferred is a modified butadiene rubber having a low cis content (A-modified low-cis BR) modified with a mixture of Examples of the A-modified lowosis BR include those described in JP-A-2009-275178.
- the oligomer is preferably a dimer to a 10mer of the low molecular compound.
- the low molecular weight compound is an organic compound having a molecular weight of 1000 or less, and a compound of the following formula (2) is preferable.
- R is a divalent hydrocarbon group or a polar group containing oxygen such as ether, epoxy or ketone, a polar group containing sulfur such as thioether or thioketone, a nitrogen such as a tertiary amino group or imino group.
- the divalent hydrocarbon group may be a saturated or unsaturated linear, branched, or cyclic group, and includes, for example, an alkylene group, an alkenylene group, a phenylene group, and the like.
- the low molecular weight compound represented by the above formula (2) examples include tetraglycidyl-1,3-bisaminomethylcyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 4-methylene-bis (N, N-diglycidylaniline), 1,4-bis (N, N-diglycidylamino) cyclohexane, N, N, N ′, N′-tetraglycidyl-p-phenylenediamine, 4 , 4′-bis (diglycidylamino) benzophenone, 4- (4-glycidylpiperazinyl)-(N, N-diglycidyl) aniline, 2- [2- (N, N-diglycidylamino) ethyl] -1 -Glycidylpyrrolidine and the like.
- tetraglycidyl-1,3-bisaminomethylcyclohexane is
- Preferred examples of the oligomer component include a dimer represented by the following formula (3) and a trimer represented by the following formula (4).
- the content of the low molecular compound is 75 to 95% by mass and the content of the oligomer is 25 to 5% in 100% by mass of the modifier (mixture). % Is preferred.
- the ratio of the low molecular weight compound and the oligomer component in the modifier can be measured by GPC. Specifically, a column capable of measuring from a low molecular compound to an oligomer component is selected and measured. In the obtained peak, a perpendicular is drawn from the first inflection point on the polymer side of the peak derived from the low molecular compound, and the area ratio of the low molecular side component to the polymer side component is determined. This area ratio corresponds to the ratio between the low molecular weight compound and the oligomer component.
- the polymer-side peak of the oligomer component has a molecular weight that is not more than 10 times the molecular weight of the low molecular weight compound determined from the standard polystyrene equivalent molecular weight, or a molecular weight that is not more than 10 times the molecular weight of the low molecular weight compound. If the component peak becomes 0 by then, the points up to the point where the component peak becomes 0 are integrated.
- the reaction of the modifier with a butadiene polymer having an active end synthesized by anionic polymerization using a polymerization initiator such as a lithium compound is carried out by reacting the modifier with the active end of the polymer.
- a modification method of butadiene rubber by a low molecular compound containing a glycidylamino group in the molecule or a mixture of the compound and its oligomer the modification method using the compound (modifier) represented by the formula (1) is used. It can be carried out.
- the cis content of the modified low-cis BR for silica is 50% by mass or less, preferably 45% by mass or less, more preferably 40% by mass or less. If it exceeds 50% by mass, the addition rate of the silica-modified group to the polymer tends to decrease, and it tends to be difficult to interact with silica.
- the minimum of the said cis content is not specifically limited, Preferably it is 10 mass% or more, More preferably, it is 20 mass% or more. If it is less than 10% by mass, the elongation at break EB and the wear resistance may be reduced.
- the vinyl content of the modified low-cis BR for silica is preferably 35% by mass or less, more preferably 30% by mass or less. If the vinyl content exceeds 35% by mass, fuel economy and breaking elongation EB may be reduced. Although the minimum of the said vinyl content is not specifically limited, Preferably it is 1 mass% or more, More preferably, it is 10 mass% or more. If it is less than 1% by mass, E * may be lowered.
- the weight average molecular weight (Mw) of the modified low-cis BR for silica is preferably 200,000 or more, more preferably 400,000 or more. If it is less than 200,000, sufficient abrasion resistance and elongation at break may not be obtained. Mw is preferably 900,000 or less, more preferably 700,000 or less. If it exceeds 900,000, the workability is deteriorated to cause dispersion failure, and there is a possibility that sufficient fuel economy, wear resistance, and elongation at break cannot be obtained.
- the cis content (cis-1,4-bonded butadiene unit amount) and the vinyl content (1,2-bonded butadiene unit amount) can be measured by infrared absorption spectrum analysis.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are gel permeation chromatograph (GPC) (GPC-8000 series, manufactured by Tosoh Corporation), detector: differential refractometer, column: manufactured by Tosoh Corporation.
- GPC gel permeation chromatograph
- detector differential refractometer
- column manufactured by Tosoh Corporation.
- the content of the modified Rhosis BR for silica in 100% by mass of the rubber component is 8% by mass or more, preferably 10% by mass or more, and more preferably 12% by mass or more. If it is less than 8% by mass, sufficient fuel economy and abrasion resistance may not be obtained.
- the content is 40% by mass or less, preferably 30% by mass or less, and more preferably 20% by mass or less. When it exceeds 40 mass%, there exists a tendency for abrasion resistance and elongation at break to fall.
- BRs are not particularly limited.
- BR1220 manufactured by Nippon Zeon Co., Ltd., BR150B manufactured by Ube Industries, Ltd., high cis content BR, VCR412 manufactured by Ube Industries, Inc., VCR617, etc.
- SPB 1,2-syndiotactic polybutadiene crystal
- IR BR rare earth element-based catalyst
- Tin-modified butadiene rubber modified with a tin compound (tin-modified BR (modified BR for carbon black)) (for example, polymerized using lithium as an initiator, having a vinyl bond content of 5 to 50% by mass and Mw / Mn of 2
- Modified butadiene rubber such as tin-modified BR having a tin atom content of 0.0 or less and a tin atom content of 50 to 3000 ppm can also be used.
- tin-modified BR modified BR for carbon black
- Modified butadiene rubber such as tin-modified BR having a tin atom content of 0.0 or less and a tin atom content of 50 to 3000 ppm
- rare earth BR is preferable.
- the rare earth BR has a high cis content, a low vinyl content, and a small ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn). Good fuel economy, elongation at break, and crack growth resistance can be obtained.
- Mw weight average molecular weight
- Mn number average molecular weight
- the rare earth BR has a very high compatibility with carbon black, the compatibility with silica is low. Therefore, when silica-modified modified ROSIS BR is used together with rare earth-based BR, rare-earth-based BR and silica-modified modified ROSIS BR form a single phase because of their close chemical composition. Silica is well dispersed in the BR phase.
- the carbon black is well dispersed in the BR phase by the rare earth BR having high compatibility with the carbon black.
- carbon black and silica can be well dispersed and distributed in the BR phase, and good wear resistance, low fuel consumption, wet grip performance, and elongation at break (especially wear resistance) can be obtained. .
- butadiene rubber (rare earth BR) synthesized using a rare earth element catalyst will be described.
- Rare earth BR is a butadiene rubber synthesized using a rare earth element-based catalyst, and has a feature that it has a high cis content and a low vinyl content.
- a general-purpose product in tire manufacture can be used.
- the rare earth element-based catalyst known catalysts can be used, and examples thereof include lanthanum series rare earth element compounds, organoaluminum compounds, aluminoxanes, halogen-containing compounds, and catalysts containing a Lewis base as necessary.
- an Nd-based catalyst using a neodymium (Nd) -containing compound as a lanthanum series rare earth element compound is particularly preferable.
- Examples of the lanthanum series rare earth element compounds include halides, carboxylates, alcoholates, thioalcolates, amides, and the like of rare earth metals having an atomic number of 57 to 71.
- the use of an Nd-based catalyst is preferable in that a BR having a high cis content and a low vinyl content can be obtained.
- the organoaluminum compound is represented by AlR a R b R c (wherein R a , R b and R c are the same or different and each represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms). Things can be used.
- the aluminoxane include a chain aluminoxane and a cyclic aluminoxane.
- halogen-containing compound examples include AlX k R d 3-k (wherein X is a halogen, R d is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, and k is 1, 1.5, 2 or 3)
- the Lewis base is used for complexing a lanthanum series rare earth element compound, and acetylacetone, ketone, alcohol and the like are preferably used.
- the rare earth element-based catalyst may be used in the state of being dissolved in an organic solvent (n-hexane, cyclohexane, n-heptane, toluene, xylene, benzene, etc.) during the polymerization of butadiene, silica, magnesia, magnesium chloride, etc. These may be used by being supported on a suitable carrier.
- the polymerization conditions may be either solution polymerization or bulk polymerization, the preferred polymerization temperature is ⁇ 30 to 150 ° C., and the polymerization pressure may be arbitrarily selected depending on other conditions.
- the rare earth-based BR preferably has a ratio (Mw / Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) of 1.2 or more, more preferably 1.5 or more. If it is less than 1.2, the workability tends to deteriorate significantly.
- the Mw / Mn is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, particularly preferably 2 or less, and most preferably 1.9 or less. If it exceeds 5, the effect of improving the wear resistance tends to decrease.
- the Mw of the rare earth BR is preferably 200,000 or more, more preferably 250,000 or more, and preferably 900,000 or less, more preferably 600,000 or less.
- the Mn of the rare earth-based BR is preferably 100,000 or more, more preferably 150,000 or more, and preferably 800,000 or less, more preferably 700,000 or less.
- the cis content of the rare earth BR is preferably 90% by mass or more, more preferably 93% by mass or more, and still more preferably 95% by mass or more. If it is less than 90% by mass, the wear resistance may be reduced.
- the vinyl content of the rare earth BR is preferably 1.8% by mass or less, more preferably 1.0% by mass or less, still more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less. If it exceeds 1.8% by mass, the wear resistance may be reduced.
- the content of the rare earth BR in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 12% by mass. % Or more. If it is less than 5% by mass, the abrasion resistance and elongation at break may not be sufficiently obtained.
- the content is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less. If it exceeds 40% by mass, sufficient fuel economy and wear resistance may not be obtained.
- the BR content in 100% by mass of the rubber component is 8% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more. If it is less than 8% by mass, the wear resistance may decrease.
- the content is preferably 60% by mass or less, more preferably 55% by mass or less. When it exceeds 60 mass%, wet grip performance, workability, and elongation at break EB may be deteriorated.
- the rubber composition of the present invention contains styrene butadiene rubber (SBR) as a rubber component. Thereby, good wet grip performance, low fuel consumption, and a reversion suppression effect are obtained.
- SBR styrene butadiene rubber
- the SBR is not particularly limited, and emulsion polymerization SBR (E-SBR), solution polymerization SBR (S-SBR), modified styrene butadiene rubber for silica modified with a compound having an interaction with silica (modified SBR for silica) ) And the like.
- E-SBR and modified SBR for silica are preferable, and it is more preferable to use these in combination.
- E-SBR has many high molecular weight components and is excellent in wear resistance and elongation at break.
- the modified SBR for silica has a strong interaction with silica, it can disperse silica well, and can improve fuel efficiency and wear resistance.
- the E-SBR is not particularly limited, and those commonly used in the tire industry can be used.
- the content of E-SBR in 100% by mass of the rubber component is preferably 10% by mass or more, more preferably 30% by mass or more. If it is less than 10% by mass, sufficient wear resistance, elongation at break and workability may not be obtained.
- the content is preferably 70% by mass or less, more preferably 60% by mass or less. When it exceeds 70 mass%, there exists a tendency for low-fuel-consumption property and abrasion resistance to fall.
- modified SBR for silica modified SBR for silica
- the modified SBR for silica one obtained by replacing the butadiene rubber that is the skeleton component of the modified BR for silica described above with a styrene butadiene rubber may be used.
- the modified SBR for silica is preferably a modified butadiene rubber (S-modified SBR) modified with the compound represented by the above formula (1), and a polymerization terminal of a solution-polymerized styrene butadiene rubber (S-SBR) ( (S-modified S-SBR (modified SBR described in JP-A No. 2010-111753)) modified with the compound represented by the above formula (1) is preferably used.
- the amount of bound styrene of the modified SBR for silica is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less. If it exceeds 40% by mass, fuel economy may be deteriorated. Moreover, the amount of bonded styrene of the modified SBR for silica is preferably 15% by mass or more, and more preferably 23% by mass or more. If it is less than 15% by mass, the wet grip performance tends to be inferior. The amount of styrene is calculated by H 1 -NMR measurement.
- the content of the modified SBR for silica in 100% by mass of the rubber component is preferably 8% by mass or more, more preferably 15% by mass or more, and still more preferably. It is 20 mass% or more. If it is less than 8% by mass, sufficient wet grip performance and low fuel consumption may not be obtained.
- the content is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 72% by mass or less, and particularly preferably 70% by mass or less. When it exceeds 80 mass%, there exists a tendency for abrasion resistance and low fuel consumption to fall.
- the content of SBR in 100% by mass of the rubber component is 25% by mass or more, preferably 30% by mass or more, more preferably 35% by mass or more. If it is less than 25% by mass, wet grip performance and reversion resistance may be deteriorated.
- the SBR content is 75% by mass or less, preferably 72% by mass or less, and more preferably 70% by mass or less. If it exceeds 75% by mass, the blending amount of NR and BR decreases, and sufficient wear resistance and workability (in the case of NR) may not be obtained.
- Examples of rubber components that can be used in the rubber composition of the present invention other than BR and SBR include natural rubber (NR), epoxidized natural rubber (ENR), isoprene rubber (IR), and highly purified NR (phosphorus content).
- NR natural rubber
- ENR epoxidized natural rubber
- IR isoprene rubber
- HPNR Highly Purified Natural Rubber
- SIBR styrene isoprene butadiene rubber
- CR chloroprene rubber
- NBR acrylonitrile butadiene rubber
- blend rubber components for example, ethylene propylene diene rubber (EPDM), butyl rubber (IIR), etc.
- EPDM ethylene propylene diene rubber
- IIR butyl rubber
- NR is preferable because good elongation at break can be obtained.
- the rubber composition of the present invention contains silica (particulate silica) having a nitrogen adsorption specific surface area of 160 to 270 m 2 / g.
- the fine particle silica may be used alone or in combination of two or more.
- the nitrogen adsorption specific surface area (N 2 SA) of the fine particle silica is preferably 170 m 2 / g or more, more preferably 195 m 2 / g or more, and further preferably 210 m 2 / g or more.
- N 2 SA nitrogen adsorption specific surface area
- the nitrogen adsorption specific surface area is preferably 260 m 2 / g or less, more preferably 250 m 2 / g or less.
- N 2 SA of silica is a value measured by the BET method according to ASTM D3037-81.
- the content of the fine particle silica is 40 parts by mass or more, preferably 50 parts by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 40 parts by mass, sufficient effects of improving fuel economy, wet grip performance, elongation at break, and wear resistance cannot be obtained.
- the content is 120 parts by mass or less, preferably 110 parts by mass or less, more preferably 105 parts by mass or less, and still more preferably 100 parts by mass or less. When it exceeds 120 parts by mass, dispersibility deteriorates, and low fuel consumption, elongation at break, and wear resistance decrease.
- the rubber composition of the present invention preferably uses a silane coupling agent in combination with silica.
- silane coupling agents are preferred.
- the mercapto-based silane coupling agent is advantageous in terms of wear resistance, as compared with ordinary Si266 and Si69, even when frictional force acts on the road surface, it maintains the bond between silica and polymer.
- the rare earth BR is closely packed in the polymer itself and the bonding force with Si266 or Si69 becomes weak, a strong bond is formed by using a mercapto system.
- Examples of the silane coupling agent having a mercapto group (—SH) include a compound represented by the following formula (I), a bond unit A represented by the following formula (II), and a bond unit B represented by the following formula (III):
- a compound containing can be preferably used.
- R 101 to R 103 each represents a branched or unbranched alkyl group having 1 to 12 carbon atoms, a branched or unbranched alkoxy group having 1 to 12 carbon atoms, or —O— (R 111 — O) z —R 112
- z R 111 represents a branched or unbranched divalent hydrocarbon group having 1 to 30 carbon atoms.
- the z R 111 may be the same or different.
- R 112 is a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms.
- Z represents an integer of 1 to 30.
- R 101 to R 103 may be the same or different, and R 104 represents a branched or unbranched carbon atom having 1 to 6 carbon atoms.
- R 201 is hydrogen, halogen, branched or unbranched alkyl group having 1 to 30 carbon atoms, branched or unbranched alkenyl group having 2 to 30 carbon atoms, branched or unbranched.
- R 202 represents a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or non-branched alkynyl group having 2 to 30 carbon atoms, or a group in which the terminal hydrogen of the alkyl group is substituted with a hydroxyl group or a carboxyl group.
- R 201 and R 202 may form a ring structure.
- Examples of the compound represented by the above formula (I) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane,
- the compound represented by the following formula (Si363 manufactured by EVONIK-DEGUSSA) and the like can be suitably used. These may be used alone or in combination of two or more.
- the content of the bond unit A is preferably 30 mol% or more, more preferably 50 mol% or more, and preferably 99 mol% or less. More preferably, it is 90 mol% or less.
- the content of the bond unit B is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, preferably 70 mol% or less, more preferably 65 mol% or less, More preferably, it is 55 mol% or less.
- the total content of the binding units A and B is preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol%.
- the content of the bond units A and B is an amount including the case where the bond units A and B are located at the terminal of the silane coupling agent.
- the form in the case where the bonding units A and B are located at the end of the silane coupling agent is not particularly limited as long as the units corresponding to the formulas (II) and (III) showing the bonding units A and B are formed. .
- Examples of the halogen for R 201 include chlorine, bromine, and fluorine.
- Examples of the branched or unbranched alkyl group having 1 to 30 carbon atoms of R 201 include a methyl group and an ethyl group.
- the alkyl group preferably has 1 to 12 carbon atoms.
- Examples of the branched or unbranched alkenyl group having 2 to 30 carbon atoms of R 201 include a vinyl group and a 1-propenyl group.
- the alkenyl group preferably has 2 to 12 carbon atoms.
- Examples of the branched or unbranched alkynyl group having 2 to 30 carbon atoms of R 201 include an ethynyl group and a propynyl group.
- the alkynyl group preferably has 2 to 12 carbon atoms.
- Examples of the branched or unbranched alkylene group having 1 to 30 carbon atoms of R 202 include an ethylene group and a propylene group.
- the alkylene group preferably has 1 to 12 carbon atoms.
- Examples of the branched or unbranched alkenylene group having 2 to 30 carbon atoms of R 202 include vinylene group and 1-propenylene group.
- the alkenylene group preferably has 2 to 12 carbon atoms.
- Examples of the branched or unbranched alkynylene group having 2 to 30 carbon atoms of R 202 include an ethynylene group and a propynylene group.
- the alkynylene group preferably has 2 to 12 carbon atoms.
- the total number of repetitions of the repeating number (x) of the bonding unit A and the repeating number (y) of the bonding unit B is preferably in the range of 3 to 300. Within this range, the mercaptosilane of the bond unit B is covered with —C 7 H 15 of the bond unit A, so that it is possible to suppress the scorch time from being shortened and to have good reactivity with silica and rubber components. Can be secured.
- NXT-Z30, NXT-Z45, NXT-Z60 manufactured by Momentive, etc. may be used as the compound containing the binding unit A represented by the formula (II) and the coupling unit B represented by the formula (III). Can do. These may be used alone or in combination of two or more.
- the compound shown by a following formula can also be used suitably as a silane coupling agent.
- the content of the silane coupling agent is preferably 1 part by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of silica. If it is less than 1 part by mass, the wear resistance, elongation at break, and viscosity (workability) tend to deteriorate. Further, the content of the silane coupling agent is preferably 15 parts by mass or less, more preferably 12 parts by mass or less. When it exceeds 15 parts by mass, there is a tendency that an effect commensurate with the increase in cost cannot be obtained.
- the rubber composition of the present invention preferably contains carbon black (particulate carbon black) having a nitrogen adsorption specific surface area of 100 to 250 m 2 / g.
- the fine particle carbon black may be used alone or in combination of two or more.
- the nitrogen adsorption specific surface area (N 2 SA) of the fine particle carbon black is preferably 120 m 2 / g or more, more preferably 140 m 2 / g or more. If it is less than 100 m 2 / g, there is a tendency that sufficient elongation at break and wear resistance cannot be obtained.
- the N 2 SA is preferably 200 m 2 / g or less, more preferably 180 m 2 / g or less. When it exceeds 250 m 2 / g, dispersibility is deteriorated, and there is a tendency that low fuel consumption, elongation at break, and wear resistance are lowered.
- N 2 SA of carbon black is obtained according to JIS K 6217-2: 2001.
- the content of the fine carbon black is preferably 1 part by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of the rubber component. If it is less than 1 part by mass, the effect of addition may not be obtained. Moreover, there is a possibility that ultraviolet deterioration of rubber cannot be prevented.
- the content is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less. If it exceeds 50 parts by mass, sufficient fuel economy and elongation at break may not be obtained.
- the average primary particle diameter of aluminum hydroxide is preferably 0.3 to 10 ⁇ m, more preferably 0.6 to 3 ⁇ m.
- the rubber composition of the present invention preferably contains sulfur.
- sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur.
- the content of sulfur is preferably 0.5 parts by mass or more, more preferably 0.7 parts by mass or more with respect to 100 parts by mass of the rubber component, and the content is preferably 2 parts by mass or less, More preferably, it is 1.7 parts by mass or less. Within the above range, the effect of the present invention can be more suitably obtained.
- the dispersibility of the fine particle silica and the fine particle carbon black is further improved, and further, the crosslinking between the polymers is made uniform. Therefore, good elongation at break can be obtained, and low fuel consumption, wet grip performance, elongation at break and wear resistance can be improved in a balanced manner.
- the resin and sulfur are attracted by van der Waals force.
- the sulfur surface is coated with the resin, and the surface energy of sulfur is reduced (cohesion is reduced).
- the difference in the SP value between the sulfur surface and the diene rubber is further reduced, so that the dispersion of sulfur is further promoted, and the resin itself has a good dispersibility and the lubricity imparted to the polymer chain of the diene rubber.
- sulfur is uniformly dispersed throughout the rubber composition, and the crosslinking between the polymers is made more uniform in the vulcanization step, so that the effect of improving the performance can be obtained more suitably.
- the rubber composition of the present invention preferably contains a liquid resin having a softening point of ⁇ 20 to 45 ° C., but the liquid resin is preferably compounded in place of oil.
- the softening point of the liquid resin is ⁇ 20 ° C. or higher, preferably ⁇ 10 ° C. or higher. If it is lower than -20 ° C, there is a possibility that the effect of improving fuel economy and elongation at break cannot be obtained sufficiently.
- the softening point is 45 ° C. or lower, preferably 40 ° C. or lower. If it exceeds 45 ° C, fuel economy, elongation at break, and wear resistance may be deteriorated.
- the softening point of the liquid resin is the temperature at which the sphere descends when the softening point specified in JIS K 6220-1: 2001 is measured with a ring and ball softening point measuring device.
- the liquid resin is not particularly limited as long as it has the above softening point.
- a liquid aromatic resin aromatic resin having the above softening point (particularly, coumarone indene resin having the above softening point)).
- liquid terpene resins terpene resins having the above softening point
- liquid rosin resins rosin resin having the above softening points
- liquid aromatic resins (particularly liquid coumarone indene resins) and liquid terpene resins are preferable, and liquid coumarone indene resins are more preferable because the effects of the present invention can be suitably obtained.
- the aromatic resin is obtained by polymerizing an aromatic fraction having 8 to 10 carbon atoms (C8-10) containing vinyltoluene, indene and methylindene as main monomers, generally obtained by thermal decomposition of naphtha. Resin.
- the aromatic fraction include styrene homologues such as ⁇ -methylstyrene and ⁇ -methylstyrene, and styrene.
- the aromatic resin may contain a coumarone unit.
- the aliphatic olefin unit, the phenol unit, and the cresol unit may be included.
- aromatic resin examples include coumarone indene resin, indene resin, aromatic vinyl polymer (resin obtained by polymerizing ⁇ -methylstyrene and / or styrene), C9 hydrocarbon resin, and the like.
- a coumarone indene resin is preferred because the effects of the present invention can be suitably obtained. That is, a coumarone indene resin having the above softening point is preferable.
- the coumarone indene resin is a resin containing coumarone and indene as monomer components constituting the resin skeleton (main chain).
- monomer components contained in the skeleton include styrene and ⁇ -methylstyrene. , Methylindene, vinyltoluene and the like.
- the terpene resin examples include polyterpene resins and terpene phenol resins, and polyterpene resins are preferable. That is, the liquid terpene resin is preferably a liquid polyterpene resin (polyterpene resin having the above softening point).
- Polyterpene resins are resins obtained by polymerizing terpene compounds and their hydrogenated products.
- the terpene compound is a hydrocarbon represented by a composition of (C 5 H 8 ) n and an oxygen-containing derivative thereof.
- Monoterpene (C 10 H 16 ), sesquiterpene (C 15 H 24 ), diterpene (C 20 H 32) For example, ⁇ -pinene, ⁇ -pinene, dipentene, limonene, myrcene, allocymene, ocimene, ⁇ -ferrandrene, ⁇ -terpinene, ⁇ -terpinene, terpinolene 1,8-cineole, 1,4-cineole, ⁇ -terpineol, ⁇ -terpineol, ⁇ -terpineol and the like.
- Polyterpene resins include ⁇ -pinene resins, ⁇ -pinene resins, limonene resins, dipentene resins, ⁇ -pinene / limonene resins, and other terpene resins made from the above-mentioned terpene compounds, as well as hydrogenation treatment of the terpene resins. Also included are hydrogenated terpene resins. Of these, limonene resin is preferred because of its excellent grip performance.
- terpene phenol resin examples include resins made from the above terpene compound and a phenol compound, and specifically, a resin obtained by condensing the terpene compound, the phenol compound and formalin.
- phenolic compounds include phenol, bisphenol A, cresol, and xylenol.
- the content of the liquid resin is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the rubber component. If the amount is less than 0.5 parts by mass, the effects of improving fuel economy, elongation at break, and wear resistance may not be sufficiently obtained.
- the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less. If it exceeds 20 parts by mass, the complex elastic modulus (E * ) and hardness may be reduced.
- the rubber composition of the present invention comprises a terpene resin having a softening point of 46 to 160 ° C, a rosin resin having a softening point of 46 to 140 ° C, a C5 petroleum resin having a softening point of 46 to 140 ° C, and a softening point of 46 to 140 ° C. It is preferable to include at least one resin selected from the group consisting of aromatic resins.
- the blending amount of BR is relatively large, and there is a concern that the wet grip performance is lowered, but by blending these resins, good wet grip performance can be obtained, low fuel consumption, wet grip performance, The elongation at break and the wear resistance can be improved more suitably. This is because these resins are distributed as 100 nm to 1 ⁇ m spheres in the rubber composition, and when grip is developed, the grip (for example, spike effect. When the road surface temperature is high, the resin dissolves and the adhesive tape effect ).
- the resin selected from the above group is preferably a terpene resin or an aromatic resin.
- the terpene resin has a high effect of improving wet grip performance and low fuel consumption, and the aromatic resin has a high effect of improving wet grip performance.
- the total content of the resin selected from the above group is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 7 parts by mass or more with respect to 100 parts by mass of the rubber component.
- the total content is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 12 parts by mass or less.
- the terpene resin having a softening point of 46 to 160 ° C. is different from the liquid terpene resin only in the softening point.
- a polyterpene resin or a terpene phenol resin can be preferably used. It can be used suitably.
- the polyterpene resin is preferably limonene resin because it has excellent grip performance.
- the terpene resin (polyterpene resin, terpene phenol resin) may contain a small amount of other monomer components such as ⁇ -methylstyrene in addition to the terpene compound as a monomer component.
- a resin obtained by using a small amount of ⁇ -methylstyrene together with the terpene compound or the phenol compound as a component is included in the terpene phenol resin.
- the softening point of the terpene resin is preferably 46 ° C or higher, more preferably 80 ° C or higher, and still more preferably 100 ° C or higher. If it is less than 46 ° C, the effect of improving the grip performance may be reduced.
- the softening point is preferably 160 ° C. or lower, more preferably 135 ° C. or lower. If the temperature exceeds 160 ° C., the dispersibility of the resin may decrease, and the elongation at break and wear resistance may decrease.
- the preferred blending amount of the terpene resin is the same as the total content of the resin selected from the above group.
- the aromatic resin having a softening point of 46 to 140 ° C. is generally an aromatic resin having 8 to 10 carbon atoms (C8-10) mainly containing vinyltoluene, indene and methylindene obtained by thermal decomposition of naphtha. Of the resins obtained by polymerizing the fraction, the resin has a softening point of 46 to 140 ° C.
- other examples of the aromatic fraction include styrene homologues such as ⁇ -methylstyrene and ⁇ -methylstyrene, and styrene.
- the aromatic resin may contain a coumarone unit.
- the aliphatic olefin unit, the phenol unit, and the cresol unit may be included.
- the softening point of the aromatic resin is 46 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, and particularly preferably 90 ° C. or higher. If it is less than 46 ° C, the effect of improving the grip performance may be reduced.
- the softening point is 140 ° C. or lower, preferably 130 ° C. or lower. If it exceeds 140 ° C., the dispersibility of the resin may be reduced, and the elongation at break and the wear resistance may be reduced.
- aromatic resin examples include coumarone indene resin, indene resin, aromatic vinyl polymer (resin obtained by polymerizing ⁇ -methylstyrene and / or styrene), C9 hydrocarbon resin, and the like.
- coumarone indene resin, indene resin, and aromatic vinyl polymer are preferred from the viewpoint that fuel economy, wet grip performance, elongation at break, and wear resistance can be obtained in a balanced manner.
- a vinyl polymer is more preferred. It is also preferable to use a coumarone indene resin and an aromatic vinyl polymer in combination.
- the coumarone indene resin which is an aromatic resin, differs from the liquid coumarone indene resin only in the softening point.
- the preferred blending amount of the coumarone indene resin is the total content of the resin selected from the above group It is the same.
- aromatic vinyl polymer styrene and ⁇ -methylstyrene are used as the aromatic vinyl monomer (unit), and either a homopolymer of each monomer or a copolymer of both monomers is used. Good.
- aromatic vinyl polymer ⁇ -methylstyrene or a homopolymer of styrene or a copolymer of ⁇ -methylstyrene and styrene is economical, easy to process, and excellent in wet grip performance.
- a copolymer of ⁇ -methylstyrene and styrene is more preferable.
- aromatic vinyl polymer for example, commercially available products such as SYLVARES SA85, SA100, SA120, SA140 manufactured by Arizona chemical, R2336 manufactured by Eastman chemical, and the like can be suitably used.
- the softening point of the aromatic vinyl polymer is preferably 46 ° C or higher, more preferably 60 ° C or higher, still more preferably 70 ° C or higher. If it is lower than 46 ° C, the wet grip performance may be lowered.
- the softening point is preferably 140 ° C. or lower, more preferably 100 ° C. or lower. If it exceeds 140 ° C., fuel efficiency may be deteriorated.
- the softening point of terpene resin, rosin resin, C5 petroleum resin, aromatic resin, and aromatic vinyl polymer is the ring and ball softening point measuring device defined by JIS K 6220-1: 2001. The temperature at which the sphere descended was measured.
- the preferable blending amount of the aromatic vinyl polymer is the same as the total content of the resin selected from the above group.
- a liquid coumarone indene resin having a softening point of ⁇ 20 to 45 ° C. and an aromatic resin having a softening point of 46 to 140 ° C. are obtained because the effects of the present invention can be more suitably obtained. It is preferable to use together.
- compounding agents commonly used in the production of rubber compositions for example, processing aids such as zinc oxide, stearic acid, fatty acid metal salts, various anti-aging agents, Wax, oil, vulcanizing agent, vulcanization accelerator and the like can be appropriately blended.
- the total content of the oil, the liquid resin, and the resin selected from the above group is preferably 2 to 35 parts by mass with respect to 100 parts by mass of the rubber component from the viewpoint that the effects of the present invention are sufficiently obtained. If aiming to improve fuel efficiency and wear resistance, 3 to 15 parts by mass is more preferable.
- the rubber composition of the present invention is produced by a general method. That is, it can be produced by a method of kneading the above components with a Banbury mixer, a kneader, an open roll or the like and then vulcanizing.
- the rubber composition can be suitably used for a tire tread.
- the rubber component, silica, carbon black, silane coupling agent and the like are discharged at a temperature of 120 to 180 ° C. (preferably 130 to 175 ° C. (about 150 ° C. when Si266 is used as the silane coupling agent) Kneading (base kneading step) until it reaches about 170 ° C. when used, or about 140 ° C. when using NXTZ or Si363, and then adding a vulcanizing agent such as sulfur, a vulcanization accelerator, etc. Kneading is started from about 50 ° C. if it is cold, and about 80 ° C. if it is continuously used.
- a vulcanizing agent such as sulfur, a vulcanization accelerator, etc. Kneading is started from about 50 ° C. if it is cold, and about 80 ° C. if it is continuously used.
- the present invention is achieved by vulcanization.
- the base kneading step is preferably performed in two or more steps, and in each step of the base kneading step, It is preferable to add and knead the silane coupling agent and the silane coupling agent separately.
- the rubber component, carbon black, silica and a part of the silane coupling agent are kneaded first.
- the remaining chemicals and knead it is more preferable to add the remaining chemicals and knead.
- the base kneading step is two steps
- a half amount of silica is added together with the total amount of the rubber component and carbon black.
- the remaining silica, the silane coupling agent and other chemicals may be added and kneaded in the second step. Thereby, the dispersibility of a silica can be improved more.
- the pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, the rubber composition containing the above components is extruded in accordance with the shape of each tire member such as a tread at an unvulcanized stage, and is molded together with the other tire members by a normal method on a tire molding machine. By doing so, an unvulcanized tire is formed. The unvulcanized tire is heated and pressurized in a vulcanizer to obtain a tire.
- the pneumatic tire of the present invention can be used as a tire for passenger cars, a tire for trucks and buses, a tire for multipurpose sports vehicles (SUV), a tire for competitions, etc., and particularly suitable as a tire for passenger cars and tires for multipurpose sports vehicles. Can be used.
- SUV multipurpose sports vehicles
- NR TSR20
- ENR ENR25 (Epoxidized natural rubber manufactured by Kumpoulang Guthrie (Malaysia), epoxidation rate: 25% mol)
- BR1 CB25 manufactured by LANXESS Co., Ltd.
- BR synthesized using an Nd-based catalyst (Nd-based BR), cis content: 97% by mass, vinyl content: 0.7% by mass, Mw / Mn: 1.78, Mw : 500,000, Mn: 280,000)
- Modified BR for silica 1 modified BR produced in copolymer production example 1 (vinyl content: 13% by mass, cis content: 38% by mass, trans content: 50% by mass, Mw / Mn: 1.19, Mw: 420,000 )
- Modified CB for CB BR1250H manufactured by Nippon Zeon Co., Ltd.
- Silica 1 Zeosil 1085Gr manufactured by Rhodia (N 2 SA: 90 m 2 / g)
- Silica 2 Zeosil 1115Gr manufactured by Rhodia (N 2 SA: 115 m 2 / g)
- Silica 3 Zeosil 1165MP manufactured by Rhodia (N 2 SA: 165 m 2 / g)
- Silica 4 Ultrasil VN3 manufactured by Evonik Degussa (N 2 SA: 175 m 2 / g)
- Silica 5 Zeosil Premium 200MP manufactured by Rhodia (N 2 SA: 215 m 2 / g)
- Silica 6 U9000Gr (N 2 SA: 235 m 2 / g) manufactured by Evonik Degussa
- Silica 7 Prototype manufactured by Tokuyama Corporation (N 2 SA: 260 m 2 / g)
- Silica 8 Prototype manufactured by Tokuyama Corporation (N 2 SA: 280 m 2 / g) Silane
- TDAE VIVETEC 500 manufactured by H & R Wax: Ozoace0355 manufactured by Nippon Seiwa Co., Ltd.
- Anti-aging agent Antigen 6C (N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.
- TMQ NOCRACK 224 manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
- Stearic acid Stearic acid “ ⁇ ” manufactured by NOF Corporation
- Zinc oxide Silver candy R made by Toho Zinc Co., Ltd.
- Powder sulfur containing 5% oil HK-200-5 manufactured by Hosoi Chemical Co., Ltd.
- TBBS Noxeller NS-G (N-tert-butyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
- DPG Noxeller D (diphenylguanidine) manufactured by Ouchi Shinsei Chemical Co., Ltd.
- Examples and Comparative Examples According to the formulation shown in Tables 1 and 2, using a 1.7 L Banbury mixer, kneading temperature of rubber component, half of silica, all of carbon black and half of silane coupling agent at 150 ° C. The kneaded material 1 was obtained by kneading. Next, using a 1.7 L Banbury mixer, the kneaded product 1 obtained, the remainder of the silica and silane coupling agent, and the remaining chemicals other than sulfur and vulcanization accelerator were kneaded at 150 ° C. The kneaded product 2 was obtained by kneading.
- the test tire was mounted on a domestic FR vehicle with a displacement of 2000 cc, and the vehicle was run on a dry asphalt road test course.
- the residual groove amount of the tire tread rubber at that time was measured (8.0 mm when new), and evaluated as wear resistance.
- the amount of remaining grooves in Comparative Example 1 was taken as 100 and displayed as an index. It shows that it is excellent in abrasion resistance, so that an index
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Abstract
Description
また、シリカ100質量部に対して、下記式(I)で表される化合物;
、下記式(II)で示される結合単位Aと下記式(III)で示される結合単位Bとを含む化合物;
、及び下記式で示される化合物;
からなる群より選択される少なくとも1種のシランカップリング剤を1~15質量部含むことが好ましい。
軟化点46~160℃のテルペン系樹脂、軟化点46~140℃のロジン系樹脂、軟化点46~140℃のC5系石油樹脂、及び軟化点46~140℃の芳香族系樹脂からなる群より選択される少なくとも1種の樹脂を含むことが好ましい。
前記空気入りタイヤは、乗用車用タイヤ又は多目的スポーツ車用タイヤであることが好ましい。
具体的には、低分子化合物からオリゴマー成分まで測定できるカラムを選択し、測定する。得られたピークにおいて、低分子化合物由来のピークの高分子側の最初の変曲点から垂線を下ろし、低分子側成分の面積と高分子側成分の面積比を求める。この面積比が低分子化合物とオリゴマー成分の比率に相当する。
なお、オリゴマー成分の高分子側ピークは、標準ポリスチレン換算分子量から求めた該低分子化合物の分子量の10倍以下の分子量となる点、あるいは該低分子化合物の分子量の10倍以下の分子量となる点までに成分ピークが0となる場合は成分ピークが0となる点までを積算する。
本発明のゴム組成物がE-SBRを含有する場合、ゴム成分100質量%中のE-SBRの含有量は、好ましくは10質量%以上、より好ましくは30質量%以上である。10質量%未満であると、充分な耐摩耗性、破断時伸び、加工性が得られないおそれがある。該含有量は、好ましくは70質量%以下、より好ましくは60質量%以下である。70質量%を超えると、低燃費性、耐摩耗性が低下する傾向がある。
なお、スチレン量は、H1-NMR測定により算出される。
なお、本明細書において、シリカのN2SAは、ASTM D3037-81に準じてBET法で測定される値である。
なお、結合単位A、Bの含有量は、結合単位A、Bがシランカップリング剤の末端に位置する場合も含む量である。結合単位A、Bがシランカップリング剤の末端に位置する場合の形態は特に限定されず、結合単位A、Bを示す式(II)、(III)と対応するユニットを形成していればよい。
なお、本明細書において、カーボンブラックのN2SAは、JIS K 6217-2:2001によって求められる。
硫黄の含有量は、ゴム成分100質量部に対して、好ましくは0.5質量部以上、より好ましくは0.7質量部以上であり、また、該含有量は、好ましくは2質量部以下、より好ましくは1.7質量部以下である。上記範囲内であると、本発明の効果がより好適に得られる。
なお、液状樹脂の軟化点は、JIS K 6220-1:2001に規定される軟化点を環球式軟化点測定装置で測定し、球が降下した温度である。
なお、該ポリテルペン樹脂としては、グリップ性能に優れるという理由から、リモネン樹脂が好ましい。なお、本発明において、テルペン系樹脂(ポリテルペン樹脂、テルペンフェノール樹脂)は、モノマー成分として、上記テルペン化合物以外にもα-メチルスチレン等の他のモノマー成分を少量含んでいてもよく、例えば、モノマー成分として、上記テルペン化合物、上記フェノール系化合物と共に少量のα-メチルスチレンを使用して得られた樹脂は、テルペンフェノール樹脂に含まれる。
なお、テルペン系樹脂、ロジン系樹脂、C5系石油樹脂、芳香族系樹脂、芳香族ビニル重合体の軟化点は、JIS K 6220-1:2001に規定される軟化点を環球式軟化点測定装置で測定し、球が降下した温度である。
すなわち、前記成分を配合したゴム組成物を、未加硫の段階でトレッドなどの各タイヤ部材の形状にあわせて押出し加工し、他のタイヤ部材とともに、タイヤ成型機上にて通常の方法で成形することにより、未加硫タイヤを形成する。この未加硫タイヤを加硫機中で加熱加圧することによりタイヤを得る。
窒素雰囲気下、250mlメスフラスコに3-(N,N-ジメチルアミノ)プロピルトリメトキシシラン(アヅマックス(株)製)を20.8g入れ、さらに無水ヘキサン(関東化学(株)製)を加え、全量を250mlにして作製した。
充分に窒素置換した30L耐圧容器にシクロヘキサン(関東化学(株)製)を18L、ブタジエン(高千穂商事(株)製)を2000g、ジエチルエーテル(関東化学(株)製)を53mmol加え、60℃に昇温した。次に、ブチルリチウム(関東化学(株)製)を16.6mL加えた後、3時間撹拌した。次に0.4mol/Lの四塩化ケイ素/ヘキサン溶液を12ml加え、30分撹拌を行った。次に、上記末端変性剤を13mL追加し30分間撹拌を行った。反応溶液に2,6-tert-ブチル-p-クレゾール(大内新興化学工業(株)製)0.2gを溶かしたメタノール(関東化学(株)製)2mLを添加後、反応溶液を18Lのメタノールが入ったステンレス容器に入れて凝集体を回収した。得られた凝集体を24時間減圧乾燥させ、変性BRを得た。Mwは420,000であり、ビニル含量は13質量%であった。
充分に窒素置換した30L耐圧容器にn-ヘキサンを18L、スチレン(関東化学(株)製)を540g、ブタジエンを1460g、テトラメチルエチレンジアミンを17mmolを加え、40℃に昇温した。次に0.4mol/Lの四塩化ケイ素/ヘキサン溶液を3.5ml加え、30分撹拌を行った。次に、ブチルリチウムを10.5mL加えた後、50℃に昇温させ3時間撹拌した。次に、上記末端変性剤を30mL追加し30分間撹拌を行った。反応溶液に2,6-tert-ブチル-p-クレゾール(大内新興化学工業(株)製)0.2gを溶かしたメタノール(関東化学(株)製)2mLを添加後、反応溶液を18Lのメタノールが入ったステンレス容器に入れて凝集体を回収した。得られた凝集体を24時間減圧乾燥させ、変性SBRを得た。結合スチレン量は27質量%であった。Mwは400,000であり、ビニル含量は53モル%であった。
充分に窒素置換した30L耐圧容器にn-ヘキサンを18L、スチレン(関東化学(株)製)を740g、ブタジエンを1260g、テトラメチルエチレンジアミンを17mmolを加え、40℃に昇温した。次に0.4mol/Lの四塩化ケイ素/ヘキサン溶液を3.5ml加え、30分撹拌を行った。次に、ブチルリチウムを10.5mL加えた後、50℃に昇温させ3時間撹拌した。次に、上記末端変性剤を30mL追加し30分間撹拌を行った。反応溶液に2,6-tert-ブチル-p-クレゾール(大内新興化学工業(株)製)0.2gを溶かしたメタノール(関東化学(株)製)2mLを添加後、反応溶液を18Lのメタノールが入ったステンレス容器に入れて凝集体を回収した。得られた凝集体を24時間減圧乾燥させ、変性SBRを得た。結合スチレン量は37質量%であった。Mwは410,000であり、ビニル含量は54モル%であった。
充分に窒素置換した30L耐圧容器にn-ヘキサンを18L、スチレン(関東化学(株)製)を520g、ブタジエンを1480g、テトラメチルエチレンジアミンを17mmolを加え、40℃に昇温した。次に0.4mol/Lの四塩化ケイ素/ヘキサン溶液を3.5ml加え、30分撹拌を行った。次に、ブチルリチウムを10.5mL加えた後、50℃に昇温させ3時間撹拌した。次に、上記末端変性剤を30mL追加し30分間撹拌を行った。反応溶液に2,6-tert-ブチル-p-クレゾール(大内新興化学工業(株)製)0.2gを溶かしたメタノール(関東化学(株)製)2mLを添加後、反応溶液を18Lのメタノールが入ったステンレス容器に入れて凝集体を回収した。得られた凝集体を24時間減圧乾燥させ、変性SBRを得た。結合スチレン量は26質量%であった。Mwは430,000であり、ビニル含量は56モル%であった。
NR:TSR20
ENR:ENR25(クンプーランガスリー社(マレーシア)製のエポキシ化天然ゴム、エポキシ化率:25%モル)
BR1:ランクセス(株)製のCB25(Nd系触媒を用いて合成したBR(Nd系BR)、シス含量:97質量%、ビニル含量:0.7質量%、Mw/Mn:1.78、Mw:50万、Mn:28万)
BR2:宇部興産(株)製のBR150B(Co系触媒を用いて合成したBR(Co系BR)、シス含量:96質量%、ビニル含量:2.1質量%、Mw/Mn:2.30、Mw:44万、Mn:19万)
シリカ用変性BR1:共重合体製造例1で作製した変性BR(ビニル含量:13質量%、シス含量:38質量%、トランス含量:50質量%、Mw/Mn:1.19、Mw:42万)
シリカ用変性BR2:住友化学(株)製の変性ブタジエンゴム(S変性BR)(ビニル含量15質量%、R1、R2及びR3=-OCH3、R4及びR5=-CH2CH3、n=3)
CB用変性BR:日本ゼオン(株)製のBR1250H(リチウム開始剤を用いて重合したスズ変性BR(カーボンブラック用変性BR)、ビニル含量:10質量%、シス含量:40質量%、トランス含量:50質量%、Mw/Mn:1.40、Mw:46万、Mn:33万、スズ原子の含有量:250ppm)
シリカ用変性SBR1:共重合体製造例2で作製した変性SBR(結合スチレン量:27質量%)
シリカ用変性SBR2:共重合体製造例3で作製した変性SBR(結合スチレン量:37質量%)
シリカ用変性SBR3:共重合体製造例4で作製した変性SBR(結合スチレン量:26質量%)
E-SBR:JSR(株)製のSBR1723(結合スチレン量:23.5質量%)
カーボンブラック:コロンビアカーボン(株)製のHP160(N2SA:165m2/g)
シリカ1:Rhodia社製のZeosil 1085Gr(N2SA:90m2/g)
シリカ2:Rhodia社製のZeosil 1115Gr(N2SA:115m2/g)
シリカ3:Rhodia社製のZeosil 1165MP(N2SA:165m2/g)
シリカ4:エボニックデグッサ社製のウルトラジルVN3(N2SA:175m2/g)
シリカ5:Rhodia社製のZeosil Premium 200MP(N2SA:215m2/g)
シリカ6:エボニックデグッサ社製のU9000Gr(N2SA:235m2/g)
シリカ7:トクヤマ(株)製の試作品(N2SA:260m2/g)
シリカ8:トクヤマ(株)製の試作品(N2SA:280m2/g)
シランカップリング剤1:エボニックデグッサ社製のSi75(ビス(3-トリエトキシシリルプロピル)ジスルフィド)
シランカップリング剤2:Momentive社製のNXT-Z45
シランカップリング剤3:Momentive社製のNXT
シランカップリング剤4:エボニックデグッサ社製のSi363
クマロンインデン樹脂:Rutgers Chemicals社製のNOVARES C10(液状クマロンインデン樹脂、軟化点:5~15℃)
芳香族ビニル重合体:Arizona chemical社製のSYLVARES SA85(α-メチルスチレンとスチレンとの共重合体、軟化点:85℃、Mw:1000)
テルペンフェノール樹脂:アリゾナケミカル社製のSylvares TP115(テルペンフェノール樹脂、軟化点:115℃、水酸基価:50KOHmg/g)
TDAE:H&R社製のVIVATEC500
ワックス:日本精蝋(株)製のOzoace0355
老化防止剤:住友化学(株)製のアンチゲン6C(N-(1,3-ジメチルブチル)-N’-フェニル-p-フェニレンジアミン)
TMQ:大内新興化学工業(株)製のノクラック224
ステアリン酸:日油(株)製のステアリン酸「椿」
酸化亜鉛:東邦亜鉛(株)製の銀嶺R
5%オイル含有粉末硫黄:細井化学(株)製のHK-200-5
TBBS:大内新興化学工業(株)製のノクセラーNS-G(N-tert-ブチル-2-ベンゾチアゾリルスルフェンアミド)
DPG:大内新興化学工業(株)製のノクセラーD(ジフェニルグアニジン)
表1~2に示す配合処方にしたがい、1.7Lのバンバリーミキサーを用いて、ゴム成分と、シリカの半量と、カーボンブラックの全量と、シランカップリング剤の半量とを混練温度が150℃になるまで混練し、混練物1を得た。次に、1.7Lのバンバリーミキサーを用いて、得られた混練物1と、シリカ及びシランカップリング剤の残りと、硫黄及び加硫促進剤以外の残りの薬品とを混練温度が150℃になるまで混練し、混練物2を得た。次に、オープンロールを用いて、得られた混練物2に硫黄および加硫促進剤を添加して混練温度が105℃になるまで混練し、未加硫ゴム組成物を得た。
得られた未加硫ゴム組成物を170℃の条件下で12分間プレス加硫し、加硫ゴム組成物を得た。
また、得られた未加硫ゴム組成物をトレッドの形状に成形し、タイヤ成型機上で他のタイヤ部材とともに貼り合わせ、170℃の条件下で12分間プレス加硫し、試験用タイヤ(タイヤサイズ:245/40R18)を得た。
(株)岩本製作所製の粘弾性スペクトロメータVESを用いて、温度30℃、周波数10Hz、初期歪10%及び動歪2%の条件下で、上記加硫ゴム組成物の複素弾性率E*(MPa)及び損失正接tanδを測定した。なお、E*が大きいほど剛性が高く、操縦安定性に優れることを示し、tanδが小さいほど発熱性が低く、低燃費性に優れることを示す。なお、tanδについては、比較例1のtanδを100として指数でも表した。指数が大きいほど、低燃費性に優れることを示す。
上記試験用タイヤを排気量2000ccの国産FR車に装着し、ウェットアスファルト路面のテストコースにて10周の実車走行を行った。その際における、操舵時のコントロールの安定性をテストドライバーが評価し、比較例1を100として指数表示をした。指数が大きいほどウェットグリップ性能に優れることを示す。
上記試験用タイヤを排気量2000ccの国産FR車に装着し、ドライアスファルト路面のテストコースにて実車走行を行った。その際におけるタイヤトレッドゴムの残溝量を計測し(新品時8.0mm)、耐摩耗性として評価した。残溝量が多いほど、耐摩耗性に優れる。比較例1の残溝量を100として指数表示した。指数が大きいほど、耐摩耗性に優れることを示す。
加硫ゴム組成物からなる3号ダンベル型試験片を用いて、JIS K 6251「加硫ゴム及び熱可塑性ゴム-引張特性の求め方」に準じて、室温にて引張試験を実施し、破断時伸びEB(%)を測定した。EBが大きいほど、破断時伸び(耐久性)に優れることを示す。
Claims (10)
- ゴム成分100質量%中、シス含量50質量%以下のシリカ用変性ブタジエンゴムの含有量が8~40質量%、スチレンブタジエンゴムの含有量が25~75質量%であり、
ゴム成分100質量部に対して、窒素吸着比表面積が160~270m2/gのシリカを40~120質量部含むトレッド用ゴム組成物。 - 前記シリカ用変性ブタジエンゴムは、下記式(1)で表される化合物により変性された変性ブタジエンゴム、分子中にグリシジルアミノ基を含む低分子化合物により変性された変性ブタジエンゴム、及び分子中にグリシジルアミノ基を含む低分子化合物と、該低分子化合物の2量体以上のオリゴマーとの混合物により変性された変性ブタジエンゴムからなる群より選択される少なくとも1種である請求項1記載のトレッド用ゴム組成物。
- 前記分子中にグリシジルアミノ基を含む低分子化合物が下記式で示される化合物である請求項2記載のトレッド用ゴム組成物。
- 前記スチレンブタジエンゴムは、シリカ用変性スチレンブタジエンゴムを含む請求項1~3のいずれかに記載のトレッド用ゴム組成物。
- シリカ100質量部に対して、下記式(I)で表される化合物;
、下記式(II)で示される結合単位Aと下記式(III)で示される結合単位Bとを含む化合物;
、及び下記式で示される化合物;
からなる群より選択される少なくとも1種のシランカップリング剤を1~15質量部含む請求項1~4のいずれかに記載のトレッド用ゴム組成物。 - ゴム成分100質量%中、希土類元素系触媒を用いて合成されたブタジエンゴムの含有量が40質量%以下である請求項1~5のいずれかに記載のトレッド用ゴム組成物。
- 軟化点-20~45℃の液状樹脂を含み、
前記液状樹脂が、液状クマロンインデン樹脂及び/又は液状テルペン系樹脂である請求項1~6のいずれかに記載のトレッド用ゴム組成物。 - 軟化点46~160℃のテルペン系樹脂、軟化点46~140℃のロジン系樹脂、軟化点46~140℃のC5系石油樹脂、及び軟化点46~140℃の芳香族系樹脂からなる群より選択される少なくとも1種の樹脂を含む請求項1~7のいずれかに記載のトレッド用ゴム組成物。
- 請求項1~8のいずれかに記載のゴム組成物を用いて作製した空気入りタイヤ。
- 乗用車用タイヤ又は多目的スポーツ車用タイヤである請求項9記載の空気入りタイヤ。
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JP2019199526A (ja) * | 2018-05-16 | 2019-11-21 | 住友ゴム工業株式会社 | タイヤ用ゴム組成物及び空気入りタイヤ |
JP7102924B2 (ja) | 2018-05-16 | 2022-07-20 | 住友ゴム工業株式会社 | タイヤ用ゴム組成物及び空気入りタイヤ |
JP2020029146A (ja) * | 2018-08-22 | 2020-02-27 | 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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JP2020059769A (ja) * | 2018-10-05 | 2020-04-16 | 住友ゴム工業株式会社 | タイヤ用ゴム組成物及び空気入りタイヤ |
JP7371323B2 (ja) | 2018-10-05 | 2023-10-31 | 住友ゴム工業株式会社 | タイヤ用ゴム組成物及び空気入りタイヤ |
JP2023500520A (ja) * | 2019-11-06 | 2023-01-06 | ブリヂストン アメリカズ タイヤ オペレーションズ、 エルエルシー | 特定のゴム組成物のトレッドを有するタイヤ及びその関連方法 |
CN114846068A (zh) * | 2019-12-19 | 2022-08-02 | 株式会社普利司通 | 轮胎 |
CN114058096B (zh) * | 2020-08-03 | 2023-08-22 | 旭化成株式会社 | 聚合物共混物及其制造方法、以及使用其的橡胶组合物和充气轮胎 |
CN114058096A (zh) * | 2020-08-03 | 2022-02-18 | 旭化成株式会社 | 聚合物共混物及其制造方法、以及使用其的橡胶组合物和充气轮胎 |
KR102411451B1 (ko) | 2020-09-29 | 2022-06-20 | 한국타이어앤테크놀로지 주식회사 | 타이어 트레드용 고무 조성물 및 이를 포함하는 타이어 |
KR20220043535A (ko) * | 2020-09-29 | 2022-04-05 | 한국타이어앤테크놀로지 주식회사 | 타이어 트레드용 고무 조성물 및 이를 포함하는 타이어 |
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JP6018207B2 (ja) | 2016-11-02 |
CN104487506A (zh) | 2015-04-01 |
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CN104487506B (zh) | 2019-06-07 |
JPWO2014021002A1 (ja) | 2016-07-21 |
DE112013003160T5 (de) | 2015-03-12 |
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