Rubber composition for tire and tire

Abstract

To provide a tire rubber composition and a tire that improve the combined properties of low fuel consumption, wet braking, and resistance to chipping.SOLUTION: The present invention relates to a rubber composition for a tire, comprising a rubber component including butadiene rubber and styrene-butadiene rubber, and silica, wherein the content of the silica is greater than the content of the styrene-butadiene rubber, the total styrene content in the rubber component is greater than the content of the butadiene rubber, and the silica has an average particle diameter of 16 nm or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a rubber composition for tires and a tire.

Background Art

[0002] Hitherto, various methods for improving low fuel consumption, wet braking, and chipping resistance performance have been studied (see, for example, Patent Documents 1 to 3). However, in recent years, further improvement of these performances has been demanded.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a rubber composition for tires and a tire that solve the above problems and can improve the overall performance of low fuel consumption, wet braking, and chipping resistance performance.

Means for Solving the Problems

[0005] The present invention relates to a rubber composition for tires containing a rubber component including butadiene rubber and styrene-butadiene rubber and silica, wherein the content of the silica > the content of the styrene-butadiene rubber, the total styrene amount in the rubber component > the content of the butadiene rubber, and the average particle diameter of the silica is 16 nm or less.

Effects of the Invention

[0006] The present invention relates to a rubber composition for tires containing a rubber component including butadiene rubber and styrene-butadiene rubber, and silica, wherein the content of the silica > the content of the styrene-butadiene rubber, the total styrene amount in the rubber component > the content of the butadiene rubber, and the average particle diameter of the silica is 16 nm or less. Therefore, the overall performance of low fuel consumption, wet braking, and chipping resistance is excellent.

Embodiments for Carrying Out the Invention

[0007] The rubber composition for tires of the present disclosure contains a rubber component including butadiene rubber and styrene-butadiene rubber, and silica, wherein the content of the silica > the content of the styrene-butadiene rubber, the total styrene amount in the rubber component > the content of the butadiene rubber, and the average particle diameter of the silica is 16 nm or less.

[0008] The reason why the above-mentioned effects can be obtained with the above rubber composition is presumably as follows. By containing styrene-butadiene rubber as a rubber component, minute domains due to the styrene component are formed in the rubber matrix, making it easier to obtain heat generation properties and followability. By setting the total styrene amount in the rubber component / the content of butadiene rubber > 1 and the content of silica / the content of styrene-butadiene rubber > 1, and by using silica with a small average particle diameter, the above-mentioned effects can be obtained more easily. Due to the above actions, it is considered that the overall performance (the sum of each index) of low fuel consumption, wet braking, and chipping resistance is improved.

[0009] The above rubber composition contains a rubber component. Here, the rubber component is a component that contributes to crosslinking, and generally has a weight average molecular weight (Mw) of 10,000 or more.

[0010] The weight average molecular weight of the rubber component is preferably 50,000 or more, more preferably 150,000 or more, still more preferably 200,000 or more, and is preferably 2,500,000 or less, more preferably 2,000,000 or less, still more preferably 1,500,000 or less. When it is within the above range, the effect tends to be obtained more favorably.

[0011] In addition, in this specification, the weight average molecular weight (Mw) can be determined by standard polystyrene conversion based on the measured value by gel permeation chromatography (GPC) (GPC-8000 series manufactured by Tosoh Corporation, detector: differential refractometer, column: TSKGEL SUPERMULTIPORE HZ-M manufactured by Tosoh Corporation).

[0012] The total styrene amount in the rubber component is preferably 5% by mass or more, more preferably 12% by mass or more, still more preferably 17% by mass or more, and is preferably 35% by mass or less, more preferably less than 25% by mass, still more preferably 20% by mass or less. When it is within the above range, the effect tends to be obtained more favorably.

[0013] Here, the total styrene amount in the rubber component is the total content of the styrene part contained in the total amount of the rubber component (unit: mass%), and can be calculated by Σ (content of each rubber component × amount of styrene in each rubber component / 100). For example, in 100% by mass of the rubber component, when 85% by mass is styrene-butadiene rubber with a styrene amount of 40% by mass, 5% by mass is styrene-butadiene rubber with a styrene amount of 25% by mass, and 10% by mass is butadiene rubber with a styrene amount of 0% by mass, the total styrene amount in the rubber component is 35.25% by mass (= 85 × 40 / 100 + 5 × 25 / 100 + 10 × 0 / 100).

[0014] The total vinyl content in the rubber component is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, even more preferably 3% by mass or more, particularly preferably 5% by mass or more, and is preferably 45% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, even more preferably 15% by mass or less, even more preferably 12% by mass or less, particularly preferably 7% by mass or less. When within the above range, the effect tends to be obtained more favorably.

[0015] Here, the total vinyl content in the rubber component is the total content (unit: part by mass) of vinyl bonds in the butadiene moieties of styrene-butadiene rubber and butadiene rubber contained in the rubber component when the total mass of the rubber component is 100, and can be calculated by Σ (content of each rubber component × ratio [mass%] of the amount of vinyl bonds in the butadiene moiety in the rubber component to the total mass of each rubber component). For example, in 100 parts by mass of the rubber component, if there are 85 parts by mass of styrene-butadiene rubber with a styrene content of 40% by mass and a vinyl content of 30% by mass, 5 parts by mass of styrene-butadiene rubber with a styrene content of 20% by mass and a vinyl content of 20% by mass, and 10 parts by mass of butadiene rubber with a vinyl content of 10% by mass, the total vinyl content in the rubber component is 17.1 parts by mass (= 85×(100[mass%] - 40[mass%])×30[mass%]+5×(100[mass%] - 20[mass%])×20[mass%]+10×10[mass%]).

[0016] Note that the styrene content and vinyl content in each rubber component can be measured by nuclear magnetic resonance (NMR) method. In addition, regarding the total styrene content and total vinyl content in the rubber component, in the examples of this specification, they are calculated in accordance with the above calculation formula. However, for example, they may also be analyzed from the tire by a pyrolysis gas chromatography-mass spectrometer (Py-GC / MS) or the like.

[0017] The above rubber composition contains butadiene rubber (BR) as the rubber component. BR is not particularly limited. For example, high cis content BR such as BR1220 manufactured by Nippon Zeon Co., Ltd., BR150B manufactured by Ube Industries, Ltd., BR1280 manufactured by LG Chem, etc., BR containing 1,2-syndiotactic polybutadiene crystal (SPB) such as VCR412 and VCR617 manufactured by Ube Industries, Ltd., butadiene rubber synthesized using a rare earth element-based catalyst (rare earth-based BR), etc., those commonly used in the tire industry can be used. These may be used alone or in combination of two or more. Among them, rare earth-based BR is preferred.

[0018] As the rare earth element-based catalyst used for the synthesis of rare earth-based BR, known ones can be used, but lanthanum series rare earth element compounds are preferred, and neodymium-containing compounds (Nd-based catalysts) are more preferred.

[0019] BR may be an oil-extended rubber extended with oil, a resin-extended rubber extended with resin, or an extended rubber extended with other softening agents. Among them, it is preferably a resin-extended rubber (resin-extended BR). These may be used alone or in combination of two or more. The softening agent content in these extended rubbers is not particularly limited, but is usually about 5 to 50 parts by mass with respect to 100 parts by mass of the rubber solid content. The oil used for the oil-extended rubber and the resin used for the resin-extended rubber are the same as those described later. In addition, examples of other softening agents include liquid polymers described later.

[0020] BR may have a functional group introduced by modification that interacts with a filler such as silica. Examples of the functional group include, for example, a silicon-containing group (-SiR3, where R is the same or different and is hydrogen, a hydroxyl group, a hydrocarbon group, an alkoxy group, etc.), an amino group, an amide group, an isocyanate group, an imino group, an imidazole group, a urea group, an ether group, a carbonyl group, an oxycarbonyl group, a mercapto group, a sulfide group, a disulfide group, a sulfonyl group, a sulfinyl group, a thiocarbonyl group, an ammonium group, an imide group, a hydrazo group, an azo group, a diazo group, a carboxy group, a nitrile group, a pyridyl group, an alkoxy group, a hydroxyl group, an oxy group, an epoxy group, etc. These functional groups may have substituents. Among them, a silicon-containing group is preferable, and -SiR3 (R is the same or different and is hydrogen, a hydroxyl group, a hydrocarbon group (preferably a hydrocarbon group having 1 to 6 carbon atoms (more preferably an alkyl group having 1 to 6 carbon atoms)) or an alkoxy group (preferably an alkoxy group having 1 to 6 carbon atoms)), and at least one of R is a hydroxyl group) is more preferable.

[0021] Specific examples of the compound (modifying agent) for introducing the functional group include 2-dimethylaminoethyltrimethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 2-dimethylaminoethyltriethoxysilane, 3-dimethylaminopropyltriethoxysilane, 2-diethylaminoethyltrimethoxysilane, 3-diethylaminopropyltrimethoxysilane, 2-diethylaminoethyltriethoxysilane, 3-diethylaminopropyltriethoxysilane, etc.

[0022] As the BR, hydrogenated BR to which hydrogen has been added can also be used. When the BR is hydrogenated BR, there are no particular limitations on the hydrogenation method and reaction conditions, and hydrogenation may be carried out by known methods and under known conditions. Usually, it is carried out under hydrogen pressure of 20 to 150°C and 0.1 to 10 MPa in the presence of a hydrogenation catalyst. Other manufacturing methods and conditions are not particularly limited either. For example, the content described in International Publication No. 2016 / 039005 can be applied. Incidentally, as a result of adding hydrogen to the butadiene portion of BR, hydrogenated BR has the same structure as a copolymer of ethylene and butadiene. Therefore, in this specification, hydrogenated BR shall include not only the hydrogenated product of BR but also the copolymer of ethylene and butadiene.

[0023] The hydrogenation rate of hydrogenated BR, with the total butadiene units before hydrogenation taken as 100 mol%, is preferably 65 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and is preferably 95 mol% or less, more preferably 92 mol% or less, still more preferably 90 mol% or less. When within the above range, the effect tends to be obtained more favorably. Incidentally, the hydrogenation rate 1 can be calculated from the spectral reduction rate of the unsaturated bond portion of the spectrum obtained by measuring 1H-NMR.

[0024] The cis amount (cis content) of BR is preferably 80 mass% or more, more preferably 85 mass% or more, still more preferably 90 mass% or more, and is preferably 99 mass% or less, more preferably 98 mass% or less, still more preferably 97 mass% or less. When within the above range, the effect tends to be obtained more favorably. Incidentally, the cis amount of BR can be measured by infrared absorption spectrum analysis.

[0025] Incidentally, the above-mentioned cis amount of BR means the cis amount of the BR when there is one type of BR, and means the average cis amount when there are multiple types. The average cis amount of BR can be calculated by {Σ(content of each BR × cis amount of each BR)} / total content of all BR. For example, in 100 mass% of the rubber component, when BR with a cis amount of 90 mass% is 20 mass% and BR with a cis amount of 40 mass% is 10 mass%, the average cis amount of BR is 73.3 mass% (=(20×90 + 10×40) / (20 + 10)).

[0026] In 100% by mass of the rubber component, the content of BR is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and is preferably 35% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less. When within the above range, the effect tends to be obtained better.

[0027] In the above rubber composition, the total styrene amount in the rubber component > the content of BR. The value of the total styrene amount in the rubber component / the content of BR is preferably 1.05 or more, more preferably 1.1 or more, still more preferably 1.15 or more, and is preferably 2.5 or less, more preferably 1.6 or less, still more preferably 1.3 or less. When within the above range, the effect tends to be obtained better. In this relationship, the content of BR and the total styrene amount in the rubber component are the contents (unit: mass%) in 100% by mass of the rubber component.

[0028] The above rubber composition contains styrene butadiene rubber (SBR) as the rubber component. SBR is not particularly limited. For example, emulsion polymerization styrene butadiene rubber (E-SBR), solution polymerization styrene butadiene rubber (S-SBR), etc. can be used. Commercially available products include those of Sumitomo Chemical Co., Ltd., JSR Corporation, Asahi Kasei Corporation, Nippon Zeon Co., Ltd., etc. These SBRs may be used alone or in combination of two or more, but it is preferable to use two or more in combination.

[0029] The styrene amount of SBR is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and is preferably 45% by mass or less, more preferably 35% by mass or less, still more preferably 25% by mass or less. When within the above range, the effect tends to be obtained better.

[0030] The vinyl content of the SBR is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and is preferably 45% by mass or less, more preferably 35% by mass or less, still more preferably 25% by mass or less. When within the above range, the effect tends to be obtained more favorably.

[0031] In particular, for the SBR, it is preferable that the styrene content is 25% by mass or less and the vinyl content is 25% by mass or less.

[0032] In addition, the styrene content of the above-mentioned SBR means the styrene content of the SBR when there is one type of SBR, and means the average styrene content when there are multiple types. The average styrene content of the SBR can be calculated by {Σ(content of each SBR × styrene content of each SBR)} / total content of all SBRs. For example, in 100% by mass of the rubber component, when the SBR with a styrene content of 40% by mass is 85% by mass and the SBR with a styrene content of 25% by mass is 5% by mass, the average styrene content of the SBR is 39.2% by mass (=(85×40 + 5×25) / (85 + 5)).

[0033] Also, the vinyl content of the above-mentioned SBR is the ratio of vinyl bonds (unit: % by mass) when the total mass of the butadiene part in the SBR is 100, and vinyl content [% by mass] + cis content [% by mass] + trans content [% by mass] = 100 [% by mass]. When there is one type of SBR, it means the vinyl content of the SBR, and when there are multiple types, it means the average vinyl content. The average vinyl content of SBR can be calculated by Σ{content of each SBR × (100 [mass%] - styrene content of each SBR [mass%]) × vinyl content of each SBR [mass%]} / Σ{content of each SBR × (100 [mass%] - styrene content of each SBR [mass%])}. For example, in 100 parts by mass of the rubber component, when there are 75 parts by mass of SBR with a styrene content of 40 mass% and a vinyl content of 30 mass%, 15 parts by mass of SBR with a styrene content of 25 mass% and a vinyl content of 20 mass%, and the remaining 10 parts by mass are other than SBR, the average vinyl content of SBR is 28 mass% (={75×(100 [mass%]-40 [mass%])×30 [mass%]+15×(100 [mass%]-25 [mass%])×20 [mass%])} / {75×(100 [mass%]-40 [mass%])+15×(100 [mass%]-25 [mass%])}).

[0034] The glass transition temperature (Tg) of SBR is preferably -10 °C or lower, more preferably -20 °C or lower, and is also preferably -80 °C or higher, more preferably -70 °C or higher. When within the above range, the effect tends to be obtained more favorably. The glass transition temperature of SBR is a value measured under the condition of a heating rate of 10 °C / min using a differential scanning calorimeter (Q200) manufactured by TA Instruments Japan Co., Ltd. in accordance with JIS-K7121.

[0035] As SBR, hydrogenated SBR to which hydrogen is added can also be used. When SBR is hydrogenated SBR, there are no particular limitations on the hydrogenation method and reaction conditions, and hydrogenation may be carried out by known methods and under known conditions. Usually, it is carried out under hydrogen pressure of 20 to 150 °C and 0.1 to 10 MPa in the presence of a hydrogenation catalyst. Other methods and conditions related to the production are not particularly limited either. For example, the content described in the above-mentioned International Publication No. 2016 / 039005 can be applied. Note that as a result of adding hydrogen to the butadiene part of SBR, hydrogenated SBR has the same structure as a copolymer of ethylene, butadiene, and styrene. Therefore, in the present specification, hydrogenated SBR shall include not only hydrogenated products of copolymers of butadiene and styrene (SBR) but also copolymers of ethylene, butadiene, and styrene.

[0036] The hydrogenation rate of the hydrogenated SBR, with the total butadiene units before hydrogenation as 100 mol%, is preferably 65 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and is preferably 95 mol% or less, more preferably 92 mol% or less, still more preferably 90 mol% or less. When within the above range, the effect tends to be obtained more favorably. In addition, the hydrogenation rate 1 can be calculated from the spectral reduction rate of the unsaturated bond part of the spectrum obtained by measuring 1H-NMR.

[0037] The SBR may be an oil-extended rubber extended with oil, a resin-extended rubber extended with resin, or an extended rubber extended with other softening agents. Among them, it is preferably a resin-extended rubber (resin-extended SBR). These may be used alone or in combination of two or more. The softening agent content in these extended rubbers is not particularly limited, but is usually about 5 to 50 parts by mass with respect to 100 parts by mass of the rubber solid content. The oil used for the oil-extended rubber and the resin used for the resin-extended rubber are the same as those described later. In addition, examples of other softening agents include the liquid polymers described later.

[0038] The SBR may have a functional group introduced therein that interacts with a filler such as silica by modification. Examples of the functional group include, for example, a silicon-containing group (-SiR3, where R is the same or different and is hydrogen, a hydroxyl group, a hydrocarbon group, an alkoxy group, etc.), an amino group, an amide group, an isocyanate group, an imino group, an imidazole group, a urea group, an ether group, a carbonyl group, an oxycarbonyl group, a mercapto group, a sulfide group, a disulfide group, a sulfonyl group, a sulfinyl group, a thiocarbonyl group, an ammonium group, an imide group, a hydrazo group, an azo group, a diazo group, a carboxy group, a nitrile group, a pyridyl group, an alkoxy group, a hydroxyl group, an oxy group, an epoxy group, etc. These functional groups may have substituents. Among them, a silicon-containing group is preferable, and -SiR3 (where R is the same or different and is hydrogen, a hydroxyl group, a hydrocarbon group (preferably a hydrocarbon group having 1 to 6 carbon atoms (more preferably an alkyl group having 1 to 6 carbon atoms)) or an alkoxy group (preferably an alkoxy group having 1 to 6 carbon atoms)), and at least one of R is a hydroxyl group) is more preferable.

[0039] Specific examples of the compound (modifying agent) for introducing the above functional group include 2-dimethylaminoethyltrimethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 2-dimethylaminoethyltriethoxysilane, 3-dimethylaminopropyltriethoxysilane, 2-diethylaminoethyltrimethoxysilane, 3-diethylaminopropyltrimethoxysilane, 2-diethylaminoethyltriethoxysilane, 3-diethylaminopropyltriethoxysilane, etc.

[0040] In 100% by mass of the rubber component, the content of SBR is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less. When within the above range, the effect tends to be obtained more favorably.

[0041] In the above rubber composition, the value of the content of SBR / the content of BR is preferably 1 or more, more preferably 2 or more, still more preferably 4 or more, even more preferably 5 or more, particularly preferably 5.5 or more, and is preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, particularly preferably 6 or less. When it is within the above range, the effect tends to be obtained more favorably. In this relationship, the content of SBR and the content of BR are the contents (unit: mass%) in 100% by mass of the rubber component.

[0042] The above rubber composition may contain an isoprene rubber as the rubber component. Examples of the isoprene rubber include natural rubber (NR), isoprene rubber (IR), modified NR, modified NR, modified IR, etc. As NR, for example, those generally used in the tire industry such as SIR20, RSS#3, TSR20, etc. can be used. IR is not particularly limited, and for example, those generally used in the tire industry such as IR2200, etc. can be used. Examples of modified NR include deproteinized natural rubber (DPNR), high-purity natural rubber (UPNR), etc., examples of modified NR include epoxidized natural rubber (ENR), hydrogenated natural rubber (HNR), grafted natural rubber, etc., and examples of modified IR include epoxidized isoprene rubber, hydrogenated isoprene rubber, grafted isoprene rubber, etc. These may be used alone or in combination of two or more. Among them, NR is preferred.

[0043] In 100% by mass of the rubber component, the content of the isoprene rubber is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less. The lower limit is not particularly limited and may be 0% by mass, but is preferably 1% by mass or more, more preferably 5% by mass or more. When it is within the above range, the effect tends to be obtained more favorably.

[0044] As rubber components other than isoprene rubber, BR, and SBR, diene rubbers such as acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), and styrene-isoprene-butadiene copolymer rubber (SIBR) can be mentioned. These may be used alone or in combination of two or more.

[0045] The rubber components other than isoprene rubber, BR, and SBR may be oil-extended rubbers extended with oil, resin-extended rubbers extended with resin, or extended rubbers extended with other softeners. Among them, resin-extended rubbers are preferred. These may be used alone or in combination of two or more. The softener content in these extended rubbers is not particularly limited, but is usually about 5 to 50 parts by mass with respect to 100 parts by mass of the rubber solid content. The oil used for the oil-extended rubber and the resin used for the resin-extended rubber are the same as those described later. In addition, examples of other softeners include the liquid polymers described later.

[0046] The rubber components other than isoprene rubber, BR, and SBR may have functional groups introduced by modification that interact with fillers such as silica. Examples of the above functional groups include silicon-containing groups (-SiR3 (R is the same or different and is hydrogen, a hydroxyl group, a hydrocarbon group, an alkoxy group, etc.)), amino groups, amide groups, isocyanate groups, imino groups, imidazole groups, urea groups, ether groups, carbonyl groups, oxycarbonyl groups, mercapto groups, sulfide groups, disulfide groups, sulfonyl groups, sulfinyl groups, thiocarbonyl groups, ammonium groups, imide groups, hydrazo groups, azo groups, diazo groups, carboxy groups, nitrile groups, pyridyl groups, alkoxy groups, hydroxyl groups, oxy groups, epoxy groups, etc. Note that these functional groups may have substituents. Among them, silicon-containing groups are preferred, and -SiR3 (R is the same or different and is hydrogen, a hydroxyl group, a hydrocarbon group (preferably a hydrocarbon group having 1 to 6 carbon atoms (more preferably an alkyl group having 1 to 6 carbon atoms)) or an alkoxy group (preferably an alkoxy group having 1 to 6 carbon atoms)), and at least one of R is a hydroxyl group) is more preferred.

[0047] Specific examples of the compound (modifying agent) for introducing the above functional group include 2-dimethylaminoethyltrimethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 2-dimethylaminoethyltriethoxysilane, 3-dimethylaminopropyltriethoxysilane, 2-diethylaminoethyltrimethoxysilane, 3-diethylaminopropyltrimethoxysilane, 2-diethylaminoethyltriethoxysilane, 3-diethylaminopropyltriethoxysilane, and the like.

[0048] The raw materials (monomers) for synthetic rubbers such as IR, SBR, and BR may be derived from underground resources such as petroleum and natural gas, or may be recycled from rubber products such as tires and non-rubber products such as polystyrene. The monomers obtained by recycling (recycled monomers) are not particularly limited, and examples include recycled polyisoprene, recycled butadiene, and recycled aromatic vinyl. Examples of the butadiene include 1,2-butadiene and 1,3-butadiene. The aromatic vinyl is not particularly limited, and examples include styrene. Among them, it is preferable to use recycled polyisoprene (recycled isoprene), recycled butadiene (recycled butadiene), and / or recycled styrene (recycled styrene) as raw materials.

[0049] The method for producing recycled monomers is not particularly limited, and examples include being synthesized from recycled naphtha obtained by decomposing rubber products such as tires. Further, the method for producing recycled naphtha is not particularly limited, and for example, rubber products such as tires may be decomposed under high temperature and high pressure, decomposed by microwaves, or extracted after mechanical pulverization.

[0050] Furthermore, the raw materials (monomers) for synthetic rubbers such as IR, SBR, and BR may be derived from biomass. In this specification, biomass refers to substances derived from natural resources such as plants. Biomass is not particularly limited, and examples include agricultural and forestry products, sugars, wood chips, plant residues after obtaining useful components, ethanol derived from plants, biomass naphtha, and the like.

[0051] The monomers derived from biomass (biomass monomers) are not particularly limited, and examples include butadiene derived from biomass and aromatic vinyl derived from biomass. Examples of the butadiene include 1,2-butadiene and 1,3-butadiene. The aromatic vinyl is not particularly limited, and examples include styrene. Also, the method for producing biomass monomers is not particularly limited, and examples include those by biological and / or chemical and / or physical conversion of animals and plants. Fermentation by microorganisms is typical of biological conversion, and examples of chemical and / or physical conversion include those by catalysts, high heat, high pressure, electromagnetic waves, critical liquids, and combinations thereof.

[0052] The polymers synthesized from biomass monomer components (biomass polymers) are not particularly limited, and examples include polybutadiene rubber synthesized from butadiene derived from biomass and aromatic vinyl / butadiene copolymers synthesized from butadiene derived from biomass and / or aromatic vinyl derived from biomass. Examples of the aromatic vinyl / butadiene copolymer include styrene-butadiene rubber synthesized from butadiene derived from biomass and / or styrene derived from biomass.

[0053] Whether the raw material of the polymer is derived from biomass can be determined by pMC (percent Modern Carbon) measured in accordance with ASTM D6866-10.

[0054] pMC refers to the 14 C concentration of the sample14 It is the ratio of C concentration and is a value used as an index indicating the biomass ratio of a compound. The significance of this value will be described below.

[0055] In one mole (6.02×10 23 pieces) of carbon atoms, there are about 6.02×10 11 pieces of 14 C, which is about one trillionth of ordinary carbon atoms. 14 14C is called a radioactive isotope, and its half-life is 5730 years and it decreases regularly. It takes 226,000 years for all of these to decay. Therefore, after carbon dioxide in the atmosphere is taken up and fixed by plants, etc., in fossil fuels such as coal, oil, and natural gas, which are considered to have passed more than 226,000 years since fixation, all of the 14 14C element has decayed. Therefore, in the 21st century, fossil fuels such as coal, oil, and natural gas do not contain 14 14C element at all. Therefore, chemical substances produced from these fossil fuels also do not contain 14 14C element at all.

[0056] On the other hand, 14 14C is constantly generated by nuclear reactions of cosmic rays in the atmosphere, and the decrease due to radioactive decay is balanced. In the earth's atmospheric environment, the amount of 14 14C is a certain amount. Therefore, the 14 14C concentration of substances derived from biomass resources circulating in the current environment is about 1×10 -12 mol% with respect to the total C atoms as described above. Therefore, by using the difference between these values, the biomass ratio of a certain compound can be calculated.

[0057] This 14 14C is generally measured as follows. Using accelerator mass spectrometry based on a tandem accelerator, 13 14C concentration ( 13 14C / 12 12C), [[ID=^44]] 14 13C concentration ( 14 13C / 12 12C) is measured. In the measurement,14 As a modern standard reference for the concentration of C, the 14 C concentration in the circulating carbon in nature in 1950 is adopted. As a specific standard substance, the oxalic acid standard provided by NIST (National Institute of Standards and Technology) is used. The specific radioactivity of carbon in this oxalic acid (the radioactivity intensity of 14 C per gram of carbon) is separated for each carbon isotope, 13 For 14 C, it is corrected to a constant value, and the value obtained by applying the decay correction from 1950 AD to the measurement date is used as the standard

[0058] Therefore, if the rubber is made of 100% biomass-derived substances, although there are regional differences and so on, currently in the normal state, it often does not reach 100, so it will show a value of about 110 pMC. On the other hand, for chemical substances derived from fossil fuels such as petroleum, when this 14 C concentration is measured, it will show a value of about 0 pMC (for example, 0.3 pMC). This value corresponds to a biomass ratio of 0% mentioned above.

[0059] From the above, using materials such as rubber with a high pMC value, that is, materials such as rubber with a high biomass ratio, in the rubber composition is suitable from the perspective of environmental protection.

[0060] The above rubber composition may contain a thermoplastic elastomer as an elastomer other than the rubber component. The thermoplastic elastomer is a copolymer (block copolymer) composed of a hard segment that plays the role of crosslinking points and a soft segment that exhibits rubber elasticity, and is usually solid at 25°C.

[0061] Examples of the hard segment include polystyrene, polypropylene, polyester, polyamide, polyvinyl chloride, polyurethane, etc., and examples of the soft segment include vinyl-polybutadiene, polyisoprene, polybutadiene, polyethylene, polychloroprene, poly-2,3-dimethylbutadiene, etc. These may be of one kind or two or more kinds.

[0062] The thermoplastic elastomer may be used alone or in combination of two or more. As commercially available products, products of Kuraray Co., Ltd., Asahi Kasei Corporation, etc. can be used. In addition, in this specification, the thermoplastic elastomer is not included in the rubber component.

[0063] The thermoplastic elastomer is preferably a thermoplastic elastomer having a styrene block (styrenic thermoplastic elastomer). Specific examples of the styrenic thermoplastic elastomer include styrene-vinyl isoprene-styrene triblock copolymer (SIS), styrene-isobutylene diblock copolymer (SIB), styrene-butadiene-styrene triblock copolymer (SBS), styrene-ethylene·butylene-styrene triblock copolymer (SEBS), styrene-ethylene·propylene-styrene triblock copolymer (SEPS), styrene-ethylene·ethylene·propylene-styrene triblock copolymer (SEEPS), styrene-butadiene·butylene-styrene triblock copolymer (SBBS), etc. These may be used alone or in combination of two or more. Among them, styrene-ethylene·ethylene·propylene-styrene triblock copolymer (SEEPS) is more preferable.

[0064] The styrene content of the styrenic thermoplastic elastomer is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less. When it is within the above range, the effect tends to be obtained more favorably.

[0065] The content of the thermoplastic elastomer is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0066] The above rubber composition contains silica as a filler. The silica is not particularly limited, and for example, silica prepared by a dry method (anhydrous silica), silica prepared by a wet method (hydrous silica), etc., which are common in the tire industry, can be used. The raw material of the silica is not particularly limited, and for example, it may be a raw material derived from a mineral such as quartz, or a raw material derived from a living organism such as rice husk (for example, silica using a biomass material such as rice husk as a raw material), or silica recycled from a product containing silica may be used. Among them, hydrous silica prepared by a wet method is preferable because it has many silanol groups. These silicas may be used alone or in combination of two or more. As commercially available products, products of Evonik, Tosoh Silica Co., Ltd., Solvay Japan Co., Ltd., Tokuyama Corporation, etc. can be used.

[0067] Silica using a biomass material as a raw material can be obtained, for example, by extracting a silicate from rice husk ash obtained by burning rice husks using a sodium hydroxide solution, and reacting the silicate with sulfuric acid in the same manner as conventional wet silica to filter, wash with water, dry, and pulverize the resulting silicon dioxide precipitate.

[0068] Silica recycled from a product containing silica can be used, for example, silica recovered from products containing silica such as electronic components such as semiconductors, tires, desiccants, and filter materials such as diatomaceous earth. The recovery method is not particularly limited, and examples include thermal decomposition and decomposition by electromagnetic waves. Among them, silica recovered from electronic components such as semiconductors or tires is preferable.

[0069] When silica crystallizes, it becomes insoluble in water and the silicic acid that is its component cannot be utilized. By controlling the combustion temperature and combustion time, crystallization of silica in rice husk ash can be suppressed (see, for example, Japanese Patent Application Laid-Open No. 2009-2594, Akita Prefectural University Web Journal B / 2019, vol. 6, p. 216-222, etc.).

[0070] Amorphous silica extracted from rice husks can be those commercially available from Wilmar Co., Ltd. and others.

[0071] The average particle diameter of the silica is 16 nm or less. The average particle diameter of the silica is preferably 15 nm or less, and preferably 6 nm or more, more preferably 9 nm or more, still more preferably 12 nm or more. When within the above range, the effect tends to be obtained more favorably.

[0072] In this specification, as the method for measuring the average particle diameter of silica, transmission electron microscope (TEM) observation is used. Specifically, silica particles are photographed with a transmission electron microscope. When the shape of the particles is spherical, the diameter of the sphere is taken as the particle diameter; when the particles are needle-shaped or rod-shaped, the minor axis is taken as the particle diameter; when the particles are amorphous, the average particle diameter from the center is taken as the particle diameter, and the average value of the particle diameters of 100 fine particles is taken as the average particle diameter.

[0073] The content of silica is preferably 80 parts by mass or more, more preferably 100 parts by mass or more, still more preferably 110 parts by mass or more, and preferably 170 parts by mass or less, more preferably 140 parts by mass or less, still more preferably 120 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0074] In the above rubber composition, the content of silica > the content of SBR. The value of the silica content / SBR content is preferably 1.15 or more, more preferably 1.25 or more, still more preferably 1.35 or more, and is preferably 2.5 or less, more preferably 2 or less, still more preferably 1.5 or less. When it is within the above range, the effect tends to be obtained more favorably. In this relationship, the silica content is the content (unit: parts by mass) relative to 100 parts by mass of the rubber component, and the SBR content is the content (unit: mass%) in 100 mass% of the rubber component.

[0075] In the above rubber composition, the value of the silica content / total styrene amount in the rubber component is preferably 2 or more, more preferably 4 or more, still more preferably 5 or more, particularly preferably 6 or more, and is preferably 15 or less, more preferably 12 or less, still more preferably 10 or less, particularly preferably 7 or less. When it is within the above range, the effect tends to be obtained more favorably. In this relationship, the silica content is the content (unit: parts by mass) relative to 100 parts by mass of the rubber component, and the total styrene amount is the content (unit: mass%) in 100 mass% of the rubber component.

[0076] Examples of fillers other than silica include carbon black, vulcanized rubber particles, aluminum hydroxide, talc, calcium compounds, short fibers, etc. These may be used alone or in combination of two or more. Among them, carbon black is preferred.

[0077] The carbon black is not particularly limited, and examples thereof include N134, N110, N220, N234, N219, N339, N330, N326, N351, N550, N762, etc. The raw material of the carbon black may be a biomass material such as lignin or vegetable oil, or may be a pyrolysis oil obtained by pyrolyzing waste tires. Further, the manufacturing method of the carbon black may be by combustion such as the furnace method, by hydrothermal carbonization (HTC), or by thermal decomposition of methane such as the thermal black method. As commercial products, products of Asahi Carbon Co., Ltd., Cabot Japan Co., Ltd., Tokai Carbon Co., Ltd., Mitsubishi Chemical Corporation, Lion Corporation, Nippon Steel Carbon Co., Ltd., Columbian Carbon Co., etc. can be used. These may be used alone or in combination of two or more kinds.

[0078] The cetyltrimethylammonium bromide (CTAB) specific surface area of the carbon black is preferably 100 m 2 / g or more, more preferably 120 m 2 / g or more, still more preferably 140 m 2 / g or more, and preferably 220 m 2 / g or less, more preferably 200 m 2 / g or less, still more preferably 180 m 2 / g or less. The CTAB specific surface area of the carbon black is a value measured in accordance with JIS K6217-3:2001.

[0079] The content of the carbon black is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, based on 100 parts by mass of the rubber component, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less. When it is within the above range, the effect tends to be obtained more favorably.

[0080] In the above rubber composition, the value of the carbon black content / silica content is preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.04 or more, and is preferably 0.09 or less, more preferably 0.07 or less, still more preferably 0.05 or less. When it is within the above range, the effect tends to be obtained more favorably. In this relationship, the carbon black content and the silica content are the contents (unit: parts by mass) relative to 100 parts by mass of the rubber component.

[0081] The vulcanized rubber particles are particles made of vulcanized rubber. Specifically, rubber powder etc. specified in JIS K 6316:2017 can be used. From the viewpoints of environmental consideration and cost, recycled rubber powder produced from crushed waste tires etc. is preferable. These may be used alone or in combination of two or more. The vulcanized rubber particles are not particularly limited, and may be non-modified vulcanized rubber particles or modified vulcanized rubber particles.

[0082] As commercially available products of vulcanized rubber particles, products of Lehigh, Murakami Rubber Industry Co., Ltd. etc. can be used. In this specification, the vulcanized rubber particles are not included in the rubber component.

[0083] The average particle diameter of the vulcanized rubber particles is preferably 50 μm or more, more preferably 100 μm or more, still more preferably 200 μm or more, and is preferably 1000 μm or less, more preferably 900 μm or less, still more preferably 800 μm or less. The average particle diameter of the vulcanized rubber particles is the average particle diameter based on mass calculated from the particle size distribution measured in accordance with JIS Z 8815:1994.

[0084] The content of the vulcanized rubber particles is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the rubber component.

[0085] In this specification, aluminum hydroxide means Al(OH)3 or Al2O3·3H2O. As commercially available products, products of Sumitomo Chemical Co., Ltd., Showa Denko K.K., Nabaltec AG, etc. can be used. These may be used alone or in combination of two or more.

[0086] The average particle diameter of aluminum hydroxide is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 0.8 μm or more, and is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less. When within the above range, the effect tends to be obtained more favorably. In this specification, as the method for measuring the average particle diameter of aluminum hydroxide, transmission electron microscope (TEM) observation is used. Specifically, aluminum hydroxide particles are photographed with a transmission electron microscope. When the shape of the particles is spherical, the diameter of the sphere is taken as the particle diameter. When the particles are needle-shaped or rod-shaped, the minor axis is taken as the particle diameter. When the particles are amorphous, the average particle diameter from the center is taken as the particle diameter, and the average value of the particle diameters of 100 fine particles is taken as the average particle diameter.

[0087] The BET specific surface area (nitrogen adsorption specific surface area, N2SA) of aluminum hydroxide is preferably 5 m 2 / g or more, more preferably 8 m 2 / g or more, still more preferably 10 m 2 / g or more, and is preferably 40 m 2 / g or less, more preferably 30 m 2 / g or less, still more preferably 20 m 2 / g or less. The BET specific surface area of aluminum hydroxide is a value measured by the BET method in accordance with ASTM D3037-81.

[0088] The content of aluminum hydroxide is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the rubber component.

[0089] The average particle diameter of talc is preferably 50 μm or less, more preferably 30 μm or less. The lower limit of the average particle diameter of talc is not particularly limited, but is preferably 1 μm or more.

[0090] The content of talc is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the rubber component.

[0091] The calcium compound is a compound containing calcium, and examples thereof include inorganic salts such as calcium oxide, calcium hydroxide, and calcium carbide; oxoacid salts such as calcium carbonate, calcium nitrate, and calcium sulfate. In addition, examples of those containing a calcium compound include eggshells (main component: calcium carbonate). These may be used alone or in combination of two or more. Among them, oxoacid salts are preferred, and calcium carbonate is more preferred. In addition, in this specification, calcium fatty acid salt is treated as a processing aid described later and is not included in the filler.

[0092] The content of the calcium compound is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the rubber component.

[0093] As the short fibers, for example, organic short fibers, inorganic short fibers, etc. can be used. Specific examples of organic short fibers include nanocellulose such as cellulose nanofiber (CNF) and cellulose nanocrystal (CNC); biomass nanomaterials such as chitin nanofiber; and chitosan nanofiber. Specific examples of inorganic short fibers include metal fibers and glass fiber systems. Commercially available products include products of Nippon Paper Industries Co., Ltd., Sugino Machine Ltd., etc. These may be used alone or in combination of two or more. Among them, organic short fibers are preferred, and nanocellulose is more preferred.

[0094] The particle size of the nanocellulose is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 25 nm or more, particularly preferably 28 nm or more, and preferably 50 nm or less, more preferably 40 nm or less, still more preferably 35 nm or less, particularly preferably 32 nm or less. When within the above range, the effect tends to be obtained better.

[0095] The particle size of the nanocellulose is the average fiber diameter measured by image analysis using a scanning electron micrograph, image analysis using a transmission electron micrograph, image analysis using an atomic force micrograph, analysis of X-ray scattering data, the pore electrical resistance method (Coulter principle method), or the like. In addition, in this specification, the average fiber diameter of the nanocellulose (cellulose fiber) is typically the average fiber diameter of an aggregate of cellulose fibers formed by an aggregate of cellulose molecules.

[0096] The content of the short fibers is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the rubber component.

[0097] The content of the filler is preferably 80 parts by mass or more, more preferably 100 parts by mass or more, still more preferably 120 parts by mass or more, and preferably 200 parts by mass or less, more preferably 160 parts by mass or less, still more preferably 140 parts by mass or less with respect to 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0098] The rubber composition preferably contains a softening agent. A softening agent is a material that imparts plasticity to the rubber component, and is a concept that includes both a softening agent that is liquid at 25°C and a softening agent that is solid at 25°C. Examples of softening agents include resins, oils, liquid polymers, ester plasticizers, and the like. Among them, resins and liquid polymers are preferred. These softening agents may be derived from mineral resources such as petroleum and natural gas, may be derived from biomass, or may be derived from naphtha recycled from rubber products or non-rubber products. Further, low molecular weight hydrocarbon components obtained by thermally decomposing and extracting used tires and products containing various components may be used as the softening agent. These softening agents may be used alone or in combination of two or more.

[0099] As the resin, for example, resins such as C5 resins, C5 / C9 resins, coumarone-indene resins, aromatic resins, terpene resins, cyclopentadiene resins, etc., and hydrogenated products thereof can be used. These may be used alone or in combination of two or more, but it is preferable to use two or more in combination. In addition, in this specification, the resin may be solid or liquid at 25°C.

[0100] The C5 resin is a polymer containing a C5 fraction as a constituent monomer. For example, in addition to a homopolymer obtained by polymerizing one type of C5 fraction alone and a copolymer obtained by copolymerizing two or more types of C5 fractions, a copolymer of a C5 fraction and another monomer copolymerizable therewith is also included. Examples of the C5 fraction include olefin hydrocarbons such as 1-pentene, 2-pentene, 2-methyl-1-butene, etc., and diolefin hydrocarbons such as 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, etc. These may be used alone or in combination of two or more. In addition, in this specification, a polymer containing a C5 fraction and an aromatic monomer (C9 fraction) as constituent monomers is treated as a C5 / C9 resin.

[0101] The content of the C5 resin is preferably 2 parts by mass or more, more preferably 6 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0102] The C5 / C9 resin is a polymer containing a C5 fraction and a C9 fraction as constituent monomers. For example, polymers obtained by polymerizing a petroleum-derived C5 fraction and a C9 fraction using a Friedel-Crafts type catalyst such as AlCl3 or BF3 can be mentioned. Specifically, copolymers mainly composed of styrene, vinyltoluene, α-methylstyrene, indene, etc. can be mentioned. In addition, in the present specification, the C5 / C9 resin is treated as a resin different from the aromatic resin and the C5 resin.

[0103] The content of the C5 / C9 resin is preferably 2 parts by mass or more, more preferably 6 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effects tend to be obtained more favorably.

[0104] The coumarone-indene resin is a polymer containing coumarone and indene as constituent monomers. For example, in addition to the copolymer of coumarone and indene, copolymers of coumarone and indene with other monomers copolymerizable therewith are also included.

[0105] The content of the coumarone-indene resin is preferably 2 parts by mass or more, more preferably 6 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effects tend to be obtained more favorably.

[0106] The aromatic resin is a polymer containing an aromatic monomer as a constituent monomer. For example, in addition to a homopolymer obtained by polymerizing one kind of aromatic monomer alone and a copolymer obtained by copolymerizing two or more kinds of aromatic monomers, copolymers of an aromatic monomer and other monomers copolymerizable therewith are also included.

[0107] Examples of the aromatic monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, and p-chlorostyrene; phenol monomers such as phenol, alkylphenol, and alkoxyphenol; naphthol monomers such as naphthol, alkylnaphthol, and alkoxynaphthol; coumarone, indene, and the like. These may be used alone or in combination of two or more. Among them, styrene monomers are preferred, and styrene and α-methylstyrene are more preferred.

[0108] Examples of other monomers include non-conjugated olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. These may be used alone or in combination of two or more.

[0109] The aromatic resin is preferably an α-methylstyrene resin (such as an α-methylstyrene homopolymer or a copolymer of styrene and α-methylstyrene), and more preferably a styrene-α-methylstyrene resin (a copolymer of styrene and α-methylstyrene).

[0110] The content of the aromatic resin is preferably 2 parts by mass or more, more preferably 6 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0111] The terpene resin is a polymer containing a terpene compound (terpene monomer) as a constituent monomer. Examples include a homopolymer obtained by polymerizing one type of terpene compound alone, a copolymer obtained by copolymerizing two or more terpene compounds, and a copolymer of a terpene compound and another monomer copolymerizable therewith.

[0112] Terpene compounds are (C5H8) n The hydrocarbons and their oxygen-containing derivatives are represented by the following composition: monoterpenes (C 10 H 16 ), sesquiterpenes (C 15 H 24 ), diterpenes (C 20 H 32 ), and examples thereof include α-pinene, β-pinene, dipentene, limonene, myrcene, alloocimene, ocimene, α-phellandrene, α-terpinene, γ-terpinene, terpinolene, 1,8-cineole, 1,4-cineole, α-terpineol, β-terpineol, γ-terpineol, etc. These may be used alone or in combination of two or more.

[0113] The terpene resin is preferably a homopolymer obtained by polymerizing one kind of terpene compound alone, or a copolymer of a terpene compound and an aromatic monomer. Furthermore, when the terpene resin is a homopolymer formed by polymerizing one type of terpene compound alone, β-pinene is preferred, and when the terpene resin is a copolymer of a terpene compound and an aromatic monomer, a copolymer of a terpene compound and styrene (terpene styrene resin) is preferred. In this specification, a polymer containing a terpene compound and an aromatic monomer as constituent monomers, such as a terpene styrene resin, is treated as a terpene resin, not an aromatic resin.

[0114] The amount of the terpene resin, relative to 100 parts by mass of the rubber component, is preferably at least 2 parts by mass, more preferably at least 6 parts by mass, and even more preferably at least 10 parts by mass, and is preferably at most 40 parts by mass, more preferably at most 30 parts by mass, and even more preferably at most 20 parts by mass. Within the above ranges, the effect tends to be more favorably obtained.

[0115] The cyclopentadiene-based resin is a polymer containing a cyclopentadiene-based monomer as a constituent monomer. For example, it includes a homopolymer obtained by polymerizing one type of cyclopentadiene-based monomer alone, a copolymer obtained by copolymerizing two or more types of cyclopentadiene-based monomers, and a copolymer of a cyclopentadiene-based monomer and another monomer copolymerizable therewith.

[0116] Examples of the cyclopentadiene-based monomer include cyclopentadiene, dicyclopentadiene, tricyclopentadiene, etc. These may be used alone or in combination of two or more. Among them, dicyclopentadiene is preferred. That is, the cyclopentadiene-based resin is preferably a polymer (DCPD-based resin) containing dicyclopentadiene (DCPD) as a constituent monomer, and a hydrogenated DCPD-based resin is more preferred.

[0117] The content of the cyclopentadiene-based resin is preferably 2 parts by mass or more, more preferably 6 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0118] The resin is preferably a modified resin (functionalized resin) into which a functional group is introduced. The modified resin can be produced by a known method, for example, it can be prepared by a slurry method, a metathesis method, etc. Specifically, for example, it can be produced by reacting a polymer serving as the polymer skeleton of the modified resin with a functional compound capable of introducing a functional group by a known method.

[0119] The polymer serving as the polymer backbone is not particularly limited, and may be, for example, the above-mentioned C5-based resin, aromatic resin, terpene resin, or other resins. These may be used alone or in combination of two or more. Among them, aromatic resins are preferred, α-methylstyrene-based resins are more preferred, and styrene-α-methylstyrene resins (copolymers of styrene and α-methylstyrene) are even more preferred.

[0120] As the functional group, a functional group containing at least one element selected from the group consisting of oxygen, silicon, and nitrogen is preferred, and a functional group containing silicon is more preferred.

[0121] The content of the modified resin is preferably 2 parts by mass or more, more preferably 6 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0122] Examples of commercially available products of the above resins include products of Maruzen Petrochemical Co., Ltd., Sumitomo Bakelite Co., Ltd., Yasuhara Chemical Co., Ltd., Tosoh Corporation, Rutgers Chemicals, BASF, Arizona Chemical, Nippon Paint Co., Ltd., Nippon Catalyst Co., Ltd., ENEOS Corporation, Arakawa Chemical Industries, Ltd., Tago Chemical Industry Co., Ltd., etc.

[0123] The content of the resin is preferably 2 parts by mass or more, more preferably 6 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0124] In the above rubber composition, the value of the resin content / total styrene amount in the rubber component is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.4 or more, particularly preferably 0.5 or more, and is preferably 5 or less, more preferably 2 or less, still more preferably 1.5 or less, particularly preferably 1.2 or less. When within the above range, the effect tends to be obtained more favorably. In this relationship, the resin content is the content (unit: parts by mass) relative to 100 parts by mass of the rubber component, and the total styrene amount in the rubber component is the content (unit: mass%) in 100 mass% of the rubber component.

[0125] In the above rubber composition, the value of the resin content / silica content is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.05 or more, particularly preferably 0.08 or more, and is preferably 0.5 or less, more preferably 0.28 or less, still more preferably 0.22 or less, particularly preferably 0.18 or less. When within the above range, the effect tends to be obtained more favorably. In this relationship, the contents of the resin and silica are the contents (unit: parts by mass) relative to 100 parts by mass of the rubber component.

[0126] The liquid polymer is a (co)polymer in a liquid state at 25°C, and examples thereof include liquid rubber and liquid resin. Among them, liquid rubber and liquid resin are preferred. In addition, the liquid polymer may be subjected to a modification treatment or a hydrogenation treatment. As commercially available products, products of Cray Valley, Kuraray Co., Ltd., etc. can be used. These may be used alone or in combination of two or more.

[0127] The weight average molecular weight (Mw) of the liquid polymer is less than 10,000, preferably 9,000 or less, more preferably 6,000 or less, still more preferably 4,500 or less, and is preferably 100 or more, more preferably 1,000 or more, still more preferably 2,000 or more. When within the above range, the effect tends to be obtained more favorably. In addition, in this specification, the liquid polymer is not included in the rubber component.

[0128] As the liquid rubber, at least one diene-based (co)polymer selected from the group consisting of butadiene, isoprene, styrene, farnesene, and derivatives thereof can be used. Specific examples include liquid styrene-butadiene copolymer (liquid SBR), liquid butadiene polymer (liquid BR), liquid isoprene polymer (liquid IR), liquid styrene-isoprene copolymer (liquid SIR), liquid farnesene polymer, liquid farnesene-butadiene copolymer, and other liquid diene-based polymers. Among them, liquid BR is preferred.

[0129] The liquid rubber may be modified with a functional group that interacts with silica, or may be modified with a functional group containing at least one element selected from the group consisting of oxygen, nitrogen, silicon, and phosphorus at the terminal and / or in the main chain. Also, the liquid rubber may be either unhydrogenated or hydrogenated.

[0130] The content of the liquid rubber is preferably 2 parts by mass or more, more preferably 6 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0131] The liquid resin is a resin that is liquid at 25°C, and the above-mentioned types of resins can be used. The liquid resin may be used alone or in combination of two or more kinds of liquid resins.

[0132] The content of the liquid resin is preferably 2 parts by mass or more, more preferably 6 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0133] The content of the liquid polymer is preferably 2 parts by mass or more, more preferably 6 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the rubber component. When it is within the above range, the effect tends to be obtained more favorably.

[0134] Examples of the oil include mineral oil, vegetable oil, animal oil and the like. Further, from the viewpoint of life cycle assessment, waste oil after being used in a rubber mixer or an engine, or refined waste cooking oil used in a cooking shop may be used.

[0135] In the present specification, the mineral oil refers to an oil derived from mineral resources such as petroleum and natural gas. Examples of the mineral oil include paraffinic oil (mineral oil), naphthenic oil, aromatic oil and the like. Specific examples of the mineral oil include, for example, MES (Mild Extract Solvated), DAE (Distillate Aromatic Extract), TDAE (Treated Distillate Aromatic Extract), TRAE (Treated Residual Aromatic Extract), RAE (Residual Aromatic Extract) and the like. Further, an oil having a low content of polycyclic aromatic (PCA) compounds can also be used for environmental measures. Examples of the low PCA content oil include MES, TDAE, heavy naphthenic oil and the like.

[0136] In this specification, vegetable oils include, for example, linseed oil, rapeseed oil, safflower oil, soybean oil, corn oil, cottonseed oil, rice bran oil, tall oil, sesame oil, perilla oil, castor oil, tung oil, pine oil, pine tar oil, sunflower oil, coconut oil, palm oil, palm kernel oil, olive oil, camellia oil, jojoba oil, macadamia nut oil, peanut oil, grape seed oil, wood rosin, and the like. Further, as vegetable oils, there may be mentioned refined oils (such as salad oil) obtained by refining the above oils, transesterified oils obtained by transesterifying the above oils, hydrogenated oils obtained by hydrogenating the above oils, heat-polymerized oils obtained by heat-polymerizing the above oils, oxidation-polymerized oils obtained by oxidizing the above oils, waste cooking oils recovered from those used as edible oils, and the like. Note that the vegetable oil may be liquid or solid at 25°C. These may be used alone or in combination of two or more kinds.

[0137] The vegetable oil according to this embodiment preferably contains acylglycerol, and more preferably contains triacylglycerol. In this specification, acylglycerol refers to a compound in which a hydroxy group of glycerin and a fatty acid are ester-bonded. The acylglycerol is not particularly limited, and may be 1-monoacylglycerol, 2-monoacylglycerol, 1,2-diacylglycerol, 1,3-diacylglycerol, or triacylglycerol. Further, the acylglycerol may be a monomer, a dimer, or a multimer of three or more units. Note that acylglycerols of two or more units can be obtained by heat polymerization, oxidation polymerization, or the like. Also, the acylglycerol may be liquid or solid at 25°C.

[0138] The method for confirming whether the above acylglycerol is contained in the rubber composition is not particularly limited, but 1 it can be confirmed by 1H-NMR measurement. For example, a rubber composition containing triacylglycerol is immersed in deuterated chloroform at 25°C for 24 hours. After removing the rubber composition, at room temperature 1When measuring 1H-NMR and setting the signal of tetramethylsilane (TMS) to 0.00 ppm, signals around 5.26 ppm, around 4.28 ppm, and around 4.15 ppm were observed, and these signals are presumed to be signals derived from hydrogen atoms bonded to carbon atoms adjacent to the oxygen atom of the ester group. In this paragraph, "around" means a range of ±0.10 ppm.

[0139] The fatty acid is not particularly limited and may be an unsaturated fatty acid or a saturated fatty acid. Examples of unsaturated fatty acids include monounsaturated fatty acids such as oleic acid, and polyunsaturated fatty acids such as linoleic acid and linolenic acid. Examples of saturated fatty acids include butyric acid and lauric acid.

[0140] Among them, it is desirable that the fatty acid contains a fatty acid with few double bonds, that is, a saturated fatty acid or a monounsaturated fatty acid, and oleic acid is preferred. As the vegetable oil containing such a fatty acid, for example, a vegetable oil containing a saturated fatty acid or a monounsaturated fatty acid may be used, or a modified vegetable oil obtained by transesterification or the like may be used. In addition, in order to produce such a vegetable oil containing a fatty acid, plants may be improved by variety improvement, genetic recombination, genome editing, or the like.

[0141] As the vegetable oil, for example, those commercially available from Idemitsu Kosan Co., Ltd., Sankyo Yuka Kogyo Co., Ltd., ENEOS Co., Ltd., Orisoy Co., Ltd., H&R Co., Ltd., Toyokuni Oil Co., Ltd., Fuji Kogyo Co., Ltd., Nisshin Oillio Group Co., Ltd., etc. can be used.

[0142] The content of the vegetable oil is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and preferably 55 parts by mass or less, more preferably 45 parts by mass or less, still more preferably 35 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0143] As commercially available oils, products of Idemitsu Kosan Co., Ltd., Sankyo Yuka Kogyo Co., Ltd., ENEOS Co., Ltd., Orisoy Co., Ltd., H&R Co., Ltd., Toyokuni Oil Co., Ltd., Showa Shell Sekiyu K.K., Fuji Kogyo Co., Ltd., Nisshin Oillio Group Co., Ltd., etc. can be used.

[0144] The oil content is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and preferably 55 parts by mass or less, more preferably 45 parts by mass or less, still more preferably 35 parts by mass or less, based on 100 parts by mass of the rubber component. When it is within the above range, the effect tends to be obtained more favorably.

[0145] The ester plasticizer is not particularly limited as long as it is a compound having an ester group in a liquid state at 25°C. Examples thereof include phthalic acid derivatives, long-chain fatty acid derivatives, phosphoric acid derivatives, sebacic acid derivatives, adipic acid derivatives, etc. These may be used alone or in combination of two or more. Among them, phosphoric acid derivatives, sebacic acid derivatives, and adipic acid derivatives are preferable, and sebacic acid derivatives are more preferable. The phthalic acid derivatives are not particularly limited, and examples thereof include phthalic acid esters such as di-2-ethylhexyl phthalate (DOP) and diisodecyl phthalate (DIDP). The long-chain fatty acid derivatives are not particularly limited, and examples thereof include long-chain fatty acid glycerin esters. The phosphoric acid derivatives are not particularly limited, and examples thereof include phosphoric acid esters such as tris(2-ethylhexyl) phosphate (TOP) and tributyl phosphate (TBP). The sebacic acid derivatives are not particularly limited, and examples thereof include sebacic acid esters such as di(2-ethylhexyl) sebacate (DOS) and diisooctyl sebacate (DIOS). The adipic acid derivatives are not particularly limited, and examples thereof include adipic acid esters such as di(2-ethylhexyl) adipate (DOA) and diisooctyl adipate (DIOA). Among them, phosphate esters, sebacic acid esters, and adipic acid esters are preferred, and sebacic acid esters are more preferred. Also, as specific compounds, TOP, DOS, and DOA are preferred, and DOS is more preferred. As the ester plasticizer, for example, products of Daihachi Chemical Industry Co., Ltd., Taoka Chemical Industry Co., Ltd., etc. can be used.

[0146] The glass transition temperature (Tg) of the ester plasticizer is preferably -110°C or higher, more preferably -100°C or higher, still more preferably -80°C or higher, and preferably -20°C or lower, more preferably -40°C or lower, still more preferably -55°C or lower. By setting it within the above range, there is a tendency to more suitably obtain the above effects. In this specification, the glass transition temperature of the ester plasticizer is a value measured using a differential scanning calorimeter (Q200) manufactured by TA Instruments Japan Co., Ltd. in accordance with JIS-K7121 under the condition of a heating rate of 10°C / min.

[0147] The content of the ester plasticizer is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.

[0148] The content of the softening agent is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, still more preferably 60 parts by mass or more, and preferably 120 parts by mass or less, more preferably 90 parts by mass or less, still more preferably 70 parts by mass or less with respect to 100 parts by mass of the rubber component. When it is within the above range, there is a tendency to obtain better effects.

[0149] In the above rubber composition, the value of the content of the softening agent / the content of the filler is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.4 or more, particularly preferably 0.5 or more, and preferably 1.5 or less, more preferably 0.9 or less, still more preferably 0.7 or less, particularly preferably 0.6 or less. When it is within the above range, there is a tendency to obtain better effects. In this regard, the contents of the softening agent and the filler are the contents (unit: parts by mass) with respect to 100 parts by mass of the rubber component.

[0150] The above rubber composition preferably contains a silane coupling agent. The silane coupling agent is not particularly limited. For example, bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(4-triethoxysilylbutyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(2-triethoxysilylethyl)trisulfide, bis(4-trimethoxysilylbutyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)disulfide, bis(4-triethoxysilylbutyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, bis(2-trimethoxysilylethyl)disulfide, bis(4-trimethoxysilylbutyl)disulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide and other sulfide-based, 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane and other mercapto-based, vinyltriethoxysilane, vinyltrimethoxysilane and other vinyl-based, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and other amino-based, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and other glycidoxy-based, 3-nitropropyltrimethoxysilane, 3-nitropropyltriethoxysilane and other nitro-based, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane and other chloro-based, etc. Among them, the mercapto-based is preferable. As commercially available products, for example, products of Degussa, Momentive, Shin-Etsu Silicone Co., Ltd., Tokyo Chemical Industry Co., Ltd., Azmax Co., Ltd., Toray Dow Corning Co., Ltd., etc. can be used. These may be used alone or in combination of two or more kinds.

[0151] In addition, as the mercapto-based silane coupling agent, in addition to the compound having a mercapto group, a compound having a structure in which the mercapto group is protected by a protecting group (for example, the compound represented by the following formula (S1)) can also be used.

[0152] Particularly preferred mercapto-based silane coupling agents include a silane coupling agent represented by the following formula (S1), and a silane coupling agent containing a bonding unit A represented by the following formula (I) and a bonding unit B represented by the following formula (II). [Chemical formula] (In the formula, R 1001 is -Cl, -Br, -OR 1006 , -O(O=)CR 1006 , -ON=CR 1006 R 1007 , -NR 1006 R 1007 and -(OSiR 1006 R 1007 )(OSiR h (OSiR 1006 R 1007 R 1008 ) selected from monovalent groups (R 1006 , R 1007 and R 1008 may be the same or different, and each is a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and h has an average value of 1 to 4). And R 1002 is R 1001 , a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, R 1003 is -[O(R 1009 O) j - group (R 1009 is an alkylene group having 1 to 18 carbon atoms, and j is an integer of 1 to 4).), R 1004 is a divalent hydrocarbon group having 1 to 18 carbon atoms, R 1005represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, and x, y, and z are numbers satisfying the relationships of x + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, and 0 ≦ z ≦ 1.)

Chemical formula

Chemical formula

[0153] In formula (S1), R 1005 , R 1006 , R 1007 and R 1008 are each independently preferably a group selected from the group consisting of linear, cyclic or branched alkyl groups, alkenyl groups, aryl groups and aralkyl groups having 1 to 18 carbon atoms. When R 1002 is a monovalent hydrocarbon group having 1 to 18 carbon atoms, it is preferably a group selected from the group consisting of linear, cyclic or branched alkyl groups, alkenyl groups, aryl groups and aralkyl groups. R 1009 is preferably a linear, cyclic or branched alkylene group, particularly preferably a linear one. R 1004Examples thereof include an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 2 to 18 carbon atoms, a cycloalkylene group having 5 to 18 carbon atoms, a cycloalkylalkylene group having 6 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, and an aralkylalkylene group having 7 to 18 carbon atoms. The alkylene group and the alkenylene group may be either linear or branched, and the cycloalkylene group, the cycloalkylalkylene group, the arylene group, and the aralkylalkylene group may have a functional group such as a lower alkyl group on the ring. This R 1004 is preferably an alkylene group having 1 to 6 carbon atoms, particularly preferably a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group.

[0154] R in formula (S1) 1002 , R 1005 , R 1006 , R 1007 , and R 1008 Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a vinyl group, a propenyl group, an allyl group, a hexenyl group, an octenyl group, a cyclopentenyl group, a cyclohexenyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, and the like. Examples of R in formula (S1) 1009 include, as linear alkylene groups, a methylene group, an ethylene group, an n-propylene group, an n-butylene group, a hexylene group, and the like, and as branched alkylene groups, an isopropylene group, an isobutylene group, a 2-methylpropylene group, and the like.

[0155] Specific examples of the silane coupling agent represented by the formula (S1) include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, 3-lauroylthiopropyltriethoxysilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane, 3-hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane, 2-octanoylthioethyltrimethoxysilane, 2-decanoylthioethyltrimethoxysilane, 2-lauroylthioethyltrimethoxysilane, etc. These may be used alone or in combination of two or more. Among them, 3-octanoylthiopropyltriethoxysilane is particularly preferred.

[0156] In the silane coupling agent containing the bonding unit A represented by the formula (I) and the bonding unit B represented by the formula (II), the content of the bonding unit A is preferably 30 mol% or more, more preferably 50 mol% or more, preferably 99 mol% or less, more preferably 90 mol% or less. Also, the content of the bonding unit B is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, preferably 70 mol% or less, more preferably 65 mol% or less, still more preferably 55 mol% or less. Further, the total content of the bonding units A and B is preferably 95 mol% or more, more preferably 98 mol% or more, particularly preferably 100 mol%. Note that the contents of the bonding units A and B are amounts including the case where the bonding units A and B are located at the ends of the silane coupling agent. The form when the bonding units A and B are located at the ends of the silane coupling agent is not particularly limited as long as it forms a unit corresponding to the formulas (I) and (II) indicating the bonding units A and B.

[0157] R in the formulas (I) and (II)11 Regarding this, examples of the halogen include chlorine, bromine, fluorine, etc. Examples of the branched or unbranched alkyl group having 1 to 30 carbon atoms include a methyl group, an ethyl group, etc. Examples of the branched or unbranched alkenyl group having 2 to 30 carbon atoms include a vinyl group, a 1-propenyl group, etc. Examples of the branched or unbranched alkynyl group having 2 to 30 carbon atoms include an ethynyl group, a propynyl group, etc.

[0158] R in formulas (I) and (II) 12 Regarding this, examples of the branched or unbranched alkylene group having 1 to 30 carbon atoms include an ethylene group, a propylene group, etc. Examples of the branched or unbranched alkenylene group having 2 to 30 carbon atoms include a vinylene group, a 1-propenylene group, etc. Examples of the branched or unbranched alkynylene group having 2 to 30 carbon atoms include an ethynylene group, a propynylene group, etc.

[0159] In the silane coupling agent containing the bonding unit A represented by formula (I) and the bonding unit B represented by formula (II), the total number of repetitions (v + w) of the number of repetitions (v) of the bonding unit A and the number of repetitions (w) of the bonding unit B is preferably in the range of 3 to 300.

[0160] The content of the silane coupling agent is preferably 3 parts by mass or more, more preferably 6 parts by mass or more, still more preferably 8 parts by mass or more, and preferably 18 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 12 parts by mass or less, based on 100 parts by mass of silica. When within the above range, the effect tends to be obtained more favorably.

[0161] The above rubber composition may contain a processing aid. Examples of the processing aid include metal salts (compounds in which the hydrogen atom of an acid is replaced by a metal ion), fatty acid amides, amide esters, fatty acid esters, etc. These may be used alone or in combination of two or more. Among them, metal salts are preferred.

[0162] Examples of the metal used in the metal salt include alkali metals such as potassium and sodium, alkaline earth metals such as calcium and barium, etc. Magnesium, zinc, nickel, molybdenum, etc. can also be used. Among them, zinc is preferred.

[0163] Examples of the acid used in the metal salt include fatty acids such as lauric acid, myristic acid, palmitic acid, etc. Boric acid, carbonic acid, hydrochloric acid, nitric acid, sulfuric acid, etc. can also be used. Among them, fatty acids are preferred.

[0164] As commercially available products of the processing aid, products of Kinoshita Chemical Co., Ltd., Ken-ei Pharmaceutical Co., Ltd., Struktol, Performance Additives, etc. can be used.

[0165] The content of the processing aid is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, still more preferably 0.5 part by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 1 part by mass or less, based on 100 parts by mass of the rubber component. When it is within the above range, the effect tends to be obtained more favorably.

[0166] The above rubber composition may contain an anti-aging agent. The anti-aging agent is not particularly limited, but examples include naphthylamine-based anti-aging agents such as phenyl-α-naphthylamine; diphenylamine-based anti-aging agents such as octylated diphenylamine and 4,4'-bis(α,α'-dimethylbenzyl)diphenylamine; p-phenylenediamine-based anti-aging agents such as N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine (77PD), N,N'-diphenyl-p-phenylenediamine (DPPD), N,N'-ditoly-p-phenylenediamine (DTPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), and N,N'-di-2-naphthyl-p-phenylenediamine (DNPD); quinoline-based anti-aging agents such as polymers of 2,2,4-trimethyl-1,2-dihydroquinoline; monophenol-based anti-aging agents such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; bis, tris, polyphenol-based anti-aging agents such as tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, etc. Among them, p-phenylenediamine-based anti-aging agents and quinoline-based anti-aging agents are preferred, and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine and polymers of 2,2,4-trimethyl-1,2-dihydroquinoline are more preferred. As commercially available products, for example, products of Seiko Chemical Co., Ltd., Sumitomo Chemical Co., Ltd., Ouchi Shinsei Chemical Industry Co., Ltd., Flexsys Co., etc. can be used. These may be used alone or in combination of two or more.

[0167] The content of the anti-aging agent is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 4 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0168] The above rubber composition may contain wax. The wax is not particularly limited, and any wax commonly used in the tire industry can be preferably used. For example, mineral waxes, plant-derived waxes, etc. can be mentioned. Mineral waxes refer to waxes derived from mineral resources such as oil and natural gas. Plant-derived waxes refer to waxes derived from natural resources such as plants. Among them, mineral waxes are preferred. Examples of plant-derived waxes include rice wax, carnauba wax, candelilla wax, etc. Examples of mineral waxes include paraffin wax, microcrystalline wax, these selected special waxes, etc., and paraffin wax is preferred. Note that the wax according to this embodiment does not contain stearic acid. As the wax, for example, those commercially available from Ouchi Shinsei Chemical Industry Co., Ltd., Nippon Seiro Co., Ltd., Paramelt Co., etc. can be used. These waxes may be used alone or in combination of two or more.

[0169] The content of the wax is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 8 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0170] The above rubber composition may contain stearic acid. As the stearic acid, conventionally known ones can be used, and as commercially available products, products of NOF Corporation, Kao Corporation, Fujifilm Wako Pure Chemical Corporation, Chiba Fatty Acids Co., Ltd., etc. can be used. These may be used alone or in combination of two or more.

[0171] The content of stearic acid is preferably 1 part by mass or more, more preferably 2.5 parts by mass or more, and preferably 8 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0172] The above rubber composition may contain zinc oxide. As zinc oxide, conventionally known ones can be used, and as commercially available products, products of Mitsui Mining & Smelting Co., Ltd., Toho Zinc Co., Ltd., Hakusui Tech Co., Ltd., Shoindo Chemical Industry Co., Ltd., Sakai Chemical Industry Co., Ltd., etc. can be used. These may be used alone or in combination of two or more.

[0173] The content of zinc oxide is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0174] The above rubber composition may contain sulfur. Examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersed sulfur, soluble sulfur, etc., which are generally used as crosslinking agents in the rubber industry. As commercially available products, products of Tsurumi Chemical Industry Co., Ltd., Karuizawa Sulfur Co., Ltd., Shikoku Kasei Kogyo Co., Ltd., Flexsys, Nippon Dry Distillation Industry Co., Ltd., Hosoi Chemical Industry Co., Ltd., etc. can be used. These may be used alone or in combination of two or more.

[0175] The content of sulfur is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, still more preferably 1.5 parts by mass or more, and preferably 8 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0176] The above rubber composition preferably contains a dibenzylamine compound. The dibenzylamine compound is a compound having at least one group (dibenzylamine group) represented by the following formula.

Chemical formula

[0177] Specific examples of the dibenzylamine compound include dibenzylamine, tetrabenzylthiuram disulfide (TBzTD), zinc dibenzyldithiocarbamate, 1,6-bis(N,N'-dibenzylthiocarbamoyldithio)hexane, and the like. As commercially available products, products of Sanshin Chemical Industry Co., Ltd., Ouchi Shinko Chemical Industry Co., Ltd., Rancess Co., Ltd., etc. can be used. These may be used alone or in combination of two or more. Among them, a compound having two dibenzylamine groups is preferable, and 1,6-bis(N,N'-dibenzylthiocarbamoyldithio)hexane is more preferable.

[0178] The content of the dibenzylamine compound is preferably 0.2 parts by mass or more, more preferably 0.6 parts by mass or more, still more preferably 1 part by mass or more, and preferably 8 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0179] The above rubber composition may contain a dialkyldithiophosphoric acid compound. As the dialkyldithiophosphoric acid compound, for example, salts of dialkyldithiophosphoric acid with metals such as zinc and molybdenum can be used. As commercially available products, products such as TP-50 manufactured by Rhein Chemie can be used. These may be used alone or in combination of two or more. Among them, the compound represented by the following formula (1) (zinc dialkyldithiophosphate) is preferable.

Chemical formula

[0180] In formula (1), R 1 ~R 4Examples of the linear or branched alkyl group represented by R include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a 4-methylpentyl group, a 2-ethylhexyl group, an octyl group, an octadecyl group, etc. On the other hand, examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, etc. Among them, from the viewpoint of easy dispersion in the rubber composition and easy production, R 1 ~R 4 is preferably a linear or branched alkyl group having 2 to 8 carbon atoms, more preferably an n-butyl group, an n-propyl group, an iso-propyl group, or an n-octyl group, and even more preferably an n-butyl group.

[0181] The content of the dialkyldithiophosphate compound is preferably 0.5 parts by mass or more, more preferably 1.5 parts by mass or more, even more preferably 2 parts by mass or more, and preferably 8 parts by mass or less, more preferably 6 parts by mass or less, even more preferably 4 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0182] The above rubber composition may contain a vulcanization accelerator. Examples of the vulcanization accelerator include benzothiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole and di-2-benzothiazolyldisulfide; thiuram-based vulcanization accelerators such as tetramethylthiuram disulfide (TMTD) and tetrakis(2-ethylhexyl)thiuram disulfide (TOT-N); sulfenamide-based vulcanization accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (TBBS), N-oxyethylene-2-benzothiazolesulfenamide, and N,N'-diisopropyl-2-benzothiazolesulfenamide; and guanidine-based vulcanization accelerators such as diphenylguanidine, diorthotolylguanidine, and orthotolylbiguanidine. As commercially available products, products of Sumitomo Chemical Co., Ltd., Ouchi Shinko Chemical Industry Co., Ltd., etc. can be used. These may be used alone or in combination of two or more.

[0183] The content of the vulcanization accelerator is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, based on 100 parts by mass of the rubber component. When within the above range, the effect tends to be obtained more favorably.

[0184] In addition to the above components, the above rubber composition may further contain additives generally used in the tire industry, such as organic peroxides. The content of these additives is preferably 0.1 to 200 parts by mass based on 100 parts by mass of the rubber component.

[0185] In this specification, various materials containing carbon atoms (for example, rubber, oil, resin, vulcanization accelerator, anti-aging agent, surfactant, etc.) may be derived from carbon dioxide in the atmosphere. As a method for obtaining the above formulation from carbon dioxide, carbon dioxide may be directly converted, or methane obtained through a methanation process of synthesizing methane from carbon dioxide may be converted.

[0186] The above rubber composition can be produced, for example, by kneading the above-mentioned components using a rubber kneading device such as an open roll or a Banbury mixer, and then vulcanizing.

[0187] As the kneading conditions, in the base kneading step of kneading additives other than the vulcanizing agent and the vulcanization accelerator, the kneading temperature is usually 100 to 180°C, preferably 120 to 170°C. In the finishing kneading step of kneading the vulcanizing agent and the vulcanization accelerator, the kneading temperature is usually 120°C or lower, preferably 85 to 110°C. Further, the composition kneaded with the vulcanizing agent and the vulcanization accelerator is usually subjected to a vulcanization treatment such as press vulcanization. The vulcanization temperature is usually 140 to 190°C, preferably 150 to 185°C. The vulcanization time is usually 5 to 15 minutes.

[0188] The above rubber composition can be used (as a rubber composition for tires) in tire members such as, for example, treads, sidewalls, undertreads, shoulders, clinches, bead apexes, breaker cushion rubbers, carcass cord cover rubbers, insulations, chafers, inner liners, etc., and side reinforcement layers of run-flat tires. Among them, it is suitable for treads. Further, when the tread has a multi-layer structure, it can be used for both the surface layer (cap tread) and the inner layer (base tread), but it is particularly suitable for the cap tread.

[0189] The tire of the present disclosure is manufactured by a normal method using the above rubber composition. That is, the above rubber composition is extruded in a shape suitable for a tread or the like at the unvulcanized stage, and together with other tire members, it is molded in a normal manner on a tire molding machine to form an unvulcanized tire. The tire is obtained by heating and pressurizing this unvulcanized tire in a vulcanizer.

[0190] The above tire (such as a pneumatic tire) can be used for passenger car tires; truck and bus tires; motorcycle tires; high-performance tires; winter tires such as studless tires; run-flat tires provided with side reinforcement layers; tires with sound-absorbing members such as sponges in the tire cavity; tires with sealing members provided with a sealant that can be sealed when punctured inside the tire or in the tire cavity; tires with electronic components such as sensors and wireless tags inside the tire or in the tire cavity, etc., and is suitable for passenger car tires.

[0191] The size of the above tire is not particularly limited. For example, the tire width can be appropriately selected within the range of 100 to 400 mm, the aspect ratio within the range of 25 to 85%, and the rim diameter within the range of 10 to 25 inches. Specific examples include 105 / 50R16, 115 / 50R17, 125 / 55R20, 135 / 45R21, 145 / 45R21, 155 / 45R18, 165 / 45R22, 175 / 45R23, 185 / 60R20, 195 / 55R14, 205 / 40R16, 215 / 40R16, 225 / 40R17, 235 / 40R17, 245 / 40R16, 255 / 40R17, 265 / 40R17, 275 / 35R18, 285 / 30R19, 295 / 45R20, etc.

[0192] It is preferable that the above tire satisfies the relational expression of the following formula for the tire outer diameter Dt and the tire section width Wt.

Equation

[0193] Specific examples of the tire that can satisfy the above formula include 145 / 60R18, 145 / 60R19, 155 / 55R18, 155 / 55R19, 155 / 70R17, 155 / 70R19, 165 / 55R20, 165 / 55R21, 165 / 60R19, 165 / 65R19, 165 / 70R18, 175 / 55R19, 175 / 55R20, 175 / 55R22, 175 / 60R18, 185 / 55R19, 185 / 60R20, 195 / 50R20, 195 / 55R20, etc.

[0194] The tire that satisfies the above formula is preferably applied to a pneumatic tire for passenger cars. This is because the pneumatic tire for passenger cars that satisfies the above formula tends to be more suitable for solving the problems of this case.

Example

[0195] The following shows examples (Examples) that are considered preferable when implementing, but the scope of the present invention is not limited to the Examples.

[0196] The following describes various chemicals used in the Examples and Comparative Examples.

[0197] (Rubber component) NR: TSR20 BR: BR150B manufactured by Ube Industries, Ltd. (vinyl content: 1% by mass, cis content: 97% by mass) SBR1: Modified SBR synthesized in Production Example 1 below (styrene content: 27% by mass, vinyl content: 55% by mass, Tg: -24°C, Mw: 450,000) SBR2: Modified SBR synthesized in Production Example 2 below (styrene content: 40% by mass, vinyl content: 25% by mass, Tg: -34°C, Mw: 1,200,000) SBR3: SLR6430 manufactured by TRINSEO (styrene content: 40% by mass, vinyl content: 24% by mass, containing 37.5 parts by mass of oil per 100 parts by mass of rubber solid content) SBR4: HPR840 manufactured by JSR Corporation (styrene content: 10% by mass, vinyl content: 42% by mass, Tg: -60°C) SBR5: Modified SBR synthesized in Production Example 3 below (styrene content: 25% by mass, vinyl content: 25% by mass, Tg: -51°C, Mw: 750,000) SBR6: Resin-extended modified SBR synthesized in Production Example 4 below (styrene content: 25% by mass, vinyl content: 25% by mass, Tg: -51°C, Mw: 750,000, containing 10 parts by mass of resin per 100 parts by mass of rubber solid content)

[0198] (Chemicals other than rubber components) Carbon black 1: N220 (CTAB specific surface area: 111m 2 / g) Carbon black 2: N134 (CTAB specific surface area: 142m 2 / g) Silica 1: Ultrasil VN3 manufactured by Evonik (average particle diameter: 17 nm) Silica 2: ULTRASIL 9100GR manufactured by Evonik (average particle size: 15 nm) Silane coupling agent 1: Si266 (bis(3-triethoxysilylpropyl) disulfide) manufactured by Evonik Degussa Silane coupling agent 2: NXT (3-octanoylthiopropyltriethoxysilane) manufactured by Momentive Liquid BR: Ricon 134 manufactured by Cray Valley Liquid resin: Ricon 340 (C5 / C9 resin) manufactured by Cray Valley Resin 1: Oppera PR-373 (C5 / C9 resin) manufactured by Exxon Mobil Resin 2: Sylvatraxx 4401 (styrene α-methylstyrene resin (copolymer of styrene and α-methylstyrene)) manufactured by Arizona Chemical Resin 3: Modified styrene α-methylstyrene resin (copolymer of styrene and α-methylstyrene) synthesized in Production Example 5 below Resin 4: Oppera PR-383 (hydrogenated DCPD-C9 resin) manufactured by Exxon Mobil Oil 1: VIVATEC 500 (aromatic oil) manufactured by H&R Oil 2: Nisshin Soybean Refined Oil manufactured by Nisshin Oillio Group, Ltd. Wax: Oz Ace 0355 manufactured by Nippon Seiro Co., Ltd. Antioxidant 1: No Crack 6C (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. Antioxidant 2: Antigen FR (quinoline-based antioxidant) manufactured by Sumitomo Chemical Co., Ltd. Dibenzylamine compound: Vulcuren VP KA9188 (1,6-bis(N,N'-dibenzylthiocarbamoyldithio)hexane) manufactured by Rancess Processing aid: ULTRA-FLOW 440 (zinc fatty acid) manufactured by Performance Additives Stearic acid: "Tsubaki" stearic acid manufactured by NOF Corporation Zinc oxide: Zinc White No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Powder sulfur manufactured by Tsurumi Chemical Industry Co., Ltd. Vulcanization accelerator 1: Nocceler CZ (N-cyclohexyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinko Chemical Industry Co., Ltd. Vulcanization accelerator 2: Nocceler M (2-mercaptobenzothiazole) manufactured by Ouchi Shinko Chemical Industry Co., Ltd. Vulcanization accelerator 3: Nocceler D (N,N'-diphenylguanidine) manufactured by Ouchi Shinko Chemical Industry Co., Ltd.

[0199] (Production Example 1) Charge cyclohexane, tetrahydrofuran, styrene, and 1,3-butadiene into a nitrogen-substituted autoclave reactor. Adjust the temperature of the reactor contents, add n-butyllithium to initiate polymerization. Polymerize under adiabatic conditions. When the polymerization conversion rate reaches 99%, add 1,3-butadiene and further polymerize. React with N,N-bis(trimethylsilyl)-3-aminopropyltriethoxysilane as a modifier. After the polymerization reaction is completed, add 2,6-di-tert-butyl-p-cresol. Then, remove the solvent by steam stripping and dry with a hot roll to obtain SBR1.

[0200] (Production Example 2) Charge cyclohexane, tetrahydrofuran, styrene, and 1,3-butadiene into a nitrogen-substituted autoclave reactor. Adjust the temperature of the reactor contents, add n-butyllithium to initiate polymerization. Polymerize under adiabatic conditions. When the polymerization conversion rate reaches 99%, add 1,3-butadiene and further polymerize. React with N-(3-dimethylaminopropyl)acrylamide as a modifier. After the polymerization reaction is completed, add 2,6-di-tert-butyl-p-cresol. Then, remove the solvent by steam stripping and dry with a hot roll to obtain SBR2.

[0201] (Production Example 3) Charge a nitrogen-substituted autoclave reactor with cyclohexane, tetrahydrofuran, styrene, and 1,3-butadiene. Adjust the temperature of the reactor contents, add n-butyllithium to initiate polymerization. Polymerize under adiabatic conditions. When the polymerization conversion rate reaches 99%, add 1,3-butadiene and further polymerize, then add 3-dimethylaminopropyltriethoxysilane as a modifier to conduct the reaction. After the polymerization reaction is completed, add 2,6-di-tert-butyl-p-cresol. Then, perform solvent removal by steam stripping and dry by a hot roll to obtain SBR5.

[0202] (Production Example 4) Add Resin 2 and SBR5 to cyclohexane at a predetermined ratio, and stir at a stirring speed of 400 rpm for 2 hours while heating under a nitrogen pressure of 0.4 bar. Dry the resulting solution to obtain resin-extended SBR (SBR6).

[0203] (Production Example 5) Add aluminum chloride and toluene to an inert gas-substituted glass flask, and dropwise add styrene and α-methylstyrene. Then, dropwise add a solution of isoprene / toluene to which allyltriethoxysilane has been added to the reaction solution by the slurry method, add water to the reaction solution to stop the reaction. Repeat the process of removing the aqueous layer by liquid separation, blow-dry the organic layer obtained by liquid separation to volatilize toluene, and dry under reduced pressure to obtain a modified styrene α-methylstyrene resin (Resin 3).

[0204] (Examples and Comparative Examples) According to the formulation contents shown in Tables 1 to 3, use a 1.7 L Banbury mixer manufactured by Kobe Steel, Ltd. to knead the materials other than sulfur, vulcanization accelerator, and dibenzylamine compound at 150 °C for 5 minutes to obtain a kneaded product. Next, add sulfur, vulcanization accelerator, and dibenzylamine compound to the kneaded product, and knead using an open roll at 80 °C for 5 minutes to obtain an unvulcanized rubber composition. Next, the unvulcanized rubber composition is molded into the shape of a cap tread, laminated together with other tire members to form an unvulcanized tire, and press-vulcanized at 150 °C for 12 minutes to manufacture a test tire (size: 175 / 60R18). The test tires thus manufactured were examined, and the results calculated based on the following evaluation methods are shown in Tables 1 to 3.

[0205] In Tables 1 to 3, the rubber content in the oil-extended rubber is described in the rubber column, and the oil content in the oil-extended rubber is added to the column of Oil 1. Also, the rubber content in the resin-extended rubber is described in the rubber column, and the resin content in the resin-extended rubber is added to the column of Resin 2.

[0206] In addition, in the following evaluation method, the evaluation criteria for calculating the index are as follows. Table 1: Comparative Example 3 Table 2: Comparative Example 4 Table 3: Comparative Example 5

[0207] (Low fuel consumption) Using a rolling resistance tester, the rolling resistance when each test tire was run at a speed of 80 km / h was measured, and the index was displayed with the evaluation criterion set to 100. The larger the index, the smaller the rolling resistance, indicating better low fuel consumption performance.

[0208] (Wet brake (wet grip)) Each test tire was mounted on a vehicle, and the braking distance from an initial speed of 80 km / h was determined on a wet asphalt road surface, and the index was displayed with the evaluation criterion set to 100. The larger the index, the shorter the braking distance, indicating better wet brake performance.

[0209] (Chipping resistance performance) The number of chipping occurrence locations in the tread part after the vehicle with each test tire mounted on all wheels had run 8000 km was counted, and the index was displayed with the evaluation criterion set to 100. The larger the index, the fewer the chipping occurrence locations, indicating excellent chipping resistance performance.

[0210]

Table 1

[0211]

Table 2

[0212]

Table 3

[0213] The rubber composition of the present invention (1) contains a rubber component including butadiene rubber and styrene-butadiene rubber, and silica, wherein the content of the silica > the content of the styrene-butadiene rubber, the total styrene amount in the rubber component > the content of the butadiene rubber, and is a rubber composition for tires in which the average particle diameter of the silica is 16 nm or less.

[0214] The rubber composition for tires of the present invention (2) is the rubber composition for tires according to the present invention (1) containing a resin.

[0215] The rubber composition for tires of the present invention (3) is the rubber composition for tires according to the present invention (1) or (2) containing two or more kinds of the styrene-butadiene rubber.

[0216] The rubber composition for tires of the present invention (4) is a rubber composition for tires in any combination with any one of the present inventions (1) to (3) in which the content of the silica is 100 parts by mass or more with respect to 100 parts by mass of the rubber component.

[0217] The rubber composition for tires of the present invention (5) is a rubber composition for tires in any combination with any one of the present inventions (1) to (4) containing a mercapto-based silane coupling agent.

[0218] The rubber composition for tires of the present invention (6) is a rubber composition for tires in any combination with any one of the present inventions (1) to (5) in which the total vinyl amount is 20% by mass or less with respect to 100% by mass of the rubber component.

[0219] The present invention (7) is a tire rubber composition of any combination of any one of the present inventions (1) to (6) containing liquid rubber.

[0220] The present invention (8) is a tire rubber composition of any combination of any one of the present inventions (1) to (7) containing two or more resins.

[0221] The present invention (9) is a tire rubber composition of any combination of any one of the present inventions (1) to (8) containing liquid resin.

[0222] The present invention (10) is a tire rubber composition of any combination of any one of the present inventions (1) to (9) containing a dibenzylamine compound.

[0223] The present invention (11) is a tire rubber composition of any combination of any one of the present inventions (1) to (10) containing a modified resin.

[0224] The present invention (12) is a tire rubber composition of any combination of any one of the present inventions (1) to (11) wherein the styrene-butadiene rubber is a resin-extended styrene-butadiene rubber.

[0225] The present invention (13) is a tire rubber composition of any combination of any one of the present inventions (1) to (12) wherein the value of the carbon black content / the silica content is 0.05 or less.

[0226] The present invention (14) is a tire using a rubber composition of any combination of any one of the present inventions (1) to (13).

Claims

1. A rubber composition containing a rubber component including butadiene rubber and styrene-butadiene rubber, and silica, wherein the content of the silica > the content of the styrene-butadiene rubber, the total styrene amount in the rubber component > the content of the butadiene rubber, and a rubber composition for a tire wherein the average particle diameter of the silica is 16 nm or less.

2. The rubber composition for a tire according to Claim 1, containing a resin.

3. The rubber composition for a tire according to Claim 1 or 2, containing two or more kinds of the styrene-butadiene rubber.

4. The rubber composition for a tire according to Claim 1 or 2, wherein the content of the silica is 100 parts by mass or more with respect to 100 parts by mass of the rubber component.

5. The rubber composition for a tire according to Claim 1 or 2, containing a mercapto-based silane coupling agent.

6. The rubber composition for a tire according to Claim 1 or 2, wherein the total vinyl amount is 20% by mass or less with respect to 100% by mass of the rubber component.

7. The rubber composition for a tire according to Claim 1 or 2, containing a liquid rubber.

8. The rubber composition for a tire according to Claim 1 or 2, containing two or more kinds of resins.

9. The rubber composition for a tire according to Claim 1 or 2, containing a liquid resin.

10. The rubber composition for a tire according to Claim 1 or 2, containing a dibenzylamine compound.

11. The rubber composition for a tire according to Claim 1 or 2, containing a modified resin.

12. The rubber composition for a tire according to Claim 1 or 2, wherein the styrene-butadiene rubber is a resin-extended styrene-butadiene rubber.

13. The rubber composition for a tire according to Claim 1 or 2, wherein the value of the content of carbon black / the content of the silica is 0.05 or less.

14. A tire using the rubber composition according to Claim 1 or 2.

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