Rubber composition for tires and tires

Abstract

To provide a tire rubber composition and tire that can improve the overall performance of wear resistance and handling stability at high speeds. [Solution] The material contains a rubber component, a filler containing an inorganic filler, and a plasticizer containing oil and resin, wherein the total amount of styrene in the rubber component is less than 25% by mass, the amount of the inorganic filler is more than 100 parts by mass and the amount of the plasticizer is more than 50 parts by mass per 100 parts by mass of the rubber component, and the amount of the rubber component + the amount of the oil

Description

Technical Field

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

Background Art

[0002] So far, various methods for improving wear resistance and handling stability have been studied (see, for example, Patent Documents 1 and 2). However, in recent years, further improvements in these performances have been demanded.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present disclosure is to provide a rubber composition for tires and a tire that solve the above problems and can improve the comprehensive performance of wear resistance and handling stability during high-speed driving.

Means for Solving the Problems

[0005] The present disclosure contains a rubber component, a filler containing an inorganic filler, and a plasticizer containing an oil and a resin, the total styrene amount in the rubber component is less than 25% by mass, and with respect to 100 parts by mass of the rubber component, the content of the inorganic filler is more than 100 parts by mass, the content of the plasticizer is more than 50 parts by mass, and the content of the rubber component + the content of the oil < the content of the resin + the content of the filler, and relates to a rubber composition for tires.

Effects of the Invention

[0006] This disclosure relates to a tire rubber composition containing a rubber component, a filler including an inorganic filler, and a plasticizer including oil and resin, wherein the total styrene content in the rubber component is less than 25% by mass, the inorganic filler content is more than 100 parts by mass and the plasticizer content is more than 50 parts by mass per 100 parts by mass of the rubber component, and the rubber component content + oil content < resin content + filler content. As such, the overall performance of wear resistance and handling stability at high speeds is good. [Modes for carrying out the invention]

[0007] The rubber composition for tires of the present disclosure contains a rubber component, a filler including an inorganic filler, and a plasticizer including an oil and a resin, wherein the total amount of styrene in the rubber component is less than 25% by mass, the amount of the inorganic filler is more than 100 parts by mass and the amount of the plasticizer is more than 50 parts by mass per 100 parts by mass of the rubber component, and the amount of the rubber component + the amount of the oil < the amount of the resin + the amount of the filler.

[0008] The reason why the above rubber composition produces the aforementioned effects is presumed to be as follows. Typically, adding fillers to a rubber composition improves wear resistance and handling stability due to the reinforcing effect of the fillers. However, when large amounts of fillers (especially inorganic fillers such as silica) are added, it becomes difficult to uniformly disperse the fillers within the rubber composition, and the reinforcing effect commensurate with the amount added tends not to be obtained. In contrast, the above-mentioned rubber composition improves the compatibility between the rubber component and the plasticizer by adjusting the total styrene content in the rubber component to less than 25% by mass, blending oil and resin as plasticizers, setting the plasticizer content to more than 50 parts by mass per 100 parts by mass of rubber component, and ensuring that the rubber component content + oil content < resin content + filler content. This allows the rubber component to be well plasticized and the filler to disperse easily. As a result, even when a large amount of inorganic filler is blended (more than 100 parts by mass per 100 parts by mass of rubber component), the filler, including the inorganic filler, can be uniformly dispersed, and a reinforcing effect commensurate with the blending amount can be obtained. Due to the effects described above, it is believed that the overall performance in terms of wear resistance and handling stability will be improved even under the more demanding conditions of high-speed driving.

[0009] The above rubber composition contains rubber components. 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, even more preferably 200,000 or more, and also preferably 2,000,000 or less, more preferably 1,500,000 or less, and even more preferably 1,000,000 or less. Within this range, a better effect tends to be obtained.

[0011] In this specification, the weight-average molecular weight (Mw) can be determined by converting the measured values ​​obtained by gel permeation chromatography (GPC) (GPC-8000 series manufactured by Tosoh Corporation, detector: differential refractometer, column: TSKGEL SUPERMULTIPORE HZ-M manufactured by Tosoh Corporation) to standard polystyrene equivalents.

[0012] The total amount of styrene in the rubber component may be less than 25% by mass, but is preferably less than 20% by mass, more preferably less than 18% by mass, and even more preferably less than 15% by mass. It is also preferably 5% or more by mass, more preferably 8% or more by mass, and even more preferably 10% or more by mass. When the amount is within the above range, a better effect tends to be obtained.

[0013] Here, the total amount of styrene in the rubber component is the total amount of styrene contained in the entire rubber component (unit: mass%), and can be calculated using the formula Σ(content of each rubber component × amount of styrene in each rubber component / 100). For example, if 85 mass% of SBR with a styrene content of 40 mass% is out of 100 mass% of the rubber component, 5 mass% of SBR with a styrene content of 25 mass% is out of 5 mass%, and 10 mass% of BR with a styrene content of 0 mass%, then the total amount of styrene in the rubber component is 35.25 mass% (= 85 × 40 / 100 + 5 × 25 / 100 + 10 × 0 / 100).

[0014] The total vinyl content in the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and also preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. Within the above range, a better effect tends to be obtained.

[0015] Here, the total amount of vinyl in the rubber component is the total amount of vinyl bonds in the butadiene portion of SBR and BR contained in the rubber component (unit: parts by mass), when the total mass of the rubber component is set to 100, and can be calculated as Σ(content of each rubber component × ratio of the amount of vinyl bonds in the butadiene portion of the rubber component to the total mass of each rubber component [mass%]). For example, if in 100 parts by mass of rubber component, there are 85 parts by mass of SBR with a styrene content of 40% by mass and a vinyl content of 30% by mass, 5 parts by mass of SBR with a styrene content of 20% by mass and a vinyl content of 20% by mass, and 10 parts by mass of BR with a vinyl content of 10% by mass, then the total amount of vinyl 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] The amounts of styrene and vinyl in each rubber component can be measured by nuclear magnetic resonance (NMR) spectroscopy. Furthermore, while the total amount of styrene and vinyl in the rubber component is calculated in accordance with the above-described formula in the examples of this specification, it may also be analyzed from the tire using, for example, a pyrolysis gas chromatograph-mass spectrometer (Py-GC / MS).

[0017] Examples of rubber components include diene rubbers such as styrene-butadiene rubber (SBR), butadiene rubber (BR), isoprene-based rubber, acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), and styrene-isoprene-butadiene copolymer rubber (SIBR). These may be used individually or in combination of two or more. Among these, SBR, BR, and isoprene-based rubber are preferred.

[0018] SBR is not particularly limited; for example, emulsion polymerized styrene-butadiene rubber (E-SBR) and solution polymerized styrene-butadiene rubber (S-SBR) can be used. Commercially available products include those from Sumitomo Chemical Co., Ltd., JSR Corporation, Asahi Kasei Corporation, and Nippon Zeon Corporation.

[0019] The styrene content of SBR is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and also preferably 40% by mass or less, more preferably 32% by mass or less, and even more preferably 28% by mass or less. Within the above range, a better effect tends to be obtained.

[0020] The vinyl content of SBR is preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 24% by mass or more, and also preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. When the content is within the above range, a better effect tends to be obtained.

[0021] The styrene content of SBR mentioned above refers to the styrene content of a single type of SBR if that type is used, and to the average styrene content if there are multiple types of SBR. The average styrene content of SBR can be calculated using the formula {Σ(content of each SBR × styrene content of each SBR)} / total content of all SBR. For example, if 85% of the rubber component is SBR with a styrene content of 40% by mass and 5% is SBR with a styrene content of 25% by mass, the average styrene content of the SBR is 39.2% by mass (=(85 × 40 + 5 × 25) / (85 + 5)).

[0022] Furthermore, the vinyl content of SBR mentioned above is the ratio of vinyl bonds when the total mass of the butadiene portion in the SBR is set to 100 (unit: mass%), and is calculated as: vinyl content [mass%] + cis content [mass%] + trans content [mass%] = 100 [mass%]. If there is only one type of SBR, it refers to the vinyl content of that SBR; if there are multiple types, it refers to the average vinyl content. The average vinyl content of SBR can be calculated using the formula: 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, if 100 parts by mass of rubber component, 75 parts by mass of SBR contain 40% styrene and 30% vinyl, and 25% styrene, If 15 parts by mass of SBR have a vinyl content of 20% by mass, and the remaining 10 parts by mass are other than SBR, the average vinyl content of SBR is 28% by 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%])}.

[0023] Hydrogenated SBRs, which have hydrogen added to them, can also be used as SBRs. When SBR is hydrogenated SBR, there are no particular limitations on the hydrogenation method or reaction conditions; hydrogenation can be carried out using known methods and conditions. Typically, this is done at 20-150°C, under a hydrogen pressure of 0.1-10 MPa, and in the presence of a hydrogenation catalyst. Other manufacturing methods and conditions are also not particularly limited; for example, the contents described in the aforementioned International Publication No. 2016 / 039005 can be applied. Furthermore, hydrogenated SBR has the same structure as a copolymer of ethylene, butadiene, and styrene as a result of hydrogen being added to the butadiene portion of SBR. Therefore, in this specification, hydrogenated SBR includes not only hydrogenated butadiene-styrene copolymers (SBR) but also copolymers of ethylene, butadiene, and styrene.

[0024] The hydrogenation rate of hydrogenated SBR is preferably 65 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, with the total butadiene units before hydrogenation being 100 mol%, and also preferably 95 mol% or less, more preferably 92 mol% or less, and even more preferably 90 mol% or less. Within the above range, better effects tend to be obtained. The hydrogenation rate is 1It can be calculated from the spectral reduction rate of the unsaturated bond region of the spectrum obtained by measuring 1H-NMR.

[0025] SBR may be oil-stretched rubber or resin-stretched rubber. These may be used individually or in combination of two or more types. The oil used in oil-extracted rubber and the resin used in resin-extracted rubber are the same as those described later. Furthermore, while the oil content in oil-extracted rubber and the resin content in resin-extracted rubber are not particularly limited, they are typically around 5 to 50 parts by mass per 100 parts by mass of rubber solids.

[0026] SBR may have functional groups that interact with fillers such as silica introduced through modification. Examples of the above functional groups include silicon-containing groups (-SiR3 (where R is the same or different and can be 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, carboxyl groups, nitrile groups, pyridyl groups, alkoxy groups, hydroxyl groups, oxy groups, epoxy groups, etc. These functional groups may have substituents. Among these, silicon-containing groups are preferred, and -SiR3 (where R is the same or different and can be 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)), with at least one of R being a hydroxyl group) is more preferred.

[0027] Specific examples of compounds (modifiers) that introduce the above functional groups include 2-dimethylaminoethyltrimethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 2-dimethylaminoethyltriethoxysilane, 3-dimethylaminopropyltriethoxysilane, 2-diethylaminoethyltrimethoxysilane, 3-diethylaminopropyltrimethoxysilane, 2-diethylaminoethyltriethoxysilane, and 3-diethylaminopropyltriethoxysilane.

[0028] The SBR content in 100% by mass of the rubber component is preferably 40% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and also preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. When the content is within the above range, a better effect tends to be obtained.

[0029] The BR is not particularly limited, and can be any BR that is common in the tire industry, such as BR1220 from Nippon Zeon Co., Ltd., BR150B from Ube Industries, Ltd., BR1280 from LG Chem, BR containing 1,2-syndiotactic polybutadiene crystals (SPB) such as VCR412 and VCR617 from Ube Industries, Ltd., or butadiene rubber synthesized using a rare earth element catalyst (rare earth BR). These may be used individually or in combination of two or more. Among these, rare earth BR is preferred.

[0030] While known rare earth element catalysts can be used for the synthesis of rare earth BRs, lanthanum series rare earth element compounds are preferred, and neodymium-containing compounds (Nd-based catalysts) are more preferred.

[0031] BR may be oil-stretched rubber or resin-stretched rubber. These may be used individually or in combination of two or more types. The oil used in oil-extracted rubber and the resin used in resin-extracted rubber are the same as those described later. Furthermore, while the oil content in oil-extracted rubber and the resin content in resin-extracted rubber are not particularly limited, they are typically around 5 to 50 parts by mass per 100 parts by mass of rubber solids.

[0032] BR may have functional groups that interact with packing materials such as silica introduced through modification. Examples of the above functional groups include silicon-containing groups (-SiR3 (where R is the same or different and can be 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, carboxyl groups, nitrile groups, pyridyl groups, alkoxy groups, hydroxyl groups, oxy groups, epoxy groups, etc. These functional groups may have substituents. Among these, silicon-containing groups are preferred, and -SiR3 (where R is the same or different and can be 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)), with at least one of R being a hydroxyl group) is more preferred.

[0033] Specific examples of compounds (modifiers) that introduce the above functional groups include 2-dimethylaminoethyltrimethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 2-dimethylaminoethyltriethoxysilane, 3-dimethylaminopropyltriethoxysilane, 2-diethylaminoethyltrimethoxysilane, 3-diethylaminopropyltrimethoxysilane, 2-diethylaminoethyltriethoxysilane, and 3-diethylaminopropyltriethoxysilane.

[0034] For BR, hydrogenated BR with added hydrogen can also be used. When BR is hydrogenated BR, there are no particular limitations on the hydrogenation method or reaction conditions; hydrogenation can be carried out using known methods and conditions. Typically, this is done at 20-150°C, under a hydrogen pressure of 0.1-10 MPa, and in the presence of a hydrogenation catalyst. Other manufacturing methods and conditions are also not particularly limited; for example, the contents described in International Publication No. 2016 / 039005 can be applied. Furthermore, hydrogenated BR has the same structure as an ethylene-butadiene copolymer as a result of hydrogen being added to the butadiene portion of BR. Therefore, in this specification, hydrogenated BR includes not only hydrogenated BR but also an ethylene-butadiene copolymer.

[0035] The hydrogenation rate of hydrogenated BR is preferably 65 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, with the total butadiene units before hydrogenation being 100 mol%, and also preferably 95 mol% or less, more preferably 92 mol% or less, and even more preferably 90 mol% or less. When the rate is within the above range, better effects tend to be obtained. The hydrogenation rate is 1 It can be calculated from the spectral reduction rate of the unsaturated bond region of the spectrum obtained by measuring 1H-NMR.

[0036] The cis content of BR is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and also preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less. When it is within the above range, the effect tends to be better obtained. The cis amount of BR can be measured by infrared absorption spectroscopy.

[0037] The cis amount of BR mentioned above refers to the cis amount of a single type of BR if there is only one type, and to the average cis amount if there are multiple types. The average cis content of BR can be calculated using the formula {Σ(content of each BR × cis content of each BR)} / total BR content. For example, if 20% of BR has a cis content of 90% and 10% has a cis content of 40% out of 100% of rubber components, the average cis content of BR is 73.3% (=(20 × 90 + 10 × 40) / (20 + 10)).

[0038] The BR content in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and also preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. When the content is within the above range, the effect tends to be better obtained.

[0039] Examples of isoprene-based rubbers include natural rubber (NR), isoprene rubber (IR), modified NR, modified NR, and modified IR. For NR, examples include SIR20, RSS#3, TSR20, etc., which are commonly used in the tire industry. For IR, there are no particular limitations; examples include IR2200, etc., which are commonly used in the tire industry. Examples of modified NR include deproteinized natural rubber (DPNR) and high-purity natural rubber (UPNR). Examples of modified NR include epoxidized natural rubber (ENR), hydrogenated natural rubber (HNR), and grafted natural rubber. Examples of modified IR include epoxidized isoprene rubber, hydrogenated isoprene rubber, and grafted isoprene rubber. These may be used individually or in combination of two or more. Among these, NR is preferred.

[0040] The isoprene-based rubber content in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and also preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. Within the above range, a better effect tends to be obtained.

[0041] Rubber components other than isoprene-based rubber, SBR, and BR may be oil-stretched rubber or resin-stretched rubber. These may be used individually or in combination of two or more. Among these, resin-stretched rubber is preferred, and resin-stretched SBR is more preferred. The oil used in oil-extracted rubber and the resin used in resin-extracted rubber are the same as those described later in the section on plasticizers. Furthermore, while the oil content in oil-extracted rubber and the resin content in resin-extracted rubber are not particularly limited, they are typically around 5 to 50 parts by mass per 100 parts by mass of rubber solids.

[0042] Rubber components other than isoprene-based rubber, SBR, and BR may be modified to introduce functional groups that interact with fillers such as silica. Examples of the above functional groups include silicon-containing groups (-SiR3 (where R is the same or different and can be 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, carboxyl groups, nitrile groups, pyridyl groups, alkoxy groups, hydroxyl groups, oxy groups, epoxy groups, etc. These functional groups may have substituents. Among these, silicon-containing groups are preferred, and -SiR3 (where R is the same or different and can be 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)), with at least one of R being a hydroxyl group) is more preferred.

[0043] 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, and the like.

[0044] Raw materials (monomers) for synthetic rubbers such as SBR and BR may be derived from petroleum or from biomass. Whether the raw material is derived from biomass can be determined by pMC (percent Modern Carbon) measured in accordance with ASTM D6866-10.

[0045] pMC is the ratio of the 14 C concentration of the sample to the 14 C concentration of the standard modern carbon (modern standard reference), and this value is used as an index indicating the biomass ratio of the compound (rubber). The significance of this value will be described below.

[0046] In one mole (6.02×10 23 atoms) of carbon atoms, there are approximately 6.02×10 11 which is about one trillionth of ordinary carbon atoms. 14 C atoms present. 14 14 C 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, in fossil fuels such as coal, petroleum, and natural gas, which are considered to have passed more than 226,000 years after carbon dioxide in the atmosphere was taken up and fixed by plants, etc., 14 14 all of the 14It contains absolutely no element C.

[0047] on the other hand, 14 C is continuously produced when cosmic rays undergo nuclear reactions in the atmosphere, and this is balanced by the decrease due to radioactive decay, resulting in a constant supply of C in the Earth's atmospheric environment. 14 The amount of C is constant. Therefore, the amount of biomass resource-derived substances currently circulating in the environment 14 As mentioned above, the carbon concentration is approximately 1 × 10¹⁶ of the total carbon atoms. -12 The values ​​are approximately in the range of mol%. Therefore, by using the difference between these values, it is possible to calculate the ratio (biomass ratio) of compounds derived from natural resources (compounds derived from biomass resources) in a given compound (rubber).

[0048] this 14 C is typically measured as follows: Using accelerator mass spectrometry based on a tandem accelerator, 13 C concentration ( 13 C / 12 C), 14 C concentration ( 14 C / 12 Perform measurement C). In the measurement, 14 As a modern standard reference for the concentration of C, the amount of cyclic carbon in nature as of 1950 14 The C concentration will be used. The specific standard material will be the oxalic acid standard provided by NIST (National Institute of Standards and Technology). The specific radioactivity of carbon in this oxalic acid (per gram of carbon) will be used. 14 The radioactivity intensity of C is separated by carbon isotope, 13 The standard value is obtained by correcting C to a constant value and applying decay correction from 1950 AD to the measurement date. 14 This value is used as the C concentration value (100%). The ratio of this value to the value of the sample actually measured is the pMC value.

[0049] Therefore, if rubber is made from 100% biomass (natural) materials, it will have a value of approximately 110 pMC, although there are regional differences (currently, under normal conditions, it is often not 100). On the other hand, regarding chemical substances derived from fossil fuels such as petroleum, 14 When the C concentration is measured, it will show approximately 0 pMC (for example, 0.3 pMC). This value corresponds to a biomass ratio of 0% as mentioned above.

[0050] Based on the above, using materials such as rubber with a high pMC value, that is, materials such as rubber with a high biomass ratio, in rubber compositions is preferable from an environmental protection standpoint.

[0051] The above rubber composition may also contain a thermoplastic elastomer as an elastomer other than the rubber component. Thermoplastic elastomers are copolymers (block copolymers) composed of hard segments that act as crosslinking points and soft segments that exhibit rubber elasticity, and are usually solid at room temperature (25°C).

[0052] Examples of hard segments include polystyrene, polypropylene, polyester, polyamide, polyvinyl chloride, and polyurethane, while examples of soft segments include vinyl-polydiene, polyisoprene, polybutadiene, polyethylene, polychloroprene, and poly2,3-dimethylbutadiene. These may be one type or two or more types.

[0053] Thermoplastic elastomers may be used alone or in combination of two or more types. Commercially available products include those from Kuraray Co., Ltd., Asahi Kasei Corporation, and others. In this specification, thermoplastic elastomers are not included in the rubber component.

[0054] The thermoplastic elastomer is preferably a thermoplastic elastomer having a styrene block (styrene-based thermoplastic elastomer). Specific examples of styrene-based thermoplastic elastomers include styrene-vinylisoprene-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), and styrene-butadiene-butylene-styrene triblock copolymer (SBBS). These may be used individually or in combination of two or more. Among these, copolymers having styrene blocks at both ends are preferred, and styrene-ethylene-propylene-styrene triblock copolymer (SEPS) is more preferred. Furthermore, SEPS may also be hydrogenated SIS obtained by adding hydrogen to styrene-vinylisoprene-styrene triblock copolymer (SIS).

[0055] The styrene content of the styrene-based thermoplastic elastomer is preferably 5% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and also preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. Within the above range, better effects tend to be obtained.

[0056] The thermoplastic elastomer content is preferably 1 to 30 parts by mass per 100 parts by mass of the rubber component.

[0057] The above rubber composition contains an inorganic filler as a filler. Examples of inorganic fillers include silica, clay, alumina, talc, calcium compounds, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium oxide, and titanium oxide. These may be used individually or in combination of two or more. Among these, silica and aluminum hydroxide are preferred, with silica being more preferred.

[0058] Examples of silica include dry-process silica (anhydrous silicic acid) and wet-process silica (hydrated silicic acid), but wet-process silica is preferred because it contains more silanol groups. The raw material for silica may be water glass (sodium silicate) or biomass material such as rice husks. Commercially available products include those from EVONIK, Tosoh Silica Co., Ltd., Solvay Japan Ltd., and Tokuyama Corporation. These may be used individually or in combination of two or more types.

[0059] The average particle size of silica is preferably 24 nm or less, more preferably 17 nm or less, even more preferably 16 nm or less, and particularly preferably 15 nm or less. It is also preferably 6 nm or more, more preferably 9 nm or more, and even more preferably 12 nm or more. When the particle size is within the above range, a better effect tends to be obtained.

[0060] In this specification, the method for measuring the average particle size of silica is transmission electron microscopy (TEM) observation. Specifically, silica particles are photographed with a transmission electron microscope, and if the particle shape is spherical, the diameter of the sphere is defined as the particle size; if it is needle-shaped or rod-shaped, the shorter axis is defined as the particle size; if it is irregularly shaped, the average particle size from the center is defined as the particle size; and the average particle size of 100 fine particles is defined as the average particle size.

[0061] The silica content is preferably 80 parts by mass or more, more preferably 100 parts by mass or more, even more preferably 120 parts by mass or more, and particularly preferably 130 parts by mass or more, per 100 parts by mass of rubber component. It is also preferably 180 parts by mass or less, more preferably 160 parts by mass or less, and even more preferably 150 parts by mass or less. When the silica content is within the above range, the effect tends to be better obtained.

[0062] In the above rubber composition, the silica content / SBR content is preferably 0.1 or more, more preferably 0.3 or more, even more preferably 0.5 or more, and also preferably 3 or less, more preferably 2 or less, and even more preferably 1 or less. Within the above range, there is a tendency to obtain better results. In this relationship, the silica content is the content per 100 parts by mass of the rubber component (unit: parts by mass), and the SBR content is the content in 100% by mass of the rubber component (unit: mass%).

[0063] In this specification, aluminum hydroxide means Al(OH)3 or Al2O3·3H2O. Commercially available products include those from Sumitomo Chemical Co., Ltd., Showa Denko K.K., Nabaltec, and others. These may be used individually or in combination of two or more types.

[0064] The average particle size of aluminum hydroxide is preferably 0.1 μm or larger, more preferably 0.5 μm or larger, even more preferably 0.8 μm or larger, and also preferably 5 μm or smaller, more preferably 3 μm or smaller, and even more preferably 1 μm or smaller. Within this range, a better effect tends to be obtained. The average particle size of aluminum hydroxide is measured using the same method as the average particle size of silica.

[0065] The BET specific surface area (nitrogen adsorption specific surface area, N2SA) of aluminum hydroxide is preferably 5 m². 2 / g or more, more preferably 8m 2 / g or more, more preferably 10m 2 It is 1 / g or more, and preferably 40m 2 / g or less, more preferably 30m 2 / g or less, more preferably 20m 2 It is less than / g. The BET specific surface area of ​​aluminum hydroxide is a value measured by the BET method in accordance with ASTM D3037-81.

[0066] The aluminum hydroxide content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of the rubber component, and also preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. Within the above range, a better effect tends to be obtained.

[0067] The average particle size of talc is preferably 50 μm or less, more preferably 30 μm or less. The lower limit of the average particle size of talc is not particularly limited, but is preferably 1 μm or more.

[0068] The talc content is preferably 1 to 50 parts by mass per 100 parts by mass of rubber component.

[0069] Calcium compounds are compounds containing calcium, such as inorganic salts like calcium oxide, calcium hydroxide, and calcium carbide; and oxo salts like calcium carbonate, calcium nitrate, and calcium sulfate. Oxo salts also include fatty acid salts such as calcium acetate and calcium stearate. Other examples of substances containing calcium compounds include eggshells (main component: calcium carbonate) and WB16 manufactured by Structol (a mixture of calcium fatty acid, fatty acid amide, and fatty acid amide ester). These may be used individually or in combination of two or more. Among these, oxo salts are preferred, and calcium carbonate is more preferred.

[0070] The calcium compound content is preferably 1 to 30 parts by mass per 100 parts by mass of the rubber component.

[0071] The inorganic filler content should be more than 100 parts by mass per 100 parts by mass of rubber component, but preferably 120 parts by mass or more, more preferably 130 parts by mass or more, even more preferably 140 parts by mass or more, and preferably 200 parts by mass or less, more preferably 180 parts by mass or less, and even more preferably 160 parts by mass or less. Within the above range, a better effect tends to be obtained.

[0072] Other fillers that can be used besides inorganic fillers include, for example, carbon black, short fibers, and vulcanized rubber particles.

[0073] The carbon black used is not particularly limited and includes N134, N110, N220, N234, N219, N339, N330, N326, N351, N550, N762, etc. The raw materials for carbon black may be biomass materials such as lignin and vegetable oil, or they may be obtained by recycling tires. The manufacturing method for carbon black may be combustion such as the furnace process, or hydrothermal carbonization (HTC). Commercially available products include those from Asahi Carbon Co., Ltd., Cabot Japan Co., Ltd., Tokai Carbon Co., Ltd., Mitsubishi Chemical Corporation, Lion Corporation, Shin-Nippon Chemical Carbon Co., Ltd., and Columbia Carbon Corporation. These may be used individually or in combination of two or more types.

[0074] The specific surface area of ​​cetyltrimethylammonium bromide (CTAB) in carbon black is preferably 110 m². 2 / g or more, more preferably 120m 2 / g or more, more preferably 130m 2 It is 1 / g or more, and preferably 200m 2 / g or less, more preferably 160m 2 / g or less, more preferably 140m 2 It is less than or equal to / g. Within the above range, there is a tendency for better results to be obtained. The CTAB specific surface area of ​​carbon black is measured according to JIS K6217-3:2001.

[0075] The carbon black content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of rubber component, and also preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. Within the above range, a better effect tends to be obtained.

[0076] Examples of short fibers that can be used include organic short fibers and inorganic short fibers. Specific examples of organic short fibers include nanocellulose such as cellulose nanofibers (CNF) and cellulose nanocrystals (CNC); biomass nanomaterials such as chitin nanofibers and chitosan nanofibers; and specific examples of inorganic short fibers include metal fibers and glass fiber systems. Commercially available products include those from Nippon Paper Industries Co., Ltd. and Sugino Machine Co., Ltd. These may be used individually or in mixtures of two or more. Among these, organic short fibers are preferred, and nanocellulose is more preferred.

[0077] The particle size of the nanocellulose is preferably 10 nm or larger, more preferably 20 nm or larger, even more preferably 25 nm or larger, and particularly preferably 28 nm or larger. It is also preferably 50 nm or smaller, more preferably 40 nm or smaller, even more preferably 35 nm or smaller, and particularly preferably 32 nm or smaller. When the particle size is within the above range, a better effect tends to be obtained.

[0078] The particle size of nanocellulose is the average fiber diameter measured by scanning electron microscopy, transmission electron microscopy, atomic force microscopy, X-ray scattering data analysis, and pore electrical resistance method (Culter principle method). In this specification, the average fiber diameter of nanocellulose (cellulose fiber) is typically the average fiber diameter of an aggregate of cellulose fibers formed by the aggregation of cellulose molecules.

[0079] The short fiber content is preferably 1 to 40 parts by mass per 100 parts by mass of rubber component.

[0080] Vulcanized rubber particles are particles made of vulcanized rubber, and specifically, rubber powder as specified in JIS K 6316:2017 can be used. From the viewpoint of environmental considerations and cost, recycled rubber powder produced from crushed waste tires is preferred. These may be used individually or in combination of two or more types.

[0081] Commercially available vulcanized rubber particles can be purchased from companies such as Lehigh and Muraoka Rubber Industries Co., Ltd.

[0082] The average particle size of the vulcanized rubber particles is preferably 50 μm or more, more preferably 100 μm or more, even more preferably 200 μm or more, and also preferably 1000 μm or less, more preferably 900 μm or less, and even more preferably 800 μm or less. The average particle size of vulcanized rubber particles is the mass-based average particle size calculated from the particle size distribution measured in accordance with JIS Z 8815:1994.

[0083] The content of vulcanized rubber particles is preferably 1 to 40 parts by mass per 100 parts by mass of rubber component.

[0084] The filler content is preferably 120 parts by mass or more, more preferably 130 parts by mass or more, even more preferably 140 parts by mass or more, per 100 parts by mass of rubber component, and also preferably 200 parts by mass or less, more preferably 180 parts by mass or less, and even more preferably 160 parts by mass or less. Within the above range, a better effect tends to be obtained.

[0085] The above rubber composition contains a resin as a plasticizer. Examples of resins that can be used include C5 resins, C9 resins, aromatic resins, terpene resins, and cyclopentadiene resins. These may be used individually or in combination of two or more. Among these, aromatic resins are preferred.

[0086] C5 resins are polymers that contain a C5 fraction as a constituent monomer. Examples include homopolymers obtained by polymerizing one type of C5 fraction alone, copolymers obtained by copolymerizing two or more types of C5 fractions, and copolymers of a C5 fraction with other monomers that can copolymerize with it.

[0087] Examples of C5 fractions include olefinic hydrocarbons such as 1-pentene, 2-pentene, and 2-methyl-1-butene, and diolefinic hydrocarbons such as 2-methyl-1,3-butadiene, 1,2-pentadiene, and 1,3-pentadiene. These may be used individually or in combination of two or more.

[0088] Other monomers include, for example, C9 fractions such as vinyltoluene, indene, and methylindene. These may be used individually or in combination of two or more.

[0089] From the viewpoint of overall performance such as wear resistance and handling stability during high-speed driving, a copolymer of C5 fraction and C9 fraction (C5 / C9 resin) is preferred for the C5 resin. In this specification, polymers containing a C5 fraction and an aromatic monomer (C9 fraction), such as C5 / C9 resins, as constituent monomers are treated as C5 resins, not as aromatic resins or C9 resins.

[0090] The content of C5 resin is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, per 100 parts by mass of rubber component, and also preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less. When the content is within the above range, the effect tends to be better obtained.

[0091] C9 resins are polymers that contain a C9 fraction as a constituent monomer. For example, they can be obtained by polymerizing the C9 fraction, which is produced as a by-product along with basic petrochemical raw materials such as ethylene and propylene during the thermal decomposition of naphtha in the petrochemical industry, using a Friedel-Crafts type catalyst such as AlCl3 or BF3. Specific examples of C9 fractions include vinyltoluene, α-methylstyrene, β-methylstyrene, γ-methylstyrene, o-methylstyrene, p-methylstyrene, and indene. C9 resins may also be obtained by copolymerizing a mixture of these C8-C10 fractions, for example, using a Friedel-Crafts type catalyst, along with the C9 fraction, including C8 fractions such as styrene, C10 fractions such as methylindene and 1,3-dimethylstyrene, and even naphthalene, vinylnaphthalene, vinylanthracene, and p-tert-butylstyrene. In this specification, C9 resins are treated as a separate type of resin from aromatic resins.

[0092] The content of C9 resin is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of rubber component.

[0093] Aromatic resins are polymers that contain aromatic monomers as constituent monomers. Examples include homopolymers obtained by polymerizing one type of aromatic monomer alone, copolymers obtained by copolymerizing two or more types of aromatic monomers, and copolymers of aromatic monomers with other monomers that can copolymerize with them.

[0094] Examples of aromatic monomers 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; and coumarone and indene. These may be used individually or in combination of two or more. Among these, styrene monomers are preferred, and styrene and α-methylstyrene are more preferred.

[0095] Other monomers include, for example, non-conjugated olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. These may be used individually or in combination of two or more.

[0096] From the viewpoint of overall performance such as wear resistance and handling stability during high-speed driving, aromatic resins are preferably α-methylstyrene resins (α-methylstyrene homopolymers, copolymers of styrene and α-methylstyrene, etc.), and styrene-α-methylstyrene resins (polymers of styrene and α-methylstyrene) are more preferably used.

[0097] The aromatic resin content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of the rubber component, and also preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less. Within the above range, a better effect tends to be obtained.

[0098] Terpene resins are polymers that contain terpene compounds (terpene monomers) as constituent monomers. Examples include homopolymers obtained by polymerizing one type of terpene compound alone, copolymers obtained by copolymerizing two or more types of terpene compounds, and copolymers of a terpene compound and other monomers that can copolymerize it.

[0099] Terpene compounds are (C5H8) n A hydrocarbon and its oxygen-containing derivative represented by the following composition, monoterpene (C 10 H 16 ), sesquiterpenes (C 15 H 24 ), diterpene (C 20 H 32 These are compounds with a terpene as their basic skeleton, classified as such, and examples include α-pinene, β-pinene, dipentene, limonene, myrcene, allocimene, 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 individually or in combination of two or more.

[0100] Terpene resins are preferably copolymers of terpene compounds and aromatic monomers, and more preferably copolymers of terpene compounds and styrene (terpene styrene resins). In this specification, polymers containing terpene compounds and aromatic monomers as constituent monomers, such as terpene styrene resins, are treated as terpene resins, not aromatic resins.

[0101] The terpene resin content is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the rubber component, and also preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less. Within the above range, a better effect tends to be obtained.

[0102] Cyclopentadiene resins are polymers that contain cyclopentadiene monomers as constituent monomers. Examples include homopolymers obtained by polymerizing one type of cyclopentadiene monomer alone, copolymers obtained by copolymerizing two or more types of cyclopentadiene monomers, and copolymers of cyclopentadiene monomers with other monomers that can copolymerize with it.

[0103] Examples of cyclopentadiene monomers include cyclopentadiene, dicyclopentadiene, and tricyclopentadiene. These may be used individually or in combination of two or more. Dicyclopentadiene is particularly preferred. Specifically, the cyclopentadiene resin is preferably a polymer (DCPD resin) containing dicyclopentadiene (DCPD) as a constituent monomer, and a hydrogenated DCPD resin is more preferred.

[0104] The content of the cyclopentadiene resin is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, even more preferably 10 parts by mass or more, and preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, per 100 parts by mass of the rubber component.

[0105] The resin may be a modified resin (functionalized resin) into which functional groups have been introduced. Modified resins can be produced by known methods, such as slurry methods and metathesis methods. Specifically, they can be produced, for example, by reacting a polymer that forms the polymer backbone of the modified resin with a functional compound that allows for the introduction of functional groups, using known methods.

[0106] The polymer forming the polymer backbone is not particularly limited and may be, for example, the C5 resin, aromatic resin, or terpene resin mentioned above, or other resins. These may be used alone or in combination of two or more. Among these, aromatic resins are preferred, α-methylstyrene resins are more preferred, and styrene-α-methylstyrene resin (a copolymer of styrene and α-methylstyrene) is even more preferred.

[0107] The functional group is preferably one containing at least one element selected from the group consisting of oxygen, silicon, and nitrogen, and more preferably one containing silicon.

[0108] The content of the modified resin is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the rubber component, and also preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less. When the content is within the above range, the effect tends to be better obtained.

[0109] In the above rubber composition, the ratio of the modified resin content to the total styrene content in the rubber component is preferably 0.3 or more, more preferably 0.5 or more, even more preferably 0.7 or more, and also preferably 1.8 or less, more preferably 1.2 or less, and even more preferably 0.9 or less. Within the above range, there is a tendency to obtain better results. In this relationship, the content of modified resin is the content per 100 parts by mass of rubber component (unit: parts by mass), and the total amount of styrene in the rubber component is the content per 100% by mass of the rubber component (unit: mass%).

[0110] Commercially available resins from companies such as Maruzen Petrochemical Co., Ltd., Sumitomo Bakelite Co., Ltd., Yasuhara Chemical Co., Ltd., Tosoh Corporation, Rutgers Chemicals, BASF, Arizona Chemical Company, Nippon Paint Chemical Co., Ltd., Nippon Shokubai Co., Ltd., JXTG Energy Corporation, Arakawa Chemical Industries, Ltd., and Taoka Chemical Industries, Ltd. can be used.

[0111] The resin content is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more, per 100 parts by mass of rubber component, and also preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less. When the content is within the above range, the effect tends to be better obtained.

[0112] The resin content in 100% by mass of plasticizer is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and also preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less. Within the above range, a better effect tends to be obtained.

[0113] In the above rubber composition, the resin content / silica content is preferably 0.05 or more, more preferably 0.12 or more, even more preferably 0.14 or more, and also preferably 0.45 or less, more preferably 0.35 or less, and even more preferably 0.30 or less. When the ratio is within the above range, a better effect tends to be obtained. In this relationship, the resin content and silica content are expressed as the content per 100 parts by mass of rubber component (unit: parts by mass).

[0114] The above rubber composition contains oil as a plasticizer. Examples of oils include process oils, vegetable oils, or mixtures thereof. Examples of process oils include paraffinic process oils, aromatic process oils, naphthenic process oils, etc. Examples of vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, rosin, pine oil, pine tar, tall oil, corn oil, rice oil, safflower oil, sesame oil, olive oil, sunflower oil, palm kernel oil, camellia oil, jojoba oil, macadamia nut oil, tung oil, etc. Waste oil recovered from vegetable oils used as cooking oil, etc. Commercial products that can be used include those from Idemitsu Kosan Co., Ltd., Sankyo Yuka Kogyo Co., Ltd., JXTG Energy Corporation, Orisoy Co., Ltd., H&R Co., Ltd., Toyokuni Oil Co., Ltd., Showa Shell Sekiyu K.K., Fuji Kosan Co., Ltd., etc. These may be used individually or in combination of two or more types.

[0115] The oil content is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more, per 100 parts by mass of rubber component, and also preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less. When the content is within the above range, a better effect tends to be obtained.

[0116] Other plasticizers include, for example, liquid polymers and ester-based plasticizers.

[0117] Liquid polymers are (co)polymers that are in a liquid state at room temperature (25°C). For example, at least one (co)polymer selected from the group consisting of butadiene, isoprene, styrene, farnesene, and their derivatives 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, and liquid farnesene-butadiene copolymer. Liquid polymers may also undergo modification or hydrogenation treatments. Commercially available products include those from Cray Valley and Kuraray Co., Ltd. These may be used individually or in combination of two or more.

[0118] The weight-average molecular weight (Mw) of the liquid polymer is preferably 9000 or less, more preferably 6000 or less, even more preferably 4500 or less, and also preferably 100 or more, more preferably 1000 or more, and even more preferably 2000 or more. Within the above range, better effects tend to be obtained. In this specification, liquid polymers are not included in the rubber component.

[0119] The liquid polymer content is preferably 1 to 20 parts by mass per 100 parts by mass of the rubber component.

[0120] The ester-based plasticizer is not particularly limited as long as it is a compound having an ester group that is in a liquid state at room temperature (25°C), but examples include phthalic acid derivatives, long-chain fatty acid derivatives, phosphoric acid derivatives, sebacic acid derivatives, and adipic acid derivatives. These may be used individually or in combination of two or more. Among these, phosphoric acid derivatives, sebacic acid derivatives, and adipic acid derivatives are preferred, with sebacic acid derivatives being more preferred. The above phthalic acid derivatives are not particularly limited, but examples include phthalic acid esters such as di-2-ethylhexyl phthalate (DOP) and diisodecyl phthalate (DIDP). The above long-chain fatty acid derivatives are not particularly limited, but examples include long-chain fatty acid glycerol esters. The above phosphate derivatives are not particularly limited, but examples include phosphate esters such as tris(2-ethylhexyl) phosphate (TOP) and tributyl phosphate (TBP). The above sebaciate derivatives are not particularly limited, but examples include sebaciate esters such as di(2-ethylhexyl) sebacate (DOS) and diisooctyl sebacate (DIOS). The above adipic acid derivatives are not particularly limited, but examples include adipic acid esters such as di(2-ethylhexyl) adipate (DOA) and diisooctyl adipate (DIOA). Among these, phosphate esters, sebacate esters, and adipic esters are preferred, with sebacate esters being more preferred. Furthermore, as for specific compounds, TOP, DOS, and DOA are preferred, with DOS being more preferred. As ester-based plasticizers, products from companies such as Daihachi Chemical Industry Co., Ltd. and Taoka Chemical Industry Co., Ltd. can be used.

[0121] The glass transition temperature (Tg) of the ester-based plasticizer is preferably -110°C or higher, more preferably -100°C or higher, even more preferably -80°C or higher, preferably -20°C or lower, more preferably -40°C or lower, and even more preferably -55°C or lower. The aforementioned effects tend to be more favorably obtained within this range. In this specification, the glass transition temperature is the value measured in accordance with JIS-K7121 using a differential scanning calorimeter (Q200) manufactured by T.A. Instruments Japan Co., Ltd., under a heating rate of 10°C / min.

[0122] The content of the ester-based plasticizer is preferably 1 to 20 parts by mass per 100 parts by mass of the rubber component.

[0123] The plasticizer content (total content of resin, oil, etc.) should be more than 50 parts by mass per 100 parts by mass of rubber component, but preferably 60 parts by mass or more, more preferably 70 parts by mass or more, and preferably 120 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 90 parts by mass or less. Within the above range, a better effect tends to be obtained.

[0124] In the above rubber composition, the content of rubber components + oil content < resin content + filler content. Furthermore, in the above rubber composition, (resin content + filler content) - (rubber component content + oil content) is preferably 5 or more, more preferably 10 or more, even more preferably 15 or more, and also preferably 70 or less, more preferably 60 or less, and even more preferably 50 or less. When it is within the above range, a better effect tends to be obtained.

[0125] In these relationships, the oil content, resin content, filler content, and silica content are expressed as the content per 100 parts by mass of rubber components (unit: parts by mass), while the rubber component content is the total content of each rubber component (unit: parts by mass), which is usually 100.

[0126] The above rubber composition may contain a silane coupling agent. The silane coupling agent is not particularly limited and includes, 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 Examples include sulfide-based compounds such as ropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, and 3-triethoxysilylpropyl methacrylate monosulfide; mercapto-based compounds such as 3-mercaptopropyltrimethoxysilane and 2-mercaptoethyltriethoxysilane; vinyl-based compounds such as vinyltriethoxysilane and vinyltrimethoxysilane; amino-based compounds such as 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane; glycidoxy-based compounds such as γ-glycidoxypropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane; nitro-based compounds such as 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane; and chloro-based compounds such as 3-chloropropyltrimethoxysilane and 3-chloropropyltriethoxysilane. Commercially available products include those from companies such as Evonik Degussa, Momentive, Shin-Etsu Silicone Co., Ltd., Tokyo Chemical Industry Co., Ltd., Azumax Co., Ltd., and Toray Dow Corning Co., Ltd. These can be used individually or in combination of two or more types.

[0127] In addition to compounds containing a mercapto group, compounds in which the mercapto group is protected by a protecting group (for example, compounds represented by the following formula (S1)) can also be used as mercapto-silane coupling agents.

[0128] Particularly suitable mercapto-silane coupling agents include silane coupling agents represented by the following formula (S1), and silane coupling agents containing a bonding unit A shown in the following formula (I) and a bonding unit B shown in the following formula (II). [ka] (In the formula, R 1001 -Cl, -Br, -OR 1006 -O(O=)CR 1006 , -ON=CR 1006 R 1007 , -NR 1006 R 1007 and -(OSiR 1006 R 1007 ) h (OSiR 1006 R 1007 R 1008 A monovalent group (R) selected from ) 1006 , R 1007 and R 1008 They may be the same or different, and each is a hydrogen atom or a monovalent hydrocarbon group with 1 to 18 carbon atoms, and the average value of h is 1 to 4. 1002 is R 1001 , hydrogen atom or monovalent hydrocarbon group having 1 to 18 carbon atoms, R 1003 is -[O(R 1009 O) j ]-group(R 1009 is an alkylene group with 1 to 18 carbon atoms, and j is an integer from 1 to 4. ), R 1004 R is a divalent hydrocarbon group having 1 to 18 carbon atoms. 1005 (where represents a monovalent hydrocarbon group with 1 to 18 carbon atoms, and x, y, and z are numbers that satisfy the relationships x + y + 2z = 3, 0 ≤ x ≤ 3, 0 ≤ y ≤ 2, and 0 ≤ z ≤ 1.) [ka] [ka] (In the formula, v is a non-negative integer and w is a non-negative integer. 11 R represents hydrogen, halogen, branched or unbranched C1-C30 alkyl group, branched or unbranched C2-C30 alkenyl group, branched or unbranched C2-C30 alkynyl group, or an alkyl group in which the terminal hydrogen is substituted with a hydroxyl group or a carboxyl group. 12 R represents a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or unbranched alkenylene group having 2 to 30 carbon atoms, or a branched or unbranched alkynylene group having 2 to 30 carbon atoms. 11 and R 12 (They may form a ring structure.)

[0129] In equation (S1), R 1005 , R 1006 , R 1007 and R 1008 Each of these is preferably independently 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. 1002 If 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. 1009 The alkylene group is preferably linear, cyclic, or branched, and is particularly preferred to be linear. 1004 Examples of these include alkylene groups having 1 to 18 carbon atoms, alkenylene groups having 2 to 18 carbon atoms, cycloalkylene groups having 5 to 18 carbon atoms, cycloalkylalkylene groups having 6 to 18 carbon atoms, arylene groups having 6 to 18 carbon atoms, and aralkylene groups having 7 to 18 carbon atoms. The alkylene groups and alkenylene groups may be linear or branched, and the cycloalkylene groups, cycloalkylalkylene groups, arylene groups, and aralkylene groups may have functional groups such as lower alkyl groups on their rings. 1004Preferably, the alkylene group has 1 to 6 carbon atoms, and in particular, linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups are preferred.

[0130] R in equation (S1) 1002 , R 1005 , R 1006 , R 1007 and R 1008 Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, cyclopentyl group, cyclohexyl group, vinyl group, propenyl group, allyl group, hexenyl group, octenyl group, cyclopentenyl group, cyclohexenyl group, phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenethyl group, naphthylmethyl group, and the like. R in equation (S1) 1009 Examples of linear alkylene groups include methylene, ethylene, n-propylene, n-butylene, and hexylene groups, while examples of branched alkylene groups include isopropylene, isobutylene, and 2-methylpropylene groups.

[0131] Specific examples of silane coupling agents represented by 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, and 2-lauroylthioethyltrimethoxysilane. These may be used individually or in combination of two or more. Among them, 3-octanoylthiopropyltriethoxysilane is particularly preferred.

[0132] In a silane coupling agent containing a bonding unit A represented by formula (I) and a bonding unit B represented by formula (II), the content of bonding unit A is preferably 30 mol% or more, more preferably 50 mol% or more, preferably 99 mol% or less, and more preferably 90 mol% or less. The content of bonding unit B is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 55 mol% or less. The total content of bonding units A and B is preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol%. The content of bonding units A and B includes the amount when bonding units A and B are located at the ends of the silane coupling agent. The form of bonding units A and B when they are located at the ends of the silane coupling agent is not particularly limited, as long as they form units corresponding to formulas (I) and (II) that represent bonding units A and B.

[0133] R in equations (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.

[0134] For 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.

[0135] 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.

[0136] 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 16 parts by mass or less, more preferably 14 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.

[0137] 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 and fatty acid amides are preferred, and metal salts are more preferred.

[0138] Examples of metals used in metal salts include alkali metals such as potassium and sodium, and alkaline earth metals such as calcium and barium. Magnesium, zinc, nickel, and molybdenum can also be used. Among these, alkali metals and alkaline earth metals are preferred.

[0139] Acids used in metal salts include fatty acids such as lauric acid, myristic acid, and palmitic acid. Boric acid, carbonic acid, hydrochloric acid, nitric acid, and sulfuric acid can also be used.

[0140] Commercially available processing aids include products from companies such as Kishida Chemical Co., Ltd., Ken-ei Pharmaceutical Co., Ltd., Structol, and Performance Additives.

[0141] The content of the processing aid is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 4.5 parts by mass or more, per 100 parts by mass of the rubber component, and also preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less. When the content is within the above range, the effect tends to be better obtained.

[0142] The above rubber composition may contain an anti-aging agent. Examples of anti-aging agents 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; N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine, and N,N′-di-2-naphthyl-p-phenylenediamine. Examples include p-phenylenediamine-based antioxidants such as 2,2,4-trimethyl-1,2-dihydroquinoline polymers and other quinoline-based antioxidants; monophenol-based antioxidants such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; and bis-, tris-, and polyphenol-based antioxidants such as tetrakis-[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane. Commercially available products include those from Seiko Chemical Co., Ltd., Sumitomo Chemical Co., Ltd., Ouchi Shinko Chemical Co., Ltd., and Flexis Co., Ltd. These may be used individually or in combination of two or more.

[0143] The amount of the antioxidant is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 4.5 parts by mass or more, per 100 parts by mass of the rubber component, and also preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less. When the amount is within the above range, a better effect tends to be obtained.

[0144] The above rubber composition may contain wax. The wax is not particularly limited and can be any petroleum-based wax such as paraffin wax or microcrystalline wax; a natural wax such as plant-based wax or animal-based wax; or a synthetic wax such as polymers of ethylene or propylene. Commercially available products from companies such as Ouchi Shinko Chemical Industry Co., Ltd., Nippon Seiro Co., Ltd., and Seiko Chemical Co., Ltd. can be used. These can be used individually or in combination of two or more types.

[0145] The wax content is preferably 1 part by mass or more, more preferably 2.5 parts by mass or more, and preferably 10 parts by mass or less, and more preferably 6 parts by mass or less, per 100 parts by mass of rubber component. Within this range, a better effect tends to be obtained.

[0146] The above rubber composition may contain stearic acid. Conventional known stearic acid can be used, and commercially available products from companies such as NOF Corporation, Kao Corporation, Fujifilm Wako Pure Chemical Industries Ltd., and Chiba Fatty Acid Co., Ltd. can be used. These may be used individually or in combination of two or more types.

[0147] The stearic acid content is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and preferably 10 parts by mass or less, and more preferably 6 parts by mass or less, per 100 parts by mass of the rubber component. Within this range, a better effect tends to be obtained.

[0148] The above rubber composition may contain zinc oxide. Conventional known zinc oxides can be used, and commercially available products from companies such as Mitsui Mining & Smelting Co., Ltd., Toho Zinc Co., Ltd., Hakusui Tech Co., Ltd., Seido Chemical Industry Co., Ltd., and Sakai Chemical Industry Co., Ltd. can be used. These may be used individually or in combination of two or more types.

[0149] The zinc oxide content is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and preferably 10 parts by mass or less, and more preferably 6 parts by mass or less, per 100 parts by mass of the rubber component. Within this range, a better effect tends to be obtained.

[0150] The above rubber composition may contain sulfur. Examples of sulfur commonly used as a crosslinking agent in the rubber industry include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, and soluble sulfur. Commercially available products from companies such as Tsurumi Chemical Industries, Karuizawa Sulfur Co., Ltd., Shikoku Chemicals Co., Ltd., Flexis Co., Ltd., Nippon Dry Distillation Co., Ltd., and Hosoi Chemical Industry Co., Ltd. can be used. These may be used individually or in combination of two or more types.

[0151] The sulfur content is preferably 0.5 parts by mass or more, more preferably 1.2 parts by mass or more, even more preferably 1.5 parts by mass or more, per 100 parts by mass of rubber component, and also preferably 3.5 parts by mass or less, more preferably 2.8 parts by mass or less, and even more preferably 2.5 parts by mass or less. Within the above range, a better effect tends to be obtained.

[0152] In the above rubber composition, the zinc oxide content / sulfur content is preferably 0.2 or more, more preferably 0.4 or more, even more preferably 0.6 or more, and also preferably 3 or less, more preferably 2 or less, and even more preferably 1 or less. When the ratio is within the above range, a better effect tends to be obtained. In this relationship, the amounts of zinc oxide and sulfur are expressed as the content per 100 parts by mass of rubber component (unit: parts by mass).

[0153] The above rubber composition may contain an organic crosslinking agent. The organic crosslinking agent is not particularly limited and includes maleimide compounds, alkylphenol-sulfur chloride condensates, organic peroxides, amine organic sulfides, and the like. These may be used individually or in combination of two or more.

[0154] The content of the organic crosslinking agent is preferably 1 to 15 parts by mass per 100 parts by mass of the rubber component.

[0155] The above rubber composition may contain a vulcanization accelerator. Examples of vulcanization accelerators include thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole and di-2-benzothiazolyl disulfide; 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-benzothiadylsulfenamide (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, dioltotolylguanidine, and orthotolylbiguanidine. Commercially available products include those from Sumitomo Chemical Co., Ltd. and Ouchi Shinko Chemical Co., Ltd. These may be used individually or in combination of two or more.

[0156] The content of the vulcanization accelerator is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 4.5 parts by mass or more, per 100 parts by mass of the rubber component, and also preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less. When the content is within the above range, a better effect tends to be obtained.

[0157] In addition to the above components, the above rubber composition may further contain additives commonly used in the tire industry, such as organic peroxides. The content of these additives is preferably 0.1 to 200 parts by mass per 100 parts by mass of the rubber component.

[0158] The above rubber composition can be produced, for example, by kneading each of the above components using a rubber kneading device such as an open roll or Banbury mixer, and then vulcanizing it.

[0159] Regarding the mixing conditions, in the base mixing step where additives other than the vulcanizing agent and vulcanization accelerator are mixed, the mixing temperature is usually 100 to 180°C, preferably 120 to 170°C. In the finish mixing step where the vulcanizing agent and vulcanization accelerator are mixed, the mixing temperature is usually 120°C or lower, preferably 85 to 110°C. Furthermore, the composition mixed with the vulcanizing agent and 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.

[0160] The above rubber composition can be used (as a tire rubber composition) in tire components such as the tread, sidewall, base tread, under tread, shoulder, clinch, bead apex, breaker cushion rubber, carcass cord covering rubber, insulation, chafer, inner liner, and side reinforcement layer of run-flat tires. It is particularly suitable for the tread (especially the part that contacts the road surface during driving (cap tread)).

[0161] The tire of this disclosure is manufactured by conventional means using the above rubber composition. Specifically, the rubber composition is extruded to match the shape of a tread or the like at the unvulcanized stage, and then molded together with other tire components in a conventional manner on a tire molding machine to form an unvulcanized tire. This unvulcanized tire is then heated and pressurized in a vulcanizing machine to obtain a tire.

[0162] The above-mentioned tires (pneumatic tires, etc.) 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 with side reinforcement layers; tires with sound-absorbing materials such as sponges inside the tire cavity; tires with sealing materials that can be sealed in the event of a puncture inside the tire or tire cavity; and tires with electronic components that have electronic components such as sensors and wireless tags inside the tire or tire cavity, and are particularly suitable for passenger car tires.

[0163] The tire sizes mentioned above are not particularly limited; for example, tire widths can be selected within the range of 100-400mm, aspect ratios within the range of 25-85%, and rim diameters within the range of 10-25 inches, as appropriate. 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.

[0164] The above-mentioned tire preferably satisfies the following relationship between the tire outer diameter Dt and the tire section width Wt.

number

[0165] Examples of tires 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.

[0166] Tires that satisfy the above formula are preferably applied to pneumatic tires for passenger cars. This is because pneumatic tires for passenger cars that satisfy the above formula tend to be more suitable for solving the problems of this invention. [Examples]

[0167] The present disclosure will be described in detail based on examples, but the present disclosure is not limited to these examples.

[0168] The various chemicals used in the examples and comparative examples are described below.

[0169] (Rubber component) NR:TSR20 SBR1: HPR840 manufactured by JSR Corporation (styrene content: 10% by mass, vinyl content: 41% by mass) SBR2: Toughden 3830 manufactured by Asahi Kasei Corporation (styrene content: 36% by mass, vinyl content: 31% by mass, oil content: 37.5 parts by mass per 100 parts by mass of rubber solids) SBR3: JSR1723 manufactured by JSR Corporation (styrene content: 23.5% by mass, vinyl content: 16.7% by mass, oil content: 37.5 parts by mass per 100 parts by mass of rubber solids) SBR4: Styrene-α-methylstyrene resin stretched SBR manufactured in the following manufacturing example 1 (styrene content: 20% by mass, vinyl content: 20% by mass, resin content: 30 parts by mass per 100 parts by mass of rubber solids). SBR5: Hydrogenated SBR produced in Production Example 2 below (styrene content: 20% by mass, vinyl content (before hydrogenation): 25% by mass, hydrogenation rate: 80 mol%) BR: Buna CB24 manufactured by LANXESS (BR synthesized using an Nd-based catalyst, cis content: 96% by mass, vinyl content: 0.7% by mass)

[0170] (Chemicals other than rubber components) Carbon Black: N134 (CTAB specific surface area: 135 m²) 2 / g) Silica 1: Evonik De Gussa's UltraSil 9100GR (average particle size: 15 nm) Silica 2: UltraSil VN3 manufactured by Evonik DeGussa (average particle size: 17nm) Silica 3: ZEOSIL 1115MP manufactured by Rhodia Corporation (average particle size: 24nm) Aluminum hydroxide: APYRAL 120E from Nabaltec (average particle size: 0.8 μm, BET specific surface area: 11 m²) 2 / g) Silane coupling agent: Si69 (bis(3-triethoxysilylpropyl)tetrasulfide) manufactured by Evonik DeGussa. Resin 1: Ricon340 (C5 / C9 resin) manufactured by Cray Valley Resin 2: YS Resin TO125 manufactured by Yasuhara Chemical Co., Ltd. (Terpene styrene resin (polymer of terpene compound and styrene)) Resin 3: Sylvatraxx 4401 (styrene-α-methylstyrene resin (polymer of α-methylstyrene and styrene)) manufactured by Arizona Chemical Corporation. Resin 4: Modified styrene-α-methylstyrene resin produced in manufacturing example 3 below. Oil: PW-380 manufactured by Idemitsu Kosan Co., Ltd. Wax: Ozoace 0355 manufactured by Nippon Seiro Co., Ltd. Stearic acid: Stearic acid "Tsubaki" manufactured by NOF Corporation Anti-aging agent 1: Nocrack 6C (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine) manufactured by Ouchi Shinko Chemical Industry Co., Ltd. Anti-aging agent 2: Nocrack RD (poly(2,2,4-trimethyl-1,2-dihydroquinoline)) manufactured by Ouchi Shinko Chemical Industry Co., Ltd. Processing aid 1: ULTRA-LUBE 160 (a mixture of fatty acid soap and fatty acid amide) manufactured by Performance Additives. Processing aid 2: Potassium tetraborate manufactured by Kishida Chemical Co., Ltd. Zinc oxide: Zinc oxide No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Powdered sulfur manufactured by Tsurumi Chemical Industries Co., Ltd. Vulcanization accelerator 1: Noxellar CZ (N-cyclohexyl-2-benzothiazolyl sulfenamide) manufactured by Ouchi Shinko Chemical Industry Co., Ltd. Vulcanization accelerator 2: Noxellar D (N,N'-diphenylguanidine) manufactured by Ouchi Shinko Chemical Industry Co., Ltd.

[0171] (Manufacturing Example 1) Styrene-α-methylstyrene resin (resin 3) and SBR were added to cyclohexane in a predetermined ratio and stirred at a stirring speed of 400 rpm for 2 hours under a nitrogen pressure of 0.4 bar while heating. The resulting solution was dried to obtain styrene-α-methylstyrene resin stretched SBR (SBR 4).

[0172] (Manufacturing example 2) n-hexane, styrene, 1,3-butadiene, TMEDA (N,N,N',N'-tetramethylethylenediamine), and n-butyllithium were added to a heat-resistant reaction vessel that had been thoroughly purged with nitrogen, and the polymerization reaction was carried out by stirring at 50°C for 5 hours. Subsequently, hydrogen gas was supplied at a pressure of 0.4 MPa-Gauge and the mixture was stirred for 20 minutes to react with unreacted lithium at the polymer terminals to obtain lithium hydride. Hydrogenation was carried out using a catalyst mainly composed of titanocene dichloride, with the hydrogen gas supply pressure set to 0.7 MPa-Gauge and the reaction temperature to 90°C. When the cumulative amount of hydrogen absorption reached the desired hydrogenation rate, the reaction temperature was reduced to room temperature, the hydrogen pressure was returned to atmospheric pressure, and the mixture was withdrawn from the reaction vessel. The reaction solution was then added to water with stirring, and the solvent was removed by steam stripping to obtain SBR5.

[0173] (Manufacturing Example 3) Aluminum chloride and toluene were added to a glass flask purged with an inert gas, and styrene and α-methylstyrene were added dropwise. Then, an isoprene / toluene solution to which allyltriethoxysilane had been added by slurry method was added dropwise to the reaction mixture, and water was added to the reaction mixture to stop the reaction. After repeating the process of removing the aqueous layer by liquid-liquid extraction, the organic layer obtained by liquid-liquid extraction was air-dried to volatilize the toluene, and then dried under reduced pressure to obtain modified styrene-α-methylstyrene resin (resin 4).

[0174] (Examples and Comparative Examples) According to the formulations shown in Tables 1 and 2, all materials except sulfur and vulcanization accelerator were mixed for 5 minutes at 150°C using a 1.7L Banbury mixer manufactured by Kobe Steel, Ltd. to obtain a mixture. Next, sulfur and vulcanization accelerator were added to the mixture and kneaded for 5 minutes at 80°C using an open roll to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was molded into a tread shape and bonded together with other tire components to form an unvulcanized tire. The tire was then press-vulcanized for 12 minutes at 150°C to produce a test tire (size: 175 / 60R18). The obtained test tire was evaluated as follows, and the results are shown in Tables 1 and 2.

[0175] In Tables 1 and 2, the rubber content in oil-applied rubber is listed in the "Rubber" column, and the oil content in oil-applied rubber is added to the "Oil" column. Similarly, the rubber content in resin-stretched rubber is listed in the "Rubber" column, and the resin content in resin-stretched rubber is added to the "Resin 2" column.

[0176] Furthermore, the evaluation criteria used when calculating the index in the evaluation below are as follows: Table 1: Comparative Example 1 Table 2: Example 11 corresponds to Comparative Example 4, Example 12 corresponds to Comparative Example 5, and Example 13 corresponds to Comparative Example 6.

[0177] (Abrasion resistance at high speeds) Each test tire was mounted on a vehicle, and the groove depth of the tread was measured after 50,000 km of driving at an average speed of 100 km / h. From the measured values, the amount of tread wear was calculated and expressed as an index with a rating of 100. A higher index indicates less wear and better wear resistance at high speeds.

[0178] (Handling stability at high speeds) A vehicle equipped with the above-mentioned test tires on all wheels was subjected to five time attack runs on a dry test course, and the best time was measured. From the measured values, the time saved compared to the time with commercially available tires (the slowest time) was calculated and expressed as an index with a rating of 100. A higher index indicates a greater time saving (shorter best time) and superior handling stability at high speeds (dry handling stability).

[0179] [Table 1]

[0180] [Table 2]

[0181] Tables 1 and 2 show that the examples demonstrated superior overall performance (sum of each index) in wear resistance and handling stability during high-speed driving compared to the comparative examples.

[0182] The present disclosure (1) is a tire rubber composition comprising a rubber component, a filler including an inorganic filler, and a plasticizer including an oil and a resin, wherein the total amount of styrene in the rubber component is less than 25% by mass, the amount of the inorganic filler is more than 100 parts by mass and the amount of the plasticizer is more than 50 parts by mass per 100 parts by mass of the rubber component, and the amount of the rubber component + the amount of the oil < the amount of the resin + the amount of the filler.

[0183] Disclosure (2) is a tire rubber composition according to Disclosure (1) in which the resin comprises an aromatic resin.

[0184] Disclosure (3) is a tire rubber composition according to Disclosure (1) or (2) wherein the filler comprises aluminum hydroxide.

[0185] Disclosure (4) is a tire rubber composition in which the rubber component is any combination of any of Disclosures (1) to (3) that includes an isoprene-based rubber.

[0186] Disclosure (5) is a tire rubber composition in any combination of the filler with any of Disclosures (1) to (4) which contains silica with an average particle size of 16 nm or less.

[0187] This disclosure (6) states that the filler is cetyltrimethylammonium bromide with a specific surface area of ​​130 m² 2 A tire rubber composition in any combination of any of (1) to (5) of this disclosure, containing carbon black of 1 / g or more.

[0188] Disclosure (7) is a tire rubber composition in any combination of any of Disclosures (1) to (6), wherein the total amount of styrene in the rubber component is less than 15% by mass.

[0189] Disclosure (8) is a tire rubber composition in which the resin is any combination of any of Disclosures (1) to (7) which includes a modified resin.

[0190] Disclosure (9) is a tire rubber composition in which the rubber component is any combination of any of Disclosures (1) to (8) which includes a resin-stretchable rubber.

[0191] Disclosure (10) is a tire rubber composition in which the rubber component is any combination of any of Disclosures (1) to (9) containing hydrogenated styrene-butadiene rubber.

[0192] Disclosure (11) relates to a tire having a tread made of a rubber composition in any combination of any of Disclosures (1) to (10).

Claims

1. It contains rubber components, fillers including inorganic fillers, and plasticizers including oil and resin. The total amount of styrene in the aforementioned rubber component is less than 25% by mass. With respect to 100 parts by mass of the rubber component, the inorganic filler is contained in a quantity exceeding 100 parts by mass, and the plasticizer is contained in a quantity exceeding 50 parts by mass. A tire rubber composition wherein the content of the rubber component plus the content of the oil is less than the content of the resin plus the content of the filler.

2. The tire rubber composition according to claim 1, wherein the resin comprises an aromatic resin.

3. The tire rubber composition according to claim 1 or 2, wherein the filler comprises aluminum hydroxide.

4. The rubber composition for tires according to any one of claims 1 to 3, wherein the rubber component comprises isoprene-based rubber.

5. The tire rubber composition according to any one of claims 1 to 4, wherein the filler comprises silica having an average particle size of 16 nm or less.

6. The aforementioned filler is cetyltrimethylammonium bromide with a specific surface area of ​​130 m². ２ A tire rubber composition according to any one of claims 1 to 5, comprising carbon black of 1g or more.

7. The tire rubber composition according to any one of claims 1 to 6, wherein the total amount of styrene in the rubber component is less than 15% by mass.

8. The rubber composition for tires according to any one of claims 1 to 7, wherein the resin comprises a modified resin.

9. The tire rubber composition according to any one of claims 1 to 8, wherein the rubber component includes resin-stretchable rubber.

10. The rubber composition for tires according to any one of claims 1 to 9, wherein the rubber component comprises hydrogenated styrene-butadiene rubber.

11. A tire having a tread made of the rubber composition according to any one of claims 1 to 10.

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