WO2025028134A1 - タイヤ用ゴム組成物、及びタイヤ - Google Patents

タイヤ用ゴム組成物、及びタイヤ Download PDF

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Publication number
WO2025028134A1
WO2025028134A1 PCT/JP2024/023989 JP2024023989W WO2025028134A1 WO 2025028134 A1 WO2025028134 A1 WO 2025028134A1 JP 2024023989 W JP2024023989 W JP 2024023989W WO 2025028134 A1 WO2025028134 A1 WO 2025028134A1
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Prior art keywords
rubber
mass
derived
tires
tire
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PCT/JP2024/023989
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English (en)
French (fr)
Japanese (ja)
Inventor
正寛 川島
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Bridgestone Corp
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Bridgestone Corp
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Priority to CN202480049754.8A priority Critical patent/CN121773158A/zh
Priority to JP2025537765A priority patent/JPWO2025028134A1/ja
Publication of WO2025028134A1 publication Critical patent/WO2025028134A1/ja
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the present invention relates to a rubber composition for tires and a tire.
  • wet grip performance From the perspective of improving vehicle safety, various technologies have been studied to improve tire performance, not only on dry road surfaces but also on wet road surfaces (hereinafter referred to as "wet grip performance"). Meanwhile, in connection with the recent global movement towards regulating carbon dioxide emissions in response to growing interest in environmental issues, there is an increasing demand for improved fuel efficiency in automobiles, and in order to meet such demands, there is a demand for improved fuel efficiency in tires (i.e. reduced rolling resistance).
  • Patent Document 1 proposes a rubber composition for tires that can provide tires with excellent wet grip performance and fuel efficiency (low loss), the rubber composition comprising a rubber component containing 50% by mass or more of at least one selected from styrene butadiene rubber and polybutadiene rubber, a filler selected from carbon black and silica, and, per 100 parts by mass of the rubber component, 5 to 50 parts by mass of polybutene and 1 to 30 parts by mass of at least one phenolic resin selected from unmodified phenolic resins and modified phenolic resins, the modified phenolic resin having a modifying group selected from a cyclic modifying group and a non-cyclic modifying group having 1 to 7 carbon atoms.
  • a rubber component containing 50% by mass or more of at least one selected from styrene butadiene rubber and polybutadiene rubber, a filler selected from carbon black and silica, and, per 100 parts by mass of the rubber component, 5 to 50 parts by mass of polybutene and
  • an object of the present invention is to provide a rubber composition for tires that can increase the proportion of sustainable materials in tires. Another object of the present invention is to provide a tire with an improved proportion of sustainable materials.
  • a rubber composition for tires comprising a rubber component (A), a filler (B), and a resin (C),
  • the rubber component (A) contains two or more types of rubber
  • the filler (B) contains plant-derived silica (B1)
  • a rubber composition for tires characterized in that the ratio of the plant-derived silica (B1) in the filler (B) is 45 mass % or more.
  • [8] A rubber composition for tires according to any one of [1] to [7], which is for use in tire treads.
  • a tire comprising a tread rubber made of the rubber composition for tires described in any one of [1] to [8].
  • the present invention it is possible to provide a rubber composition for tires that can increase the proportion of sustainable materials in tires. Furthermore, according to the present invention, it is possible to provide a tire with an improved proportion of sustainable materials.
  • FIG. 1 is a cross-sectional view of one embodiment of a tire of the present invention.
  • the compounds described herein may be derived in whole or in part from fossil sources, from biological sources such as plant sources, from recycled sources such as used tires, or from a mixture of two or more of fossil, biological and/or renewable sources.
  • the "proportion of sustainable materials” refers to the total mass ratio of materials derived from biological resources (biomass resources) and materials derived from renewable resources (recycled resources) in the target rubber composition for tires and tires.
  • the biological resources refer to carbon-neutral organic resources derived from living organisms, and include, for example, those stored in the form of starch or cellulose, the bodies of animals that grow by eating plants, and products obtained by processing plants or animals, and are resources other than fossil resources (petroleum, coal, natural gas, etc.).
  • the biological resources may be edible or non-edible, but from the standpoint of not competing with food and of effective resource utilization, it is preferable that they are non-edible.
  • biological resources include cellulosic crops (pulp, kenaf, wheat straw, rice straw, waste paper, papermaking residues, etc.), wood, charcoal, compost, food waste, vegetable oil residues, fishery residues, livestock waste, food waste, wastewater sludge, natural rubber, cotton, oils and fats (palm oil, castor oil, cottonseed oil, soybean oil, linseed oil, rapeseed oil, coconut oil, peanut oil, tall oil, corn oil, rice oil, safflower oil, sesame oil, oats, etc.).
  • cellulosic crops pulp, kenaf, wheat straw, rice straw, waste paper, papermaking residues, etc.
  • wood, charcoal, compost food waste, vegetable oil residues, fishery residues, livestock waste, food waste, wastewater sludge, natural rubber, cotton, oils and fats (palm oil, castor oil, cottonseed oil, soybean oil, linseed oil, rapeseed oil, coconut oil, peanut oil, tall oil
  • biological resources examples include: leaf oil, sunflower oil, palm kernel oil, camellia oil, jojoba oil, macadamia nut oil, tung oil, coconut oil, etc.), carbohydrate crops (corn, wheat, rice, rice husks, rice bran, old rice, potatoes, buckwheat, cassava, sago palm, sugarcane, etc.), bagasse (i.e., the residue after squeezing juice from sugarcane), soybeans, soybean pulp, essential oils (pine oil, orange oil, eucalyptus oil, etc.), pulp black liquor, algae, etc.
  • biological resources include those that have been processed (i.e., biological resource-derived substances).
  • Examples of the processing methods include biological processing methods that utilize the functions of microorganisms, plants, animals, and tissue cultures thereof; chemical processing methods that utilize acids, alkalis, catalysts, thermal energy, light energy, etc.; physical processing methods such as micronization, compression, microwave processing, and electromagnetic wave processing; and the like.
  • Examples of the biological resources include those that have been extracted and purified from the biological resources or the biological resources that have been processed (i.e., biological resource-derived substances). For example, sugars, proteins, amino acids, fatty acids, fatty acid esters, etc., purified from the biological resources can be used.
  • sugars examples include sucrose, glucose, trehalose, fructose, lactose, galactose, xylose, allose, talose, gulose, altrose, mannose, idose, arabinose, apiose, maltose, cellulose, starch, chitin, etc., derived from biological resources.
  • proteins include compounds derived from biological resources and formed by linking amino acids (preferably L-amino acids), including oligopeptides such as dipeptides.
  • amino acids examples include valine, leucine, isoleucine, arginine, lysine, asparagine, glutamine, phenylalanine, etc., derived from biological resources, and among these, valine, leucine, isoleucine, arginine, and phenylalanine are preferred.
  • the amino acids may be L-amino acids or D-amino acids, but L-amino acids are preferred from the viewpoints of abundance in nature and ease of availability.
  • the fatty acids include butyric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, etc., which are derived from biological resources.
  • fatty acid esters include modified products of vegetable oils, animal oils, and fats and oils derived from biological resources. These biological resources may contain various materials and impurities.
  • recycled resources refers to resources obtained by regenerating (recycling) products that have been used once, or that have been collected without being used, or that have been discarded.
  • recycled resources include resources obtained by regenerating (recycling) used rubber products such as used tires.
  • the rubber composition for a tire of this embodiment includes a rubber component (A), a filler (B), and a resin (C).
  • the rubber composition for a tire of this embodiment is characterized in that the rubber component (A) includes two or more kinds of rubber, the filler (B) includes plant-derived silica (B1), and the ratio of the plant-derived silica (B1) in the filler (B) is 45 mass% or more.
  • the plant-derived silica (B1) is a material derived from a biological resource (biomass resource), and the ratio of the plant-derived silica (B1) in the filler (B) is 45 mass% or more, so that the rubber composition for tires of this embodiment has a high ratio of sustainable materials. Therefore, by applying the rubber composition for tires of this embodiment to tires, it is possible to increase the ratio of sustainable materials in the tires.
  • a rubber composition for tires that contains a rubber component (A), a filler (B), and a resin (C), wherein the rubber component (A) contains two or more kinds of rubber, even if 45 mass % or more of the filler (B) is plant-derived silica (B1), performance such as wet grip performance (grip performance on wet road surfaces) and fuel efficiency performance (low loss property) is not impaired.
  • the rubber composition for tires of the present embodiment includes a rubber component (A) that provides rubber elasticity to the composition.
  • the rubber component (A) preferably has a sustainability rate of 30 mass% or more, more preferably 40 mass% or more, more preferably 50 mass% or more, more preferably 60 mass% or more, more preferably 70 mass% or more, even more preferably 80 mass% or more, even more preferably 90 mass% or more, and particularly preferably 100 mass%.
  • the "sustainability rate" of the rubber component (A) refers to the total mass ratio of components derived from biological resources (biomass resources) and components derived from recycled resources (recycled resources) in the rubber component (A).
  • the rubber component (A) the rubber derived from biological resources and the rubber derived from recycled resources are preferable.
  • the proportion of the monomer components derived from biological resources in 100 mol% of the monomer components constituting the rubber derived from biological resources is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, still more preferably 90 mol% or more, particularly preferably 95 mol% or more, and may be 100 mol%.
  • the proportion of the monomer components derived from recycled resources in 100 mol% of the monomer components constituting the rubber derived from recycled resources is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, still more preferably 90 mol% or more, particularly preferably 95 mol% or more, and may be 100 mol%.
  • the rubber component (A) is a component that contributes to crosslinking, and usually has a weight average molecular weight (Mw) of 10,000 or more, preferably 50,000 or more, more preferably 150,000 or more, and even more preferably 200,000 or more, and preferably 5,000,000 or less, more preferably 2,000,000 or less, more preferably 1,500,000 or less, and even more preferably 1,300,000 or less.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of the rubber component (A) can be determined, for example, in terms of standard polystyrene based on a measured value 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).
  • GPC gel permeation chromatography
  • the rubber component (A) is preferably a diene-based rubber, and the diene-based rubber is preferably an isoprene-based rubber or a butadiene-based rubber.
  • the isoprene-based rubber refers to a rubber that contains units derived from isoprene as monomer units
  • the butadiene-based rubber refers to a rubber that contains units derived from butadiene as monomer units.
  • the isoprene-based rubber may be natural rubber (NR), synthetic isoprene rubber (IR), modified natural rubber (modified NR), modified natural rubber (modified NR), modified synthetic isoprene rubber (modified IR), etc.
  • Natural rubber (NR) may be, for example, RSS#3, TSR20 (for example, SIR20 or STR20), etc., which are common in the tire industry.
  • the origin of natural rubber (NR) is not particularly limited, and examples include rubber derived from Hevea brasiliensis, guayule, and Russian dandelion.
  • Synthetic isoprene rubber (IR) is not particularly limited, and examples include rubber derived from IR2200, etc., which are common in the tire industry.
  • Modified NR may be, for example, deproteinized natural rubber (DPNR), high-purity natural rubber (UPNR), etc.
  • Modified NR may be, for example, epoxidized natural rubber (ENR), hydrogenated natural rubber (HNR), grafted natural rubber, etc.
  • modified IR include epoxidized synthetic isoprene rubber, hydrogenated synthetic isoprene rubber, and grafted synthetic isoprene rubber. These isoprene-based rubbers may be used alone or in combination of two or more. Among these, NR is preferred as the isoprene-based rubber.
  • the isoprene-based rubber preferably has a sustainability rate of 30% by mass or more, more preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 70% by mass or more, even more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass.
  • NR natural rubber
  • a polymer synthesized using isoprene derived from biological resources or isoprene derived from renewable resources as a monomer component.
  • the synthesized polymer may be a homopolymer of a monomer derived from biological resources, a homopolymer of a monomer derived from renewable resources, a copolymer of a monomer derived from biological resources and a monomer derived from renewable resources, or a copolymer of a monomer derived from biological resources and/or a monomer derived from renewable resources and a monomer derived from a fossil resource (petroleum, etc.).
  • the butadiene-based rubber may be butadiene rubber (BR), aromatic vinyl compound-butadiene copolymer rubber (e.g., styrene-butadiene rubber (SBR)), etc.
  • BR butadiene rubber
  • SBR styrene-butadiene rubber
  • the butadiene that is the raw material for butadiene-based rubber is preferably derived from biological resources or recycled resources.
  • the butadiene rubber (BR) may, for example, be a high cis content butadiene rubber, a low cis content butadiene rubber, or a butadiene rubber containing syndiotactic polybutadiene crystals.
  • Commercially available products may be used as the butadiene rubber (BR), and examples of commercially available butadiene rubber include products from UBE Elastomers Co., Ltd., ENEOS Materials Corporation, Asahi Kasei Corporation, and Zeon Corporation. These butadiene rubbers may be used alone or in combination of two or more types.
  • the aromatic vinyl compound-butadiene copolymer rubber may be, for example, emulsion-polymerized aromatic vinyl compound-butadiene copolymer rubber (e.g., emulsion-polymerized styrene-butadiene rubber (E-SBR)), solution-polymerized aromatic vinyl compound-butadiene copolymer rubber (e.g., solution-polymerized styrene-butadiene rubber (S-SBR)), etc.
  • E-SBR emulsion-polymerized styrene-butadiene rubber
  • S-SBR solution-polymerized aromatic vinyl compound-butadiene copolymer rubber
  • the aromatic vinyl compound (aromatic vinyl monomer) may be, for example, styrene, vinylnaphthalene, divinylnaphthalene, etc. These aromatic vinyl compounds may be used alone or in combination of two or more. Among these, styrene is preferred, and styrene derived from biological resources and styrene derived from recycled resources are particularly preferred. That is, SBR is preferred as the aromatic vinyl compound-butadiene copolymer rubber. The styrene may have a substituent.
  • the aromatic vinyl compound-butadiene copolymer rubber may be a commercially available product, such as those from Asahi Kasei Corporation, ENEOS Materials Corporation, Zeon Corporation, and Sumitomo Chemical Co., Ltd. These aromatic vinyl compound-butadiene copolymer rubbers may be used alone or in combination of two or more.
  • the butadiene-based rubber has a sustainability rate of preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 70% by mass or more, even more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass.
  • a polymer synthesized using butadiene derived from biological resources, butadiene derived from renewable resources, aromatic vinyl compounds derived from biological resources (e.g., styrene derived from biological resources), and aromatic vinyl compounds derived from renewable resources (e.g., styrene derived from renewable resources) as monomer components may be used.
  • the synthesized polymer may be a homopolymer of a monomer derived from biological resources, a homopolymer of a monomer derived from renewable resources, a copolymer of a monomer derived from biological resources and a monomer derived from renewable resources, or a copolymer of a monomer derived from biological resources and/or a monomer derived from renewable resources and a monomer derived from a fossil resource (petroleum, etc.).
  • butadiene rubber (B-BR) derived from biological resources biological resources
  • aromatic vinyl compound-butadiene copolymer rubber derived from biological resources e.g., styrene-butadiene rubber (B-SBR) derived from biological resources (biomass resources)
  • B-SBR styrene-butadiene rubber
  • NR natural rubber
  • the materials for rubber compositions for tires require large-scale manufacturing equipment to be produced, so they are usually produced in large factories in specific regions, and a lot of energy is required to store and transport the raw materials and products.
  • materials derived from biological resources are derived from local agricultural products, forests, etc., and can be produced on a small scale through microbial fermentation and catalytic reactions.
  • materials derived from renewable resources can be obtained, for example, by dismantling and pyrolyzing used tires to extract the materials that make up the tires, such as rubber, fillers, and steel cords.
  • sulfur can be obtained from biological resources or processed products of biological resources by a method including a desulfurization step of desulfurizing biological resources or processed products of biological resources to remove sulfur-containing substances from the biological resources or processed products of biological resources, a recovery step of recovering sulfur from the desulfurization residue generated in the desulfurization step, and a processing step of processing the recovered sulfur into sulfur for vulcanization (for example, the method described in Japanese Patent Application No.
  • materials for rubber compositions for tires can be obtained from various wastes and used items.
  • sustainable materials materials derived from biological resources or materials derived from recycled resources
  • LCE energy consumption
  • LCC reducing costs
  • the ratio of monomer components derived from biological resources, monomer components derived from renewable resources, and monomer components derived from fossil resources can be appropriately selected according to the supply situation of biological resources, renewable resources, and fossil resources (e.g., monomer components derived from fossil resources) and/or market demand (e.g., demand for biological resources as food), and the monomer components derived from biological resources, monomer components derived from renewable resources, and monomer components derived from fossil resources can be polymerized to obtain rubber derived from sustainable materials (materials derived from biological resources or materials derived from renewable resources) that has the same performance as conventional synthetic rubber.
  • monomer components derived from renewable resources it may be difficult to separate them from monomer components derived from fossil resources due to the manufacturing process of the monomer. In such cases, the impact on the environment can be evaluated by adopting the concept of mass balance.
  • the ratio of each monomer unit (e.g., unit derived from isoprene, unit derived from butadiene, unit derived from aromatic vinyl compound) in the entire rubber component (A) can be appropriately adjusted depending on the member to which the rubber component is applied.
  • the ratio of each monomer unit in the entire rubber component can be adjusted, for example, by appropriately combining the above-mentioned isoprene-based rubber and butadiene-based rubber.
  • the ratio of cis-bond units in the butadiene-based units can also be appropriately adjusted depending on the member to which the rubber component is applied.
  • the term "monomer unit” refers to a structural unit of a polymer
  • the term “unit derived from isoprene” refers to a structural unit in a polymer constituted based on the monomer isoprene (including the isoprene unit in natural rubber)
  • the term “unit derived from butadiene” refers to a structural unit in a polymer constituted based on the monomer butadiene
  • the term “unit derived from an aromatic vinyl compound” refers to a structural unit in a polymer constituted based on the monomer aromatic vinyl compound.
  • the ratio of each monomer unit is measured by NMR.
  • the rubber component (A) may contain diene rubbers such as acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), and styrene-isoprene-butadiene copolymer rubber (SIBR) in addition to the above-mentioned isoprene-based rubber, butadiene rubber (BR), and aromatic vinyl compound-butadiene copolymer rubber (e.g., SBR). These rubber components may be used alone or in combination of two or more.
  • NBR acrylonitrile-butadiene rubber
  • CR chloroprene rubber
  • IIR butyl rubber
  • SIBR styrene-isoprene-butadiene copolymer rubber
  • SBR aromatic vinyl compound-butadiene copolymer rubber
  • the rubber component (A) may be modified to introduce functional groups that interact with fillers such as carbon black and silica.
  • functional groups include amino groups, amide groups, isocyanate groups, imino groups, imidazole groups, urea 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, ether groups, carbonyl groups, oxycarbonyl groups, silyl groups, alkoxysilyl groups, mercapto groups, sulfide groups, disulfide groups, sulfonyl groups, sulfinyl groups, and thiocarbonyl groups.
  • These functional groups may have a substituent. These functional groups may be introduced into the rubber component alone or in combination of two or more. Among these, amino groups, alkoxy groups, and alkoxysilyl groups are preferred, and substituted amino groups in which the hydrogen atom of an amino group is substituted with an alkyl group having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkoxysilyl groups having 1 to 6 carbon atoms are even more preferred.
  • the functional group can be introduced, for example, by reacting a compound (modifier) having the functional group with the rubber component.
  • the functional group is a modified functional group that has an interactive property with fillers such as silica and carbon black, and examples thereof include a nitrogen-containing functional group, a silicon-containing functional group, and an oxygen-containing functional group.
  • examples of compounds (modifiers) having a nitrogen-containing functional group include amino group-containing compounds
  • examples of compounds (modifiers) having a silicon-containing functional group include silicon halides and hydrocarbyloxysilane compounds.
  • Examples of compounds (modifiers) having an oxygen-containing functional group include alkoxy group-containing compounds, alkylene oxide group-containing compounds, and trialkylsilyloxy group-containing compounds. More specifically, examples of the compounds include those described in International Publication Nos. 2016/194316 and 2019/117256. These modifiers may be used alone or in combination of two or more.
  • the rubber derived from sustainable materials can be produced in the same manner as conventional synthetic rubber derived from fossil resources, for example, by using monomer components derived from biological resources or monomer components derived from renewable resources, and, if necessary, monomer components derived from fossil resources.
  • the rubber derived from sustainable materials can also be obtained by reactions with microorganisms or enzyme reactions.
  • the method described in JP 2022-179158 A can be used as a method for preparing rubber derived from biological resources from the above-mentioned biological resources.
  • the method described in JP 2022-179158 A can be used.
  • B-BR butadiene rubber
  • B-SBR styrene-butadiene rubber
  • methods for obtaining B-BR and B-SBR from biological resources include artificial polymerization methods, polymerization methods in vivo, and polymerization methods using biological enzymes.
  • the molecular weight, branching, microstructure, etc. of the obtained B-BR and B-SBR can be appropriately adjusted by changing the polymerization conditions according to the target tire performance according to known methods.
  • butadiene obtained from the biological resources butadiene derived from alkyl alcohols (preferably ethanol and butanol, more preferably butanol), butadiene derived from alkenes (preferably ethylene), and butadiene derived from unsaturated carboxylic acids (preferably tiglic acid) can be suitably used. Two or more of these butadienes may be used in combination.
  • styrene obtained from the biological resource styrene obtained from a plant (preferably a plant belonging to the family Hamamelidaceae, Styracaceae, or Apocynaceae, more preferably a plant belonging to the genera Liquidamus, Styrax, or Catharanthus, and even more preferably Sweetgum, Styrax rosa, or Catharanthus roseus) or a microorganism (preferably a microorganism belonging to the genera Penicillium or Escherichia, more preferably P. citrinum or transformed E. coli) can be suitably used. Two or more of these styrenes may be used in combination.
  • bioethanol and bioethylene are mainly produced using sugars and/or cellulose as biological resources, and other biological resources such as proteins, lipids, and amino acids cannot be effectively utilized. Furthermore, sugars compete with food, and excessive use of cellulose leads to deforestation. Therefore, it is preferable to use multiple types of monomer components derived from biological resources as the monomer components derived from the biological resources, or to use monomer components derived from biological resources, monomer components derived from renewable resources, and monomer components derived from fossil resources in combination, and further to appropriately adjust the ratio of these monomer components.
  • butadiene derived from multiple types of biological resources with different origins as the butadiene derived from biological resources
  • styrene derived from multiple types of biological resources with different origins as the styrene derived from biological resources. This allows multiple types of biological resources to be effectively utilized.
  • the rubber component (A) contains two or more types of rubber. By containing two or more types of rubber, it becomes easier to achieve desired physical properties, such as wet grip performance and low fuel consumption performance.
  • the rubber component (A) preferably contains an isoprene skeleton rubber.
  • the isoprene skeleton rubber is a rubber whose main skeleton is isoprene units, and specific examples thereof include the above-mentioned natural rubber (NR), synthetic isoprene rubber (IR), modified natural rubber (modified NR), modified natural rubber (modified NR), modified synthetic isoprene rubber (modified IR), etc.
  • the content of the isoprene skeleton rubber in the rubber component (A) is preferably 10% by mass or more, more preferably 15% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, preferably 35% by mass or more, and even more preferably 41% by mass or more, from the viewpoint of improving the fuel efficiency performance of the tire (reducing the rolling resistance) and improving the wear resistance of the tire.
  • the content of the isoprene skeleton rubber in the rubber component (A) is preferably 90% by mass or less, more preferably 70% by mass or less, more preferably 65% by mass or less, more preferably 60% by mass or less, and even more preferably 57% by mass or less.
  • the rubber component (A) preferably contains styrene-butadiene rubber (SBR).
  • SBR styrene-butadiene rubber
  • the content of styrene-butadiene rubber in the rubber component (A) is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 41% by mass or more.
  • the content of styrene-butadiene rubber in the rubber component (A) is preferably 90% by mass or less, more preferably 80% by mass or less, more preferably 70% by mass or less, more preferably 60% by mass or less, more preferably 58% by mass or less, and even more preferably 53% by mass or less.
  • the rubber component (A) preferably contains the isoprene skeleton rubber and the styrene-butadiene rubber.
  • the rubber component (A) contains the isoprene skeleton rubber and the styrene-butadiene rubber, the effect of improving the wet grip performance and fuel economy performance of the tire is increased.
  • the mass ratio of the isoprene skeleton rubber to the styrene-butadiene rubber (SBR) isoprene skeleton rubber/SBR
  • SBR isoprene skeleton rubber/SBR
  • isoprene skeleton rubber/SBR mass ratio of the isoprene skeleton rubber to the styrene-butadiene rubber
  • the styrene-butadiene rubber (SBR) may be unmodified or modified.
  • SBR styrene-butadiene rubber
  • a hydrocarbyloxysilane compound represented by the following general formula (I) a hydrocarbyloxysilane compound represented by the following general formula (II)
  • R 11 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
  • R 12 and R 13 each independently represent a hydrolyzable group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
  • R 14 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when q1 is 2, may be the same or different.
  • R 15 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when q2 is 2 or greater, R 15 may be the same or different.
  • R 21 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
  • R 22 is a dimethylaminomethyl group, a dimethylaminoethyl group, a diethylaminomethyl group, a diethylaminoethyl group, a methylsilyl(methyl)aminomethyl group, a methylsilyl(methyl)aminoethyl group, a methylsilyl(ethyl)aminomethyl group, a methylsilyl(ethyl)aminoethyl group, a dimethylsilylaminomethyl group, a dimethylsilylaminoethyl group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r1 is 2 or more, they may be the same or different.
  • R 23 is a hydrocarbyloxy group having 1 to 20 carbon atoms, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r2 is 2, they may be the same or different.
  • A3 is a monovalent group having at least one functional group selected from (thio)epoxy, (thio)isocyanate, (thio)ketone, (thio)aldehyde, imine, amide, isocyanuric acid trihydrocarbyl ester, (thio)carboxylate, (thio)carboxylic acid metal salt, carboxylic acid anhydride, carboxylic acid halide, and carbonic acid dihydrocarbyl ester.
  • (thio)epoxy refers to epoxy and thioepoxy
  • (thio)isocyanate refers to isocyanate and thioisocyanate
  • (thio)ketone refers to ketone and thioketone
  • (thio)aldehyde refers to aldehyde and thioaldehyde
  • (thio)carboxylate refers to carboxylate and thiocarboxylate
  • (thio)carbonate metal salt refers to carboxylate and thiocarbonate metal salt.
  • R 31 is a single bond or a divalent inactive hydrocarbon group, and the divalent inactive hydrocarbon group preferably has 1 to 20 carbon atoms.
  • R 32 and R 33 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms
  • n is an integer of 0 to 2
  • the multiple R 32s may be the same or different
  • the multiple OR 33s may be the same or different.
  • the molecule of the hydrocarbyloxysilane compound represented by the general formula (III) does not contain an active proton or an onium salt.
  • the imine includes ketimine, aldimine, and amidine
  • the (thio)carboxylic acid ester includes unsaturated carboxylic acid ester such as acrylate and methacrylate.
  • examples of the metal in the metal salt of the (thio)carboxylic acid include alkali metals, alkaline earth metals, Al, Sn, and Zn.
  • Preferred examples of the divalent inactive hydrocarbon group of R 31 include alkylene groups having 1 to 20 carbon atoms. The alkylene group may be linear, branched, or cyclic, with linear alkylene groups being particularly preferred.
  • linear alkylene groups include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene, and dodecamethylene.
  • R 32 and R 33 include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms.
  • the alkyl group and the alkenyl group may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a vinyl group, a propenyl group, an allyl group, a hexenyl group, an octenyl group, a cyclopentenyl group, and a cyclohexenyl group.
  • the aryl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
  • the aralkyl group may have a substituent such as a lower alkyl group on the aromatic ring, examples of which include a benzyl group, a phenethyl group, and a naphthylmethyl group.
  • n is an integer of 0 to 2, preferably 0, and it is necessary that the molecule does not contain active protons or onium salts.
  • hydrocarbyloxysilane compound represented by the above general formula (III) examples include (thio)epoxy group-containing hydrocarbyloxysilane compounds, such as 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2-glycidoxyethyl)methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, 2-(3,4-epoxycyclohexyl) Preferred examples of the compound include ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(methyl)dimethoxysilane, 2-(3,4-epoxycyclohexyl)
  • triethoxysilyl compounds include N-(1-methylpropylidene)-3-(triethoxysilyl)-1-propanamine and trimethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds, ethyldimethoxysilyl compounds, and the like corresponding to these triethoxysilyl compounds.
  • N-(1-methylpropylidene)-3-(triethoxysilyl)-1-propanamine and N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine are particularly preferred.
  • R 41 , R 42 and R 43 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms.
  • R 44 , R 45 , R 46 , R 47 and R 49 each independently represent an alkyl group having 1 to 20 carbon atoms.
  • R 48 and R 51 each independently represent an alkylene group having 1 to 20 carbon atoms.
  • R 50 represents an alkyl group or a trialkylsilyl group having 1 to 20 carbon atoms.
  • m represents an integer of 1 to 3; p represents 1 or 2.
  • R 41 to R 51 , m and p are each independent, and i, j and k each independently represent an integer of 0 to 6, with the proviso that (i+j+k) is an integer of 3 to 10.
  • A4 represents a hydrocarbon group having 1 to 20 carbon atoms, or an organic group having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom and a phosphorus atom and having no active hydrogen.
  • the coupling agent represented by the general formula (IV) is preferably at least one selected from the group consisting of tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine, and tetrakis(3-trimethoxysilylpropyl)-1,3-bisaminomethylcyclohexane.
  • Z is tin or silicon
  • X is chlorine or bromine.
  • (R 5 ) is selected from the group consisting of alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, and aralkyl having 7 to 20 carbon atoms, where specific examples of (R 5 ) include a methyl group, an ethyl group, an n-butyl group, a neophyl group, a cyclohexyl group, an n-octyl group, and a 2-ethylhexyl group.
  • tin tetrachloride As the coupling agent represented by the above general formula (V), tin tetrachloride, (R 5 )SnCl 3 , (R 5 ) 2 SnCl 2 , (R 5 ) 3 SnCl and the like are preferred, and among these, tin tetrachloride is particularly preferred.
  • (Q) is a solubilizing component selected from the group consisting of hydrocarbons, ethers, amines or mixtures thereof
  • (AM) is represented by the following formula (VII): [In formula (VII), R 71 and R 72 each independently represent an alkyl, cycloalkyl or aralkyl group having 1 to 12 carbon atoms.] or the following formula (VIII): [In formula (VIII), R 81 represents an alkylene having 3 to 16 methylene groups, a linear or branched alkyl having 1 to 12 carbon atoms, a cycloalkyl, a bicycloalkyl, an aryl, a substituted alkylene having an aralkyl as a substituent, oxydiethylene, or an N-alkylamino-alkylene group.]
  • Q of general formula (VI) above renders the lithioamine soluble in a hydrocarbon solvent.
  • Q also includes dienyl or vinyl aromatic polymers or copolymers having a degree of polymerization of 3 to about 300 polymerization units. These polymers and copolymers include polybutadiene, polystyrene, polyisoprene, and copolymers thereof.
  • Other examples of Q include polar ligands [e.g., tetrahydrofuran (THF), tetramethylethylenediamine (TMEDA), etc.].
  • the lithioamine represented by the general formula (VI) may be mixed with an organic alkali metal.
  • the organic alkali metal is preferably selected from the group consisting of compounds represented by the general formulas: (R 91 )M, (R 92 )OM, (R 93 )C(O)OM, (R 94 )(R 95 )NM and (R 96 )SO 3 M, where each of (R 91 ), (R 92 ), (R 93 ), (R 94 ), (R 95 ) and (R 96 ) is selected from the group consisting of alkyl, cycloalkyl, alkenyl, aryl and phenyl having about 1 to about 12 carbon atoms.
  • the metal component M is selected from the group consisting of Na, K, Rb and Cs.
  • M is Na or K.
  • the mixture may also contain the organo-alkali metal, preferably in a mixing ratio of about 0.5 to about 0.02 equivalents per equivalent of lithium in the lithioamine.
  • a chelating agent can be used to prevent the polymerization from becoming uneven.
  • Useful chelating agents include, for example, tetramethylethylenediamine (TMEDA), oxolanyl cyclic acetals, and cyclic oligomeric oxolanyl alkanes. Cyclic oligomeric oxolanyl alkanes are particularly preferred, and a specific example is 2,2-bis(tetrahydrofuryl)propane.
  • Examples of the vinylpyridine include 2-vinylpyridine and 4-vinylpyridine.
  • a randomizer can also be used in synthesizing the styrene-butadiene rubber (SBR).
  • SBR styrene-butadiene rubber
  • the randomizer refers to a compound that has the effect of controlling the microstructure of a conjugated diene polymer, for example, increasing the number of 1,2 bonds in the butadiene portion in styrene-butadiene, or controlling the composition distribution of monomer units in a conjugated diene compound-aromatic vinyl compound copolymer, for example, randomizing styrene units and butadiene units in styrene-butadiene rubber.
  • the ratio of the randomizer to the polymerization initiator is preferably 0.01 to 1.0, more preferably 0.05 to 0.8.
  • An organic lithium compound such as butyl lithium can be used as the polymerization initiator.
  • the randomizer may be selected from known compounds that have been generally used as randomizers.
  • ethers and tertiary amines such as dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, oxolanylpropane oligomers [particularly those containing 2,2-bis(2-tetrahydrofuryl)-propane], triethylamine, pyridine, N-methylmorpholine, N,N,N',N'-tetramethylethylenediamine, and 1,2-dipiperidinoethane.
  • Potassium salts such as potassium tert-amylate and potassium tert-butoxide, and sodium salts such as sodium tert-amylate may also be used.
  • the rubber composition for tires of this embodiment further preferably contains a styrene-butadiene rubber having a styrene binding amount of 15 mass% or less as the styrene-butadiene rubber.
  • a rubber composition containing a styrene-butadiene rubber having a styrene binding amount of 15 mass% or less to a tire, the wet grip performance of the tire can be significantly improved.
  • the styrene binding amount is preferably 1 mass% or more, more preferably 3 mass% or more, and is preferably 13 mass% or less, and more preferably 11 mass% or less.
  • the amount of styrene bonds in styrene-butadiene rubber can be determined from the integral ratio of 1 H-NMR spectrum.
  • the rubber composition for tires of the present embodiment contains a filler (B).
  • the content of the filler (B) in the rubber composition for tires is preferably in the range of 40 to 125 parts by mass relative to 100 parts by mass of the rubber component (A).
  • the reinforcement of the rubber composition for tires is sufficient and the abrasion resistance of the tire can be improved, and when the content is 125 parts by mass or less, the elastic modulus of the rubber composition for tires is not too high, and the wet grip performance of the tire is improved.
  • the content of the filler (B) in the rubber composition for tires is more preferably 45 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 55 parts by mass or more relative to 100 parts by mass of the rubber component (A).
  • the content of the filler (B) in the rubber composition for a tire is more preferably 110 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 90 parts by mass or less, per 100 parts by mass of the rubber component (A).
  • the filler (B) contains plant-derived silica (B1).
  • the plant-derived silica (B1) is a material derived from a biological resource (biomass resource), and thus the inclusion of the plant-derived silica (B1) increases the ratio of sustainable materials in the rubber composition for tires, and the application of the rubber composition to tires increases the ratio of sustainable materials in the tires, thereby reducing the environmental impact.
  • silica (B1) derived from plants silica derived from silicic acid plants is preferred from the viewpoint of reducing environmental load.
  • the silicic acid plants are present in, for example, mosses, ferns, horsetails, Cucurbitaceae, Urticaceae, and Gramineae plants.
  • Gramineae plants are preferred, that is, as the silica (B1) derived from plants, silica derived from Gramineae plants is preferred.Since the raw material of the silica derived from Gramineae plants can be procured locally near tire manufacturing plants, it can reduce the energy and cost of transportation and storage, and is environmentally preferred from various viewpoints.
  • Examples of the Gramineae plant include rice, bamboo grass, sugarcane, etc., and among these, rice is preferred.
  • Rice is widely cultivated for food, so it can be procured locally in a wide area, and rice husks are generated in large quantities as industrial waste, so it is easy to secure the amount. Therefore, from the viewpoint of availability, silica derived from rice husks (hereinafter also referred to as "rice husk silica”) is particularly preferred as plant-derived silica (B1).
  • rice husk silica silica derived from rice husks
  • rice husk silica that become industrial waste can be effectively utilized, and since the raw material can be procured locally near the tire manufacturing plant, the energy and cost of transportation and storage can be reduced, which is environmentally preferable from various viewpoints.
  • the rice husk silica may be a powder of rice husk charcoal obtained by carbonizing rice husks by heating, or may be precipitated silica produced by a wet method using an aqueous alkali silicate solution, which is prepared by extracting rice husk ash generated when rice husks are burned in a biomass boiler using rice husks as fuel with an alkali.
  • the method for producing the rice husk charcoal is not particularly limited, and various known methods can be used.
  • rice husks can be pyrolyzed by steaming them in a kiln to obtain rice husk charcoal.
  • the rice husk charcoal thus obtained is pulverized using a known pulverizer (e.g., a ball mill), and then sorted and classified into a predetermined particle size range to obtain a powder of rice husk charcoal.
  • a known pulverizer e.g., a ball mill
  • the precipitated silica derived from rice husks can be produced by the method described in JP 2019-38728 A.
  • the ratio of the plant-derived silica (B1) in the filler (B) is 45% by mass or more.
  • the filler (B) may contain silica other than the plant-derived silica (B1).
  • examples of the silica include wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, etc., and among these, wet silica is preferred because it has a large number of silanol groups.
  • These silicas other than the plant-derived silica (B1) may be used alone or in combination of two or more.
  • silica other than the plant-derived silica (B1) commercially available products can be used, and examples of the commercially available silica include products from Tosoh Silica Co., Ltd., Evonik Corporation, Solvay Corporation, Solvay Japan Co., Ltd., Tokuyama Corporation, etc.
  • silica obtained by extracting silicic acid components from scraps of silicon wafers which are the raw material for semiconductors, glass bottles, etc., and recycling the silica used in the production.
  • the plant-derived silica (B1) preferably has a nitrogen adsorption specific surface area (BET method) of 80 m 2 /g or more and less than 330 m 2 /g.
  • BET method nitrogen adsorption specific surface area
  • the nitrogen adsorption specific surface area (BET method) of silica is 80 m 2 /g or more, the tire can be sufficiently reinforced and the rolling resistance can be sufficiently reduced.
  • the nitrogen adsorption specific surface area (BET method) of silica is less than 330 m 2 /g, the elastic modulus of the tire does not increase too much, and sufficient wet grip performance can be obtained.
  • the nitrogen adsorption specific surface area (BET method) of the plant-derived silica (B1) is more preferably 100 m 2 /g or more, more preferably 130 m 2 /g or more, more preferably 150 m 2 /g or more, more preferably 170 m 2 /g or more, more preferably 180 m 2 /g or more, more preferably 190 m 2 /g or more, and even more preferably 195 m 2 /g or more.
  • the nitrogen adsorption specific surface area (BET method) of the plant-derived silica (B1) is more preferably 300 m 2 /g or less, more preferably 280 m 2 /g or less, and even more preferably 270 m 2 /g or less.
  • the nitrogen adsorption specific surface area (N 2 SA) of silica is a value measured by the BET method in accordance with ASTM D3037-93.
  • the content of the plant-derived silica (B1) is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 55 parts by mass or more, per 100 parts by mass of the rubber component (A). Also, from the viewpoint of further improving the wet grip performance, the content of the plant-derived silica (B1) is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, and even more preferably 80 parts by mass or less, per 100 parts by mass of the rubber component (A).
  • the filler (B) preferably contains carbon black.
  • carbon black carbon black derived from plants and carbon black obtained by recycling (i.e., regenerated carbon black) are particularly preferred.
  • carbon black derived from plants include those derived from castor oil and rosin oil.
  • regenerated carbon black include carbon black obtained by decomposition (particularly thermal decomposition) of crosslinked rubber products such as used tires, and carbon black obtained from waste oil.
  • the crosslinked rubber products used for the decomposition may be grouped according to the type of rubber component that has been compounded in advance, and then the decomposition process may be carried out for each group.
  • the crosslinked rubber products may be grouped according to the type of filler that has been compounded in advance (e.g., type of carbon black, type of silica, mixing ratio of carbon black and silica, etc.), and then the decomposition process may be carried out for each group.
  • the crosslinked rubber products may be grouped according to both the type of rubber component and the type of filler, and then the decomposition process may be carried out for each group.
  • the tires when the crosslinked rubber product used for the decomposition is derived from tires, the tires may be grouped in advance by type (e.g., for passenger cars, trucks and buses, large vehicles such as off-road vehicles, aircraft, agricultural vehicles, etc.), and the decomposition process may be carried out for each group.
  • the tires may be grouped in advance by tire components (e.g., tread rubber, sidewall rubber, bead rubber, steel cord coated rubber, organic fiber coated rubber, pad rubber, cushion rubber, etc.), and the decomposition process may be carried out for each group.
  • the tires may be grouped both by type and by tire components, and the decomposition process may be carried out for each group. When the decomposition process is carried out for each group in this way, recycled carbon black with more uniform physical properties is obtained, and when it is blended again into the rubber component, a rubber composition with better performance is obtained.
  • the grade of the carbon black is not particularly limited, and examples thereof include N134, N110, N220, N234, N219, N339, N330, N326, N351, N550, and N762.
  • Commercially available carbon black products can be used, and examples of commercially available carbon black products include products from Asahi Carbon Co., Ltd., Cabot Japan Co., Ltd., Tokai Carbon Co., Ltd., Mitsubishi Chemical Co., Ltd., Lion Corporation, Nippon Steel Carbon Co., Ltd., Birla Carbon Co., Ltd., and the like. These carbon blacks may be used alone or in combination of two or more types.
  • the nitrogen adsorption specific surface area (N 2 SA) of the carbon black is not particularly limited, and can be appropriately adjusted depending on, for example, the tire category to which it is applied, the tire components, the target performance, etc.
  • the nitrogen adsorption specific surface area (N 2 SA) of the carbon black is preferably 20 m 2 /g or more, more preferably 50 m 2 /g or more, more preferably 70 m 2 /g or more, even more preferably 90 m 2 /g or more, and preferably 200 m 2 /g or less, more preferably 150 m 2 /g or less, and even more preferably 130 m 2 /g or less.
  • the nitrogen adsorption specific surface area (N 2 SA) of carbon black is determined in accordance with JIS K 6217-2:2017 (ISO 4652:2012).
  • the content of the carbon black 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 (A). Also, from the viewpoint of the workability of the rubber composition, the content of the carbon black is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less, per 100 parts by mass of the rubber component (A).
  • the silica content is 50% by mass or more and less than 100% by mass of the total amount of the silica and carbon black. By satisfying this range, it is possible to achieve a high level of balance between wet grip performance and fuel economy. Furthermore, from the viewpoint of further improving the balance between wet grip performance and fuel economy, it is more preferable that the silica content is 70% by mass or more and less than 100% by mass of the total amount of the silica and carbon black, more preferably 80% by mass or more and less than 100% by mass, and even more preferably 90% by mass or more and less than 100% by mass.
  • examples of the filler (B) include calcium carbonate, talc, alumina, clay, aluminum hydroxide, mica, etc.
  • the rubber composition for tires of the present embodiment contains a resin (C).
  • the resin (C) include terpene resins, rosin resins, C5 resins, C5 - C9 resins, C9 resins, cyclopentadiene resins, aromatic resins, coumarone resins, indene resins, coumarone-indene resins, olefin resins, polyurethane resins, and acrylic resins. These resins (C) may be used alone or in combination of two or more.
  • terpene resins, rosin resins, C5 resins, C5 - C9 resins, C9 resins, cyclopentadiene resins, and aromatic resins are preferred, and terpene resins and rosin resins are particularly preferred.
  • Terpene resins and rosin resins are naturally derived, sustainable resins, and therefore can reduce the environmental impact and can further improve tire performance, such as grip performance on various road surface conditions, such as dry road surfaces, wet road surfaces, snowy road surfaces, frozen road surfaces, etc.
  • C5 resins, C9 resins, C5- C9 resins, and cyclopentadiene resins can improve wear resistance and fuel economy in a well-balanced manner.
  • Aromatic resins can improve grip performance, wear resistance, and rubber strength in a well-balanced manner .
  • the resin (C) may be hydrogenated, i.e., may be a hydrogenated resin (hydrogenated resin).
  • functional groups that interact with fillers such as carbon black and silica may be introduced into the resin (C) by modification.
  • functional groups include amino groups, amide groups, isocyanate groups, imino groups, imidazole groups, urea 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, ether groups, carbonyl groups, oxycarbonyl groups, silyl groups, alkoxysilyl groups, mercapto groups, sulfide groups, disulfide groups, sulfonyl groups, sulfinyl groups, and thiocarbonyl groups.
  • the terpene resin is a solid resin obtained by blending turpentine, which is obtained at the same time when rosin is obtained from pine trees, or a polymerization component separated from the turpentine, and polymerizing it using a Friedel-Crafts catalyst, and examples of the terpene resin include ⁇ -pinene resin and ⁇ -pinene resin.
  • Terpene resins also include terpene-aromatic compound resins, and representative examples of the terpene-aromatic compound resins include terpene-phenol resin and styrene-terpene resin.
  • the terpene-phenol resin can be obtained by reacting terpenes with various phenols using a Friedel-Crafts catalyst, or by further condensing with formalin.
  • the styrene-terpene resin can be obtained by reacting styrene with terpenes using a Friedel-Crafts catalyst.
  • monoterpene hydrocarbons such as ⁇ -pinene and limonene are preferred, those containing ⁇ -pinene are more preferred, and ⁇ -pinene is particularly preferred.
  • the rosin-based resins include natural resin rosins such as gum rosin, tall oil rosin, and wood rosin contained in raw pine resin and tall oil, and modified rosins, rosin derivatives, and modified rosin derivatives such as polymerized rosin and its partially hydrogenated rosin; glycerin ester rosin and its partially hydrogenated rosin and fully hydrogenated rosin; pentaerythritol ester rosin and its partially hydrogenated rosin and polymerized rosin.
  • natural resin rosins such as gum rosin, tall oil rosin, and wood rosin contained in raw pine resin and tall oil
  • modified rosins, rosin derivatives, and modified rosin derivatives such as polymerized rosin and its partially hydrogenated rosin; glycerin ester rosin and its partially hydrogenated rosin and fully hydrogenated rosin; pentaerythritol ester rosin and its partially hydrogenated ros
  • the C5 resin includes aliphatic petroleum resins obtained by (co)polymerizing C5 fractions obtained by thermal cracking of naphtha in the petrochemical industry.
  • the C5 fractions usually include olefinic hydrocarbons such as 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl-1-butene, and diolefinic hydrocarbons such as 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, and 3-methyl-1,2-butadiene.
  • the C5 - C9 resin refers to a C5 - C9 synthetic petroleum resin
  • examples of the C5 -C9 resin include solid polymers obtained by polymerizing petroleum-derived C5 - C11 fractions using Friedel-Crafts catalysts such as AlCl3 and BF3 , and more specifically, copolymers mainly composed of styrene, vinyltoluene, ⁇ -methylstyrene, indene, etc.
  • a resin with a small amount of C9 or more components is preferred from the viewpoint of compatibility with the rubber component.
  • "a small amount of C9 or more components” means that the amount of C9 or more components in the total amount of the resin is less than 50 mass%, preferably 40 mass% or less.
  • the C9 resin refers to a C9 synthetic petroleum resin, for example, a solid polymer obtained by polymerizing a C9 fraction using a Friedel-Crafts type catalyst such as AlCl3 or BF3 .
  • Examples of the C9 resin include copolymers mainly composed of indene, ⁇ -methylstyrene, vinyltoluene, etc.
  • the cyclopentadiene resin refers to a resin containing a unit derived from a cyclopentadiene monomer as a monomer unit.
  • examples of the cyclopentadiene resin include a homopolymer of a cyclopentadiene monomer, a copolymer of two or more cyclopentadiene monomers, and a copolymer of a cyclopentadiene monomer and another monomer.
  • examples of the cyclopentadiene monomer include cyclopentadiene, dicyclopentadiene, and tricyclopentadiene, and among these, dicyclopentadiene is preferred, that is, the cyclopentadiene resin is preferably a dicyclopentadiene resin.
  • the dicyclopentadiene resin refers to a resin obtained by polymerizing dicyclopentadiene using a Friedel-Crafts catalyst such as AlCl3 or BF3 .
  • dicyclopentadiene resins include homopolymers of dicyclopentadiene, copolymers of dicyclopentadiene and aromatic monomers, and copolymers of dicyclopentadiene and C9 fractions (vinyl toluene, indene, etc.).
  • the aromatic resin refers to a resin that contains units derived from aromatic monomers as monomer units.
  • Examples of the aromatic resin include homopolymers of aromatic monomers, copolymers of two or more aromatic monomers, and copolymers of aromatic monomers and other monomers.
  • aromatic monomers examples include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, p-methoxystyrene, p-tert-butylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, and p-phenylstyrene; phenolic monomers such as phenol, alkylphenol, and alkoxyphenol; and naphthol monomers such as naphthol, alkylnaphthol, and alkoxynaphthol.
  • the resin (C) preferably has a softening point of 30° C. or higher, more preferably 60° C. or higher, more preferably 80° C. or higher, more preferably higher than 110° C., more preferably 116° C. or higher, more preferably 120° C. or higher, more preferably 123° C. or higher, and even more preferably 127° C. or higher.
  • the resin (C) preferably has a softening point of 160° C. or lower, more preferably 150° C. or lower, more preferably 145° C. or lower, more preferably 141° C. or lower, and even more preferably 136° C. or lower.
  • the softening point of the resin (C) is the temperature at which the ball drops when the softening point defined in JIS K 6220-1:2015 (ISO 28641:2010) is measured using a ring and ball softening point tester.
  • resins can be used as the resin (C), and examples of commercially available resins that can be used include products from ENEOS Corporation, Arakawa Chemical Industries, ExxonMobil Corporation, Clayton, Yasuhara Chemical Co., Ltd., Maruzen Petrochemical Co., Ltd., Sumitomo Bakelite Co., Ltd., Tosoh Corporation, Rutgers Chemicals, BASF, Clayton Polymers, Nippon Paint Chemical Co., Ltd., Nippon Shokubai Co., Ltd., and Taoka Chemical Co., Ltd.
  • the content of the resin (C) is not particularly limited, and can be adjusted as appropriate depending on, for example, the tire category to which it is applied, the tire components, the target performance, and the like.
  • the content of the resin (C) is preferably in the range of 1 to 50 parts by mass, and more preferably in the range of 10 to 40 parts by mass, per 100 parts by mass of the rubber component (A).
  • the content of the resin (C) is 1 to 50 parts by mass per 100 parts by mass of the rubber component (A)
  • the wet grip performance and fuel efficiency performance of the tire can be further improved, while the precipitation of the resin from the tire can be suppressed, and deterioration of the tire's appearance can be suppressed.
  • the resin (C) is preferably a hydrogenated resin (hereinafter, sometimes referred to as "hydrogenated resin") having a softening point higher than 110°C and a weight average molecular weight in terms of polystyrene of 200 to 1600 g/mol.
  • hydrogenated resin a hydrogenated resin having a softening point higher than 110°C and a weight average molecular weight in terms of polystyrene of 200 to 1600 g/mol.
  • resins that can be used as raw materials for the hydrogenated resin include the above-mentioned C5 resins, C5 - C9 resins, C9 resins, terpene resins, dicyclopentadiene resins, and terpene-aromatic compound resins, and these resins may be used alone or in combination of two or more.
  • the tire can be sufficiently reinforced and the rolling resistance can be reduced.
  • the softening point of the hydrogenated resin is preferably 115°C or higher, more preferably 118°C or higher, more preferably 123°C or higher, and even more preferably 127°C or higher.
  • the softening point of the hydrogenated resin is preferably 145°C or lower, more preferably 138°C or lower, and even more preferably 133°C or lower.
  • the hydrogenated resin in terms of polystyrene is 200 g/mol or more, the hydrogenated resin is less likely to precipitate from the tire and the effects of the hydrogenated resin can be fully exerted, and if it is 1600 g/mol or less, the hydrogenated resin is fully compatible with the rubber component (A).
  • the polystyrene-equivalent weight average molecular weight of the hydrogenated resin is preferably 500 g/mol or more, more preferably 550 g/mol or more, more preferably 600 g/mol or more, more preferably 650 g/mol or more, more preferably 700 g/mol or more, and even more preferably 750 g/mol or more.
  • the polystyrene-equivalent weight average molecular weight of the hydrogenated resin is more preferably 1400 g/mol or less, more preferably 1350 g/mol or less, more preferably 1300 g/mol or less, more preferably 1250 g/mol or less, more preferably 1200 g/mol or less, more preferably 1150 g/mol or less, more preferably 1100 g/mol or less, more preferably 1050 g/mol or less, more preferably 1000 g/mol or less, and even more preferably 950 g/mol or less.
  • the weight average molecular weight can be determined by measuring the average molecular weight of the hydrogenated resin by gel permeation chromatography (GPC) under the following conditions, and calculating the weight average molecular weight in terms of polystyrene.
  • GPC gel permeation chromatography
  • the softening point (TsHR) (unit: °C) of the hydrogenated resin relative to the polystyrene-equivalent weight average molecular weight (MwHR) (unit: g/mol) of the hydrogenated resin is preferably 0.15 or more [0.15 ⁇ (TsHR/MwHR)].
  • the (TsHR/MwHR) is more preferably 0.08 or more, more preferably 0.09 or more, more preferably 0.098 or more, more preferably 0.102 or more, more preferably 0.11 or more, more preferably 0.12 or more, more preferably 0.14 or more, more preferably 0.155 or more, more preferably 0.158 or more, more preferably 0.160 or more, and even more preferably 0.162 or more.
  • (TsHR/MwHR) is preferably 0.2 or less, more preferably 0.185 or less, more preferably 0.178 or less, more preferably 0.172 or less, more preferably 0.168 or less, and even more preferably 0.163 or less.
  • the content of the hydrogenated resin is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and even more preferably 9 parts by mass or more, per 100 parts by mass of rubber component (A). Also, from the viewpoint of suppressing precipitation of the hydrogenated resin from the tire and suppressing deterioration of the tire's appearance, the content of the hydrogenated resin is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, per 100 parts by mass of rubber component (A).
  • the resin used as the raw material for the hydrogenated resin may contain, for example, a resin obtained by copolymerizing a C5 fraction with dicyclopentadiene (DCPD) ( C5 -DCPD resin).
  • DCPD dicyclopentadiene
  • the C5 -DCPD resin is considered to be included in the dicyclopentadiene resin.
  • the dicyclopentadiene-derived component in the total amount of the resin is less than 50% by mass, the C5 -DCPD resin is considered to be included in the C5 resin.
  • a small amount of a third component is copolymerized.
  • the hydrogenated resin is preferably at least one selected from the group consisting of hydrogenated C5 resins, hydrogenated C5 - C9 resins, and hydrogenated dicyclopentadiene resins (hydrogenated DCPD resins), more preferably at least one selected from the group consisting of hydrogenated C5 resins and hydrogenated C5 - C9 resins, and even more preferably hydrogenated C5 resins.
  • the hydrogenated resin is a resin having a hydrogenated DCPD structure or a hydrogenated cyclic structure in at least a monomer.
  • the rubber composition for tires of this embodiment may contain a nonionic surfactant.
  • the nonionic surfactant improves the fuel economy and wear resistance of the rubber composition for tires obtained.
  • the nonionic surfactant at least one selected from polyhydric alcohol type, polyoxyethylene alkyl ether type, polyoxyethylene alkyl phenyl ether type, polyoxyethylene polyoxypropylene glycol type, polyethylene glycol type, glycoside type, fatty acid alkanolamide type, etc. is used.
  • the nonionic surfactant may be used alone or in combination of two or more types.
  • examples of the polyhydric alcohol type include fatty acid esters of glycerin (glycerol), fatty acid esters of pentaerythritol, fatty acid esters of polyoxyethylene sorbitan, fatty acid esters of polyoxyethylene sorbit, and fatty acid esters of sorbitan.
  • Specific examples include palm oil-derived hardened fatty acid glycerin, lipophilic glycerin monostearate, self-emulsifying glycerin monostearate, lipophilic glycerin monooleate, glycerin monocaprylate, propylene glycol monostearate, sorbitan monostearate, monooleate, and the like.
  • fatty acids examples include sorbitan tristearate, sorbitan sesquioleate, sorbitan coconut oil fatty acid, sorbitan monopalmitate, sorbitan tristearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan triisostearate, and polyoxyethylene sorbitan tetraoleate.
  • the polyoxyethylene alkyl ether type includes mono- or di-alkyl or alkenyl ethers of polyoxyethylene, and specific examples include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyldodecyl ether, etc.
  • the polyoxyethylene alkylphenyl ether type may be at least one selected from polyoxyethylene benzyl phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene distyrenated phenyl ether, etc.
  • the polyoxyethylene polyoxypropylene glycol type includes at least one selected from polyoxyethylene polyoxypropylene glycol and its mono- or di-fatty acid esters, etc.
  • the polyethylene glycol type includes mono- or di-fatty acid esters of polyethylene glycol, and specific examples include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, etc.
  • the glucoside type includes alkyl glucosides in which the alkyl group has 8 to 20 carbon atoms, and specific examples include decyl glucoside and lauryl glucoside.
  • the fatty acid alkanolamide type includes fatty acid diethanolamides and fatty acid N-alkylethanolamides, and more specifically, palm kernel oil fatty acid diethanolamide, lauric acid diethanolamide, coconut oil fatty acid N-methylethanolamide, etc.
  • Nonionic surfactants for the rubber composition for tires of this embodiment include polyoxyethylene hydrogenated castor oil, isostearyl glyceryl ether, etc.
  • glycerin fatty acid esters are preferred, and as glycerin fatty acid esters, those in which the number of carbon atoms of the fatty acid is 8 to 28, which include glycerin fatty acid monoesters and glycerin fatty acid diesters, and in which the content of glycerin fatty acid monoesters is 40 to 100% by mass are more preferred.
  • the content of the nonionic surfactant in the rubber composition for tires of this embodiment is preferably 0.1 parts by mass or more and 7 parts by mass or less, more preferably 0.2 parts by mass or more and 6 parts by mass or less, and even more preferably 0.3 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the rubber component (A), from the viewpoint of sufficiently improving fuel economy and abrasion resistance.
  • the mass ratio of the hydrogenated resin to the nonionic surfactant is preferably 0.7 to 500, more preferably 1 to 30, and even more preferably 5 to 20.
  • the rubber composition for tires of this embodiment preferably contains a silane coupling agent.
  • the silane coupling agent include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysily
  • silane coupling agent a commercially available product can be used, and examples of the commercially available silane coupling agent include products from Evonik, Momentive, Shin-Etsu Silicone Co., Ltd., Dow Corning Toray Co., Ltd., Tokyo Chemical Industry Co., Ltd., and Azumax Co., Ltd. These silane coupling agents may be used alone or in combination of two or more.
  • bioethanol can also be used as a raw material for the silane coupling agent.
  • Bioethanol is produced mainly using sugars and/or cellulose as biological resources, and other biological resources such as proteins, lipids, and amino acids cannot be effectively utilized.
  • sugars compete with food, and excessive use of cellulose leads to deforestation. Therefore, it is preferable to use multiple types of ethanol derived from biological resources (bioethanol) as the raw material for the silane coupling agent, or to use a combination of ethanol derived from biological resources (bioethanol), ethanol derived from renewable resources, and ethanol derived from fossil resources, depending on the supply situation of various biological resources, the supply situation of renewable resources, the supply situation of fossil resources, and market demands (for example, demand for biomass resources as food).
  • bioethanol biological resources
  • bioethanol ethanol derived from renewable resources
  • ethanol derived from fossil resources depending on the supply situation of various biological resources, the supply situation of renewable resources, the supply situation of fossil resources, and market demands (for example, demand for biomass resources as food).
  • the content of the silane coupling agent can be adjusted as appropriate depending on, for example, the tire category to which it is applied, the tire components, the target performance, etc.
  • the content of the silane coupling agent is preferably 1 part by mass or more, more preferably 6 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 12 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the plant-derived silica (B1) (or the total amount of silica).
  • the rubber composition for tires of this embodiment may contain rubber powder.
  • the rubber powder may be obtained by crushing used rubber products such as used tires, and removing reinforcing materials such as steel materials and fibers, dust, glass, sand, stones, etc., as desired, or by preparing a new vulcanized rubber composition to produce rubber powder and crushing it.
  • rubber powder can be obtained from vulcanized rubber by the method described in "Rubber Chemistry and Technology".
  • mechanical treatment or low-temperature treatment may be used.
  • various crushing devices such as a cracker mill and a granulator can be used to mechanically crush the vulcanized rubber into fine particles.
  • the finely chopped vulcanized rubber is frozen at a very low temperature and then crushed into fine particles.
  • a magnetic separator or the like can be used to remove steel materials
  • an air separator or the like can be used to remove fibers.
  • the rubber powder may be a commercially available product, and examples of the commercially available rubber powder include products from Global Corporation or Nanton Huili Rubber Corporation. From the viewpoint of reducing the environmental load, it is preferable to use rubber powder obtained by crushing used rubber products such as used tires. The rubber powder may be used alone or in combination of two or more kinds.
  • the composition of the rubber powder is not particularly limited, and depends on the composition of the vulcanized rubber of the raw material, such as used rubber products (used tires).
  • the rubber powder contains a rubber component, carbon black, silica, etc.
  • the rubber component, carbon black, silica, etc. contained in the rubber powder may be the same as or different from the rubber component, carbon black, silica, etc. that may be contained in the rubber composition for tires of the present embodiment described above.
  • the rubber powder has a volume average particle size of preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, even more preferably 200 ⁇ m or less, and even more preferably 100 ⁇ m or less.
  • the volume average particle size is measured by a laser diffraction particle size distribution measuring device, for example, "CAPA500” manufactured by Horiba, Ltd.
  • the rubber powder has a 60 mesh sieve residue of preferably less than 1 mass%, more preferably 0.5 mass% or less, and even more preferably 0.1 mass% or less, with no particular lower limit. Also, the rubber powder has an 80 mesh sieve residue of preferably less than 10 mass%, more preferably 1 mass% or less, and even more preferably 0.5 mass% or less, with no particular lower limit. In this specification, the sieve residue is measured in accordance with ASTM D5644-01.
  • the rubber powder has an acetone extractable content of preferably 12% by mass or less, more preferably 11% by mass or less, and even more preferably 10% by mass or less, and preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more.
  • the acetone extractables in the rubber crumb means the acetone extractables (%) determined by the acetone extraction method in accordance with JIS K6350.
  • the amount of the rubber powder is not particularly limited, and can be adjusted as appropriate depending on, for example, the tire category to which the tire is applied, the tire components, the target performance, etc.
  • the amount of the rubber powder is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more, and is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, more preferably 100 parts by mass or less, more preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less, relative to 100 parts by mass of the rubber component (A).
  • the rubber composition for tires of this embodiment may contain a liquid softener.
  • the "liquid softener” is a compounding agent that is liquid at 25°C (room temperature) and has the effect of softening the rubber composition.
  • the liquid softener is not particularly limited, and examples thereof include oil and liquid polymer, among which oil is preferred. These liquid softeners may be used alone or in combination of two or more.
  • the oil is a general term for extender oil contained in the rubber component and liquid oil added as a compounding agent to the rubber composition, and examples thereof include vegetable oil, process oil, oil obtained by recycling vegetable oil or process oil, or a mixture thereof. From the viewpoint of reducing the environmental load, vegetable oil and oil obtained by recycling are preferred.
  • examples of the vegetable oil include palm oil, castor oil, cottonseed oil, soybean oil, linseed oil, rapeseed oil, coconut oil, peanut oil, 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, coconut oil, etc.
  • Examples of the process oil include paraffin-based process oil, aromatic process oil, naphthene-based process oil, etc.
  • the oil can be a commercially available product, and examples of the commercially available oil include products from Idemitsu Kosan Co., Ltd., Sankyo Yuka Kogyo Co., Ltd., ENEOS Corporation, Orisoi Co., Ltd., H&R Corporation, Toyokuni Oil Mills Co., Ltd., and Nisshin Oillio Group Co., Ltd. These oils can be used alone or in combination of two or more types.
  • the liquid polymer is preferably a liquid diene polymer.
  • the liquid diene polymer include liquid styrene-butadiene copolymer (liquid SBR), liquid polybutadiene (liquid BR), liquid polyisoprene (liquid IR), liquid styrene-isoprene copolymer (liquid SIR), liquid styrene-butadiene-styrene block copolymer (liquid SBS block polymer), liquid styrene-isoprene-styrene block copolymer (liquid SIS block polymer), liquid polyfarnesene, and liquid farnesene-butadiene copolymer.
  • These liquid polymers may be hydrogenated, or the ends or main chains may be modified with functional groups (polar groups). These liquid polymers may be used alone or in combination of two or more.
  • the content of the liquid softener is not particularly limited, and can be adjusted as appropriate depending on, for example, the tire category to which it is applied, the tire components, the target performance, etc.
  • the content of the liquid softener is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably 100 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less, relative to 100 parts by mass of the rubber component (A).
  • the rubber composition for tires of the present embodiment may contain an antioxidant, such as N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine (77PD), N,N'-diphenyl-p-phenylenediamine (DPPD), N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymer (TMDQ), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (AW), and 6-anilino-2,2,4-trimethyl-1,2-dihydroquinoline.
  • an antioxidant such as N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), N,N'-bis(1,4-dimethylp
  • antiaging agent a commercially available product can be used, and examples of the commercially available antiaging agent include products from Ouchi Shinko Chemical Industry Co., Ltd., Sumitomo Chemical Co., Ltd., Seiko Chemical Co., Ltd., Flexis Co., Ltd., etc. These antiaging agents may be used alone or in combination of two or more.
  • the content of the anti-aging agent is not particularly limited, and can be adjusted as appropriate depending on, for example, the tire category to which it is applied, the tire components, the target performance, etc.
  • the content of the anti-aging agent is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and even more preferably 2 parts by mass or more, and is preferably 12 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, relative to 100 parts by mass of the rubber component (A).
  • the rubber composition for tires of this embodiment may contain a wax.
  • the wax include natural waxes such as vegetable wax and animal wax; petroleum waxes such as paraffin wax and microcrystalline wax; and synthetic waxes such as ethylene polymers and propylene polymers.
  • Commercially available products can be used as the wax, and examples of commercially available products of the wax include products from Seiko Chemical Co., Ltd., Nippon Seiro Co., Ltd., Ouchi Shinko Chemical Co., Ltd., and the like. These waxes may be used alone or in combination of two or more.
  • the wax content is not particularly limited and can be adjusted as appropriate depending on, for example, the tire category to which it is applied, the tire components, the target performance, etc.
  • the wax content is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and is preferably 10 parts by mass or less, more preferably 6 parts by mass or less, per 100 parts by mass of the rubber component (A).
  • the rubber composition for tires of the present embodiment may contain stearic acid.
  • stearic acid a commercially available product may be used, and as the commercially available product of the stearic acid, products of NOF Corporation, Kao Corporation, FUJIFILM Wako Pure Chemical Industries, Ltd., Chiba Fatty Acid Co., Ltd., etc. may be used. These commercially available products of stearic acid may be used alone or in combination of two or more.
  • the content of the stearic acid is not particularly limited, and can be adjusted as appropriate depending on, for example, the tire category to which it is applied, the tire components, the target performance, etc.
  • the content of stearic acid is preferably 1 part 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 (A).
  • the rubber composition for tires of this embodiment may contain zinc oxide (zinc white).
  • zinc oxide not only zinc metal but also zinc oxide obtained from recycled zinc or zinc dross (i.e., obtained by recycling) is preferable.
  • zinc oxide commercially available products can be used, and examples of the commercially available zinc oxide include products from Hakusui Tech Co., Ltd., Seido Chemical Industry Co., Ltd., Sakai Chemical Industry Co., Ltd., Mitsui Mining & Smelting Co., Ltd., Toho Zinc Co., Ltd., etc. These commercially available zinc oxide products may be used alone or in combination of two or more.
  • the amount of zinc oxide is not particularly limited, and can be adjusted as appropriate depending on, for example, the tire category to which the rubber is applied, the tire components, the target performance, etc.
  • the amount of zinc oxide is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and is preferably 10 parts by mass or less, more preferably 6 parts by mass or less, per 100 parts by mass of the rubber component (A).
  • the rubber composition for tires of this embodiment preferably contains sulfur.
  • the sulfur may be derived from fossil resources, recycled resources, or materials derived from biological resources. From the viewpoint of reducing the environmental load, it is particularly preferable to use sulfur obtained from waste derived from biological resources. Examples of a method for obtaining sulfur from waste derived from biological resources include the method described in the above-mentioned Japanese Patent Application No. 2022-140390.
  • the sulfur may be powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, soluble sulfur, or the like, which are generally used as crosslinking agents in the rubber industry.
  • sulfur commercially available products can be used, and examples of commercially available sulfur products include products from Tsurumi Chemical Industry Co., Ltd., Hosoi Chemical Industry Co., Ltd., Karuizawa Sulfur Co., Ltd., Shikoku Chemical Industry Co., Ltd., and Flexis Co., Ltd. These sulfurs may be used alone or in combination of two or more types.
  • the sulfur content is not particularly limited, and can be adjusted as appropriate depending on, for example, the tire category to which the rubber is applied, the tire components, the target performance, etc.
  • the sulfur content is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 0.8 parts by mass or more, and is preferably 8 parts by mass or less, and more preferably 5 parts by mass or less, per 100 parts by mass of the rubber component (A).
  • the rubber composition for tires of the present embodiment preferably contains a vulcanization accelerator.
  • the vulcanization accelerator may be derived from fossil resources, recycled resources, or biological resources, but is preferably derived from biological resources from the viewpoint of reducing environmental load.
  • the vulcanization accelerator derived from biological resources can be obtained, for example, by the method disclosed in JP-A-2005-139239.
  • vulcanization accelerator examples include sulfenamide-based vulcanization accelerators such as N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N,N-dicyclohexyl-2-benzothiazolylsulfenamide, N-tert-butyl-2-benzothiazolylsulfenamide (TBBS), N-oxyethylene-2-benzothiazolesulfenamide, and N,N'-diisopropyl-2-benzothiazolesulfenamide; 1,3-diphenylguanidine (DPG), 1,3-diphenylguanidine (DPG), and 1,3-diphenylguanidine (DPG).
  • CBS N-cyclohexyl-2-benzothiazolylsulfenamide
  • TBBS N-tert-butyl-2-benzothiazolylsulfenamide
  • DPG 1,3-diphenylguanidine
  • DPG 1,3-
  • vulcanization accelerator examples include guanidine-based vulcanization accelerators such as o-tolylguanidine and o-tolylbiguanidine; thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole (M) and di-2-benzothiazolyl disulfide (MBTS, DM); and thiuram-based vulcanization accelerators such as tetramethylthiuram disulfide (TMTD), tetrastearylthiuram disulfide, tetrabenzylthiuram disulfide (TBzTD), and tetrakis(2-ethylhexyl)thiuram disulfide (TOT-N).
  • TMTD tetramethylthiuram disulfide
  • TzTD tetrastearylthiuram disulfide
  • TBzTD tetrabenzylthiuram disulfide
  • TOT-N tetrakis(
  • vulcanization accelerators Commercially available products can be used as the vulcanization accelerator, and examples of the commercially available vulcanization accelerators include products from Ouchi Shinko Chemical Industry Co., Ltd., Sumitomo Chemical Co., Ltd., and the like. These vulcanization accelerators may be used alone or in combination of two or more.
  • the content of the vulcanization accelerator is not particularly limited, and can be adjusted as appropriate depending on, for example, the tire category to which it is applied, the tire components, the target performance, etc.
  • the content of the vulcanization accelerator is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more, and is preferably 8 parts by mass or less, more preferably 6 parts by mass or less, and even more preferably 5.5 parts by mass or less, relative to 100 parts by mass of the rubber component (A).
  • the rubber composition for tires of the present embodiment may contain cellulose nanofibers (CNF).
  • the cellulose nanofibers can be blended into a rubber composition to reinforce the rubber composition.
  • the cellulose nanofiber is preferably a modified cellulose nanofiber, and the modified cellulose nanofiber is a fine fiber made from modified cellulose.
  • the fiber diameter of the cellulose nanofiber is not particularly limited, but is about 3 to 500 nm.
  • the average fiber diameter and average fiber length of the cellulose nanofiber can be obtained by averaging the fiber diameter and fiber length obtained from the results of observing each fiber using a scanning electron microscope (SEM), an atomic force microscope (AFM), or a transmission electron microscope (TEM).
  • SEM scanning electron microscope
  • AFM atomic force microscope
  • TEM transmission electron microscope
  • the cellulose nanofiber can be obtained by defibrating cellulose.
  • the average fiber length and average fiber diameter of the fine fibers can be adjusted by oxidation treatment and defibration treatment.
  • the raw material for the cellulose nanofibers is not particularly limited as long as it contains cellulose, and examples thereof include plants (e.g., wood, bamboo, hemp, jute, kenaf, agricultural waste, cloth, pulp (softwood unbleached kraft pulp (NUKP), softwood bleached kraft pulp (NBKP), hardwood unbleached kraft pulp (LUKP), hardwood bleached kraft pulp (LBKP), bleached kraft pulp (BKP), softwood unbleached sulfite pulp (NUSP), softwood bleached sulfite pulp (NBSP), thermomechanical pulp (TMP), recycled pulp, waste paper, etc.), animals (e.g., ascidians), algae, microorganisms (e.g., acetic acid bacteria (Acetobacter)), microbial products, etc. These cellulose raw materials may be used alone or in combination of two or more types.
  • plants e.g., wood, bamboo, hemp, jute, kenaf, agricultural waste, cloth
  • the amount of the cellulose nanofiber is not particularly limited, and can be adjusted as appropriate depending on, for example, the tire category to which it is applied, the tire components, the target performance, etc.
  • the amount of the cellulose nanofiber is preferably in the range of 1 to 100 parts by mass, more preferably in the range of 5 to 70 parts by weight, and even more preferably in the range of 10 to 40 parts by mass, per 100 parts by mass of the rubber component (A).
  • the rubber composition for tires of this embodiment may contain porous cellulose particles.
  • the porous cellulose particles are preferably cellulose particles having a porous structure with a porosity of 75 to 95%, and by compounding them with a rubber composition, performance on ice can be improved.
  • the porosity of the porous cellulose particles is 75% or more, the effect of improving performance on ice is excellent, and when the porosity is 95% or less, the strength of the particles can be increased.
  • the porosity is more preferably 80 to 90%.
  • the porosity of the porous cellulose particles can be calculated by measuring the volume of a certain mass of a sample (i.e., the porous cellulose particles) with a measuring cylinder, calculating the bulk density, and using the following formula.
  • Porosity (%) ⁇ 1 - [bulk specific gravity of sample (g/mL)] / [true specific gravity of sample (g/mL)] ⁇ x 100
  • the true specific gravity of cellulose is 1.5.
  • the particle size of the porous cellulose particles is not particularly limited, but from the viewpoint of abrasion resistance, the average particle size is preferably 1000 ⁇ m or less.
  • the lower limit of the average particle size is not particularly limited, but it is preferably 5 ⁇ m or more.
  • the average particle size is more preferably 100 to 800 ⁇ m, and even more preferably 200 to 800 ⁇ m.
  • the porous cellulose particles are preferably spherical particles having a major axis/minor axis ratio of 1 to 2. By using particles having such a spherical structure, the dispersibility in the rubber composition is improved, which contributes to improving performance on ice and maintaining abrasion resistance, etc.
  • the major axis/minor axis ratio is more preferably 1.0 to 1.5.
  • the average particle size and the long axis/short axis ratio of the porous cellulose particles are determined as follows: That is, the porous cellulose particles are observed under a microscope to obtain an image, and the long axis and short axis of the particles (when the long axis and short axis are the same, the length in a certain axis direction and the length in an axis direction perpendicular to the long axis) of 100 particles are measured using the image, and the average particle size is obtained by calculating the average value, and the long axis/short axis ratio is obtained by averaging the values obtained by dividing the long axis by the short axis.
  • porous cellulose particles are commercially available from Rengo Co., Ltd. under the name "Viscopearl” and are also described in JP-A-2001-323095 and JP-A-2004-115284, and can be suitably used.
  • the content of the porous cellulose particles is not particularly limited, and can be adjusted as appropriate depending on, for example, the tire category to which it is applied, the tire components, the target performance, etc.
  • the content of the porous cellulose particles is preferably in the range of 0.3 to 20 parts by mass, more preferably in the range of 1 to 15 parts by weight, and even more preferably in the range of 3 to 15 parts by mass, per 100 parts by mass of the rubber component (A).
  • the rubber composition for tires of this embodiment may contain solid fine particles.
  • the solid fine particles can improve the performance on ice by blending them with the rubber composition.
  • the solid fine particles preferably have an average particle diameter of 1 ⁇ m or more, and preferably 1000 ⁇ m or less, and more preferably 300 ⁇ m or less.
  • the solid fine particles include powders derived from plants such as rice husks, walnut powder, and walnut shells; powders derived from animals such as eggshells (eggshell powder) and bone powder; powders derived from natural minerals such as whitebait; inorganic fine particles such as graphite and zinc oxide whiskers; water-soluble metal salt fine particles such as magnesium sulfate and metal salts of lignin sulfonate; non-metallic fibers such as glass fibers; and the like.
  • rice husks, walnut shells, eggshells, and whitebait are preferred.
  • the content of the solid fine particles is not particularly limited, and can be adjusted as appropriate depending on, for example, the tire category to which it is applied, the tire components, the target performance, etc.
  • the content of the solid fine particles is preferably in the range of 0.3 to 20 parts by mass, more preferably in the range of 1 to 15 parts by weight, and even more preferably in the range of 3 to 15 parts by mass, per 100 parts by mass of the rubber component (A).
  • the rubber composition for tires of the present embodiment may further contain various additives generally used in the tire industry, such as organic peroxides, etc.
  • the content of these additives is not particularly limited and can be appropriately adjusted depending on, for example, the tire category to which the composition is applied, the tire components, the target performance, etc.
  • the content is preferably in the range of 0.1 to 200 parts by mass per 100 parts by mass of the rubber component (A).
  • the method for producing the rubber composition for tires of the present embodiment is not particularly limited, but for example, the rubber composition can be produced by blending the plant-derived silica (B1), the resin (C), and various components appropriately selected as necessary with the rubber component (A), and kneading, heating, extruding, etc.
  • the obtained rubber composition can be vulcanized to produce a vulcanized rubber.
  • kneading there are no particular limitations on the conditions for the kneading, and the input volume of the kneading device, the rotation speed of the rotor, the ram pressure, etc., as well as the conditions for the kneading temperature, kneading time, type of kneading device, etc., can be appropriately selected according to the purpose.
  • kneading devices include Banbury mixers, intermixes, kneaders, rolls, etc., which are typically used for kneading rubber compositions.
  • heat-in process temperature heat-in process time
  • heat-in process equipment heat-in process equipment
  • other conditions can be appropriately selected depending on the purpose.
  • the heat-in process equipment include a heat-in process roll machine that is typically used for heat-in process of rubber compositions.
  • extrusion conditions there are no particular limitations on the extrusion conditions, and various conditions such as extrusion time, extrusion speed, extrusion equipment, and extrusion temperature can be appropriately selected depending on the purpose.
  • extrusion equipment include extruders that are typically used for extruding rubber compositions.
  • the extrusion temperature can be appropriately determined.
  • vulcanization equipment There are no particular limitations on the vulcanization equipment, method, conditions, etc., and they can be selected appropriately depending on the purpose.
  • vulcanization equipment include a mold vulcanizer that uses a mold to vulcanize rubber compositions.
  • the vulcanization temperature is, for example, about 100 to 190°C.
  • the rubber composition for tires of this embodiment can be applied to various components of tires, for example, treads (cap tread, base tread, under tread), cushion rubber, shoulders, sidewalls, clinches, bead fillers, carcass coating rubber, insulation, chafers, inner liners, etc., and can also be used for side reinforcing layers of run-flat tires, etc.
  • treads cap tread, base tread, under tread
  • cushion rubber shoulders, sidewalls, clinches, bead fillers, carcass coating rubber, insulation, chafers, inner liners, etc.
  • the rubber composition of this embodiment can also be applied to rubber crawlers, seismic isolation rubber, hoses, etc.
  • the rubber composition for tires of this embodiment is suitable for tire treads and rubber crawler treads because it does not impair wet grip performance and fuel efficiency performance.
  • the tire of the present embodiment is characterized by having a tread rubber made of the above-mentioned rubber composition for tires.
  • the tire of the present embodiment includes a tread rubber made of the above-mentioned rubber composition for tires, and therefore the ratio of sustainable materials is improved without compromising performance.
  • Fig. 1 is a cross-sectional view of an embodiment of a tire of the present invention.
  • the tire 1 of this embodiment shown in Fig. 1 has a pair of bead portions 2, a pair of sidewall portions 3, and a tread portion 4 connected to both sidewall portions 3, and further includes a carcass 5 extending in a toroidal shape between the pair of bead portions 2 to reinforce these portions 2, 3, and 4, and a belt 6 disposed on the outer side of a crown portion of the carcass 5 in the tire radial direction.
  • the carcass 5 of the tire 1 shown in FIG. 1 is composed of one carcass ply made of multiple parallel-arranged cords covered with a coating rubber, and the carcass 5 is composed of a main body portion that extends in a toroidal shape between the bead cores 7 embedded in the bead portions 2, and a folded-up portion that is wound up radially outward around each bead core 7 from the inner side toward the outer side in the tire width direction, but the number and structure of the plies of the carcass 5 in the tire of the present invention are not limited to this.
  • the belt 6 of the tire 1 shown in FIG. 1 is made up of two belt layers 6A and 6B, but in the tire of the present invention, the number of belt layers constituting the belt 6 is not limited to this, and the number of belt layers may be three or more.
  • the belt layers 6A and 6B are usually made up of rubberized layers of cords (preferably steel cords) that extend at an angle to the tire equatorial plane, and the two belt layers 6A and 6B are laminated to form the belt 6 so that the cords constituting the belt layers 6A and 6B cross each other with the tire equatorial plane in between.
  • the tire 1 of this embodiment has tread rubber 8 on the outermost surface of the tread portion 4, and the tire rubber composition of this embodiment described above is used for the tread rubber 8. Therefore, the tire 1 of this embodiment has an improved ratio of sustainable materials.
  • the tire of the present invention may have a tread rubber made of the tire rubber composition of the present embodiment described above, and various modifications may be made to it.
  • a tread rubber made of the tire rubber composition of the present embodiment described above, and various modifications may be made to it.
  • the tire of this embodiment can be manufactured by a normal method using the above-mentioned rubber composition as the tread rubber.
  • the tire of this embodiment can be obtained by molding and vulcanizing an unvulcanized rubber composition according to the type of tire to be applied, or by molding and then vulcanizing a semi-vulcanized rubber that has been subjected to a pre-vulcanization process or the like.
  • the tire of this embodiment is preferably a pneumatic tire, and the gas to be filled in the pneumatic tire can be normal air or air with an adjusted oxygen partial pressure, or an inert gas such as nitrogen, argon, or helium.
  • Each rubber composition was produced according to a conventional method with the formulation shown in Table 1.
  • the details of Modified SBR-A and Modified SBR-B in Table 1 are as follows. For each rubber composition obtained, the total mass ratio of materials derived from biological resources (biomass resources) and materials derived from recycled resources (recycled resources) was calculated to calculate the sustainable material ratio. A larger value indicates a better effect.
  • SBR-A> This is a styrene-butadiene rubber (SBR) obtained using butyllithium as an initiator, and the terminals are modified with N,N-bis(trimethylsilyl)-3-[diethoxy(methyl)silyl]propylamine, and the glass transition temperature is ⁇ 62° C.
  • SBR styrene-butadiene rubber
  • SBR-B This is a styrene-butadiene rubber (SBR) obtained using butyl lithium as an initiator, and its terminals are modified with N-(1,3-dimethylbutylidene)-3-triethoxysilyl-1-propanamine. Its Tg is -38°C.
  • glycerin fatty acid ester (nonionic surfactant)
  • the glycerin fatty acid ester was prepared by synthesizing the fatty acid by replacing octanoic acid with an equimolar amount of palm oil-derived hydrogenated fatty acid and then molecular distilling the resulting glycerin fatty acid ester (glycerin fatty acid ester composition) according to the method described in Production Example 1 of WO 2014/098155.
  • the glycerin fatty acid monoester content of the obtained glycerin fatty acid ester was 97% by mass.
  • the rubber composition of the embodiment according to the present invention has an improved ratio of sustainable materials, and by applying it to tires, the ratio of sustainable materials in the tires can be improved.
  • Tire 2 Bead portion 3: Sidewall portion 4: Tread portion 5: Carcass 6: Belt 6A, 6B: Belt layer 7: Bead core 8: Tread rubber

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
PCT/JP2024/023989 2023-07-31 2024-07-02 タイヤ用ゴム組成物、及びタイヤ Pending WO2025028134A1 (ja)

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JP2004115284A (ja) 2002-09-24 2004-04-15 Rengo Co Ltd セラミックス多孔化材及びこれを用いたセラミックスの多孔化方法
JP2005139239A (ja) 2003-11-04 2005-06-02 Sanshin Chem Ind Co Ltd 天然油脂由来のアミンを使用した加硫促進剤およびゴム組成物
WO2014098155A1 (ja) 2012-12-19 2014-06-26 株式会社ブリヂストン ゴム組成物及びそれを用いたタイヤ
WO2016194316A1 (ja) 2015-06-01 2016-12-08 株式会社ブリヂストン ゴム組成物及びタイヤ
JP2019038728A (ja) 2017-08-28 2019-03-14 味の素株式会社 沈降シリカの製造法
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WO2019229692A1 (en) * 2018-05-31 2019-12-05 Pirelli Tyre S.P.A. Tyres for vehicles and elastomeric compositions for tyres comprising particular silicas from rice husk ash
JP2019218464A (ja) 2018-06-19 2019-12-26 株式会社ブリヂストン タイヤ用ゴム組成物及びタイヤ
JP2022140390A (ja) 2021-03-12 2022-09-26 アバイア マネジメント エル．ピー． デバイスハンドオフ
JP2022179158A (ja) 2021-05-21 2022-12-02 住友ゴム工業株式会社 乗用車タイヤ用ゴム組成物及び乗用車タイヤ
JP2022179157A (ja) * 2021-05-21 2022-12-02 住友ゴム工業株式会社 キャップトレッド及び乗用車タイヤ
JP2023060806A (ja) * 2021-10-18 2023-04-28 住友ゴム工業株式会社 タイヤ
US20230174743A1 (en) * 2021-12-02 2023-06-08 The Goodyear Tire & Rubber Company Tire tread rubber composition comprising rice husk ash silica
JP2023091770A (ja) * 2021-12-20 2023-06-30 ザ・グッドイヤー・タイヤ・アンド・ラバー・カンパニー 再生可能な含有物を過半量有するトレッドゴム組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001323095A (ja) 2000-05-12 2001-11-20 Rengo Co Ltd 多孔性セルロース粒子、機能性粒子及びこれらを用いた化粧品
JP2004115284A (ja) 2002-09-24 2004-04-15 Rengo Co Ltd セラミックス多孔化材及びこれを用いたセラミックスの多孔化方法
JP2005139239A (ja) 2003-11-04 2005-06-02 Sanshin Chem Ind Co Ltd 天然油脂由来のアミンを使用した加硫促進剤およびゴム組成物
WO2014098155A1 (ja) 2012-12-19 2014-06-26 株式会社ブリヂストン ゴム組成物及びそれを用いたタイヤ
WO2016194316A1 (ja) 2015-06-01 2016-12-08 株式会社ブリヂストン ゴム組成物及びタイヤ
JP2019038728A (ja) 2017-08-28 2019-03-14 味の素株式会社 沈降シリカの製造法
WO2019117256A1 (ja) 2017-12-13 2019-06-20 株式会社ブリヂストン タイヤ用ゴム組成物
WO2019229692A1 (en) * 2018-05-31 2019-12-05 Pirelli Tyre S.P.A. Tyres for vehicles and elastomeric compositions for tyres comprising particular silicas from rice husk ash
JP2019218464A (ja) 2018-06-19 2019-12-26 株式会社ブリヂストン タイヤ用ゴム組成物及びタイヤ
JP2022140390A (ja) 2021-03-12 2022-09-26 アバイア マネジメント エル．ピー． デバイスハンドオフ
JP2022179158A (ja) 2021-05-21 2022-12-02 住友ゴム工業株式会社 乗用車タイヤ用ゴム組成物及び乗用車タイヤ
JP2022179157A (ja) * 2021-05-21 2022-12-02 住友ゴム工業株式会社 キャップトレッド及び乗用車タイヤ
JP2023060806A (ja) * 2021-10-18 2023-04-28 住友ゴム工業株式会社 タイヤ
US20230174743A1 (en) * 2021-12-02 2023-06-08 The Goodyear Tire & Rubber Company Tire tread rubber composition comprising rice husk ash silica
JP2023091770A (ja) * 2021-12-20 2023-06-30 ザ・グッドイヤー・タイヤ・アンド・ラバー・カンパニー 再生可能な含有物を過半量有するトレッドゴム組成物

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