Classifications

• • 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
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• • 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
  • C08L9/06—Copolymers with styrene
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2296—Oxides; Hydroxides of metals of zinc
• • 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
  • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
  • C08K2003/3045—Sulfates
  • C08K2003/3063—Magnesium sulfate
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/003—Additives being defined by their diameter
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/004—Additives being defined by their length
• • 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
  • C08K3/02—Elements
  • C08K3/06—Sulfur
• • 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
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T10/00—Road transport of goods or passengers
  • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
  • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

• the present invention relates to a rubber composition containing an inorganic fiber material and a tire having an internal member composed of the rubber composition.
• a technique is known in which a bio-derived nanomaterial such as cellulose fiber is blended into a tire member to give anisotropy to the modulus of rubber (for example, Patent Document 1).
• An object of the present invention is to provide a rubber composition having a high degree of both fracture strength and anisotropy.
• the present invention [1] A rubber composition containing a rubber component, an inorganic fiber material, and a coupling agent. [2] The rubber composition according to [1] above, wherein the ratio (M100a / M100b) of 100% modulus M100a in the columnar direction to 100% modulus M100b in the anti-columnar direction is 1.10 or more. [3] The rubber composition according to the above [1] or [2], further containing carbon black (preferably 1 to 100 parts by mass, more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the rubber component).
• the inorganic fiber material is contained in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the rubber component, the average diameter D of the inorganic fiber material is 1.0 to 2000 nm, and the average length L is 0.10 to 100 ⁇ m.
• the inorganic fiber material is one or more inorganic fiber materials selected from the group consisting of magnesium sulfate fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, and sepiolite.
• a tire internal member composed of the rubber composition according to any one of the above [1] to [11].
• a rubber composition having a high degree of both breaking strength and anisotropy is provided. Further, the tire provided with the tire internal member made of the rubber composition has improved riding comfort and steering stability in a well-balanced manner.
• the rubber composition of the present disclosure contains a rubber component, an inorganic fiber material, and a coupling agent, it exhibits excellent breaking strength and anisotropy.
• an inorganic fiber material By blending an inorganic fiber material with the rubber composition, it is possible to give anisotropy to the modulus of the rubber, but it is considered that the inorganic fiber material is less likely to be dispersed in the rubber component than a filler such as carbon black. .. Therefore, it is considered that the entire rubber matrix cannot be reinforced and it is difficult to obtain sufficient fracture strength and anisotropy. Therefore, by blending a coupling agent together with the inorganic fiber material, it is possible to improve the dispersibility of the inorganic fiber material in the rubber matrix, reinforce the entire matrix, and orient the inorganic fiber material in a uniform state. , Anisotropy is also considered to be improved.
• the rubber composition (vulcanized rubber) of the present disclosure is a value of the ratio of 100% modulus M100a in the columnar direction to 100% modulus M100b in the anti-arration direction as an index of anisotropy.
• M100a / M100b sometimes referred to as "modulus ratio" in the present specification
• modulus ratio is preferably 1.10 or more, more preferably 1.15 or more, still more preferably 1.20 or more.
• the upper limit of the modulus ratio is not particularly limited, but is usually 2.00 or less, and may be 1.80 or less, 1.60 or less, or 1.50 or less.
• the modulus ratio By setting the modulus ratio to 1.10 or more, a supple response to the anti-columnar direction of the inorganic fiber material oriented in a highly dispersed state by the coupling agent is realized, and the rigidity in the columnar direction is increased. It is possible to improve the responsiveness.
• the "columnar direction” means the rolling direction when the sheet is formed by extrusion or shearing
• the "reverse columnar direction” means the direction perpendicular to the columnar direction. means.
• the columnar direction of the inorganic fibers may be any of the circumferential direction, the radial direction, and the width direction of the tire, but the ride comfort and the steering stability are balanced. From the viewpoint of improving the tires, it is preferable to arrange them along the tire circumferential direction.
• a supple response to the input (vibration) from the vertical direction of the tire during rolling is realized, and by increasing the rigidity in the orientation direction (tire circumferential direction), steering is performed. Improves responsiveness to time input. Therefore, it is considered that the riding comfort and the steering stability are improved in a well-balanced manner.
• ⁇ Rubber component examples of the rubber component that can be used in the present disclosure include diene such as isoprene rubber, styrene butadiene rubber (SBR), butadiene rubber (BR), styrene isoprene butadiene rubber (SIBR), chloroprene rubber (CR), and acrylonitrile butadiene rubber (NBR).
• diene such as isoprene rubber, styrene butadiene rubber (SBR), butadiene rubber (BR), styrene isoprene butadiene rubber (SIBR), chloroprene rubber (CR), and acrylonitrile butadiene rubber (NBR).
• diene such as isoprene rubber, styrene butadiene rubber (SBR), butadiene rubber (BR), styrene isoprene butadiene rubber (SIBR), chloroprene rubber (CR), and acrylonit
• the rubber component may be a rubber component containing at least one selected from the group consisting of isoprene-based rubber, SBR, and BR, may be a rubber component containing isoprene-based rubber, and may be a rubber component containing isoprene-based rubber and BR. It may be a rubber component consisting only of isoprene-based rubber and BR, a rubber component containing BR, a rubber component containing BR and SBR, or a rubber component consisting only of BR and SBR. It may be a rubber component containing isoprene-based rubber, SBR and BR isoprene-based rubber, or may be a rubber component containing only isoprene-based rubber, SBR and BR.
• the content of the diene rubber in 100% by mass of the rubber component is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 85% by mass or more. Further, it may be a rubber component composed of only diene-based rubber.
• isoprene rubber As the isoprene-based rubber, for example, isoprene rubber (IR), natural rubber, and other rubbers commonly used in the tire industry can be used. Natural rubber includes non-modified natural rubber (NR), epoxidized natural rubber (ENR), hydrogenated natural rubber (HNR), deproteinized natural rubber (DPNR), high-purity natural rubber, and grafted natural rubber. Modified natural rubber and the like are also included. These isoprene-based rubbers may be used alone or in combination of two or more.
• the NR is not particularly limited, and a tire that is common in the tire industry can be used, and examples thereof include SIR20, RSS # 3, and TSR20.
• the content in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and further preferably 30% by mass from the viewpoint of breaking strength.
• the above is particularly preferable.
• the upper limit of the content in the isoprene-based rubber component is not particularly limited, but is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and particularly preferably 75% by mass or less.
• SBR solution polymerization SBR
• E-SBR emulsion polymerization SBR
• modified SBR modified SBR
• SBR is preferred.
• modified SBR include modified SBR (condensate, one having a branched structure, etc.) coupled with SBR having a modified terminal and / or main chain, tin, a silicon compound, or the like.
• SBR there are an oil-extending type in which the flexibility is adjusted by adding a spreading oil and a non-oil-extending type in which no extending oil is added, and both of them can be used.
• SBR include SBR manufactured and sold by JSR Corporation, Asahi Kasei Chemicals Co., Ltd., Zeon Corporation, and the like. These SBRs may be used alone or in combination of two or more.
• the styrene content of SBR is preferably 15% by mass or more, more preferably 18% by mass or more, and even more preferably 20% by mass or more. Further, from the viewpoint of polymer dispersibility and fuel efficiency, 60% by mass or less is preferable, 55% by mass or less is more preferable, and 50% by mass or less is further preferable. In this specification, the styrene content of SBR is calculated by 1 1 H-NMR measurement.
• the content in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and further preferably 20% by mass from the viewpoint of wear resistance performance.
• the above is particularly preferable.
• the upper limit of the content of SBR in the rubber component is not particularly limited, but is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and particularly preferably 75% by mass or less.
• the BR is not particularly limited, and for example, a BR having a cis 1,4 bond content (cis content) of less than 50% (Rare earth BR), a BR having a cis 1,4 bond content of 90% or more (Hisis BR), and the like.
• a BR having a cis 1,4 bond content (cis content) of less than 50% (Rare earth BR)
• Hisis BR a BR having a cis 1,4 bond content of 90% or more
• BR rare earth butadiene rubber
• SPB containing BR syndiotactic polybutadiene crystals
• modified BR Hysis modified BR, Locis modified BR
• These BRs may be used alone or in combination of two or more.
• the cis 1,4 bond content of HISIS BR is preferably 95% or more, more preferably 97% or more.
• HISIS BR low temperature characteristics and wear resistance can be improved.
• examples of the HISIS BR include HISIS BR manufactured and sold by Nippon Zeon Corporation, Ube Industries, Ltd., JSR Corporation, and the like.
• examples of the rare earth BR include rare earth BR manufactured and sold by LANXESS Co., Ltd. and the like.
• the SPB-containing BR includes 1,2-syndiotactic polybutadiene crystals that are not simply dispersed in BR, but are dispersed after being chemically bonded to BR.
• Examples of the SPB-containing BR include SPB-containing BR manufactured and sold by Ube Industries, Ltd. and the like.
• the modified BR is obtained by polymerizing 1,3-butadiene with a lithium initiator and then adding a tin compound, and further, the terminal of the modified BR molecule is bonded by a tin-carbon bond (tin).
• Modified BR butadiene rubber having a condensed alkoxysilane compound at the active end of the butadiene rubber
• modified BR for silica examples include a tin-modified polymer manufactured by ZS Elastomer Co., Ltd., an S-modified polymer (modified for silica), and the like.
• the content in 100% by mass of the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and further preferably 20% by mass from the viewpoint of wear resistance performance.
• the above is more preferable, and 25% by mass or more is particularly preferable.
• the upper limit of the content of BR in the rubber component is not particularly limited, but is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and particularly preferably 75% by mass or less.
• the rubber composition according to the present disclosure contains an inorganic fiber material.
• an inorganic fiber material By giving anisotropy to the strength and rigidity of the inorganic fiber material oriented in the tire circumferential direction, a flexible response to the input (vibration) from the vertical direction of the tire during rolling is realized, and the orientation direction (tire). By increasing the rigidity (in the circumferential direction), the responsiveness to the input during steering is improved.
• the inorganic fiber material that can be used in the present disclosure is not particularly limited, and examples thereof include magnesium sulfate fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, sepiolite, glass fiber, and the like, and magnesium sulfate fiber.
• magnesium sulfate fiber calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, and one or more inorganic fiber materials selected from the group consisting of sepiolite are preferable, and magnesium sulfate fiber is more preferable.
• the above-mentioned inorganic fiber material may be used alone or in combination of two or more.
• Fibers magnesium sulfate, MgSO 4 ⁇ 5Mg (OH) basic magnesium sulfate fiber which is represented by 2 ⁇ 3H 2 O are preferred.
• the calcium silicate fiber, calcium silicate fiber represented by 6CaO ⁇ 6SiO 2 ⁇ H 2 O are preferred.
• potassium titanate fiber potassium titanate fiber represented by K 2 O ⁇ 6 TiO 2 or K 2 O ⁇ 8 TiO 2 is preferable.
• the sepiolite, sepiolite represented by Mg 8 Si 12 O 30 (OH ) 4 (H 2 O) 4 ⁇ 8H 2 O are preferred.
• the inorganic fiber material a commercially available material may be used, or a material manufactured by a known manufacturing method may be used. Specific examples of the inorganic fiber material include inorganic fiber materials manufactured and sold by Ube Material Industries Ltd., Otsuka Chemical Co., Ltd., Shikoku Chemicals Corporation, Omi Mining Co., Ltd., and the like.
• the content of the inorganic fiber material with respect to 100 parts by mass of the rubber component is preferably 1.0 part by mass or more, more preferably 1.5 parts by mass or more, and 2.0 parts by mass or more from the viewpoint of anisotropy of the rubber composition. Is more preferable, and 2.5 parts by mass or more is particularly preferable. From the viewpoint of the breaking strength of the rubber composition, 50 parts by mass or less is preferable, 45 parts by mass or less is more preferable, 40 parts by mass or less is further preferable, and 30 parts by mass or less is particularly preferable.
• the average diameter (also referred to as average fiber diameter or average width) D of the inorganic fiber material is preferably 1.0 nm or more, more preferably 2.0 nm or more, and more preferably 3.0 nm or more from the viewpoint of rigidity and processability of the rubber composition. Is even more preferable. Further, from the viewpoint of rigidity and breaking strength of the rubber composition, 2000 nm or less is preferable, 1000 nm or less is more preferable, 500 nm or less is further preferable, and 100 nm or less is particularly preferable.
• the average length (also referred to as average fiber length) L of the inorganic fiber material is preferably 0.10 ⁇ m or more, more preferably 0.15 ⁇ m or more, still more preferably 0.20 ⁇ m or more, from the viewpoint of anisotropy of the rubber composition. 0.50 ⁇ m or more is particularly preferable. Further, from the viewpoint of rigidity and breaking strength of the rubber composition, 100 ⁇ m or less is preferable, 80 ⁇ m or less is more preferable, 60 ⁇ m or less is further preferable, and 40 ⁇ m or less is particularly preferable.
• the average diameter D and the average length L refer to image analysis of scanning electron micrographs, image analysis of transmission micrographs, analysis of X-ray scattering data, pore electrical resistance method (Coulter principle method), and the like. Can be measured by.
• the aspect ratio L / D of the inorganic fiber material is preferably 2 or more, more preferably 4 or more, further preferably 6 or more, and particularly preferably 8 or more, from the viewpoint of anisotropy of the rubber composition. Further, from the viewpoint of the breaking strength of the rubber composition, 1000 or less is preferable, 500 or less is more preferable, 250 or less is further preferable, and 100 or less is particularly preferable.
• the rubber composition according to the present disclosure contains a cup rig agent.
• the inorganic fiber material is less likely to be dispersed in the rubber component than a filler such as carbon black, but the dispersibility of the inorganic fiber material is improved and the anisotropy is also improved by adding a coupling agent.
• the coupling agent that can be used in the present disclosure is not particularly limited, and examples thereof include a silane coupling agent that binds to silica and a rubber component, carbon black, and a carbon coupling agent that binds to a rubber component.
• silane coupling agent is not particularly limited, and in the rubber industry, any silane coupling agent conventionally used in combination with silica can be used.
• a silane coupling agent having the following mercapto group Silane coupling agent having a sulfide group such as (3-triethoxysilylpropyl) disulfide and bis (3-triethoxysilylpropyl) tetrasulfide; silane coupling having a vinyl group such as vinyltriethoxysilane and vinyltrimethoxysilane.
• a silane coupling agent having an amino group such as 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane; ⁇ -glycidoxypropyltriethoxy.
• Glycydoxy-based silane coupling agents such as silane and ⁇ -glycidoxypropyltrimethoxysilane; nitro-based silane coupling agents such as 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane; 3-chloropropyl Examples thereof include chloro-based silane coupling agents such as trimethoxysilane and 3-chloropropyltriethoxysilane.
• a silane coupling agent having a sulfide group and / or a silane coupling agent having a mercapto group is preferable, and a silane coupling agent having a sulfide group is more preferable.
• These silane coupling agents may be used alone or in combination of two or more.
• the silane coupling agent having a mercapto group includes a compound represented by the following formula (1) and / or a binding unit A represented by the following formula (2) and a binding unit B represented by the following formula (3). It is preferable that the compound contains.
• R 101 , R 102 , and R 103 are independently alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or -O- (R 111- O) z- R 112.
• Z R 111s independently represent divalent hydrocarbon groups having 1 to 30 carbon atoms;
• R 112 is an alkyl having 1 to 30 carbon atoms, an alkenyl having 2 to 30 carbon atoms, and a carbon number of carbon atoms.
• R 202 represents an alkylene having 1 to 30 carbon atoms, an alkenylene having 2 to 30 carbon atoms, or an alkynylene having 2 to 30 carbon atoms;
• a ring structure may be formed by R 201 and R 202.
• Examples of the compound represented by the formula (1) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and the following chemical formula ( Examples thereof include a compound represented by 4) (Si363 manufactured by Ebonic Degusa), and a compound represented by the following chemical formula (4) can be preferably used. These may be used alone or in combination of two or more.
• Examples of the compound containing the binding unit A represented by the formula (2) and the binding unit B represented by the formula (3) include those manufactured and sold by Momentive and the like. These may be used alone or in combination of two or more.
• the carbon coupling agent is not particularly limited, but is a tetrasulfide compound such as bis (dimethylaminoethyl) tetrasulfide (DME) and bis (dimethylaminopropyl) tetrasulfide (DMP); 1,2-bis (benzimidazolyl-). 2) Benzimidazole compounds such as ethane (EBZ) and 1,4'-bis (mercaptobenzimidazolyl-2) butane (C4SBZ); pyrithion metal salts and the like can be mentioned. These carbon coupling agents may be used alone or in combination of two or more.
• the content of the coupling agent (preferably the silane coupling agent) with respect to 100 parts by mass of the rubber component is preferably 1.0 part by mass or more, more preferably 1.5 parts by mass or more, from the viewpoint of enhancing the dispersibility of the inorganic fiber material. It is preferable, and more preferably 2.0 parts by mass or more. From the viewpoint of breaking strength, 40 parts by mass or less is preferable, 30 parts by mass or less is more preferable, 20 parts by mass or less is further preferable, and 15 parts by mass or less is particularly preferable.
• the content of the inorganic fiber material with respect to 100 parts by mass of the rubber component is A (parts by mass), the content of silica is B (parts by mass), and the content of the coupling agent (preferably silane coupling agent) is X (parts by mass). Then, it is preferable that A, B, and X satisfy the following formula (5). 0.09A + 0.08B ⁇ X ⁇ 0.35A + 0.08B ... (5)
• the rubber composition may contain carbon black, silica, aluminum hydroxide, calcium carbonate, alumina, clay, talc, or the like, which are generally used in the rubber industry. Among them, it is preferable to contain carbon black, and it is more preferable to contain carbon black and silica.
• carbon black Since carbon black has high heat generation during mixing, it is considered that it is possible to promote plasticization during mixing and to make it easier for the inorganic fiber material to react with the coupling agent and disperse in the rubber matrix.
• the reinforcing effect can be obtained without having anisotropy, so that the minimum required fracture strength can be imparted in the anti-arrangement direction of the inorganic fiber.
• silica is inferior in reinforcing effect to carbon black and inorganic fiber materials, but it can be supplely reinforced, so it is possible to reinforce the entire rubber matrix while ensuring suppleness in the anti-columnar direction. It is considered to be.
• the carbon black is not particularly limited, and general ones in the tire industry such as GPF, FEF, HAF, ISAF, SAF can be used. Specifically, N110, N115, N120, N125, N134, N135, N219, N220. , N231, N234, N293, N299, N326, N330, N339, N343, N347, N351, N356, N358, N375, N539, N550, N582, N630, N642, N650, N660, N683, N754, N762, N765.
• N774, N787, N907, N908, N990, N991 and the like can be preferably used, and in-house synthesized products and the like can also be preferably used.
• These carbon blacks may be used alone or in combination of two or more.
• the nitrogen adsorption specific surface area (N 2 SA) of carbon black is preferably 30 m 2 / g or more, more preferably 35 m 2 / g or more, still more preferably 40 m 2 / g or more, from the viewpoint of weather resistance and reinforcing properties. Further, from the viewpoint of dispersibility, fuel efficiency, fracture characteristics and durability, 250 m 2 / g or less is preferable, and 220 m 2 / g or less is more preferable.
• the N 2 SA of carbon black in the present specification is A of JIS K 6217-2: 2017 "Carbon black for rubber-Basic characteristics-Part 2: How to obtain specific surface area-Nitrogen adsorption method-Single point method". It is a value measured according to the method.
• the lower limit of CTAB of carbon black is not particularly limited, but from the viewpoint of reinforcing property, 30 m 2 / g or more is preferable, 40 m 2 / g or more is more preferable, and 50 m 2 / g or more is further preferable.
• CTAB is a value that correlates with the size of the particle size of carbon black, and the larger the CTAB, the smaller the particle size of carbon black.
• the CTAB of carbon black in the present specification is a value measured according to JIS K 6217-3: 2001 "Carbon black for rubber-Basic characteristics-Part 3: How to obtain specific surface area-CTAB adsorption method". is there.
• the content of the rubber component with respect to 100 parts by mass is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and 15 parts by mass or more, from the viewpoint of weather resistance and reinforcing property. More than parts by mass is particularly preferable. From the viewpoint of fuel efficiency, 100 parts by mass or less is preferable, 80 parts by mass or less is more preferable, and 60 parts by mass or less is further preferable.
• silica is not particularly limited, and for example, silica prepared by a dry method (anhydrous silica), silica prepared by a wet method (hydrous silica), and the like, which are common in the tire industry, can be used. Of these, hydrous silica prepared by a wet method is preferable because it has a large number of silanol groups. These silicas may be used alone or in combination of two or more.
• the nitrogen adsorption specific surface area (N 2 SA) of silica is preferably 140 m 2 / g or more, more preferably 150 m 2 / g or more, still more preferably 160 m 2 / g or more, from the viewpoint of fuel efficiency and wear resistance. 170 m 2 / g or more is particularly preferable. Further, from the viewpoint of fuel efficiency and workability, 350 m 2 / g or less is preferable, 300 m 2 / g or less is more preferable, and 250 m 2 / g or less is further preferable.
• the N 2 SA of silica in the present specification is a value measured by the BET method according to ASTM D3037-93.
• the content of the rubber component with respect to 100 parts by mass is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and 20 parts by mass or more from the viewpoint of fuel efficiency performance. Is particularly preferable. From the viewpoint of workability, 110 parts by mass or less is preferable, 100 parts by mass or less is more preferable, 90 parts by mass or less is further preferable, and 80 parts by mass or less is particularly preferable.
• the total content of silica and carbon black with respect to 100 parts by mass of the rubber component is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, further preferably 30 parts by mass or more, and 35 parts by mass or more from the viewpoint of reinforcing property. Especially preferable. From the viewpoint of workability, 200 parts by mass or less is preferable, 170 parts by mass or less is more preferable, 150 parts by mass or less is further preferable, and 130 parts by mass or less is particularly preferable.
• the content of silica in the total content of silica and carbon black is preferably 50% or more, more preferably 70% or more, still more preferably 80% or more.
• the content of the inorganic fiber material in the total content of the inorganic fiber material, silica, and carbon black is preferably 5% by mass or more, more preferably 8% by mass or more. This makes it easier to obtain the anisotropy effect of the inorganic fiber material.
• the content of the inorganic fiber material in the total content of the inorganic fiber material, silica, and carbon black is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less.
• the rubber composition contains a compounding agent generally used in the tire industry, for example, a plasticizer, a wax, an antiaging agent, a vulcanizing agent such as stearic acid, zinc oxide, and sulfur.
• a vulcanization accelerator or the like can be appropriately contained, and it is preferable to contain a plasticizer.
• a plasticizer By containing a plasticizer, the viscosity of the rubber is lowered at the time of mixing, and the inorganic fiber material is easily dispersed, so that the anisotropy and the breaking strength tend to be improved.
• the plasticizer include oil, resin components, liquid rubber and the like.
• oil examples include mineral oils such as aromatic oils, process oils, and paraffin oils. Above all, it is preferable to use process oil because it reduces the burden on the environment.
• the content of the rubber component with respect to 100 parts by mass is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and 7 parts by mass or more from the viewpoint of processability. Especially preferable. From the viewpoint of wear resistance, 80 parts by mass or less is preferable, 70 parts by mass or less is more preferable, 60 parts by mass or less is further preferable, and 50 parts by mass or less is particularly preferable.
• the oil content also includes the amount of oil contained in the oil spread rubber.
• the resin component is not particularly limited, and examples thereof include petroleum resin, terpene resin, rosin resin, and phenol resin commonly used in the tire industry.
• Examples of the petroleum resin include C5 petroleum resin, aromatic petroleum resin, C5C9 petroleum resin and the like. These resin components may be used alone or in combination of two or more.
• C5 petroleum resin refers to a resin obtained by polymerizing a C5 fraction.
• the C5 fraction include petroleum fractions having 4 to 5 carbon atoms such as cyclopentadiene, pentene, pentadiene, and isoprene.
• a dicyclopentadiene resin DCPD resin
• DCPD resin dicyclopentadiene resin
• aromatic petroleum resin refers to a resin obtained by polymerizing a C9 fraction, which may be hydrogenated or modified.
• the C9 fraction include petroleum fractions having 8 to 10 carbon atoms such as vinyltoluene, alkylstyrene, indene, and methyl indene.
• aromatic petroleum resins include, for example. Kumaron inden resin, Kumaron resin, inden resin, and aromatic vinyl-based resin are preferably used.
• aromatic vinyl resin a homopolymer of ⁇ -methylstyrene or styrene or a copolymer of ⁇ -methylstyrene and styrene is preferable because it is economical, easy to process, and has excellent heat generation. , A polymer of ⁇ -methylstyrene and styrene is more preferable.
• aromatic vinyl-based resin for example, those commercially available from Clayton, Eastman Chemical, etc. can be used.
• C5C9-based petroleum resin refers to a resin obtained by copolymerizing the C5 fraction and the C9 fraction, and may be hydrogenated or modified.
• Examples of the C5 fraction and the C9 fraction include the above-mentioned petroleum fraction.
• the C5C9-based petroleum resin for example, those commercially available from Tosoh Corporation, LUHUA, etc. can be used.
• the terpene-based resin is a polyterpene resin consisting of at least one selected from terpene compounds such as ⁇ -pinene, ⁇ -pinene, limonene, and dipentene; an aromatic-modified terpene resin made from the terpene compound and an aromatic compound; Examples thereof include terpene phenolic resins made from terpene compounds and phenolic compounds; and hydrogenated terpene resins (hydrogenated terpene resins).
• the aromatic compound used as a raw material for the aromatic-modified terpene resin include styrene, ⁇ -methylstyrene, vinyltoluene, and divinyltoluene.
• the phenolic compound which is a raw material of the terpene phenol resin include phenol, bisphenol A, cresol, xylenol and the like.
• the rosin-based resin is not particularly limited, and examples thereof include a natural resin rosin and a rosin-modified resin obtained by modifying it by hydrogenation, disproportionation, dimerization, esterification, or the like.
• the phenol-based resin is not particularly limited, and examples thereof include phenol formaldehyde resin, alkylphenol formaldehyde resin, alkylphenol acetylene resin, and oil-modified phenol formaldehyde resin.
• the content of the rubber component with respect to 100 parts by mass is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more.
• the content of the resin component is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 20 parts by mass or less.
• the liquid rubber is not particularly limited as long as it is a polymer in a liquid state at room temperature (25 ° C.), and is, for example, liquid butadiene rubber (liquid BR), liquid styrene butadiene rubber (liquid SBR), liquid isoprene rubber (liquid IR), and liquid. Examples thereof include styrene isoprene rubber (liquid SIR) and liquid farnesene rubber. These liquid rubbers may be used alone or in combination of two or more.
• the content of the rubber component with respect to 100 parts by mass is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more.
• the content of the liquid rubber is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 20 parts by mass or less.
• the content of the plasticizer with respect to 100 parts by mass of the rubber component is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more. , 7 parts by mass or more is particularly preferable.
• the content of the plasticizer is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, further preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less. If the content of the plasticizer exceeds 90 parts by mass, the entire rubber matrix is softened by the plasticizer, and sufficient reinforcing property by the inorganic fiber material cannot be obtained, so that anisotropy and fracture strength tend to decrease. ..
• the content of the rubber component with respect to 100 parts by mass is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and 1.5 parts by mass or more from the viewpoint of weather resistance of rubber. More preferred. Further, from the viewpoint of preventing whitening of the tire by bloom, 10 parts by mass or less is preferable, and 5 parts by mass or less is more preferable.
• the anti-aging agent is not particularly limited, and examples thereof include amine-based, quinolin-based, quinone-based, phenol-based, and imidazole-based compounds, and anti-aging agents such as carbamate metal salts.
• -(1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N' -Di-2-naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-bis (1,4-Dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3
• the content of the rubber component with respect to 100 parts by mass is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and 1.5 parts by mass, from the viewpoint of ozone crack resistance of the rubber. More than parts by mass is more preferable. Further, from the viewpoint of wear resistance performance and wet grip performance, 10 parts by mass or less is preferable, and 5 parts by mass or less is more preferable.
• the content of the rubber component with respect to 100 parts by mass is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and further preferably 1.5 parts by mass or more from the viewpoint of processability. preferable. Further, from the viewpoint of the vulcanization rate, 10 parts by mass or less is preferable, and 5 parts by mass or less is more preferable.
• the content of the rubber component with respect to 100 parts by mass is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and further preferably 1.5 parts by mass or more from the viewpoint of processability. preferable. Further, from the viewpoint of wear resistance performance, 10 parts by mass or less is preferable, and 5 parts by mass or less is more preferable.
• Sulfur is preferably used as the vulcanizing agent.
• the sulfur powdered sulfur, oil-treated sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur and the like can be used.
• the content of the rubber component with respect to 100 parts by mass is 0.5 parts by mass or more from the viewpoint of ensuring a sufficient vulcanization reaction and obtaining good grip performance and wear resistance.
• 1.0 part by mass or more is more preferable, and 1.5 parts by mass or more is further preferable.
• 5.0 parts by mass or less is preferable, 4.5 parts by mass or less is more preferable, and 4.0 parts by mass or less is further preferable.
• vulcanizing agents other than sulfur examples include Tackylol V-200 manufactured by Taoka Chemical Industry Co., Ltd., DURALINK HTS (1,6-hexamethylene-sodium dithiosulfate / dihydrate) manufactured by Flexis, and Rankses ( Examples thereof include vulcanizing agents containing sulfur atoms such as KA9188 (1,6-bis (N, N'-dibenzylthiocarbamoyldithio) hexane) manufactured by KA9188 Co., Ltd., and organic peroxides such as dicumyl peroxide. ..
• the vulcanization accelerator is not particularly limited, but is, for example, sulfenamide-based, thiazole-based, thiuram-based, thiourea-based, guanidine-based, dithiocarbamic acid-based, aldehyde-amine-based or aldehyde-ammonia-based, and imidazoline.
• Sulfenamide-based vulcanization accelerators and guanidine-based vulcanization accelerators are preferable, and these two types are used in combination, and among them, sulfenamide-based vulcanization accelerators and guanidine-based vulcanization accelerators are preferable from the viewpoint that desired effects can be obtained more preferably. It is more preferable to do so.
• Examples of the sulfenamide-based vulcanization accelerator include CBS (N-cyclohexyl-2-benzothiazolyl sulfenamide), TBBS (Nt-butyl-2-benzothiazolyl sulfenamide), and N-oxyethylene-. Examples thereof include 2-benzothiazolyl sulfenamide, N, N'-diisopropyl-2-benzothiazolyl sulfenamide, N, N-dicyclohexyl-2-benzothiazolyl sulfenamide and the like. Examples of the thiazole-based vulcanization accelerator include 2-mercaptobenzothiazole and dibenzothiazolyl disulfide.
• Examples of the thiuram-based vulcanization accelerator include tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetrabenzylthiuram disulfide (TBzTD) and the like.
• Examples of the guanidine-based vulcanization accelerator include 1,3-diphenylguanidine (DPG), dioltotrilguanidine, orthotrilbiguanidine and the like. These vulcanization accelerators may be used alone or in combination of two or more.
• the content of the rubber component with respect to 100 parts by mass is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, and further preferably 1.5 parts by mass or more.
• the content of the vulcanization accelerator with respect to 100 parts by mass of the rubber component is preferably 8 parts by mass or less, more preferably 7 parts by mass or less, and further preferably 6 parts by mass or less.
• the rubber composition of the present disclosure can be produced by a known method, for example, with a known kneader used in the general rubber industry such as a Banbury mixer, a kneader, and an open roll, and among the above-mentioned components, vulcanization is added. It can be produced by a method of kneading components other than the vulcanizing agent and the vulcanization accelerator, adding the vulcanizing agent and the vulcanization accelerator to the kneading agent, further kneading the mixture, and then vulcanizing. For example, in the kneading step, kneading is performed at 80 ° C. to 170 ° C. for 1 minute to 30 minutes, and in the vulcanization step, vulcanization is performed at 130 ° C. to 190 ° C. for 3 minutes to 20 minutes.
• a known kneader used in the general rubber industry such as a Banbury mixer,
• the rubber composition of the present disclosure realizes a supple response to an input (vibration) from the vertical direction of the tire at the time of rolling by orienting the inorganic fibers in the tire circumferential direction, and realizes a flexible response in the orientation direction (tire circumferential direction). It is considered that the responsiveness to the input at the time of steering is improved by increasing the rigidity of the tire. Therefore, for cap tread, base tread, sidewall, sidewall inner layer, inner liner, strip apex, bead apex, clinch apex, bead reinforcement layer, insulation, insert, etc. that are continuous in the tire circumferential direction. It can be preferably used, and it is considered that the same effect can be obtained in either case.
• tire internal members such as base tread, sidewall inner layer, inner liner, strip apex, bead apex, bead reinforcing layer, insulation, and insert.
• tire internal members such as base tread, sidewall inner layer, inner liner, strip apex, bead apex, bead reinforcing layer, insulation, and insert.
• the "internal member” is not limited to the above-mentioned member, but refers to a tire member other than the member that forms the outer surface when the tire is attached to the rim and filled with air.
• the tire of the present disclosure can be manufactured by a usual method using the above-mentioned rubber composition. That is, an unvulcanized rubber composition obtained by blending each of the above components with the rubber component as necessary is extruded according to the shape of the corresponding tire member, and the inorganic fiber material is oriented in the columnar direction. Obtain the composition. Then, the rubber composition is bonded together with other tire members on a tire molding machine so that the inorganic fiber material is oriented in the tire circumferential direction, and molded by a usual method to form an unvulcanized tire. A tire can be manufactured by heating and pressurizing this unvulcanized tire in a vulcanizer.
• the tire of the present disclosure may be a pneumatic tire or a non-pneumatic tire. Further, it is suitable for competition tires, passenger car tires, large passenger car tires, large SUV tires, and motorcycle tires, and can be used as summer tires, winter tires, and studless tires, respectively.
• NR TSR20 BR: Ube Industries, Ltd. Ubepol BR150B (cis content: 97%)
• SBR1 Toughden 3830 manufactured by Asahi Kasei Corporation (unmodified S-SBR, styrene content: 32% by mass, oil-extended product containing 37.5 parts by mass of oil with respect to 100 parts by weight of rubber component)
• SBR2 Asahi Kasei Corporation's Asaprene 1205 (unmodified S-SBR, styrene content: 25% by mass)
• Carbon Black Show Black N220 manufactured by Cabot Japan Co., Ltd.
• Inorganic fiber material 1 Mosheidi manufactured by Ube Material Industries Ltd. (basic magnesium sulfate fiber, average fiber diameter: 500 to 1000 nm, average fiber length: 8 to 30 ⁇ m)
• Inorganic fiber material 2 Sepiolite (average fiber diameter: 5 to 30 nm, average fiber length: 0.2 to 2.0 ⁇ m)
• Inorganic fiber material 3 Zonoheidi manufactured by Ube Material Industries Ltd.
• Silane coupling agent Si69 (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Evonik Degussa Oil: Process oil X-140 manufactured by ENEOS Co., Ltd.
• Anti-aging agent Ozonone 6C (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine) manufactured by Seiko Kagaku Co., Ltd.
• Stearic acid Stearic acid "Camellia” manufactured by NOF CORPORATION
• Zinc oxide Zinc oxide No.
• Examples and Comparative Examples In accordance with the formulation shown in Tables 1 and 2, materials other than sulfur and the vulcanization accelerator were kneaded using a Banbury mixer manufactured by Kobe Steel, Ltd. to obtain a kneaded product. Next, sulfur and a vulcanization accelerator were added to the obtained kneaded product and kneaded using an open roll to obtain an unvulcanized rubber composition. From the obtained unvulcanized rubber composition, a sheet having a thickness of 0.5 mm was prepared by an open roll. The obtained unvulcanized rubber sheets were stacked to form a 1.5 mm sheet, and press vulcanized at 150 ° C. for 15 minutes to prepare a test vulcanized rubber sheet.
• the unvulcanized rubber composition was extruded according to the shape of the sidewall inner layer with an extruder equipped with a base having a predetermined shape to obtain a sidewall inner layer in which the inorganic fiber material was oriented in the columnar direction. .. Then, the sidewall inner layer is bonded together with other tire members on the tire molding machine so that the inorganic fiber material is oriented in the tire circumferential direction to form an unvulcanized tire, and pressed for 12 minutes under the condition of 170 ° C. A tire (size: 205 / 65R15) was manufactured by vulcanization.
• the rubber composition of the present disclosure containing the inorganic fiber material and the coupling agent can highly achieve both fracture strength and anisotropy. Further, it can be seen that the tire of the present disclosure provided with the tire internal member composed of the rubber composition has improved riding comfort and steering stability in a well-balanced manner.

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• 2020
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