[go: up one dir, main page]

WO2016140217A1 - Composition de caoutchouc pour pneus, et pneu - Google Patents

Composition de caoutchouc pour pneus, et pneu Download PDF

Info

Publication number
WO2016140217A1
WO2016140217A1 PCT/JP2016/056231 JP2016056231W WO2016140217A1 WO 2016140217 A1 WO2016140217 A1 WO 2016140217A1 JP 2016056231 W JP2016056231 W JP 2016056231W WO 2016140217 A1 WO2016140217 A1 WO 2016140217A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber composition
diene polymer
fatty acid
mass
rubber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/056231
Other languages
English (en)
Japanese (ja)
Inventor
健二 中谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bridgestone Corp
Original Assignee
Bridgestone Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bridgestone Corp filed Critical Bridgestone Corp
Publication of WO2016140217A1 publication Critical patent/WO2016140217A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
    • B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/22—Component parts, details or accessories; Auxiliary operations
    • B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
    • B29B7/286—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control measuring properties of the mixture, e.g. temperature, density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
    • B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
    • B29B7/18—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/183—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft having a casing closely surrounding the rotors, e.g. of Banbury type
    • 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 tire rubber composition, and more particularly to a tire rubber composition and a tire suitable for tires used for passenger cars, trucks, buses and the like.
  • an inorganic filler such as silica As a method for obtaining such a rubber composition having low exothermicity, a method using an inorganic filler such as silica as a filler is known.
  • an inorganic filler such as silica is blended in an inorganic filler-containing rubber composition, the inorganic filler, particularly silica, aggregates in the rubber composition (aggregation due to hydroxyl groups on the silica surface).
  • silane coupling agents are used. Therefore, various attempts have been made for the purpose of further enhancing the activity of the coupling function of the silane coupling agent in order to suitably solve the above problems by blending the silane coupling agent.
  • a rubber component (A) containing a modified conjugated diene polymer obtained by using a modifier containing a functional group having an affinity for silica, a filler containing an inorganic filler (B), and silane coupling Rubber composition comprising agent (C) and at least one accelerator (D) selected from guanidines, sulfenamides, thiazoles, thiurams, glycerin fatty acid ester compositions, thioureas, dithiocarbamic acids and xanthogenic acids
  • the rubber composition is kneaded in a plurality of stages, and in the first stage of kneading, all or part of the rubber component (A), the inorganic filler (B), the silane coupling agent (
  • a method for producing a rubber composition characterized in that all or part of C) and the accelerator (D) are added and kneaded is known (for example, see Patent Document 1 by the present applicant). .
  • Patent Document 1 A method for
  • a method for obtaining a rubber composition having low exothermicity as a method of further dispersing silica using a modified polymer, for example, as a modified polymer, a conjugated diene monomer is polymerized or copolymerized using an initiator.
  • a modified polymer obtained by modifying the active end of the polymer with a modifier for the polymer but if these modified polymers are used, the viscosity of the unvulcanized rubber increases. There is a problem.
  • a filler that is 40% by weight or more of white rubber with respect to 100 parts by weight of a rubber containing 90 parts by weight or more of a diene rubber, and 0.2 to 8 nonionic surfactants 2 parts by weight of a rubber composition with improved chargeability (see, for example, Patent Document 2), 2) at least one polymer selected from the group of diene rubbers, and 100 parts by weight of rubber in the rubber composition
  • a rubber composition for a tire tread comprising 5 to 100 parts by weight of finely powdered precipitated silicic acid, 0 to 80 parts by weight of carbon black, and 0.5 to 20 parts by weight of at least one non-aromatic viscosity reducing substance.
  • non-aromatic viscosity-reducing substance is glycerin-monostearate, sorbitan-monostearate, sorbitan-monooleate and trimethylolpropane (2-ethyl-2-hydride).
  • a rubber composition for tire treads characterized in that it is at least one substance selected from the group consisting of (roxymethyl-1,3-propanediol) (for example, see Patent Document 3), 3) natural rubber and / or
  • a rubber composition comprising a specific amount of silica and a glycerol fatty acid monoester having 8 to 28 carbon atoms in combination with at least one rubber component selected from diene-based synthetic rubber (see, for example, Patent Document 4) It has been known.
  • Patent Document 2 contains a description of the effect of preventing charging that is different from the present invention, which may occur at the time of silica compounding, by blending glycerin fatty acid monoester in one of the Examples. There is no description or suggestion about the viscosity reducing effect.
  • the said patent document 3 is disclosing the proximity
  • the present invention intends to solve the above-described problems of the prior art, and even if a modified polymer is used for the rubber component, the filler containing silica is highly advanced without deteriorating the viscosity of the unvulcanized rubber.
  • An object of the present invention is to provide a rubber composition for tires which is excellent in wear resistance and low loss properties, and has improved workability and workability, and a tire using this rubber composition.
  • the present inventor has, as a diene polymer, a rubber component (A) containing a diene polymer having specific properties, and an inorganic filler (B) having silica.
  • an activator (D) comprising at least one selected from a filler, a silane coupling agent (C), a vulcanization accelerator, a thiourea, and a thiadiazole, and a carbon number of 8 to
  • a first composition comprising a glycerin fatty acid ester composition (E) having a glycerin fatty acid monoester content of 28 exceeding a specific value is prepared, and a first composition is prepared by kneading the first mixture.
  • Manufacturing method With tire rubber composition produced by, it found that the rubber composition for a tire of the above objects and tire is obtained, it was accomplished the present invention.
  • the diene polymer has at least one modified functional group having at least three modified functional groups capable of interacting with silica only in the range of 1 ⁇ 4 of the total chain length from the terminal.
  • Rubber component (A) containing a diene polymer having a monomer structure of a diene polymer in between, a filler containing an inorganic filler (B) having silica, a silane coupling agent (C), and vulcanization Glycerol having a glycerin fatty acid monoester content of more than 85% by mass of an activating agent (D) consisting of at least one selected from accelerators, thioureas and thiadiazoles, and a glycerol fatty acid monoester having 8 to 28 carbon atoms
  • Preparing a first mixture comprising a fatty acid ester composition (E) and preparing a preliminary composition by kneading the first mixture;
  • Preparing a second mixture Preparing a first mixture comprising
  • the diene polymer is a molecular chain comprising a step of forming a molecular chain of a diene polymer having no modified functional group, and a monomer structure of the modified functional group and the diene polymer. And having at least one modified functional group capable of interacting with the silica only in the range of 1 ⁇ 4 of the total chain length from the terminal.
  • the rubber according to any one of (1) to (6) above, wherein the content of the diene polymer in the rubber component (A) is 10% by mass or more. Composition.
  • the activator (D) is a guanidine.
  • the glycerin fatty acid ester composition (E) described above is characterized in that the content of glycerin fatty acid monoester having 8 to 28 carbon atoms is more than 95% by mass.
  • the amount of the glycerin fatty acid ester composition (E) is 0.2 to 7 parts by mass with respect to 100 parts by mass of the rubber component (A).
  • a tire comprising the tire rubber composition according to any one of (1) to (12) above as a tread member.
  • the filler containing silica is highly dispersed without deteriorating the viscosity of the unvulcanized rubber, and it is excellent in wear resistance and low loss, and greatly improves workability and workability.
  • a tire rubber composition and a tire using the tire rubber composition for a tread member are provided.
  • the rubber composition for tires of the present invention as a diene polymer, has three or more modified functional groups capable of interacting with silica only in the range of 1 ⁇ 4 of the total chain length from the end, Rubber component (A) containing a diene polymer having a monomer structure of a diene polymer between at least one of the modified functional groups, a filler containing an inorganic filler (B) having silica, and a silane coupling agent (C), and all or part of an activator (D) consisting of at least one selected from vulcanization accelerators, thioureas, and thiadiazoles, and a glycerol fatty acid monoester content of 8 to 28 carbon atoms.
  • Rubber component (A) containing a diene polymer having a monomer structure of a diene polymer between at least one of the modified functional groups, a filler containing an inorganic filler (B) having silica, and a silane coupling agent (C
  • a first mixture containing a glycerin fatty acid ester composition (E) in excess of 85% by mass is prepared, and a preliminary composition is prepared by kneading the first mixture, and a first step is added to the preliminary composition.
  • Sulfur agent (F) A second step of preparing a rubber composition by preparing an added second mixture and kneading the second mixture, wherein the rubber composition is produced by a method for producing a rubber composition. .
  • the rubber component contained in the rubber composition of the present invention has a diene polymer.
  • the diene polymer has at least one modified functional group capable of interacting with the silica only in a range of 1 ⁇ 4 of the total chain length from the terminal, and at least one of the modified polymer. It has a monomer structure of a diene polymer between functional groups. In this diene polymer, the reason why the modified functional group is arranged only in the range of 1 ⁇ 4 of the total chain length from the end is that an effect of dispersing silica more efficiently can be obtained.
  • the aggregate of silica can be efficiently broken by having three or more modified functional groups and having a monomer structure of a diene polymer between at least one modified functional group. .
  • a more remarkable effect can be obtained as compared with a diene polymer having only individual characteristics.
  • the diene polymer may be a modified diene copolymer or a modified diene homopolymer.
  • a copolymer of a diene monomer and an aromatic vinyl compound or a homopolymer of a diene monomer is preferable, and 60 to 100% by weight of a diene monomer and 0 to 40% by weight of a diene monomer are preferable.
  • a polymer (homopolymer) or copolymer obtained by polymerizing an aromatic vinyl compound is more preferable. This is because the rubber composition can be further improved in low loss, fracture characteristics, and wear resistance.
  • examples of the aromatic vinyl compound as a monomer include styrene, ⁇ -methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, and 2,4,6- Examples thereof include trimethylstyrene, and among these, styrene is particularly preferable.
  • aromatic vinyl compounds may be used alone or in combination of two or more.
  • the modified functional group capable of interacting with the silica forms a covalent bond between the functional group and the silica surface or an intermolecular force weaker than the covalent bond (ion-dipolar).
  • This is a functional group capable of forming an electromagnetic force acting between molecules such as dipole interaction, dipole-dipole interaction, hydrogen bond, van der Waals force and the like.
  • a nitrogen-containing functional group, a silicon-containing functional group, an oxygen-containing functional group, etc. are mentioned.
  • the state having three or more modified functional groups only in the range of 1/4 of the total chain length from the end means that the diene polymer has a range of 1/4 from the end (range of 25% from the end).
  • the end of the diene polymer means at least one of the ends, and the range having the modified functional group is 1 of the total chain length from one end (tip) of the diene polymer. / 4 range, or may be in the range of 1/4 of the total chain length from both ends.
  • only one of the ends is It is preferable that it exists in.
  • the state having a monomer structure of a diene polymer between at least one of the modified functional groups is only in a range of 1 ⁇ 4 of the total chain length from the end of the diene polymer.
  • the monomer structure of the diene polymer between the modified functional group and the modified functional group eg, 1,3-butadiene when the diene polymer is polybutadiene
  • a styrene-butadiene copolymer it means styrene and / or 1,3-butadiene
  • the modified functional groups are not bonded to each other.
  • the monomer structure of the diene polymer is present between all the modified functional groups (that is, all the modified functional groups in the diene polymer are directly bonded to each other). More preferred).
  • the polymerization method for obtaining the diene polymer may be any of anionic polymerization, coordination polymerization, and emulsion polymerization.
  • the modifying agent may be a modifying agent that reacts with the polymerization active terminal of anionic polymerization or coordination polymerization, or may be an amide portion of a lithium amide compound used as a polymerization initiator.
  • a modifier may be copolymerized as a monomer.
  • the molecular weight of the diene polymer is not particularly limited, but good fracture resistance and wear resistance can be obtained by setting the peak molecular weight to 50,000 or more, and good processing by setting the molecular weight to 700,000 or less. From the viewpoint of obtaining the properties, it is preferably 50,000 to 700,000. Further, in order to obtain good fracture resistance and wear resistance while obtaining good workability, 100,000 to 350,000 is desirable.
  • the content of the diene polymer in the rubber component is preferably 10% by mass or more.
  • the content of the diene polymer in the rubber component is less than 10% by mass, the effect of improving the dispersibility of the filler is small, and the effect of improving the low loss property, fracture characteristics, and wear resistance of the rubber composition. Because it is small.
  • the modifier is a modifier containing a functional group having an interaction property with silica, and is preferably a modifier having at least one atom selected from a silicon atom, a nitrogen atom and an oxygen atom.
  • the modifier is preferably an alkoxysilane compound.
  • the alkoxysilane compound is not particularly limited, but is more preferably an alkoxysilane compound represented by the following general formula (I).
  • R 1 and R 2 each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
  • a is an integer of 0 to 2
  • the OR 2 there is a plurality the plurality of OR 2 may be the same or different from each other, also in the molecule active proton is not included.
  • alkoxysilane compound represented by the general formula (I) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane.
  • the modifier may be a hydrocarbyloxysilane compound.
  • the hydrocarbyloxysilane compound is preferably a hydrocarbyloxysilane compound represented by the following general formula (II).
  • a 1 is a divalent group that forms a cyclic structure by bonding to Si.
  • R 21 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 n1 is 2 In these cases, they may be the same or different, and R 23 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.
  • R 22 is a monovalent aliphatic or alicyclic group having 1 to 20 carbon atoms A hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, both of which are nitrogen atoms and / Or may contain a silicon atom, in the case of n2 is 2 or more, which may be the same or different from each other, or forms a ring together, R 24 is C 1 -C A divalent aliphatic or alicyclic hydrocarbon group of ⁇ 20 or a divalent aromatic hydrocarbon group of 6 to 18 carbon atoms, and when n4 is 2 or more, they may be the same or different.
  • a trimethylsilyl group or a tert-butyldimethylsilyl group is preferable, and a trimethylsilyl group is particularly preferable.
  • a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms means “a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or 3 to 20 carbon atoms”.
  • the hydrocarbyloxysilane compound represented by the general formula (II) is more preferably a hydrocarbyloxysilane compound represented by the following general formula (III).
  • a 2 is NRa (Ra is 1 A trivalent silyl group or a tert-butyldimethylsilyl group, particularly preferably a trimethylsilyl group), or a sulfur group, a valent hydrocarbon group, a hydrolyzable group or a nitrogen-containing organic group.
  • R 25 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
  • R 27 is a group having 1 to 20 carbon atoms.
  • R 26 represents 1 to 20 monovalent aliphatic or alicyclic hydrocarbons
  • R 28 is the same or different from each other, or together forms a ring
  • R 28 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent hydrocarbon
  • the hydrocarbyloxysilane compound represented by the general formula (III) is more preferably a hydrocarbyloxysilane compound represented by the following general formula (IV) or (V).
  • R 35 is a monovalent aliphatic or alicyclic carbon atom having 1 to 20 carbon atoms.
  • R 36 is a divalent fat having 1 to 20 carbon atoms.
  • R 37 represents a dimethylaminomethyl group, a dimethylaminoethyl group, a diethylaminomethyl group, a diethylaminoethyl group, a methylsilyl (methyl ) Aminomethyl group, methylsilyl (methyl) aminoethyl group, methylsilyl (ethyl) aminomethyl group, methylsilyl (ethyl) aminoethyl group, dimethylsilylaminomethyl group, dimethylsilylaminoethyl group, monovalent monovalent C 1-20 An aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r1 is 2 or more, they are the same or different.
  • R 38 is a hydrocarbyloxy group, monovalent 1-20 carbon atoms aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms having 1 to 20 carbon atoms Yes, when r2 is 2, they may be the same or different.
  • the modifier is preferably a hydrocarbyloxysilane compound having two or more nitrogen atoms represented by the following general formula (VI) or (VII).
  • TMS is a trimethylsilyl group
  • R 40 is a trimethylsilyl group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic group having 6 to 18 carbon atoms.
  • R 41 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 group having 6 to 18 carbon atoms.
  • R 42 is a hydrocarbon group
  • R 42 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.
  • TMS is a trimethylsilyl group
  • R 43 and R 44 are each independently a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a group having 6 to 18 carbon atoms.
  • a divalent aromatic hydrocarbon group, R 45 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;
  • the plurality of R 45 may be the same or different.
  • the hydrocarbyloxysilane compound represented by the general formula (II) is a hydrocarbyloxysilane compound represented by the following general formula (VIII).
  • r1 + r2 3 (where r1 is an integer of 0 to 2, r2 is an integer of 1 to 3), TMS is a trimethylsilyl group, and R 46 is a carbon number.
  • a plurality of R 47 or R 48 may be the same or different.
  • the modifier is preferably a hydrocarbyloxysilane compound represented by the following general formula (IX).
  • X is a halogen atom
  • R 49 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon having 6 to 18 carbon atoms.
  • R 50 and R 51 are each independently a hydrolyzable group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic carbon group having 6 to 18 carbon atoms.
  • R 50 and R 51 are bonded to form a divalent organic group, and R 52 and R 53 are each independently a halogen atom, a hydrocarbyloxy group, or a carbon number of 1 to 20 A monovalent aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
  • R 50 and R 51 are preferably hydrolyzable groups, and the hydrolyzable group is preferably a trimethylsilyl group or a tert-butyldimethylsilyl group, and particularly preferably a trimethylsilyl group.
  • hydrocarbyloxysilane compounds represented by the general formulas (II) to (IX) are preferably used as a modifier when the modified conjugated diene polymer is produced by anionic polymerization.
  • the hydrocarbyloxysilane compounds represented by the general formulas (II) to (IX) are preferably alkoxysilane compounds.
  • a suitable modifier for modifying the diene polymer by anionic polymerization specifically, 3,4-bis (trimethylsilyloxy) -1-vinylbenzene, 3,4-bis (trimethylsilyloxy) ) At least one compound selected from benzaldehyde, 3,4-bis (tert-butyldimethylsilyloxy) benzaldehyde, 2-cyanopyridine, 1,3-dimethyl-2-imidazolidinone and 1-methyl-2-pyrrolidone Is mentioned.
  • the modifier is preferably an amide portion of a lithium amide compound used as a polymerization initiator in anionic polymerization.
  • lithium amide compound examples include lithium hexamethylene imide, lithium pyrrolidide, lithium piperide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethylamide, lithium diethylamide, lithium dibutylamide, lithium dipropylamide, lithium diheptylamide. , Lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiverazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium ethylbenzylamide and lithium methylphenethylamide A preferred example is at least one compound.
  • the modifying agent that becomes the amide portion of lithium hexamethylene imide is hexamethyleneimine
  • the modifying agent that becomes the amide portion of lithium pyrrolidide is pyrrolidine
  • the modifying agent that becomes the amide portion of lithium piperide is piperidine.
  • At least one compound selected from 2-cyanopyridine and 3,4-ditrimethylsilyloxybenzaldehyde is preferably exemplified.
  • at least one compound selected from 3,4-ditrimethylsilyloxybenzaldehyde and 4-hexamethyleneiminoalkylstyrene is preferably exemplified.
  • the modifier preferably used in these emulsion polymerizations is preferably copolymerized as a monomer containing nitrogen atoms and / or silicon atoms during emulsion polymerization.
  • the diene polymer preferably has a peak molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of 50,000 to 700,000.
  • GPC gel permeation chromatography
  • the diene polymer preferably has a glass transition point (Tg) measured by a differential scanning calorimeter (DSC) of 0 ° C. or less.
  • the rubber component may be a natural rubber (NR), a styrene-butadiene copolymer (SBR), a polybutadiene rubber (BR), a poly, in addition to the diene polymer described above.
  • IR isoprene rubber
  • IIR butyl rubber
  • ethylene-propylene copolymer etc.
  • these rubber components may be used alone or as a blend of two or more.
  • the content of the diene polymer in the rubber component is preferably 10% by mass or more.
  • the content of the diene polymer in the rubber component is less than 10% by mass, the effect of improving the dispersibility of the filler is small, and the effect of improving the low loss property, fracture characteristics, and wear resistance of the rubber composition. Because it is small.
  • a step of forming a molecular chain of a diene polymer having no modified functional group (a range of 3/4 of the total chain length from the end of the diene polymer), and
  • the above-mentioned modified diene system is obtained by passing through a step of forming a molecular chain comprising the functional group and the monomer structure of the diene polymer (in the range of 1/4 of the total chain length from the end of the diene polymer).
  • a polymer can be produced. Which is the step of forming the molecular chain of the diene polymer not having the modified functional group and the step of forming the molecular chain composed of the functional group and the monomer structure of the diene polymer? You may go first.
  • examples of the formation of a molecular chain composed of the functional group and the monomer structure of the diene polymer include the following methods (1) to (4).
  • a method of alternately charging a compound having (4) A monomer component of the diene polymer and a site that can be copolymerized with the monomer component and can be introduced with a modified functional group by chemically reacting with the modified functional group-containing compound. And a compound having the same at the same time.
  • all the modified functional groups have a monomer structure of the diene polymer (that is, all the modified functional groups in the diene polymer are directly
  • the above-described method 1 or 3 is preferable from the viewpoint that a structure that is not bonded) can be more reliably formed, and the above-described method 2 or 4 is preferable in order to shorten the time required for production and increase productivity.
  • Examples of the compound having a site which can be copolymerized with the monomer component of the diene polymer and can introduce a modified functional group by chemically reacting with the modified functional group-containing compound include p -Methylstyrene and the like.
  • silica and inorganic compounds represented by the following general formula (X) can be used as the filler containing the inorganic filler (B) having silica used in the rubber composition for tires of the present invention.
  • M 1 is a metal selected from the group consisting of aluminum, magnesium, titanium, calcium, and zirconium, oxides or hydroxides of these metals, and hydrates thereof, Or at least one selected from carbonates of these metals, and a, x, y and z are each an integer of 1 to 5, an integer of 0 to 10, an integer of 2 to 5, and an integer of 0 to 10 is there.
  • the inorganic compound when both x and z are 0, is at least one metal selected from aluminum, magnesium, titanium, calcium and zirconium, these metal oxides or metal water. Oxides as well as hydrates or carbonates of these metals.
  • silica is preferable from the viewpoint of achieving both low rolling properties and wear resistance.
  • Any commercially available silica can be used, among which wet silica, dry silica, and colloidal silica are preferably used, and wet silica is particularly preferably used.
  • the BET specific surface area (measured according to ISO 5794/1) of silica is preferably 40 to 350 m 2 / g. Silica having a BET surface area within this range has an advantage that both rubber reinforcement and dispersibility in a rubber component can be achieved.
  • silica having a BET surface area in the range of 80 to 350 m 2 / g is more preferable, and silica having a BET surface area in the range of 120 to 350 m 2 / g is particularly preferable.
  • Examples of the inorganic compound represented by the general formula (X) include alumina (Al 2 O 3 ) such as ⁇ -alumina and ⁇ -alumina, and alumina monohydrate (Al 2 O 3 .H) such as boehmite and diaspore. 2 O), Gibbsite, Bayerite, etc.
  • alumina Al 2 O 3
  • Al 2 O 3 .H alumina monohydrate
  • boehmite and diaspore. 2 O Gibbsite, Bayerite, etc.
  • M 1 in the general formula (X) is at least one selected from aluminum metal, aluminum oxide or hydroxide, hydrates thereof, and aluminum carbonate.
  • These inorganic compounds represented by the general formula (X) may be used alone or in combination of two or more.
  • the average particle size of these inorganic compounds is preferably in the range of 0.01 to 10 ⁇ m, more preferably in the range of 0.05 to 5 ⁇ m, from the viewpoint of kneading workability, wear resistance, and wet grip performance.
  • the inorganic filler (B) in the present invention may be used alone or in combination with silica and one or more inorganic compounds represented by the general formula (X).
  • the content of the silica is preferably 60 to 250 parts by mass, more preferably 70 to 150 parts by mass, and 75 to 120 parts by mass with respect to 100 parts by mass of the rubber component. Is particularly preferred.
  • the content of the silica is less than 60 parts by mass, since the amount of silica is small, there is a possibility that the effect of improving the fracture characteristics and wear resistance may not be sufficiently obtained, and when the content exceeds 250 parts by mass. Further, since the amount of silica is too large, the elongation and processability of the rubber composition may be deteriorated.
  • the filler of the tire rubber composition according to the present invention may contain carbon black in addition to the inorganic filler (B) described above, if desired.
  • carbon black is not particularly limited.
  • the nitrogen adsorption specific surface area (N 2 SA, measured according to JIS K 6217-2: 2001) is preferably 30 to 250 m 2 / g.
  • This carbon black may be used individually by 1 type, and may be used in combination of 2 or more type. In the present invention, carbon black is not included in the inorganic filler (B).
  • the inorganic filler (B) of the tire rubber composition according to the present invention is preferably used in an amount of 20 to 120 parts by mass with respect to 100 parts by mass of the rubber component (A). If it is 20 parts by mass or more, it is preferable from the viewpoint of securing wet performance, and if it is 120 parts by mass or less, it is preferable from the viewpoint of improving low heat generation. Further, it is more preferable to use 30 to 100 parts by mass.
  • the filler of the tire rubber composition according to the present invention is preferably used in an amount of 20 to 150 parts by mass with respect to 100 parts by mass of the rubber component (A).
  • the inorganic filler (B) is preferably 40% by mass or more from the viewpoint of achieving both wet performance and low heat build-up, and more preferably 70% by mass or more.
  • the silane coupling agent (C) used in the tire rubber composition of the present invention is not particularly limited, and various general-purpose silane coupling agents can be used.
  • the following general formulas (XI) and (XII) are used.
  • the compound is one or more selected from the group consisting of the compounds represented.
  • the tire rubber composition according to the present invention is further excellent in workability at the time of rubber processing, and the tire rubber composition having better wear resistance. Will be obtained.
  • the following general formulas (XI) and (XII) will be described in order.
  • R 1 s may be the same or different and each is a linear, cyclic or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkoxyalkyl group having 2 to 8 carbon atoms.
  • the groups R 2 may be the same or different, each of which is a linear, cyclic or branched alkyl group having 1 to 8 carbon atoms, and R 3 may be the same or different, each having a straight chain of 1 to 8 carbon atoms.
  • silane coupling agent (C) represented by the general formula (XI) include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, and bis (3-methyl Dimethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide, bis (3-methyldimethoxysilylpropyl) Disulfide, bis (2-triethoxysilylethyl) disulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide, bis (3-methyldimethoxysilylpropyl) trisulfide Bis (2-trie
  • R 4 s may be the same or different and are each a linear, cyclic or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkoxy group having 2 to 8 carbon atoms.
  • An alkyl group, R 5 may be the same or different, each is a linear, cyclic or branched alkyl group having 1 to 8 carbon atoms, and R 6 may be the same or different and each has 1 to 8 linear or branched alkylene groups,
  • R 7 is represented by the general formulas (—S—R 8 —S—), (—R 9 —S m1 —R 10 —) and (—R 11 —S m2 —R 12).
  • R 8 ⁇ R 13 may be the same or different, each a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms), 3 carbon atoms
  • a divalent alicyclic hydrocarbon group of ⁇ 20, a divalent aromatic group or a divalent organic group containing a hetero element other than sulfur and oxygen, m1, m , M3 may be the same or different and each is an average value of 1 or more and less than 4.
  • k may be the same or different, and each is an average value of 1 to 6
  • s and t are They may be the same or different and each has an average value of 0 to 3, provided that both s and t are not 3. ]
  • silane coupling agent (C) represented by the general formula (XII), Average composition formula (CH 3 CH 2 O) 3 Si— (CH 2 ) 3 —S 2 — (CH 2 ) 6 —S 2 — (CH 2 ) 3 —Si (OCH 2 CH 3 ) 3 , Average composition formula (CH 3 CH 2 O) 3 Si— (CH 2 ) 3 —S 2 — (CH 2 ) 10 —S 2 — (CH 2 ) 3 —Si (OCH 2 CH 3 ) 3 , Average composition formula (CH 3 CH 2 O) 3 Si— (CH 2 ) 3 —S 3 — (CH 2 ) 6 —S 3 — (CH 2 ) 3 —Si (OCH 2 CH 3 ) 3 , Average composition formula (CH 3 CH 2 O) 3 Si— (CH 2 ) 3 —S 4 — (CH 2 ) 6 —S 4 — (CH 2 ) 3 —Si (OCH 2 CH 3 ) 3 , Average composition formula (
  • the silane coupling agent (C) used in the present invention is particularly preferably a compound represented by the general formula (XI) among the compounds represented by the general formulas (XI) and (XII). This is because the activator (D) such as a vulcanization accelerator tends to activate the polysulfide bond site that reacts with the rubber component (A).
  • a silane coupling agent (C) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the silane coupling agent (C) used in the present invention is preferably 1 to 20% by mass of the inorganic filler (B). If the amount is less than 1% by mass, the effect of improving the low heat build-up of the tire rubber composition is difficult to be exhibited. On the other hand, if the amount exceeds 20% by mass, the cost of the tire rubber composition becomes excessive and the economic efficiency is lowered. is there. Further, it is more preferably 3 to 20% by mass of the inorganic filler (B), and particularly preferably 4 to 10% by mass of the inorganic filler (B).
  • Activators (D) such as vulcanization accelerators
  • guanidines examples include 1,3-diphenylguanidine (DPG), 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, dicatechol borate di-o-tolylguanidine salt, 1,3 -Di-o-cumenyl guanidine, 1,3-di-o-biphenyl guanidine, 1,3-di-o-cumenyl-2-propionyl guanidine, and the like can be mentioned.
  • DPG 1,3-diphenylguanidine
  • 1,3-di-o-tolylguanidine 1-o-tolylbiguanide
  • dicatechol borate di-o-tolylguanidine salt 1,3 -Di-o-cumenyl guanidine
  • 1,3-di-o-biphenyl guanidine 1,3-di-o-cumenyl-2-propionyl guanidine
  • 1,3-diphenyl guanidine, 1,3- Di-o-tolylguanidine and 1-o-tolylbiguanide are preferred because of their high reactivity, and 1,3-diphenylguanidine (DPG) is particularly preferred because of its higher reactivity.
  • sulfenamides examples include N-cyclohexyl-2-benzothiazolylsulfenamide, N, N-dicyclohexyl-2-benzothiazolylsulfenamide, N-tert-butyl-2-benzo Thiazolylsulfenamide, N-oxydiethylene-2-benzothiazolylsulfenamide, N-methyl-2-benzothiazolylsulfenamide, N-ethyl-2-benzothiazolylsulfenamide, N-propyl- 2-benzothiazolylsulfenamide, N-butyl-2-benzothiazolylsulfenamide, N-pentyl-2-benzothiazolylsulfenamide, N-hexyl-2-benzothiazolylsulfenamide, N- Pentyl-2-benzothiazolylsulfenamide, N-octyl- -Benzothiazolyls
  • thiazoles examples include 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, zinc salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2- (N , N-diethylthiocarbamoylthio) benzothiazole, 2- (4′-morpholinodithio) benzothiazole, 4-methyl-2-mercaptobenzothiazole, di- (4-methyl-2-benzothiazolyl) disulfide, 5-chloro- 2-mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, 2-mercapto-6-nitrobenzothiazole, 2-mercapto-naphtho [1,2-d] thiazole, 2-mercapto-5-methoxybenzothiazole, 6-amino -2-Merka DOO benzothiazole and the like. Of these, 2-mercaptobenzothiazole (
  • thiurams examples include tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrapropyl thiuram disulfide, tetraisopropyl thiuram disulfide, tetrabutyl thiuram disulfide, tetrapentyl thiuram disulfide, tetrahexyl thiuram disulfide, tetraheptyl thiuram disulfide, Tetraoctyl thiuram disulfide, tetranonyl thiuram disulfide, tetradecyl thiuram disulfide, tetradodecyl thiuram disulfide, tetrastearyl thiuram disulfide, tetrabenzyl thiuram disulfide, tetrakis (2-ethylhex
  • dithiocarbamates examples include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dipropyldithiocarbamate, zinc diisopropyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dipentyldithiocarbamate, zinc dihexyldithiocarbamate, and diheptyl.
  • Zinc dithiocarbamate zinc dioctyldithiocarbamate, zinc di (2-ethylhexyl) dithiocarbamate, zinc didecyldithiocarbamate, zinc diddecyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, Zinc dibenzyldithiocarbamate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, dip Copper pyrdithiocarbamate, copper diisopropyldithiocarbamate, copper dibutyldithiocarbamate, copper dipentyldithiocarbamate, copper dihexyldithiocarbamate, copper diheptyldithiocarbamate, copper dioctyldithiocarbamate, copper di (2-ethylhexyl)
  • zinc dibenzyldithiocarbamate zinc N-ethyl-N-phenyldithiocarbamate, zinc dimethyldithiocarbamate and copper dimethyldithiocarbamate are preferred because of their high reactivity.
  • xanthates examples include zinc methylxanthate, zinc ethylxanthate, zinc propylxanthate, zinc isopropylxanthate, zinc butylxanthate, zinc pentylxanthate, zinc hexylxanthate, heptylxanthate Zinc, zinc octylxanthate, zinc 2-ethylhexylxanthate, zinc decylxanthate, zinc dodecylxanthate, potassium methylxanthate, potassium ethylxanthate, potassium propylxanthate, potassium isopropylxanthate, potassium butylxanthate, pentyl Potassium xanthate, potassium hexylxanthate, potassium heptylxanthate, octylxan Potassium genate, potassium 2-ethylhexylxanthate,
  • thiourea examples include thiourea, N, N′-diphenylthiourea, trimethylthiourea, N, N′-diethylthiourea, N, N′-dimethylthiourea, and N, N ′.
  • -Dibutylthiourea ethylenethiourea, N, N'-diisopropylthiourea, N, N'-dicyclohexylthiourea, 1,3-di (o-tolyl) thiourea, 1,3-di (p-tolyl) thiourea 1,1-diphenyl-2-thiourea, 2,5-dithiobiurea, guanylthiourea, 1- (1-naphthyl) -2-thiourea, 1-phenyl-2-thiourea, p-tolylthiourea, o -Tolylthiourea and the like.
  • thiourea N, N′-diethylthiourea, trimethylthiourea, N, N′-diphenylthiourea and N, N′-dimethylthiourea are preferable because of their high reactivity.
  • the thiadiazole to be used include thiadiazole, dimercaptothiadiazole, and monosubstituted products thereof.
  • dimercaptothiadiazole include 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-thiadiazole 5-thiobenzoate, and monosubstituted compounds include sodium salts. , Potassium, lithium, ammonium and zinc salts.
  • activators (D) such as vulcanization accelerators are guanidines, thioureas and thiadiazoles having higher reactivity, and particularly preferred are 1,3-diphenylguanidine (DPG), thiourea, N , N′-diethylthiourea, 2,5-dimercapto-1,3,4-thiadiazole.
  • DPG 1,3-diphenylguanidine
  • the molar amount of the activator (D) such as a vulcanization accelerator in the rubber composition in the first step of kneading is 0.1 to 1.0 times the molar amount of the silane coupling agent (C).
  • the number of molecules (number of moles) of the activator (D) such as the vulcanization accelerator is 0.3 to 1.0 times the number of molecules (number of moles) of the silane coupling agent (C).
  • the total content of the activator (D) is 0.3 to 6 parts by weight, more preferably 0.3 to 2.5 parts by weight, particularly preferably 100 parts by weight of the rubber component. Is preferably 0.5 to 1.5 parts by mass. If the total content of this activator (D) is less than 0.3 parts by mass, the low-loss effect is low. On the other hand, if it exceeds 6 parts by mass, the effect on the viscosity and shrinkage is large and the uniformity is deteriorated. I will let you. Since the activator (D) such as a vulcanization accelerator is also used as a sulfur vulcanization accelerator, it is not necessary to add all of it in the first first step, and it becomes the final stage of the first step kneading. In the second step, an appropriate amount (part) may be blended as desired.
  • the activator (D) such as a vulcanization accelerator is also used as a sulfur vulcanization accelerator, it is not necessary to add all of it in the first first step, and it becomes the
  • the glycerin fatty acid ester in the glycerin fatty acid ester composition used in the present invention is one in which a fatty acid (carbon number of 8 to 28) is ester-bonded to at least one of the three OH groups possessed by glycerin. Depending on the number, glycerin fatty acid monoester, glycerin fatty acid diester, and glycerin fatty acid triester are separated.
  • the glycerin fatty acid ester composition (E) used in the present invention has a glycerin fatty acid monoester content of 8 to 28 carbon atoms that exceeds 85% by mass. For example, glycerin fatty acid diester or glycerin fatty acid triester or glycerin may be included.
  • the fatty acid constituting the glycerin fatty acid ester activates the silane coupling agent (C) with the vulcanization accelerator (D), and the unvulcanized rubber by the activator (D) such as the vulcanization accelerator.
  • fatty acid having 8 to 28 carbon atoms, preferably 8 to 22 carbon atoms, more preferably 10 to 18 carbon atoms, and still more preferably 12 to 18 carbon atoms.
  • the fatty acid may be saturated, unsaturated, linear or branched, but is particularly preferably a linear saturated fatty acid.
  • fatty acid examples include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid and the like. Lauric acid, palmitic acid and stearic acid are preferred, and palmitic acid and stearic acid are particularly preferred. Note that fatty acids having less than 8 carbon atoms have a low affinity with the polymer, and bloom tends to occur. On the other hand, in the case of fatty acids having more than 28 carbon atoms, the improvement in workability improvement effect is not different from that of 28 or less carbon atoms, and the cost increases, which is not preferable.
  • the glycerin fatty acid ester composition (E) used in the present invention has 8 to 28 carbon atoms in the fatty acid, and the glycerin fatty acid monoester content in the composition exceeds 85% by mass.
  • the processability is prevented from deteriorating, the vulcanization speed is also delayed, and the processability is improved by reducing the viscosity of the silica-blended unvulcanized rubber, High performance such as heat resistance can be achieved.
  • the monoester content in the glycerin fatty acid ester composition is 85% by mass or less, the filler containing silica cannot be highly dispersed, and the effects of the present invention are wear resistance and low loss. Therefore, it is impossible to achieve a high balance between workability and workability. Therefore, in the glycerin fatty acid ester composition, the monoester content is preferably 90% by mass or more, and more preferably 95% by mass from the viewpoint of reducing the unvulcanized rubber viscosity. Further, from the viewpoint of rubber physical properties and production of the glycerin fatty acid ester composition, the monoester content is preferably 99% by mass or less. That is, the most preferable numerical range is 95 to 99% by mass.
  • the total content of the glycerin fatty acid diester and the glycerin fatty acid triester is preferably less than 10% by mass from the viewpoint of preventing an excessive decrease in rubber physical properties (such as a decrease in storage elastic modulus) after vulcanization. Yes, more preferably 5% by mass or less, still more preferably 3% by mass or less, and may be 0.3% by mass or more from the viewpoint of productivity.
  • glycerin may remain as an unreacted raw material.
  • the content of glycerin is preferably less than 5% by mass, more preferably 3% by mass or less, from the viewpoint of suppressing deterioration in heat resistance, and 0.3% by mass from the viewpoint of productivity. % Or more.
  • the glycerin fatty acid ester composition may be used in two or more different glycerin fatty acid monoester and diester contents.
  • the glycerin fatty acid ester composition to be used can be produced by an esterification method produced from glycerin obtained by decomposing fats and oils and a fatty acid, a transesterification method using fats and oils and glycerin as raw materials, and the like.
  • Examples of the method for producing a controlled amount of monoester in the ester composition include the following methods 1) to 3). 1) A method for controlling the equilibrium composition of esterification by changing the charging ratio of the fatty acid component and the glycerin component in the esterification method or transesterification method. Glycerin can be further removed by distillation.
  • Glycerin fatty acid esters with reduced environmental impact can be used by using the above-mentioned raw oils and fatty acids derived from natural products. Furthermore, as the glycerin fatty acid ester composition used in the present invention, a commercially available product with a controlled monoester amount can be used. Examples of commercially available products include stearic acid monoglyceride (Excel manufactured by Kao Corporation). S-95, monoester amount exceeding 95% by mass).
  • the monoglyceride content in the glycerin fatty acid ester composition refers to that obtained by GPC analysis (gel permeation chromatography) according to the following formula (XIII): It means the area ratio in GPC analysis of monoglyceride with respect to the total of glycerin, monoglyceride, diglyceride (glycerin fatty acid diester) and triglyceride (glycerin fatty acid triester).
  • G is the glycerin area of GPC
  • MG is the monoglyceride area of GPC
  • DG is the diglyceride area of GPC
  • TG is the triglyceride area of GPC.
  • the measurement conditions for GPC are as follows. [GPC measurement conditions] GPC measurement was performed using the following measuring apparatus, and THF (tetrahydrofuran) as an eluent was flowed at a flow rate of 0.6 ml / min, and the column was stabilized in a constant temperature bath at 40 ° C. The measurement was performed by injecting 10 ⁇ L of a 1% by mass sample solution dissolved in THF.
  • the diglyceride content in the glycerin fatty acid ester composition means an area ratio in the GPC analysis of diglyceride with respect to the total of glycerin, monoglyceride, diglyceride and triglyceride.
  • the glycerol fatty acid ester composition which controlled the amount of monoester which can be used is given, for example, the fatty acid C8 glyceryl caprylate containing composition, the fatty acid C10 glyceryl decanoate containing composition, fatty acid, for example Glyceryl laurate-containing composition with 12 carbon atoms, glyceryl myristate-containing composition with 14 carbon atoms of fatty acid, glyceryl palmitate with 16 carbon atoms of fatty acid, glyceryl stearate-containing composition with 18 carbon atoms of fatty acid , Glyceryl behenate-containing compositions with fatty acid 22 carbon atoms, glyceryl montanate-containing compositions with 28 carbon atoms of fatty acids, among them, glyceryl laurate-containing compositions, glyceryl palmitate-containing compositions, Glyceryl stearate containing compositions are preferred.
  • the blending amount of the glycerin fatty acid ester composition used in the present invention is preferably 0.2 parts by mass or more, more preferably 0.3 parts, from the viewpoint of reducing the viscosity of the unvulcanized rubber with respect to 100 parts by mass of the rubber component. From the viewpoint of suppressing an excessive decrease in physical properties of rubber after vulcanization (such as a decrease in storage elastic modulus), preferably 0.5 parts by mass or more, more preferably 0.5 parts by mass or more, and particularly preferably 1 part by mass or more.
  • Vulcanizing agent (F) examples of the vulcanizing agent used in the present invention include sulfur and sulfur such as insoluble sulfur, and the blending amount thereof is preferably 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the rubber component. More preferably, it is 1.0 to 5.0 parts by mass.
  • the rubber composition for tires of the present invention has three or more modified functional groups capable of interacting with silica only in the range of 1 ⁇ 4 of the total chain length from the end, Rubber component (A) containing a diene polymer having a monomer structure of a diene polymer between at least one of the modified functional groups, a filler containing an inorganic filler (B) having silica, and a silane coupling agent (C), and all or part of an activator (D) consisting of at least one selected from vulcanization accelerators, thioureas, and thiadiazoles, and a glycerol fatty acid monoester content of 8 to 28 carbon atoms.
  • Rubber component (A) containing a diene polymer having a monomer structure of a diene polymer between at least one of the modified functional groups, a filler containing an inorganic filler (B) having silica, and a silane coupling agent (C), and all or part of an activator
  • a first mixture containing a glycerin fatty acid ester composition (E) in excess of 85% by mass is prepared, and a preliminary composition is prepared by kneading the first mixture, and a first step is added to the preliminary composition.
  • the activator (D) consisting of at least one selected from vulcanization accelerators, thioureas, and thiadiazoles, a glycerol fatty acid monoester having 8 to 28 carbon atoms
  • a glycerol fatty acid monoester having 8 to 28 carbon atoms
  • Adding and kneading the glycerin fatty acid ester composition (E) whose content exceeds 85% by mass enhances the activity of the coupling function of the silane coupling agent (C) and disperses the inorganic filler (B).
  • the activator (D) such as a vulcanization accelerator, the content of glycerol fatty acid monoester having 8 to 28 carbon atoms is 85% by mass
  • the activator (D) such as a vulcanization accelerator
  • the content of glycerol fatty acid monoester having 8 to 28 carbon atoms is 85% by mass
  • the rubber component (A) containing the silane coupling agent (C) and the diene polymer having the above characteristics is because the reaction with) can proceed.
  • the lower limit value of this time is more preferably 30 seconds or more, and the upper limit value is more preferably 150 seconds or less, and particularly preferably 120 seconds or less. If this time is 10 seconds or more, the reaction of (B) and (C) can be sufficiently advanced. Even if this time exceeds 180 seconds, the reaction of (B) and (C) has already proceeded sufficiently, so that it is difficult to enjoy further effects, and the upper limit is preferably set to 180 seconds.
  • the maximum temperature of the rubber composition in the rubber composition in the first step of kneading is preferably 120 to 190 ° C. This is because the reaction between the inorganic filler (B) containing silica and the silane coupling agent (C) sufficiently proceeds. From this viewpoint, the maximum temperature of the rubber composition in the first stage of kneading is more preferably 130 to 190 ° C, and further preferably 140 to 180 ° C.
  • the kneading step of the tire rubber composition in the present invention includes a rubber component (A) containing the above-mentioned diene polymer, a filler containing an inorganic filler (B) having silica, a silane coupling agent (C), And all or part of the activator (D) consisting of at least one selected from vulcanization accelerators, thioureas and thiadiazoles, and the content of glycerol fatty acid monoester having 8 to 28 carbon atoms exceeds 85% by mass
  • a first mixture containing a glycerin fatty acid ester composition (E) is prepared, and a preliminary composition is prepared by kneading the first mixture, and a vulcanizing agent (F) is added to the preliminary composition.
  • a second step of preparing a rubber composition by kneading the second mixture, and a rubber composition for a tire manufactured by a method for manufacturing a rubber composition comprising: And includes at least two steps of a first kneading step that does not include the vulcanizing agent (F) and a second step of kneading that includes the vulcanizing agent. ) May not be included.
  • compounding agents usually used in the rubber industry such as anti-aging agents, softeners, stearic acid, zinc white, vulcanization accelerators, etc.
  • various compounding agents are kneaded in the first step or the second step of kneading, or in the intermediate stage between the first step and the second step, if necessary.
  • a Banbury mixer, a roll, an intensive mixer, or the like is used as the kneading apparatus in the present invention.
  • the tire rubber composition of the present invention is obtained by kneading, heating, extruding, etc. in the above process, and after molding, vulcanization is performed, and tire tread, under tread, carcass, sidewall, bead It can use suitably for the use of the tire member of tires, such as a part.
  • the tire rubber composition configured as described above exhibits the effect of reducing wear resistance and rolling resistance by highly dispersing the filler containing silica without deteriorating the viscosity of the unvulcanized rubber.
  • the tire rubber composition has greatly improved workability and workability. That is, the rubber composition for tires of the present invention has three or more modified functional groups capable of interacting with silica as a diene polymer only in a range of 1 ⁇ 4 of the total chain length from the end.
  • a rubber component (A) containing a diene polymer having a monomer structure of a diene polymer between at least one of the modified functional groups, a filler containing an inorganic filler (B) having silica, and a silane cup Contains a ring agent (C) and all or part of an activator (D) consisting of at least one selected from vulcanization accelerators, thioureas and thiadiazoles, and a glycerol fatty acid monoester having 8 to 28 carbon atoms
  • a first step of preparing a first mixture containing a glycerin fatty acid ester composition (E) in an amount exceeding 85% by mass and preparing the preliminary composition by kneading the first mixture; and the preliminary composition In addition Preparing a second mixture to which the agent (F) has been added, and preparing a rubber composition by kneading the second mixture, which is produced by a method for producing a rubber composition comprising a second
  • silica is used.
  • Hydrophobic surface of inorganic filler (B) by adding at least one glycerin fatty acid ester composition having a fatty acid number of 8 to 28 which is controlled to exceed 85% by mass of the monoester that also acts as a lubricant, the activity of a vulcanization accelerator or the like
  • the silane coupling agent (C) is activated by the agent (D), and the viscosity of the unvulcanized rubber is deteriorated by the activator (D) consisting of at least one selected from vulcanization accelerators, thioureas, and thiadiazoles.
  • an inorganic filler (B) such as silica as a monoester alone, and also has a lubricant action, so that the viscosity is further reduced, and the hydrophobic action and the lubricant action of silica etc. Due to the plasticizing action, the deterioration of viscosity is largely suppressed, and the dispersion of the filler containing the inorganic filler (B) containing silica can be maintained at a high level. It is presumed that the workability and workability are improved by reducing the viscosity, the wear resistance and rolling resistance (RR) are improved, and the low heat build-up is also improved.
  • RR wear resistance and rolling resistance
  • the tire of the present invention is characterized by using the tire rubber composition for a tread member.
  • a tire using the rubber composition as a tread member, particularly a tread rubber, is excellent in low loss property, fracture characteristics, and wear resistance.
  • the tire of the present invention is not particularly limited except that the tire rubber composition described above is used for any of the tread members, and can be produced according to a conventional method.
  • inert gas such as nitrogen, argon, helium other than normal or the air which adjusted oxygen partial pressure, can be used.
  • Modified polymers A to M were produced according to the following procedure.
  • the polymerization conversion at this time was almost 100%. Thereafter, 0.5 ml of a 5 mass% isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) was added to stop the reaction, followed by drying according to a conventional method to obtain a modified polymer B.
  • BHT 2,6-di-t-butyl-p-cresol
  • the polymerization reaction system was charged with a cyclohexane solution of 1,3-butadiene containing 12 g of 1,3-butadiene, a cyclohexane solution of styrene containing 3 g of styrene, and 2.85 mmol of 3,4-bis (trimethylsilyl) as a modifier.
  • a mixed solution of (oxy) -1-vinylbenzene was added at once, and the polymerization reaction was further carried out for 1 hour. The polymerization conversion at this time was almost 100%.
  • a cyclohexane solution of 1,3-butadiene containing 15 g of 1,3-butadiene and a cyclohexane solution of styrene containing 3.48 g of styrene and 0.27 g of p-methylstyrene were added to the polymerization reaction system, and the polymerization reaction was continued for another hour. Went. When the polymerization conversion rate reached 99%, 0.57 mmol of tetraethyl orthosilicate was added as a terminal modifier and reacted for 15 minutes.
  • the polymer molecular properties of the modified polymers A to M are the bound styrene content (wt%), vinyl viscosity (wt%), Mooney viscosity (ML 1 + 4/100 ° C.), peak average molecular weight, and glass transition temperature as follows: went.
  • the styrene unit content in the modified polymer was calculated from the integral ratio of the 1 H-NMR spectrum.
  • the vinyl viscosity (wt%) was calculated from the integral ratio of the 1 H-NMR spectrum.
  • the Mooney viscosity of the modified polymer was measured at 100 ° C. using an RLM-01 type tester manufactured by Toyo Seiki Co., Ltd.
  • glycerin fatty acid ester composition A As the glycerin fatty acid ester composition to be used, the following two glycerin fatty acid ester compositions A and B were used.
  • Glycerin fatty acid ester composition A According to the method described in Production Example 1 of International Publication No. 2014/098155, a fatty acid was synthesized by changing from octanoic acid to an equivalent molar amount of a palm-derived hardened fatty acid, and further prepared by molecular distillation. The glycerin fatty acid monoester content of the obtained glycerin fatty acid ester composition A was 97% by mass.
  • glycerin fatty acid ester composition B (glycerin fatty acid ester having 16 fatty acid carbon atoms) was produced.
  • the resulting product was subjected to adsorption filtration under pressure to obtain a monoglyceride-containing composition.
  • the composition obtained was measured by GPC and calculated by the method described above to determine the composition of each component.
  • the content of glycerin fatty acid monoester is 64% by mass
  • the content of glycerin fatty acid diester is 34% by mass
  • the content of glycerin fatty acid triester is 1% by mass
  • the content was 1% by mass.
  • Examples 1 to 18 and Comparative Examples 1 to 11 A rubber composition for a tire was prepared by the following methods with the formulation shown in Table 2 below. (Method for preparing rubber compositions for tires of Examples 1 to 18 and Comparative Examples 3 and 6 to 11) In Examples 1 to 18 and Comparative Examples 3 and 6 to 11, each component in the column of the first step of kneading in Table 3 below so that the maximum temperature of the rubber composition in the first step of kneading is 150 ° C. Were adjusted and kneaded with a Banbury mixer to prepare a rubber composition for each tire.
  • a rubber composition for a tire was prepared by kneading a second mixture obtained by adding sulfur or the like as a vulcanizing agent (F).
  • * 1 to * 15 are as follows.
  • the present invention If the kneading of the present invention is not used even if the coalescence or diene polymer outside the scope of the present invention, the glycerin fatty acid ester composition of the present invention or the glycerin fatty acid ester composition outside the scope of the present invention is used, the present invention It can be seen that the effects of the invention, such as kneaded skin (workability), wear resistance, and low loss, cannot be achieved at a high level.
  • Examples 1 to 18 that are within the scope of the present invention, that is, the diene polymer and glycerin fatty acid ester that are kneaded through the first and second processes of the present invention and are within the scope of the present invention. It has been found that when the composition is used, the effects of the present invention, such as kneaded skin (workability), wear resistance, and low loss, can be achieved at a high level.
  • the rubber composition for tires of the present invention can be suitably used for tire members such as tire treads, undertreads, carcass, sidewalls, bead portions, and the like, particularly for tread members.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne une composition de caoutchouc pour pneus, présentant une excellente dispersion d'une charge contenant de la silice, résistance à l'usure, une résistance au roulement réduite et une aptitude au façonnage, améliorée de façon spectaculaire, sans nuire à la viscosité du caoutchouc non vulcanisé. L'invention concerne également un pneu mettant en œuvre ladite composition de caoutchouc dans l'élément de bande de roulement de ce dernier. Une composition de caoutchouc pour pneus produite au moyen d'un procédé de production d'une composition de caoutchouc pour pneus qui comprend : une première étape dans laquelle un premier mélange est préparé de manière à contenir un constituant de caoutchouc (A) qui comprend, en tant que un polymère diénique, un polymère diénique ayant une structure de monomère d'un polymère diénique entre au moins un groupe fonctionnel modifié, et qui a au moins trois groupes fonctionnels modifiés qui peuvent interagir avec de la silice, uniquement dans la plage de 1/4 de la longueur de chaîne à partir de l'extrémité, une charge contenant une charge minérale (B) ayant de la silice, un agent de couplage silane (C), tout ou partie d'au moins un activateur (D) choisi parmi un promoteur de vulcanisation, une thiourée et un thiadiazole, et une composition d'ester d'acide gras et de glycérine (E) contenant plus de 85 % en masse d'un monoester de glycérine et d'acide gras en C8-28, ledit mélange étant ensuite mélangé pour préparer une composition préliminaire ; et une deuxième étape dans laquelle un deuxième mélange obtenu par l'ajout d'un agent de vulcanisation (F) à la composition préparatoire est préparé et malaxé pour préparer une composition de caoutchouc.
PCT/JP2016/056231 2015-03-05 2016-03-01 Composition de caoutchouc pour pneus, et pneu Ceased WO2016140217A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015043824A JP6053844B2 (ja) 2015-03-05 2015-03-05 タイヤ用ゴム組成物及びタイヤ
JP2015-043824 2015-03-05

Publications (1)

Publication Number Publication Date
WO2016140217A1 true WO2016140217A1 (fr) 2016-09-09

Family

ID=56846515

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/056231 Ceased WO2016140217A1 (fr) 2015-03-05 2016-03-01 Composition de caoutchouc pour pneus, et pneu

Country Status (2)

Country Link
JP (1) JP6053844B2 (fr)
WO (1) WO2016140217A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016006153A (ja) * 2014-05-29 2016-01-14 株式会社ブリヂストン タイヤ用ゴム組成物
JP2016160422A (ja) * 2015-03-05 2016-09-05 株式会社ブリヂストン ゴム組成物及びタイヤ
WO2018230406A1 (fr) * 2017-06-16 2018-12-20 株式会社ブリヂストン Composition de caoutchouc pour bande de roulement de pneu et pneu
WO2021125299A1 (fr) * 2019-12-19 2021-06-24 株式会社ブリヂストン Composition de caoutchouc et pneu
WO2021125300A1 (fr) * 2019-12-19 2021-06-24 株式会社ブリヂストン Composition de caoutchouc et pneu
US11241912B2 (en) 2017-03-21 2022-02-08 Compagnie Generale Des Etablissements Michelin Tire comprising a tread
US11390117B2 (en) 2017-01-31 2022-07-19 Compagnie Generale Des Etablissements Michelin Tire comprising a rubber composition

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106459505B (zh) * 2014-06-17 2018-07-13 株式会社普利司通 橡胶组合物及其制造方法、和轮胎
US20180030251A1 (en) * 2015-03-05 2018-02-01 Bridgestone Corporation Rubber composition, method for producing diene-based polymer, and tire
JP6244033B2 (ja) * 2015-03-05 2017-12-06 株式会社ブリヂストン ゴム組成物及びタイヤ
JP6835401B2 (ja) * 2016-08-30 2021-02-24 株式会社ブリヂストン ゴム組成物及びタイヤ
JP7516355B2 (ja) * 2019-04-01 2024-07-16 株式会社Ｅｎｅｏｓマテリアル 架橋物及びタイヤ

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012128194A1 (fr) * 2011-03-24 2012-09-27 Jsr株式会社 Composition de caoutchouc et procédé pour le fabriquer et pneu
WO2014098155A1 (fr) * 2012-12-19 2014-06-26 株式会社ブリヂストン Composition de caoutchouc, et pneu fabriqué avec cette composition
WO2015147274A1 (fr) * 2014-03-27 2015-10-01 横浜ゴム株式会社 Composition de caoutchouc et pneumatique la contenant
JP2016006153A (ja) * 2014-05-29 2016-01-14 株式会社ブリヂストン タイヤ用ゴム組成物
JP2016037601A (ja) * 2014-08-07 2016-03-22 横浜ゴム株式会社 ゴム組成物およびそれを用いた空気入りタイヤ

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6004677B2 (ja) * 2011-03-31 2016-10-12 住友化学株式会社 変性共役ジエン系重合体の製造方法、変性共役ジエン系重合体、及び重合体組成物
JP6157806B2 (ja) * 2012-05-15 2017-07-05 住友化学株式会社 共役ジエン系重合体変性物及び重合体組成物
JP6041530B2 (ja) * 2012-05-23 2016-12-07 旭化成株式会社 変性ブタジエン系重合体、変性ブタジエン系重合体の製造方法、ゴム組成物、及びタイヤ
JP6229654B2 (ja) * 2012-07-20 2017-11-15 Jsr株式会社 変性共役ジエン系重合体、重合体組成物、架橋体及びタイヤの製造方法
JP6303732B2 (ja) * 2014-03-31 2018-04-04 日本ゼオン株式会社 変性共役ジエン系重合体の製造方法
JP6354493B2 (ja) * 2014-09-26 2018-07-11 日本ゼオン株式会社 変性共役ジエン系重合体の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012128194A1 (fr) * 2011-03-24 2012-09-27 Jsr株式会社 Composition de caoutchouc et procédé pour le fabriquer et pneu
WO2014098155A1 (fr) * 2012-12-19 2014-06-26 株式会社ブリヂストン Composition de caoutchouc, et pneu fabriqué avec cette composition
WO2015147274A1 (fr) * 2014-03-27 2015-10-01 横浜ゴム株式会社 Composition de caoutchouc et pneumatique la contenant
JP2016006153A (ja) * 2014-05-29 2016-01-14 株式会社ブリヂストン タイヤ用ゴム組成物
JP2016037601A (ja) * 2014-08-07 2016-03-22 横浜ゴム株式会社 ゴム組成物およびそれを用いた空気入りタイヤ

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016006153A (ja) * 2014-05-29 2016-01-14 株式会社ブリヂストン タイヤ用ゴム組成物
JP2016160422A (ja) * 2015-03-05 2016-09-05 株式会社ブリヂストン ゴム組成物及びタイヤ
US11390117B2 (en) 2017-01-31 2022-07-19 Compagnie Generale Des Etablissements Michelin Tire comprising a rubber composition
US11241912B2 (en) 2017-03-21 2022-02-08 Compagnie Generale Des Etablissements Michelin Tire comprising a tread
JP2019001922A (ja) * 2017-06-16 2019-01-10 株式会社ブリヂストン タイヤトレッド用ゴム組成物及びタイヤ
CN110770290A (zh) * 2017-06-16 2020-02-07 株式会社普利司通 轮胎胎面用橡胶组合物和轮胎
WO2018230406A1 (fr) * 2017-06-16 2018-12-20 株式会社ブリヂストン Composition de caoutchouc pour bande de roulement de pneu et pneu
WO2021125299A1 (fr) * 2019-12-19 2021-06-24 株式会社ブリヂストン Composition de caoutchouc et pneu
WO2021125300A1 (fr) * 2019-12-19 2021-06-24 株式会社ブリヂストン Composition de caoutchouc et pneu
JPWO2021125299A1 (fr) * 2019-12-19 2021-06-24
JPWO2021125300A1 (fr) * 2019-12-19 2021-06-24
CN114867778A (zh) * 2019-12-19 2022-08-05 株式会社普利司通 橡胶组合物和轮胎
JP7483755B2 (ja) 2019-12-19 2024-05-15 株式会社ブリヂストン ゴム組成物及びタイヤ
JP7518858B2 (ja) 2019-12-19 2024-07-18 株式会社ブリヂストン ゴム組成物及びタイヤ

Also Published As

Publication number Publication date
JP6053844B2 (ja) 2016-12-27
JP2016160418A (ja) 2016-09-05

Similar Documents

Publication Publication Date Title
JP6053844B2 (ja) タイヤ用ゴム組成物及びタイヤ
JP6703369B2 (ja) タイヤ用ゴム組成物
JP6244033B2 (ja) ゴム組成物及びタイヤ
JP6010662B2 (ja) ゴム組成物の製造方法
JP5977517B2 (ja) ゴム組成物の製造方法、そのゴム組成物及びそれを用いた空気入りタイヤ
CN103562296B (zh) 橡胶组合物的制造方法
JP5845247B2 (ja) ゴム組成物の製造方法
JP5740406B2 (ja) ゴム組成物の製造方法
JP5683597B2 (ja) ゴム組成物の製造方法
WO2012115211A1 (fr) Composition de caoutchouc et pneu obtenu à l'aide de celle-ci, et procédé de fabrication d'une composition de caoutchouc
WO2012043854A1 (fr) Procédé de fabrication d'une composition de caoutchouc
WO2012043856A1 (fr) Procédé de fabrication d'une composition de caoutchouc
WO2016009775A1 (fr) Procédé de fabrication de composition de caoutchouc pour pneumatique, et pneumatique
JP2016160422A (ja) ゴム組成物及びタイヤ
JP5649515B2 (ja) ゴム組成物の製造方法
WO2016093282A1 (fr) Procédé de production d'une composition de caoutchouc
JP6353777B2 (ja) ゴム組成物の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16758910

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16758910

Country of ref document: EP

Kind code of ref document: A1