WO2016186155A1 - Procédé de production d'une composition de caoutchouc - Google Patents

Procédé de production d'une composition de caoutchouc Download PDF

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Publication number
WO2016186155A1
WO2016186155A1 PCT/JP2016/064820 JP2016064820W WO2016186155A1 WO 2016186155 A1 WO2016186155 A1 WO 2016186155A1 JP 2016064820 W JP2016064820 W JP 2016064820W WO 2016186155 A1 WO2016186155 A1 WO 2016186155A1
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Prior art keywords
group
rubber composition
production method
formula
examples
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PCT/JP2016/064820
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English (en)
Japanese (ja)
Inventor
泰生 上北
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住友化学株式会社
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Priority to JP2017519391A priority Critical patent/JPWO2016186155A1/ja
Publication of WO2016186155A1 publication Critical patent/WO2016186155A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • B60C5/00—Inflatable pneumatic tyres or inner tubes
    • B60C5/12—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim
    • B60C5/14—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim with impervious liner or coating on the inner wall of the tyre
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

  • the present invention relates to a method for producing a rubber composition.
  • the present invention has been made paying attention to the circumstances as described above, and is selected from the group consisting of a compound represented by the following formula (I), a salt thereof, a solvate thereof, and a solvate of the salt. It is to suppress an increase in the viscosity of the rubber composition due to the use of at least one.
  • the present invention that can achieve the above object is as follows.
  • R 1 represents a C 2-12 alkanediyl group which may have one or more substituents, a C 3-10 cycloalkanediyl group which may have one or more substituents, or one or more substituents.
  • R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, a hydroxy group, one or more C 1-6 alkoxy group which may have one or more substituents, or one or more substituents.
  • R 4 represents a hydroxy group, a C 1-6 alkoxy group which may have one or more substituents, or a C 6-14 aryloxy group which may have one or more substituents.
  • X represents —NH— or —O—.
  • Step 1 for preparing a kneaded product by kneading at least one selected from the group consisting of a compound represented by the formula: salt thereof, solvate thereof and solvate of the salt thereof, a rubber component, and carbon black;
  • Step 2 for preparing the cooled kneaded product by subjecting the obtained kneaded product to a cooling operation, and Step 3 for kneading the obtained cooled kneaded product Manufacturing method.
  • step 1 The production method according to any one of [1] to [10], wherein the kneading in step 1 is performed for 1 minute or more at a rotation speed of 5 rpm or more.
  • the rubber composition to be produced contains at least one total amount selected from the group consisting of the compound represented by formula (I), a salt thereof, a solvate thereof, and a solvate of the salt.
  • the rubber composition to be produced contains at least one total amount selected from the group consisting of the compound represented by formula (I), a salt thereof, a solvate thereof, and a solvate of the salt.
  • the production method according to any one of [1] to [36] wherein the amount is 0.01 to 20 parts by weight per 100 parts by weight of the rubber component.
  • the rubber composition to be produced contains at least one total amount selected from the group consisting of the compound represented by formula (I), a salt thereof, a solvate thereof, and a solvate of the salt
  • the production method according to any one of [1] to [36], wherein the amount is 0.1 to 10 parts by weight per 100 parts by weight of the rubber component.
  • a carboxylate of the compound represented by the formula (I), wherein at least one selected from the group consisting of the compound represented by the formula (I), a salt thereof, a solvate thereof and a solvate of the salt thereof The production method according to any one of [1] to [57], which is a solvate of [60] At least one selected from the group consisting of a compound represented by the formula (I), a salt thereof, a solvate thereof and a solvate of the salt is an alkali carboxylate of the compound represented by the formula (I) Any one of the above [1] to [57], which is at least one selected from the group consisting of hydrates of metal salts and hydrates of alkaline earth metal carboxylates of the compounds represented by formula (I) The manufacturing method as described in one.
  • a method for producing a rubber composition containing a sulfur component wherein the rubber composition obtained by the production method according to any one of [1] to [64] and a sulfur component are kneaded. Manufacturing method.
  • a rubber composition containing no sulfur component obtained by the production method according to any one of [1] to [64].
  • a rubber composition containing a sulfur component obtained by the production method according to any one of [65] to [68].
  • a vulcanized rubber composition obtained by vulcanizing the rubber composition containing the sulfur component according to [70].
  • a vulcanized tire including the vulcanized rubber composition according to [71].
  • a tire belt member comprising the vulcanized rubber composition according to [71] and a steel cord.
  • a tire carcass member comprising the vulcanized rubber composition according to [71] and a carcass fiber cord.
  • a tire member comprising the vulcanized rubber composition according to [71].
  • the tire member according to [75] which is a tire sidewall member, a tire inner liner member, a tire cap tread member, or a tire undertread member.
  • a method for producing a vulcanized rubber composition comprising vulcanizing a rubber composition containing a sulfur component obtained by the production method according to any one of [65] to [68] .
  • the viscosity of the rubber composition is increased by using at least one selected from the group consisting of the compound represented by the formula (I), a salt thereof, a solvate thereof and a solvate of the salt. Can be suppressed.
  • R 1 in the formula (I) is a C 2-12 alkanediyl group optionally having one or more substituents, and a C 3-10 cycloalkanediyl group optionally having one or more substituents. It represents a divalent C 6-12 aromatic hydrocarbon group which may have one or more substituents, or a combination thereof.
  • C xy means that the number of carbon atoms is x or more and y or less (x, y: integer).
  • the alkanediyl group includes both a linear alkanediyl group and a branched alkanediyl group.
  • examples of the “C 2-12 alkanediyl group” include an ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, propylene group, 1-methyltrimethylene group, 2-methyl group.
  • Trimethylene 1-ethyltrimethylene, 2-ethyltrimethylene, 1-propyltrimethylene, 2-propyltrimethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1-ethyltetra Methylene group, 2-ethyltetramethylene group, 1-propyltetramethylene group, 2-propyltetramethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1-ethylpentamethylene group Group, 2-ethylpentamethylene group, 3-ethylpentamethylene group, 1-propyl Rupentamethylene group, 2-propylpentamethylene group, 3-propylpentamethylene group, 1-methylhexamethylene group, 2-methylhexamethylene group, 3-methylhexamethylene group, 1-ethylhexamethylene group, 2-ethyl Examples include a hexamethylene group, a 3-ethylhexamethylene group, a 1-
  • Examples of the substituent that the C 2-12 alkanediyl group may have include a C 1-6 alkoxy group, a C 1-6 alkoxy-carbonyl group, a C 1-7 acyl group, and a C 1-7 acyl- Examples thereof include an oxy group and a C 6-14 aryl group which may have one or more substituents.
  • the explanation of the C 1-6 alkoxy group will be given later.
  • examples of the “C 3-10 cycloalkanediyl group” include cyclopropane-1,2-diyl group, cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane -1,4-diyl group, cycloheptane-1,4-diyl group, cyclooctane-1,5-diyl group, cyclononane-1,5-diyl group, and cyclodecane-1,6-diyl group.
  • Examples of the substituent that the C 3-10 cycloalkanediyl group may have include a C 1-6 alkyl group, a C 1-6 alkoxy group, a C 1-6 alkoxy-carbonyl group, and a C 1-7 acyl. Group, a C 1-7 acyl-oxy group, and a C 6-14 aryl group optionally having one or more substituents.
  • examples of the “divalent C 6-12 aromatic hydrocarbon” include a phenylene group (eg, 1,4-phenylene group), a naphthylene group (eg, 1,4-naphthylene group, 1, 5-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group) and biphenyldiyl group (eg, 1,1′-biphenyl-4,4′-diyl group).
  • a phenylene group eg, 1,4-phenylene group
  • a naphthylene group eg, 1,4-naphthylene group, 1, 5-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group
  • biphenyldiyl group eg, 1,1′-biphenyl-4,4′-diyl group
  • Examples of the substituent that the divalent C 6-12 aromatic hydrocarbon group may have include, for example, a C 1-6 alkyl group, a C 1-6 alkoxy group, a C 1-6 alkoxy-carbonyl group, C Examples thereof include a 1-7 acyl group, a C 1-7 acyl-oxy group, a C 6-14 aryl group, and a sulfo group.
  • the sulfo group is a group represented by —SO 3 H.
  • R 1 is preferably a C 2-12 alkanediyl group or a divalent C 6-12 aromatic hydrocarbon group, more preferably a C 2-12 alkanediyl group or a phenylene group, still more preferably a phenylene group. Particularly preferred is a 1,4-phenylene group.
  • R 2 and R 3 in formula (I) are each independently a hydrogen atom, a halogen atom, a hydroxy group, an optionally substituted C 1-6 alkoxy group, or one or more substituents.
  • halogen atom examples include fluorine, chlorine, bromine and iodine.
  • the alkoxy group includes both a linear alkoxy group and a branched alkoxy group.
  • examples of the “C 1-6 alkoxy group” include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a pentyloxy group. And hexyloxy group.
  • Examples of the substituent that the C 1-6 alkoxy group may have include a C 1-6 alkoxy group, a C 1-6 alkoxy-carbonyl group, a C 1-7 acyl group, and a C 1-7 acyl-oxy group.
  • Group, and a C 6-14 aryl group which may have one or more substituents.
  • the alkyl group includes both a linear alkyl group and a branched alkyl group.
  • examples of the “C 1-6 alkyl group” include a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, s-butyl group, t-butyl group, 2 -Methylbutyl group, 2-ethylbutyl group, 3-methylbutyl group, 3-ethylbutyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group.
  • Examples of the substituent that the C 1-6 alkyl group may have include a C 1-6 alkoxy group, a C 1-6 alkoxy-carbonyl group, a C 1-7 acyl group, and a C 1-7 acyl-oxy group.
  • Group, and a C 6-14 aryl group which may have one or more substituents.
  • examples of the “C 6-14 aryl group” include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, and a 9-anthryl group.
  • Examples of the substituent that the C 6-14 aryl group may have include, for example, a C 1-6 alkyl group, a C 1-6 alkoxy group, a C 1-6 alkoxy-carbonyl group, a C 1-7 acyl group, Examples thereof include a C 1-7 acyl-oxy group, a C 6-14 aryl group, and a sulfo group.
  • examples of the “C 1-7 acyl group” include a formyl group, a C 1-6 alkyl-carbonyl group (eg, acetyl group, pivaloyl group), and a benzoyl group.
  • examples of the “C 1-6 alkoxy group” contained in the C 1-6 alkoxy-carbonyl group and the “C 1-7 acyl group” contained in the C 1-7 acyl-oxy group include, for example, Can be mentioned.
  • Examples of the “C 3-10 cycloalkenediyl group formed by combining R 2 and R 3 together with the carbon atom to which they are bonded” include a cyclopropene-1,2-diyl group, Cyclobutene-1,2-diyl group, cyclopentene-1,2-diyl group, cyclohexene-1,2-diyl group, cycloheptene-1,2-diyl group, cyclooctene-1,2-diyl group, cyclononene-1, Examples thereof include 2-diyl group and cyclodecene-1,2-diyl group.
  • Examples of the substituent that the C 3-10 cycloalkenediyl group may have include a C 1-6 alkyl group, a C 1-6 alkoxy group, a C 1-6 alkoxy-carbonyl group, and a C 1-7 acyl. Group, a C 1-7 acyl-oxy group, and a C 6-14 aryl group optionally having one or more substituents.
  • R 2 and R 3 are each independently preferably a hydrogen atom or a C 1-6 alkyl group, more preferably a hydrogen atom.
  • R 4 in formula (I) is a hydroxy group (—OH), a C 1-6 alkoxy group optionally having one or more substituents, or a C optionally having one or more substituents. Represents a 6-14 aryloxy group.
  • examples of the “C 6-14 aryl group” contained in the C 6-14 aryloxy group include those described above.
  • R 4 is preferably a hydroxy group or a C 1-6 alkoxy group, more preferably a hydroxy group.
  • X in the formula (I) represents —NH— or —O—.
  • X is preferably —NH—.
  • Compound (I) is preferably represented by the formula (II):
  • the salt of compound (I) includes (a) an amine salt formed by —NH 2 of compound (I) and another acid, and (b) —NH— of compound (I) when X is —NH—.
  • Examples include amine salts formed by-and other acids, and (c) carboxylates formed by -COOH of compound (I) and other bases when R 4 is a hydroxy group.
  • the other acid that forms the amine salt of (a) and (b) may be either an organic acid or an inorganic acid, and the base that forms the carboxylate salt of (c) is an organic base or an inorganic base. Either is acceptable.
  • the salt of compound (I) is preferably a carboxylate, more preferably at least one selected from the group consisting of an alkali metal carboxylate and an alkaline earth metal carboxylate, and more preferably an alkali carboxylate A metal salt, particularly preferably a sodium carboxylate.
  • the solvent that forms the solvate of compound (I) and the solvate of the salt of compound (I) may be water or an organic solvent (for example, methanol).
  • the solvent forming the solvate is preferably water or methanol, more preferably water.
  • Compound (I) or the like is preferably a solvate of a salt of compound (I), more preferably a solvate of a carboxylate salt of compound (I), and more preferably a carboxylic acid of compound (I).
  • Compound (I) and the like can be produced by the method described in Patent Document 1 or a method according to the method.
  • the amount of compound (I) and the like used (that is, at least one total amount selected from the group consisting of the compound represented by formula (I), a salt thereof, a solvate thereof and a solvate of the salt)
  • the amount is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 20 parts by weight, still more preferably 0.1 to 10 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. Part.
  • Rubber component As the rubber component, natural rubber (NR) and modified natural rubber (for example, epoxidized natural rubber, deproteinized natural rubber); polyisoprene rubber (IR), styrene / butadiene copolymer rubber (SBR), Various synthetic rubbers such as polybutadiene rubber (BR), acrylonitrile / butadiene copolymer rubber (NBR), isoprene / isobutylene copolymer rubber (IIR), ethylene / propylene / diene copolymer rubber (EPDM), halogenated butyl rubber (HR), etc. Is illustrated. Only 1 type may be used for a rubber component and it may use 2 or more types together.
  • NR natural rubber
  • modified natural rubber for example, epoxidized natural rubber, deproteinized natural rubber
  • IR polyisoprene rubber
  • SBR styrene / butadiene copolymer rubber
  • BR polybutadiene rubber
  • NBR
  • the rubber component preferably contains a diene rubber.
  • the diene rubber means a rubber made from a diene monomer having a conjugated double bond.
  • the diene rubber include natural rubber, modified natural rubber, polyisoprene rubber, chloroprene rubber, styrene / butadiene copolymer rubber, polybutadiene rubber, and nitrile rubber.
  • the diene rubber is preferably highly unsaturated, and more preferably natural rubber. It is also effective to use natural rubber in combination with another rubber (for example, styrene / butadiene copolymer rubber or polybutadiene rubber).
  • the amount of the diene rubber in the rubber component is preferably 50% by weight or more, more preferably 70 to 100% by weight, still more preferably 80 to 100% by weight. is there.
  • Examples of natural rubber include natural rubber of grades such as RSS # 1, RSS # 3, TSR20, and SIR20.
  • examples of the epoxidized natural rubber include those having a degree of epoxidation of 10 to 60 mol% (for example, ENR25 and ENR50 manufactured by Kumphuran Guthrie).
  • As the deproteinized natural rubber a deproteinized natural rubber having a total nitrogen content of 0.3% by weight or less is preferable.
  • Other modified natural rubbers include, for example, polar groups obtained by reacting natural rubber with 4-vinylpyridine, N, N, -dialkylaminoethyl acrylate (eg, N, N, -diethylaminoethyl acrylate), 2-hydroxy acrylate, and the like. Modified natural rubber containing
  • SBR examples include emulsion polymerization SBR and solution polymerization SBR described in pages 210 to 211 of “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association. Among these, solution polymerization SBR is preferable for the rubber composition for treads.
  • the solution polymerization SBR examples include a modified solution polymerization SBR obtained by modification with a modifying agent and having at least one element of nitrogen, tin and silicon at the molecular end.
  • the modifier include lactam compounds, amide compounds, urea compounds, N, N-dialkylacrylamide compounds, isocyanate compounds, imide compounds, silane compounds having an alkoxy group, aminosilane compounds, tin compounds and silane compounds having an alkoxy group.
  • a combined modifier of an alkyl acrylamide compound and a silane compound having an alkoxy group may be used alone or in combination.
  • modified solution polymerization SBR examples include solution polymerization SBR and JSR in which molecular ends are modified using 4,4′-bis (dialkylamino) benzophenone such as “Nipol (registered trademark) NS116” manufactured by Nippon Zeon Co., Ltd.
  • solutions polymerization SBR in which molecular ends are modified using a tin halide compound such as “SL574” manufactured by the company, and silane-modified solution polymerization SBR such as “E10” and “E15” manufactured by Asahi Kasei.
  • oil-extended SBR in which oil such as process oil or aroma oil is added to emulsion polymerization SBR and solution polymerization SBR is also preferable for the rubber composition for tread.
  • the BR may be either a solution polymerization BR having a low vinyl content or a solution polymerization BR having a high vinyl content, but a solution polymerization BR having a high vinyl content is preferred.
  • a modified solution polymerization BR having at least one element of nitrogen, tin, or silicon at the molecular end obtained by modification with a modifier is particularly preferred.
  • the modifier include 4,4′-bis (dialkylamino) benzophenone, tin halide compound, lactam compound, amide compound, urea compound, N, N-dialkylacrylamide compound, isocyanate compound, imide compound, and alkoxy group.
  • Examples thereof include a silane compound having an alkoxy group (for example, a trialkoxysilane compound), an aminosilane compound, a tin compound and a silane compound having an alkoxy group, and a combined modifier having an alkylacrylamide compound and an silane compound having an alkoxy group. These modifiers may be used alone or in combination.
  • Examples of the modified solution polymerization BR include tin-modified BR such as “Nipol (registered trademark) BR 1250H” manufactured by Nippon Zeon.
  • BR can be preferably used for a rubber composition for a tread and a rubber composition for a sidewall.
  • BR may be used in a blend with SBR and / or natural rubber (NR).
  • NR natural rubber
  • the amount of SBR and / or NR in the rubber component is 60 to 100% by weight, and the amount of BR is 0 to 40% by weight.
  • the amount of SBR and / or NR in the rubber component is preferably 10 to 70% by weight, the amount of BR is 90 to 30% by weight, and more preferably the amount of NR. Is 40 to 60% by weight, and the amount of BR is 60 to 40% by weight.
  • a blend of modified SBR and non-modified SBR, a blend of modified BR and non-modified BR, and the like can be preferably used.
  • SBR which is excellent in wear resistance and hysteresis loss reduction performance
  • SBR is used as a base material in rubber components, and in truck and bus tires.
  • Higher strength NR is optionally used as a base material together with SBR, and these base materials can be blended with BR as necessary to obtain a tread excellent in wear resistance, fatigue resistance and impact resilience. Therefore, it is preferable.
  • NR and SBR are blended in a passenger car tire, or NR and BR are blended, and NR in a truck / bus tire. It is preferable to use a blend of BR and BR since bending resistance and crack growth resistance can be obtained.
  • the rubber composition produced in the present invention is used for a tire belt, it is preferable to use NR and / or IR as a rubber component because a high elastic modulus and good adhesion to reinforcing fibers can be obtained. .
  • the rubber composition produced in the present invention is used as an inner liner of a tire, it is preferable to blend IIR, SBR, and NR as a rubber component, or blend IIR and NR. And bending resistance is preferable.
  • Carbon Black examples include those described on page 494 of “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association. Carbon black may use only 1 type and may use 2 or more types together. Examples of carbon black include HAF (High Absorption Furnace), SAF (Super Abrasion Furnace), ISAF (Intermediate SAF), ISAF-HM (Intermediate SAF-High Fur, and FEF (Fast East Fur, FAS ), SRF (Semi-Reinforcing Furnace) is preferable.
  • HAF High Absorption Furnace
  • SAF Super Abrasion Furnace
  • ISAF Intermediate SAF
  • ISAF-HM Intermediate SAF-High Fur
  • FEF Flust East Fur, FAS
  • SRF Semi-Reinforcing Furnace
  • the amount of carbon black used is preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, still more preferably 30 to 60 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. Part.
  • Sulfur component examples include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur, morpholine disulfide, and tetramethylthiuram disulfide. Usually, powdered sulfur is preferred, and insoluble sulfur is preferred when the rubber composition produced in the present invention is used for producing tire members having a large amount of sulfur such as belt members.
  • the amount of the sulfur component used is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, still more preferably 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. 0.1 to 10 parts by weight.
  • Other components in addition to the above-mentioned compound (I) and the like, rubber components, carbon black, and sulfur components.
  • Other components include fillers other than carbon black, compounds capable of binding to silica, vulcanization accelerators, vulcanization accelerators, resins, viscoelasticity improvers, anti-aging agents, oils, waxes, peptizers, Examples thereof include a retarder, a compound having an oxyethylene unit, and a catalyst (such as cobalt naphthenate).
  • a retarder such as cobalt naphthenate
  • all may use only 1 type and may use 2 or more types together.
  • fillers other than carbon black examples include silica (for example, hydrous silica), aluminum hydroxide, bituminous coal pulverized material, talc, clay (particularly, calcined clay), and titanium oxide.
  • silica examples include silica having a CTAB specific surface area of 50 to 180 m 2 / g and silica having a nitrogen adsorption specific surface area of 50 to 300 m 2 / g.
  • examples of commercially available silica products include “Nipsil (registered trademark) AQ” and “Nipsil (registered trademark) AQ-N” manufactured by Tosoh Silica Co., Ltd., “Ultrazil (registered trademark) VN3” and “Ultrazil” manufactured by Degussa.
  • silica having a pH of 6 to 8, (ii) silica containing 0.2 to 1.5% by weight of sodium, (iii) true spherical silica having a roundness of 1 to 1.3, (iv) ) Silicone oil (eg, dimethyl silicone oil), organosilicon compound containing ethoxysilyl group, silica surface-treated with alcohol (eg, ethanol, polyethylene glycol), etc. (v) two or more different nitrogen adsorption specific surface areas Mixtures of silica with can be used as fillers.
  • silicone oil eg, dimethyl silicone oil
  • organosilicon compound containing ethoxysilyl group silica surface-treated with alcohol (eg, ethanol, polyethylene glycol), etc.
  • two or more different nitrogen adsorption specific surface areas Mixtures of silica with can be used as fillers.
  • the amount of silica used is preferably in the range of 10 to 120 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention.
  • the silica / carbon black weight ratio is preferably 0.7 / 1 to 1 / 0.1.
  • aluminum hydroxide examples include aluminum hydroxide having a nitrogen adsorption specific surface area of 5 to 250 m 2 / g and a DOP oil supply amount of 50 to 100 ml / 100 g.
  • the average particle size of the bituminous coal pulverized product is usually 0.1 mm or less, preferably 0.05 mm or less, more preferably 0.01 mm or less. Even if a bituminous coal pulverized product having an average particle size exceeding 0.1 mm is used, the hysteresis loss of the rubber composition may not be sufficiently reduced, and the fuel efficiency may not be sufficiently improved. Further, when the rubber composition produced in the present invention is used as a composition for an inner liner, even if a bituminous coal pulverized product having an average particle size of more than 0.1 mm is used, the air permeability of the composition is sufficient. May not be improved.
  • the lower limit of the average particle diameter of the bituminous coal pulverized product is not particularly limited, but is preferably 0.001 mm or more. If it is less than 0.001 mm, the cost tends to increase.
  • the average particle size of the bituminous coal pulverized product is a mass-based average particle size calculated from a particle size distribution measured according to JIS Z 8815-1994.
  • the specific gravity of the bituminous coal pulverized product is preferably 1.6 or less, more preferably 1.5 or less, and even more preferably 1.3 or less. When a bituminous coal pulverized product having a specific gravity exceeding 1.6 is used, the specific gravity of the entire rubber composition increases, and there is a possibility that the fuel efficiency of the tire cannot be sufficiently improved.
  • the specific gravity of the pulverized bituminous coal is preferably 0.5 or more, and more preferably 1.0 or more. If a bituminous coal pulverized product having a specific gravity of less than 0.5 is used, workability during kneading may be deteriorated.
  • the amount is usually 5 parts by weight or more, preferably 10 parts by weight or more, and usually 70 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention.
  • it is preferably 60 parts by weight or less. If this amount is less than 5 parts by weight, the effect of the pulverized bituminous coal may not be sufficiently obtained, and if it exceeds 70 parts by weight, the workability during kneading may be deteriorated.
  • silica When silica is used as the filler, it is preferable to use a compound capable of binding to silica such as a silane coupling agent.
  • the compound include bis (3-triethoxysilylpropyl) tetrasulfide (eg, “Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (eg, “Si— 75 "), bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-diethoxymethylsilylpropyl) disulfide, 3-octanoylthiopropyltriethoxysilane (also known as” octanethioic acid S- [3- ( Triethoxysilyl) propyl] ester ", for example," NXT silane "manufactured by General Electronic Silicons), octanethioic acid S- [3- ⁇ (2-methyl-1,
  • bis (3-triethoxysilylpropyl) tetrasulfide eg “Si-69” manufactured by Degussa
  • bis (3-triethoxysilylpropyl) disulfide eg “Si-75” manufactured by Degussa
  • 3-octanoylthiopropyltriethoxysilane for example, “NXT silane” manufactured by General Electronic Silicons
  • the addition timing of the compound capable of binding to silica is not particularly limited, but it is preferably blended with the rubber component at the same time as silica.
  • the amount of the compound capable of binding to silica is preferably 2 to 10 parts by weight, more preferably 7 to 9 parts by weight per 100 parts by weight of silica.
  • the blending temperature is preferably 80 to 200 ° C, more preferably 110 to 180 ° C.
  • silica when silica is used as a filler, in addition to compounds capable of binding to silica, monohydric alcohols such as ethanol, butanol and octanol; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, poly It is also preferable to use polyhydric alcohols such as ether polyols; N-alkylamines; amino acids; liquid polybutadienes whose molecular ends are carboxy-modified or amine-modified.
  • monohydric alcohols such as ethanol, butanol and octanol
  • ethylene glycol diethylene glycol, triethylene glycol
  • polyethylene glycol, polypropylene glycol, pentaerythritol polypropylene glycol
  • polyhydric alcohols such as ether polyols; N-alkylamines; amino acids; liquid polybutadienes whose molecular ends are carb
  • vulcanization accelerators include thiazole-based vulcanization accelerators described in pages 412 to 413 of Rubber Industry Handbook ⁇ Fourth Edition> (issued by the Japan Rubber Association on January 20, 1994), Examples thereof include phenamide vulcanization accelerators and guanidine vulcanization accelerators.
  • vulcanization accelerator examples include N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), and N, N-dicyclohexene.
  • CBS N-cyclohexyl-2-benzothiazolylsulfenamide
  • BSS N-tert-butyl-2-benzothiazolylsulfenamide
  • N N-dicyclohexene
  • DCBS 2-mercaptobenzothiazole
  • MBTS dibenzothiazyl disulfide
  • DPG diphenylguanidine
  • N-cyclohexyl-2-benzothiazolylsulfenamide CBS
  • N-tert-butyl-2-benzothiazolylsulfenamide BVS
  • vulcanization accelerators N-cyclohexyl-2-benzothiazolylsulfenamide
  • DCBS N-dicyclohexyl-2-benzothiazolylsulfenamide
  • MBTS dibenzothiazyl disulfide
  • DPG diphenylguanidine
  • N-cyclohexyl-2-benzothiazolylsulfenamide CBS
  • N-tert-butyl-2-benzothiazolylsulfene vulcanization accelerators
  • BBS amide
  • DCBS N-dicyclohexyl-2-benzothiazolylsulfenamide
  • MBTS dibenzothiazyl disulfide
  • DPG diphenylguanidine
  • the ratio of the sulfur component to the vulcanization accelerator is not particularly limited, but the weight ratio of the sulfur component / vulcanization accelerator is preferably 1/10 to 10/1, more preferably 1/5 to 5/1, A preferred range is 1/2 to 2/1.
  • EV vulcanization which is a method of improving heat resistance, in which the ratio of sulfur component / vulcanization accelerator is 1 or less, is preferably used in applications that particularly require improvement in heat resistance. It is done.
  • vulcanization accelerating aid examples include zinc oxide, stearic acid, citraconimide compound, alkylphenol / sulfur chloride condensate, organic thiosulfate compound, and formula (III): R 16 —S—S—R 17 —S—S—R 18 (III) (Wherein R 17 represents a C 2-10 alkanediyl group, and R 16 and R 18 each independently represents a monovalent organic group containing a nitrogen atom.) The compound represented by these is mentioned.
  • zinc oxide is included in the concept of a vulcanization
  • vulcanization acceleration aid zinc oxide, stearic acid, and citraconic imide compounds are preferable, and zinc oxide and stearic acid are more preferable.
  • the amount thereof is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. More preferably, it is 0.1 to 10 parts by weight.
  • the amount is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. More preferably, it is 0.1 to 5 parts by weight.
  • biscitraconimides are preferable because they are thermally stable and have excellent dispersibility in the rubber component.
  • citraconimide compounds it is particularly stable thermally, particularly excellent in dispersibility in the rubber component, and can provide a vulcanized rubber composition having high hardness (Hs) (reversion control).
  • Hs high hardness
  • 1,3-biscitraconimidomethylbenzene represented by the following formula is preferred.
  • n is an integer of 0 to 10
  • X is an integer of 2 to 4
  • R 19 is a C 5-12 alkyl group.
  • N is preferably an integer of 1 to 9 because the dispersibility of the alkylphenol / sulfur chloride condensate (IV) in the rubber component is good.
  • the alkylphenol-sulfur chloride condensate (IV) tends to become thermally unstable.
  • X is 1, the sulfur content (sulfur in the alkylphenol-sulfur chloride condensate (IV)) Less weight).
  • X is preferably 2 for the reason that high hardness can be expressed efficiently (reversion suppression).
  • R 19 is a C 5-12 alkyl group.
  • R 19 is preferably a C 6-9 alkyl group because the dispersibility of the alkylphenol / sulfur chloride condensate (IV) in the rubber component is good.
  • n 0 to 10
  • X is 2
  • R 19 is an octyl group
  • sulfur content is 24% by weight.
  • the tack roll V200 is mentioned.
  • a vulcanized rubber composition having high hardness (Hs) can be obtained (reversion suppression).
  • Hs hardness
  • m is an integer of 3 to 10.
  • organic thiosulfate compound salt (V) An organic thiosulfate compound salt (V) containing crystal water may be used.
  • the organic thiosulfate compound salt (V) include lithium salt, potassium salt, sodium salt, magnesium salt, calcium salt, barium salt, zinc salt, nickel salt, cobalt salt, etc., potassium salt, sodium salt Is preferred.
  • M is an integer of 3 to 10, preferably an integer of 3 to 6.
  • m is 2 or less, there is a tendency that sufficient heat fatigue resistance cannot be obtained.
  • m is 11 or more, the effect of improving the heat fatigue resistance by the organic thiosulfate compound salt (V) may not be sufficiently obtained.
  • the organic thiosulfate compound salt (V) is preferably a sodium salt monohydrate or a sodium salt dihydrate from the viewpoint of being stable at normal temperature and pressure, and obtained from sodium thiosulfate from the viewpoint of cost.
  • the organic thiosulfate compound salt (V) is more preferable, and sodium 1,6-hexamethylenedithiosulfate dihydrate represented by the following formula is more preferable.
  • R 17 is a C 2-10 alkanediyl group, preferably a C 4-8 alkanediyl group, and more preferably a linear C 4-8 alkanediyl group.
  • R 17 is preferably linear.
  • the carbon number of R 17 is 1 or less, thermal stability may be poor. If the carbon number of R 17 is 11 or more, the distance between the polymers via the vulcanization accelerating aid becomes long, and the effect of adding the vulcanization accelerating aid may not be obtained.
  • R 16 and R 18 are each independently a monovalent organic group containing a nitrogen atom.
  • the monovalent organic group containing a nitrogen atom those containing at least one aromatic ring are preferred, and those containing an aromatic ring and a ⁇ N—C ( ⁇ S) — group are more preferred.
  • R 16 and R 18 may be the same or different, but are preferably the same for reasons such as ease of production.
  • Examples of the compound (III) include 1,2-bis (dibenzylthiocarbamoyldithio) ethane, 1,3-bis (dibenzylthiocarbamoyldithio) propane, 1,4-bis (dibenzylthiocarbamoyldithio) butane 1,5-bis (dibenzylthiocarbamoyldithio) pentane, 1,6-bis (dibenzylthiocarbamoyldithio) hexane, 1,7-bis (dibenzylthiocarbamoyldithio) heptane, 1,8-bis (di Examples include benzylthiocarbamoyldithio) octane, 1,9-bis (dibenzylthiocarbamoyldithio) nonane, 1,10-bis (dibenzylthiocarbamoyldithio)
  • Examples of commercially available products of compound (III) include VULCUREN TRIAL PRODUCT KA9188 and VULCUREN VP KA9188 (1,6-bis (dibenzylthiocarbamoyldithio) hexane) manufactured by Bayer.
  • the rubber composition may contain an organic compound such as resorcinol, a resin such as a resorcinol resin, a modified resorcinol resin, a cresol resin, a modified cresol resin, a phenol resin, and a modified phenol resin.
  • an organic compound such as resorcinol
  • a resin such as a resorcinol resin, a modified resorcinol resin, a cresol resin, a modified cresol resin, a phenol resin, and a modified phenol resin.
  • resorcinol examples include resorcinol manufactured by Sumitomo Chemical Co., Ltd.
  • the resorcinol resin include resorcinol / formaldehyde condensate.
  • modified resorcinol resin examples include those obtained by alkylating a part of the resorcinol resin repeating unit.
  • Penacolite resins B-18-S and B-20 manufactured by India Spec, Sumikanol 620 manufactured by Taoka Chemical Industries, R-6 manufactured by Uniroyal, SRF1501 manufactured by Schenectady Chemical, Ash Examples include Arofine 7209 manufactured by Land.
  • cresol resin examples include a cresol / formaldehyde condensate.
  • modified cresol resin examples include those obtained by modifying the terminal methyl group of the cresol resin to a hydroxy group, and those obtained by alkylating some of the repeating units of the cresol resin. Specifically, Sumikanol 610 manufactured by Taoka Chemical Industry Co., Ltd., PR-X11061 manufactured by Sumitomo Bakelite Co., Ltd., and the like can be given.
  • phenolic resins include phenol / formaldehyde condensates.
  • modified phenolic resins include resins obtained by modifying phenolic resins with cashew oil, tall oil, linseed oil, various animal and vegetable oils, unsaturated fatty acids, rosin, alkylbenzene resins, aniline, melamine, and the like.
  • Examples of other resins include methoxylated methylol melamine resins such as “SUMIKANOL 507AP” manufactured by Sumitomo Chemical Co., Ltd .; Coumarone resin NG4 (softening point 81-100 ° C.) manufactured by Nippon Steel Chemical Co., Ltd., manufactured by Kobe Oil Chemical Co., Ltd.
  • Coumarone-indene resin such as “Process Resin AC5” (softening point 75 ° C.); Terpene resin such as terpene resin, terpene / phenol resin, and aromatic modified terpene resin; “Nicanol® A70” manufactured by Mitsubishi Gas Chemical Company ”(Softening point 70 to 90 ° C.) and the like; hydrogenated rosin derivatives; novolac alkylphenol resins; resol alkylphenol resins; C5 petroleum resins; liquid polybutadiene.
  • Process Resin AC5 softening point 75 ° C.
  • Terpene resin such as terpene resin, terpene / phenol resin, and aromatic modified terpene resin
  • hydrogenated rosin derivatives novolac alkylphenol resins
  • resol alkylphenol resins C5 petroleum resins
  • Examples of the viscoelasticity improver include N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (for example, “Sumifine (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), Dithiouracil compounds described in JP-A-63-23942, “Tactrol (registered trademark) AP”, “Tactrol (registered trademark) V-200” manufactured by Taoka Chemical Co., Ltd., alkylphenols described in JP-A-2009-138148, Sulfur chloride condensate, bis (3-triethoxysilylpropyl) tetrasulfide (eg “Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (eg “Si-75” manufactured by Degussa) ), Bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-dieth
  • N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine for example, “Sumifine® 1162” manufactured by Sumitomo Chemical Co., Ltd.
  • bis (3-triethoxysilyl) Propyl) tetrasulfide eg “Si-69” manufactured by Degussa
  • bis (3-triethoxysilylpropyl) disulfide eg “Si-75” manufactured by Degussa
  • 1,6-bis (dibenzylthiocarbamoyl) Dithio) hexane for example, “KA9188” manufactured by Bayer
  • hexamethylene bisthiosulfate disodium salt dihydrate for example, “Parkalink 900” manufactured by Flexis
  • Tecchiroll registered trademark
  • AP Tetrasulfide
  • Anti-aging agents include those described on pages 436 to 443 of “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association.
  • Anti-aging agents include N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (abbreviation “6PPD”, for example, “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical), reaction of aniline and acetone. Products (abbreviated as “TMDQ”), poly (2,2,4-trimethyl-1,2-) dihydroquinoline) (for example, “Antioxidant FR” manufactured by Matsubara Sangyo Co., Ltd.), synthetic wax (paraffin wax etc.) A wax is preferably used.
  • the amount is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. Parts, more preferably 0.1 to 5 parts by weight.
  • Examples of the oil include process oil and vegetable oil.
  • Examples of the process oil include paraffinic process oil, naphthenic process oil, and aromatic process oil.
  • Examples of commercially available products include aromatic oil (“NC-140” manufactured by Cosmo Oil Co., Ltd.) and process oil (“Diana Process PS32” manufactured by Idemitsu Kosan Co., Ltd.).
  • wax examples include “Sannok (registered trademark) wax” manufactured by Ouchi Shinsei Chemical Co., Ltd. and “OZOACE-0355” manufactured by Nippon Seiwa Co., Ltd.
  • the peptizer is not particularly limited as long as it is usually used in the rubber field. For example, it is described in pages 446 to 449 of “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association. And aromatic mercaptan peptizers, aromatic disulfide peptizers, and aromatic mercaptan metal salt peptizers. Of these, dixylyl disulfide and o, o'-dibenzamide diphenyl disulfide ("Noctizer SS" manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) are preferable. Only one type of peptizer may be used, or two or more types may be used in combination.
  • the amount of peptizer used is not particularly limited, but is preferably 0.01 to 1 part by weight, preferably 0.05 to 0, per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. More preferably, 5 parts by weight.
  • retarder examples include phthalic anhydride, benzoic acid, salicylic acid, N-nitrosodiphenylamine, N- (cyclohexylthio) phthalimide (CTP), sulfonamide derivatives, diphenylurea, bis (tridecyl) pentaerythritol diphosphite, and the like.
  • CTP Cyclohexylthio phthalimide
  • the amount of the retarder used is not particularly limited, but is preferably 0.01 to 1 part by weight, preferably 0.05 to 0.5 parts by weight per 100 parts by weight of the rubber component contained in the rubber composition produced in the present invention. Part is more preferred.
  • q is preferably 2 or more, and more preferably 3 or more.
  • q is preferably 16 or less, and more preferably 14 or less. When q is 17 or more, the compatibility with the rubber component and the reinforcing property tend to decrease.
  • the position of the oxyethylene unit in the compound having an oxyethylene unit may be a main chain, a terminal, or a side chain.
  • a compound having oxyethylene units at least in the side chain is preferred from the viewpoint of sustaining the effect of preventing static electricity accumulation on the obtained tire surface and reducing electric resistance.
  • Examples of the compound having an oxyethylene unit in the main chain include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, monoethylene glycol, diethylene glycol, triethylene glycol, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene polyoxypropylene Examples thereof include alkyl ethers, polyoxyethylene alkylamines, polyoxyethylene styrenated alkyl ethers, and polyoxyethylene alkyl amides.
  • the number of oxyethylene units is preferably 4 or more, more preferably 8 or more per 100 carbon atoms constituting the main chain.
  • the electrical resistance tends to increase.
  • the number of oxyethylene units is preferably 12 or less, and more preferably 10 or less.
  • the number of oxyethylene units is 13 or more, the compatibility with the rubber component and the reinforcing property tend to be lowered.
  • the main chain is preferably composed mainly of polyethylene, polypropylene or polystyrene.
  • the production method of the present invention includes step 1 of preparing a kneaded product by kneading compound (I) and the like, a rubber component, and carbon black.
  • the rubber component and carbon black such as compound (I) may all be kneaded in the total amount used in step 1, and they are divided and part of them is kneaded in step 1, and then The remaining kneaded product and the cooled kneaded product obtained in step 2 may be kneaded in step 3.
  • Step 1 an internal mixer including a Banbury mixer, an open kneader, a pressure kneader, an extruder, an injection molding machine, or the like can be used.
  • an internal mixer including a Banbury mixer, an open kneader, a pressure kneader, an extruder, an injection molding machine, or the like can be used.
  • the rotational speed of kneading in step 1 is preferably 5 rpm or more, more preferably 10 rpm or more, further preferably 10 to 100 rpm, and particularly preferably 10 to 90 rpm.
  • the kneading time in step 1 is preferably 1 minute or more, more preferably 1 to 10 minutes, and further preferably 2 to 8 minutes.
  • the kneading may be continued by first kneading at a low rotation speed (for example, 10 rpm) and then increasing the rotation speed (for example, 50 rpm).
  • the apparatus set temperature at the start of kneading in step 1 is preferably 100 to 180 ° C., more preferably 120 to 180 ° C., still more preferably 140 to 180 ° C., and particularly preferably 150 to 170 ° C.
  • the discharge temperature of the kneaded product after kneading in step 1 is preferably 150 ° C. or higher, more preferably 155 to 200 ° C., and further preferably 160 to 185 ° C.
  • the production method of the present invention includes step 2 of preparing the cooled kneaded product by subjecting the obtained kneaded product to a cooling operation.
  • the kneaded product is preferably cooled to 120 ° C. or lower, more preferably 100 ° C. or lower, and still more preferably 80 ° C. or lower.
  • the temperature lower limit of the kneaded product after cooling is not particularly limited, but the temperature of the kneaded product after cooling is preferably 0 ° C. or higher, more preferably 5 ° C. or higher.
  • Examples of the cooling operation include (i) forced cooling of the kneaded product (for example, water cooling or forced air cooling), and (ii) processing the kneaded product into a sheet or board using, for example, an open roll. (The kneaded product is cooled when it comes into contact with an open roll or the like), (iii) After the kneaded product is processed into a sheet or board, the sheet or board kneaded product is forcibly cooled or allowed to cool. And the like. In order to efficiently and uniformly cool the kneaded material, it is preferable that the cooling operation includes processing the kneaded material into a sheet shape or a board shape.
  • the thickness of the kneaded material processed into a sheet or board is preferably 1 to 500 mm, more preferably 1 to 400 mm, and still more preferably 1 to 100 mm.
  • the cooling operation in the present invention does not include that the obtained kneaded product is simply left to stand and the temperature is naturally lowered (ie, allowed to cool) without performing the above-described operation.
  • paragraph [0057] of Patent Document 2 first, the rubber component, carbon black, and compound I described in Patent Document 2 (ie, (2Z) -4-[(4-aminophenyl) amino] -4 -Oxo-2-butenoate) is kneaded with a Banbury mixer (first kneading) and discharged to prepare a master batch, and then the master batch and other components are kneaded with a Banbury mixer (second kneading). That is, two-stage kneading is described.
  • Patent Document 2 does not describe performing a cooling operation on the master batch obtained by the first kneading.
  • the manufacturing method of this invention includes the process 3 which knead
  • the kneaded product containing the rubber component and carbon black, such as compound (I) is once cooled, and the resulting kneaded kneaded product is kneaded to shear the rubber component (low rubber component).
  • the present invention is not limited to such estimation.
  • an internal mixer including a Banbury mixer, an open kneader, a pressure kneader, an extruder, and an injection molding machine can be used.
  • the rotational speed of the initial kneading in the step 3 is preferably 40 to 100 rpm, more preferably 45 to 90 rpm, and further preferably 46 to 80 rpm. Preferably it is 0.5 to 10 minutes, more preferably 0.5 to 8 minutes, and still more preferably 0.5 to 6 minutes. After first kneading at such a rotational speed and sufficiently shearing the rubber component, the rotational speed is decreased (for example, 10 rpm) to sufficiently knead the rubber component and other components.
  • the rotational speed may be increased again (for example, 50 rpm) and kneading may be performed.
  • the apparatus set temperature at the start of kneading in step 3 is preferably 100 to 180 ° C, more preferably 120 to 170 ° C, and still more preferably 140 to 170 ° C.
  • the cooled and kneaded product obtained in step 2 is charged into the kneading apparatus while maintaining the temperature after cooling, and heated after the start of kneading in step 3.
  • the discharge temperature of the kneaded product after kneading in step 3 is preferably 100 to 180 ° C, more preferably 100 to 175 ° C, and still more preferably 100 to 170 ° C.
  • the present invention also provides a production method including kneading the rubber composition obtained as described above and a sulfur component.
  • a sulfur component for example, an open roll, a calendar, or the like can be used.
  • the kneading temperature of the sulfur component is preferably 60 to 120 ° C.
  • a vulcanized rubber composition can be produced by vulcanizing a rubber composition containing a sulfur component.
  • the vulcanization temperature is preferably 120 to 180 ° C.
  • a person skilled in the art can appropriately set the vulcanization time according to the composition of the rubber composition.
  • Vulcanization is usually carried out at normal pressure or under pressure.
  • kneading of other ingredients may be performed in any one of step 1, step 3 and other steps (for example, a kneading step).
  • the anti-aging agent in the kneaded product acts on the compound (I) or the like in the step 1, and the compound (I) or the like In some cases, the effect of reducing tan ⁇ is weakened.
  • the components other than the antioxidant and the vulcanization accelerator are preferably kneaded with the rubber component or the like before the sulfur component kneading step, that is, in either the mastication step, step 1 or step 3. .
  • Components other than the anti-aging agent and the vulcanization accelerator may be divided and kneaded with a rubber component or the like in two or more steps of the mastication step, step 1 and step 3.
  • the present invention also provides a rubber composition containing no sulfur component, a rubber composition containing a sulfur component, and a vulcanized rubber composition obtained by the above-described production method.
  • the rubber composition and vulcanized rubber composition of the present invention are useful for producing various products.
  • a vulcanized tire and a tire member are preferable.
  • the tire member include a tire belt member including the vulcanized rubber composition of the present invention and a steel cord, a tire carcass member including the vulcanized rubber composition of the present invention and a carcass fiber cord, and a tire sidewall member. , A tire inner liner member, a tire cap tread member, or a tire under tread member.
  • the vulcanized tire is manufactured by first manufacturing a tire member, combining these to manufacture a raw tire, and vulcanizing the raw tire.
  • the tire manufactured using the rubber composition of the present invention has a low loss coefficient (tan ⁇ ) and can achieve low fuel consumption.
  • the vulcanized rubber composition of the present invention can be used not only for the tire applications described above but also as various anti-vibration rubbers.
  • anti-vibration rubbers include anti-vibration rubbers for automobiles such as engine mounts, strut mounts, bushes, and exhaust hangers.
  • the anti-vibration rubber can be manufactured by first processing a rubber composition containing a sulfur component into a predetermined shape and then vulcanizing it.
  • NR Natural rubber (RSS # 1)
  • CB1 Carbon black HAF (Asahi Carbon Co., Ltd., trade name “Asahi # 70”)
  • CB2 Carbon Black ISAF (Asahi Carbon Co., Ltd., trade name “Asahi # 80”)
  • CB3 Carbon black FEF (Asahi Carbon Co., Ltd., trade name “Asahi # 60”)
  • Compound (I-1) (2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoate sodium dihydrate
  • Stearic acid “Lunac S20” manufactured by Kao Corporation
  • Anti-aging agent “Antigen (registered trademark) 6C” (N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd. - sulfur
  • step 1 in the present invention is referred to as “non-pro first step”, step 2 as “cooling step”, step 3 as “non-pro second step”, and sulfur component kneading step as “pro”. Step ".
  • ⁇ Non-pro first step> The natural rubber was put into a pressure kneader (TD1-5MDX manufactured by Toshin Co., Ltd.) whose apparatus set temperature at the start of kneading was 155 ° C., and then kneaded for 2 minutes at a rotation speed of 50 rpm. To this, components other than the rubber component were added in the amounts shown in Tables 1 to 5 below, and kneading was performed at the rotational speeds and times shown in Tables 1 to 5 below, and the kneaded product was discharged. The discharge temperatures are shown in Tables 1 to 5 below.
  • ⁇ Cooling process> The kneaded product obtained in the first step of non-pro was processed into a sheet having a thickness of 3 to 5 mm using an open roll (laboratory mill manufactured by Kansai Roll Co., Ltd.) having a set temperature of 50 ° C.
  • the sheet-like kneaded material was allowed to cool in an air atmosphere at room temperature until the temperature after cooling shown in 1 to 5 was reached.
  • ⁇ Non-pro second step> The rubber composition obtained in the above cooling process is put into a pressure kneader (TD1-5MDX manufactured by Toshin Co., Ltd.) whose apparatus set temperature at the start of kneading is 155 ° C., and sheared for 1 minute at a rotation speed of 50 rpm. Then, the components are added in the amounts shown in Tables 1 to 5 below, and kneaded for 1 minute at a rotational speed of 10 rpm and further for 1 minute at a rotational speed of 50 rpm, to obtain a rubber composition containing no sulfur component. It was. The discharge temperatures are shown in Tables 1 to 5 below.
  • ⁇ Vulcanization process> Using a vulcanizing press, the vulcanization temperature was set to 145 ° C., and the vulcanization time was 90% vulcanization time (tc (90)) obtained by rheometer measurement according to JIS K 6300-2. A vulcanized rubber composition was obtained by vulcanizing the rubber composition obtained by the pro process at a value obtained by adding 5 minutes to the value.
  • ⁇ Non-pro first step> The natural rubber was put into a pressure kneader (TD1-5MDX manufactured by Toshin Co., Ltd.) whose apparatus set temperature at the start of kneading was 155 ° C., and then kneaded for 2 minutes at a rotation speed of 50 rpm. To this, components other than the rubber component were added in the amounts shown in Tables 1 to 5 below, and kneading was performed at the rotational speeds and times shown in Tables 1 to 5 below, and the kneaded product was discharged. The discharge temperatures are shown in Tables 1 to 5 below.
  • ⁇ Vulcanization process> Using a vulcanizing press, the vulcanization temperature was set to 145 ° C, and the vulcanization time was added to the value of tc (90) obtained by rheometer measurement in accordance with JIS K 6300-2 by 5 minutes. By setting the time and vulcanizing the rubber composition obtained by the pro process, a vulcanized rubber composition was obtained.
  • Examples 1 to 4, Comparative Examples 1 and 2, and Reference Examples 1 and 2 The rubber compositions and vulcanized rubber compositions of Examples 1 to 4, Comparative Examples 1 and 2, and Reference Examples 1 and 2 were produced using the above-described operations and the components and conditions shown in Table 1 below.
  • the relative viscosity values and the relative tan ⁇ values of Examples 1 and 2 and Comparative Example 1 shown in Table 1 below are the Mooney of the rubber composition of Reference Example 1 in Formula (1) and Formula (2), respectively.
  • the viscosity and the tan ⁇ value of the vulcanized rubber composition were calculated, and the relative viscosity values and the relative tan ⁇ values of Examples 3 and 4 and Comparative Example 2 were calculated using the equations (1) and (2), respectively.
  • the value was calculated using the Mooney viscosity of the rubber composition of Reference Example 2 and the value of tan ⁇ of the vulcanized rubber composition.
  • Examples 5 to 7, Comparative Example 3, and Reference Example 3 The rubber compositions and vulcanized rubber compositions of Examples 5 to 7, Comparative Example 3, and Reference Example 3 were produced by the above operation and the components and conditions shown in Table 2 below.
  • the relative viscosity values and the relative tan ⁇ values of Examples 5 to 7 and Comparative Example 3 shown in Table 2 below are the Mooney values of the rubber composition of Reference Example 3 in Formula (1) and Formula (2), respectively.
  • the viscosity and tan ⁇ value of the vulcanized rubber composition were used for calculation.
  • Example 5 kneading was carried out at 50 rpm for 1 to 3 minutes after kneading at 10 rpm for 2 minutes in the non-pro first step. Even in Example 5 in which kneading was performed at 10 rpm for 2 minutes and at 50 rpm for 1 minute in the non-pro first step, the relative value of the viscosity was 1, and the increase and decrease in viscosity could be suppressed. From this result, it is estimated that the suppression of the increase in viscosity is caused by performing the second step of non-pro after cooling.
  • Examples 8 to 15, Comparative Examples 4 and 5, and Reference Examples 4 and 5 The rubber compositions and vulcanized rubber compositions of Examples 8 to 15, Comparative Examples 4 and 5, and Reference Examples 4 and 5 were produced using the above-described operations and the components and conditions shown in Table 3 below.
  • the relative values of the viscosity and the tan ⁇ of Examples 8 to 12 and Comparative Example 4 shown in Table 3 below are the Mooney of the rubber composition of Reference Example 4 in Formula (1) and Formula (2), respectively.
  • the viscosity and the tan ⁇ value of the vulcanized rubber composition were calculated, and the relative viscosity values and the tan ⁇ values of Examples 13 to 15 and Comparative Example 5 were calculated using the formulas (1) and (2), respectively.
  • the value was calculated using the Mooney viscosity of the rubber composition of Reference Example 5 and the tan ⁇ value of the vulcanized rubber composition.
  • Examples 16 to 21, Comparative Examples 6 to 8, and Reference Examples 6 to 8 The rubber compositions and vulcanized rubber compositions of Examples 16 to 21, Comparative Examples 6 to 8, and Reference Examples 6 to 8 were produced using the above-described operations and the components and conditions shown in Table 4 below.
  • the relative values of viscosity and tan ⁇ of Examples 16 and 17 and Comparative Example 6 shown in Table 4 below are the Mooney of the rubber composition of Reference Example 6 in Formula (1) and Formula (2), respectively.
  • the viscosity and the tan ⁇ value of the vulcanized rubber composition were calculated, and the relative viscosity values and the relative tan ⁇ values of Examples 18 and 19 and Comparative Example 7 were calculated using the equations (1) and (2), respectively.
  • Example 2 the Mooney viscosity of the rubber composition of Reference Example 7 and the tan ⁇ value of the vulcanized rubber composition were calculated, and the relative values of the viscosity and tan ⁇ of Examples 20 and 21 and Comparative Example 8 were In the formulas (1) and (2), the Mooney viscosity of the rubber composition of Reference Example 8 and the tan ⁇ value of the vulcanized rubber composition were used.
  • Examples 22 and 23, Comparative Examples 9 and 10, and Reference Example 9 The rubber compositions and vulcanized rubber compositions of Examples 22 and 23, Comparative Examples 9 and 10, and Reference Example 9 were produced using the above-described operations and the components and conditions shown in Table 5 below.
  • the relative viscosity values and the relative tan ⁇ values of Examples 22 and 23 and Comparative Examples 9 and 10 shown in Table 5 below are the rubber composition of Reference Example 9 in Formula (1) and Formula (2), respectively.
  • the Mooney viscosity and the tan ⁇ value of the vulcanized rubber composition were used for calculation.
  • the rubber composition obtained by the production method of the present invention is useful for production of various products (for example, vulcanized tires and tire members).

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

Abstract

La présente invention concerne un procédé de production d'une composition de caoutchouc, qui ne contient pas d'ingrédient soufré, le procédé comprenant : l'étape 1, dans laquelle au moins une substance choisie dans le groupe constitué par les composés représentés par la formule (I), des sels correspondants, des solvates correspondants et des solvates des sels, un ingrédient de caoutchouc et du noir de carbone sont malaxés pour préparer un mélange malaxé ; l'étape 2, dans laquelle le mélange malaxé obtenu est refroidi pour préparer un mélange malaxé refroidi ; et l'étape 3, dans laquelle le mélange malaxé obtenu refroidi est malaxé. (Les définitions des groupes dans la formule (I) sont données dans la description.)
PCT/JP2016/064820 2015-05-20 2016-05-19 Procédé de production d'une composition de caoutchouc WO2016186155A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020075945A (ja) * 2018-11-05 2020-05-21 Ｔｏｙｏ Ｔｉｒｅ株式会社 防振ゴム用ゴム組成物および防振ゴムならびに防振ゴム用ゴム組成物の製造方法
JP2020075944A (ja) * 2018-11-05 2020-05-21 Ｔｏｙｏ Ｔｉｒｅ株式会社 防振ゴム用ゴム組成物および防振ゴム

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005232354A (ja) * 2004-02-20 2005-09-02 Bridgestone Corp ゴム組成物及びそれを用いたタイヤ
JP2011026441A (ja) * 2009-07-24 2011-02-10 Sumitomo Rubber Ind Ltd ゴム組成物の製造方法
JP2014084312A (ja) * 2012-10-25 2014-05-12 Sumitomo Chemical Co Ltd 加硫ゴムの粘弾性特性を改善するための化合物及び該化合物を含んでなるゴム組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005232354A (ja) * 2004-02-20 2005-09-02 Bridgestone Corp ゴム組成物及びそれを用いたタイヤ
JP2011026441A (ja) * 2009-07-24 2011-02-10 Sumitomo Rubber Ind Ltd ゴム組成物の製造方法
JP2014084312A (ja) * 2012-10-25 2014-05-12 Sumitomo Chemical Co Ltd 加硫ゴムの粘弾性特性を改善するための化合物及び該化合物を含んでなるゴム組成物

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020075945A (ja) * 2018-11-05 2020-05-21 Ｔｏｙｏ Ｔｉｒｅ株式会社 防振ゴム用ゴム組成物および防振ゴムならびに防振ゴム用ゴム組成物の製造方法
JP2020075944A (ja) * 2018-11-05 2020-05-21 Ｔｏｙｏ Ｔｉｒｅ株式会社 防振ゴム用ゴム組成物および防振ゴム
JP7248411B2 (ja) 2018-11-05 2023-03-29 Ｔｏｙｏ Ｔｉｒｅ株式会社 防振ゴム用ゴム組成物および防振ゴムならびに防振ゴム用ゴム組成物の製造方法
JP7288749B2 (ja) 2018-11-05 2023-06-08 Ｔｏｙｏ Ｔｉｒｅ株式会社 防振ゴム用ゴム組成物および防振ゴム

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