WO2023228463A1 - Procédé de production d'une composition de caoutchouc, composition de caoutchouc et pneu - Google Patents

Procédé de production d'une composition de caoutchouc, composition de caoutchouc et pneu Download PDF

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WO2023228463A1
WO2023228463A1 PCT/JP2023/000858 JP2023000858W WO2023228463A1 WO 2023228463 A1 WO2023228463 A1 WO 2023228463A1 JP 2023000858 W JP2023000858 W JP 2023000858W WO 2023228463 A1 WO2023228463 A1 WO 2023228463A1
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group
carbon atoms
rubber composition
formula
rubber
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PCT/JP2023/000858
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English (en)
Japanese (ja)
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円 木村
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株式会社ブリヂストン
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    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the present invention relates to a method for producing a rubber composition, a rubber composition, and a tire.
  • an inorganic filler such as silica as a filler
  • inorganic fillers tend to aggregate in the rubber composition (aggregation occurs due to hydroxyl groups on the surface of the silica).
  • Various techniques have been developed to improve the dispersibility of fillers in rubber compositions.
  • Patent Document 1 discloses that chemical interaction between the rubber component and the filler is enhanced by containing a rubber component having a diene rubber, a reinforcing filler, and a compound having a specific amidine structure. discloses a technique for improving the elastic modulus and tan ⁇ by increasing the dispersibility of a reinforcing filler in a rubber composition. Furthermore, Patent Document 2 discloses that a conjugated diene polymer modified with a modifier containing an oligosiloxane and a specific compound having a tertiary amino group is used together with a filler to increase the dispersibility of the filler. A technique for improving low loss properties has been disclosed.
  • Patent Documents 1 and 2 may not be able to provide sufficient low loss properties, and further technologies are needed. Improvement was desired.
  • an object of the present invention is to provide a method for producing a rubber composition that can improve the dispersibility of fillers and obtain a rubber composition with excellent low loss properties.
  • Another object of the present invention is to provide a rubber composition with excellent low loss properties and a tire with reduced rolling resistance.
  • a conjugated diene polymer modified with a modifier containing oligosiloxane and a specific compound having a tertiary amino group is used as a rubber component, and a specific type of vulcanization accelerator is added in the first stage of the kneading process.
  • a specific type of vulcanization accelerator is added in the first stage of the kneading process.
  • the method for producing a rubber composition of the present invention includes a rubber component (A) containing at least one selected from natural rubber and synthetic diene rubber, a filler containing an inorganic filler (B), and a silane cup.
  • a method for producing a rubber composition comprising a ring agent (C) and a vulcanization accelerator (D), kneading the rubber composition in multiple stages; In the first step of the kneading, the rubber component (A), part or all of the inorganic filler (B), part or all of the silane coupling agent (C), and the vulcanization accelerator ( D) is kneaded;
  • the rubber component is characterized in that it contains a modified copolymer modified with a modifier containing a compound represented by formula (1).
  • the rubber composition of the present invention is characterized in that it is obtained by the method for manufacturing the rubber composition of the present invention described above. By providing the above configuration, excellent low loss properties can be achieved.
  • the tire of the present invention is characterized by using the rubber composition of the present invention described above. By providing the above configuration, an excellent rolling resistance reduction effect can be achieved.
  • the present invention it is possible to provide a method for producing a rubber composition that can improve the dispersibility of fillers and obtain a rubber composition with excellent low loss properties. Further, according to the present invention, it is possible to provide a rubber composition with excellent low loss properties and a tire with reduced rolling resistance.
  • the method for producing a rubber composition of the present invention includes a rubber component (A) containing at least one selected from natural rubber and synthetic diene rubber, a filler containing an inorganic filler (B), and a silane cup. This is a method for producing a rubber composition containing a ring agent (C) and a vulcanization accelerator (D).
  • the method for producing a rubber composition of the present invention includes kneading the rubber composition in multiple stages, In the first step of the kneading, the rubber component (A), part or all of the inorganic filler (B), part or all of the silane coupling agent (C), and the vulcanization accelerator ( D) is kneaded;
  • the rubber component is characterized in that it contains a modified copolymer modified with a modifier containing a compound represented by formula (1).
  • R 1 to R 8 are each independently an alkyl group having 1 to 20 carbon atoms
  • L 1 and L 2 are each independently an alkylene group having 1 to 20 carbon atoms
  • n is an integer from 2 to 4.
  • the rubber component (A) a conjugated diene polymer modified with a modifier containing a compound represented by the formula (1) containing an oligosiloxane and a tertiary amino group, which are filler-affinity functional groups, is used.
  • the use of the silane coupling agent (C) can improve the coupling function of the silane coupling agent (C) by adjusting the kneaded material prepared in the first step of the kneading.
  • these synergistic effects can greatly improve the low heat generation property of the obtained rubber composition.
  • the kneading device used for kneading there is no particular restriction on the kneading device used for kneading, and it can be appropriately selected depending on the purpose.
  • various conditions such as the rotational speed of the rotor, ram pressure, kneading temperature, and type of kneading device in the kneading can be selected as appropriate.
  • the rubber composition is kneaded in multiple stages. Then, in the first step of the kneading, the rubber component (A), a part or all of the inorganic filler (B), a part or all of the silane coupling agent (C), and the vulcanization accelerator. Knead agent (D).
  • the vulcanization accelerator (D) is added in the first stage of kneading is to increase the activity of the coupling function of the silane coupling agent (C).
  • the method for producing a rubber composition of the present invention in the first step of the kneading, all or a part of the rubber component (A), the inorganic filler (B), and the silane coupling agent (C) are mixed. Adding the vulcanization accelerator (D) after kneading all or part of the vulcanization accelerator (D) and further kneading further suppresses the reduction in the effect of improving the coupling function activity due to the combination of the vulcanization accelerator (D). Preferable because it can be done.
  • the reaction between the inorganic filler (B) and the silane coupling agent (C) has sufficiently progressed, the reaction between the silane coupling agent (C) and the rubber component (A) is allowed to proceed. This is because it can be done.
  • the time until the addition of the vulcanization accelerator (D) in the middle of the first step is more preferably 30 seconds or more, and the upper limit is more preferably 150 seconds or less, even more preferably 120 seconds or less. If this time is 10 seconds or more, the reaction between (B) and (C) can proceed sufficiently. Even if this time exceeds 180 seconds, the reaction between (B) and (C) has already progressed sufficiently, so it is difficult to enjoy any further effects, so it is preferable to set the upper limit to 180 seconds.
  • the molar amount X of the organic acid in the rubber composition in the first stage of kneading has the following relationship with the molar amount Y of the vulcanization accelerator (D) as shown in the following formula [3] .
  • This is to suitably suppress the reduction in the activity improvement effect of the coupling function due to the presence of a large amount of organic acid due to the addition of the accelerator (D). 0 ⁇ X ⁇ 1.5 ⁇ Y ... [3]
  • the organic acid is added in the second stage of kneading or later.
  • the maximum temperature of the rubber composition in the first stage of kneading is preferably 120 to 190°C. This is to allow the reaction between the inorganic filler (B) and the silane coupling agent (C) to proceed sufficiently. From this point of view, the maximum temperature of the rubber composition in the first stage of kneading is more preferably 130 to 190°C, and even more preferably 140 to 180°C.
  • the kneading step includes at least a first stage of kneading that does not contain any other vulcanizing agent except the vulcanization accelerator (D), and a final stage of kneading that contains a vulcanizing agent, etc.
  • the process includes two stages, and may include an intermediate stage of kneading which does not contain any other vulcanizing agent except the accelerator (D), if necessary.
  • the vulcanizing agent and the like refer to a vulcanizing agent and a vulcanization accelerator.
  • the first stage of kneading refers to the first stage of kneading both the rubber component (A), the inorganic filler (B) and the silane coupling agent (C).
  • the step of kneading A) with a filler other than the inorganic filler (B) or the step of pre-kneading only the rubber component (A) is not included.
  • the method for producing a rubber composition of the present invention comprises a rubber component (A) containing at least one selected from natural rubber and synthetic diene rubber, and a filler containing an inorganic filler (B). silane coupling agent (C), and a vulcanization accelerator (D).
  • A a rubber component containing at least one selected from natural rubber and synthetic diene rubber
  • B a filler containing an inorganic filler
  • C silane coupling agent
  • D a vulcanization accelerator
  • the rubber composition produced by the production method of the present invention includes a rubber component (A) containing at least one selected from natural rubber and synthetic diene rubber.
  • a rubber component (A) containing at least one selected from natural rubber and synthetic diene rubber as the rubber component By containing at least one selected from natural rubber and synthetic diene rubber as the rubber component, the abrasion resistance of the rubber composition can be improved.
  • the dispersibility of the inorganic filler (B) can be improved by modifying it with a modifier containing a compound represented by formula (1) described below.
  • the type of synthetic diene rubber contained in the rubber component (A) is not particularly limited, and can be appropriately selected depending on the required performance.
  • BR butadiene rubber
  • BR means polybutadiene, which is a polymer of 1,3-butadiene, and does not include copolymers of butadiene and other polymers, etc.
  • isoprene rubber (IR) isoprene rubber
  • SBR styrene butadiene rubber
  • SIBR styrene isoprene butadiene rubber
  • CR chloroprene rubber
  • NBR acrylonitrile butadiene rubber
  • the natural rubber and the synthetic diene rubber may be composed of only unmodified rubber or may be composed of modified rubber.
  • the synthetic diene rubber contained in the rubber component (A) does not contain a modified copolymer modified with a modifier containing a compound represented by formula (1) described below. shall be. Therefore, natural rubber and synthetic diene rubber modified with a modifier containing a compound represented by formula (1) described below are included in the modified copolymer described below.
  • the rubber component (A) may contain rubber other than diene rubber (non-diene rubber) as long as it does not impair the object of the present invention.
  • non-diene rubber examples include ethylene propylene diene rubber (EPDM), ethylene propylene rubber (EPM), butyl rubber (IIR), and the like.
  • the rubber component is a modified copolymer (hereinafter simply referred to as "modified conjugated diene polymer”) modified with a modifier containing a compound represented by formula (1). ).
  • modified conjugated diene polymer a conjugated diene polymer modified with a modifier containing a compound represented by the formula (1) containing an oligosiloxane and a tertiary amino group, which are filler-affinity functional groups.
  • the dispersibility of the inorganic filler (B) such as silica can be improved.
  • the rubber composition of the present invention has greatly improved low heat generation properties and improved filler dispersibility, so it has other properties such as reinforcing properties, handling stability when applied to tires, processability, etc. There is no deterioration in physical properties.
  • R 1 to R 8 are each independently an alkyl group having 1 to 20 carbon atoms; L 1 and L 2 are each independently an alkylene group having 1 to 20 carbon atoms. and n is an integer from 2 to 4.
  • R 1 to R 4 may each independently be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; In the case of 12 aryl group, aryloxy group with 6 to 12 carbon atoms, alkanoyloxy group with 2 to 12 carbon atoms (alkanoyl, RaCOO - , in this case, Ra is an alkyl group with 1 to 9 carbon atoms), 7 carbon atoms It may be substituted with one or more substituents selected from the group consisting of an aralkyloxy group having 1 to 13 carbon atoms, an arylalkyl group having 7 to 13 carbon atoms, and an alkylaryl group having 7 to 13 carbon atoms.
  • R 1 to R 4 may be substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, and even more specifically, R 1 to R 4 may each independently be substituted or unsubstituted. It may also be an unsubstituted alkyl group having 1 to 6 carbon atoms.
  • R 5 to R 8 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, specifically, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. 10 alkyl groups, more specifically may be substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, and when substituted, the substituents as previously explained for R 1 to R 4 May be replaced.
  • R 5 to R 8 are not alkyl groups but hydrolyzable substituents, the bonds of NR 5 R 6 and NR 7 R 8 are hydrolyzed to N-H in the presence of water, resulting in polymerization. It can have a negative effect on the processability of coalescence.
  • R 1 to R 4 may be a methyl group or an ethyl group
  • R 5 to R 8 may be an alkyl group having 1 to 10 carbon atoms. can.
  • the amino groups in the compound represented by formula (1) are preferably tertiary amino groups.
  • the tertiary amino group allows the compound represented by formula (1) to have even better processability when used as a modifier. Note that if a protecting group for protecting an amino group or hydrogen is bonded to R 5 to R 8 , it may be difficult to achieve the effect of the compound represented by formula (1). There is sex. When hydrogen is bonded, the anion reacts with hydrogen during the modification process and loses its reactivity, making the modification reaction itself impossible.
  • L 1 and L 2 in the compound represented by formula (1) are each independently substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms. More specifically, L 1 and L 2 each independently represent an alkylene group having 1 to 10 carbon atoms, and more specifically, an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, or a propylene group. It can be based on
  • the bond between Si and N may be broken during the subsequent treatment process, and the secondary amino groups generated at this time may be washed away by water during the post-treatment.
  • the silica filler due to the amino group member that promotes bonding with the inorganic filler (B) such as silica, and as a result, the dispersant The dispersion effect may be reduced.
  • L 1 and L 2 each independently have a carbon number of 1 to 3, such as a methylene group, an ethylene group, or a propylene group. More preferably, it is an alkylene group, and more specifically, it can be a propylene group. Furthermore, L 1 and L 2 may be substituted with the substituents described above for R 1 to R 4 .
  • the compound represented by the formula (1) is preferably, for example, any one of the compounds represented by the following formulas (1a) to (1e). This is because superior low heat generation properties can be achieved.
  • the compound represented by the formula (1) has an alkoxysilane structure bonded to the activated terminal of the conjugated diene polymer, and a Si-O-Si structure and three or more bonded to the terminal.
  • affinity for fillers such as silica the amino groups of silica promote bonding between the filler and the modified conjugated diene polymer compared to conventional modifiers containing one amino group in the molecule. I can do it.
  • the degree of bonding of the activated terminals of the conjugated diene polymer is uniform, and when observing changes in molecular weight distribution before and after coupling, it is found that the molecular weight distribution does not become larger after coupling and remains constant compared to before.
  • the physical properties of the modified conjugated diene polymer itself do not deteriorate, and the agglomeration of the filler in the rubber composition can be prevented and the dispersibility of the filler can be improved, thereby improving the processability of the rubber composition. I can do it.
  • R 1 to R 8 , L 1 and L 2 , and n are the same as those defined in the formula (1) above, and R' and R'' are It is an optional substituent that has no effect.
  • R' and R'' may each independently be the same as any one of R 1 to R 4 .
  • reaction of Reaction Formula 1 is carried out under acidic conditions, and any acid that is generally used in condensation reactions can be used without limitation. Those skilled in the art can select the most suitable acid according to various process variables such as the type of reactor in which the reaction is carried out, starting materials, and reaction temperature.
  • copolymers can be used as the copolymer modified with a modifier containing the compound represented by formula (1), but a copolymer having a conjugated diene unit and an aromatic vinyl unit is preferred. It is preferable that there be. Note that the conjugated diene units and aromatic vinyl units may be randomly arranged and bonded to form a random copolymer.
  • the content of aromatic vinyl units in the copolymer (the mass occupied by the aromatic vinyl units relative to the total mass of the copolymer) is preferably 40% by mass or less. This is because the low heat generation property of the rubber composition can be further improved. From the same viewpoint, the content of the aromatic vinyl unit is preferably 30% by mass or less, more preferably 20% by mass or less. In addition, from the viewpoint of maintaining good handling stability and wear resistance when the rubber composition is applied to tires, the content of aromatic vinyl units in the copolymer should be 3% by mass or more. It is preferable that there be.
  • the type of conjugated diene monomer that becomes the conjugated diene unit is not particularly limited.
  • One or more types can be used.
  • aromatic vinyl monomer that becomes the aromatic vinyl unit.
  • styrene ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene and 1-vinyl-5-
  • One or more types selected from the group consisting of hexylnaphthalene can be used.
  • the copolymer of the modified copolymer can be a combination of the above-mentioned conjugated diene monomer and aromatic vinyl monomer, but among them, styrene-butadiene rubber is preferable. . This is because excellent low heat generation properties can be achieved more reliably without deteriorating other performances, and the wet performance when applied to tires is also excellent.
  • the modified copolymer may have a narrow molecular weight distribution: Mw/Mn (also referred to as polydispersity index (PDI)) of 1.1 to 3.0. If the molecular weight distribution of the modified copolymer exceeds 3.0 or is less than 1.1, the tensile properties and viscoelasticity may deteriorate when applied to a rubber composition. Considering the remarkable effect of improving the tensile properties and viscoelasticity of the polymer by controlling the molecular weight distribution of the modified copolymer, the molecular weight distribution of the modified copolymer is preferably 1.3 to 2.0. In addition, by using the modifier, the modified copolymer has a molecular weight distribution similar to that of the copolymer before modification.
  • Mw/Mn also referred to as polydispersity index (PDI)
  • PDI polydispersity index
  • the molecular weight distribution of the modified copolymer can be calculated from the ratio of weight average molecular weight (Mw) to log average molecular weight (Mn) (Mw/Mn).
  • Mw weight average molecular weight
  • Mn log average molecular weight
  • Mw/Mn log average molecular weight
  • Mn number average molecular weight
  • Mw represents the molecular weight distribution of the polymer composition.
  • the average overall molecular weight can be expressed in grams per mole (g/mol).
  • the weight average molecular weight and the number average molecular weight are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC).
  • the modified copolymer satisfies the above molecular weight distribution conditions and has a number average molecular weight (Mn) of 50,000 g/mol to 2,000,000 g/mol, more specifically, 200,000 g/mol. It can be from mol to 800,000g/mol.
  • the weight average molecular weight (Mw) of the modified copolymer can be from 100,000 g/mol to 4,000,000 g/mol, more specifically from 300,000 g/mol to 1,500,000 g/mol.
  • the weight average molecular weight (Mw) of the modified copolymer is less than 100,000 g/mol or the number average molecular weight (Mn) is less than 50,000 g/mol
  • the tensile properties when applied to a rubber composition are There is a risk of deterioration.
  • the weight average molecular weight (Mw) exceeds 4,000,000 g/mol or the number average molecular weight (Mn) exceeds 2,000,000 g/mol, the processability of the modified copolymer may be reduced.
  • the properties of the rubber composition may deteriorate, making kneading difficult and making it difficult to sufficiently improve the physical properties of the rubber composition.
  • the modified copolymer according to one embodiment of the present invention simultaneously satisfies the conditions of weight average molecular weight (Mw) and number average molecular weight (Mn) in addition to the molecular weight distribution,
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • the present invention can provide a method for producing the modified copolymer using a modifier containing the compound represented by the formula (1).
  • a modifier containing the compound represented by the formula (1) Specifically, in the method for producing the modified copolymer, 1) an aromatic vinyl monomer and a conjugated diene monomer are polymerized in a hydrocarbon solvent in the presence of an organic alkali metal compound, and at least The method may include the steps of preparing an active polymer having an alkali metal bonded to one end thereof, and 2) reacting the active polymer with a modifier including a compound represented by Formula 1.
  • the above step 1) is a step for producing an active polymer having an alkali metal bonded to at least one terminal, in which an aromatic vinyl monomer is prepared in a hydrocarbon solvent in the presence of an organic alkali metal compound. This can be carried out by polymerizing a conjugated diene monomer and a conjugated diene monomer.
  • hydrocarbon solvent is not particularly limited, and for example, one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene. can be used.
  • the organic alkali metal compound can be used in an amount of 0.1 mmol to 1.0 mmol based on 100 g of the total monomer.
  • the organic alkali metal compound is not particularly limited, but includes, for example, methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, 1 selected from the group consisting of naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxid
  • the polymerization in step 1) may be carried out by further adding a polar additive if necessary, and the polar additive is 0.001 part by weight based on 100 parts by weight of the monomers. It can be added in an amount of ⁇ 1.0 part by weight. Specifically, it can be added in an amount of 0.005 part by weight to 0.5 part by weight, more specifically 0.01 part by weight to 0.3 part by weight, based on 100 parts by weight of the total monomer.
  • polar additives examples include tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis(3-dimethylamino)
  • ethyl ethyl
  • (dimethylaminoethyl)ethyl ether trimethylamine
  • triethylamine triethylamine
  • tripropylamine tetramethylethylenediamine
  • the polymerization in step 1) can be performed through adiabatic polymerization or isothermal polymerization.
  • the adiabatic polymerization refers to a polymerization method that includes a step of adding an organic alkali metal compound and then polymerizing it with the heat of self-reaction without optionally applying heat
  • the isothermal polymerization refers to a polymerization method that includes a step of adding an organic alkali metal compound and polymerizing it with the heat of self-reaction without applying any heat. This is a polymerization method in which the temperature of the polymer is maintained constant by adding heat or removing heat after the compound is added.
  • the polymerization may be carried out at a temperature range of 20°C to 200°C, specifically 0°C to 150°C, more specifically 10°C to 120°C. can.
  • step 2) is a modification reaction step in which the active polymer is reacted with a modifier containing the compound represented by the formula (1), in order to produce a modified copolymer.
  • the modifier containing the compound represented by the formula (1) may be the same as described above.
  • the compound represented by the formula (1) can be used in a proportion of 0.1 to 2.0 mol per 1 mol of the organic alkali metal compound.
  • the reaction in step 2) is a modification reaction for introducing functional groups into the polymer, and each of the reactions is carried out at a temperature range of 0°C to 90°C for 1 minute to 5 hours. It may be.
  • the above-mentioned manufacturing method may further include one or more steps of recovering the solvent and unreacted monomer and drying after the step 2), if necessary.
  • the modified copolymer is modified with a modifier containing the compound represented by formula (1), but it is further modified with a modifier containing the compound represented by formula (2). It is preferable that Since the dispersibility of the filler in the rubber composition can be further improved, it is possible to achieve both low heat generation and a higher level of handling stability when applied to tires, and further improve wear resistance and processability. You can also do it.
  • R 1 to R 3 each independently represent hydrogen; an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; Heteroalkyl group having 1 to 30 carbon atoms, heteroalkenyl group having 2 to 30 carbon atoms; heteroalkynyl group having 2 to 30 carbon atoms; cycloalkyl group having 5 to 30 carbon atoms; aryl group having 6 to 30 carbon atoms; or carbon number 3 to 30 heterocyclic group; R 4 is a single bond; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted cyclocarbon group having 5 to 20 carbon atoms; Alkylene group; or a substituted or unsubstituted arylene group having 5 to 20 carbon atoms, where the substituent is an alkyl group having 1 to 10 carbon atoms,
  • R 6 is a substituent-substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituent substituted or unsubstituted cycloalkylene group having 5 to 20 carbon atoms; or a substituent A substituted or unsubstituted arylene group having 6 to 20 carbon atoms, where the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cycloalkyl group having 6 to 20 carbon atoms.
  • R 7 and R 8 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted or unsubstituted.
  • R 9 is an alkylene group having 1 to 20 carbon atoms;
  • R 9 is hydrogen; an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a hetero group having 1 to 30 carbon atoms; Alkyl group; heteroalkenyl group having 2 to 30 carbon atoms; heteroalkynyl group having 2 to 30 carbon atoms; cycloalkyl group having 5 to 30 carbon atoms; aryl group having 6 to 30 carbon atoms; heterocycle having 3 to 30 carbon atoms group,
  • X is an N, O or S atom, and when X is O or S, R9 is absent.
  • R 10 is a substituent-substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituent substituted or unsubstituted cycloalkylene group having 5 to 20 carbon atoms; or a substituent A substituted or unsubstituted arylene group having 6 to 20 carbon atoms, where the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms.
  • R 11 and R 12 each independently represent an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms; ; Heteroalkenyl group having 2 to 30 carbon atoms; Heteroalkynyl group having 2 to 30 carbon atoms; Cycloalkyl group having 5 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; Heterocyclic group having 3 to 30 carbon atoms; be.
  • R 1 to R 3 are independently hydrogen; an alkyl group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkenyl group having 2 to 10 carbon atoms; is an alkynyl group having 1 to 10 carbon atoms;
  • R 4 is a single bond; or an unsubstituted alkylene group having 1 to 10 carbon atoms;
  • R 5 is an alkyl group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms ; an alkynyl group having 2 to 10 carbon atoms; or a functional group represented by the following chemical formula (2a) or (2b);
  • R 6 is an unsubstituted group having 1 to 10 carbon atoms; is an alkylene group
  • R 7 and R 8 are each independently an unsubstituted alkylene group having 1 to 10 carbon atoms
  • R 7 is an alkyl group having 1 to 10
  • the compound represented by the above formula (2) can be a compound represented by the following formulas (2-1) to (2-3).
  • the modifier containing the compound represented by formula (2) is used as a modification initiator.
  • a modifying group derived from the compound represented by formula (2) can be added to the copolymer.
  • the polymerization of the conjugated diene monomer and the aromatic vinyl monomer can be, for example, anionic polymerization, and as a specific example, an anion active site is formed at the polymerization end by a growth polymerization reaction using anions. Living anionic polymerization may also be used.
  • the polymerization may be temperature-programmed polymerization, isothermal polymerization, or constant-temperature polymerization (adiabatic polymerization), and the constant-temperature polymerization may be carried out optionally after adding a modifier containing the compound represented by formula (2).
  • It refers to a polymerization method that includes a step of polymerizing with self-reaction heat without applying heat to the polymer
  • the temperature rising polymerization refers to a polymerization method in which the temperature is increased by optionally adding heat after adding a modification initiator.
  • the isothermal polymerization refers to a polymerization method in which after the modification initiator is added, heat is applied to increase the heat or heat is removed to maintain a constant temperature of the polymer.
  • the content of the modified copolymer in the rubber component (A) is not particularly limited, but can be 0.1 to 90% by mass, preferably 10 to 90% by mass, and 20 to 80% by mass. It is more preferable that it is mass %.
  • the content of the modified copolymer is 0.1% by weight or more, low heat build-up can be improved while maintaining good other physical properties, and as a result, molded products manufactured using the rubber composition, such as , effects such as tire fuel efficiency, wear characteristics, and braking characteristics can be obtained more reliably.
  • the rubber composition produced by the production method of the present invention contains a filler containing an inorganic filler (B).
  • the inorganic filler (B) for example, silica and an inorganic compound represented by the following general formula (XI) can be used.
  • M1 is a metal selected from the group consisting of aluminum, magnesium, titanium, calcium, and zirconium, an oxide or hydroxide of these metals, and a hydrate thereof, or At least one selected from carbonates of these metals, and d, 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. .
  • the inorganic compound is at least one metal, metal oxide, or metal hydroxide selected from aluminum, magnesium, titanium, calcium, and zirconium. becomes.
  • silica is preferred from the viewpoint of achieving both low rolling properties and wear resistance.
  • Any commercially available silica can be used, and among these, wet silica, dry silica, and colloidal silica are preferably used, and wet silica is particularly preferred.
  • the BET specific surface area (measured according to ISO 5794/1) of the silica is preferably 40 to 350 m 2 /g. Silica having a BET surface area within this range has the advantage of being able to achieve both rubber reinforcing properties and dispersibility into the rubber component.
  • silica with a BET surface area in the range of 80 to 350 m 2 /g is more preferred, and silica with a BET surface area in the range of 120 to 350 m 2 /g is particularly preferred.
  • Examples of the inorganic compound represented by the general formula (XI) include alumina ( Al 2 O 3 ) such as ⁇ -alumina and ⁇ -alumina, alumina monohydrate (Al 2 O 3 .H 2 O) such as boehmite and diaspore; Aluminum hydroxide [Al(OH) 3 ], aluminum carbonate [Al 2 (CO 3 ) 2 ], magnesium hydroxide [Mg(OH) 2 ], magnesium oxide (MgO), magnesium carbonate (MgCO 3 ), talc (3MgO ⁇ 4SiO2 ⁇ H2O ), attapulgite (5MgO ⁇ 8SiO2 ⁇ 9H2O ), titanium white ( TiO2 ), titanium black ( TiO2n-1 ), calcium oxide (CaO), water Calcium oxide [Ca(OH) 2 ], magnesium aluminum oxide (MgO ⁇ Al 2 O 3 ), clay (Al 2 O 3 ⁇ 2SiO 2 ), kaolin (Al 2 O 3 ⁇ 2Si
  • M1 in the general formula (XI) is at least one selected from aluminum metal, aluminum oxides or hydroxides, hydrates thereof, or aluminum carbonates.
  • These inorganic compounds represented by the general formula (XI) 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 the balance between kneading workability, abrasion resistance, and wet grip performance.
  • silica may be used alone, or silica and one or more types of inorganic compounds represented by general formula (III) may be used in combination.
  • the filler may contain carbon black in addition to the above-mentioned inorganic filler (B), if desired.
  • carbon black is not particularly limited, and includes, for example, high, medium or low structure SAF, ISAF, IISAF, N339, HAF, FEF, GPF, SRF grade carbon black, especially SAF, ISAF, IISAF, N339, HAF, Preferably, FEF grade carbon black is used.
  • the nitrogen adsorption specific surface area (N2SA, measured according to JIS K6217-2:2001) is preferably 30 to 250 m 2 /g.
  • One type of carbon black may be used alone, or two or more types may be used in combination. Note that, in the present invention, carbon black is not included in the inorganic filler (B).
  • the inorganic filler (B) is preferably used in an amount of 20 to 120 parts by mass based on 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 ensuring wet performance, and if it is 120 parts by mass or less, it is preferable from the viewpoint of improving low heat generation property. Furthermore, it is more preferable to use 30 to 100 parts by mass. Further, the filler is preferably used in an amount of 20 to 150 parts by mass per 100 parts by mass of the rubber component (A).
  • the content of 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 rubber composition produced by the production method of the present invention contains a silane coupling agent (C).
  • the silane coupling agent (C) is preferably at least one compound selected from the group consisting of compounds represented by the following general formulas (I) to (IV).
  • the rubber composition produced by the production method of the present invention has better workability during rubber processing and can be used for pneumatic tires with better wear resistance. can be given.
  • R 1 may be the same or different, and each represents a straight chain, cyclic or branched alkyl group having 1 to 8 carbon atoms, or a straight chain or branched alkoxyalkyl group having 2 to 8 carbon atoms
  • R 2 may be the same or different, each a straight chain, cyclic or branched alkyl group having 1 to 8 carbon atoms
  • R 3 may be the same or different, each being a straight chain or branched chain having 1 to 8 carbon atoms.
  • a has an average value of 2 to 6
  • p and r may be the same or different, and each has an average value of 0 to 3, provided that both p and r are not 3.
  • silane coupling agent (C) represented by the above general formula (I) include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, 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)
  • R 9 , R 10 and R 11 are each a hydrogen atom or a monovalent hydrocarbon having 1 to 18 carbon atoms
  • h is an average value of 1 to 4
  • R 5 is R 4 , a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms
  • R 6 is R 4
  • R 5 is a hydrogen atom or a -[O(R 12 O) j ]0.5- group
  • R 12 is an alkylene group having 1 to 18 carbon atoms, and j is an integer of 1 to 4
  • R 7 is It is a divalent hydrocarbon group having 1 to 18 carbon atoms
  • R 8 is a monovalent hydrocarbon group having 1 to
  • R 8 , R 9 , R 10 and R 11 may be the same or different, and each is preferably a linear, cyclic or branched alkyl group or alkenyl group having 1 to 18 carbon atoms. , an aryl group, and an aralkyl group.
  • R5 is a monovalent hydrocarbon group having 1 to 18 carbon atoms, it is a group selected from the group consisting of a linear, cyclic or branched alkyl group, alkenyl group, aryl group and aralkyl group. It is preferable.
  • R 12 is preferably a linear, cyclic or branched alkylene group, and particularly preferably a linear one.
  • R 9 is, for example, an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 2 to 18 carbon atoms, a cycloalkylene group having 5 to 18 carbon atoms, a cycloalkylalkylene group having 6 to 18 carbon atoms, or an arylene group having 6 to 18 carbon atoms. and an aralkylene group having 7 to 18 carbon atoms.
  • the alkylene group and alkenylene group may be linear or branched, and the cycloalkylene group, cycloalkylalkylene group, arylene group, and aralkylene group may have a substituent such as a lower alkyl group on the ring. may have.
  • R 7 is preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups. can.
  • Specific examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms as R 5 , R 8 , R 9 , R 10 and R 11 in the above general formula (II) include a methyl group, an ethyl group, and an n-propyl group.
  • R 12 in the above general formula (II) examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, decamethylene group, dodecamethylene group, and the like.
  • silane coupling agent (C) represented by the general formula (II) include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, and 3-decanoylthiopropyltriethoxysilane.
  • Ethoxysilane 3-lauroylthiopropyltriethoxysilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane , 3-hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane, Examples include 2-octanoylthioethyltrimethoxysilane, 2-decanoylthioethyltrimethoxysilane, and 2-lau
  • each R 13 when there is a plurality of R 13s , they may be the same or different, and each R 13 is a straight chain, cyclic or branched alkyl group having 1 to 8 carbon atoms, or a straight chain or branched alkoxy group having 2 to 8 carbon atoms. It is an alkyl group or a hydrogen atom, and when there is a plurality of R 14s , they may be the same or different, and each is a linear, cyclic, or branched alkyl group having 1 to 8 carbon atoms, and when there is a plurality of R 15s , they are linear, cyclic, or branched alkyl groups.
  • R 16 is any of the general formulas (-S-R 17 -S-), (-R 18 -S m1 -R 19 -) and (-R 20 -S m2 -R 21 -S m3 -R 22 -) (R 17 to R 22 are each a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent aromatic group, or a divalent organic group containing a hetero element other than sulfur and oxygen) , m1, m2, and m3 each have an average value of 1 or more and less than 4.), the plurality of k's may be the same or different, each has an average value of 1 to 6, and s and t each have an average value of The value is 0 to 3. However, both s and t cannot be 3.
  • silane coupling agent (C) represented by the above general formula (III)
  • 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 4 -(CH 2 ) 6 -S 4 -(CH 2 ) 3 - Si(OCH 2 CH 3 ) 3 Average composition formula (CH 3 CH 2 O) 3 Si-
  • R 23 is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and multiple G's may be the same or different, and each is an alkanediyl group or an alkenediyl group having 1 to 9 carbon atoms.
  • the plurality of Z a may be the same or different, each being a functional group capable of bonding to two silicon atoms, and [-0-] 0.5 , [-0-G-] 0. 5 and [-O-G-O-] 0.5
  • the plurality of Z b 's may be the same or different, and each is a functional group that can bond to two silicon atoms.
  • R b and R b are each a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms.
  • Z a u , Z b v and Z c w in the multiple A parts may be the same or different
  • Z a in the multiple B parts u , Z b v and Z c w may be the same or different.
  • silane coupling agent (C) represented by the general formula (IV) include chemical formula (V), chemical formula (IV), and chemical formula (VII).
  • silane coupling agent represented by the chemical formula (V) "NXT Low-VSilane” manufactured by Momentive Performance Materials is available as a commercial product. Further, as the silane coupling agent represented by the chemical formula (VI), the trademark “NXT Ultra Low-VSilane” manufactured by Momentive Performance Materials is also available as a commercial product. Further, as the silane coupling agent represented by the chemical formula (VII), it can be mentioned as "NXT-Z", a trademark manufactured by Momentive Performance Materials.
  • the silane coupling agents obtained by the above general formula (II), chemical formula (V), and chemical formula (VI) have a protected mercapto group, so during initial vulcanization (scorch) during processing before the vulcanization step.
  • silane coupling agents obtained by chemical formulas (V), (VI), and (VII) have a large number of alkoxysilane carbon atoms, they generate less volatile compounds VOC (especially alcohol), which is preferable in terms of the working environment.
  • the silane coupling agent of chemical formula (VII) is more preferable because it provides low heat build-up as a tire performance.
  • the silane coupling agent (C) is particularly preferably a compound represented by the above general formula (I) among the compounds represented by the above general formulas (I) to (IV). This is because the vulcanization accelerator (D) tends to activate the polysulfide bonding site that reacts with the rubber component (A).
  • the silane coupling agent (C) may be used alone or in combination of two or more.
  • the amount of the silane coupling agent (C) in the rubber composition is such that the mass ratio ⁇ silane coupling agent (C)/inorganic filler (B) ⁇ is between (1/100) and (20/100).
  • the mass ratio is more preferably (3/100) to (20/100), and particularly preferably the mass ratio is (4/100) to (10/100).
  • the rubber composition produced by the production method of the present invention contains a vulcanization accelerator (D).
  • a vulcanization accelerator D
  • vulcanization accelerators such as guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamates, thioureas, and xanthates, which are preferably mentioned, will be described in detail.
  • Examples of the vulcanization accelerator for guanidines include 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolyl biguanide, di-o-tolylguanidine salt of dicatechol borate, 1, Examples include 3-di-o-cumenylguanidine, 1,3-di-o-biphenylguanidine, 1,3-di-o-cumenyl-2-propionylguanidine, and 1,3-diphenylguanidine, 1,3 -di-o-tolylguanidine and 1-o-tolyl biguanide are preferred because of their high reactivity.
  • the vulcanization accelerators for the thiazoles include 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, zinc salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, and 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-mercaptobenzothiazole and the like.
  • Examples of the thiuram vulcanization accelerator include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrapropylthiuram disulfide, tetraisopropylthiuram disulfide, tetrabutylthiuram disulfide, tetrapentylthiuram disulfide, tetrahexylthiuram disulfide, tetraheptylthiuram disulfide, Tetraoctylthiuram disulfide, tetranonylthiuram disulfide, tetradecylthiuram disulfide, tetradodecylthiuram disulfide, tetrastearylthiuram disulfide, tetrabenzylthiuram disulfide, tetrakis(2-ethylhexyl)thiuram disulfide,
  • Examples of the vulcanization accelerator for the thioureas include N,N'-diphenylthiourea, trimethylthiourea, N,N'-diethylthiourea, N,N'-dimethylthiourea, N,N'-dibutylthiourea, and 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, etc. It will be done. Among these, N,N'-diethylthiourea, trimethylthiourea, N,N'-diphenylthiourea and N,N'-dimethylthiourea are preferred because of their high reactivity.
  • Examples of the vulcanization accelerator for the dithiocarbamates 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 didodecyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, Zinc dibenzyldithiocarbamate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dipropyldithiocarbamate, copper diisopropyldithiocarbamate, copper dibutyldithiocarbamate, copper dipentyldithiocarbamate, copper dihexyldithiocarbamate, copper diheptyldithiocarbamate, dioctyldithiocarbamine copper acid, copper di(2-ethylhe
  • zinc dibenzyldithiocarbamate zinc N-ethyl-N-phenyldithiocarbamate, zinc dimethyldithiocarbamate and copper dimethyldithiocarbamate are preferred because of their high reactivity.
  • Examples of the vulcanization accelerator for the xanthate salts include zinc methylxanthate, zinc ethylxanthate, zinc propylxanthate, zinc isopropylxanthate, zinc butylxanthate, zinc pentylxanthate, zinc hexylxanthate, and zinc heptylxanthate.
  • the modified copolymer in the rubber component (A) is modified at both ends, the blended viscosity tends to increase, but by using the guanidine vulcanization accelerator, the blended viscosity can be increased. This is because the increase can be suppressed and better workability can be obtained.
  • the number of molecules (number of moles) of the vulcanization accelerator (D) in the rubber composition in the first stage of kneading is the number of molecules (number of moles) of the silane coupling agent (C). It is preferably 0.1 to 1.0 times that of This is because if it is 0.1 times or more, activation of the silane coupling agent (C) will occur sufficiently, and if it is 1.0 times or less, the vulcanization rate will not be greatly affected. More preferably, the number of molecules (moles) of the vulcanization accelerator (D) is 0.2 to 0.6 times the number of molecules (moles) of the silane coupling agent (C).
  • the vulcanization accelerator (D) since the vulcanization accelerator (D) is also used as an accelerator for sulfur vulcanization, it may be added in an appropriate amount even in the final stage of kneading, if desired.
  • a vulcanization accelerator in the final stage of kneading it is not limited to the above-mentioned vulcanization accelerator (D), and any known vulcanization accelerator may also be blended.
  • the number of molecules (number of moles) of the organic acid compound in the rubber composition in the first stage of kneading is 1.5 times the number of molecules (number of moles) of the vulcanization accelerator (D). It is preferable that it is below. This is to suitably suppress the reduction in the effect of improving the activity of the coupling function due to the addition of the vulcanization accelerator (D).
  • the organic acid compounds include stearic acid, palmitic acid, myristic acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, capric acid, pelargonic acid, caprylic acid, enanthic acid, caproic acid, oleic acid, vaccenic acid, and linoleic acid.
  • Examples include organic acids such as acids, saturated fatty acids and unsaturated fatty acids such as linolenic acid and nervonic acid, resin acids such as rosin acid and modified rosin acid, esters of the saturated fatty acids and unsaturated fatty acids, and resin acids.
  • stearic acid accounts for 50 mol% or more of the organic acid compound contained in the rubber composition in the first stage of kneading, since it can also fully exhibit its function as a vulcanization accelerator. It is preferable that there be.
  • the rubber component (A) contains at least one selected from emulsion polymerized styrene-butadiene copolymer and natural rubber, 50 mol of the organic acid compound contained in the rubber composition in the first stage of kneading.
  • % or more is preferably at least one compound selected from rosin acid and fatty acid contained in at least one selected from the emulsion polymerized styrene-butadiene copolymer and the natural rubber.
  • the rosin acid (including modified rosin acid) and fatty acid contained in the emulsion polymerized styrene-butadiene copolymer are derived from the emulsifier necessary for polymerizing the emulsion polymerized styrene-butadiene copolymer.
  • Natural rubber also usually contains small amounts of fatty acids.
  • the rubber composition produced by the production method of the present invention contains the above-mentioned rubber component (A), a filler containing an inorganic filler (B), a silane coupling agent (C), and a vulcanization accelerator (D). ), etc.
  • compounding components commonly used in the rubber industry such as anti-aging agents, softeners, etc., are appropriately selected within the range that does not impair the purpose of the present invention, and within the range of normal compounding amounts. It can be blended with Commercially available products can be suitably used as these compounding agents.
  • any known anti-aging agent can be used and is not particularly limited.
  • phenol-based anti-aging agents imidazole-based anti-aging agents, amine-based anti-aging agents, etc. can be mentioned.
  • These anti-aging agents can be used alone or in combination of two or more.
  • the rubber composition produced by the production method of the present invention preferably further contains a softener from the viewpoint of achieving excellent low loss properties and abrasion resistance.
  • the softening agent include naphthenic base oils, paraffinic base oils, aromatic base oils, and the like.
  • the content of the lubricant is preferably 2 to 30 parts by mass based on 100 parts by mass of the rubber component. If the content of the lubricant exceeds 30 parts by mass based on 100 parts by mass of the rubber component, there is a risk that the lubricant will ooze out onto the surface of the rubber product or that the wear resistance may decrease.
  • naphthenic base oils and paraffinic base oils have the effect of helping to diffuse into polymers and react, and this is because oils with lower pour points diffuse better into polymers.
  • the classification of the naphthenic base oil, the paraffinic base oil, and the aromatic base oil is determined by the CA value, CP value, and CN value.
  • the naphthenic base oils are classified as TDAE, SRAE, RAE, Black Oil, and the like.
  • spindle oil and paraffin oil are classified as the paraffin base oil.
  • more preferable effects can be obtained with a mixed oil such as A/O Mix (Sankyo Yuka Kogyo Co., Ltd.), which is a mixture of the naphthenic base oil and the naphthenic asphalt.
  • the timing of blending these lubricating oils is not particularly limited, and for example, the oil may be extended during the production of the rubber component, or may be added when kneading the rubber composition.
  • various compounding agents such as a vulcanization activator such as zinc white and an anti-aging agent, which are usually blended into the rubber composition, are added to the rubber composition as needed in the first stage of kneading. It is kneaded in the stage or the final stage, or in an intermediate stage between the first stage and the final stage.
  • a kneading device in the production method of the present invention a Banbury mixer, a roll, an intensive mixer, a kneader, a twin-screw extruder, etc. are used.
  • the rubber composition of the present invention is characterized in that it is obtained by the method for manufacturing the rubber composition of the present invention described above.
  • the rubber composition obtained by the production method of the present invention has high filler dispersibility and excellent low loss properties.
  • the tire of the present invention is characterized by using the rubber composition of the present invention described above.
  • the rubber composition of the present invention As a tire material, it is possible to reduce rolling resistance.
  • the tire of the present invention is not particularly limited, except that the rubber composition of the present invention described above is used for any of the tire members, and can be manufactured according to a conventional method.
  • inert gas such as nitrogen, argon, helium, etc. can be used.
  • the rubber composition of the present invention described above is used in any of the tire members, and among the tire members, tread rubber, sidewall rubber, cord or fiber coated rubber, bead filler, or gum chafer is used. It is preferably used for. This is because, if applied to these members, the rubber composition of the present invention can fully enjoy the excellent low loss effect and further benefit from the rolling resistance reducing effect.
  • the type of tire of the present invention is not particularly limited, but passenger car tires, studless tires, and run-flat tires are preferred from the standpoint of being able to more effectively achieve both improved wear resistance and reduced rolling resistance.
  • it is preferably a tire for a truck or bus.
  • Rubber composition samples were prepared using the formulation and kneading method shown in Table 1.
  • Table 1 shows the maximum temperature of the mixture in the first kneading stage.
  • a second kneading step is performed after the first kneading step. Note that kneading is performed using a Banbury mixer.
  • ⁇ Performance evaluation> (1) Compound viscosity For each sample rubber composition, after preheating for 1 minute at 130°C using RPA2000 (manufactured by Alpha Technologies), the compound viscosity after 0.1 minutes was measured at a frequency of 1 Hz and a strain of 100%. Measure. The smaller the value, the better the workability. Table 1 shows the measurement results of each Example and each Comparative Example. The smaller the measured value, the higher the dispersibility of silica, indicating better results.
  • modified SBR-2 A styrene solution containing 60% by weight of styrene dissolved in n-hexane was added to the first reactor of a continuous reactor in which three reactors were connected in series at a rate of 0.84 kg/h at a rate of 1,3% in n-hexane.
  • Agent (2-1) is injected at a rate of 292.5.0 g/h.
  • the temperature of the first group reactor is maintained at 50°C, and when the polymerization conversion rate reaches 43%, the transfer The polymer is transferred from the first reactor to the second reactor through piping. Subsequently, a 1,3-butadiene solution in which 60% by weight of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 0.68 kg/h. At this time, the temperature of the second group reactor is maintained at 65°C, and when the polymerization conversion rate is 95% or more, the polymer is transferred from the second reactor to the third reactor through the transfer pipe. do.
  • the temperature of the third reactor is maintained at 65°C.
  • a solution of IR1520 (BASF) dissolved at 30% by weight as an antioxidant is injected into the polymerization solution discharged from the third reactor at a rate of 170 g/h and stirred.
  • the obtained polymer is poured into warm water heated with steam, stirred, and the solvent is removed to obtain modified SBR-2.
  • the styrene content was 5% by mass, and the vinyl content in the butadiene moiety was 37%.
  • *3 SBR-3 is manufactured under the following conditions. Charge 2.750 g of cyclohexane, 2.00 g of tetrahydrofuran, 160 g of styrene, 165 g of 1,3-butadiene, and 34.9 mg (0.10 mmol) of potassium dodecylbenzenesulfonate (DBS-K) into a 5-liter autoclave reactor purged with nitrogen. .
  • DBS-K potassium dodecylbenzenesulfonate
  • modified SBR-3 After adding 2,6-di-tert-butyl-p-cresol to the polymer solution after the reaction, the solvent is removed by steam stripping, and the rubber is dried with a hot roll to obtain modified SBR-3. Furthermore, as a result of measuring the microstructure of the obtained modified SBR-3, the styrene content was 35% by mass, and the vinyl content in the butadiene portion was 27%. *4 SBR-4 is manufactured under the following conditions.
  • a styrene solution containing 60% by weight of styrene dissolved in n-hexane was added to the first reactor of a continuous reactor in which three reactors were connected in series at a rate of 6.58 kg/h and 1,3% of styrene was dissolved in n-hexane.
  • a solution of n-butyllithium dissolved at 10% by mass was injected at a rate of 59.0 g/h, and the temperature of the first group reactor was maintained at 50°C.
  • a 1,3-butadiene solution containing 60% by mass of 1,3-butadiene dissolved in n-hexane is injected into the second reactor at a rate of 0.95 kg/h.
  • the temperature of the second reactor was maintained at 65°C.
  • the present invention it is possible to provide a method for producing a rubber composition that can improve the dispersibility of fillers and obtain a rubber composition with excellent low loss properties. Further, according to the present invention, it is possible to provide a rubber composition with excellent low loss properties and a tire with reduced rolling resistance.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention vise à fournir un procédé de production d'une composition de caoutchouc, le procédé permettant l'obtention d'une composition de caoutchouc qui présente une dispersibilité améliorée d'une charge, tout en ayant une faible tangente de perte.　Afin d'obtenir ce qui précède, la présente invention concerne un procédé de production d'une composition de caoutchouc qui contient un composant de caoutchouc (A) qui contient au moins un caoutchouc qui est sélectionné parmi les caoutchoucs naturels et les caoutchoucs diéniques synthétiques, une charge qui contient une charge inorganique (B), un agent de couplage au silane (C) et un accélérateur de vulcanisation (D). Ce procédé de production d'une composition de caoutchouc est caractérisé en ce que : la composition de caoutchouc est malaxée en une pluralité d'étapes ; dans une première étape du malaxage, le composant de caoutchouc (A), une partie ou la totalité de la charge inorganique (B), une partie ou la totalité de l'agent de couplage de silane (C) et de l'accélérateur de vulcanisation (D) sont malaxés ; et le composant de caoutchouc contient un copolymère modifié qui a été modifié avec un agent de modification qui contient un composé représenté par la formule (1).
PCT/JP2023/000858 2022-05-27 2023-01-13 Procédé de production d'une composition de caoutchouc, composition de caoutchouc et pneu WO2023228463A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011236368A (ja) * 2010-05-12 2011-11-24 Sumitomo Rubber Ind Ltd サイドウォール用ゴム組成物及び空気入りタイヤ
WO2017077714A1 (fr) * 2015-11-05 2017-05-11 株式会社ブリヂストン Composition de caoutchouc, et pneumatique
JP2019001943A (ja) * 2017-06-16 2019-01-10 住友ゴム工業株式会社 ゴム組成物の製造方法
JP2019534373A (ja) * 2017-01-03 2019-11-28 エルジー・ケム・リミテッド 変性共役ジエン系重合体の製造方法
JP2019206643A (ja) * 2018-05-29 2019-12-05 横浜ゴム株式会社 タイヤ用ゴム組成物の製造方法
JP2021085025A (ja) * 2019-11-29 2021-06-03 株式会社ブリヂストン ゴム組成物及びタイヤ
JP2021098765A (ja) * 2019-12-19 2021-07-01 株式会社ブリヂストン タイヤ
EP3971238A1 (fr) * 2019-11-29 2022-03-23 LG Chem, Ltd. Agent de modification, et polymère de diène conjugué modifié produit à l'aide de celui-ci
JP2022521596A (ja) * 2019-11-29 2022-04-11 エルジー・ケム・リミテッド 変性共役ジエン系重合体

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011236368A (ja) * 2010-05-12 2011-11-24 Sumitomo Rubber Ind Ltd サイドウォール用ゴム組成物及び空気入りタイヤ
WO2017077714A1 (fr) * 2015-11-05 2017-05-11 株式会社ブリヂストン Composition de caoutchouc, et pneumatique
JP2019534373A (ja) * 2017-01-03 2019-11-28 エルジー・ケム・リミテッド 変性共役ジエン系重合体の製造方法
JP2019001943A (ja) * 2017-06-16 2019-01-10 住友ゴム工業株式会社 ゴム組成物の製造方法
JP2019206643A (ja) * 2018-05-29 2019-12-05 横浜ゴム株式会社 タイヤ用ゴム組成物の製造方法
JP2021085025A (ja) * 2019-11-29 2021-06-03 株式会社ブリヂストン ゴム組成物及びタイヤ
EP3971238A1 (fr) * 2019-11-29 2022-03-23 LG Chem, Ltd. Agent de modification, et polymère de diène conjugué modifié produit à l'aide de celui-ci
JP2022521596A (ja) * 2019-11-29 2022-04-11 エルジー・ケム・リミテッド 変性共役ジエン系重合体
JP2021098765A (ja) * 2019-12-19 2021-07-01 株式会社ブリヂストン タイヤ

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