WO2023171628A1 - Composition polymère ainsi que son procédé de production, produit réticulé, et pneumatique - Google Patents

Composition polymère ainsi que son procédé de production, produit réticulé, et pneumatique Download PDF

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WO2023171628A1
WO2023171628A1 PCT/JP2023/008379 JP2023008379W WO2023171628A1 WO 2023171628 A1 WO2023171628 A1 WO 2023171628A1 JP 2023008379 W JP2023008379 W JP 2023008379W WO 2023171628 A1 WO2023171628 A1 WO 2023171628A1
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polymer
conjugated diene
component
compound
polymer composition
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PCT/JP2023/008379
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Japanese (ja)
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利充 菊池
寛文 千賀
龍源 中濱
天斗 福本
拓哉 佐野
俊之 早川
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株式会社Ｅｎｅｏｓマテリアル
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • Conjugated diene polymers obtained by polymerization using conjugated diene compounds have good properties such as heat resistance, abrasion resistance, mechanical strength, and moldability, so they are used in pneumatic tires, anti-vibration rubber, Widely used in various industrial products such as hoses.
  • Polymer compositions used to manufacture pneumatic tire treads, sidewalls, etc. contain conjugated diene polymers as well as reinforcing agents such as carbon black and silica to improve product durability and wear resistance. It is known to incorporate inorganic fillers. Furthermore, conventionally, in order to increase the affinity between the conjugated diene polymer and the reinforcing agent, a conjugated diene polymer modified with a compound containing silicon or nitrogen has been used (for example, Patent Document 1 (See 3).
  • the functional groups may react with each other or the functional groups themselves may be eliminated during the solvent removal process. It is assumed that radical side reactions such as these and side reactions with metal residues (for example, hydrogenation catalysts, etc.) may occur. Furthermore, there is a concern that the Mooney viscosity of the conjugated diene polymer is likely to change due to variations in the time for desolvation due to such side reactions occurring during desolvation.
  • the present disclosure has been made in view of the above-mentioned problems, and it is possible to reduce the process load and stabilize quality in the manufacturing process of a conjugated diene polymer, and to obtain a crosslinked product in which performance deterioration is suppressed.
  • One object is to provide a polymer composition.
  • the present disclosure provides the following polymer composition, method for producing the same, crosslinked product, and tire.
  • [2] A crosslinked product obtained by crosslinking the polymer composition of [1] above.
  • [3] A tire in which a tread, a sidewall, or both are formed using the polymer composition of [1] above.
  • [4] A method for producing the polymer composition of [1] above, which comprises polymerizing a monomer containing a conjugated diene compound and an aromatic vinyl compound in the presence of an alkali metal or an alkaline earth metal, and hydrogenating the monomer.
  • a step of obtaining a polymer solution containing the component (A) by mixing the polymer solution and the component (B) to form a mixture containing the component (A) and the component (B).
  • a method for producing a polymer composition comprising the steps of obtaining a liquid, and removing the solvent from the mixed liquid and drying it.
  • the present disclosure it is possible to reduce the process load and stabilize the quality in the manufacturing process of a conjugated diene polymer. Furthermore, by stabilizing the quality of the conjugated diene polymer during the manufacturing process, a crosslinked product with suppressed performance deterioration can be obtained.
  • a numerical range described using " ⁇ " represents a range that includes the numerical values described before and after " ⁇ " as a lower limit value and an upper limit value.
  • the polymer composition of the present disclosure (hereinafter also referred to as “the present composition") contains (A) a conjugated diene polymer and (B) a hindered phenol compound having a molecular weight of 250 to 2,000.
  • the present composition contains (A) a conjugated diene polymer and (B) a hindered phenol compound having a molecular weight of 250 to 2,000.
  • (A) component Conjugated diene polymer>
  • the conjugated diene polymer that is component (A) (hereinafter also referred to as "(A) conjugated diene polymer”) has a structural unit derived from a conjugated diene compound and a structural unit derived from an aromatic vinyl compound. It is a copolymer.
  • the conjugated diene polymer includes a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), a structural unit represented by the following formula (3), and a structural unit represented by the following formula (
  • the composition ratios (molar ratios) of the structural units represented by 4) in the polymer are p, q, r, and s, respectively
  • the molecular structure of the conjugated diene polymer is not particularly limited.
  • the conjugated diene polymer may be a linear polymer (hereinafter also referred to as "linear polymer”) or a polymer having a multi-branched structure (hereinafter also referred to as “branched polymer”). or a mixture thereof.
  • Conjugated diene polymer is a conjugated diene polymer with four or more branches, in that it is possible to obtain a crosslinked product with suppressed deterioration of physical properties (for example, deterioration of strength, viscoelastic properties, and abrasion resistance). It is preferable to include.
  • Part or all of the conjugated diene polymer (A) contained in the present composition contains a functional group (hereinafter referred to as "specific functional group") containing at least one element selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus. (also called “base”).
  • specific functional group a functional group containing at least one element selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus.
  • a polymer having a specific functional group (hereinafter also referred to as a "functional group-containing polymer"), the position of the specific functional group in the polymer is not particularly limited.
  • the functional group-containing polymer include polymers having specific functional groups in the molecular chain (that is, between the ends of the molecular chain), at the ends of the molecular chain, or in both of these.
  • the functional group-containing polymer may have the specific functional group at the polymerization start end, or at the polymerization end end, and may have the specific functional group at the end of the polymerization end. It may be present at both the starting end and the polymerization ending end.
  • the functional group-containing polymer may have a specific functional group at a part of the terminal end in one polymer molecule, or may have a specific functional group at all the terminal ends in one polymer molecule.
  • Functional group-containing polymers are particularly effective in improving the various physical properties (e.g., mechanical strength, abrasion resistance, viscoelastic properties, fuel efficiency, etc.) of the crosslinked product obtained using the present composition. It is preferable that the above terminal has a specific functional group.
  • the term "functional group” refers to a group having a specific structure within the molecule of an organic compound, and refers to an atomic group or bonding style that characterizes the compound.
  • Specific functional groups possessed by the functional group-containing polymer include, for example, a primary amino group, a secondary amino group, a tertiary amino group, a nitrogen-containing group in which two hydrogen atoms of a primary amino group are protected, and a secondary amino group.
  • Examples include a sulfur-containing group, a nitrogen-containing heterocyclic group (for example, a group having a heterocycle such as a pyridine ring and an imide ring), a hydrocarbyloxysilyl group, a hydrocarbyloxycarbonyl group, an ether bond, a thioether bond, and the like.
  • the functional group-containing polymer contained in the conjugated diene polymer includes a conjugated diene polymer having an active end, a reaction point with the active end of the conjugated diene polymer, and a compound having a specific functional group.
  • modified polymer can be preferably used.
  • a compound hereinafter also referred to as a "modifier” having a reactive site with the active end of the conjugated diene polymer and a specific functional group
  • the number of reactive sites with the active end may be one, or two or more. There may be.
  • Specific examples of the specific functional group possessed by the modifier include the same groups and bonds as specific examples of the specific functional group possessed by the functional group-containing polymer.
  • Such a modified polymer can be obtained by using, as a modifying agent, a coupling agent or a terminal modifying agent, which will be described later, and a compound having a specific functional group during production of the modified polymer.
  • the modified polymer may be a polymer obtained by further using, in addition to a coupling agent or a terminal modifying agent, a starting terminal modifying agent to be described later in the reaction for obtaining the modified polymer.
  • the conjugated diene polymer (A) contains a functional group-containing polymer (preferably a modified polymer)
  • the branched polymer and the functional group-containing polymer may be separate polymers with different molecular structures and physical properties.
  • the conjugated diene polymer (A) may contain a branched polymer and also contain a functional group-containing polymer. .
  • the conjugated diene polymer (A) contains a branched polymer having a specific functional group, thereby stabilizing the quality. From the viewpoint of improving compound properties such as tensile strength while aiming at the above, it is more preferable to contain a branched polymer having a specific functional group at two or more terminals, and it is even more preferable to contain a branched polymer having a specific functional group at four or more terminals. preferable.
  • the conjugated diene polymer is an aggregate of polymers having structural units derived from a conjugated diene compound.
  • Specific embodiments of the conjugated diene polymer (A) include the following embodiments [a1] to [a4].
  • [a1] One or more polymers selected from the group consisting of a branched polymer with 4 or more branches (hereinafter also referred to as "first polymer”), a linear polymer, and a branched polymer with 3 or less branches (hereinafter referred to as "second polymer”) polymer), and the first polymer and the second polymer are functional group-containing polymers.
  • the conjugated diene polymer can be produced by a method including the following polymerization step and hydrogenation step.
  • the conjugated diene polymer (A) may also be produced by a method that includes at least one of the following reaction steps and modification steps in addition to the polymerization step and hydrogenation step.
  • the method for producing (A) the conjugated diene polymer the molecular structure and the like of the (A) conjugated diene polymer will also be explained.
  • the polymerization step is a step of polymerizing monomers containing a conjugated diene compound and an aromatic vinyl compound to obtain a conjugated diene polymer having an active terminal.
  • Conjugated diene compounds used in polymerization include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2- Examples include phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, and 2-chloro-1,3-butadiene. Among these, at least one selected from the group consisting of 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene is preferred, and one or both of 1,3-butadiene and isoprene are more preferred. preferable.
  • One type of conjugated diene compound may be used alone, or two or more types may be used.
  • Aromatic vinyl compounds used in polymerization include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, ⁇ -methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t -Butylstyrene, 5-t-butyl-2-methylstyrene, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N , N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-
  • the proportion of structural units derived from an aromatic vinyl compound in the conjugated diene polymer is more than 0% by mass and 45% by mass or less with respect to the total structural units constituting the (A) conjugated diene polymer. It is preferable that By setting it as the said range, a crosslinked body with high strength and excellent wear resistance can be obtained while maintaining the processability of the polymer composition.
  • the proportion of the structural units derived from the aromatic vinyl compound is more preferably 2% by mass or more, and preferably 5% by mass or more, based on the total structural units constituting the (A) conjugated diene polymer. More preferred.
  • the proportion of the structural units derived from the aromatic vinyl compound is more preferably 40% by mass or less, and more preferably 38% by mass or less, based on the total structural units constituting the (A) conjugated diene polymer. It is even more preferable that the amount is 35% by mass or less, and even more preferably 35% by mass or less.
  • the content ratio of structural units derived from an aromatic vinyl compound in the polymer is a value measured by 1 H-NMR.
  • the conjugated diene polymer (A) is preferably a copolymer containing 1,3-butadiene and styrene in its monomer composition, since it has high living properties in anionic polymerization.
  • the conjugated diene polymer contains a conjugated diene compound and an aromatic It is preferable to have a random copolymerization portion with irregular distribution with the group vinyl compound.
  • the conjugated diene polymer is a random copolymer of a conjugated diene compound and an aromatic vinyl compound; It may further have a chain portion of a conjugated diene compound formed by additionally adding a conjugated diene compound after polymerization.
  • the conjugated diene polymer may have a polymerization block portion containing an aromatic vinyl compound as a main component.
  • the conjugated diene polymer has a polymerization block portion mainly composed of an aromatic vinyl compound, the contact area with equipment due to the flow of the polymer during drying of the (A) conjugated diene polymer This is preferable in that it is possible to suppress the increase, thereby suppressing the adhesion of the polymer to equipment.
  • the position of the polymerization block portion containing an aromatic vinyl compound as a main component in the conjugated diene polymer is not particularly limited.
  • the conjugated diene polymer may have a polymerization block portion mainly composed of an aromatic vinyl compound at the end of the molecular chain, or within the molecular chain (between the ends). It's okay.
  • Conjugated diene polymers can simplify the production process of conjugated diene polymers while also suppressing the adhesion of polymers to equipment. It is preferable that the polymer block portion, which is the main component, is present at the end of the molecular chain.
  • the polymerization block portion containing an aromatic vinyl compound as a main component has structural units derived from the aromatic vinyl compound in an amount of 80% by mass or more, and preferably 85% by mass or more based on the total structural units constituting the polymerization block portion. It is more preferable that the content is 90% by mass or more.
  • the conjugated diene polymer has a polymerization block portion mainly composed of an aromatic vinyl compound
  • 35% of the total amount of structural units derived from the aromatic vinyl compound possessed by the (A) conjugated diene polymer % by mass or more may constitute the polymer block portion
  • 40 mass % or more may constitute the polymer block portion.
  • 80% by mass or more of the total amount of structural units derived from the conjugated diene compound contained in the conjugated diene polymer (A) constitutes a random copolymerization portion
  • 90% by mass or more constitutes a random copolymerization portion. It is preferable that it constitutes a section.
  • the monomers used in the polymerization reaction to obtain the conjugated diene polymer may contain compounds other than the conjugated diene compound and the aromatic vinyl compound (hereinafter also referred to as "other monomers"). good.
  • other monomers include acrylonitrile, methyl (meth)acrylate, and ethyl (meth)acrylate.
  • the proportion of other monomers used is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount of monomers used for polymerization.
  • the polymerization method used may be any of a solution polymerization method, a gas phase polymerization method, and a bulk polymerization method. Among these, solution polymerization method is particularly preferred. Further, as the polymerization method, either a batch method or a continuous method may be used.
  • a solution polymerization method as an example of a specific polymerization method, a monomer containing a conjugated diene compound and an aromatic vinyl compound is mixed in an organic solvent with a polymerization initiator and a vinyl content used as necessary. Examples include a method of polymerizing in the presence of a regulator (hereinafter also referred to as "randomizer").
  • a metal compound containing an alkali metal or an alkaline earth metal can be used as the polymerization initiator.
  • compounds containing alkali metals are preferred.
  • Specific examples of metal compounds include alkyllithiums such as methyllithium, ethyllithium, n-propyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium; 1,4-dilithiobutane, phenyllithium, stilbenelithium, Naphthyl lithium, 1,3-bis(1-lithio-1,3-dimethylpentyl)benzene, 1,3-phenylenebis(3-methyl-1-phenylpentylidene) dilithium, naphthyl sodium, naphthyl potassium, ethoxy potassium, etc. can be mentioned.
  • lithium compounds are preferred.
  • the metal compound used as a polymerization initiator may be a metal amide compound containing an alkali metal or an alkaline earth metal.
  • an amino group preferably can introduce a secondary amino group or a tertiary amino group.
  • the conjugated diene polymer (A) obtained by polymerizing monomers in the presence of a metal amide compound has the advantage that the strength of the crosslinked product can be increased, and that the crosslinked product has low fuel consumption when used in tires. This is preferable because it can enhance the effect of improving performance.
  • the metal amide compound is preferably a compound obtained by mixing a lithium compound (e.g., alkyl lithium, etc.) and a compound having a nitrogen atom (hereinafter also referred to as "initiating terminal modifier").
  • the starting terminal modifier is preferably a secondary amine compound.
  • the metal amide compound when polymerizing in the presence of a metal amide compound, the metal amide compound is prepared by mixing the lithium compound and the starting terminal modifier in advance, and the prepared metal amide compound is added to the polymerization system to perform polymerization. You may do so.
  • a metal amide compound may be prepared by adding a lithium compound and an initiating terminal modifier to the polymerization system and mixing the two in the polymerization system, followed by polymerization.
  • the amount of the polymerization initiator used is preferably 0.01 to 20 mmol, more preferably 0.05 to 15 mmol, per 100 g of monomer used for polymer synthesis.
  • the randomizer can be used for the purpose of adjusting the vinyl bond content, which represents the content of vinyl bonds in the polymer.
  • randomizers include dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-di(tetrahydrofuryl)propane, 2-(2-ethoxyethoxy)-2-methylpropane, triethylamine, pyridine. , N-methylmorpholine, tetramethylethylenediamine, potassium dodecylbenzenesulfonate, and the like.
  • One type of randomizer can be used alone or two or more types can be used in combination.
  • an organic solvent inert to the polymerization reaction can be preferably used.
  • the organic solvent used in the polymerization include chain or cyclic aliphatic hydrocarbons, aromatic hydrocarbons, and the like. Among these, hydrocarbons having 3 to 8 carbon atoms are preferred, and specific examples include propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, and 1-butene.
  • an organic solvent one type can be used individually or two or more types can be used in combination.
  • the monomer concentration in the reaction solvent is preferably 5 to 50% by mass, and 10 to 30% by mass, from the viewpoint of maintaining a balance between productivity and ease of polymerization control. is more preferable.
  • the temperature of the polymerization reaction is preferably -20°C to 150°C, more preferably 0 to 120°C.
  • the polymerization reaction is preferably carried out under sufficient pressure to maintain the monomer substantially in a liquid phase. Such pressure can be obtained by pressurizing the inside of the reactor with a gas inert to the polymerization reaction. Through such a polymerization reaction, a conjugated diene polymer having an active terminal can be obtained.
  • the vinyl bond content in the structural unit derived from 1,3-butadiene is preferably 15 to 85 mol%.
  • the vinyl bond content is preferably 20 mol% or more, more preferably 25 mol% or more.
  • the vinyl bond content of the conjugated diene polymer is preferably 75 mol% or less, more preferably 65 mol% or less.
  • vinyl bond content refers to the content of structural units having 1,2-bonds with respect to all structural units derived from 1,3-butadiene that the conjugated diene polymer before hydrogenation has. This is a value indicating a percentage. Vinyl bond content is determined by 1 H-NMR equipment.
  • the conjugated diene polymer obtained in the polymerization step is treated with a compound having four or more functional groups that can react with the active end of the conjugated diene polymer (hereinafter also referred to as a "coupling agent"). ) is reacted.
  • a compound having four or more functional groups that can react with the active end of the conjugated diene polymer hereinafter also referred to as a "coupling agent”
  • the conjugated diene polymer having an active end and the coupling agent four or more molecular chains of the conjugated diene polymer are bonded to one molecule of the coupling agent, thereby forming (A) the conjugated diene polymer.
  • A the conjugated diene polymer
  • a compound having at least one element selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus, tin, and silicon can be preferably used.
  • specific element selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus, tin, and silicon
  • the strength of the resulting crosslinked product can be further increased.
  • coupling agents include tetrachlorosilane, bis(trichlorosilyl)ethane, and the like.
  • a coupling agent as a functional group having a specific element, a nitrogen-containing group formed by protecting two hydrogen atoms of a primary amino group, a nitrogen-containing group formed by protecting one hydrogen atom of a secondary amino group, etc. groups, tertiary amino groups, imino groups, nitrogen-containing heterocyclic groups (for example, groups having heterocycles such as pyridine rings and imide rings), hydroxyl groups, oxygen-containing groups in which the hydrogen atom of the hydroxyl group is protected, and thiol groups.
  • a compound having a functional group hereinafter also referred to as "functional group F1" such as a sulfur-containing group with a protected hydrogen atom or a hydrocarbyloxysilyl group can also be used.
  • the coupling agent having the functional group F1 include N,N,N',N'-tetra(3-trimethoxysilylpropyl)ethylenediamine, N,N,N',N'-tetra(3-trimethoxysilylpropyl), ethoxysilylpropyl)ethylenediamine, N,N,N'-tris(3-trimethoxysilylpropyl)-N'-methyl-ethylenediamine, N,N,N',N'-tetra(3-trimethoxysilylpropyl)- 1,3-propanediamine, N,N,N',N'-tetra(3-trimethoxysilylpropyl)-1,4-butanediamine, bis(3-trimethoxysilylpropyl)-[2-(dimethylamino) )ethyl]amine, bis(3-trimethoxysilylpropyl)-[2-(2,2-dimethoxy
  • the crosslinked product obtained from the polymer composition can be Strength and viscoelastic properties can be improved.
  • the reaction between the conjugated diene polymer having an active end and the coupling agent is preferably carried out as a solution reaction.
  • the amount of the coupling agent used (the total amount when two or more types are used) is appropriately set so that the content ratio of the branched polymer with four or more branches in the conjugated diene polymer (A) is within the desired range. be able to.
  • (A) In the production process of conjugated diene polymers (especially drying treatment), it suppresses the adhesion of polymer to equipment, thereby suppressing equipment contamination due to polymer retention and heat storage combustion of the accumulated polymer, and desolvation.
  • the amount of the coupling agent to be used is determined by the amount of the polymerization initiator (i.e. It is preferably 0.01 mol or more, and more preferably 0.02 mol or more, per 1 mol of metal atoms involved in polymerization in the metal compound.
  • the amount of the coupling agent to be used is determined from the viewpoint of adjusting the coupling rate to a desired value and obtaining a polymer composition that exhibits good processability and a crosslinked product with excellent viscoelastic properties.
  • a coupling agent it is preferably 0.2 mol or less, more preferably 0.1 mol or less, per 1 mol of metal atoms involved in polymerization in the initiator.
  • one type may be used individually, and two or more types may be used in combination.
  • the reaction temperature is usually in the same range as the polymerization reaction. Specifically, the temperature is preferably -20°C to 150°C, more preferably 0 to 120°C. If the reaction temperature is low, the viscosity of the polymer after reaction tends to increase, and if the reaction temperature is high, the polymerization active terminal tends to be deactivated.
  • the reaction time is preferably 1 minute to 5 hours, more preferably 2 minutes to 1 hour.
  • the conjugated diene polymer (A) before hydrogenation which contains a branched polymer having four or more branches.
  • the conjugated diene polymer after the coupling reaction may contain a linear polymer.
  • the linear polymer contained in the polymer solution after the coupling reaction is an unreacted polymer that did not react with the coupling agent among the linear polymers contained in the conjugated diene polymer having an active end.
  • the conjugated diene polymer obtained by the polymerization step or reaction step has a specific functional group
  • the polymer may be directly subjected to the next hydrogenation step.
  • the conjugated diene polymer obtained by the polymerization step or reaction step whether or not there is a specific functional group, the active terminal of the conjugated diene polymer and the specific functional group are removed before the hydrogenation step.
  • a treatment may be performed in which a compound capable of reacting with the active end of the conjugated diene polymer (excluding a coupling agent; hereinafter also referred to as "terminal modifier" is reacted.
  • the conjugated diene polymer obtained in the polymerization step or reaction step contains a polymer having an active end
  • the molecular chain of the linear conjugated diene polymer is terminally modified.
  • a polymer bonded to the agent that is, having a specific functional group
  • the terminal modifier is a compound that differs from the coupling agent in that it has 1 to 3 reactive sites with the active end of the conjugated diene polymer.
  • a preferred specific example of the terminal modifier includes at least one selected from the group consisting of a compound represented by the following formula (5) and a compound represented by the following formula (6).
  • a 11 has at least one element selected from the group consisting of nitrogen, phosphorus, oxygen, and sulfur, has no active hydrogen, and has nitrogen and phosphorus with respect to R 35 .
  • R 33 and R 34 are each independently a hydrocarbyl group .
  • R 35 is a hydrocarbylene group.
  • t is an integer of 0 to 2.
  • a 12 has at least one element selected from the group consisting of nitrogen, phosphorus, oxygen, and sulfur, has no active hydrogen, and has nitrogen and phosphorus with respect to R 39 .
  • R 36 and R 37 are each independently a hydrocarbyl group.
  • R 38 is a hydrocarbyl group. It is a carbylene group.
  • R 39 is a single bond or a hydrocarbylene group.
  • u is 0 or 1. However, when u is 0, multiple R 37s in the formula are the same or different from each other. )
  • the hydrocarbyl group is a linear or branched chain having 1 to 20 carbon atoms.
  • An alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms is preferable.
  • the hydrocarbylene group represented by R 38 and R 39 is a linear or branched alkanediyl group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. is preferred.
  • the hydrocarbylene group represented by R 38 is preferably a linear or branched alkanediyl group having 1 to 20 carbon atoms.
  • t is preferably 0 or 1.
  • At least one element selected from the group consisting of nitrogen, phosphorus, oxygen, and sulfur, which A 11 has when A 11 is the monovalent functional group, and when A 12 is the monovalent functional group, may be protected with, for example, a trisubstituted hydrocarbylsilyl group.
  • active hydrogen refers to a hydrogen atom bonded to an atom other than a carbon atom, and preferably refers to a hydrogen atom having a lower bond energy than a carbon-hydrogen bond of polymethylene.
  • (thio)epoxy group includes epoxy groups and thioepoxy groups.
  • a 11 may be a group that can become an onium ion with an onium salt forming agent.
  • the terminal modifier has such a group (A 11 )
  • excellent shape retention can be imparted to the polymer.
  • Specific examples of A11 include a nitrogen-containing group in which two hydrogen atoms of a primary amino group are protected, a nitrogen-containing group in which one hydrogen atom of a secondary amino group is protected, a tertiary amino group, and an imino group.
  • pyridyl group phosphorus-containing group in which two hydrogen atoms of a primary phosphino group are protected, phosphorus-containing group in which one hydrogen atom of a secondary phosphino group is protected, tertiary phosphino group, epoxy group, thioepoxy group, an oxygen-containing group formed by protecting the hydrogen atom of a hydroxyl group, a sulfur-containing group formed by protecting the hydrogen atom of a thiol group, and a hydrocarbyloxycarbonyl group.
  • a group having a nitrogen atom is preferable because it has good affinity with silica, and a nitrogen-containing group in which two hydrogen atoms of a tertiary amino group or a primary amino group are protected is preferable. It is more preferable that Note that the protected group is a group in which A 11 and A 12 are converted into functional groups that are inert to the polymerization active terminal.
  • the onium salt generating agent is a Bronsted acid or a compound that produces a Bronsted acid upon contact with water.
  • terminal modifier examples include compounds represented by formula (5), such as N,N-bis(trimethylsilyl)aminopropyltrimethoxysilane, N,N-dimethylaminopropyltriethoxysilane, and N,N-dimethylaminopropyltriethoxysilane.
  • the compound represented by formula (6) examples include 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1,2-azacylorizine, 2,2-diethoxy-1-(3 -trimethoxysilylpropyl)-1,2-azacylorizine, 2,2-dimethoxy-1-phenyl-1,2-azacylorizine, 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclopentane, 2 -(2,2-dimethoxy-1,2-azacylolidin-1-yl)-N,N-diethylethan-1-amine, 2-(2,2-dimethoxy-1,2-azacylolidin-1-yl)- Examples include N,N-dimethylethane-1-amine, 3-(2,2-dimethoxy-1,2-azacylolidin-1-yl)-N,N-diethylpropan-1-amine, and the like.
  • the terminal modifier one type may be used alone
  • the reaction between the conjugated diene polymer having an active terminal and the terminal modifier can be carried out, for example, as a solution reaction.
  • This solution reaction may be carried out either batchwise or continuously.
  • the method of adding the terminal modifier is not particularly limited, and examples thereof include a method of adding at once, a method of adding in portions, a method of adding continuously.
  • the amount of the terminal modifier to be used may be appropriately set depending on the type of compound used in the reaction, but it is preferably 0.05 mol per mol of metal atoms involved in the polymerization reaction that the polymerization initiator has. or more, and more preferably 0.1 mol or more.
  • the terminal modifier in an amount of 0.1 molar equivalent or more, the modification reaction can proceed sufficiently, and the effect of improving the dispersibility of the inorganic filler can be enhanced.
  • the amount of the terminal modifier is preferably 1.0 mol or less, more preferably 0.8 mol or less, per 1 mol of the metal atom of the polymerization initiator that participates in the polymerization reaction.
  • the reaction temperature is usually the same as the temperature of the polymerization reaction, preferably -20 to 150°C, more preferably 0 to 120°C, and 20 to 100°C. It is even more preferable that there be.
  • the temperature of the modification reaction is low, the viscosity of the polymer solution tends to increase.
  • the temperature of the modification reaction is high, the polymerization active terminal is likely to be deactivated.
  • the reaction time for terminal modification is preferably 1 minute to 5 hours, more preferably 2 minutes to 1 hour.
  • the coupling rate of the conjugated diene polymer is determined by the proportion of the branched polymer present in the (A) conjugated diene polymer, the molecular weight of the conjugated diene polymer having an active end, and the coupling agent used. It can be set depending on the number of functional groups, etc.
  • the coupling rate of the (A) conjugated diene polymer is preferably 10% or more, It is more preferably 15% or more, and even more preferably 20% or more.
  • the coupling rate of the conjugated diene polymer (A) is preferably 70% or less, from the viewpoint of obtaining a polymer composition with good processability and the viewpoint of obtaining a crosslinked product with excellent viscoelastic properties, and 60% or less. % or less, more preferably 50% or less.
  • coupling rate refers to the linear conjugated diene polymer having an active end used in the reaction of a linear conjugated diene polymer having an active end with a modifier. It refers to the proportion (% by mass) of the linear conjugated diene polymer used in the reaction among the diene polymers. Specifically, the amount of coupling agent Alternatively, it represents the proportion (% by mass) of a polymer in which two or more molecular chains of linear conjugated diene polymers are bonded via a terminal modifier.
  • the coupling rate is calculated by separating the waveform of a molecule in which two or more linear conjugated diene polymer chains are bonded together from a GPC curve obtained using gel permeation chromatography (GPC). , can be calculated from the peak area ratio.
  • the conjugated diene polymer having an active end obtained in the polymerization step the conjugated diene polymer having an active end and the polymerization termination using alcohol etc. After reacting with the agent, the next hydrogenation step may be performed. In this case, it is preferable to use a starting terminal modifier in the polymerization step to obtain a conjugated diene polymer having a specific functional group.
  • the conjugated diene polymer obtained by the above polymerization step, reaction step, or modification step is hydrogenated (hereinafter also referred to as "hydrogenation"). Any method and conditions for the hydrogenation reaction can be used as long as a conjugated diene polymer having a desired hydrogenation rate can be obtained.
  • Examples of such hydrogenation methods include methods using catalysts mainly composed of organometallic compounds of titanium; catalysts consisting of organometallic compounds of iron, nickel, and cobalt and organometallic compounds such as alkyl aluminum; A method using an organic complex of an organometallic compound such as ruthenium or rhodium; A method using a catalyst in which a metal such as palladium, platinum, ruthenium, cobalt, or nickel is supported on a carrier such as carbon, silica, or alumina. Examples include methods. Among the various methods, a homogeneous catalyst consisting of an organometallic compound of titanium alone or an organometallic compound of titanium and an organometallic compound of lithium, magnesium, or aluminum (for example, Japanese Patent Publication No.
  • Japanese Patent Publication No. The method of hydrogenating under mild conditions at low pressure and low temperature using the catalyst described in Japanese Patent Publication No. 37970 is industrially preferable, and is also suitable because of its high hydrogenation selectivity to the double bond of butadiene.
  • the hydrogenation of the conjugated diene polymer is preferably carried out using a solvent that is inert to the catalyst and in which the conjugated diene polymer is soluble.
  • Preferred solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, and n-octane; cyclic aliphatic hydrocarbons such as cyclohexane and cycloheptane; aromatic hydrocarbons such as benzene and toluene; and diethyl ether. and ethers such as tetrahydrofuran.
  • the solvent used for hydrogenation may be one of the above compounds, or a mixture containing them as main components.
  • the hydrogenation reaction is generally carried out by holding a conjugated diene polymer at a predetermined temperature under hydrogen or an inert atmosphere, adding a hydrogenation catalyst with or without stirring, and then introducing hydrogen gas to a predetermined temperature. It is carried out by applying pressure.
  • the inert atmosphere means an atmosphere that does not react with substances involved in the hydrogenation reaction, and includes, for example, helium, neon, argon, and the like. Air and oxygen are not preferred because they oxidize the catalyst and cause deactivation of the catalyst. Further, nitrogen is not preferable because it acts as a catalyst poison during the hydrogenation reaction and reduces hydrogenation activity. In particular, it is most preferable that the inside of the hydrogenation reactor be in an atmosphere containing only hydrogen gas.
  • the hydrogenation reaction process can be a batch process, a continuous process, or a combination thereof.
  • a titanocene diaryl compound when used as a hydrogenation catalyst, it may be added alone to the reaction solution as it is, or may be added as a solution in an inert organic solvent.
  • the inert organic solvent used when the catalyst is used as a solution various solvents that do not react with substances involved in the hydrogenation reaction can be used. Preferably, it is the same solvent as used in the hydrogenation reaction.
  • the preferable amount of the catalyst added is 0.02 to 20 mmol per 100 g of the conjugated diene polymer before hydrogenation.
  • the conjugated diene polymer includes a structural unit represented by the above formula (1), a structural unit represented by the formula (2), a structural unit represented by the formula (3), and a structural unit represented by the formula (4).
  • the composition ratio (molar ratio) of the structural units represented by in the polymer is p, q, r, and s, respectively
  • the value ⁇ of the (A) conjugated diene polymer is less than 0.60, the amount of unsaturated bonds in the (A) conjugated diene polymer is large, so the change in Mooney viscosity due to the difference in dissolution time becomes large. There is a tendency that the quality of the conjugated diene polymer (A) becomes unstable or that the heat storage and combustibility of the conjugated diene polymer (A) attached to the equipment increases. Furthermore, there is a concern that the strength and viscoelastic properties of the crosslinked product may deteriorate due to the destabilization of the quality of the conjugated diene polymer (A).
  • the value ⁇ of the conjugated diene polymer exceeds 0.98, crosslinking cannot proceed sufficiently, and the strength of the crosslinked product tends to decrease and the viscoelastic properties tend to decrease. It tends to be difficult to secure adhesiveness in a laminated crosslinked product that is laminated with other conjugated diene material sheets and vulcanized.
  • the value ⁇ of the conjugated diene polymer (A) is more preferably 0.65 or more, still more preferably 0.70 or more, and even more preferably 0.75 or more. Further, the value ⁇ of the conjugated diene polymer (A) is more preferably 0.97 or less, even more preferably 0.95 or less, and even more preferably 0.92 or less.
  • the value ⁇ represented by formula (i) corresponds to the hydrogenation rate of the conjugated diene polymer.
  • the hydrogenation rate of the conjugated diene polymer is 60%.
  • the hydrogenation rate and value ⁇ of the conjugated diene polymer can be adjusted by adjusting the hydrogenation reaction time or controlling the cumulative supply amount of hydrogen.
  • the hydrogenation rate is a value measured using a 1 H-NMR device.
  • a preferred method for obtaining the conjugated diene polymer is to solution polymerize monomers containing 1,3-butadiene and styrene in the presence of a polymerization initiator (preferably a metal amide compound), and to obtain the resulting polymer. After a coupling agent is added to the combined solution and a coupling reaction is performed, a terminal modifier is preferably added, and then a hydrogenation step is performed.
  • a crosslinked product having excellent various physical properties (strength, abrasion resistance, viscoelastic properties, vulcanization adhesiveness, etc.) can be obtained, and is also industrially useful.
  • the weight average molecular weight (Mw) of the conjugated diene polymer measured using gel permeation chromatography (GPC) in terms of polystyrene indicates that the crosslinked product has high strength and excellent wear resistance. From the viewpoint of yield, it is preferably 1.5 ⁇ 10 5 to 2.0 ⁇ 10 6 .
  • the Mw of the conjugated diene polymer is more preferably 1.8 ⁇ 10 5 or more, and still more preferably 2.0 ⁇ 10 5 or more. Moreover, Mw is more preferably 1.6 ⁇ 10 6 or less, still more preferably 1.4 ⁇ 10 6 or less.
  • the weight average molecular weight of the conjugated diene polymer referred to herein is a value determined from all peaks of a GPC curve measured by GPC before hydrogenation. In the following, it is also referred to as "total average molecular weight.”
  • the molecular weight distribution (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn)) of the total amount of polymer (i.e., aggregate of different molecular weights) measured by GPC ( Weight average molecular weight/number average molecular weight) is preferably 1.1 or more and 4.0 or less.
  • a molecular weight distribution of 1.1 or more is preferable in terms of excellent processability, and a molecular weight distribution of 4.0 or less is preferable in that low hysteresis loss properties of the resulting crosslinked product can be sufficiently improved.
  • the molecular weight distribution of the conjugated diene polymer is more preferably 1.2 or more. Further, the molecular weight distribution of the conjugated diene polymer (A) is more preferably 3.5 or less, still more preferably 3.0 or less.
  • the peak top molecular weight of the peak with the smallest molecular weight (hereinafter also referred to as "1st peak molecular weight”) measured by GPC is preferably 0.8 x 10 5 to 1.0 The range is ⁇ 10 6 .
  • the 1st peak molecular weight is more preferably 0.9 ⁇ 10 5 or more, and even more preferably 1.0 ⁇ 10 5 or more.
  • the 1st peak molecular weight is more preferably 8.0 ⁇ 10 5 or less, and even more preferably 5.0 ⁇ 10 5 or less.
  • the 1st peak molecular weight is a value determined from a GPC curve measured by GPC before hydrogenation.
  • the conjugated diene polymer preferably contains one or more polymers (second polymer) selected from the group consisting of a linear polymer and a branched polymer having three or less branches, together with a four-branched or more branched polymer. .
  • the second polymer is a hydrogenated product of the conjugated diene polymer obtained by the above polymerization step, or a conjugated diene polymer obtained by the reaction step and reacted with the coupling agent. It is a hydrogenated product of a polymer that did not.
  • the second polymer preferably has a specific functional group at some or all of the end portions, and more preferably has a specific functional group at all of the end portions.
  • a linear polymer modified at both ends can be obtained by using a metal amide compound as a polymerization initiator in the polymerization step and performing the above modification step.
  • the proportion of the branched polymer having four or more branches in the conjugated diene polymer (A) is preferably 10% by mass or more based on the total amount (100% by mass) of the conjugated diene polymer (A).
  • the proportion of the branched polymer having four or more branches in the conjugated diene polymer is more preferably 15% by mass or more, and even more preferably 20% by mass or more.
  • the proportion of the branched polymer having four or more branches in the conjugated diene polymer (A) is preferably 70% by mass or less from the viewpoint of improving the processability of the polymer composition and the viscoelastic properties of the crosslinked product, The content is more preferably 60% by mass or less, and even more preferably 50% by mass or less.
  • the proportion (mass%) of branched polymers with 4 or more branches in the conjugated diene polymer is determined from the GPC curve obtained using GPC. It can be calculated by separating the waveform of the coupled molecules (coupling polymer) into components.
  • the proportion of the modified polymer in the (A) conjugated diene polymer is preferably 60% by mass or more based on the total amount of the (A) conjugated diene polymer.
  • the proportion of the modified polymer in the conjugated diene polymer is more preferably 70% by mass or more, and even more preferably 80% by mass or more.
  • the proportion (mass%) of the modified polymer in the conjugated diene polymer (A) was calculated by adding the proportion of the linear polymer having a partial structure derived from the terminal modifier and the coupling rate.
  • the reaction rate of the terminal modifier in the reaction between the conjugated diene polymer having an active terminal and the terminal modifier is determined by gas chromatography measurement of the polymer solution after the modification reaction with the terminal modifier. It can be calculated by quantifying the amount.
  • the conjugated diene polymer preferably has a nitrogen content of 50 ppm or more based on the total amount of the (A) conjugated diene polymer.
  • the proportion of nitrogen in the (A) conjugated diene polymer is preferably 500 ppm or less, more preferably 450 ppm or less, based on the total amount of the (A) conjugated diene polymer.
  • the nitrogen content of the polymer is a value measured in accordance with the chemiluminescence method of JIS K2609:1998 (Crude oil and petroleum products - Nitrogen content test method). The details of the measurement method follow the method described in Examples described later.
  • the conjugated diene polymer (A) having nitrogen can be produced by using a nitrogen-containing compound (preferably a secondary amine compound) as an initiating terminal modifier, or by using a nitrogen-containing monomer. It can be obtained by employing a method of polymerization using a nitrogen-containing compound, a method of using a nitrogen-containing compound as a terminal modifier, a method of using a nitrogen-containing compound as a coupling agent, or a combination of two or more of these methods. .
  • a nitrogen-containing compound preferably a secondary amine compound
  • the present composition contains a hindered phenol compound (hereinafter also referred to as "compound (B)”) with a molecular weight of 250 to 2,000.
  • hindered phenol compound refers to carbons on both sides of the carbon to which the hydroxyl group is bonded (i.e., to the carbons constituting the aromatic ring (preferably benzene ring) to which the hydroxyl group is bonded).
  • a compound having a partial structure hereinafter also referred to as a "hindered phenol structure" in which groups each having one or more carbon atoms are bonded to two ortho positions.
  • a group having one or more carbon atoms (hereinafter also referred to as "specific group Good, but not particularly limited.
  • specific group Xb include a saturated or unsaturated chain hydrocarbon group having 1 to 40 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 40 carbon atoms, and an aromatic group having 6 to 40 carbon atoms.
  • group hydrocarbon groups, and groups in which one or more of the methylene groups and hydrogen atoms in these hydrocarbon groups are replaced with a functional group (e.g., hydroxyl group, (meth)acryloyl group, -O-, -S-, etc.) can be mentioned.
  • At least one of the two specific groups Xb in the hindered phenol structure preferably has 2 or more carbon atoms, and 4 or more carbon atoms. It is more preferable that there be.
  • At least one of the two specific groups Xb in the hindered phenol structure of the compound (B) is bonded to the carbon constituting the aromatic ring through a tertiary carbon. That is, in the compound (B), carbon is bonded to at least one of the carbons on both sides of the carbon in the aromatic ring to which the hydroxyl group is bonded, and the carbon is preferably a quaternary carbon.
  • Such hindered phenol compounds include N-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, tetrakis ⁇ methylene-3-(3',5'- di-t-butyl-4-hydroxyphenyl)propionate ⁇ methane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, distearyl(4-hydroxy-3-methyl) -5-t-butylbenzyl)malonate, triethylene glycol-bis ⁇ 3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate ⁇ , 1,6-hexanediol-bis ⁇ 3-(3 ,5-di-t-butyl-4-hydroxyphenyl)propionate ⁇ , 2,4-bis-(N-octylthio)-6-(4-hydroxyphenyl ⁇ 3,5-di-t-butyl
  • Examples of the (meth)acrylate compound having a hindered phenol structure include a compound represented by the following formula (7).
  • R 1 to R 5 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R 6 is a hydrogen atom or a methyl group.
  • the alkyl group having 1 to 10 carbon atoms represented by R 1 to R 5 includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, Examples include isobutyl group, tert-butyl group, and 1,1-dimethylpropyl group.
  • R 1 and R 2 are sterically hindered, such as isopropyl group, sec-butyl group, tert-butyl group, and 1,1-dimethylpropyl group, in terms of high stabilizing effect and ease of production. Large bulky alkyl groups are preferred.
  • R 3 and R 4 are preferably a tert-butyl group or a 1,1-dimethylpropyl group from the viewpoint of suppressing the reaction that produces a quinoid structure accompanied by hydrogen abstraction.
  • R 5 is preferably a methyl group, ethyl group, n-propyl group or n-butyl group.
  • (B) As a compound (B), it can be highly effective in suppressing equipment contamination caused by volatile matter and bleed substances during the drying process of polymers, and can stabilize quality by suppressing changes in Mooney viscosity due to variations in desolvation time, (A) It is highly effective in reducing the process load in the process of manufacturing conjugated diene polymers, and various properties such as the strength, abrasion resistance, viscoelastic properties of the crosslinked product, and low fuel consumption performance when used in tires Among them, hindered phenol compounds having an unsaturated group can be preferably used in that they can enhance the improvement effect.
  • the unsaturated group examples include a vinyl group, a (meth)acryloyl group, and a vinylphenyl group.
  • the hindered phenol compound having an unsaturated group as component (B) preferably has a (meth)acryloyl group, and the compound represented by formula (7) is more preferable.
  • R 1 and R 2 are tert-butyl groups
  • R 3 and R 4 are methyl groups
  • R 5 and R 6 are hydrogen atoms
  • R 1 to R 4 are tert-pentyl groups.
  • a compound in which R 5 is a methyl group and R 6 is a hydrogen atom is preferred.
  • the molecular weight of the compound (B) is 250 to 2,000. If the molecular weight of the hindered phenol compound added to the present composition is less than 250, the hindered phenol compound will easily migrate to the mixed solvent phase during the desolvation process, and the amount remaining in the polymer will tend to decrease. There is a concern that thermal storage combustion and volatilization of polymer components adhering to equipment during the drying process of the polymer cannot be sufficiently suppressed. Therefore, it is necessary to frequently perform treatment to remove components attached to the equipment, which increases the process load. Furthermore, if the molecular weight of the hindered phenol compound exceeds 2,000, there is a concern that the compatibility with the conjugated diene polymer (A) will decrease, leading to a decrease in performance.
  • the molecular weight of the compound (B) is preferably 300 or more, more preferably 350 or more. Moreover, the molecular weight of the compound (B) is preferably 1,800 or less, more preferably 1,500 or less, and even more preferably 1,200 or less.
  • the compounding amount of (B) compound (the total amount when two or more types are used) is 0.1 parts by mass or more and 2.2 parts by mass or less with respect to 100 parts by mass of (A) conjugated diene polymer. It is preferable that there be.
  • the blending amount of the compound (B) is more preferably 0.2 parts by mass or more, and more preferably 0.4 parts by mass or more with respect to 100 parts by mass of the conjugated diene polymer (A). It is even more preferable that there be. Furthermore, by setting the blending amount of the compound (B) to 2.2 parts by mass or less, it is possible to increase the effect of suppressing equipment contamination caused by volatile components and bleed products during the drying treatment of the polymer, and to use the present composition. There is a tendency that it is possible to suppress a decrease in the strength of the crosslinked product obtained by the above process and a decrease in fuel efficiency when used in tires.
  • the compounding amount of the compound is more preferably 1.8 parts by mass or less, even more preferably 1.4 parts by mass or less, and 1.0 parts by mass or less, based on 100 parts by mass of the (A) conjugated diene polymer. It is even more preferable that the amount is not more than parts by mass.
  • the (B) compound one type may be used alone, or two or more types may be used in combination.
  • composition may further contain the following components.
  • composition contains at least one type selected from the group consisting of phosphorus stabilizers and organic sulfur stabilizers as component (C), and has a molecular weight of 250 to 2,000. It may further contain a compound (hereinafter also referred to as "(C) specific stabilizer").
  • this composition has the effect of reducing the change in Mooney viscosity with respect to desolution time and achieving quality stability with a smaller amount of additive, and ( A) During the drying process of the conjugated diene polymer, it is possible to obtain the effect of suppressing heat storage combustion and component volatilization due to the adhesion of the conjugated diene polymer (A) to the equipment. This makes it possible to improve equipment contamination and the performance of the crosslinked product in a well-balanced manner.
  • compounds known as phosphorus antioxidants and organic sulfur antioxidants and having a molecular weight within the range of 250 to 2,000 can be used.
  • Specific examples of these include tris(2,4-di-t-butylphenyl) phosphite and tetrakis(2,4-di-t-butylphenyl) as phosphorus stabilizers with a molecular weight of 250 to 2,000.
  • -4-,4'-bisphenylene phosphite tris(nonylphenyl) phosphite, distearylpentaerythol diphosphite, bis(2,4,di-t-butylphenyl)pentaerythol phosphite, bis( 2,6,di-t-butyl-4-methylphenyl)pentaerythol phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, tetrakis(2,4-di- (t-butylphenyl) 4,4'-bisphenylene-di-phosphite and the like.
  • the phosphorus stabilizer one kind can be used alone or two or more kinds can be used in combination.
  • organic sulfur stabilizers with a molecular weight of 250 to 2,000 include didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, and bis[3-(dodecylthio)propionic acid].
  • 2,2-bis[[3-(dodecylthio)-1-oxopropyloxy]methyl]-1,3-propanediyl, pentaerythritol tetrakis (3-dodecylthiopropionate), thiobis(N-phenyl- ⁇ - Examples include organic thio acid compounds such as naphthylamine).
  • the organic sulfur stabilizer one type can be used alone or two or more types can be used in combination.
  • the blending amount of the specific stabilizer (if two or more types are used, the total amount) is 0.01 parts by mass or more and 2.0 parts by mass with respect to 100 parts by mass of (A) conjugated diene polymer.
  • the following is preferable.
  • the blending amount of the specific stabilizer (C) is more preferably 0.02 parts by mass or more, and even more preferably 0.05 parts by mass or more, based on 100 parts by mass of the conjugated diene polymer (A).
  • the blending amount of the specific stabilizer (C) is more preferably 1.5 parts by mass or less, and even more preferably 1.2 parts by mass or less, based on 100 parts by mass of the (A) conjugated diene polymer.
  • (C) By setting the blending amount of the specific stabilizer within the above range, it is possible to reduce the change in Mooney viscosity due to variations in desolvation time, and to reduce the adhesion of (A) conjugated diene polymer to equipment during drying. The effect of suppressing thermal storage combustion and volatilization of components can be obtained while reducing the amount of the additive of the (B) compound.
  • the specific stabilizer (C) only a phosphorus stabilizer, only an organic sulfur stabilizer, or a combination of a phosphorus stabilizer and an organic sulfur stabilizer may be used. It's okay.
  • composition may contain an inorganic filler.
  • examples of the inorganic filler include silica and carbon black, and fillers other than silica and carbon black (hereinafter also referred to as "other fillers").
  • the inorganic filler blended into the present composition preferably contains one or both of silica and carbon black.
  • the present composition can contain silica.
  • the amount of silica blended is preferably in the range of 20 to 120 parts by weight, more preferably in the range of 30 to 100 parts by weight, based on 100 parts by weight of the rubber component containing the conjugated diene polymer (A).
  • the blending amount of silica is 20 parts by mass or more based on 100 parts by mass of the rubber component, the low hysteresis loss property, fracture characteristics, and abrasion resistance of the polymer composition can be sufficiently improved;
  • the amount is less than 1.9 parts, the processability of the polymer composition can be sufficiently improved.
  • the "rubber component" contained in the polymer composition refers to a polymer that can be cured to exhibit rubber elasticity by heat curing or the like.
  • the cured product exhibits the property of causing large deformation (for example, deformation that stretches more than twice as much when stretched at room temperature) with a small force at room temperature, and rapidly returning to almost its original shape when the force is removed.
  • Silica is not particularly limited, and examples thereof include wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like. Among these, wet silica is preferred. As silica, one type may be used alone, or two or more types may be used in combination. Furthermore, the BET specific surface area of silica (value measured according to ISO 5794/1) is preferably in the range of 40 to 350 m 2 /g, more preferably in the range of 80 to 350 m 2 /g, and more preferably in the range of 120 to 350 m 2 A range of /g is particularly preferred.
  • Silica having a BET specific surface area within this range has the advantage of being able to achieve both rubber reinforcing properties and dispersibility in the (A) modified diene polymer.
  • the first silica has a CTAB (cetyltrimethylammonium bromide) specific surface area of 180 m 2 /g or more, a BET specific surface area of 185 m 2 /g or more, and an aggregate size of 45 nm or more, and a CTAB specific surface area of 95 m 2 /g or less, and a second silica having a BET specific surface area of 100 m 2 /g or less may be used in combination.
  • CTAB cetyltrimethylammonium bromide
  • the present composition comprises a first silica having a CTAB specific surface area of 180 m 2 /g or more, a BET specific surface area of 185 m 2 /g or more, and an aggregate size of 45 nm or more;
  • the second silica may have a surface area of 100 m 2 /g or less.
  • the CTAB specific surface area of the first silica is preferably 190 m 2 /g or more, more preferably 195 m 2 /g or more, even more preferably 197 m 2 /g or more.
  • the CTAB specific surface area of the first silica is preferably 350 m 2 /g or less, more preferably 300 m 2 /g or less, even more preferably 250 m 2 /g or less.
  • the CTAB specific surface area exceeds 350 m 2 /g, the dispersibility is poor and agglomeration tends to occur easily, so that physical properties tend to deteriorate.
  • the BET specific surface area of the first silica is preferably 190 m 2 /g or more, more preferably 195 m 2 /g or more, and still more preferably 210 m 2 /g or more.
  • the BET specific surface area is preferably 350 m 2 /g or less, more preferably 300 m 2 /g or less, even more preferably 260 m 2 /g or less.
  • the BET specific surface area exceeds 350 m 2 /g, the dispersibility is poor and agglomeration tends to occur easily, so that physical properties tend to deteriorate. Note that the BET specific surface area of silica is measured according to ASTM D3037-81.
  • the aggregate size of the first silica is 45 nm or more, preferably 50 nm or more, more preferably 55 nm or more, and still more preferably 60 nm or more. Further, the aggregate size is preferably 100 nm or less, more preferably 80 nm or less, still more preferably 70 nm or less, particularly preferably 67 nm or less. By having such an aggregate size, it is possible to provide excellent fuel efficiency and wear resistance while having good dispersibility (processability). Note that the aggregate size of silica can be measured by the method described in JP-A-2011-140613.
  • the average primary particle diameter of the first silica is preferably 25 nm or less, more preferably 22 nm or less, even more preferably 17 nm or less, particularly preferably 14 nm or less.
  • the lower limit of the average primary particle diameter is not particularly limited, but is preferably 3 nm or more, more preferably 5 nm or more, and still more preferably 7 nm or more.
  • the carbon black-like structure with the above-mentioned aggregate size can further improve the dispersibility (processability) of silica, resulting in low fuel consumption and wear resistance. can be further improved.
  • the average primary particle size of silica can be determined by observing silica using a transmission or scanning electron microscope, measuring the particle size of 400 or more silica primary particles observed within the field of view, and averaging the particle size. .
  • the CTAB specific surface area of the second silica is preferably 10 m 2 /g or more, more preferably 20 m 2 /g or more, even more preferably 30 m 2 /g or more. If the CTAB specific surface area is less than 10 m 2 /g, the reinforcing properties will be low, and it may be difficult to sufficiently ensure the mechanical strength and abrasion resistance required for a polymer composition for tire manufacturing.
  • the CTAB specific surface area is preferably 80 m 2 /g or less, more preferably 60 m 2 /g or less, even more preferably 50 m 2 /g or less. If the CTAB specific surface area exceeds 95 m 2 /g, the dispersibility of silica may deteriorate, making it difficult to improve fracture strength and abrasion resistance.
  • the BET specific surface area of the second silica is preferably 10 m 2 /g or more, more preferably 20 m 2 /g or more, even more preferably 30 m 2 /g or more. If the BET specific surface area is less than 10 m 2 /g, the reinforcing properties will be low, and it may be difficult to ensure the mechanical strength and abrasion resistance required for a polymer composition for tire manufacturing.
  • the BET specific surface area is preferably 85 m 2 /g or less, more preferably 60 m 2 /g or less, even more preferably 50 m 2 /g or less. If the BET specific surface area exceeds 100 m 2 /g, the dispersibility of silica may deteriorate, making it difficult to improve fracture strength and abrasion resistance.
  • the average primary particle diameter of the second silica is preferably 20 nm or more, more preferably 25 nm or more, even more preferably 30 nm or more, particularly preferably 35 nm or more, and most preferably 55 nm or more.
  • the upper limit of the average primary particle diameter is not particularly limited, but is preferably 500 nm or less, more preferably 200 nm or less, still more preferably 100 nm or less, particularly preferably 70 nm or less. By having such an average primary particle diameter, sufficient fracture strength and wear resistance can be ensured.
  • Carbon black The present composition preferably contains carbon black from the viewpoint of fracture characteristics and wear resistance of the polymer composition. Carbon black is not particularly limited, and includes, for example, GPF, FEF, HAF, ISAF, and SAF grade carbon black.
  • the nitrogen adsorption specific surface area (N2SA) of carbon black is not particularly limited, but is preferably 50 to 200 m 2 /g, more preferably 70 to 150 m 2 /g. Nitrogen adsorption specific surface area (N 2 SA) is the value obtained by measuring the amount of nitrogen adsorbed on the carbon black surface in accordance with JIS K6217-2:2001 "Part 2: How to determine specific surface area - Nitrogen adsorption method - Single point method" It is.
  • One type of carbon black may be used alone, or two or more types may be used in combination.
  • the amount of carbon black in the present composition is preferably in the range of 1 to 150 parts by weight, more preferably in the range of 5 to 120 parts by weight, based on 100 parts by weight of the conjugated diene polymer (A).
  • the present composition may contain other fillers in addition to silica and carbon black as inorganic fillers.
  • Other fillers 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, gibbsite, bayerite, etc.
  • the amount of the inorganic filler containing silica and carbon black is preferably 30 parts by mass or more, more preferably 40 parts by mass, based on 100 parts by mass of the rubber component containing (A) the conjugated diene polymer. That's all. Further, the amount of the inorganic filler blended is preferably 150 parts by mass or less, more preferably 130 parts by mass or less, based on 100 parts by mass of the rubber component containing the conjugated diene polymer (A). If the amount of inorganic filler in this composition is within the above range, when this composition is applied to a tire tread, the tire will have low rolling resistance, braking performance on wet roads, and good performance on dry roads. It is possible to improve the handling performance and wear resistance in a more highly balanced manner.
  • ⁇ Component (E) Other rubber components
  • the present composition may contain only (A) the conjugated diene polymer as a rubber component, in addition to the conjugated diene polymer (A), the present disclosure
  • a rubber component different from the conjugated diene polymer (A) (hereinafter also referred to as "other rubber component”) may be contained within a range that does not impair the effects of (A).
  • Other rubber components include, for example, at least one diene rubber selected from natural rubber, isoprene rubber, butadiene rubber, emulsion polymerization or solution polymerization styrene-butadiene rubber, butyl rubber, halogenated butyl rubber, and ethylene-propylene rubber. can be used.
  • other rubber components are preferably natural rubber, butadiene rubber, or styrene-butadiene rubber.
  • the manner in which the other rubber components and (A) the conjugated diene polymer are mixed is not particularly limited.
  • the other rubber components and (A) the conjugated diene polymer may be mixed during the usual kneading using a Banbury mixer, rolls, etc., or the (A) conjugated diene polymer may be mixed with the (A) conjugated diene polymer after polymerization.
  • Other rubber components may be mixed into the polymer solution containing the rubber, and then the solvent removal and drying steps may be performed.
  • the blending amount of other rubber components is preferably 80% by mass or less, and more preferably 80% by mass or less based on the total amount of rubber components ((A) conjugated diene polymer and other rubber components) contained in the polymer composition. Preferably it is 60% by mass or less.
  • a liquid rubber can also be used as part or all of the other rubber components from the viewpoint of further improving dry grip performance, wet grip performance, and blowout resistance.
  • liquid rubber examples include liquid polyisoprene (liquid IR), liquid polybutadiene (liquid BR), liquid styrene-butadiene copolymer (liquid SBR), and liquid ethylene-propylene copolymer (liquid EP).
  • liquid SBR having a weight average molecular weight of 1,000 to 100,000, preferably 2,000 to 80,000 can be used.
  • the weight average molecular weight means the weight average molecular weight in terms of polystyrene analyzed by gel permeation chromatography (GPC). Note that the liquid rubber used in this composition refers to one that has fluidity at 23°C.
  • Thermoplastic/thermosetting resin Thermoplastic/thermosetting resin
  • the present composition may contain a thermoplastic/thermosetting resin (hereinafter also simply referred to as "(F) resin").
  • Resins include styrene resins, polyethylene, C5 resins, C9 resins, C5/C9 resins, from the viewpoint of obtaining crosslinked products with excellent properties such as strength, abrasion resistance, and crack growth resistance. It is preferably at least one selected from the group consisting of dicyclopentadiene resins, alkylphenol resins, and terpene resins.
  • As the resin one type may be used alone, or two or more types may be used in combination.
  • the styrenic resin is a polymer obtained using a styrene monomer, and in particular, the structural units derived from the styrenic monomer are added to the total amount of monomer units possessed by the styrenic resin. It is preferable that the polymer contains 20% by mass or more.
  • Styrenic monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, o-chloro Examples include styrene, m-chlorostyrene, p-chlorostyrene, and the like. Among these, the styrenic monomer is preferably at least one of styrene and ⁇ -methylstyrene.
  • the styrenic resin may be a homopolymer obtained by polymerizing one type of styrenic monomer, or a copolymer obtained by copolymerizing two or more types of styrenic monomers.
  • the styrenic resin may also be a copolymer obtained using a styrene monomer and another monomer that can be copolymerized with the styrene monomer.
  • Other monomers include acrylonitriles such as acrylonitrile and methacrylonitrile; unsaturated carboxylic acids such as acrylics and methacrylic acid; unsaturated carboxylic acid esters such as methyl acrylate and methyl methacrylate; chloroprene and butadiene isoprene. dienes such as; olefins such as 1-butene and 1-pentene; ⁇ , ⁇ -unsaturated carboxylic acids such as maleic anhydride or acid anhydrides thereof, and the like.
  • the softening point of the styrene resin is preferably 30°C or higher, more preferably 60°C or higher, and even more preferably 80°C or higher. When the softening point is 30° C. or higher, the effect of improving crack growth resistance tends to be easily obtained in the crosslinked body. Further, the softening point of the styrene resin is preferably 160°C or lower, more preferably 130°C or lower, and even more preferably 100°C or lower. When the softening point is 160° C. or less, the dispersibility of the resin becomes good, and crack growth resistance, abrasion resistance, and breaking strength tend to be improved.
  • the softening point of the styrene resin is a value measured using a ring and ball softening point measuring device according to the method specified in JIS K 6220-1:2015
  • the softening point of the styrene resin is a value measured using a ring and ball softening point measuring device. This is the temperature when the ball falls onto the bottom plate.
  • styrene resin a block polymer (thermoplastic elastomer) having a conjugated diene polymer block as a soft segment and a polystyrene block as a hard segment can also be used.
  • a block polymer thermoplastic elastomer
  • the effect of improving crack growth resistance can be increased, which is preferable.
  • a portion of the carbon-carbon double bonds in the structural unit derived from the conjugated diene compound may be hydrogenated.
  • conjugated diene compound constituting the conjugated diene polymer block examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. Can be mentioned.
  • the conjugated diene compound one kind can be used alone or two or more kinds can be used in combination.
  • the conjugated diene compound is preferably at least one of 1,3-butadiene and isoprene.
  • the content of conjugated diene units in the block polymer is preferably 20% by mass or more, more preferably 30% by mass or more. Moreover, it is preferable that the content rate of a conjugated diene unit is 80 mass % or less, and it is more preferable that it is 70 mass % or less.
  • the content of the polystyrene block in the block polymer is preferably 20% by mass or more, since it can further increase the breaking strength. Moreover, it is preferable that the content rate of a polystyrene type block is 80 mass % or less, and it is more preferable that it is 70 mass % or less. Note that the respective content ratios of the polystyrene block, conjugated diene polymer block, and conjugated diene unit in the block polymer can be calculated from the integral ratio of the 1 H-NMR spectrum.
  • block polymer examples include styrene-butadiene block copolymer, styrene-isoprene block copolymer, epoxidized product of styrene-butadiene block copolymer, styrene-butadiene block copolymer, or styrene-isoprene block copolymer.
  • SBS styrene-butadiene-styrene block copolymers
  • SIS styrene-isoprene-styrene block copolymers
  • SBBS styrene-butadiene-butylene-styrene block copolymers
  • hydrogenated products of these copolymers epoxies of styrene-butadiene-styrene block copolymers (SIS), styrene-isoprene-styrene block copolymers (SIS), styrene-butadiene-butylene-styrene block copolymers (SBBS), and styrene-butadiene-styrene block copolymers and hydrogenated products of these copolymers.
  • SBS styrene-butadiene-styrene block copolymers
  • SIS styrene-is
  • SBS or SIS having a conjugated diene polymer block whose soft segment is not hydrogenated, or an epoxidized product of a styrene-butadiene-styrene block copolymer is preferably used as the block polymer because it is easily crosslinked. be able to.
  • polyethylene examples include low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), and the like.
  • the C5 resin is a solid polymer (C5 synthetic petroleum resin) obtained by polymerizing a C5 fraction using a Friedel-Crafts catalyst (AlCl 3 , BF 3 , etc.).
  • Specific examples of C5 resins include copolymers containing isoprene, cyclopentadiene, 1,3-pentadiene, and 1-pentene as main components, copolymers of 2-pentene and dicyclopentadiene, and 1,3-pentadiene.
  • Examples include polymers containing pentadiene as a main component.
  • the C9 resin is a solid polymer (C9 synthetic petroleum resin) obtained by polymerizing a C9 fraction using a Friedel-Crafts catalyst (AlCl 3 , BF 3 , etc.).
  • C9-based resins include copolymers containing indene, methylindene, vinyltoluene, etc. as main components.
  • the C5/C9 resin is a solid polymer (C5/C9 synthetic petroleum resin) obtained by polymerizing C5 to C9 fractions using a Friedel-Crafts catalyst (AlCl 3 , BF 3, etc.).
  • Specific examples of C5/C9 resins include copolymers containing vinyltoluene, indene, etc. as main components.
  • the C5/C9 resin a resin containing a small amount of C9 or higher components is preferable from the viewpoint of compatibility with the rubber component.
  • the content of C9 or higher components in the total amount of the resin is preferably less than 50% by mass, and more preferably 40% by mass or less.
  • Dicyclopentadiene resin is a petroleum resin that uses dicyclopentadiene in the C5 fraction as the main raw material.
  • dicyclopentadiene-based resins include Marukaretz M series (M-890A, M-845A, M-990A, etc.) manufactured by Maruzen Petrochemical Co., Ltd.
  • alkylphenol resin include alkylphenol-acetylene resin such as p-tert-butylphenol-acetylene resin, alkylphenol-formaldehyde resin with a low degree of polymerization, and the like.
  • Terpene resin is a solid resin obtained by blending turpentine oil, which is obtained at the same time as rosin from Pine trees, or polymerization components separated from this oil, and polymerizing it using a Friedel-Crafts type catalyst. Examples include ⁇ -pinene resin and ⁇ -pinene resin.
  • turpentine oil obtained by blending turpentine oil, which is obtained at the same time as rosin from Pine trees, or polymerization components separated from this oil, and polymerizing it using a Friedel-Crafts type catalyst. Examples include ⁇ -pinene resin and ⁇ -pinene resin.
  • commercial products can be used, such as the "YS Resin” series (PX-1250, TR-105, etc.) manufactured by Yasuhara Chemical Co., Ltd., and the "Picolite” manufactured by Hercules Corporation. series (A115, S115, etc.).
  • a typical example of the terpene-aromatic compound resin is a terpene-phenol resin.
  • This terpene-phenol resin can be obtained by a method in which terpenes and various phenols are reacted using a Friedel-Crafts type catalyst, or further condensed with formalin.
  • monoterpene hydrocarbons such as ⁇ -pinene and limonene are preferred, those containing ⁇ -pinene are more preferred, and ⁇ -pinene is particularly preferred.
  • a terpene-phenol resin having a small proportion of phenol component is suitable.
  • the ratio of the phenol component is small refers to the fact that the phenol component in the total amount of the resin is less than 50% by mass, preferably 40% by mass or less.
  • a terpene-aromatic compound resin particularly a terpene-phenol resin
  • the handling performance can be further improved.
  • the terpene-aromatic compound resin commercially available products can be used.
  • Examples of commercially available products include “Tamanol 803L", “Tamanol 901” (manufactured by Arakawa Chemical Co., Ltd.) under the trade name, "YS Polyster (registered trademark)” series (manufactured by Yasuhara Chemical Co., Ltd.), and the like.
  • the blending ratio of the resin (F) is preferably 1 part by mass or more based on 100 parts by mass of the rubber component contained in the present composition.
  • the blending ratio of the resin (F) is more preferably 3 parts by mass or more, and even more preferably 7 parts by mass or more, based on 100 parts by mass of the rubber component.
  • the blending ratio of (F) resin is preferably 50 parts by mass or less based on 100 parts by mass of the rubber component contained in the composition, from the viewpoint of maintaining good performance of the composition.
  • the amount is preferably 30 parts by mass or less, and still more preferably 25 parts by mass or less.
  • the resin (F) one type may be used alone, or two or more types may be used in combination.
  • silane coupling agent in this composition, a silane coupling agent may be blended to further improve the dispersibility of silica.
  • the silane coupling agent used is not particularly limited.
  • the silane coupling agent is preferably a sulfur-containing silane coupling agent, such as bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)disulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, Examples include ⁇ -mercaptopropyltriethoxysilane and 3-octanoylthiopropyltriethoxysilane.
  • the amount of the silane coupling agent blended is preferably 1 to 20 parts by mass based on 100 parts by mass of silica contained in the present composition. If the amount of the silane coupling agent is less than 1 part by mass, there is a concern that the effect of improving the dispersibility of silica will be reduced due to the small amount of the silane coupling agent. On the other hand, if the amount of the silane coupling agent exceeds 20 parts by mass, the processability of the polymer composition and the elongation at break of the crosslinked product may decrease.
  • the blending amount of the silane coupling agent is more preferably 5 to 15 parts by mass based on 100 parts by mass of silica contained in the present composition.
  • Crosslinking agent The present composition may contain a crosslinking agent. By containing the crosslinking agent in the present composition, a crosslinked product with improved strength and wear resistance can be obtained.
  • the crosslinking agent include sulfur, halogenated sulfur, organic peroxides, quinone dioximes, organic polyvalent amine compounds, alkylphenol resins having a methylol group, and sulfur is usually used.
  • the amount of the crosslinking agent blended is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the total amount of rubber components contained in the composition.
  • Extender oil A process oil that is generally used for extending elastomers may be blended into the present composition as an oil for oil extension (extender oil).
  • the method of adding process oil is not particularly limited. For example, it may be compounded as an oil-extended rubber by spreading process oil in a conjugated diene polymer solution after polymerization and then removing the process oil, or it may be compounded as an oil-extended rubber by spreading the process oil into the conjugated diene polymer solution after polymerization, or by adding process oil to the conjugated diene polymer solution during kneading to obtain a rubber compound (compounded rubber). Processing oils may be incorporated into the polymer composition by adding the oil directly.
  • Preferred process oils include a variety of oils known in the art, such as aromatic oils, paraffinic oils, naphthenic oils, vegetable oils, and oils with a low content of polycyclic aromatics (low polyaromatics).
  • PCA oil e.g. mild extraction solvate (MES), treated distillate aromatic extract (TDAE) from distillate oil, special aromatic extraction from residual oil. (SRAE: special residual aromatic extract), heavy naphthenic oil, etc.
  • MES mild extraction solvate
  • TDAE treated distillate aromatic extract
  • SRAE special residual aromatic extract
  • Examples of commercially available MES, TDAE and SRAE include Catenex SNR (heavy paraffin made by solvent dewaxing of distillate) from Shell as MES, Vivatec 500 from H&R Wasag AG as TDAE, and Japan Energy Corp as SRAE.
  • Examples include NC140 manufactured by .
  • the amount of process oil blended is preferably 10 to 100 parts by mass based on 100 parts by mass of the total amount of polymer
  • this composition also contains vulcanized rubber, such as zinc white, stearic acid, softeners, vulcanization accelerators, compatibilizers, vulcanization aids, processing aids, and scorch inhibitors.
  • vulcanized rubber such as zinc white, stearic acid, softeners, vulcanization accelerators, compatibilizers, vulcanization aids, processing aids, and scorch inhibitors.
  • Various additives commonly used in polymer compositions for obtaining can be blended. These blending ratios can be appropriately selected depending on the various components within a range that does not impair the effects of the present disclosure.
  • the present composition can be obtained by mixing (A) the conjugated diene polymer and (B) the compound.
  • the manner in which the present composition is obtained by mixing the conjugated diene polymer (A) and the compound (B) is not particularly limited.
  • the present composition is capable of reducing (A) the conjugated diene polymer by adding the (B) compound to a polymer solution containing the (A) conjugated diene polymer after polymerization. It is preferable that the mixture is obtained by mixing the combined substance and the compound (B), and then removing the solvent and drying.
  • the present composition is preferably manufactured by a method including Step A, Step B, and Step C below.
  • Step A By polymerizing a monomer containing a conjugated diene compound and an aromatic vinyl compound in the presence of an alkali metal or an alkaline earth metal and hydrogenating it, (A) a polymer solution containing a conjugated diene polymer.
  • the process of obtaining Step B A step of mixing the polymer solution obtained in Step A and the (B) compound to obtain a mixed solution containing the (A) conjugated diene polymer and the (B) compound.
  • Step C A step of removing the solvent from the liquid mixture obtained in Step B and drying it.
  • Step A is a step that includes the above-mentioned polymerization step and hydrogenation step, and optionally includes one or both of a reaction step and a modification step.
  • the above description applies to the details of each step.
  • Step B from the viewpoint of simplifying the manufacturing process, the polymer solution containing the (A) conjugated diene polymer obtained in Step A is used as it is, and the polymer solution and the (B) compound are mixed. It is preferable.
  • the amount of the compound (B) is as described above.
  • (C) a specific stabilizer is blended into the present composition, the (C) specific stabilizer is blended during kneading to obtain a blended composition (so-called compounded rubber), thereby combining (A) with a conjugated diene polymer.
  • (C) It may be mixed with a specific stabilizer.
  • step B the (A) conjugated diene polymer and (C) the specific stabilizer may be mixed by adding the (C) specific stabilizer to the polymer solution.
  • the latter method an embodiment in which the specific stabilizer (C) is added to the polymer solution in step B) is preferable in that the effect of blending the specific stabilizer (C) can be sufficiently enhanced.
  • the (C) specific stabilizer may be added to the polymer solution at the same time as the (B) compound, or the (B) specific stabilizer may be added to the polymer solution before or after the addition of the compound.
  • a specific stabilizer may be added to the polymer solution later. The amount of the compound (C) is as described above.
  • Step C the method of removing the solvent from the liquid mixture containing the conjugated diene polymer (A) and the compound (B) and drying the mixture is not particularly limited.
  • the solvent can be removed from the mixed solution and dried by known desolvation operations such as steam stripping and drying operations such as heat treatment.
  • a solid polymer composition from which the solvent has been removed (hereinafter also referred to as "polymer composition P") can be obtained as one embodiment of the present composition.
  • the polymer composition P may be solid particles (crumbs), or may be rubber veils obtained by compression molding crumbs into a desired shape (for example, a rectangular parallelepiped shape).
  • the total content of (A) the conjugated diene polymer, (B) the compound, and (I) the extender oil that is optionally blended is 95% by mass or more based on the entire composition.
  • the content is preferably 97% by mass or more, and more preferably 97% by mass or more.
  • polymer composition Q By blending the above-mentioned various components ((D) to (I) components, etc.) into the obtained polymer composition P as necessary, it can be made into a blended composition as another embodiment of the present composition.
  • a polymer composition or blended composition hereinafter also referred to as "polymer composition Q" can be obtained.
  • the blended composition is prepared by mixing the polymer composition P with various additives (components (D) to (I), etc.) that are optionally used in a polymer composition for obtaining a vulcanized rubber, and preferably It can be obtained by kneading using a kneader such as a type kneader (for example, a roll) or an internal kneader (for example, a Banbury mixer). By crosslinking (vulcanizing) the compounded rubber thus obtained after molding, a crosslinked product (ie, vulcanized rubber) is obtained.
  • a kneader such as a type kneader (for example, a roll) or an internal kneader (for example, a Banbury mixer).
  • a crosslinked product obtained using the polymer composition of the present disclosure containing (A) a conjugated diene polymer and (B) a compound can be applied to various rubber products.
  • the crosslinked product obtained using the present composition can be used, for example, in tire applications such as tire treads, undertreads, carcass, sidewalls, and bead parts; seals such as packings, gaskets, weather strips, and O-rings.
  • Materials Interior and exterior skin materials for various vehicles such as automobiles, ships, aircraft, and railways; Building materials; Anti-vibration rubbers for industrial machinery and equipment;
  • Various hoses such as diaphragms, rolls, radiator hoses, air hoses, etc. It can be applied to hose covers; belts such as power transmission belts; linings; dust boots; medical equipment materials; fenders; insulating materials for electric wires; and other industrial products.
  • the polymer composition of the present disclosure containing (A) a conjugated diene polymer and (B) a compound, it is possible to suppress the adhesion of the (A) conjugated diene polymer to equipment during drying treatment, and also to prevent the adhesion of the equipment to equipment. It is possible to suppress thermal storage combustion and volatilization of components due to the polymer, and to obtain a crosslinked product that has good physical properties required for tire applications, such as tensile strength, abrasion resistance, and viscoelastic properties, while easing the process load in the manufacturing process. can. Therefore, a polymer composition containing (A) a conjugated diene polymer and (B) a compound can be particularly suitably used as a material for a tire tread, a sidewall, or both.
  • Tires can be manufactured according to conventional methods. For example, a polymer composition is mixed in a kneading machine and formed into a sheet, which is then placed in a predetermined position (for example, outside the carcass in the case of sidewalls) and vulcanized to form a tread. Alternatively, it can be formed as a sidewall to obtain a pneumatic tire.
  • the value ⁇ represented by the above formula (i) is 0.60 to 0.98
  • [Means 2] The polymer composition according to [Means 1], wherein the content of the component (B) is 0.1 to 2.2 parts by mass based on 100 parts by mass of the component (A).
  • [Means 3] The polymer composition according to [Means 1] or [Means 2], wherein the proportion of nitrogen contained in the component (A) is 50 ppm or more based on the total amount of the component (A).
  • [Means 4] The polymer composition according to any one of [Means 1] to [Means 3], wherein the component (A) has a polymer block portion containing 80% by mass or more of structural units derived from an aromatic vinyl compound. thing.
  • [Means 5] The polymer composition according to any one of [Means 1] to [Means 4], which contains a branched polymer having a branch number of 4 or more as the component (A).
  • [Means 6] The polymer composition according to [Means 5], wherein the proportion of the branched polymer having a branch number of 4 or more is 15% by mass or more based on the total amount of the component (A).
  • [Means 7] The polymer composition according to any one of [Means 1] to [Means 6], wherein the component (B) has a molecular weight of 350 to 1,200.
  • [Means 8] The polymer composition according to any one of [Means 1] to [Means 7], which contains a compound having a carbon-carbon unsaturated bond as the component (B).
  • [Means 9] [Means 1] to [Means 8] further containing at least one component selected from the group consisting of phosphorus stabilizers and organic sulfur stabilizers and having a molecular weight of 250 to 2,000.
  • [Means 10] The polymer composition according to any one of [Means 1] to [Means 9], wherein the value ⁇ is 0.75 to 0.92.
  • [Means 11] [Means 1] to [Means 1], wherein the total content of the component (A), the component (B), and the optionally added extender oil is 95% by mass or more based on the entire composition.
  • [Means 12] The polymer composition according to any one of [Means 1] to [Means 10], further containing an inorganic filler.
  • [Means 13] A crosslinked product obtained by crosslinking the polymer composition according to any one of [Means 1] to [Means 10] and [Means 12].
  • [Means 14] A tire in which a tread, a sidewall, or both are formed using the polymer composition according to any one of [Means 1] to [Means 10] and [Means 12].
  • [Means 15] A method for producing the polymer composition according to any one of [Means 1] to [Means 12], comprising: a conjugated diene compound and an aromatic vinyl compound in the presence of an alkali metal or an alkaline earth metal; A step of obtaining a polymer solution containing the component (A) by polymerizing and hydrogenating a monomer containing the component (A); A method for producing a polymer composition, comprising the steps of: obtaining a mixed solution containing the component and the component (B); and removing the solvent from the mixed solution and drying it.
  • ⁇ Coupling rate (mass%): From the GPC curve obtained using GPC (product name: HLC-8020, manufactured by Tosoh Corporation) for the polymer before hydrogenation, it was determined that two or more linear conjugates The waveform of the molecule to which the molecular chains of the diene polymer were bonded was separated into components and calculated from the peak area ratio.
  • - Hydrogenation rate and ⁇ Calculated from 1 H-NMR spectrum measured with a 100 MHz device using ethylene tetrachloride as a solvent.
  • ⁇ Content of branched polymer with 4 branches or more (mass%): Based on the GPC curve obtained using GPC (product name: HLC-8020, manufactured by Tosoh Corporation) for the polymer before hydrogenation, 4 branches or more The waveform of the molecule to which the molecular chains of the linear conjugated diene polymer were bonded was separated into components, and the calculation was made from the peak area ratio.
  • the ratio W1 is the number of moles of the polymerization initiator (M1) used in the production of the polymer, the number of moles of the coupling agent (M2), and the number of moles of the amount of the terminal modifier consumed during modification with the terminal modifier (M3). and the coupling ratio (C/E) using the following formula.
  • W1 [%] (100-C/E) x M3/(M1-4 x M2)
  • M3 the number of moles (M3) of the terminal modifier consumed during modification with the terminal modifier was calculated by quantifying the unreacted terminal modifier by gas chromatography measurement of the polymer solution after the modification reaction.
  • ppm Nitrogen content (ppm): Measured according to the chemiluminescence method of JIS K2609:1998 (Crude oil and petroleum products - Nitrogen content test method).
  • a trace total nitrogen analyzer (“TN-2100H” manufactured by Mitsubishi Chemical Analytech)
  • the sample was thermally decomposed under argon gas flow, and then the sample was oxidized by combustion in an oxygen atmosphere.
  • the nitrogen monoxide reacted with ozone gas under dehydration conditions, the detected luminescence intensity in the range of 590 to 2500 nm was measured, and the nitrogen content was calculated from the area of the luminescence intensity.
  • Polymerization was carried out under adiabatic conditions. After the polymerization conversion rate reached 99%, 111 g of 1,3-butadiene was added (additional butadiene), and polymerization was further carried out for 3 minutes to obtain a reaction solution containing a polymer. To the obtained reaction solution, 2.0 mmol of tetrachlorosilane was added and reacted for 5 minutes, and further, 28 mmol of N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane was added and reacted for 15 minutes. Next, the reaction solution was heated to 80° C. or higher, hydrogen was introduced into the system, and the reaction was allowed to proceed for 1 hour.
  • a small amount of the polymer solution was extracted from the reaction vessel to obtain a conjugated diene polymer before hydrogenation for analysis. Then, 1.64 g of diethylaluminum chloride, 3.67 g of bis( ⁇ 5-cyclopentadienyl) titanium (furfuryloxy) chloride, and 1.67 g of n-butyllithium were added, and water was added while maintaining the hydrogen pressure of 1.0 MPa. An addition reaction was performed. After the reaction, the hydrogen pressure is maintained at 0.7 MPa or more and hydrogen is supplied until a predetermined integrated hydrogen value is reached.Then, the reaction solution is returned to room temperature and pressure and taken out from the reaction vessel, and then hydrogenated. A polymer solution containing conjugated diene polymer A-1 was obtained.
  • Hydrogenated conjugated diene polymer A was produced in the same manner as in Production Example 1, except that the polymerization recipe was changed as shown in Tables 1 and 2, and the hydrogenation rate was changed as shown in Tables 3 and 4. A polymer solution containing -2 to A-11, A-13 to A-18, A-21, and A-22 was obtained. In addition, in Production Examples 2 to 11 and 13 to 15, hydrogenated conjugated diene polymers A-2 to A-11, A-13, A-21, and A-22 were produced, respectively, and in Comparative Production Examples 2 to 5, Hydrogenated conjugated diene polymers A-14 to A-18 were produced, respectively. Tables 3 and 4 show various physical property values of hydrogenated conjugated diene polymers A-2 to A-11, A-13 to A-18, A-21, and A-22.
  • the reaction solution was cooled to 30° C., 700 g of styrene and 2,289 g of 1,3-butadiene were added, and further polymerization was carried out. After the polymerization conversion rate reached 99% or more, 111 g of 1,3-butadiene was added and polymerization was continued for an additional 3 minutes to obtain a reaction solution containing a polymer. To the obtained reaction solution, 2.0 mmol of tetrachlorosilane was added and reacted for 5 minutes, and further, 28 mmol of N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane was added and reacted for 15 minutes.
  • reaction solution was heated to 80° C. or higher, hydrogen was introduced into the system, and the reaction was allowed to proceed for 1 hour.
  • a small amount of the polymer solution was extracted from the reaction vessel to obtain a conjugated diene polymer before hydrogenation.
  • the hydrogen pressure is maintained at 0.7 MPa or more and hydrogen is supplied until a predetermined integrated hydrogen value is reached. Then, the reaction solution is returned to room temperature and pressure and taken out from the reaction vessel, and then hydrogenated. A polymer solution containing conjugated diene polymer A-12 was obtained. A small amount of the obtained polymer solution was extracted, the solvent was removed by steam stripping, and the solution was dried using a heated roll whose temperature was controlled to 130° C. to obtain hydrogenated conjugated diene polymer A-12.
  • the polymerization recipe of hydrogenated conjugated diene polymer A-12 is shown in Table 2, and various physical property values of hydrogenated conjugated diene polymer A-12 are shown in Table 4.
  • Hydrogenated conjugated diene polymer A-19,A was produced in the same manner as in Production Example 12 except that the polymerization recipe was changed as shown in Table 2 and the hydrogenation rate was changed as shown in Table 4 A polymer solution containing -20 was obtained.
  • Table 4 shows various physical properties of hydrogenated conjugated diene polymers A-19 and A-20.
  • V-1 Potassium dodecylbenzenesulfonate
  • INI-1 Piperidine
  • Md-1 N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane
  • Cp-1 Tetrachlorosilane
  • Example 1 ⁇ Production of polymer composition P To the polymer solution containing the hydrogenated conjugated diene polymer A-1 obtained in Production Example 1, for 100 parts by mass of the hydrogenated conjugated diene polymer A-1, 0.2 parts by mass of hindered phenol compound B-1 as component (B), 0.3 parts by mass of hindered phenol compound B-2, and 0.3 parts by mass of phosphoric acid ester compound C-1 as component (C). Parts by mass were mixed. The resulting mixed solution was desolvented for 2 hours by steam stripping, and dried using a heated roll whose temperature was controlled at 130°C, resulting in hydrogenated conjugated diene polymer A-1 and hindered phenol compound B. -1, a hindered phenol compound B-2, and a phosphoric acid ester compound C-1. Table 5 shows the formulation of polymer composition P-1.
  • the mixture obtained above was cooled to room temperature, and then a vulcanization accelerator and sulfur were added thereto and kneaded.
  • the kneaded polymer composition Q-1 was molded and vulcanized in a vulcanization press at 160° C. for a predetermined time to obtain a crosslinked product (vulcanized rubber).
  • a manufacturing process evaluation we evaluated the MV change rate, thermal storage combustion suppression ability, volatility, and equipment adhesion by extending the desolution time as shown below, and as a blend physical property evaluation, we evaluated the tensile strength of the obtained crosslinked product, Abrasion resistance, rolling resistance and vulcanization adhesion were evaluated. The results are shown in Table 8.
  • MV change rate due to extension of desolvation time Polymer composition P' was obtained in the same manner as in the production of polymer composition P except that the steam stripping time was changed from 2 hours to 8 hours. Mooney viscosity (MV) was measured for each of polymer composition P and polymer composition P', and MV measurement values (MV-P, MV-P') were obtained, respectively. Mooney viscosity was measured in accordance with JIS K6300-1 using an L rotor under conditions of preheating for 1 minute, rotor operating time for 4 minutes, and temperature of 100°C. Using the MV measurement values (MV-P, MV-P'), the MV change rate was calculated using the following formula.
  • MV change rate MV-P'/MV-P
  • heat storage combustion suppression performance was judged from A to C based on the following criteria.
  • A 97% or more and less than 99% of the polymer composition could be recovered, and there was little adhesion of the polymer composition to the wire mesh.
  • B 95% or more and less than 97% of the polymer composition could be recovered, and there was a large amount of the polymer composition attached to the wire mesh.
  • C The recovery rate of the polymer composition was less than 95%, and the polymer composition adhered to the wire mesh very often. If the evaluation is between AA and B, it can be determined that the adhesion to equipment during the drying process using a band dryer, extruder, etc. during production of the polymer composition is at a practical level. A C judgment indicates that it does not reach a practical level.
  • Abrasion resistance Using a crosslinked body as a measurement sample, measurement was performed at 25° C. under a load of 10 N using a DIN abrasion tester (manufactured by Toyo Seiki Co., Ltd.) in accordance with JIS K6264-2:2005. It was expressed as an index based on Comparative Example 1, and the rolling resistance was evaluated using the index. The larger the value, the higher the wear resistance and the better. From the obtained index, the wear resistance was judged from A to C based on the following criteria. A: 115 or more B: 105 or more and less than 115 and allowable range C: less than 105
  • Rolling resistance Using a crosslinked body as a measurement sample, measurements were made using a dynamic spectrometer (manufactured by Rheometrics, Inc., USA) under conditions of tensile dynamic strain of 0.7%, angular velocity of 100 radians per second, and 50°C. . It was expressed as an index based on Comparative Example 2, and rolling resistance was evaluated using the index. The larger the value, the lower the rolling resistance and the better. Based on the obtained index, rolling resistance was judged from AA to C based on the following criteria. AA: 125 or more A: 115 or more and less than 125 B: 105 or more and less than 115 and allowable range C: less than 105
  • Vulcanization adhesion A pre-vulcanized sheet of polymer composition Q and a pre-vulcanized sheet containing natural rubber as a main component are laminated with PET film sandwiched between the ends, and the temperature By vulcanizing at 170° C. for 15 minutes, a laminate vulcanized product was obtained in which the portions not sandwiching the PET film were vulcanized and bonded. In order to measure the adhesive strength at a width of 15 mm, a strip-shaped sample piece was taken from the laminated vulcanizate from the part where PET was sandwiched to the part where PET was not sandwiched, and the PET film was removed to prepare a test piece.
  • a vulcanized sheet made of polymer composition Q was placed on one side of an autograph tester equipped with a constant temperature bath, and a vulcanized sheet of natural rubber was placed on the other side, and the sheets were chucked up and down in an atmosphere of 70°C.
  • a peel test was conducted at a speed of 50 mm/min to measure the adhesive strength.
  • the obtained adhesive strength values were evaluated as an index based on Comparative Example 1. It can be said that the larger the value, the higher the adhesive force, and the better the vulcanization adhesion. Based on the obtained index, the vulcanization adhesion was judged from AA to C based on the following criteria.
  • Examples 2 to 15, Comparative Examples 1 to 7 In place of the polymer solution containing hydrogenated conjugated diene polymer A-1, each polymer solution containing hydrogenated conjugated diene polymers A-2 to A-22 was used, and the types and amounts of additives. Polymer compositions P-2 to P-22 were produced as polymer composition P in the same manner as in Example 1, except that the values were changed as shown in Tables 5 and 6. In addition, when producing the polymer composition P, in Examples 2 to 15, polymer solutions containing hydrogenated conjugated diene polymers A-2 to A-13, A-21, and A-22, respectively, were used, and in Comparative Example In Examples 1 to 7, polymer solutions containing hydrogenated conjugated diene polymers A-14 to A-20, respectively, were used.
  • each component was mixed according to the formulation shown in Table 7 in the same manner as in Example 1 except that polymer compositions P-2 to P-22 were used instead of polymer composition P-1.
  • Polymer compositions Q-2 to Q-22 were each produced by kneading. Further, crosslinked products were produced using each of the produced polymers Q-2 to Q-22, and various evaluations were conducted in the same manner as in Example 1. The results are shown in Tables 8 and 9.
  • the polymer compositions of Examples 1 to 15 were evaluated as ⁇ AA'' and ⁇ A'' in terms of MV change rate, heat storage combustion suppression ability, volatility, and equipment adhesion due to extended desolvation time. ” or “B”. From these results, it can be said that the polymer compositions of Examples 1 to 15 can reduce the load in the manufacturing process and have good quality stability.
  • the crosslinked products obtained from the polymer compositions of Examples 1 to 15 had improved tensile strength, abrasion resistance, rolling resistance, and vulcanization properties due to suppressed changes in the Mooney viscosity of the polymer during the manufacturing process.
  • the evaluation of adhesive properties was also good, and various compounding characteristics were excellent.
  • the polymer compositions of Nos. and 5 were evaluated as "C" in one or more of the manufacturing process evaluation items, and were inferior in terms of manufacturing process load and quality stability.
  • the compounding characteristics were rated "C” in one or more evaluation items.
  • the polymer composition of Comparative Example 6 containing hydrogenated conjugated diene polymer A-19 with a hydrogenation rate of 99% had good manufacturing process evaluations, but The evaluation of adhesiveness was "C", and the compounding characteristics were poor.
  • a polymer composition having a specific functional group containing a species element it is possible to reduce the process load and stabilize the quality in the production process of a conjugated diene polymer, and moreover, a crosslinked product with suppressed performance deterioration can be obtained. It has become clear that it can be obtained.

Abstract

L'invention concerne une composition polymère contenant: (A) un polymère de diène conjugué qui contient une unité structurelle dérivée d'un composé de diène conjugué et une unité structurelle dérivée d'un composé vinyle aromatique, pour lequel polymère la valeur α représentée par la formule mathématique (i), est comprise entre 0,60 et 0,98 lorsque le rapport de composition (rapport molaire) dans le polymère des unités structurelles représentées par la formule (1), des unités structurelles représentées par la formule (2), des unités structurelles représentées par la formule (3), et des unités structurelles représentées par la formule (4) sont respectivement p, q, r, et s; et (B) un composé phénol encombré dont la masse moléculaire est comprise entre 250 et 2000, la totalité ou un partie du composant (A) possédant un groupe fonctionnel contenant au moins un élément choisi dans le groupe comprenant: azote, oxygène, soufre et phosphore.　α=(p+(0,5xr))/(p+q+(0,5xr)+s)...(i)
PCT/JP2023/008379 2022-03-08 2023-03-06 Composition polymère ainsi que son procédé de production, produit réticulé, et pneumatique WO2023171628A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006299280A (ja) * 2001-03-26 2006-11-02 Jsr Corp 水添変性重合体及びその製造方法並びにそれを含む組成物
WO2014126184A1 (fr) * 2013-02-14 2014-08-21 Jsr株式会社 Procédé de production de polymère diène conjugué hydrogéné
JP2022028238A (ja) * 2020-08-03 2022-02-16 旭化成株式会社 ゴム組成物、及びタイヤ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006299280A (ja) * 2001-03-26 2006-11-02 Jsr Corp 水添変性重合体及びその製造方法並びにそれを含む組成物
WO2014126184A1 (fr) * 2013-02-14 2014-08-21 Jsr株式会社 Procédé de production de polymère diène conjugué hydrogéné
JP2022028238A (ja) * 2020-08-03 2022-02-16 旭化成株式会社 ゴム組成物、及びタイヤ

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