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    • 专利摘要:
    1/1 summary “tire member, hydrogenated conjugated diene polymer, and, polymer composition for tire member formation” is provided with a tire member that has good consumption performance fuel and exhibits greater strength and more excellent abrasion resistance compared to conventional ones. the tire member is obtained by crosslinking a composition containing a hydrogenated conjugated diene polymer and a crosslinking agent. the hydrogenated conjugated diene polymer is a hydrogenated product of a conjugated diene polymer that has a structural unit derived from butadiene and comprises a functional group at one end or at both ends. the functional group is composed of one or more groups selected from the group consisting of an amino group, an imino group, a pyridyl group, a phosphine group, a thiol group, and a hydrocarbiloxysilyl group.
    公开号:BR112015020527B1
    申请号:R112015020527
    申请日:2014-02-27
    公开日:2020-06-09
    发明作者:Senga Hirofumi；Nosaka Naoya；Tanaka Ryoji；Abe Shigeru；Adachi Takumi
    申请人:Jsr Corp；
    IPC主号:
    专利说明:

    TIRE MEMBER
    Technical Field
    [001] The present invention relates to a tire member, a hydrogenated conjugated diene polymer, and a polymer composition.
    Fundamentals of Technique
    [002] In tires, it is necessary to improve the performance of low fuel consumption. In order to satisfy such a requirement, an end-modified diene rubber was developed (see the following Patent Document 1). Since the modified modified diene rubber has good compaction ability with a filler as a reinforcing agent, such as carbon black or silica, compared to ordinary unmodified diene rubbers, the low fuel consumption performance can be improved with the suppression of heat generation.
    [003] On the other hand, as not only the low fuel consumption performance, but also the extension of the tire's life contribute to the reduction of environmental burden, a material having high strength and excellent abrasion resistance was requested.
    Related Technique Document
    Patent Document
    [004] Patent Document 1: JP-A-61-103904
    Summary of the Invention
    Problems to be solved by the invention
    [005] The present invention was made in consideration of the above and an objective of the invention is to provide a tire member that is satisfactory in low fuel consumption performance and exhibits greater resistance and more excellent abrasion resistance compared to conventional ones.
    Means to Solve Problems
    [006] As a result of extensive studies to address the
    Petition 870200028220, of 03/02/2020, p. 8/58
    2/39 problems with conventional technologies as described above, the present inventors have found that the above problems can be solved using a hydrogenated conjugated diene polymer which is a hydrogenated product of a polymer obtained by polymerizing monomer (s) including butadiene, and so on. they solved the invention. Specifically, the invention provides the following tire member, hydrogenated conjugated diene polymer, and polymer composition.
    [007] [1] A tire member obtained by subjecting a composition containing a hydrogenated conjugated diene polymer and a crosslinking agent to a crosslinking treatment, wherein the hydrogenated conjugated diene polymer is a hydrogenated product of a conjugated diene polymer. which has a structural unit derived from butadiene and has a functional group at one end or both ends and the functional group is one or more groups selected from the group consisting of an amino group, an imino group, a pyridyl group, a phosphine group, a thiol group, and a hydrocarbiloxysilyl group.
    [2] A hydrogenated conjugated diene polymer, which is a hydrogenated product of a conjugated diene polymer that has a structural unit derived from butadiene and has a functional group at one end or both ends of the polymer chain and in which the group Functional is at least one group selected from the group consisting of an amino group, an imino group, a pyridyl group, a phosphine group, a thiol group, and a hydrocarbiloxysilyl group.
    [3] A polymer composition for the formation of the tire member, which contains the hydrogenated conjugated diene polymer of [2] above and a crosslinking agent.
    Effects of the invention
    [008] According to the invention, when a specific hydrogenated conjugated diene polymer having a structural unit derived from
    Petition 870200028220, of 03/02/2020, p. 9/58
    3/39 butadiene is used, it is possible to obtain a vulcanized rubber capable of obtaining a tire limb exhibiting low fuel consumption, high strength and low abrasion performance.
    Modalities for Carrying Out the Invention
    [009] The sequence will describe matters that refer to the implementation of the present invention in detail.
    <Conjugated diene polymer>
    [0010] The conjugated diene polymer before hydrogenation, which is used for the production of the hydrogenated conjugated diene polymer of the invention, can be a 1,3-butadiene homopolymer, can be a random 1,3-butadiene copolymer and a conjugated diene compound other than 1,3-butadiene, can be a random copolymer of 1,3butadiene and an aromatic vinyl compound, or it can be a random copolymer of 1,3-butadiene, a conjugated diene compound other than 1 , 3butadiene, and an aromatic vinyl compound. Of these, like the conjugated diene polymer, a polymer obtained by polymerizing monomers including 1,3-butadiene and an aromatic vinyl compound is preferred in view of the long-life properties in an anionic polymerization. Incidentally, in the invention, the term that the conjugated diene polymer prior to hydrogenation is random copolymerization means that a chain composed of the structural units derived from the aromatic vinyl compound that varies by an amount of 8 or more units is contained in a ratio of 10% by weight or less with respect to all of the structural units derived from the aromatic vinyl compound that is contained in the conjugated diene polymer prior to hydrogenation. The conjugated diene compound other than 1,3-butadiene is not particularly limited as long as it can be copolymerized with 1,3-butadiene and the aromatic vinyl compound. In the invention, the term conjugated diene compound is used as a collective concept of 1,3-butadiene and, as a component
    Petition 870200028220, of 03/02/2020, p. 10/58
    4/39 optional, the conjugated diene compound is different from 1,3-butadiene.
    [0011] Here, the content of the chain composed of the structural units derived from the aromatic vinyl compound that varies by an amount of 8 or more units can be calculated as a ratio of the integrated value of the sequence range (a) to the sum of the integrated values of individual chemical shift ranges of the following (a) to (c) in ΉNMR spectrum of a conjugated diene polymer before or after hydrogenation measured using deuterated chloroform as a solvent. For example, in the case where aromatic vinyl is styrene, the ratio of styrene can be calculated by determining the ratio of the integrated value of the range from (a) to the sum of the integrated values of the individual ranges from (a) to (c) and multiplying the ratio by 2.5. In this way, a chain state of the structural units derived from the aromatic vinyl compound can be trapped.
    (a) a chain of 8 or more of the aromatic vinyl compounds: 6.00 <S <6.68 (b) a chain of 2 to 7 of the aromatic vinyl compounds:
    6.68 <S <6.89 (c) a short chain of aromatic vinyl compounds: 6.89 <S <8.00
    [0012] In the copolymer of the conjugated diene compound and the aromatic vinyl compound, the amount of the aromatic vinyl compound to be used is preferably 10 to 50% by weight, and more preferably 15 to 40% by weight with respect to total amount of monomers to be used in the polymerization, from the point of view of good balance between low hysteresis loss properties and wet skid resistance of the polymer obtained by the crosslinking treatment. When the content of the aromatic vinyl compound is controlled within the above range, it becomes possible to achieve both productivity and strength.
    [0013] As the conjugated diene compound to be used in
    Petition 870200028220, of 03/02/2020, p. 11/58
    5/39 polymerization of the conjugated diene compound or the conjugated diene compound and the aromatic vinyl compound, 1,3butadiene may be mentioned, which is an essential component and furthermore, as the conjugated diene compound other than 1,3-butadiene, for example, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene , 2-chloro-1,3-butadiene, and the like. Incidentally, the conjugated diene compounds can be used alone or two or more of them can be used in combination. [0014] In addition, as the aromatic vinyl compound, for example, styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, α-methyl styrene, 2,4-dimethyl styrene, 2,4 -di-isopropyl styrene, 4-t-butyl styrene, 5-t-butyl-2-methyl styrene, vinyl ethyl benzene, divinyl benzene, trivinyl benzene, divinyl naphthalene, t-butoxy styrene, vinylbenzyldimethylamine, (4-vinylbenzyl) dimethylaminoethyl ether , Ν, Ν-dimethylaminoethyl styrene, N, Ndimethylaminomethyl styrene, 2-ethyl styrene, 3-ethyl styrene, 4-ethyl styrene, 2-t-butyl styrene, 3-t-butyl styrene, 4-t-butyl styrene, vinylxylene, vinyl naphthalene, vinyl pyridine, diphenyl ethylene, diphenyl ethylene containing tertiary amino group such as 1- (4-N, N-dimethylaminophenyl) -1-phenyl ethylene, and the like. Of these, styrene and α-methyl styrene are particularly preferable as the aromatic vinyl compound. Aromatic vinyl compounds can be used alone or two or more of them can be used in combination.
    [0015] Incidentally, the conjugated diene compounds and the aromatic vinyl compounds exemplified in the above said all have the similar effects in view that it is possible to obtain a conjugated diene polymer having an active end. Therefore, even that not described in the Examples to be described later can be used in the invention.
    [0016] At the time of polymerization, a monomer other than conjugated diene compounds and aromatic vinyl compounds can be used. Examples of the other monomer include acrylonitrile, methyl
    Petition 870200028220, of 03/02/2020, p. 12/58
    6/39 (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and the like. The amount of the other monomer to be used is preferably 40% by weight or less, more preferably 30% by weight or less, and additionally preferably 20% by weight or less based on the total amount of monomers to be used in the polymerization.
    [0017] The conjugated diene polymer in the invention can be produced by carrying out polymerization using, as monomer (s), the conjugated diene compound and, if necessary, the aromatic vinyl compound and the other (s) ) monomer (s). Like the polymerization method, either a solution polymerization method, a gas phase polymerization method, and a volume polymerization method can be used, but the solution polymerization method is particularly preferable. Additionally, as the type of polymerization, both a batch type and a continuous type can be used.
    [0018] In the case where the solution polymerization method is used, as an example of specific polymerization methods, a method may be mentioned by subjecting the monomer (s) including the conjugated diene compound to anionic polymerization in a solvent organic in the presence of a polymerization initiator and a randomizer that is used as needed.
    [0019] As a polymerization initiator, at least any of an alkali metal compound and an alkaline earth metal compound can be used. Like the alkali metal compound and the alkaline earth metal compound, those commonly used as polymerization initiators can be used, and examples of these include alkyls such as methyl lithium, ethyl lithium, n-propyl lithium, n-butyl -lithium, sec-butyl-lithium, and t-butyl-lithium, 1,4-dilithiobutane, phenyl-lithium, stylbenolithium, naphthylithium, 1,3-bis (lithium-1,3-dimethylpentyl) benzene, 1,3- phenylene-bis (3-methyl-1-phenylpentylidene) dilithium, naphthyl sodium, naphthyl potassium, di-n-butyl magnesium, di-n
    Petition 870200028220, of 03/02/2020, p. 13/58
    7/39 hexylmagnesium, ethoxotassium, calcium stearate, and the like. Of these, lithium compounds are preferable.
    [0020] Furthermore, a polymerization reaction can be carried out in the presence of a compound (R) obtained by mixing at least any of the alkali metal compound and the alkaline earth metal compound and a compound (Bl) having a functional group that interacts with silica. By carrying out polymerization in the presence of compound (R), a functional group having interaction with silica can be introduced to the polymerization initiation end of the conjugated diene polymer. Here, interaction means that a covalent bond is formed between molecules or a weaker intermolecular force than a covalent bond (for example, an electromagnetic force that works between molecules, such as ion-dipole interaction, dipole-dipole interaction, a bond hydrogen, Van der Waals force) is formed. In addition, the "functional group that interacts with silica means a group having at least one atom that interacts with silica, such as a nitrogen atom, a sulfur atom, a phosphorus atom, or an oxygen atom.
    [0021] In particular, compound (R) is preferably a reaction product of a lithium compound such as an alkyl lithium with a nitrogen-containing compound such as a secondary amine compound. Specific examples of the nitrogen-containing compound include dimethylamine, diethylamine, dipropylamine, dibutylamine, dodecamethyleneimine, N, N'-dimethylN'-trimethylsilyl-1,6-diaminohexane, piperidine, pyrrolidine, hexamethylene imine, heptamethylene imine, dicyclohexylamine N-methylbenzylamine, di- (2ethylhexyl) amine, diallylamine, morpholine, N- (trimethylsilyl) piperazine, N- (tertbutyldimethylsilyl) piperazine, 1,3-ditrimethylsilyl-l, 3,5-triazinane, and the like. Incidentally, in the case of carrying out the polymerization in the presence of the compound (R), the compound (R) can be prepared by mixing the alkali metal compound or the alkaline earth metal compound with the compound (Bl) of
    Petition 870200028220, of 03/02/2020, p. 14/58
    8/39 beforehand and then the prepared compound (R) can be added in a polymerization system to carry out the polymerization. Alternatively, compound (R) can be prepared by adding the alkali metal compound or the alkaline earth metal compound and the compound (Bl) in a polymerization system and mixing both in a polymerization system and then the polymerization can be carried out.
    [0022] The randomizer can be used for the purpose of adjusting and similar to the content ratio of vinyl bonds (bonds 1,2 and bonds 3,4) (vinyl content). Examples of the randomizer include dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-di (tetrahydrofuryl) propane, 2- (2ethoxyethoxy) -2-methylpropane, triethylamine, pyridine, N- methylmorpholine, tetramethyl ethylenediamine, and the like. They can be used alone or two or more of them can be used in combination.
    [0023] The organic solvent to be used in the polymerization can be any one as long as it is an inactive reaction organic solvent. For example, an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, or the like can be used. In particular, hydrocarbons having 3 to 8 carbon atoms are preferable. Of these, a hydrocarbon having 3 to 8 carbon atoms is preferable, and specific examples thereof include propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, trans-2butene, cis-2-butene, 1-pentine, 2-pentine, 1-hexene, 2-hexene, benzene, toluene, xylene, ethyl benzene, heptane, cyclopentane, methylcyclopentane, methylcyclohexane, 1-pentene, 2 -pentene, cyclohexene and the like. Organic solvents can be used alone or two or more of them can be used in combination.
    [0024] In the case where solution polymerization is used, the concentration of monomer in a reaction solvent is preferably 5
    Petition 870200028220, of 03/02/2020, p. 15/58
    9/39 to 50% by mass and more preferably from 10 to 30% by mass, from the point of view of maintaining a balance between productivity and ease of polymerization control. The temperature of a polymerization reaction is preferably from -20 to 150 ° C, more preferably from 0 to 120 ° C, and particularly preferably from 20 to 100 ° C. In addition, a polymerization reaction is preferably conducted under a pressure sufficient to maintain the monomer (s) substantially in a liquid phase. Such pressure can be achieved through a method of pressurizing the interior of a reactor with an inactive gas for a polymerization reaction, or a similar method.
    [0025] As stated above, a conjugated diene polymer having an active end can be obtained. The weight average molecular weight (Mw) of the conjugated diene polymer in terms of polystyrene by gel permeation chromatography (GPC) is preferably 1.0 x 10 5 to 2.0 x 10 6 . When Mw is less than 1.0 x 10 5 , the low fuel consumption performance and abrasion resistance tend to decrease in the crosslinked polymer obtained when using the polymer composition. When Mw is greater than 2.0 x 10 6 , the workability of the polymer composition tends to decrease. Mw is more preferably from 1.2 x 10 5 to 1.5 x 10 6 and additionally preferably from 1.5 x 10 5 to 1.0 x 10 6 .
    [0026] In addition, the content of 1,2-vinyl in the structural unit derived from butadiene is preferably 5 to 70% by weight, more preferably 10 to 60% by weight, and additionally preferably from 25 to 60% by weight. When the 1,2-vinyl content is less than 5% by mass, the adhesion properties are likely to decrease excessively and, when the content exceeds 70% by mass, the abrasion resistance tends to be worse. Incidentally, the vinyl content is a value measured by 1 H-NMR.
    [0027] The conjugated diene polymer obtained by the present
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    10/39 polymerization can have a polyisoprene block at one end or both ends of it. When you have the polyisoprene block, it becomes possible to vulcanize a polymer having a high hydrogenation rate efficiently. The 1.4 / 3.4 bond ratio in the polyisoprene block is preferably in the range 60/40 to 98/2. When the bond ratio 1.4 / bond 3.4 is within the range, it becomes possible to achieve both flexibility and crosslinking efficiency of the crosslinked rubber.
    <Modification Step>
    [0028] A functional group that interacts with silica can be introduced at a polymerization termination end of the conjugated diene polymer by a step of reacting the active end of the conjugated diene polymer obtained by the above polymerization step with a compound (B2) having a functional group that interacts with silica. Incidentally, in the invention, the end means a portion, which exists at one end of the molecular chain, different from the structure derived from the monomer having a carbon-carbon double bond.
    [0029] The conjugated diene polymer to be used in the modification reaction (hereinafter, also referred to as the end modification reaction) can be one in which the polymerization initiation end is not modified or is modified as long as the polymer has an active end. In addition, compound (B2) is not particularly limited as long as it has a functional group that interacts with silica and is capable of reacting with an active polymerization end. Preferred specific examples of compound (B2) include, for example, (I) a compound (B2-1) represented by the following formula (1):
    [Chemical Formula 1] (r 3 ) (R 4 —oV-Si — R 5 —A 1 (1) / 3-n where Al is a monovalent functional group that has at least
    Petition 870200028220, of 03/02/2020, p. 17/58
    11/39 minus an atom selected from the group consisting of a nitrogen atom, a phosphorus atom, and a sulfur atom, does not have an active hydrogen, and bonds with R 5 with a nitrogen atom, an atom phosphorus, or a sulfur atom; R 3 and R4 are each a hydrocarbon group, R 5 is a hydrocarbilene group, and n is an integer from 0 to 2, provided that, in the case where R 3 and R4 exist in plurality, a plurality of R 3 'and R4's can the same or may be different;
    (II) a compound (B2-2) having, in the molecule, at least one functional group (xl) selected from the group consisting of a cyclic ether group, (thio) carbonyl group, and an iso (thio) cyanate group and at least one group (x2) different from the functional group (xl), which has at least one atom selected from the group consisting of a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom (provided that at least one of the nitrogen atom, the phosphorus atom, and the sulfur atom can be protected with a tri-substituted hydrocarbylsilyl group) and does not have an active hydrogen;
    (III) a compound (B2-3) having two or more iso (thio) cyanate groups on the molecule; and the like. Like compound (B2), they can be used either alone or as a combination of two or more of them. Incidentally, here, the (thio) carbonyl group means a carbonyl group and a thiocarbonyl group and the iso (thio) cyanate group means an isocyanate group and an isothiocyanate group.
    [0030] In the above formula (1), the hydrocarbyl group of R 3 and R4 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
    [0031] R 5 is preferably a straight 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.
    Petition 870200028220, of 03/02/2020, p. 18/58
    12/39
    [0032] n is preferably 0 or 1 from the point of view of increasing the reactivity with the conjugated diene polymer,
    Al has at least one atom (hereinafter, also referred to as a specific atom) selected from the group consisting of a nitrogen atom, a phosphorus atom, and a sulfur atom and bonds with R 5 with the atom specific. The specific atom does not bond with any active hydrogen and, for example, can be protected with a tri-substituted hydrocarbylsilyl group or the like. Incidentally, the active hydrogen here means a hydrogen atom bonded with an atom other than a carbon atom, and preferably means one having less binding energy than that of a polymethylene carbon hydrogen bond.
    [0033] In particular, Al is preferably a group capable of becoming an onion-type ion by the action of an onion-type salt-forming agent. When compound (B2) has such a group (Al), excellent shape retention properties can be transmitted to the modified conjugated diene polymer.
    [0034] Specific examples of Al include a nitrogen-containing group in which two hydrogen atoms from a primary amino group are replaced with two protecting groups, a nitrogen-containing group in which a hydrogen atom from a secondary amino group is replaced with a protecting group, a tertiary amino group, an imino group, a pyridyl group, a phosphorus-containing group in which two hydrogen atoms of a primary phosphine group are replaced with two protecting groups, a phosphorus-containing group in which one atom of hydrogen from a secondary phosphine group is replaced with a protecting group, a tertiary phosphine group, a sulfur-containing group in which a hydrogen atom from a thiol group is replaced with a protecting group, and the like. Of these, from the point of view of good affinity for silica, Al is preferably a
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    13/39 group having a nitrogen atom. Incidentally, the protecting group is a functional group that converts Al to an inactive functional group to an active polymerization end and, for example, tri-substituted hydrocarbylsilyl group and the like can be mentioned.
    [0035] As specific examples of the above compound (B2-1), it can be mentioned, as compounds having the nitrogen-containing group in which two hydrogen atoms of a primary amino group are replaced with two protecting groups, the nitrogen-containing group wherein a hydrogen atom of a secondary amino group is replaced with a protecting group, or the tertiary amino group and an alkoxysilyl group, for example, N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, Nbis (trimethylsilyl) aminopropylmethyldiethoxysilane, N , N ', N'-tris (trimethylsilyl) -N- (2aminoethyl) -3-aminopropyltriethoxysilane, 3- (4-trimethylsilyl-1 piperazine) propylmethyldimethoxysilane, and the like.
    [0036] As compounds having the imino group or the pyridyl group and the alkoxysilyl group, N- (1,3-dimethylbutylidene) -3 (triethoxysilyl) -l-propanoamine, N- (l-methylpropylidene) -3- (triethoxysilyl) -lpropanoamine, N- (4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -lpropanoamine, N- (cyclohexylidene) -3- (triethoxysilyl) -l-propanoamine, and trimethoxysilyl compounds of methyldiethoxysilyl, and ethyldimethoxysilyl compounds corresponding to these triethoxysilyl compounds, N- (3-trimethoxy-silylpropyl) -4,5-dihydroimidazole, N- (3-tri-methoxy-ethyl-propyl) -4,5-dihydro-imidazole, N- (3-trimethoxy-ethyl-propyl) - 4,5-imidazole, N- (3-triethoxysilylpropyl) -4,5-imidazole, 3-hexamethyleneiminopropyltrimethoxysilane, 3hexamethyleneiminopropylmethyldimethoxysilane, and compounds in which the alkyl group or the alkanodiyl group in the above mentioned compounds is replaced with an alkyl group having 1 to 6 atoms carbon or an alkanediyl group having 1 to 6 carbon atoms, respectively, and the like.
    [0037] As the compounds having a group containing phosphorus in
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    14/39 that two hydrogen atoms of a primary phosphine group are replaced with two protecting groups, the phosphorus-containing group in which a hydrogen atom of a secondary phosphine group is replaced with a protective group, the tertiary phosphine group, or the sulfur-containing group in which a hydrogen atom of a thiol group is substituted with a protecting group and the alkoxysilyl group, P, Pbis (trimethylsilyl) phosphinopropylmethyldimethoxysilane, P, Pbis (trimethylsilyl) phosphinopropyltrimethoxysilane, 3-methoxy-methoxy-methoxy-3-methoxy diphenylphosphinopropyltrimethoxysilane, 3-diphenylphosphinopropyltriethoxysilane, 3diphenylphosphinopropylmethyldimethoxysilane, Strimethylsilylmercaptopropylmethyldimethoxysilane, strimethylsilmercaptopropyltrimethoxylsilane, strimethylsilane, strimethylsilane used with an alkyl group having 1 to 6 carbon atoms or an alkanediyl group having 1 to 6 carbon atoms, respectively, and the like. In addition, as the compound having an iso (thio) cyanate group, 3 isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like can be mentioned.
    [0038] In the compound (B2-2), the group (x2) is preferably a group containing a nitrogen atom that does not bond with an active hydrogen. Specific examples thereof include, as compounds having the cyclic ether group, for example, epoxyamine compound such as tetraglycidyl-1,3bisaminomethylcyclohexane; as compounds having the (thio) carbonyl group, for example, 4-aminoacetophenones such as 4-N, N-dimethylbenzoacetophenone;
    bis (dihydrocarbilaminoalkyl) ketones such as 1,7-bis (methyl ethylamino) -4
    Petition 870200028220, of 03/02/2020, p. 21/58
    15/39 heptanone; dihydrocarbilaminoalkyl (meth) acrylates such as 2dimethylaminoethyl acrylate; hydrocarbilimidazobdinones such as 1,3-dimethyl-
    2-imidazobdinone; N-hydrocarbilpyrobdones such as 1-phenyl-2-pyrrobdin; N-hydrocarbilcaprolactams such as N-methyl-α-caprolactam; N-dihydrocarbilformamides such as Ν, Ν-diethylformamide; N, N-dihydrocarbilacetamides such as Ν, Ν-dimethylacetamide; (met) acrylamides such as Ν, Ν-dimethylacrylamide; and the like; as compounds having the iso (thio) cyanate group, for example, 3-isocyanatopropyltrimethoxysilane and the like. [0039] As the compound (B2-3), for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triphenyl isocyanate, p-phenylene diisocyanate, tris (isocyanatophenyl) thiophosphate, xylene diisocyanate, benzene-
    1,2,4-triisocyanate, naphthalene-1, 2,5,7-tetraisocyanate, 1,4-phenylene diisothiocyanate, and the like.
    [0040] As the compound (B2), in view of strong affinity to silica, it is preferable to use the compound (B2-1), particularly. Incidentally, in the case where the silane compound (B2-1) is used, for the purpose of adjusting the Mooney viscosity of the modified conjugated diene polymer, silicon tetrachloride or an epoxy-containing compound (eg, tetraglycidyl-1, 3-bisaminomethylcyclohexane or the like) can be used together with the silane compound (B2-1). In view that it is possible to obtain a modified conjugated diene polymer having a modified polymerization termination end, the compounds (B2) exemplified above all have similar effects. Therefore, even that not described in the Examples to be described later can be used in the invention. Incidentally, a structure represented by the following formula (1-1) is introduced at the end of the polymer by reacting the compound represented by the above formula (1) with the modified conjugated diene polymer.
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    16/39
    [Chemical Formula 2] r 3 „—Si — R 5 —A 4 (1-1) ϊ ° - ρ6 ) 2. „ Where R 6 is a hydrogen atom or a hydrocarbon group and R 6 's have a plurality they may be the same or they may be different; A4, R 3 , R 5 , en can be the same meanings as Al, R 3 , R 5 , en in the above formula (1).
    [0041] The end modification reaction can be carried out, for example, as a solution reaction. The solution reaction can be carried out using a solution containing unreacted monomer after the end of a polymerization reaction in the polymerization step or it can be carried out after the conjugated diene polymer contained in the solution is isolated and dissolved in a solvent suitable such as cyclohexane. In addition, the tip modification reaction can be performed using either a batch or a continuous system. At this time, a method of adding compound (B2) is not particularly limited, and a batch addition method, a split addition method, a continuous addition method, and the like can be mentioned.
    [0042] The amount of the compound (B2) to be used in the end modification reaction can be defined appropriately depending on the type of the compound to be used in the reaction, but preferably it is 0.1 molar equivalents or more and more preferably 0.3 molar equivalents or more, based on the metal atom that is contained in a polymerization initiator and participates in a polymerization reaction. When the amount is controlled to 0.1 molar equivalents or more, the modification reaction can be allowed to proceed sufficiently and the dispersion capacity of the silica can be improved accordingly.
    [0043] The temperature of the end modification reaction is
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    17/39 commonly the same as the polymerization reaction temperature described above, and preferably is -20 to 150 ° C, more preferably 0 to 120 ° C, and particularly preferably 20 to 100 ° C. When the temperature of the modification reaction is low, the viscosity of the modified conjugated diene polymer tends to increase. On the other hand, when the temperature of the modification reaction is high, an active polymerization end is prone to be deactivated. The reaction time of the modification reaction is preferably 1 minute to 5 hours and more preferably 2 minutes to 1 hour.
    <Hydrogenation Reaction>
    [0044] The hydrogenated conjugated diene polymer of the invention can be obtained by hydrogenating the conjugated diene polymer obtained above. As methods and conditions for the hydrogenation reaction, it is possible to use any methods and conditions as long as a polymer having a desired hydrogenation rate is obtained. Examples of the hydrogenation methods include a method of using a catalyst containing an organometallic compound of titanium as a hydrogenation catalyst, a method of using a catalyst composed of an organic compound of iron, nickel, or cobalt and an organometallic compound such as an alkyl aluminum, a method of using an organic complex of an organometallic compound of ruthenium or rhodium, a method of using a catalyst obtained by supporting a metal such as palladium, platinum, ruthenium, cobalt, or nickel on a support such as carbon , silica, or alumina, and similar methods. Of several methods, a hydrogenation method under mild conditions of low pressure and low temperature using a homogeneous catalyst composed of an organometallic compound of titanium alone or the compound and an organometallic compound of lithium, magnesium or aluminum (JP-B-63-4841 , JP-B-1-37970) is industrially preferable and is still suitable for the purpose of the invention as long as the selectivity of
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    18/39 hydrogenation for the butadiene double bond is also high.
    [0045] Hydrogenation is carried out in a solvent that is inactive for the catalyst and is capable of solubilizing the conjugated diene polymer. A preferred solvent is an aliphatic hydrocarbon such as n-pentane, nhexane, or n-octane, an alicyclic hydrocarbon such as cyclohexane or cyclohexane, an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether or tetra -hydrofuran alone or as a mixture containing them as a main component.
    [0046] The hydrogenation reaction is generally carried out by maintaining a polymer at a predetermined temperature under a hydrogen or inert atmosphere, adding a hydrogenation catalyst under agitation or without agitation, and subsequently introducing a hydrogen gas to achieve pressurization to a pressure predetermined. The inert atmosphere means an atmosphere, such as helium, neon, or argon, that does not react with any materials that participate in the hydrogenation reaction. Air and oxygen are not preferable as they oxidize the catalyst to initiate deactivation of the catalyst. In addition, nitrogen is not preferable since it acts as a catalyst poison at the time of the hydrogenation reaction to decrease hydrogenation activity. In particular, the interior of a hydrogenation reaction vessel is suitably an atmosphere of a hydrogen gas alone.
    [0047] In the hydrogenation reaction process to obtain the hydrogenated conjugated diene polymer, either a batch process, a continuous process, and a combination thereof can be used. In addition, in the case where a diaryl titanocene-based compound is used as a hydrogenation catalyst, it can be added alone to the reaction solution as is or can be added as a solution of an inactive organic solvent. As the inactive organic solvent to be used in the case where the catalyst is used as a solution, the various solvents above that do not
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    19/39 react with any materials that participate in the hydrogenation reaction can be used. Preferably, the solvent is the same solvent as the solvent to be used in the hydrogenation reaction. In addition, the amount of the catalyst to be added is 0.02 to 20 mmol per 100 g of the polymer before hydrogenation.
    [0048] A preferable method for obtaining the hydrogenated conjugated diene polymer constituting the invention is a method by subjecting a conjugated diene polymer prior to hydrogenation to solution polymerization using an organolithium catalyst and using the resulting polymer solution in the next hydrogenation reaction without additional treatment, a method which is industrially useful. The hydrogenated conjugated diene polymer constituting the invention is obtained by removing the solvent from the solution obtained above and isolating the polymer.
    [0049] With respect to the hydrogenation rate of the hydrogenated conjugated diene polymer of the invention, the hydrogenation rate of the butadiene-derived structural unit is preferably 70% or more. When the rate of hydrogenation is controlled to 70% or more, the hydrogenated copolymer having greater resistance can be obtained. For this reason, the hydrogenation rate is more preferably 80% or more and additionally preferably 90% or more. Incidentally, the rate of hydrogenation can be measured by 1 H-NMR.
    The polymer composition for forming the tire member according to the invention contains the hydrogenated conjugated diene polymer and a crosslinking agent. The content ratio of the hydrogenated conjugated diene polymer in the polymer composition is preferably 20% by weight or more, more preferably 30% by weight or more, and additionally preferably 40% by weight or more with respect to the total amount of the polymer composition. . As the crosslinking agent, sulfur, sulfur halides, organic peroxides, quinone dioximes,
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    20/39 polyvalent organic amine compounds, and alkylphenol resins having a methylol group, and the like can be mentioned and commonly, sulfur is used. The amount of sulfur to be mixed is preferably 0.1 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight based on 100 parts by weight of the total amount of polymer components contained in the polymer composition. .
    [0051] In the polymer composition, in addition to the hydrogenated conjugated diene polymer, the other rubber component can be mixed. The type of the rubber component is not particularly limited and butadiene rubber (BR, for example, BR with high cis content having 90% or more cis-1,4 bond, BR which contains syndiotactic 1,2-polybutadiene) can be mentioned (SPB), etc.), styrene-butadiene rubber (SBR), natural rubber (NR), isoprene rubber (IR), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, and the like. BR and SBR are more preferred.
    [0052] In the polymer composition, as a filler, several reinforcement fillers such as carbon black, silica, clay, and calcium carbonate can be used. Carbon black, silica, or a combined use of carbon black and silica is preferred. The total amount of silica and carbon black in the polymer composition is preferably 20 to 130 parts by weight and more preferably 25 to 110 parts by weight based on 100 parts by weight of the total amount of polymer components contained in the composition of polymer.
    [0053] In the polymer composition, in addition to the components described above, various additives that are commonly used in the rubber tire composition, such as anti-aging agents, zinc white, stearic acid, softeners, sulfur, and vulcanization accelerators can be used. mixed.
    [0054] The hydrogenated conjugated diene polymer composed of said
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    21/39 above can be used properly as a material for tire tread and sidewalls due to the high strength.
    [0055] The tire can be produced according to a common method. In particular, the polymer composition for the formation of the tire member is formed in a sidewall rubber by mixing the composition in a mixing machine such as a roller or a mixer and subjecting the sheet formed to vulcanization and conforming to the arrangement of the even to the outside of a housing according to a common method, thereby obtaining a tire.
    Examples
    [0056] The present invention will be described specifically below based on the Examples, but the invention should not be construed as limited to these Examples. Incidentally, parts and% in the Examples and Comparative Examples are on a mass basis unless otherwise stated. Methods of measuring various physical property values are shown below.
    [Linked styrene content (%)]: determined by '500 MHz HNMR.
    [Vinyl content (%)]: was determined by '500 MHz H-NMR.
    [Glass transition temperature (° C)]: was measured according to ASTMD3418.
    [Molecular weight before modification]: was determined in terms of polystyrene from the retention time corresponding to the maximum peak point on a GPC curve obtained using gel permeation chromatography (GPC) (HLC-8120GPC (trade name ( manufactured by Tosoh Corporation)).
    (Conditions for GPC)
    Column: GMHXL trade name (manufactured by Tosoh
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    Corporation), 2 columns
    Column temperature: 40 ° C
    Mobile phase: tetrahydrofuran
    Flow rate: 1.0 ml / minute
    Sample concentration: 10 mg / 20 ml
    [Mooney viscosity (ML1 + 4, 100 ° C)]: It was determined according to JIS K6300-1 using an L rotor under preheating conditions for 1 minute, a rotor operating time of 4 minutes, and a temperature of 100 ° C.
    [Hydrogenation rate (%)]: It was determined by 'H-NMR 500MHz.
    [Long chain ratio of styrene (mass%)]: The long chain ratio of Ost styrene which is the chain ratio composed of the structural units of styrene that varies 8 or more units with respect to all the structural units of styrene in polymer was determined as follows. From the 500 MHz 'H-NMR spectrum measured using deuterated chloroform as a solvent, a ratio of the integrated value E (a) of the range of (a) to the sum E (a, b, c) of the integrated values of individual chemical shift ranges from the following (a) to (c) was determined, the ratio was multiplied by 2.5, and the resulting value was taken as the 0st content ratio of the long styrene chain (the following numerical formula ( 1)).
    (a) a chain of 8 or more of the aromatic vinyl compounds: 6.00 <S <6.68 (b) a chain of 2 to 7 of the aromatic vinyl compounds:
    6.68 <S <6.89 (c) a short chain of aromatic vinyl compounds: 6.89 <S <8.00
    0st [% by weight] = (E (a) / E (a, b, c)) x 2.5 ... (1) <Examples and Comparative Examples of the Method for
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    Produce hydrogenated conjugated diene block polymers>
    <Production of hydrogenation catalysts>
    [0057] Hydrogenation catalysts (catalysts A and B) were produced by the following methods.
    [Production example 1]
    Catalyst A
    [0058] A bottle with three necks having a volume of 1 L, equipped with a stirrer and a drip funnel, was replaced with dry nitrogen and 200 ml of anhydrous tetrahydrofuran and 0.2 mol of tetrahydrofurfuryl alcohol have been added to it. Next, an n-butyl lithium (hereinafter also referred to as n-BuLi) / cyclohexane solution (0.2 mol) was added dropwise to the three-neck flask at 15 ° C to perform a reaction, thus obtaining a tetrahydrofuran solution of tetrahydrofurfuryloxylithium.
    [0059] Then, a bottle with three necks having a volume of 1 L, equipped with a stirrer and a drip funnel, was replaced with dry nitrogen and 49.8 g (0.2 mol) of bis dichloride ( q5cyclopentadienyl) titanium and 250 ml of anhydrous tetrahydrofuran were added to it. The tetrahydrofuran solution of tetrahydrofurfuryloxylithium obtained by the method described above was added dropwise thereto over a period of about 1 hour at room temperature with stirring. After about 2 hours, a reddish brown solution was filtered and an undissolved portion was washed with dichloromethane.
    [0060] Next, the filtrate and the washing solution were combined and the solvents were removed under reduced pressure, thus obtaining a catalyst A [bis (q5-cyclopentadienyl) titanium (tetrahydrofurfuryloxy) chloride] (also referred to as ”[ chlorobis (2,4cyclopentadienyl) titanium (IV) tetrahydrofurfuryl alkoxide]). Incidentally, the yield was 95%.
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    [Production example 2]
    Catalyst B
    [0061] A bottle with three necks having a volume of 1 L, equipped with a stirrer and a drip funnel, was replaced with dry nitrogen and 200 ml of anhydrous tetrahydrofuran and 0.2 mol of furfuryl alcohol were added at the same. Then, a solution of cyclohexane / n-BuLi (0.2 mol) was added dropwise to the three-neck flask at 15 ° C to carry out a reaction, thereby obtaining a solution of furfuryloxylithium tetrahydrofuran.
    [0062] Then, a bottle with three necks having a volume of 1 L, equipped with a stirrer and a drip funnel, was replaced with dry nitrogen and 49.8 g (0.2 mol) of bis (q5cyclopentadienyl) titanium dichloride and 250 ml of anhydrous tetrahydrofuran were added to it. The furfuryloxylithium tetrahydrofuran solution obtained by the method described above was added dropwise thereto over a period of about 1 hour at room temperature with stirring. After about 2 hours, a reddish brown solution was filtered and an undissolved portion was washed with dichloromethane.
    [0063] Next, the filtrate and the washing solution were combined and the solvents were removed under reduced pressure, thereby obtaining a catalyst B [bis (r | 5-cyclopentadienyl) titanium (furfuryloxy) chloride] (also referred to as [chlorobis (2,4-cyclopentadienyl) titanium (IV) furfuryl alkoxide]). Incidentally, the yield was 97%.
    Example 1
    [Synthesis of conjugated diene rubber C and evaluation thereof]
    [0064] In an autoclave reactor having an internal volume of 10 liters that was subjected to substitution with nitrogen, 5,000 g of cyclohexane, 75.0 g of tetrahydrofuran, 250 g of styrene, and 730 g of 1.3butadiene were loaded. After adjusting the temperature of the contents in the
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    25/39 reactor to 10 ° C, the cyclohexane solution containing n-butyl lithium (11.60 mmol) was added to it to initiate polymerization. The polymerization was carried out under adiabatic conditions, and the maximum temperature reached 85 ° C.
    [0065] At the moment when the polymerization conversion reached 99%, 20 g of butadiene was added additionally and the polymerization was carried out additionally for 5 minutes to obtain a reaction solution containing a polymer. Then, 8.5 g of N, Nbis (trimethylsilyl) aminopropylmethyldiethoxysilane were added and reacted with an active point of the polymer for 30 minutes.
    [0066] Subsequently, the reaction solution was heated to 80 ° C or more and hydrogen was introduced into the system.
    [0067] Then, 0.73 g of catalyst B, 1.16 g of diethyl aluminum chloride, and 0.27 g of n-butyl lithium were added to it and these were reacted in order to maintain a pressure of hydrogen 1.0 MPa. After reaching a predetermined integrated hydrogen flow rate, the reaction solution was returned to ordinary temperature and ordinary pressure and extracted from the reaction vessel to obtain a polymer solution.
    [0068] Subsequently, an aqueous solution (temperature: 80 ° C) in which the pH was adjusted to pH 8.5 (pH at 80 ° C by a glass electrode method, the same should apply here below) with ammonia as a pH adjuster was placed in a solvent removal tank, the polymer solution above was additionally added to it (a ratio of 200 parts by weight of the aqueous solution to 100 parts by weight of the polymer solution), the solvent removal was carried out at a temperature of the liquid phase of the solvent removal tank: 95 ° C by steam extraction (vapor temperature: 190 ° C) of 2 hours, and drying was carried out by a hot roller in which the temperature was controlled to 110 ° C, thus obtaining the conjugated diene rubber C.
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    [0069] Table 1 shows the polymerization formula of the conjugated diene rubber C and Table 2 shows properties of the resulting conjugated diene rubber C. Additionally, using a conjugated diene rubber C, the rubber composition prepared by the composition formulation shown in Table 3 was vulcanized and physical property assessment was performed. Table 4 shows results.
    Example 2
    [Synthesis of conjugated diene rubber D and evaluation thereof]
    [0070] In an autoclave reactor having an internal volume of 10 liters that was subjected to substitution with nitrogen, 5,000 g of cyclohexane, 75.0 g of tetrahydrofuran, and 100 g of isoprene were loaded. After adjusting the temperature of the contents in the reactor to 10 ° C, the cyclohexane solution containing n-butyl lithium (11.60 mmol) was added to it to initiate polymerization. The polymerization was carried out under adiabatic conditions, and the maximum temperature reached 25 ° C.
    [0071] Then, 250 g of styrene and 630 g of 1,3-butadiene were added additionally and polymerization was carried out. The polymerization was carried out under adiabatic conditions, and the maximum temperature reached 80 ° C.
    [0072] At the moment when the polymerization conversion reached 99%, 20 g of butadiene was added additionally and the polymerization was carried out additionally for 5 minutes to obtain a reaction solution containing a polymer. Then, 8.5 g of N, Nbis (trimethylsilyl) aminopropylmethyldiethoxysilane were added and reacted with an active point of the polymer for 30 minutes.
    [0073] Subsequently, the reaction solution was heated to 80 ° C or more and hydrogen was introduced into the system.
    [0074] Then, 0.73 g of catalyst B, 1.16 g of diethyl aluminum chloride, and 0.27 g of n-butyl lithium were added to it and these were
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    27/39 reacted in order to maintain a hydrogen pressure of 1.0 MPa. After reaching a predetermined integrated hydrogen flow rate, the reaction solution was returned to ordinary temperature and ordinary pressure and extracted from the reaction vessel to obtain a polymer solution.
    [0075] Subsequently, an aqueous solution (temperature: 80 ° C) in which the pH was adjusted to pH 8.5 (pH at 80 ° C by a glass electrode method, the same should apply here below) with ammonia as a pH adjuster was placed in a solvent removal tank, the polymer solution above was additionally added to it (a ratio of 200 parts by weight of the aqueous solution to 100 parts by weight of the polymer solution), the solvent removal was carried out at a temperature of the liquid phase of the solvent removal tank: 95 ° C by steam extraction (vapor temperature: 190 ° C) of 2 hours, and drying was carried out by a hot roller in which the temperature was controlled to 110 ° C, thus obtaining a conjugated diene rubber D.
    [0076] Table 1 shows the polymerization formula of a conjugated diene rubber D and Table 2 shows properties of the resulting conjugated diene rubber D. Additionally, using a conjugated diene rubber D, the rubber composition prepared by the mixture formulation shown in Table 3 was vulcanized and physical property assessment was performed. Table 4 shows results.
    Example 3
    [Synthesis of conjugated diene rubber and evaluation thereof]
    [0077] In an autoclave reactor having an internal volume of 10 liters that was subjected to substitution with nitrogen, 5,000 g of cyclohexane, 0.6 g of tetrahydrofuran, and 100 g of isoprene were loaded. After adjusting the temperature of the contents in the reactor to 10 ° C, the cyclohexane solution containing n-butyl lithium (11.60 mmol) was added to it to initiate polymerization. The polymerization was carried out under
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    28/39 adiabatic, and the maximum temperature reached 25 ° C.
    [0078] Then, after 74.4 g of tetrahydrofuran were added to it, 250 g of styrene and 630 g of 1,3-butadiene were added additionally and polymerization was carried out. The polymerization was carried out under adiabatic conditions, and the maximum temperature reached 80 ° C.
    [0079] At the moment when the polymerization conversion reached 99%, 20 g of butadiene was added additionally and the polymerization was carried out additionally for 5 minutes to obtain a reaction solution containing a polymer. Then, 8.5 g of N, Nbis (trimethylsilyl) aminopropylmethyldiethoxysilane were added and reacted with an active point of the polymer for 30 minutes.
    [0080] Subsequently, the reaction solution was heated to 80 ° C or more and hydrogen was introduced into the system.
    [0081] Then, 0.73 g of catalyst B, 0.33 g of diethyl aluminum chloride, and 0.18 g of tetrachlorosilane were added to it and these were reacted in order to maintain a hydrogen pressure of 1.0 MPa. After reaching a predetermined integrated hydrogen flow rate, the reaction solution was returned to ordinary temperature and ordinary pressure and extracted from the reaction vessel to obtain a polymer solution.
    [0082] Subsequently, an aqueous solution (temperature: 80 ° C) in which the pH was adjusted to pH 8.5 (pH at 80 ° C by a glass electrode method, the same should apply here below) with ammonia as a pH adjuster was placed in a solvent removal tank, the polymer solution above was additionally added to it (a ratio of 200 parts by weight of the aqueous solution to 100 parts by weight of the polymer solution), the solvent removal was carried out at a temperature of the liquid phase of the solvent removal tank: 95 ° C by steam extraction (vapor temperature: 190 ° C) of 2 hours, and drying was carried out by a hot roller in which the temperature was controlled to 110 ° C,
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    29/39 thus obtaining a conjugated diene rubber E.
    [0083] Table 1 shows the polymerization formula of a conjugated diene rubber E, and Table 2 shows properties of the resulting conjugated diene rubber E. Additionally, using a conjugated diene rubber, the rubber composition prepared by the formulation of mixture shown in Table 3 was vulcanized and physical property assessment was performed. Table 4 shows results.
    Example 4
    [Synthesis of conjugated diene rubber X and evaluation thereof]
    [0084] In an autoclave reactor having an internal volume of 10 liters that was subjected to substitution with nitrogen, 5,000 g of cyclohexane, 75.0 g of tetrahydrofuran, 250 g of styrene, and 730 g of 1.3butadiene were loaded. After adjusting the temperature of the contents in the reactor to 10 ° C, the cyclohexane solution containing n-butyl lithium (11.60 mmol) was added to it to initiate polymerization. The polymerization was carried out under adiabatic conditions, and the maximum temperature reached 85 ° C.
    [0085] At the moment when the polymerization conversion reached 99%, 20 g of butadiene was added additionally and the polymerization was carried out additionally for 5 minutes to obtain a reaction solution containing a polymer. Then, 8.5 g of N, Nbis (trimethylsilyl) aminopropylmethyldiethoxysilane were added and reacted with an active point of the polymer for 30 minutes.
    [0086] Subsequently, the reaction solution was heated to 80 ° C or more and hydrogen was introduced into the system.
    [0087] Then, 0.73 g of catalyst A, 1.16 g of diethyl aluminum chloride, and 0.27 g of n-butyl lithium were added to it and these were reacted in order to maintain a pressure of hydrogen 1.0 MPa. After reaching a predetermined integrated hydrogen flow rate, the solution
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    30/39 reaction was returned to ordinary temperature and ordinary pressure and extracted from the reaction vessel to obtain a polymer solution. [0088] Subsequently, an aqueous solution (temperature: 80 ° C) in which the pH was adjusted to pH 8.5 (pH at 80 ° C by a glass electrode method, the same should apply here below) with ammonia as a pH adjuster was placed in a solvent removal tank, the polymer solution above was additionally added to it (a ratio of 200 parts by weight of the aqueous solution to 100 parts by weight of the polymer solution), the solvent removal was carried out at a temperature of the liquid phase of the solvent removal tank: 95 ° C by steam extraction (vapor temperature: 190 ° C) of 2 hours, and drying was carried out by a hot roller in which the The temperature was controlled to 110 ° C, thus obtaining a conjugated diene X rubber.
    [0089] Table 1 shows the polymerization formula of a conjugated diene rubber X and Table 2 shows properties of the resulting conjugated diene rubber X. Additionally, using a conjugated diene rubber X, the rubber composition prepared by the mixture formulation shown in Table 3 was vulcanized and physical property assessment was performed. Table 4 shows results.
    Example 5
    [Synthesis of conjugated diene rubber Z and evaluation thereof]
    [0090] In an autoclave reactor having an internal volume of 10 liters that was subjected to substitution with nitrogen, 5,000 g of cyclohexane, 75.0 g of tetrahydrofuran, 250 g of styrene, and 730 g of 1.3butadiene were loaded. After adjusting the temperature of the contents in the reactor to 10 ° C, the cyclohexane solution containing n-butyl lithium (11.60 mmol) was added to it to initiate polymerization. The polymerization was carried out under adiabatic conditions, and the maximum temperature reached 85 ° C.
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    [0091] At the moment when the polymerization conversion reached 99%, 20 g of butadiene was added additionally and the polymerization was carried out additionally for 5 minutes to obtain a reaction solution containing a polymer. Then, 8.5 g of N, Nbis (trimethylsilyl) aminopropylmethyldiethoxysilane were added and reacted with an active point of the polymer for 30 minutes.
    [0092] Subsequently, the reaction solution was heated to 80 ° C or more and hydrogen was introduced into the system.
    [0093] Then, 0.73 g of catalyst B, 1.16 g of diethyl aluminum chloride, and 0.27 g of n-butyl lithium were added to it and these were reacted in order to maintain a pressure of hydrogen 1.0 MPa. After reaching a predetermined integrated hydrogen flow rate, the reaction solution was returned to ordinary temperature and ordinary pressure and extracted from the reaction vessel to obtain a polymer solution.
    [0094] Subsequently, an aqueous solution (temperature: 80 ° C) in which the pH was adjusted to pH 8.5 (pH at 80 ° C by the glass electrode method, the same should apply here below) with ammonia as a pH adjuster was placed in a solvent removal tank, the above polymer solution was additionally added to it (a ratio of 200 parts by weight of the aqueous solution to 100 parts by weight of the polymer solution), to solvent removal was carried out at a temperature of the liquid phase of the solvent removal tank: 95 ° C by steam extraction (vapor temperature: 190 ° C) of 2 hours, and drying was carried out by a hot roller at which temperature was controlled to 110 ° C, thereby obtaining a conjugated diene rubber Z.
    [0095] Table 1 shows the polymerization formula of a conjugated diene rubber Z and Table 2 shows properties of the resulting conjugated diene rubber Z. Additionally, using a conjugated diene rubber Z, the rubber composition prepared by the mixture formulation
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    32/39 shown in Table 3 was vulcanized and physical property assessment was performed. Table 4 shows results.
    Comparative Example 1
    [Synthesis of conjugated diene rubber S and evaluation thereof]
    [0096] In an autoclave reactor having an internal volume of 5 liters that was subjected to substitution with nitrogen, 2,750 g of cyclohexane, 50,0 g of tetrahydrofuran, 125 g of styrene, and 365 g of 1,3butadiene were loaded. After adjusting the temperature of the contents in the reactor to 10 ° C, the cyclohexane solution containing n-butyllithium (5.80 mmol) was added to it to initiate polymerization. The polymerization was carried out under adiabatic conditions, and the maximum temperature reached 85 ° C.
    [0097] At the moment when the polymerization conversion reached 99%, 10 g of butadiene was added additionally and the polymerization was carried out additionally for 5 minutes. Then, 2.0 g of 2,6-di-tert-butylp-cresol were added to the resulting polymer solution. Subsequently, solvent removal was carried out by steam extraction using hot water which was adjusted to pH = 9 with sodium hydroxide and a rubber was dried by a hot roller where the temperature was controlled to 110 ° C, thereby obtaining a conjugated diene rubber S.
    [0098] Table 1 shows the polymerization formula of a conjugated diene rubber S and Table 2 shows properties of the resulting conjugated diene rubber S. Additionally, using the modified conjugated diene rubber, the rubber composition prepared by the formulation of mixture shown in Table 3 was vulcanized and physical property assessment was performed. Table 4 shows results.
    Comparative Example 2
    [Synthesis of T-conjugated diene rubber and evaluation thereof]
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    [0099] In an autoclave reactor having an internal volume of 5 liters that was subjected to substitution with nitrogen, 5,000 g of cyclohexane, 75.0 g of tetrahydrofuran, and 30 g of styrene were loaded. After adjusting the temperature of the contents in the reactor to 10 ° C, the cyclohexane solution containing n-butyl lithium (11.6 mmol) was added to it to initiate polymerization. The polymerization was carried out under adiabatic conditions, and the maximum temperature reached 15 ° C.
    [00100] Then, 190 g of styrene and 730 g of 1,3-butadiene were added additionally and polymerization was carried out. The polymerization was carried out under adiabatic conditions, and the maximum temperature reached 80 ° C.
    [00101] At the moment when the polymerization conversion reached 99%, 30 g of styrene was added additionally and the polymerization was carried out additionally for 10 minutes. Then, 20 g of 1,3-butadiene was added additionally and the polymerization was carried out additionally for 5 minutes to obtain a reaction solution containing a polymer.
    [00102] Subsequently, the reaction solution was heated to 80 ° C or more and hydrogen was introduced into the system.
    [00103] Then, 0.73 g of catalyst B, 0.33 g of diethyl aluminum chloride, and 0.18 g of tetrachlorosilane were added to it and these were reacted in order to maintain a hydrogen pressure of 1.0 MPa. After reaching a predetermined integrated hydrogen flow rate, the reaction solution was returned to ordinary temperature and ordinary pressure and extracted from the reaction vessel to obtain a polymer solution.
    [00104] Subsequently, an aqueous solution (temperature: 80 ° C) in which the pH was adjusted to pH 8.5 (pH at 80 ° C by a glass electrode method, the same should apply here below) with ammonia as a pH adjuster was placed in a solvent removal tank, the
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    34/39 above polymer solution was additionally added (a ratio of 200 parts by weight of the aqueous solution to 100 parts by weight of the polymer solution), solvent removal was carried out at a temperature of the liquid phase of the tank solvent removal: 95 ° C by steam extraction (steam temperature: 190 ° C) for 2 hours, and drying was carried out by a hot roller in which the temperature was controlled to 110 ° C, thus obtaining a rubber of conjugated diene T.
    [00105] Table 1 shows the polymerization formula of a conjugated diene rubber Tea Table 2 shows properties of the resulting conjugated diene rubber T. Additionally, using a conjugated diene rubber T, the rubber composition prepared by the mixture formulation shown in Table 3 was vulcanized and physical property assessment was performed. Table 4 shows results.
    Comparative Example 3
    [Synthesis of Y conjugated diene rubber and evaluation thereof]
    [00106] In an autoclave reactor having an internal volume of 10 liters that was subjected to substitution with nitrogen, 5,000 g of cyclohexane, 75.0 g of tetrahydrofuran, 250 g of styrene, and 730 g of 1.3butadiene were loaded. After adjusting the temperature of the contents in the reactor to 10 ° C, the cyclohexane solution containing n-butyl lithium (11.60 mmol) was added to it to initiate polymerization. The polymerization was carried out under adiabatic conditions, and the maximum temperature reached 85 ° C.
    [00107] At the moment when the polymerization conversion reached 99%, 20 g of butadiene were added additionally and the polymerization was carried out additionally for 5 minutes to obtain a reaction solution containing a polymer.
    [00108] Subsequently, the reaction solution was heated to 80 ° C or more and hydrogen was introduced into the system.
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    [00109] Then, 0.73 g of catalyst B, 0.33 g of diethyl aluminum chloride, and 0.18 g of tetrachlorosilane were added to it and these were reacted in order to maintain a hydrogen pressure of 1.0 MPa. After reaching a predetermined integrated hydrogen flow rate, the reaction solution was returned to ordinary temperature and ordinary pressure and extracted from the reaction vessel to obtain a polymer solution.
    [00110] Subsequently, an aqueous solution (temperature: 80 ° C) in which the pH was adjusted to pH 8.5 (pH at 80 ° C by a glass electrode method, the same should apply here below) with ammonia as a pH adjuster was placed in a solvent removal tank, the above polymer solution was additionally added to it (a ratio of 200 parts by weight of the aqueous solution to 100 parts by weight of the polymer solution), solvent removal was carried out at a temperature of the liquid phase of the solvent removal tank: 95 ° C by steam extraction (vapor temperature: 190 ° C) of 2 hours, and drying was carried out by a hot roller in which the The temperature was controlled to 110 ° C, thereby obtaining a Y conjugated diene rubber.
    [00111] Table 1 shows the polymerization formula of a Y-conjugated diene rubber and Table 2 shows properties of the resulting Y-conjugated diene rubber. Additionally, using a Y-conjugated diene rubber, the rubber composition prepared by the mixture formulation shown in Table 3 was vulcanized and physical property assessment was performed. Table 4 shows results.
    Petition 870200028220, of 03/02/2020, p. 42/58 ο CG
    CG
    [Table 1]
    E ω x
    And the
    AND
    AND
    s
    AND
    The X a.
    E ω x b;
    E ω x b;
    E ω x b;
    E <o c o

    [Table 3]
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    37/39
    Petition 870200028220, of 03/02/2020, p. 44/58
    38/39
    [Kneading the Rubber Composition and Characteristic Evaluation] [00112] Using a plastomill (internal capacity: 250 cc) fitted with a temperature control device, such as first stage kneading, a conjugated diene rubber, silica, a coupling agent silane, stearic acid, an anti-aging agent, and zinc white were kneaded under the conditions of a 72% fill rate and a rotary number of 60 rpm. Then, as a second stage kneading, after cooling the mixture obtained above to room temperature, sulfur and a vulcanization accelerator were kneaded. It can be molded and then vulcanized in a vulcanization press at 160 ° C for a predetermined time and the following characteristic evaluation showing the following tire performance has been carried out.
    (i) Mooney viscosity: It was measured using an L rotor under preheating conditions for 1 minutes, a rotor operating time of 4 minutes, and a temperature of 100 ° C according to JIS K6300-1: 2013, using a rubber composition before vulcanization as a measurement sample.
    (ii) Tensile strength: 300% modulus was measured according to JIS K6251: 2010. The value is indicated as an index and a higher numerical value means greater and better tensile strength.
    (iii) tannum at 0 ° C: It was measured under the conditions of a 0.14% tensile dynamic deformation, an angular velocity of 100 radians per second, and 0 ° C using a dynamic spectrometer (manufactured by US Rheometrics), using a vulcanized rubber as a measurement sample. The value is indicated as an index and a higher numerical value means greater and better skid resistance on wet floors.
    (iv) tannum at 70 ° C: It was measured under the conditions of a 0.7% tensile dynamic deformation, an angular velocity of 100 radians per second, and 70 ° C using a dynamic spectrometer (manufactured by
    Petition 870200028220, of 03/02/2020, p. 45/58
    39/39
    USA Rheometrics), using a vulcanized rubber as a measurement sample. The value is indicated as an index and a higher numerical value means lower and better low hysteresis loss properties.
    (v) Abrasion resistance: It was measured at 25 ° C with a 10 N load according to JIS K6264-2: 2005 using a DIN abrasion tester (manufactured by Toyo Seiki Co., Ltd.), using a rubber vulcanized as a measurement sample. The value is indicated as an index and a higher numerical value means better abrasion resistance.
    [00113] As it is apparent from Table 4, it is noticed that the tensile strength and abrasion resistance are improved in the composition of polymers using hydrogenated conjugated diene rubbers C, D, E, X, and Z without transmitting the balance between wet skid resistance and low hysteresis loss properties.
    Industrial Applicability
    [00114] The present invention can be used appropriately for tires.
    权利要求:
    Claims (12)
    [1]
    1. Tire limb obtained by subjecting a composition containing a hydrogenated conjugated diene polymer and a crosslinking agent to a crosslinking treatment, characterized by the fact that the hydrogenated conjugated diene polymer is a hydrogenated product of a conjugated diene polymer that has a structural unit derived from butadiene and has a functional group at one end or both ends and the functional group is one or more groups selected from the group consisting of an amino group, an imino group, a pyridyl group, a phosphine group , a thiol group, and a hydrocarbiloxysilyl group;
    the hydrogenation rate of the butadiene-derived structural unit of the hydrogenated conjugated diene polymer is 90% or more; and the hydrogenated conjugated diene polymer has a structural unit derived from styrene.
    [2]
    Tire member according to claim 1, characterized in that the hydrogenated conjugated diene polymer has a structure represented by the following general formula (1-1) as a structure containing the functional group at the end (s) ):
    [Chemical Formula 1]
    R 3 n —Si — R 5 —A 4 (1-1)

    [3]
    Tire member according to claim 1 or 2, characterized in that, in the hydrogenated conjugated diene polymer, a chain composed of structural units derived from styrene that varies by an amount of 8 or more units is contained in a ratio of 10% by weight or less in relation to the total of structural units derived from styrene.
    [4]
    Tire member according to any one of claims 1 to 3, characterized in that the hydrogenated conjugated diene polymer has a structural unit derived from a conjugated diene compound other than butadiene.
    [5]
    Tire member according to claim 4, characterized in that the conjugated diene compound other than butadiene is isoprene.
    [6]
    Tire member according to any one of claims 1 to 5, characterized in that the hydrogenated conjugated diene polymer is a hydrogenated product of a polymer obtained by polymerizing monomers including 50 to 90 parts by mass of butadiene, 10 to 50 parts by weight of styrene, and 0 to 40 parts by weight of a conjugated diene compound other than butadiene.
    [7]
    Tire member according to any one of claims 1 to 6, characterized in that the content of 1,2-vinyl in the structure derived from butadiene in the polymer obtained by polymerization of monomer (s) including butadiene is 5 to 70 %.
    [8]
    Tire member according to any one of claims 1 to 7, characterized in that the hydrogenated conjugated diene polymer has a polyisoprene block.
    [9]
    9. Tire member according to claim 8, characterized by the fact that the 1.4 / 3.4 connection ratio of the
    Petition 870200028220, of 03/02/2020, p. 48/58
    3/3 polyisoprene is 60/40 to 98/2.
    [10]
    Tire member according to any one of claims 1 to 9, characterized in that the composition contains one or more selected from silica and carbon black.
    [11]
    Tire member according to any one of claims 1 to 10, characterized in that the tire member is a tread.
    [12]
    Tire member according to any one of claims 1 to 10, characterized in that the tire member is a sidewall.
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    SG11201505666PA|2015-09-29|
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    TW201437244A|2014-10-01|
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    KR20150122138A|2015-10-30|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS634841B2|1983-01-20|1988-02-01|Asahi Chemical Ind|
    JPH0137970B2|1984-04-18|1989-08-10|Asahi Chemical Ind|
    JPH0530842B2|1984-10-26|1993-05-11|Nippon Zeon Co|
    JP3988495B2|2001-03-26|2007-10-10|Ｊｓｒ株式会社|Hydrogenated modified polymer, process for producing the same, and composition containing the same|
    ES2307678T3|2001-03-26|2008-12-01|Jsr Corporation|HYDROGENATED MODIFIED POLYMER, PROCEDURE TO PRODUCE THE SAME AND COMPOSITION CONTAINING THE SAME.|
    EP1600479B1|2001-09-04|2009-01-21|JSR Corporation|Resin composition and golf ball|
    WO2003029299A1|2001-09-27|2003-04-10|Jsr Corporation|Conjugated diolefin polymer rubber, process for producing polymer rubber, rubber composition, composite, and tire|
    WO2003037946A2|2001-10-31|2003-05-08|Societe De Technologie Michelin|Method of preparing block copolymers for tyre tread compositions and the copolymers thus prepared|
    FR2854404B1|2003-04-29|2005-07-01|Michelin Soc Tech|METHOD OF OBTAINING GRAFT ELASTOMER WITH FUNCTIONAL GROUPS ALONG THE CHAIN AND RUBBER COMPOSITIONS|
    CN100554285C|2005-04-15|2009-10-28|株式会社普利司通|Modified conjugated diene copolymer, rubber combination and tire|
    EP3173441B1|2006-02-02|2018-10-17|JSR Corporation|Hydrogenated diene polymer composition and molded rubber article|
    US8410215B2|2006-08-23|2013-04-02|Jsr Corporation|Thermoplastic resin composition and molded article obtained from the same|
    US20080103261A1|2006-10-25|2008-05-01|Bridgestone Corporation|Process for producing modified conjugated diene based polymer, modified conjugated diene based polymer produced by the process, rubber composition, and tire|
    EP2138537B1|2007-03-28|2019-01-16|JSR Corporation|Modified hydrogenated diene polymer composition|
    JP5246733B2|2007-03-30|2013-07-24|旭化成ケミカルズ株式会社|Modified polymer excellent in affinity with inorganic filler, method for producing the same, and composition thereof|
    WO2008142890A1|2007-05-17|2008-11-27|Sumitomo Rubber Industries, Ltd.|Ply, clinch and tread formed using specified rubber composition, and pneumatic tire utilizing them|
    JP5282531B2|2007-11-07|2013-09-04|Ｊｓｒ株式会社|Method for producing hydrogenated conjugated diene polymer rubber, hydrogenated conjugated diene polymer rubber, composition thereof, and rubber molded product|
    WO2009060931A1|2007-11-08|2009-05-14|Jsr Corporation|Hydrogenated conjugated diene polymer rubber and method for producing the same|
    US8058357B2|2007-12-31|2011-11-15|Bridgestone Corporation|Vulcanizable compositions and tire treads prepared therewith|
    CN102348748B|2009-03-11|2013-09-04|Jsr株式会社|Rubber composition and pneumatic tire|
    JP5858041B2|2011-04-26|2016-02-10|Jsr株式会社|Modified conjugated diene rubber, method for producing the same, and rubber composition|
    MY168298A|2011-09-08|2018-10-24|Asahi Kasei Chemicals Corp|Method for Producing Modified Conjugated Diene-based Polymer, Modified Conjugated Diene-based Polymer, Modified Conjugated Diene-based Polymer Composition, Rubber Composition, and Tire|JP6627293B2|2014-09-08|2020-01-08|住友ゴム工業株式会社|Pneumatic tire|
    US10428203B2|2014-09-08|2019-10-01|Sumitomo Rubber Industries, Ltd.|Pneumatic tire|
    JP6631059B2|2014-09-08|2020-01-15|住友ゴム工業株式会社|Pneumatic tire|
    JP6627294B2|2014-09-08|2020-01-08|住友ゴム工業株式会社|Pneumatic tire|
    WO2016039008A1|2014-09-08|2016-03-17|住友ゴム工業株式会社|Pneumatic tire|
    US20170233562A1|2014-09-08|2017-08-17|Sumitomo Rubber Industries, Ltd.|Pneumatic tire|
    EP3178878B1|2014-09-08|2019-06-05|Sumitomo Rubber Industries, Ltd.|Pneumatic tire|
    JP6356549B2|2014-09-08|2018-07-11|住友ゴム工業株式会社|Pneumatic tire|
    JP6627511B2|2014-09-08|2020-01-08|住友ゴム工業株式会社|Pneumatic tire|
    JP6627295B2|2014-09-30|2020-01-08|住友ゴム工業株式会社|Pneumatic tire|
    BR112018001141A2|2015-07-22|2018-09-11|Jsr Corp|polymer, method for producing a polymer, polymer composition, and tire|
    EP3336108B1|2015-08-10|2019-06-26|JSR Corporation|Conjugated diene polymer and method for producing same, polymer composition, crosslinked polymer, and tire|
    EP3347381B1|2015-09-10|2019-08-07|Bridgestone Corporation|Methods for preparation of functionalized polymers|
    WO2017047451A1|2015-09-14|2017-03-23|Jsr株式会社|Method for producing hydrogenated conjugated diene polymer, hydrogenated conjugated diene polymer, polymer composition, cross-linked polymer, and tire|
    JP6252705B2|2015-11-26|2017-12-27|Jsr株式会社|Method for producing hydrogenated conjugated diene polymer, hydrogenated conjugated diene polymer, polymer composition, crosslinked polymer and tire|
    JP6716942B2|2016-02-18|2020-07-01|住友ゴム工業株式会社|Pneumatic tire and method for manufacturing pneumatic tire|
    JP6805502B2|2016-02-18|2020-12-23|住友ゴム工業株式会社|Pneumatic tires|
    EP3424961B1|2016-03-03|2020-11-18|JSR Corporation|Rubber based on hydrogenated conjugated diene, rubber composition, crosslinked rubber, and tire|
    EP3495394A4|2016-08-05|2020-03-18|Sumitomo Chemical Company, Limited|Method for producing modified conjugated diene polymer and method for producing polymer composition|
    WO2018062473A1|2016-09-30|2018-04-05|Jsr株式会社|Method for producing rubber composition, and tire|
    JP6972534B2|2016-10-31|2021-11-24|住友ゴム工業株式会社|Polymer for kneading machine input|
    JP6862787B2|2016-11-22|2021-04-21|住友ゴム工業株式会社|Pneumatic tires|
    JP6870978B2|2016-12-15|2021-05-12|Ｔｏｙｏ Ｔｉｒｅ株式会社|Rubber composition for tires and pneumatic tires using it|
    JP2020514446A|2016-12-21|2020-05-21|株式会社ブリヂストン|High strength hydrogenated polymer and rubber composition incorporating the same|
    JP2018172548A|2017-03-31|2018-11-08|住友化学株式会社|Conjugated diene-based polymer and process for producing same|
    KR102147479B1|2017-09-21|2020-08-24|주식회사 엘지화학|A reinforcing materials for rubber comprising aluminosilicate particles and rubber composition for tires comprising the same|
    TW201934636A|2017-10-25|2019-09-01|日商Ｊｓｒ股份有限公司|Polymer composition and tire|
    JP2019085454A|2017-11-02|2019-06-06|住友ゴム工業株式会社|Diene copolymer and rubber composition|
    BR112020017663A2|2018-03-07|2020-12-22|Kuraray Co., Ltd|POLYMER OF MODIFIED LIQUID DIENE AND RUBBER COMPOSITION|
    EP3810664A1|2018-06-20|2021-04-28|Bridgestone Corporation|High strength hydrogenated polymers, and rubber compositions incorporating same|
    EP3623417B1|2018-09-10|2021-06-23|Kraton Polymers Research B.V.|Rubber composition and method for making thereof|
    JP2020045388A|2018-09-14|2020-03-26|Jsr株式会社|Rubber composition, crosslinked product, and tire|
    WO2020158678A1|2019-01-30|2020-08-06|Jsr株式会社|Rubber composition, crosslinked body and tire|
    WO2020175258A1|2019-02-25|2020-09-03|Jsr株式会社|Rubber composition, cross-linked body, and tire|
    JPWO2020196899A1|2019-03-27|2020-10-01|
    TW202041540A|2019-04-01|2020-11-16|日商Ｊｓｒ股份有限公司|Cross-linked product and tire|
    TW202110916A|2019-08-30|2021-03-16|日商Ｊｓｒ股份有限公司|Polymer composition, cross-linked product and tire|
    JP2022028238A|2020-08-03|2022-02-16|旭化成株式会社|Rubber composition and tires|
    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-04-14| B09A| Decision: intention to grant|
    2020-06-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/02/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    2020-06-30| B16C| Correction of notification of the grant|Free format text: REF. RPI 2579 DE 09/06/2020 QUANTO AO TITULO. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2013039072|2013-02-28|
    PCT/JP2014/054933|WO2014133097A1|2013-02-28|2014-02-27|Tire member, hydrogenated conjugated diene polymer and polymer composition|
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