Briquetting compact

Abstract

The present invention provides a briquette of a rubber-like block copolymer satisfying the following conditions 1 to 6: Condition 1: the content of a vinyl aromatic monomer unit is 9 mass% or more and 50 mass% or less; Condition 2: the proportion of a vinyl aromatic monomer block is 3 mass% or more and less than 30 mass%; Condition 3: the iodine value is 3 to 250; Condition 4: the proportion of an ethylene structure is 3 mass% or more; Condition 5: the weight average molecular weight is in the range of 80,000 to 1,000,000; and Condition 6: at least one block at the molecular terminal is a specific block I or a block II.

Description

TECHNICAL FIELD

[0001] The present application relates to a briquette molded body. BACKGROUND

[0002] In recent years, in the field of rubber for tire treads, shoe soles for shoes, sheets, films, and asphalt modification, rubber compositions using a molded body containing a rubbery polymer having an ethylene structure and into which a crosslinkable unsaturated group is introduced as a raw material have been proposed for the purpose of improving mechanical strength (for example, see Patent Documents 1 to 4).

[0003] PRIOR ART DOCUMENTS

[0004] PATENT DOCUMENTS

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2010-270314

[0006] Patent Document 2: International Publication No. 2019 / 151126

[0007] Patent Document 3: International Publication No. 2019 / 151127

[0008] Patent Document 4: International Publication No. 2019 / 078083 SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] However, rubber compositions using a molded body containing a rubbery polymer having an ethylene structure and into which a crosslinkable unsaturated group is introduced as a raw material have been observed to have a tendency to have low rigidity and low wear resistance when used as a tread of a tire or a sole of a shoe. In addition, although there are examples in which a hydrogenated product of a rubbery block copolymer is used as a tire raw material, a tendency has been observed in which, when the hydrogenated product of the rubbery block copolymer is mixed with other tire materials, the mixture becomes sticky or causes poor mixing if the mixing conditions are not precisely set. According to the present inventors' studies, although one of the reasons is presumably that the rubbery block copolymer is generally molded into a pellet shape, and thus the melting conditions differ from those of other briquette-shaped materials, even in the case where the structure of the polymer (rubbery block copolymer) is the same, there is a tendency to stick to the wall of a container or the like and not be well molded when the shape is changed from a pellet shape to a briquette shape.

[0011] Therefore, an object of the present application is to provide a rubbery block copolymer briquette molded body that is easily mixed with other materials (for example, briquette-shaped materials), and in the case where a rubber composition is produced by mixing the rubbery block copolymer briquette molded body with other materials, the rigidity and wear resistance are excellent.

[0012] MEANS FOR SOLVING THE PROBLEMS

[0013] The present inventors have conducted intensive studies in order to solve the problems of the prior art described above, and as a result, have found that, by making the rubbery block copolymer used in the molded body have a specific structure and a specific molecular weight, the rubbery block copolymer is easily molded into a briquette molded body, and the briquette molded body of the rubbery block copolymer is easily mixed with other materials (e.g., materials in the form of briquettes), and the rubber composition obtained by mixing the briquette molded body of the rubbery block copolymer with other materials has good rigidity and wear resistance, thereby completing the present application.

[0014] That is, the present application is as described below. [1]

[0016] A briquette molded body of a rubbery block copolymer that satisfies the following conditions 1 to 6:

[0017] Condition 1: the content of the vinyl aromatic monomer unit is 9 mass% or more and 50 mass% or less;

[0018] Condition 2: the proportion of the vinyl aromatic monomer block is 3 mass% or more and less than 30 mass%;

[0019] Condition 3: the iodine value is 3 to 250;

[0020] Condition 4: the proportion of the ethylene structure is 3 mass% or more;

[0021] Condition 5: the weight average molecular weight is in the range of 80,000 to 1,000,000;

[0022] Condition 6: at least one block at the molecular terminal is the following Block I or the following Block II,

[0023] Block I: a block containing an ethylene structure, a conjugated diene structure, and an α-olefin structure;

[0024] Block II: a block in which the content of the vinyl aromatic monomer unit is 80 mass% or less, and which contains a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure. [2]

[0026] The briquette molded body described in [1], in which the content of the α-olefin structure in the rubbery block copolymer is 10 mass% or more. [3]

[0028] The briquette molded body described in [1] or [2], in which the number of the vinyl aromatic monomer block in the rubbery block copolymer is one. [4]

[0030] The briquette formed body according to any one of [1] to [3], wherein the rubbery block copolymer contains a nitrogen atom. [5]

[0032] The briquette formed body according to any one of [1] to [4], wherein the rubbery block copolymer has a modification ratio of 40 mass% or more as measured by column adsorption GPC. [6]

[0034] The briquette formed body according to any one of [1] to [5], wherein the rubbery block copolymer has one peak in a gel permeation chromatography (GPC) curve. [7]

[0036] The briquette formed body according to any one of [1] to [5], wherein the rubbery block copolymer has two or more peaks in a gel permeation chromatography (GPC) curve, and the peak area of the peak having the smallest molecular weight is 5% or more and less than 95% of the total peak area. [8]

[0038] The briquette formed body according to any one of [1] to [7], wherein the rubbery block copolymer has an α-olefin structure content of 40 mass% or less. [9]

[0040] The briquette formed body according to any one of [1] to [8], wherein the ratio of the proportion of the vinyl aromatic monomer block to the content of the vinyl aromatic monomer unit (the proportion of the vinyl aromatic monomer block / the content of the vinyl aromatic monomer unit) in the rubbery block copolymer is 0.28 to 1.00.

[10]

[0042] The briquette formed body according to any one of [1] to [9], wherein the weight average molecular weight of the vinyl aromatic monomer block in the rubbery block copolymer is 10,000 or more.

[11]

[0044] The briquette formed body of the rubbery block copolymer according to any one of [1] to

[10] , wherein the rubbery block copolymer has a residual solvent content of 5,000 ppm or less and a moisture content of 0.05 to 1.5 mass% or less in the briquette formed body.

[12]

[0046] The method for producing the briquette formed body according to any one of [1] to

[11] , comprising the following steps:

[0047] a step of polymerizing at least a vinyl aromatic monomer and a conjugated diene monomer using an organic lithium compound as a polymerization initiator to obtain a rubbery block copolymer;

[0048] a step of hydrogenating the rubbery block copolymer to obtain a hydrogenated product of the rubbery block copolymer; and

[0049] a step of molding the hydrogenated product of the rubbery block copolymer to obtain a briquette molded body.

[13]

[0051] The production method of the briquette molded body according to

[12] , wherein a step of adding a vinyl aromatic monomer is provided after the copolymerization of the vinyl aromatic monomer and the conjugated diene monomer or after the polymerization of the conjugated diene monomer.

[14]

[0053] The production method of the briquette molded body according to

[12] or

[13] , wherein a step of coupling the rubbery block copolymer with a coupling agent is provided.

[15]

[0055] A production method of a rubber composition, comprising a step of mixing a rubber component of a briquette molded body containing the rubbery block copolymer according to any one of [1] to

[11] and a crosslinking agent in an amount of 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the rubber component.

[16]

[0057] The production method of the rubber composition according to

[15] , wherein the crosslinking agent is at least one selected from the group consisting of organic peroxides, azo compounds, and sulfur compounds.

[17]

[0059] The production method of the rubber composition according to

[15] or

[16] , wherein a filler is mixed in the mixing step of the crosslinking agent.

[18]

[0061] The production method of the rubber composition according to any one of

[15] to

[17] , wherein the rubber component contains another rubber component other than the rubbery block copolymer.

[19]

[0063] The production method of the rubber composition according to

[18] , wherein the other rubber component is at least one selected from the group consisting of polybutadiene rubber, natural rubber, and ethylene-vinyl acetate copolymer.

[20]

[0065] A method for manufacturing a shoe sole of a shoe, which has a step of molding the rubber composition obtained by the method described in any one of

[15] to

[19] .

[21]

[0067] A method for manufacturing a tire tread, which has a step of molding the rubber composition obtained by the method described in any one of

[15] to

[19] .

[22]

[0069] A method for manufacturing a tire bead, which has a step of molding the rubber composition obtained by the method described in any one of

[15] to

[19] .

[0070] Effects of the Invention

[0071] According to the present invention, it is possible to provide a briquetted molding of a rubber-like block copolymer, which is easily mixed with other materials (for example, materials in the form of briquettes), and a rubber composition obtained by mixing with other materials is excellent in rigidity and wear resistance. DETAILED DESCRIPTION

[0072] Hereinafter, a specific embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail.

[0073] Note that the present embodiment below is for illustrating the present invention, and the present invention is not limited to the following embodiment. The present invention can be suitably modified within the scope of the gist thereof and implemented.

[0074] [Briquetted molding]

[0075] The briquetted molding of the present embodiment is a briquetted molding of a rubber-like block copolymer satisfying the following conditions 1 to 6.

[0076] Condition 1: The content of the vinyl aromatic monomer unit is 9 mass% or more and 50 mass% or less.

[0077] Condition 2: The proportion of the vinyl aromatic monomer block is 3 mass% or more and less than 30 mass%.

[0078] Condition 3: The iodine value is 3 to 250.

[0079] Condition 4: The proportion of the ethylene structure is 3 mass% or more.

[0080] Condition 5: The weight average molecular weight is in the range of 80,000 to 1,000,000.

[0081] Condition 6: At least one block at the molecular terminal is the following block I or the following block II.

[0082] Block I: A block containing an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0083] Block II: a block containing 80 mass% or less of a vinyl aromatic monomer unit and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0084] The briquette molded body of the present embodiment is a briquette molded body of a rubbery block copolymer satisfying the above-described conditions 1 to 6, whereby it is easily mixed with other materials (for example, materials in the form of briquettes), and a rubber composition obtained by mixing with other materials is excellent in rigidity and wear resistance.

[0085] [Rubbery block copolymer]

[0086] The rubbery block copolymer used in the briquette molded body of the present embodiment has an iodine value of 3 to 250, a proportion of ethylene structure of 3 mass% or more, a content of vinyl aromatic monomer unit of 9 mass% or more and 50 mass% or less, a proportion of vinyl aromatic monomer block of 3 mass% or more and less than 30 mass%, a weight average molecular weight in the range of 80,000 to 1,000,000, and at least one block at the molecular terminal is the above-described Block I or the above-described Block II. In the present embodiment, the concept of "briquette molded body of a rubbery block copolymer" includes the following manner: it is, for example, a molded body in the form of briquettes which is obtained by adding components such as an operating oil after polymerization of a rubbery block copolymer and which is generally used in the rubber industry, and is basically composed of a rubbery block copolymer, but contains components such as moisture or residual solvent which are inevitably contained; components such as oil and resin which are added within a range not affecting the properties of the rubbery block copolymer.

[0087] (Iodine value)

[0088] The rubbery block copolymer used in the present embodiment has an iodine value of 3 to 250. For example, from the viewpoint of co-crosslinkability when used as a rubber composition for crosslinking, and the viewpoint of softness when a tire is produced, the rubbery block copolymer used in the present embodiment has an iodine value of 3 or more, preferably 10 or more, more preferably 15 or more, further preferably 30 or more, and particularly preferably 50 or more. On the other hand, for example, from the viewpoint of mechanical strength and wear resistance when used as a tire, the rubbery block copolymer used in the present embodiment has an iodine value of 250 or less, preferably 200 or less, more preferably 150 or less, further preferably 100 or less, and particularly preferably 70 or less.

[0089] In the present embodiment, the iodine value can be measured according to the method described in "JIS K 0070:1992". The iodine value is a value expressed by converting the amount of halogen that reacts with 100 g of the subject substance into grams of iodine, and therefore the unit of the iodine value is "g / 100 g".

[0090] The rubbery block copolymer having an iodine value of 3 to 250 has a double bond, which can be obtained by appropriately adjusting the content of the conjugated diene monomer and the hydrogenation rate in the manufacturing method of the rubbery block copolymer described later. Specifically, in the case of copolymerizing the conjugated diene monomer with the vinyl aromatic monomer, for example, the iodine value decreases when the content of the conjugated diene monomer is low. In the case of hydrogenating the conjugated diene monomer, the iodine value decreases when the hydrogenation rate is high.

[0091] (vinyl aromatic monomer block)

[0092] The proportion of the vinyl aromatic monomer block in the rubbery block copolymer used in the present embodiment is 50 mass% or more. In the present specification, the "vinyl aromatic monomer block" refers to a shape formed when a vinyl aromatic monomer is polymerized as a raw material. In the rubbery block copolymer used in the present embodiment, the proportion of the vinyl aromatic monomer block is 50 mass% or more. In the present specification, the "vinyl aromatic monomer" refers to a monomer having a vinyl group and an aromatic group. The vinyl group is a group represented by -CH=CH2, and the aromatic group is a group represented by -C6H5. The vinyl aromatic monomer includes, for example, styrene, α-methylstyrene, p-methylstyrene, p- chlorostyrene, vinyltoluene, and the like. In the present embodiment, the proportion of the vinyl aromatic monomer block in the rubbery block copolymer is preferably 60 mass% or more, more preferably 70 mass% or more, and even more preferably 80 mass% or more. In the present embodiment, the proportion of the vinyl aromatic monomer block in the rubbery block copolymer is preferably 99 mass% or less, more preferably 95 mass% or less, and even more preferably 90 mass% or less. In the rubbery block copolymer used in the present embodiment, when the proportion of the vinyl aromatic monomer block is the above lower limit value or more, the rubbery block copolymer has a high proportion of the vinyl aromatic monomer block, and thus the rubbery block copolymer has a high strength. In the rubbery block copolymer used in the present embodiment, when the proportion of the vinyl aromatic monomer block is the above upper limit value or less, the rubbery block copolymer has a high proportion of the conjugated diene monomer block, and thus the rubbery block copolymer has a high rubber elasticity.

[0093] (rubber composition)

[0094] In the present embodiment, the "rubber composition" is a composition containing the rubbery block copolymer and can contain other rubber components or resins, fillers such as silica, carbon, and the like, and is a composition that exhibits rubber elasticity as a whole.

[0095] (vinyl aromatic monomer block)

[0096] The proportion of the vinyl aromatic monomer block in the rubbery block copolymer used in the present embodiment is 3% by mass or more and less than 30% by mass. When the proportion of the vinyl aromatic monomer block in the rubbery block copolymer used in the present embodiment is 3% by mass or more, the cold flow resistance of the briquette molded body of the rubbery block copolymer is excellent, and the rigidity of the vulcanizate of the rubber composition containing the rubbery block copolymer is excellent. As for the polymer portion other than the vinyl aromatic monomer block, there is no particular limitation as long as the content of the ethylene structure and the content of the vinyl aromatic are satisfied, and in order to exhibit the "rubbery" properties, the content of the ethylene structure is preferably 3% by mass or more and 70% by mass or less, and the content of the vinyl aromatic unit is preferably 9% by mass or more and 50% by mass or less.

[0097] The proportion of the vinyl aromatic monomer block in the rubbery block copolymer used in the present embodiment is preferably more than 5% by mass, more preferably 10% by mass or more, further preferably 13% by mass or more, and still further preferably 15% by mass or more from the viewpoint of low compression set of the rubber composition.

[0098] On the other hand, when the proportion of the vinyl aromatic monomer block in the rubbery block copolymer used in the present embodiment is less than 30% by mass, the rubbery block copolymer has a tendency to have good softness and processability when the rubber composition is produced. From the same viewpoint, the proportion of the vinyl aromatic monomer block in the rubbery block copolymer used in the present embodiment is more preferably 25% by mass or less, further preferably 20% by mass or less, and particularly preferably 17% by mass or less.

[0099] (Weight average molecular weight of the vinyl aromatic monomer block)

[0100] As for the weight average molecular weight of the vinyl aromatic monomer block in the rubbery block copolymer used in the present embodiment, the molecular weight is preferably 10,000 or more, more preferably 20,000 or more, further preferably 30,000 or more, still further preferably 50,000 or more, and yet further preferably 100,000 or more from the viewpoint of high mechanical strength of the rubber composition. On the other hand, the weight average molecular weight of the vinyl aromatic monomer block in the rubbery block copolymer used in the present embodiment is preferably 40,000 or less, more preferably 30,000 or less, and further preferably 20,000 or less from the viewpoint of moldability of the rubbery block copolymer.

[0101] Note that, in the present embodiment, the vinyl aromatic monomer block refers to a block in which 8 or more vinyl aromatic monomer units are linked.

[0102] In addition, regarding the content of the vinyl aromatic monomer block, in the case where the copolymer is a butadiene-styrene copolymer, the polymer can be decomposed by the method described in I. M. Kolthoff, et al., J. Polym. Sci. 1, 429 (1946), and the amount of polystyrene insoluble in methanol is analyzed, whereby the content can be calculated. As another method, as described in International Publication No. 2014-133097, it can be measured by a known method such as measurement of the chain of the styrene unit using NMR. Note that in the present embodiment, the content of the vinyl aromatic monomer block can be measured by the method described in the Examples below.

[0103] (Number of vinyl aromatic monomer blocks)

[0104] The rubbery block copolymer used in the present embodiment has at least one vinyl aromatic monomer block. In the case where a vinyl aromatic monomer block is present, even if the content of the vinyl aromatic monomer unit is the same, the cold flow resistance is good compared to a rubbery block copolymer that does not have a vinyl aromatic monomer block, and the rigidity when a rubber composition containing the rubbery block copolymer is made into a vulcanizate is also excellent.

[0105] In the case where two or more vinyl aromatic monomer blocks are present, it is easy to have thermoplasticity, and there is a tendency to easily stick when the rubbery block copolymer of the present embodiment is compression molded. Therefore, in the case where good compression moldability is valued, or from the aspect of preventing mixing failure due to rubber elasticity when mixed with other materials (for example, a material in the form of a compression-molded product), the number of vinyl aromatic monomer blocks in the rubbery block copolymer is preferably one.

[0106] In addition, regarding the weight average molecular weight of the vinyl aromatic monomer block, the above-described polystyrene insoluble in methanol can be subjected to the method using GPC described in the Examples below to be obtained.

[0107] (Block structure of rubbery block copolymer)

[0108] From the aspect of compression moldability, the block structure of the rubbery block copolymer used in the present embodiment preferably has, for example, a structure represented by the following general formula.

[0109] (a-b)n

[0110] (b-a-b)n

[0111] a-(a-b)n

[0112] b-(a-b)n

[0113] b-(a-b)n-X

[0114] [(b-a)k]m-X

[0115] [(b-a)k-b]m-X

[0116] Further, from the viewpoint of productivity of the rubbery block copolymer, the block structure of the rubbery block copolymer used in the present embodiment is more preferably a structure represented by the general formula (a-b)n, (b-a-b)n, [(b-a)k]m-X, [(b-a)k-b]m-X, and more preferably a structure represented by (a-b)n, [(b-a)k]m-X.

[0117] Note that in each of the above general formulae, a represents an aromatic vinyl monomer block, and b represents a block composed of an ethylene structure, a conjugated diene structure, and an α-olefin structure, or a block composed of 80% by mass or less of a vinyl aromatic monomer unit and an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0118] In the present specification, regarding the "conjugated diene structure", as in the case where a conjugated diene is polymerized as a monomer, it refers to a structure in which a double bond remains in the resulting polymer. For example, in the case where butadiene is polymerized, the portion in which 1,4-bonding is formed is a polymer chain having a double bond, and corresponds to the "conjugated diene structure". On the other hand, as described above, even if a conjugated diene is used as a raw material, the double bond of the portion in which hydrogenation reaction has occurred disappears, and thus becomes an ethylene structure, and does not belong to the conjugated diene structure.

[0119] In the present specification, regarding the "α-olefin structure", as in the case where an α-olefin is polymerized as a monomer, it refers to a structure in which an olefin portion forms a polymer chain, and the portion other than the olefin in the monomer branches from the polymer chain. For example, in the case where butadiene is polymerized, a vinyl bond is formed in the portion in which 1,2-bonding is formed, but if hydrogenation reaction is performed thereon, it becomes an α-olefin structure.

[0120] n and k are integers of 1 or more, and preferably integers of 1 to 5.

[0121] m is an integer of 2 or more, and preferably an integer of 2 to 11.

[0122] X represents a residue of a coupling agent or a residue of a multifunctional initiator.

[0123] Further, in the above general formula [(b-a)k]m-X, since the polymer block a is bonded only by the residue of the coupling agent or the residue of the multifunctional initiator X, the number of the vinyl aromatic monomer blocks is regarded as one.

[0124] In the rubber-like block copolymer used in this embodiment, when there are two or more aromatic vinyl monomer blocks (blocks represented by 'a' in the above general formulas, hereinafter also referred to as "polymer block (a)") and other blocks (blocks represented by 'b' in the above general formulas, hereinafter also referred to as "polymer block (b)"), their molecular weight, composition and other structures may be the same or different.

[0125] In addition, the boundaries of each segment do not need to be clearly distinguished.

[0126] In this embodiment, at least one block at the end of the molecule in the rubbery block copolymer is a polymer block (b), namely block I or block II described below.

[0127] Block I: A block composed of ethylene structure, conjugated diene structure and α-olefin structure;

[0128] Block II: A block containing less than 80% by mass of vinyl aromatic monomer units and including vinyl aromatic monomer units, ethylene structures, conjugated diene structures and α-olefin structures.

[0129] (Structure of Segment II)

[0130] The microstructure of block II (vinyl aromatic monomer units, ethylene structure, conjugated diene structure, and α-olefin structure) is not particularly limited. It can be uniformly distributed (randomly), or it can exhibit a gradient, step-like, convex, or concave distribution. However, from the perspective of polymerization efficiency, a random or gradient distribution is preferred. In this specification, "gradual distribution" or "gradual structure" refers to a state where the proportion of vinyl aromatic monomer units in the block increases or decreases slowly. The distribution of the ethylene structure, conjugated diene structure, and α-olefin structure is not related to the determination of "gradual structure." Typically, because vinyl aromatics polymerize more slowly than conjugated dienes, when copolymerization is carried out without or with only a small amount of a polymerization rate modifier, the conjugated diene is consumed in a high proportion first, leaving a high residual proportion of vinyl aromatics. Therefore, in the blocks formed in the latter half of polymerization, the proportion of vinyl aromatics increases slowly, easily becoming a gradient distribution.

[0131] It is speculated that when the microstructure of block II is random, the exothermic index tanδ=G” / G'=loss modulus / storage modulus of the rubber composition becomes narrower. The tanδ value at high temperature is low, which means low exothermic performance. When used in tire parts, it has excellent fuel economy.

[0132] There are no particular limitations on how the microstructure of block II can be made random. For example, methods such as adding polar substances during polymerization or continuously supplying monomers to the polymerizer can be used.

[0133] On the other hand, it is presumed that in the case where the microstructure of Block II is tapered, the index of heat release at the time of production of a rubber composition, tan δ = G" / G' = loss modulus / storage modulus, becomes wide, and the wet grip performance and winter performance are excellent when used for a tire member.

[0134] In the rubbery block copolymer used in the present embodiment, when at least one of the blocks at the molecular terminal is the polymer block (b), in the case where the molecular weight is low, the rubbery block copolymer does not easily flow, and the tackiness and adhesion at the time of briquetting molding can be suppressed; on the other hand, even in the case where the molecular weight is high, there is a tendency that the rubbery block copolymer melts at the briquetting molding temperature, and the briquetting molding becomes easy.

[0135] In addition, as necessary, a polymer block other than the polymer blocks (a) and (b) can be contained in the rubbery block copolymer at 40 mass% or less. However, from the viewpoint of the balance of the breaking strength, wet skid resistance, and wear resistance when used for a tire or a shoe sole, the content of the polymer block other than the polymer blocks (a) and (b) is preferably 30 mass% or less, more preferably 20 mass% or less, further preferably 10 mass% or less, and particularly preferably 5 mass% or less.

[0136] In the case where the coupling agent is added after the polymerization of the monomers, in order to improve the reaction rate of the coupling agent, it is preferable to make the coupling agent react with the terminal of the polymer block (b).

[0137] The coupling agent used in the coupling reaction step can be any structure as long as it is a reactive compound of 2 or more functions, and it is preferable to be a reactive compound of 2 or more functions having a silicon atom.

[0138] By using a reactive compound having a silicon atom as the coupling agent, the conjugated diene-based polymer used in the present embodiment becomes a polymer having a silicon atom.

[0139] The microstructure (distribution of cis, trans, and vinyl structures in the vinyl aromatic compound, conjugated diene, and ethylene structure and a-olefin structure, etc.) in the polymer blocks (a) and (b) is not particularly limited, and can be uniformly distributed, or can be distributed in a tapered, stepped, convex, or concave manner. In addition, two or more of the distribution forms can coexist.

[0140] In the case where the rubbery block copolymer used in the present embodiment is obtained by at least polymerizing a conjugated diene monomer or copolymerizing a conjugated diene monomer and, if necessary, other monomers, and then hydrogenating (hydrogenating) a part or most of the double bonds in the polymer, the distribution of the hydrogenation rate between the molecules or between the polymer blocks is not particularly limited, and can be uniform, can be non-uniform, or can have a distribution.

[0141] In this embodiment, the polymer block (b) in the rubber-like block copolymer is a block composed of an ethylene structure, a conjugated diene structure, and an α-olefin structure; or a block composed of a vinyl aromatic monomer unit content of 80% by mass or less and composed of a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure. From the perspective of mechanical strength when the rubber composition is made, a block composed of an ethylene structure, a conjugated diene structure, and an α-olefin structure is preferred.

[0142] When the polymer block (b) is a block composed of vinyl aromatic monomer units, ethylene structures, conjugated diene structures, and α-olefin structures, and the content of vinyl aromatic monomer units in the polymer block (b) is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 12% by mass or more, from the perspective of anti-slip properties and tear strength when the rubber composition is made, the content of vinyl aromatic monomer units in the polymer block (b) is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, from the perspective of softness and elongation at break, the content of vinyl aromatic monomer units in the polymer block (b) is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0143] From the perspective of abrasion resistance of the rubber composition, the content of ethylene structure in the polymer block (b) is preferably 3% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. On the other hand, from the perspective of softness and resistance to compression set when the rubber composition is made, the content of ethylene structure in the polymer block (b) is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

[0144] From the perspective of the anti-slip properties when the rubber composition is made, the content of α-olefin structure in the polymer block (b) is preferably 10% by mass or more, more preferably 12% by mass or more, and even more preferably 15% by mass or more. On the other hand, from the perspective of tensile strength, the content of α-olefin structure in the polymer block (b) is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

[0145] From the perspective of balancing heat aging resistance, mechanical strength, and flexibility, the other monomers such as 1,2-butadiene in the polymer block (b) are preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0146] The content of the polymer block (b) in the rubbery block copolymer used in the present embodiment is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more, from the viewpoint of the tensile energy and the wear resistance when the rubber composition containing the rubbery block copolymer is made into a vulcanizate. On the other hand, the content of the polymer block (b) in the rubbery block copolymer used in the present embodiment is preferably 96% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less, from the viewpoint of the rigidity when the rubber composition is made.

[0147] In addition, the polymer block (b) in the rubbery block copolymer used in the present embodiment can have a main chain branching structure. The main chain branching structure is a structure in which the branching point in the portion derived from the vinyl-based monomer containing an alkoxysilyl group or a halosilyl group is 2 or more branching points, preferably 3 or more branching points, and more preferably 4 or more branching points.

[0148] In addition, the branching point forming the main chain branching structure preferably has 2 or more polymer chains, and more preferably has 3 or more polymer chains other than the main chain.

[0149] In particular, in the main chain branching structure composed of the vinyl-based monomer containing an alkoxysilyl group or a halosilyl group, when the signal detection is performed by Si-NMR, 29 When the signal detection is performed by Si-NMR, a peak derived from the main chain branching structure is detected in the range of -45 ppm to -65 ppm, and further in the range of -50 ppm to -60 ppm. The above-mentioned portion derived from the vinyl-based monomer containing an alkoxysilyl group or a halosilyl group is preferably a monomer unit of a compound represented by the following formula (1) or (2) and has a branching point of a polymer chain derived from the monomer unit of the compound represented by the following formula (1) or (2).

[0150] [Chemical Formula 1]

[0151]

[0152] [Chemical Formula 2]

[0153]

[0154] (In formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and can have a branching structure in a part thereof.

[0155] R 2 ~ R 3each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and can have a branched structure in a part thereof. In the case where two or more R 1 ~R 3 each independently.

[0156] X 1 represents a halogen atom. In the case where two or more X 1 each independently.

[0157] M represents an integer of 0 to 2, n represents an integer of 0 to 3, and 1 represents an integer of 0 to 3. (m+n+l) represents 3.

[0158] (in formula (2), R 2 ~R 5 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and can have a branched structure in a part thereof.

[0159] In the case where two or more R 2 ~R 5 each independently. X 2 ~X 3 each independently represents a halogen atom. In the case where two or more X 2 ~X 3 each independently. M represents an integer of 0 to 2, n represents an integer of 0 to 3, and 1 represents an integer of 0 to 3.

[0160] (m+n+l) represents 3.

[0161] a represents an integer of 0 to 2, b represents an integer of 0 to 3, and c represents an integer of 0 to 3. (a+b+c) represents 3.

[0162] (Content of vinyl aromatic monomer unit)

[0163] From the viewpoint of deformation resistance at the time of transportation of the briquette molded body, breaking strength at the time of production of a rubber composition, and wet skid resistance, the content of the vinyl aromatic monomer unit in the rubber-like block copolymer used in the present embodiment mode is 9% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more. On the other hand, from the viewpoint of cutting property at the time of measurement at the time of production of the briquette molded body, fuel efficiency and wear resistance at the time of use of the rubber composition for a tire tread, the content of the vinyl aromatic monomer unit in the rubber-like block copolymer used in the present embodiment mode is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less.

[0164] In addition, in the case where high modulus is required, such as in foamed shoe soles for shoes, run-flat tire members, and the like, the content of the vinyl aromatic monomer units in the rubbery block copolymer used in the present embodiment is preferably 30% by mass or more.

[0165] (Ratio of the proportion of the vinyl aromatic monomer block to the content of the vinyl aromatic monomer units)

[0166] From the aspect of cold flow resistance, the ratio of the proportion of the vinyl aromatic monomer block to the content of the vinyl aromatic monomer units in the rubbery block copolymer is preferably 0.28 to 1.00. In addition, from the aspect of rigidity when a rubber composition is produced, the ratio is more preferably 0.30 or more, further preferably 0.50 or more, and particularly preferably 0.60 or more. On the other hand, from the aspect of the hardness of the briquette and the processability of the briquette when the briquette of the present embodiment is kneaded, the ratio is more preferably 0.90 or less, further preferably 0.80 or less, and particularly preferably 0.70 or less.

[0167] Note that, in the present embodiment, the content of the vinyl aromatic monomer units in the rubbery block copolymer can be measured by the method described in the Examples below.

[0168] (Content of α-olefin structure)

[0169] From the aspect of the productivity of the rubbery block copolymer and the tensile strength when a rubber composition is produced, the content of the α-olefin structure in the rubbery block copolymer used in the present embodiment is preferably 10% by mass or more, more preferably 12% by mass or more, and further preferably 15% by mass or more. On the other hand, from the aspect of the heat aging resistance and the ozone resistance in the rubbery block copolymer, the content of the α-olefin structure in the rubbery block copolymer used in the present embodiment is preferably 65% by mass or less, more preferably 60% by mass or less, further preferably 52% by mass or less, and particularly preferably 40% by mass or less.

[0170] Thus, there is a tendency that a rubber composition for tires, particularly a rubber composition suitable for a tire bead, having excellent tensile strength and ozone resistance can be obtained.

[0171] The content of the α-olefin structure (e.g., butene content) in the rubbery block copolymer can be controlled by the vinyl bond content before the hydrogenation reaction and the hydrogenation rate.

[0172] Note that, in the present embodiment, the content of the α-olefin structure (e.g., butene content) in the rubbery block copolymer can be measured by the method described in the Examples below.

[0173] (amount of vinyl bonding of conjugated diene monomer unit)

[0174] Although the same as the above meaning, in the case where the rubbery block copolymer is produced by hydrogenation after polymerization or copolymerization of the conjugated diene monomer, the amount of vinyl bonding of the conjugated diene monomer unit in the rubbery block copolymer before hydrogenation is preferably 10 mol% or more, more preferably 14 mol% or more, further preferably 20 mol% or more, particularly preferably 25 mol%. On the other hand, the amount of vinyl bonding of the conjugated diene monomer unit in the rubbery block copolymer before hydrogenation is preferably 65 mol% or less, more preferably 60 mol% or less, further preferably 52 mol% or less, particularly preferably 40 mol% or less.

[0175] As a method of controlling the amount of vinyl bonding of the conjugated diene monomer unit of the rubbery block copolymer within the preferable range, there is no particular limitation, and for example, a method of adjusting the addition amount of a polar substance, a method of adjusting the polymerization temperature, and the like can be given.

[0176] (molecular weight of rubbery block copolymer)

[0177] From the viewpoint of moldability of the press cake, compatibility at the time of producing a rubber composition, and elongation at break at the time of producing a vulcanizate from the rubber composition, the weight average molecular weight of the rubbery block copolymer used in the present embodiment is 80,000 or more, preferably 100,000 or more, more preferably 120,000 or more, further preferably 150,000 or more. On the other hand, from the viewpoint of processability at the time of producing a rubber composition, the weight average molecular weight of the rubbery block copolymer used in the present embodiment is 1,000,000 or less, preferably 700,000 or less, more preferably 600,000 or less, further preferably 500,000 or less.

[0178] As a method of controlling the weight average molecular weight of the rubbery block copolymer within the above range, there is no particular limitation, and for example, a method of adjusting the addition amount of a polymerization initiator, a method of adjusting the addition amount of a coupling agent or a modifier, and the like can be given.

[0179] From the viewpoint of compatibility at the time of producing a rubber composition, and fuel efficiency at the time of using the rubber composition for a tire, the molecular weight distribution (= weight average molecular weight / number average molecular weight) of the rubbery block copolymer used in the present embodiment is preferably 2.0 or less, more preferably 1.8 or less, further preferably 1.6 or less. On the other hand, from the viewpoint of processability at the time of producing a rubber composition, the molecular weight distribution (= weight average molecular weight / number average molecular weight) of the rubbery block copolymer used in the present embodiment is preferably 1.05 or more, more preferably 1.1 or more, further preferably 1.2 or more.

[0180] There are no particular limitations on the method for controlling the molecular weight distribution of rubbery block copolymers within the aforementioned range. For example, methods such as adjusting the amount of polar substance added or adjusting the polymerization temperature can be cited.

[0181] The weight-average molecular weight and molecular weight distribution of the rubbery block copolymer used in this embodiment can be calculated from the molecular weight converted from polystyrene as determined by gel permeation chromatography (hereinafter also referred to as "GPC") as described in the embodiments described later.

[0182] (Number of peaks in rubbery block copolymers)

[0183] Regarding the rubbery block copolymer used in this embodiment, a preferred embodiment is a rubbery block copolymer with only one peak in the GPC curve determined by gel permeation chromatography (hereinafter also referred to as "GPC"). When using a rubbery block copolymer with only one peak in the GPC curve, there is a tendency to obtain a rubber composition with uniformly dispersed filler when the briquette of this embodiment is compounded with the filler. The mechanism of this tendency is not yet clear, but it is believed that the tendency to uniformly disperse the filler is achieved by making the molecular weight consistent. It should be noted that the number of peaks is a factor set considering the influence on mixing ease; in contrast, peaks less than 5% by mass in the GPC curve have little influence on mixing ease and are therefore not included in the peak count.

[0184] To obtain the rubbery block copolymer, it is preferable to add the deactivating agent (described later) after the polymerization or hydrogenation step of the rubbery block copolymer used in this embodiment, for example. This suppresses coupling reactions caused by impurities during the polymerization step, resulting in a rubbery block copolymer with only one peak in the GPC curve. Furthermore, it improves the purity of the monomers and solvents introduced into the reactor, which is also effective in reducing the amount of polymer deactivated during polymerization.

[0185] As another preferred mode of the rubbery block copolymer used in the present embodiment, the number of peaks in the GPC curve measured using GPC can be two or more, and the peak area of the peak with the smallest molecular weight can be 5% or more and less than 95% relative to the total peak area. Thus, compared with a rubbery block copolymer having the same molecular weight in which the number of peaks in the GPC curve is one, the rubbery block copolymer has a tendency to have excellent processability when producing a rubber composition, and the viscosity of a rubber composition into which a filler is incorporated is reduced. To obtain such a rubbery block copolymer, for example, a coupling agent or a modifier can be added after the polymerization step of the rubbery block copolymer used in the present embodiment. From the viewpoint of the solution viscosity of the rubbery block copolymer at the time of production, the peak area of the peak with the smallest molecular weight is preferably 30% or more, and more preferably 50% or more, relative to the total peak area. On the other hand, from the viewpoints of the briquetting formability and the elongation at break when the rubber composition is vulcanized, the peak area of the peak with the smallest molecular weight is preferably less than 80%, and more preferably less than 70%, relative to the total peak area.

[0186] (Mooney viscosity)

[0187] The Mooney viscosity of the rubbery block copolymer, the rubber composition containing the rubbery block copolymer is an index including information on the molecular weight, the molecular weight distribution, the degree of branching, the content of the softening agent, and the like of the rubbery block copolymer.

[0188] From the viewpoints of the abrasion resistance and the breaking strength when the rubber composition is vulcanized, the Mooney viscosity of the rubbery block copolymer used in the present embodiment measured at 100°C is preferably 40 or more, more preferably 50 or more, and further preferably 55 or more. On the other hand, from the viewpoints of the productivity of the rubbery block copolymer, the rubber composition, and the processability when a composition into which a filler or the like is incorporated is produced, the Mooney viscosity of the rubbery block copolymer used in the present embodiment measured at 100°C is preferably 180 or less, more preferably 150 or less, further preferably 130 or less, and particularly preferably 110 or less.

[0189] Note that, in the present embodiment, the Mooney viscosity is obtained by the method described in ISO 289 described in the Examples below.

[0190] [Modifier and modification rate]

[0191] From the viewpoint of improving the dispersibility of an inorganic filler such as silica when a rubber composition is produced, the rubbery block copolymer used in the present embodiment preferably contains a nitrogen atom.

[0192] In the rubbery block copolymer of the present embodiment, the modification rate of the rubbery block copolymer measured by the column adsorption GPC method is preferably 40% by mass or more, more preferably 60% by mass or more, and further preferably 70% or more from the viewpoint of the dispersibility of the silica in the rubber composition. On the other hand, the upper limit of the modification rate measured by the column adsorption GPC method in the rubbery block copolymer of the present embodiment is not particularly limited, and is, for example, 98% by mass.

[0193] In the present embodiment, the "modification rate" represents the mass ratio of the polymer having a functional group containing a nitrogen atom with respect to the total amount of the rubbery block copolymer.

[0194] As for the introduction position of the nitrogen atom in the rubbery block copolymer used in the present embodiment, it can be contained at any position of the polymerization starting end, the molecular chain (including the graft product), and the polymerization end of the rubbery block copolymer.

[0195] In the case where the rubbery block copolymer used in the present embodiment is produced by polymerizing a conjugated diene monomer and then hydrogenating, as a method of introducing a nitrogen atom into the rubbery block copolymer, a method of introducing using a coupling agent containing a tin atom or a nitrogen atom is preferred, and a method of introducing using a coupling agent containing a nitrogen atom is more preferred from the viewpoints of the production rate of the rubbery block copolymer, the ease of obtaining a rubbery block copolymer with a high modification rate, and the improvement in wear resistance and fuel efficiency when a rubber composition containing the rubbery block copolymer is made into a vulcanizate.

[0196] As the coupling agent containing a nitrogen atom, an isocyanate compound, an isothiocyanate compound, an isocyanuric acid derivative, a carbonyl compound containing a nitrogen group, a vinyl compound containing a nitrogen group, an epoxy compound containing a nitrogen group, an alkoxysilane compound containing a nitrogen group, an amide compound, and the like are preferred from the viewpoints of the production rate and the high modification rate.

[0197] As these coupling agents containing a nitrogen atom, an amide compound and an alkoxysilane compound containing a nitrogen group are more preferred from the viewpoints of the production rate of the rubbery block copolymer, the ease of obtaining a rubbery block copolymer with a high modification rate, the tensile strength when a rubber composition containing the rubbery block copolymer is made into a tire, and the low fuel efficiency.

[0198] As the amide compound, as a preferable example, 1,3-diethyl-2-imidazolinone, 1,3-dimethyl-2-imidazolinone, 1,3-dipropyl-2-imidazolinone, 1-methyl-3-ethyl-2-imidazolinone, 1-methyl-3-propyl-2-imidazolinone, 1-methyl-3-butyl-2-imidazolinone, 1,3-dihydro-1,3-dimethyl-2H-imidazol-2-one, 1,3-diethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-propyl-2-imidazolidinone, 1-methyl-3-butyl-2-imidazolidinone, and the like can be given.

[0199] As the alkoxysilane compound containing a nitrogen atom, as a preferable example, 2,2-dimethoxy-l-(3-trimethoxysilylpropyl)-l-aza-2-silacyclopentane, 2,2-diethoxy-l-(3-triethoxysilylpropyl)-l-aza-2-silacyclopentane, 2,2-dimethoxy-l-(4-trimethoxysilylbutyl)-l-aza-2-silacyclohexane, 2,2-dimethoxy-l-(5-trimethoxysilylpentyl)-l-aza-2-silacycloheptane, 2,2-dimethoxy-l-(3-dimethoxymethylsilylpropyl)-l-aza-2-silacyclopentane, 2,2-diethoxy-l-(3-diethoxyethylsilylpropyl)-l-aza-2-silacyclopentane, 2-methoxy, 2-methyl-l-(3-trimethoxysilylpropyl)-l-aza-2-silacyclopentane, 2-ethoxy, 2-ethyl-l-(3-triethoxysilylpropyl)-l-aza-2-silacyclopentane, 2-methoxy, 2-methyl-l-(3-dimethoxymethylsilylpropyl)-l-aza-2-silacyclopentane, and 2-ethoxy, 2-ethyl-l-(3-diethoxyethylsilylpropyl)-l-aza-2-silacyclopentane, tri(3-trimethoxysilylpropyl)amine, tri(3-methyldimethoxysilylpropyl)amine, tri(3-triethoxysilylpropyl)amine, tri(3-methyldiethoxysilylpropyl)amine, tri(trimethoxysilylmethyl)amine, tri(2-trimethoxysilyl ethyl)amine, and tri(4-trimethoxysilylbutyl)amine, tetra[3-(2,2-dimethoxy-l-aza-2-silacyclopentane)propyl]-l,3-propanediamine, tetra(3-trimethoxysilylpropyl)-l,3-propanediamine, tetra(3-trimethoxysilylpropyl)-l,3-bisaminomethylcyclohexane, and N1-(3-(bis(3-(trimethoxysilyl)propyl)amino)propyl)-N1-methyl-N3-(3-(methyl(3-(trimethoxysilyl)propyl)amino)propyl)-N3-(3-(trimethoxysilyl)propyl)-l,3-propanediamine, 3-(4-methylpiperazin-l-yl)propyltrimethoxysilane, 3-(4-methylpiperazin-l-yl)propyltriethoxysilane.

[0200] [Polymerization method and hydrogenation method of rubbery block copolymer]

[0201] As for the production method of the rubbery block copolymer used in the present embodiment, there is no particular limitation as long as a rubbery block copolymer satisfying the above-mentioned conditions can be obtained.

[0202] The specific production method of the rubbery block copolymer used in the present embodiment is not particularly limited, and for example, a method including at least a step of polymerizing a conjugated diene monomer or a step of hydrogenating after copolymerizing a conjugated diene monomer with a monomer used as needed; a method including a step of polymerizing a conjugated diene monomer (without hydrogenation) or a step of copolymerizing a conjugated diene monomer with a monomer used as needed (without hydrogenation) can be given.

[0203] The conjugated diene monomer is not particularly limited, and for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, and 1,3-heptadiene, and the like can be given. Among these, from the aspect of easiness in industrial acquisition, 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is particularly preferred. They can be used alone or in combination with two or more kinds.

[0204] The monomer used as needed is not particularly limited, and from the aspect of mechanical strength at the time of tire production, a vinyl aromatic monomer is preferably copolymerized with a conjugated diene monomer and used. The vinyl aromatic monomer is not particularly limited, and for example, styrene, p-methylstyrene, α-methylstyrene, vinyl toluene, vinyl xylene, vinyl naphthalene, diphenyl ethylene, vinylbenzyl dimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, a diphenyl ethylene containing a tertiary amino group (for example, 1-(4-N,N-dimethylaminophenyl)-1-phenyl ethylene), and the like can be given. Among these, from the aspect of easiness in industrial acquisition, styrene is preferred. They can be used alone or in combination with two or more kinds.

[0205] Other monomers used as needed can be used.

[0206] The other monomer is not particularly limited, and for example, an unsaturated carboxylic acid ester, an unsaturated carboxylic acid, an α,β-unsaturated nitrile compound, an α-olefin (butene, propylene, butene, pentene, hexene, and the like), ethylene, myrcene, ethylidenenorbornene, isopropylidenenorbornene, cyclopentadiene, divinylbenzene, and the like can be given.

[0207] In the production method of the rubbery block copolymer, as the method of polymerizing a conjugated diene monomer or copolymerizing a conjugated diene monomer with a monomer used as needed (without hydrogenation), for example, a method of producing by a coordination polymerization method described in International Publication No. 2019 / 078083, International Publication No. 2019 / 111496, International Publication No. 2019 / 142501, International Publication No. 2019 / 171679, International Publication No. 2019 / 216100, which does not exemplify a block structure, can be given.

[0208] In this case, the vinyl aromatic monomer, ethylene, α-olefin, conjugated diene monomer, and other monomers added at the time of polymerization are preferably the same as the above-described monomer species exemplified in the case where the conjugated diene monomer is polymerized or the conjugated diene monomer is copolymerized with the monomers used as necessary after hydrogenation.

[0209] From the aspect of easy control of the block structure, the rubbery block copolymer used in the present embodiment is preferably produced by anionic polymerization, and is preferably produced by at least polymerizing the conjugated diene monomer or copolymerizing the conjugated diene monomer with the monomers used as necessary after hydrogenation (hydrogenation) of part or most of the double bonds in the polymer.

[0210] As the method of hydrogenation after at least polymerization of the conjugated diene monomer or copolymerization of the conjugated diene monomer with the monomers used as necessary, a method of polymerizing the conjugated diene monomer by anionic polymerization, copolymerizing with other monomers as necessary, and then hydrogenating under various additives and conditions is preferred, as described in International Publication No. 96 / 05250, Japanese Patent Application Publication No. 2000-053706, International Publication No. 2003 / 085010, International Publication No. 2019 / 151126, International Publication No. 2019 / 151127, International Publication No. 2002 / 002663, and International Publication No. 2015 / 006179.

[0211] The above-described polymerization step and hydrogenation (hydrogenation) step can each be either of a batch type or a continuous type.

[0212] Note that the rubbery block copolymer used in the present embodiment also includes a hydrogenated product of the rubbery block copolymer after hydrogenation.

[0213] [Subsequent step to the polymerization step or hydrogenation step of the rubbery block copolymer]

[0214] It is preferred to add a deactivating agent, a neutralizing agent, or the like after the polymerization step or hydrogenation step of the rubbery block copolymer used in the present embodiment.

[0215] As the deactivating agent, the following substances can be given, but are not limited thereto: for example, water; alcohols such as methanol, ethanol, and isopropanol.

[0216] As the neutralizing agent, the following substances can be given, but are not limited thereto: for example, carboxylic acids such as stearic acid, oleic acid, and versatic acid (a mixture of carboxylic acids having 9 to 11 carbon atoms, centered on 10 carbon atoms); aqueous solutions of inorganic acids; carbon dioxide.

[0217] From the viewpoint of preventing gel generation and processing stability, a rubber stabilizer is preferably added after the polymerization step of the rubbery block copolymer of the present embodiment.

[0218] As the rubber stabilizer, known substances such as antioxidants such as 2,6-di-tert-butyl-4-hydroxytoluene (hereinafter also referred to as "BHT"), 3-(4'-hydroxy-3',5'-di-tert-butylphenyl) propionic acid n-octadecyl ester, 2-methyl-4,6-bis[(octylthio)methyl]phenol, and the like can be used, but are not limited thereto.

[0219] The rubbery block copolymer used in the present embodiment contains a rubber softener as needed. The content of the rubber softener is preferably 30% by mass or less.

[0220] In the rubbery block copolymer of the present embodiment, 1 to 30% by mass of a rubber softener can be added in order to improve the productivity of the rubbery block copolymer and the processability when compounding inorganic fillers and the like at the time of tire production. On the other hand, in the rubbery block copolymer of the present embodiment, 1 to 15% by mass of a rubber softener is preferably used in order to compound fillers and to increase the degree of freedom of compounding at the time of production of a rubber composition.

[0221] From the viewpoint of deterioration over time at the time of tire production, the content of the rubber softener in the briquette molded body of the rubbery block copolymer of the present embodiment is more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0222] As the rubber softener, there is no particular limitation, and examples include extender oils, liquid rubbers, resins, and the like.

[0223] As the rubber softener, extender oils are preferred from the viewpoints of processability, productivity, and economy.

[0224] As the method of adding a rubber softener to the rubbery block copolymer, the following method is preferred, but is not limited thereto: the rubber softener is added to a polymer solution, mixed, and a polymer solution containing a rubber softener is produced, and then desolvation is performed.

[0225] As the preferred extender oil, for example, aromatic oil, naphthene oil, paraffin oil, and the like can be cited. Among these, from the environmental safety aspect and the aspect of preventing oil bleeding and wet grip properties, a substitute aromatic oil in which the polycyclic aromatic (PCA) component based on the IP346 method is 3 mass% or less is preferred. As the substitute aromatic oil, there is no particular limitation, and for example, TDAE (Treated Distillate Aromatic Extracts), MES (Mild Extraction Solvate), and the like shown in Kautschuk Gummi Kunststoffe 52(12) 799 (1999), and RAE (Residual Aromatic Extracts) can be cited.

[0226] Various additives can be further added to the rubbery block copolymer used in the present embodiment as needed. As the additives, the extender shown below, or a resin component as a tackifier, and the like can be added in the form of a master batch in the process before molding. In this case, the additive is preferably 15 mass% or less.

[0227] [Method of removing solvent from polymerization solvent]

[0228] In the method of producing the rubbery block copolymer used in the present embodiment, the method of removing the solvent from the polymer solution is not particularly limited, and for example, a method of flashing, stripping, and using a drying conveyor, a devolatilization extruder, a drum dryer, a devolatilization kneader, and the like after dehydration can be cited.

[0229] From the aspect of small heat history, a method of using at least stripping is preferred.

[0230] As an example of the method of stripping and the process before and after the same, there is no particular limitation, and for example, the method described in Japanese Patent Application Publication No. 10-168101, Japanese Patent Application Publication No. 10-204136, International Publication No. 2013-146530, Japanese Patent Application Publication No. 2019-131810, and the like can be cited.

[0231] In the method of producing the rubbery block copolymer used in the present embodiment, it is preferred to implement a desolventizing process of removing the solvent from the polymer solution by stripping, and a screening process of separating from the polymer slurry with stripping water and taking out the water-containing pellets before the extrusion drying process.

[0232] In addition, before the stripping, a flashing process can be provided in order to increase the solution concentration.

[0233] By carrying out a desolventizing process for removing the solvent from the polymer solution by stripping before the extrusion drying process, a slurry of porous granular pellets containing no solvent but moisture can be obtained, which is dispersed in hot water.

[0234] By carrying out a sieving process for separating the slurry of the polymer from the stripping water and taking out the moisture-containing pellets, porous granular pellets containing moisture can be obtained.

[0235] Further, it is preferable to carry out a dewatering process using a roll, a screw compression wringer, or the like, as needed. By these dewatering processes, moisture-containing pellets having a further reduced moisture content can be obtained at a stage prior to the extrusion drying process.

[0236] From the viewpoint of resistance to scattering at the time of drying, the particle diameter of the moisture-containing pellets is preferably 0.1 mm or more. More preferably, it is 0.5 mm or more. On the other hand, from the viewpoint of drying property of the residual solvent or moisture in the pellets and resistance to expansion of the molded body after briquetting, it is preferably 30 mm or less. More preferably, it is 20 mm or less.

[0237] As a method for adjusting the particle diameter of the pellets, there are a case where the desolventizing is carried out to produce the pellets, and a case where the produced pellets are processed to adjust. In the case where the adjustment is carried out in the process of producing the pellets by desolventizing, there are no particular limitations, and for example, a method for adjusting the molecular weight, composition, structure of the polymer; a method for adjusting the amount of the rubber softener added to the polymer solution; a method for adjusting the pore diameter of the die of the extrusion dryer; a method for adjusting the conditions at the time of desolventizing by pouring the polymer solution into hot water; and the like can be mentioned. In the above-mentioned method for adjusting the molecular weight, composition, structure of the polymer, in order to prevent the adhesion of the pellets to each other due to tackiness, the weight average molecular weight is preferably 80,000 or more. Further, if the vinyl aromatic monomer block is less than 30 mass%, the pellets do not become tight and have a tendency to inhibit drying failure in the drying process. Furthermore, if the iodine value is 250 or less, the pellets have a good foaming property in the extrusion drying process and have a tendency to have a good drying property of the residual solvent and moisture.

[0238] The latter case where the produced pellets are processed to adjust is not particularly limited, and for example, a method for sieving the pellets; a method for crushing and pulverizing the pellets by using a mixer, a granulator can be mentioned.

[0239] There are no particular limitations on the conditions for contacting the polymerized rubbery block copolymer solution with hot water or steam. For example, the following methods can be used: adjusting the solution injection pressure; adjusting the steam pressure, temperature, and amount; adding dispersants such as polyoxyalkylene ether phosphate or its salts, or surfactants such as nonylphenoxy polyethylene glycol phosphate or its salts to the steam; adjusting the shape and rotation speed of the rotating blades used during mixing; and so on.

[0240] For economic and metal removal reasons, it is preferable to include an alcohol compound as a deactivating agent in the polymer solution, and even more preferable to pre-add a dispersant or surfactant that is added during stripping.

[0241] (Residual solvent content)

[0242] Regarding the residual solvent content in the briquette molded body of the rubbery block copolymer of this embodiment, from the perspective of reducing odor and VOCs, a low residual solvent content is preferable. Specifically, the residual solvent content in the briquette molded body of this embodiment is preferably 5000 ppm or less, more preferably 3000 ppm or less, and even more preferably 1500 ppm or less. In addition, from the perspective of economic balance, the residual solvent content in the briquette molded body of this embodiment is preferably 50 ppm or more, more preferably 150 ppm or more, and even more preferably 300 ppm or more.

[0243] It should be noted that, in this embodiment, the residual solvent content refers to the amount of solvent remaining in the briquette molded body.

[0244] In addition, in this embodiment, the residual solvent content can be determined by the method described in the following embodiments.

[0245] (Moisture content)

[0246] The moisture content of the rubber-like block copolymer briquette molded article of this embodiment is preferably 0.05% by mass or more and 1.5% by mass or less. In the briquette molded article of this embodiment, from the viewpoint of suppressing gelation during drying after solvent removal, the moisture content is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more. On the other hand, in the briquette molded article of this embodiment, from the viewpoint of suppressing condensation and discoloration resistance, the moisture content is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.8% by mass or less.

[0247] In addition, in this embodiment, the moisture content can be measured by the method described in the embodiments described later.

[0248] (Rubber softener)

[0249] In addition, from the viewpoint of productivity and processability, the briquetted molding of the rubbery block copolymer of the present embodiment can contain a rubber softening agent. The content of the rubber softening agent in the briquetted molding of the present embodiment is preferably 30% by mass or less. From the viewpoint of annual deterioration when the briquetted molding is made into a tire, the content of the rubber softening agent in the briquetted molding of the present embodiment is more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0250] [Method for producing briquetted molding]

[0251] As the method for producing the briquetted molding of the present embodiment, there is no particular limitation as long as a briquetted molding of a rubbery block copolymer satisfying the above-described conditions 1 to 6 is obtained, and for example, a method having the following steps can be given: a step of obtaining a rubbery block copolymer by polymerizing at least a vinyl aromatic monomer and a conjugated diene monomer using an organolithium compound as a polymerization initiator; a step of hydrogenating the above-described rubbery block copolymer to obtain a hydrogenated product of the rubbery block copolymer; and a step of molding the above-described hydrogenated product of the rubbery block copolymer to obtain a briquetted molding.

[0252] In the method for producing the briquetted molding of the present embodiment, it is preferable to have a step of adding a vinyl aromatic monomer after the copolymerization of the vinyl aromatic monomer and the conjugated diene monomer, or after the polymerization of the conjugated diene monomer.

[0253] In the method for producing the briquetted molding of the present embodiment, it is preferable to have a step of coupling the above-described rubbery block copolymer using a coupling agent.

[0254] The shape of the briquetted molding of the rubbery block copolymer of the present embodiment is not particularly limited, and from the viewpoint of operability, a block shape is preferable. In addition, regarding the size of the briquetted molding of the present embodiment, from the viewpoints of molding easiness and operability, the capacity of the briquetted molding is preferably 1,000 cm 3 or more, more preferably 5,000 cm 3 or more, further preferably 10,000 cm 3 or more. Regarding the weight and shape of the briquetted molding of the present embodiment, a rectangular parallelepiped briquet of 17.5 kg to 35 kg is particularly preferable, and the size of such a rectangular parallelepiped briquet is not particularly limited, and for example, it is appropriate to be around 30 to 40 cm in width, 60 to 80 cm in length, and 10 to 30 cm in height.

[0255] The molding method for making the rubbery block copolymer into a briquetted molding is, for example, preferably a method of producing a rubbery block copolymer having a specific surface area of 0.7 m 2 / g to 3.2 m2 / g of agglomerates, the rubber-like block copolymer agglomerates are compressed and molded. From the perspective of formability, it is preferable to also have a step of screening the rubber-like block copolymer agglomerates before molding.

[0256] When rubber-like block copolymer pellets are compressed into shape, the specific surface area of ​​the molded body is lower than that of the pellets because the pellets may adhere closely together. The compactness of the pellets during compression molding can be adjusted by the molecular weight, composition or structure of the rubber-like block copolymer, the composition of the rubber softener, and the temperature and pressure during compression. For example, if it is desired to improve the compactness of the pellets and reduce the specific surface area of ​​the compressed body, it is preferable to reduce the molecular weight of the rubber-like block copolymer, increase the amount of rubber softener, and increase the temperature and pressure during compression.

[0257] The specific surface area of ​​the molded body is 0.005–0.05 m². 2 From the perspective of film packaging properties, a concentration of 0.01–0.04 m / g is more preferable. 2 / g. The specific surface area of ​​the molded body is 0.005m². 2 When the content is above / g, the expansion of the compressed block can be suppressed, and the specific surface area of ​​the molded body is 0.05m². 2 When the ratio is below / g, the peeling of agglomerates from the molded body can be reduced, and therefore it is preferred.

[0258] The specific surface area of ​​the molded body can be determined using the BET method.

[0259] Typically, the specific surface area of ​​a large molded body may vary depending on the location, so it is preferable to take a sample from near the center of the molded body.

[0260] The rubber-like block copolymer pellets are preferably sieved according to particle size before molding, and then mixed in an appropriate ratio.

[0261] If the specific surface area of ​​the molded body formed by directly using the desolventized granules exceeds the upper limit of the above range, the composition of large-diameter granules can be increased and the composition of small-diameter granules can be reduced in the sieved granules. If the specific surface area does not meet the lower limit, the composition of large-diameter granules can be reduced and the composition of small-diameter granules can be increased.

[0262] The molding compression pressure of the molded article is preferably 3 to 30 MPa, more preferably 10 to 20 MPa. When the compression pressure during molding is below 30 MPa, the device can be designed compactly and the installation efficiency is good; when the compression pressure during molding is above 3 MPa, the moldability is good. With good moldability, the surface of the molded article is smooth, and polymer peeling will not occur after the molding process, and it has the tendency to suppress post-molding expansion.

[0263] The temperature of the rubbery block copolymer at the time of molding is preferably 30 to 120°C, and more preferably 50 to 100°C, from the viewpoints of reducing the residual solvent content and suppressing thermal deterioration. When the temperature of the rubbery block copolymer at the time of molding is 30°C or higher, the moldability is good. On the other hand, when the temperature is 120°C or lower, the generation of gel due to thermal deterioration of the rubbery block copolymer can be suppressed, and thus is preferable.

[0264] The higher the temperature and pressure at the time of molding, the smaller the specific surface area of the briquette.

[0265] The pressure holding time at the time of molding is preferably 3 to 30 seconds, and more preferably 5 to 20 seconds. When the pressure holding time at the time of compression is 30 seconds or less, the production efficiency is good. When the pressure holding time is 5 seconds or more, the moldability is good.

[0266] In order to avoid the adhesion of the molded bodies to each other, it is preferable to package the molded bodies with a resin film (a packaging sheet).

[0267] The kind of the resin of the film is not particularly limited, and for example, polyethylene, an ethylene copolymer resin, polystyrene, high-impact polystyrene, and PET can be given.

[0268] From the viewpoints of the operability at the time of handling the molded bodies and the fact that condensation is less likely to occur at the gap between the packaging sheet and the briquette, it is preferable that the adhesion of the packaging sheet be good.

[0269] The molded bodies are housed in a container for transportation. When the expansion rate of the molded bodies after 1 day from the molding is less than 5%, the housing in the container is good, and is preferable.

[0270] [Rubber composition and rubber composition for crosslinking]

[0271] The production method of the filler-containing rubber composition of the present embodiment preferably has a step of mixing a filler in the briquette molded body of the above-described rubbery block copolymer.

[0272] In addition, the production method of the silica-containing rubber composition of the present embodiment preferably has a step of mixing silica in the briquette molded body of the above-described rubbery block copolymer.

[0273] In addition, the production method of the rubber composition of the present embodiment preferably has a step of mixing a crosslinking agent in the rubber component of the briquette molded body of the above-described rubbery block copolymer, the crosslinking agent being 0.1 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the rubber component.

[0274] The above-described crosslinking agent is not particularly limited, and for example, the crosslinking agent described later can be given, and is preferably at least one selected from the group consisting of organic peroxides, azo compounds, and sulfur compounds.

[0275] The filler is preferably mixed in the above kneading step. The filler used herein is not particularly limited, and examples of the filler include the fillers described below.

[0276] The above rubber component preferably contains a rubber component other than the rubbery block copolymer.

[0277] The rubber component other than the rubbery block copolymer is not particularly limited, and examples of the rubber component other than the rubbery block copolymer include the rubber components described below, and is preferably at least one selected from the group consisting of polybutadiene rubber, natural rubber, and ethylene-vinyl acetate copolymer.

[0278] The rubber composition and the rubber composition for crosslinking of the present embodiment contain the briquetted molded body of the above rubbery block copolymer.

[0279] The rubber composition of the present embodiment can be used without crosslinking, and from the viewpoint of higher mechanical strength and the like, a crosslinking agent is preferably added to produce a rubber composition for crosslinking, and after crosslinking, a crosslinked body is produced and used for various purposes.

[0280] The rubber composition and the rubber composition for crosslinking of the present embodiment contain at least the briquetted molded body of the above rubbery block copolymer, and further contain other rubber, a filler, a crosslinking agent, and the like as necessary.

[0281] The other rubber is not particularly limited, and can be appropriately selected depending on the purpose, and examples of the other rubber include styrene-butadiene rubber (emulsion polymerization type, solution polymerization type), natural rubber, polyisoprene, butadiene rubber (high-cis polybutadiene, low-cis polybutadiene, syndiotactic 1,2-polybutadiene, acrylonitrile-butadiene rubber (NBR), chloroprene rubber, ethylene-α-olefin copolymer rubber such as ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), butyl rubber, polysulfide rubber, silicone rubber, fluororubber, polyurethane rubber, ethylene-vinyl acetate copolymer, and a rubbery block copolymer having no both of the polymer blocks (a) and (b) and having an iodine value of 3 to 250, an ethylene structure of > 3 mass%, and a vinyl aromatic monomer block of < 10 mass%, and the like. The shape of these rubbers is preferably briquetted. These substances can be used alone or in combination of two or more. As to the combination, the dry polymers can be combined after polymerization, or can be combined in a solution state during polymerization.

[0282] Among these rubbers, from the viewpoints of economy and tear strength of the rubber composition, natural rubber, high-cis polybutadiene, and ethylene-vinyl acetate copolymer are preferably used in combination.

[0283] In the rubber composition and the rubber composition for crosslinking of the present embodiment, in the case where other rubber is contained in the above rubbery block copolymer, although it can be appropriately selected depending on the required properties, the mass ratio of the rubbery block copolymer / other rubber is preferably 20 / 80 to 100 / 0, more preferably 30 / 70 to 90 / 10.

[0284] In the rubber composition and the rubber composition for crosslinking of the present embodiment, from the aspects of tensile strength and elongation at break, 3 to 40 parts by mass of the resin is preferably contained with respect to 100 parts by mass of the rubber component in the rubber composition, from the aspect of tensile energy, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more of the resin is contained. On the other hand, in the rubber composition and the rubber composition for crosslinking of the present embodiment, from the aspect of easiness in mixing of the rubber composition, 30 parts by mass or less, further preferably 25 parts by mass or less of the resin is more preferably contained with respect to 100 parts by mass of the rubber component in the rubber composition.

[0285] The resin used in the present embodiment is a compound that is solid at room temperature (23°C) and is substantially based on carbon and hydrogen (other atoms can also be contained).

[0286] The resin is not particularly limited, and examples thereof include aliphatic, alicyclic, aromatic, hydrogenated aromatic, aliphatic / aromatic based on aliphatic and / or aromatic monomers. The resin can be a petroleum resin, or a natural or synthetic resin other than petroleum-based.

[0287] Specific examples of the resin are not particularly limited, and examples thereof include a hydrocarbon resin selected from the group consisting of a homopolymer or copolymer resin of cyclopentadiene (CPD), a homopolymer or copolymer resin of dicyclopentadiene (DCPD), a homopolymer or copolymer resin of terpene, a homopolymer or copolymer resin of C5 fraction, a homopolymer or copolymer resin of C9 fraction, a homopolymer or copolymer resin of α-methylstyrene, and a blend of these resins. In the above copolymer resins, more specifically, a copolymer selected from the group consisting of a (D)CPD / vinyl aromatic copolymer resin, a (D)CPD / terpene copolymer resin, a terpene / phenol copolymer resin, a (D)CPD / C5 fraction copolymer resin, a (D)CPD / C9 fraction copolymer resin, a terpene / vinyl aromatic copolymer resin, a terpene / phenol copolymer resin, a C5 fraction / vinyl aromatic copolymer resin, and a blend of these resins is preferred, but not particularly limited.

[0288] The resin can be used alone or in combination of two or more.

[0289] The glass transition temperature of the resin is preferably 30°C or higher, more preferably 40°C or higher, from the viewpoint of tensile strength and elongation at break. On the other hand, the glass transition temperature of the resin is preferably 100°C or lower, more preferably 80°C or lower, from the viewpoint of ease of mixing of the crosslinkable rubber composition.

[0290] The rubber composition and the crosslinkable rubber composition of the present embodiment preferably contain a filler, from the viewpoint of improving the reinforcing property.

[0291] The filler is not particularly limited, and examples thereof include carbon black, silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass hollow spheres, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, titanium oxide, potassium titanate, barium sulfate, and the like. Of these, carbon black is preferably used. These components can be used alone or in combination of two or more.

[0292] The carbon black is not particularly limited, and can be appropriately selected depending on the purpose, and examples thereof include FEF, GPF, SRF, HAF, N339, IISAF, ISAF, SAF, and the like. These components can be used alone or in combination of two or more.

[0293] The nitrogen adsorption specific surface area of the above-mentioned silica, which is measured by the BET adsorption method, is preferably 170 to 300 mm 2 / g, more preferably 200 to 300 mm 2 / g, from the viewpoint of the strength and processability of the rubber composition.

[0294] The above-mentioned carbon black is preferably carbon black having a nitrogen adsorption specific surface area of 50 mg / g or more and a dibutyl phthalate (DBP) oil absorption of 80 mL / 100 g or more, from the viewpoint of the strength of the rubber composition.

[0295] Note that the nitrogen adsorption specific surface area is measured by a method according to JIS K6217, and the DBP oil absorption is measured by a method according to ASTM D2414.

[0296] Silica is preferred from the viewpoint of the reinforcing property, and the content of silica is preferably higher than that of carbon black.

[0297] Of the silica, sedimentation silica is more preferred.

[0298] The amount of the filler to be mixed in the rubber composition and the rubber composition for crosslinking of the present embodiment is not particularly limited and can be appropriately selected according to the purpose, but is preferably 10 to 130 parts by mass, more preferably 30 to 90 parts by mass, with respect to 100 parts by mass of the rubber component. When the amount of the filler to be mixed is 10 parts by mass or more, the effect of improving the reinforcement due to the mixed filler can be obtained, and by making it 130 parts by mass or less, the decrease in the processability and moldability of the rubber composition can be avoided.

[0299] The rubber composition and the rubber composition for crosslinking of the present embodiment can contain a silane coupling agent from the viewpoint of improving the dispersibility of the filler and the strength of the tensile properties of the crosslinked body. The silane coupling agent has a function of making the interaction between the rubber component and the inorganic filler close, and is preferably a compound having a group having affinity or binding property with the rubber component and the filler, respectively, and having a sulfur bonding moiety and an alkoxysilyl or silanol moiety in one molecule. As such a compound, there is no particular limitation, and for example, bis-[3-(triethoxysilyl)-propyl]-tetrasulfide, bis-[3-(triethoxysilyl)-propyl]-disulfide, bis-[2-(triethoxysilyl)-ethyl]-tetrasulfide, thiooctanoic acid S-[3-(triethoxysilyl)propyl] ester, and a condensate of thiooctanoic acid S-[3-(triethoxysilyl)propyl] ester and [(triethoxysilyl)-propyl] mercaptan, a silane loaded with at least one thiol (-SH) functional group (referred to as mercapto silane) and / or at least one masked mercapto group can be mentioned.

[0300] The content of the silane coupling agent in the rubber composition for crosslinking of the present embodiment is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less, and further preferably 1.0 parts by mass or more and 15 parts by mass or less, with respect to 100 parts by mass of the above-described filler. When the content of the silane coupling agent is in the above-described range, there is a tendency that the above-described additive effect based on the silane coupling agent can be more significant.

[0301] A crosslinking agent can be used as needed in the rubber composition for crosslinking of the present embodiment. The above-described crosslinking agent is not particularly limited and can be appropriately selected according to the purpose, and for example, a sulfur-based crosslinking agent, an organic peroxide-based crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, a sulfur compound-based crosslinking agent, an oxime-nitrosamine-based crosslinking agent, an azo compound-based crosslinking agent, a polyphosphoric acid compound-based crosslinking agent, and the like can be mentioned, and they can be used in combination. Note that, among these, a sulfur-based crosslinking agent (vulcanizing agent) is more preferable as a rubber composition for tires. In particular, sulfur is further preferable.

[0302] The content of the crosslinking agent in the crosslinking rubber composition of the present embodiment is preferably 0.1 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the rubber component. In terms of high tensile strength and rapid crosslinking speed, the content of the crosslinking agent is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 1.5 parts by mass or more relative to 100 parts by mass of the rubber component. On the other hand, in terms of suppression of uneven crosslinking and high tensile strength, the content of the crosslinking agent is preferably 20 parts by mass or less. More preferably, the content is 5 parts by mass or less, and further preferably 3 parts by mass or less.

[0303] In the crosslinking rubber composition of the present embodiment, a vulcanization accelerator can also be further used in combination with the vulcanizing agent.

[0304] The vulcanization accelerator is not particularly limited, and examples include guanidine-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, sulfenamide-based, thiourea-based, thiuram-based, dithiocarbamate-based, xanthate-based, and the like.

[0305] In addition, various additives such as other softening agents and fillers, heat-resistant stabilizers, antistatic agents, weather-resistant stabilizers, anti-aging agents, coloring agents, lubricants, and the like other than those described above can be used in the crosslinking rubber composition of the present embodiment. As the other softening agents, publicly known softening agents can be used. As the other fillers, specifically, examples include but are not particularly limited to, for example, calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate. As the heat-resistant stabilizers, antistatic agents, weather-resistant stabilizers, anti-aging agents, coloring agents, and lubricants described above, publicly known materials can be used, respectively.

[0306] (Mixing method of crosslinking rubber composition)

[0307] As the method of mixing the rubber component, the silica-based inorganic filler, carbon black and other fillers, the silane coupling agent, and the additives such as the rubber softening agent, examples include but are not limited to, for example, a melt mixing method using a common mixer such as an open mill, a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, and the like; and a method of dissolving and mixing each component and then heating to remove the solvent. Among these methods, a melt mixing method using a roll, a Banbury mixer, a kneader, or an extruder is preferable in terms of productivity and good mixability. In addition, either of a method of mixing the rubber component and the other fillers, the silane coupling agent, and the additives at one time, and a method of mixing in two or more times can be applied.

[0308] (Use)

[0309] The rubber composition of the present embodiment is preferably used as a crosslinking rubber composition for tire members, interior and exterior materials for automobiles, vibration isolators, belts, foams, copper-clad laminates, cable gels, various industrial products, and the like.

[0310] Among these, it is suitable for shoe soles for shoes, tire members.

[0311] The manufacturing method of the shoe sole for shoes of the present embodiment has a step of molding the rubber composition obtained by the above method.

[0312] As a specific example of manufacturing the shoe sole for shoes of the present embodiment, there is no particular limitation, and for example, a method of mixing a rubber composition containing a rubber component, silica, a silane coupling agent, and an additive can be cited. As the rubber component, 10 to 30 parts by mass of the above rubber-like block copolymer is preferably mixed from the aspect of grip, 60 to 70 parts by mass of a high-cis polybutadiene is preferably mixed from the aspect of wear resistance, and 10 to 20 parts by mass of a polyisoprene rubber is preferably mixed from the aspect of tear strength. Mixing of the above rubber composition is preferably performed at 120 to 160°C in general. Further, mixing and kneading of sulfur and a vulcanization accelerator are performed. The temperature at this time is preferably less than 120°C. A blowing agent is preferably further added to the above rubber composition. Next, the obtained composition is put into a prescribed mold, and foaming is performed by raising the temperature, or after being molded into an arbitrary shape using an extrusion molding machine, foaming is performed by heating in a heating tank, whereby vulcanization occurs at the same time as foaming, and a shoe sole member is obtained. The vulcanization temperature is preferably 140 to 180°C, and the vulcanization time is preferably 5 to 30 minutes.

[0313] As the shoe sole member, a midsole, an outsole, and more preferably an outsole are preferred.

[0314] In addition, the briquette molded body of the rubber-like block copolymer of the present embodiment has high strength, and thus has high foaming ratio, and a lighter shoe sole can be manufactured.

[0315] Regarding the composition of the crosslinking rubber composition when manufacturing a shoe sole, the composition described in the Examples described later can be used, for example.

[0316] The manufacturing method of the tire tread of the present embodiment has a step of molding the rubber composition obtained by the above method.

[0317] The manufacturing method of the tire bead of the present embodiment has a step of molding the rubber composition obtained by the above method.

[0318] As a specific example of manufacturing a tire, there is no particular limitation, and for example, a method of performing mixing of a rubber composition containing a rubber component and carbon black, silica, a silane coupling agent, and an additive can be cited. As the rubber component, from the aspects of grip performance and fuel consumption reduction, it is preferable to mix 60 to 80 parts by mass of the above-described rubber-like block copolymer, from the aspect of wear resistance, it is preferable to mix 10 to 30 parts by mass of a high-cis polybutadiene, and from the aspect of tear strength, it is preferable to mix 10 to 20 parts by mass of a natural rubber.

[0319] Mixing of the above-described rubber composition is preferably performed generally at 100 to 180°C. Further, mixing of sulfur and a vulcanization accelerator, and mixing are performed. The temperature at this time is preferably less than 120°C.

[0320] As a molding method, there is no particular limitation, and for example, a method in which components such as a tire body layer, a ring band layer, a tread layer, and the like, which are generally used in tire manufacturing, composed of at least one selected from the group consisting of an uncured crosslinking rubber composition and a tire cord, are sequentially overlapped and attached on a tire molding drum, the drum is pulled out, and a green tire is manufactured can be cited. Subsequently, the green tire is subjected to heat vulcanization in a conventional method, and thus a desired tire (for example, a pneumatic tire) can be manufactured. The vulcanization temperature is preferably 140 to 190°C, and the vulcanization time is preferably 5 to 15 minutes.

[0321] As a tire component, it can be used in tire portions such as a tread, a body, a side, a bead, and the like of various tires such as fuel consumption reduction tires, all-season tires, high-performance tires, snow tires, studless tires, and the like. In particular, since the wear resistance, fuel consumption reduction, wet skid resistance, and balance with snow performance after being manufactured into a vulcanizate are excellent, it can be appropriately used as a tire component for a fuel consumption reduction tire or a high-performance tire use, a tire tread use of a snow tire.

[0322] As for the composition of the crosslinking rubber composition at the time of manufacturing a tire component, for example, the composition described in the following examples can be performed.

[0323] Examples

[0324] The present embodiment will be described in more detail below by citing specific examples and comparative examples, but the present embodiment is not limited in any way by the following examples and comparative examples.

[0325] Various physical properties in the examples and comparative examples were measured by the following methods.

[0326] (Weight average molecular weight (Mw) of rubber-like block copolymer, coupling rate, peak area of lowest molecular side)

[0327] The chromatogram was measured using a GPC measuring device in which three columns to which a polystyrene-based gel was added as a filler were connected, and the weight average molecular weight (Mw) of the rubbery block copolymer was calculated based on a calibration curve obtained using a standard polystyrene.

[0328] As the eluent, tetrahydrofuran (hereinafter also referred to as "THF") to which 5 mmol / L of triethylamine was added was used. As the column, as the guard column, a product manufactured by Tosoh Corporation under the trade name "TSKguard column Super H-H" was used, and as the column, products manufactured by Tosoh Corporation under the trade names "TSKgel Super H5000", "TSKgel Super H6000", and "TSKgel Super H7000" were used.

[0329] A differential refractive index (hereinafter also referred to as "RI") detector (product manufactured by Tosoh Corporation under the trade name "HLC8020") was used under conditions in which the oven temperature was 40°C and the THF flow rate was 0.6 mL / min. A sample for measurement of 10 mg was dissolved in 20 mL of THF to prepare a measurement solution, 20 μL of the measurement solution was injected into the GPC measuring device, and measurement was performed.

[0330] As for the coupling ratio of the rubbery block copolymer and the peak area of the lowest molecular side (the peak area of the peak of the smallest molecular weight), in the case where the chromatogram was bimodal or more (the number of peaks was two or more), the proportion of the peak area of the uncoupled (the peak of the lowest molecular side) to the peak area of the coupled (the peak of the high molecular weight side) was calculated. At this time, the peaks of less than 5 mass% in the GPC curve had little effect on the ease of mixing, and thus were not included in the number of peaks, and the coupling was not calculated.

[0331] (Molecular weight of the aromatic vinyl monomer block (polymer block (a)))

[0332] As the sample, a rubbery block copolymer before hydrogenation was used, and the polymer was decomposed by the method of Kolthoff (the method described in I. M. Kolthoff, et al., J. Polym. Sci. 1, 429 (1946)). The molecular weight of polystyrene that was not dissolved in methanol (weight average molecular weight of the styrene block) was measured by the same method as the weight average molecular weight of the rubbery block copolymer described above.

[0333] (Mooney viscosity of the rubbery block copolymer)

[0334] The Mooney viscosity of the rubbery block copolymer was measured using a Mooney viscometer (product manufactured by Shimazu Seisakusho Corporation under the trade name "VR1132") in accordance with ISO 289, using an L-shaped rotor.

[0335] The measurement temperature was set to 100°C.

[0336] First, the sample is preheated for 1 minute at the test temperature, and then the rotor is rotated at 2 rpm, and the torque after 4 minutes is measured as the Mooney viscosity (ML (1+4) ).

[0337] (Modification rate of rubbery block copolymer)

[0338] The modification rate of the rubbery block copolymer is measured by the column adsorption GPC method as follows. The measurement is performed using the property that the rubbery block copolymer modified with the functional group containing a nitrogen atom is adsorbed by the column.

[0339] For the sample solution containing the sample and a low molecular weight internal standard polystyrene, the adsorption amount on the silica-based column is measured from the difference between the chromatogram obtained by measurement using a polystyrene-based column and the chromatogram obtained by measurement using a silica-based column, and the modification rate of the rubbery block copolymer is calculated.

[0340] Specifically, the modification rate of the rubbery block copolymer is calculated as shown below.

[0341] Preparation of sample solution: 10 mg of the sample and 5 mg of the standard polystyrene are dissolved in 20 mL of THF as a sample solution.

[0342] THF to which 5 mmol / L of triethylamine is added is used as an eluent, 20 μL of the sample solution is injected into the apparatus, and the measurement is performed. As for the column, the guard column uses a product name "TSKguard column Super H-H" manufactured by Tosoh Corporation, and the column uses a product name "TSKgel Super H5000", "TSKgel Super H6000", "TSKgel Super H7000" manufactured by Tosoh Corporation. The measurement is performed using an RI detector (HLC8020 manufactured by Tosoh Corporation) under the conditions of a column oven temperature of 40°C and a THF flow rate of 0.6 mL / minute, and a chromatogram is obtained.

[0343] GPC measurement conditions using a silica-based column: A product name "HLC-8320 GPC" manufactured by Tosoh Corporation is used, THF is used as an eluent, 50 μL of the sample solution is injected into the apparatus, and a chromatogram is obtained using an RI detector under the conditions of a column oven temperature of 40°C and a THF flow rate of 0.5 mL / minute. As for the column, a product name "Zorbax PSM-1000S", "PSM-300S", "PSM-60S" is used in connection, and a product name "DIOL 4.6 x 12.5 mm 5 micron" as a guard column is connected to the front stage thereof.

[0344] Method for calculating the modification rate: In the chromatogram obtained using the polystyrene column, let the total peak area be 100, the peak area of the sample be Pl, and the peak area of the standard polystyrene be P2. In the chromatogram obtained using the silica column, let the total peak area be 100, the peak area of the sample be P3, and the peak area of the standard polystyrene be P4. The modification rate (%) is calculated by the following formula.

[0345] Modification rate (%) = [1 - (P2 x P3) / (Pl x P4)] x 100

[0346] (Where Pl + P2 = P3 + P4 = 100)

[0347] (Iodine value of the rubbery block copolymer)

[0348] The iodine value of the rubbery block copolymer was calculated according to the method described in "JIS K 0070: 1992".

[0349] (Bonded styrene amount (content of vinyl aromatic monomer unit), proportion of ethylene structure, α-olefin amount, content of conjugated diene structure, of the rubbery block copolymer)

[0350] As the sample, a rubbery block copolymer was used, and the bonded styrene amount, the proportion of ethylene structure, the α-olefin amount, and the proportion of conjugated diene structure were measured by 1 H-NMR measurement. 1 The conditions for H-NMR measurement are described below.

[0351] (Measurement conditions)

[0352] Measurement device: JNM-LA400 (manufactured by JEOL)

[0353] Solvent: deuterated chloroform

[0354] Sample for measurement: Rubbery block copolymer or polymer block

[0355] Sample concentration: 50 mg / mL

[0356] Observation frequency: 400 MHz

[0357] Chemical shift reference: TMS (tetramethylsilane)

[0358] Pulse delay: 2.904 seconds

[0359] Number of scans: 64

[0360] Pulse width: 45°

[0361] Measurement temperature: 26°C

[0362] (styrene block amount (ratio of vinyl aromatic monomer block) of rubbery block copolymer)

[0363] The proportion of the chain of 8 or more styrene structural units linked together as a styrene block was calculated as follows. From the 400 MHz H-NMR spectrum measured with deuterated chloroform as the solvent, the ratio of the integral values of each chemical shift range of the following (X) was calculated, and the content of the styrene block included in the rubbery block copolymer was calculated. 1 H-NMR spectrum, the ratio of the integral values of each chemical shift range of the following (X) was calculated, and the content of the styrene block included in the rubbery block copolymer was calculated.

[0364] (X) aromatic vinyl compound chain 8 or more: 6.00 ≦ S < 6.68

[0365] (ratio of the proportion of vinyl aromatic monomer block to the content of vinyl aromatic monomer unit)

[0366] The ratio (BS / TS) of the proportion of the vinyl aromatic monomer block (hereinafter referred to as "BS") and the content of the vinyl aromatic monomer unit (hereinafter referred to as "TS") determined as described above was calculated.

[0367] (water content)

[0368] The briquette molded body after 24 hours after molding was cut in half, and the rubbery block copolymer near the center was heated at 150°C for 8 minutes using a halogen moisture meter, and the water content in the briquette molded body was calculated from the mass decrease amount.

[0369] Water content (mass %) = mass decrease amount of rubbery block copolymer before and after heating / mass of rubbery block copolymer before heating x 100

[0370] (residual solvent content)

[0371] The residual solvent content in the briquette molded body was analyzed using a headspace analysis system. The analysis device used a headspace sampler (manufactured by Agilent Technologies, "G1888") and a gas chromatograph ("6890N" manufactured by Agilent Technologies). The briquette molded body after 24 hours after molding was cut in half, and 0.1 g of the rubbery block copolymer near the center was sealed in a 20 mL headspace bottle, heated at 150°C for 30 minutes using a headspace sampler, and 1 mL of the gas phase portion after heating was injected into a gas chromatograph (GC). Using a calibration curve for hexane concentration prepared in advance, the amount of each volatile component was calculated by hexane conversion.

[0372] (cold flow resistance)

[0373] Regarding the cold flow resistance of the briquette molded body, a load of 5 kg was applied at an external temperature of 25°C and a humidity of 50%, and the change rate (%) of the thickness (H60) after 72 hours was calculated using the following formula.

[0374] Thickness change rate (%) = (H0 - H60) × 100 / H0

[0375] H0 represents the thickness of the pressed block after it has just been formed.

[0376] The smaller the rate of change of thickness (index), the less cold flow there is in the stored rubber block, and the better its processability.

[0377] If the index is less than 10, it is marked with ◎; if it is 10 or more but less than 20, it is marked with 〇; if it is 20 or more but less than 40, it is marked with △; and if it is 40 or more, it is marked with ×.

[0378] In practical applications, a value less than 40 is sufficient, and less than 20 is preferred.

[0379] (Preparation of hydrogenation catalyst)

[0380] In the examples and comparative examples described later, the hydrogenation catalyst used in the preparation of the rubber-like block copolymer was prepared by the following method.

[0381] (Manufacturing Example 1)

[0382] One liter of dried and purified cyclohexane was added to a reaction vessel that had been purged with nitrogen, along with 100 mmol of bis(n5-cyclopentadiene)titanium dichloride. While stirring thoroughly, a solution of n-hexane containing 200 mmol of trimethylaluminum was added. The reaction was carried out at room temperature for about 3 days to obtain the hydrogenation catalyst (TC-1).

[0383] (Polymerization of rubber-like block copolymers)

[0384] (Polymerization Example 1) Rubber-like block copolymer (polymer 1)

[0385] A 40L autoclave equipped with a stirrer and jacket, and capable of temperature control, was used as the reactor. 3216g of 1,3-butadiene, 1084g of styrene, 25800g of cyclohexane (pre-removed impurities), and 3.10g of tetrahydrofuran (THF), a polar substance, were added to the reactor, and the reactor temperature was maintained at 45°C. 4.10g of n-butyllithium, acting as a polymerization initiator, was then supplied to the reactor to initiate the polymerization reaction.

[0386] After the polymerization reaction begins, the temperature inside the reactor starts to rise due to the exothermic effect of polymerization, eventually reaching 85°C.

[0387] After the monomer conversion rate in the reactor reached 99%, 2.05 g of methanol was added to the polymer solution as a reaction terminator, and a portion of the rubbery block copolymer solution before hydrogenation was drawn out for analysis, and desolventized with a drier to obtain the rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0388] Thereafter, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added to the rubbery block copolymer solution before hydrogenation, based on 100 parts by mass of the rubbery block copolymer before hydrogenation, and a hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain a rubbery block copolymer (Polymer 1). The iodine value of the obtained rubbery block copolymer (Polymer 1) was 40.

[0389] To the solution of the obtained rubbery block copolymer (Polymer 1), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and drying treatment was performed. The results of the analysis of the rubbery block copolymer (Polymer 1) are shown in Table 1. The proportions of the polymer block (a) and the polymer block (b) and the proportions of the respective components (mass%) were calculated from the proportions (mass%) of the respective components of the rubbery block copolymer and the amount of the styrene block of the rubbery block copolymer.

[0390] In addition, at least one block at the molecular terminal of the rubbery block copolymer (Polymer 1) was the following block II.

[0391] Block II: a block having a content of 80 mass% or less of a vinyl aromatic monomer unit and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0392] (Rubbery Block Copolymer (Polymer 2))

[0393] Using the same method as in Polymerization Example 1, after the start of the polymerization reaction, after the monomer conversion rate in the reactor reached 99%, 4.4 g of dimethyl dimethoxy silane was added to the polymer solution, and a coupling reaction was performed for 20 minutes. To the polymer solution, 0.8 g of methanol was added as a reaction terminator, and a portion of the rubbery block copolymer solution before hydrogenation was drawn out for analysis, and desolventized with a drier to obtain the rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0394] Thereafter, to the rubbery block copolymer solution before hydrogenation, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added relative to 100 parts by mass of the rubbery block copolymer before hydrogenation on a Ti basis, and a hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain a rubbery block copolymer (Polymer 2). The iodine value of the obtained rubbery block copolymer (Polymer 2) was 48.

[0395] To the solution of the obtained rubbery block copolymer (Polymer 2), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and drying treatment was performed. The results of the analysis of the rubbery block copolymer (Polymer 2) are shown in Table 1. The proportions of the polymer block (a) and the polymer block (b) and the proportions of the respective components (mass %) were calculated from the proportions (mass %) of the respective components of the rubbery block copolymer and the styrene block amount of the rubbery block copolymer.

[0396] In addition, at least one block of the molecular terminal of the rubbery block copolymer (Polymer 2) is the following block II.

[0397] Block II: a block in which the content of the vinyl aromatic monomer unit is 80 mass % or less and which contains a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0398] (Rubbery Block Copolymer (Polymer 3))

[0399] Using the same method as in Polymerization Example 1, after the monomer conversion rate in the reactor reached 99% after the start of the polymerization reaction, 11.2 g of 3-(4-methylpiperazin-1-yl)propyltriethoxysilane was added to the polymer solution, and a coupling reaction was performed for 20 minutes. To the polymer solution, 0.8 g of methanol was added as a reaction terminator, and a portion of the rubbery block copolymer solution before hydrogenation was withdrawn for analysis, and the solvent was removed with a drying machine to obtain a rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0400] Thereafter, to the rubbery block copolymer solution before hydrogenation, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added relative to 100 parts by mass of the rubbery block copolymer before hydrogenation on a Ti basis, and a hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain a rubbery block copolymer (Polymer 2). The iodine value of the obtained rubbery block copolymer (Polymer 2) was 48.

[0401] To the obtained solution of the rubbery block copolymer (polymer 3), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol as antioxidants were added, and a drying treatment was performed. The results of the analysis of the rubbery block copolymer (polymer 3) are shown in Table 1. The proportions of the polymer block (a) and the polymer block (b) and the proportions of the components (mass %) were calculated from the proportions (mass %) of the respective components of the rubbery block copolymer, and the amount of the styrene block of the rubbery block copolymer. The rubbery block copolymer (polymer 3) contained a nitrogen atom.

[0402] In addition, at least one block of the molecular terminal of the rubbery block copolymer (polymer 3) is the following block II.

[0403] Block II: a block containing 80 mass % or less of a vinyl aromatic monomer unit, and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0404] (Rubbery block copolymer (polymer 4))

[0405] A high-pressure vessel having a content volume of 40 L, provided with a stirrer and a jacket, and capable of temperature control was used as a reactor, and 2330 g of 1,3-butadiene, 1694 g of styrene, 25800 g of cyclohexane, 3.10 g of tetrahydrofuran (THF) as a polar substance, and 2.41 g of 2,2-bis(2-tetrahydrofuryl)propane were added to the reactor, and the temperature inside the reactor was maintained at 35°C. Further, 2.42 g of n-butyllithium as a polymerization initiator was supplied to the above reactor, and the polymerization reaction was initiated.

[0406] After the initiation of the polymerization reaction, the temperature inside the reactor started to rise due to the exothermic heat generated by the polymerization, and after the monomer conversion rate in the reactor reached 99%, 276 g of styrene was added after 5 minutes, and the reaction was further performed.

[0407] The temperature inside the reactor reached 82°C. After reaching this reaction temperature peak, 1.21 g of methanol as a reaction terminator was added after 2 minutes, and a part of the solution of the rubbery block copolymer before hydrogenation was extracted for analysis, and was desolvated with a drying machine to obtain the rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0408] Thereafter, to the rubbery block copolymer solution before hydrogenation, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added based on 100 parts by mass of the rubbery block copolymer before hydrogenation, and a hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 60 minutes to obtain a rubbery block copolymer (Polymer 4). The iodine value of the obtained rubbery block copolymer (Polymer 4) was 16.

[0409] To the solution of the obtained rubbery block copolymer (Polymer 4), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and drying treatment was performed. The results of the analysis of the rubbery block copolymer (Polymer 4) are shown in Table 1. The proportions of the polymer block (a) and the polymer block (b) and the proportions of the respective components (mass %) were calculated from the proportions (mass %) of the respective components of the rubbery block copolymer and the styrene block amount of the rubbery block copolymer.

[0410] In addition, at least one block at the molecular terminal of the rubbery block copolymer (Polymer 4) was the following block II.

[0411] Block II: a block having a content of 80 mass % or less of a vinyl aromatic monomer unit and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0412] (Rubbery Block Copolymer (Polymer 5))

[0413] To the polymer solution, 4.68 g of n-butyllithium was added as a polymerization initiator, 4.67 g of 2,2-bis(2-tetrahydrofuryl)propane was added as a polar substance, and otherwise, the same method as in Polymerization Example 4 was used, and the monomers were added similarly after the start of the polymerization reaction. After the monomer conversion rate in the reactor reached 99%, 8.3 g of 3-(4-methylpiperazin-1-yl)propyltriethoxysilane was added to the polymer solution, and a coupling reaction was performed for 20 minutes. To the polymer solution, 0.6 g of methanol was added as a reaction terminator, and a part of the rubbery block copolymer solution before hydrogenation was drawn out, desolvated with a drier, and a rubbery block copolymer before hydrogenation was obtained. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0414] Thereafter, to the rubbery block copolymer solution before hydrogenation, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added based on 100 parts by mass of the rubbery block copolymer before hydrogenation, and hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 60 minutes to obtain a rubbery block copolymer (Polymer 5). The iodine value of the obtained rubbery block copolymer (Polymer 5) was 20.

[0415] To the solution of the obtained rubbery block copolymer (Polymer 5), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and drying treatment was performed. The results of the analysis of the rubbery block copolymer (Polymer 5) are shown in Table 1. The proportions of the polymer block (a) and the polymer block (b) and the proportions of the respective components (mass%) were calculated from the proportions (mass%) of the respective components of the rubbery block copolymer and the styrene block amount of the rubbery block copolymer. The rubbery block copolymer (Polymer 5) contained nitrogen atoms.

[0416] In addition, at least one block at the molecular terminal of the rubbery block copolymer (Polymer 5) was the following block II.

[0417] Block II: a block having a content of 80 mass% or less of a vinyl aromatic monomer unit and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0418] (Rubbery block copolymer (Polymer 6))

[0419] A high-pressure vessel having a content volume of 40 L, a stirrer, and a jacket capable of temperature control was used as a reactor, and 3880 g of 1,3-butadiene, 420 g of styrene, 25800 g of cyclohexane, and 3.10 g of tetrahydrofuran (THF) as a polar substance, from which impurities had been previously removed, were charged into the reactor, and the temperature inside the reactor was maintained at 45°C. Further, 4.89 g of n-butyllithium as a polymerization initiator was supplied to the above reactor, and the polymerization reaction was initiated.

[0420] After the start of the polymerization reaction, after the monomer conversion rate in the reactor reached 99%, 2.44 g of methanol as a reaction terminator was added to the polymer solution, and a part of the rubbery block copolymer solution before hydrogenation was drawn out, and solvent was removed by a drier to obtain a rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0421] Thereafter, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added to the rubbery block copolymer solution before hydrogenation, based on 100 parts by mass of the rubbery block copolymer before hydrogenation, and a hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes, to obtain a rubbery block copolymer (Polymer 6). The iodine value of the obtained rubbery block copolymer (Polymer 6) was 106.

[0422] To the solution of the obtained rubbery block copolymer (Polymer 6), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and drying treatment was performed. The results of the analysis of the rubbery block copolymer (Polymer 6) are shown in Table 1. The proportions of the polymer block (a) and the polymer block (b) were calculated from the proportions (mass%) of the respective components of the rubbery block copolymer, and the amount of the styrene block of the rubbery block copolymer.

[0423] In addition, at least one block at the molecular terminal of the rubbery block copolymer (Polymer 6) was the following block II.

[0424] Block II: a block having a content of 80% by mass or less of a vinyl aromatic monomer unit, and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0425] (Rubbery block copolymer (Polymer 7))

[0426] A high-pressure vessel having a content volume of 40 L, a stirrer, and a jacket, which can be temperature-controlled, was used as a reactor, and 2477 g of 1,3-butadiene, 1823 g of styrene, 25800 g of cyclohexane, and 3.10 g of tetrahydrofuran (THF) as a polar substance, from which impurities had been previously removed, were added to the reactor, and the temperature inside the reactor was maintained at 45°C. Further, 3.33 g of n-butyllithium as a polymerization initiator was supplied to the above reactor, and the polymerization reaction was initiated.

[0427] After the start of the polymerization reaction, after the monomer conversion rate in the reactor reached 99%, 1.66 g of methanol as a reaction terminator was added to the polymer solution, and a part of the rubbery block copolymer solution before hydrogenation was extracted, and the solvent was removed with a drier, to obtain a rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0428] After that, to the solution of the rubbery block copolymer before hydrogenation, the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added at 70 ppm based on Ti with respect to 100 parts by mass of the rubbery block copolymer before hydrogenation, and hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain a rubbery block copolymer (Polymer 7). The iodine value of the obtained rubbery block copolymer (Polymer 7) was 46.

[0429] To the solution of the obtained rubbery block copolymer (Polymer 7), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and drying treatment was performed. The results of the analysis of the rubbery block copolymer (Polymer 7) are shown in Table 1. The proportions of the polymer block (a) and the polymer block (b) and the proportions of the respective components (mass%) were calculated from the proportions (mass%) of the respective components of the rubbery block copolymer and the styrene block amount of the rubbery block copolymer.

[0430] In addition, at least one block at the molecular terminal of the rubbery block copolymer (Polymer 7) was the following block II.

[0431] Block II: a block having a content of 80 mass% or less of a vinyl aromatic monomer unit and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0432] (Rubbery Block Copolymer (Polymer 8))

[0433] Using the same method as in Polymerization Example 1, after the monomer conversion rate in the reactor reached 99% after the start of the polymerization reaction, 2.05 g of methanol was added as a reaction terminator to the polymer solution, and a part of the solution of the rubbery block copolymer before hydrogenation was withdrawn for analysis, and the solvent was removed with a drier to obtain the rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0434] After that, to the solution of the rubbery block copolymer before hydrogenation, the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added at 70 ppm based on Ti with respect to 100 parts by mass of the rubbery block copolymer before hydrogenation, and hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain a rubbery block copolymer (Polymer 7). The iodine value of the obtained rubbery block copolymer (Polymer 7) was 46.

[0435] To the obtained solution of the rubbery block copolymer (polymer 8), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and a drying treatment was performed. The results of the analysis of the rubbery block copolymer (polymer 8) are shown in Table 1.

[0436] The proportions of the polymer block (a) and the polymer block (b), and the proportions of the components (mass %) were calculated from the proportions (mass %) of the respective components of the rubbery block copolymer, and the styrene block amount of the rubbery block copolymer.

[0437] In addition, at least one block of the molecular terminal of the rubbery block copolymer (polymer 8) is the following block II.

[0438] Block II: a block having a content of 80 mass % or less of a vinyl aromatic monomer unit, and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0439] (Rubbery block copolymer (polymer 9))

[0440] In addition to further adding 6.91 g of 2,2-bis(2-tetrahydrofuryl)propane as a polar substance, using the same method as in Polymerization Example 1, after the monomer conversion rate in the reactor reached 99% after the start of the polymerization reaction, 2.05 g of methanol was added as a reaction terminator to the polymer solution, a part of the rubbery block copolymer solution before hydrogenation was withdrawn for analysis, and the solvent was removed with a drier to obtain a rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0441] Thereafter, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added to 100 parts by mass of the rubbery block copolymer before hydrogenation with respect to Ti as a hydrogenation catalyst, and a hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 30 minutes to obtain a rubbery block copolymer (polymer 9). The iodine value of the obtained rubbery block copolymer (polymer 9) was 172.

[0442] To the obtained solution of the rubbery block copolymer (polymer 9), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and drying treatment was performed. The results of the analysis of the rubbery block copolymer (polymer 9) are shown in Table 1. The proportions of the polymer block (a) and the polymer block (b) and the proportions (mass%) of the respective components were calculated from the proportions (mass%) of the respective components of the rubbery block copolymer and the amount of the styrene block of the rubbery block copolymer.

[0443] In addition, at least one block of the molecular terminal of the rubbery block copolymer (polymer 9) is the following block II.

[0444] Block II: a block having a content of 80 mass% or less of a vinyl aromatic monomer unit and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an a-olefin structure.

[0445] (Rubbery block copolymer (polymer 10))

[0446] The same method as in Polymerization Example 1 was used, except that the amount of n-butyllithium as the polymerization initiator was made 1.68 g, and after the start of the polymerization reaction, after the monomer conversion rate in the reactor reached 99%, 0.84 g of methanol as a reaction terminator was added to the polymer solution, and a part of the solution of the rubbery block copolymer before hydrogenation was drawn off for analysis, and the solvent was removed with a drier to obtain the rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0447] Thereafter, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added to 100 parts by mass of the rubbery block copolymer before hydrogenation, with respect to Ti, and hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 30 minutes to obtain the rubbery block copolymer (polymer 10). The iodine value of the obtained rubbery block copolymer (polymer 10) was 197.

[0448] To the obtained solution of the rubbery block copolymer (polymer 10), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and drying treatment was performed. The results of the analysis of the rubbery block copolymer (polymer 10) are shown in Table 1. The proportions of the polymer block (a) and the polymer block (b) and the proportions (mass%) of the respective components were calculated from the proportions (mass%) of the respective components of the rubbery block copolymer and the amount of the styrene block of the rubbery block copolymer.

[0449] In addition, at least one block of the molecular terminal of the rubbery block copolymer (polymer 10) is the following block II.

[0450] Block II: a block having a content of 80 mass% or less of a vinyl aromatic monomer unit and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an a-olefin structure.

[0451] (Rubbery block copolymer (polymer 11))

[0452] A high-pressure vessel having a content of 40 L, a stirrer, and a jacket, which can be temperature-controlled, was used as a reactor, and 3655 g of 1,3-butadiene, 25800 g of cyclohexane, and 3.10 g of tetrahydrofuran (THF) as a polar substance, from which impurities had been previously removed, were added to the reactor, and the temperature inside the reactor was maintained at 35°C. Further, 3.66 g of n-butyllithium as a polymerization initiator was supplied to the above reactor, and the polymerization reaction was initiated.

[0453] After the initiation of the polymerization reaction, the temperature inside the reactor started to rise due to the exothermic heat generated by the polymerization, and after the monomer conversion rate in the reactor reached 99%, 645 g of styrene was added after 5 minutes, and the reaction was further performed.

[0454] The temperature inside the reactor reached 80°C. After reaching the peak of the reaction temperature, 1.83 g of methanol as a reaction terminator was added after 2 minutes, and a part of the rubbery block copolymer solution before hydrogenation was extracted and desolvated with a drier to obtain the rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0455] Thereafter, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added to the rubbery block copolymer solution before hydrogenation, based on 100 parts by mass of the rubbery block copolymer before hydrogenation, with reference to Ti, and a hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain the rubbery block copolymer (polymer 11). The iodine value of the obtained rubbery block copolymer (polymer 11) was 128.

[0456] To the obtained solution of the rubbery block copolymer (polymer 11), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and a drying treatment was performed. The results of the analysis of the rubbery block copolymer (polymer 11) are shown in Table 2. The proportions of the polymer block (a) and the polymer block (b) were calculated from the proportions (mass%) of the respective components of the rubbery block copolymer, the amount of the styrene block of the rubbery block copolymer.

[0457] In addition, at least one block at the molecular terminal of the rubbery block copolymer (polymer 11) is the following block I.

[0458] Block I: a block containing an ethylene structure, a conjugated diene structure, and an α-olefin structure

[0459] (Rubbery block copolymer (polymer 12))

[0460] A high-pressure vessel having a content volume of 40 L, a stirrer, and a jacket capable of temperature control was used as a reactor, and 3225 g of 1,3-butadiene from which impurities had been removed in advance, 25800 g of cyclohexane, and 3.10 g of tetrahydrofuran (THF) as a polar substance were charged into the reactor, and the temperature inside the reactor was maintained at 35°C. Further, 3.15 g of n-butyllithium as a polymerization initiator was supplied to the reactor, and the polymerization was initiated.

[0461] After the initiation of the polymerization, the temperature inside the reactor started to rise due to the heat of polymerization, and after the monomer conversion in the reactor reached 99%, 1075 g of styrene was added after 5 minutes, and the reaction was further performed.

[0462] The temperature inside the reactor reached 80°C. After reaching the peak of the reaction temperature, 1.57 g of methanol as a reaction terminator was added after 2 minutes, and a part of the solution of the rubbery block copolymer before hydrogenation was taken out, and the solvent was removed by a drier to obtain the rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0463] Thereafter, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added to the solution of the rubbery block copolymer before hydrogenation, based on 100 parts by mass of the rubbery block copolymer before hydrogenation, and the hydrogenation was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain the rubbery block copolymer (polymer 12). The iodine value of the obtained rubbery block copolymer (polymer 12) was 113.

[0464] To the obtained solution of the rubbery block copolymer (polymer 12), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and a drying treatment was performed. The results of the analysis of the rubbery block copolymer (polymer 12) are shown in Table 2. The proportions of the polymer block (a) and the polymer block (b) were calculated from the proportions (mass %) of the respective components of the rubbery block copolymer, the amount of the styrene block of the rubbery block copolymer.

[0465] In addition, at least one block of the molecular terminal of the rubbery block copolymer (polymer 12) is the following block I.

[0466] Block I: a block containing an ethylene structure, a conjugated diene structure, and an α-olefin structure

[0467] (Rubbery block copolymer (polymer 13))

[0468] A high-pressure vessel having a content volume of 40 L, a stirrer, and a jacket capable of temperature control was used as a reactor, and 3677 g of 1,3-butadiene, 366 g of styrene, 25800 g of cyclohexane, 3.10 g of tetrahydrofuran (THF) as a polar substance, and 3.29 g of 2,2-bis(2-tetrahydrofuryl)propane were added to the reactor, and the temperature inside the reactor was maintained at 35°C. Further, 1.58 g of n-butyllithium as a polymerization initiator was supplied to the reactor, and the polymerization was initiated.

[0469] After the initiation of the polymerization, the temperature inside the reactor started to rise due to the heat of polymerization, and after the monomer conversion in the reactor reached 99%, 258 g of styrene was added after 5 minutes, and the reaction was further performed.

[0470] The temperature inside the reactor reached 85°C. After reaching this reaction temperature peak, 0.79 g of methanol as a reaction terminator was added after 2 minutes, and a part of the solution of the rubbery block copolymer before hydrogenation was taken out for analysis, and the solvent was removed by a drier to obtain the rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0471] Thereafter, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added to the solution of the rubbery block copolymer before hydrogenation, based on 100 parts by mass of the rubbery block copolymer before hydrogenation, with respect to Ti, and a hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain the rubbery block copolymer (polymer 13). The iodine value of the obtained rubbery block copolymer (polymer 13) was 94.

[0472] 12.6 g of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants to the solution of the obtained rubbery block copolymer (polymer 13), and the mixture was dried. The results of the analysis of the rubbery block copolymer (polymer 13) are shown in Table 2. The proportions of polymer blocks (a) and (b) and the proportions of each component (mass%) were calculated based on the proportions (mass%) of each component of the rubbery block copolymer and the amount of styrene blocks in the rubbery block copolymer.

[0473] In addition, at least one block at the molecular end of the rubbery block copolymer (polymer 13) is block II as described below.

[0474] Block II: A block containing less than 80% by mass of vinyl aromatic monomer units and including vinyl aromatic monomer units, ethylene structures, conjugated diene structures and α-olefin structures.

[0475] (Polymerization Example 14) Rubber-like block copolymer (Polymer 14)

[0476] Except for using 5.54 g of 2,2-bis(2-tetrahydrofuranyl)propane, polymerization was initiated using the same method as in polymerization example 13. After the polymerization reaction started, the temperature inside the reactor began to rise due to the exothermic effect of polymerization. After the monomer conversion rate in the reactor reached 99%, 258 g of styrene was added after 5 minutes to further carry out the reaction.

[0477] The final temperature inside the reactor reached 87°C. After reaching this peak reaction temperature, 0.79 g of methanol was added as a reaction terminator after 2 minutes. A portion of the unhydrogenated rubbery block copolymer solution was extracted for analysis, and the solvent was removed using a dryer to obtain the unhydrogenated rubbery block copolymer. The molecular weight of the aromatic vinyl monomer (styrene) block was determined using the above method.

[0478] Subsequently, a hydrogenation catalyst (TC-1) prepared in Manufacturing Example 1, comprising 70 ppm (based on Ti) of 100 parts by mass of the rubbery block copolymer before hydrogenation, was added to the solution of the rubbery block copolymer before hydrogenation. The hydrogenation reaction was carried out for 50 minutes at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C to obtain the rubbery block copolymer (polymer 14). The obtained rubbery block copolymer (polymer 14) had an iodine value of 95.

[0479] 12.6 g of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants to the solution of the obtained rubbery block copolymer (polymer 14), and the mixture was dried. The results of the analysis of the rubbery block copolymer (polymer 14) are shown in Table 2. The proportions of polymer blocks (a) and (b) and the proportions of each component (mass%) were calculated based on the proportions (mass%) of each component of the rubbery block copolymer and the amount of styrene blocks in the rubbery block copolymer.

[0480] In addition, at least one block at the molecular end of the rubbery block copolymer (polymer 14) is block II as described below.

[0481] Block II: A block containing less than 80% by mass of vinyl aromatic monomer units and including vinyl aromatic monomer units, ethylene structures, conjugated diene structures and α-olefin structures.

[0482] (Polymerization Example 15) Rubber-like block copolymer (Polymer 15)

[0483] Except for using 8.89 g of 2,2-bis(2-tetrahydrofuranyl)propane, polymerization was initiated using the same method as in polymerization example 13. After the polymerization reaction started, the temperature inside the reactor began to rise due to the exothermic effect of polymerization. After the monomer conversion rate in the reactor reached 99%, 258 g of styrene was added after 5 minutes to further carry out the reaction.

[0484] The final temperature inside the reactor reached 88°C. After reaching this peak reaction temperature, 0.79 g of methanol was added as a reaction terminator after 2 minutes. A portion of the unhydrogenated rubbery block copolymer solution was extracted for analysis, and the solvent was removed using a dryer to obtain the unhydrogenated rubbery block copolymer. The molecular weight of the aromatic vinyl monomer (styrene) block was determined using the above method.

[0485] Subsequently, a hydrogenation catalyst (TC-1) prepared in Manufacturing Example 1, comprising 70 ppm (based on Ti) of 100 parts by mass of the rubbery block copolymer before hydrogenation, was added to the solution of the rubbery block copolymer before hydrogenation. The hydrogenation reaction was carried out for 50 minutes at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C to obtain a rubbery block copolymer (polymer 15). The obtained rubbery block copolymer (polymer 14) had an iodine value of 97.

[0486] To the obtained solution of the rubbery block copolymer (polymer 15), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and a drying treatment was performed. The results of the analysis of the rubbery block copolymer (polymer 15) are shown in Table 2. The proportions of the polymer block (a) and the polymer block (b) were calculated from the proportions (mass%) of the respective components of the rubbery block copolymer, the amount of the styrene block of the rubbery block copolymer, and the proportions (mass%) of the respective components.

[0487] In addition, at least one block at the molecular terminal of the rubbery block copolymer (polymer 15) is the following block II.

[0488] Block II: a block having a content of 80 mass% or less of a vinyl aromatic monomer unit and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0489] (Rubbery block copolymer (polymer 16))

[0490] A high-pressure vessel having a content volume of 40 L, a stirrer, and a jacket capable of temperature control was used as a reactor, and 3818 g of 1,3-butadiene, 353 g of styrene, 25800 g of cyclohexane, 3.10 g of tetrahydrofuran (THF) as a polar substance, and 3.29 g of 2,2-bis(2-tetrahydrofuryl)propane were added to the reactor, and the temperature inside the reactor was maintained at 35°C. Further, 1.58 g of n-butyllithium as a polymerization initiator was supplied to the above reactor, and the polymerization reaction was initiated.

[0491] After the initiation of the polymerization reaction, the temperature inside the reactor started to rise due to the heat of polymerization, and after the monomer conversion rate in the reactor reached 99%, 129 g of styrene was added after 5 minutes, and the reaction was further performed.

[0492] The temperature inside the reactor reached 83°C. After reaching this reaction temperature peak, 0.79 g of methanol as a reaction terminator was added after 2 minutes, and a part of the solution of the rubbery block copolymer before hydrogenation was extracted and desolvated with a drier to obtain the rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0493] After that, to the solution of the rubbery block copolymer before hydrogenation, the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added at 70 ppm based on Ti with respect to 100 parts by mass of the rubbery block copolymer before hydrogenation, and hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain a rubbery block copolymer (Polymer 16). The iodine value of the obtained rubbery block copolymer (Polymer 16) was 97.

[0494] To the solution of the obtained rubbery block copolymer (Polymer 16), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and drying treatment was performed. The results of the analysis of the rubbery block copolymer (Polymer 16) are shown in Table 2. The proportions of the polymer block (a) and the polymer block (b) and the proportions of the respective components (mass%) were calculated from the proportions (mass%) of the respective components of the rubbery block copolymer and the amount of the styrene block of the rubbery block copolymer.

[0495] In addition, at least one block of the molecular terminal of the rubbery block copolymer (Polymer 16) was the following block II.

[0496] Block II: a block containing 80 mass% or less of a vinyl aromatic monomer unit and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0497] (Rubbery block copolymer (Polymer 17))

[0498] The polymerization was started in the same manner as in Polymerization Example 16, and 129 g of styrene was added in the same manner, and the reaction was further performed. After reaching the peak of the reaction temperature, 2.16 g of 1,3-dimethyl-2-imidazolidinone was added after 2 minutes, and modification reaction was performed for 20 minutes. To the polymer solution, 0.79 g of methanol was added as a reaction terminator, and a part of the solution of the rubbery block copolymer before hydrogenation was extracted, and solvent was removed by a drier to obtain a rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0499] After that, to the solution of the rubbery block copolymer before hydrogenation, the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added at 70 ppm based on Ti with respect to 100 parts by mass of the rubbery block copolymer before hydrogenation, and hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain a rubbery block copolymer (Polymer 16). The iodine value of the obtained rubbery block copolymer (Polymer 16) was 97.

[0500] To the obtained solution of the rubbery block copolymer (polymer 17), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and a drying treatment was performed. The results of the analysis of the rubbery block copolymer (polymer 17) are shown in Table 2. The proportions of the polymer block (a) and the polymer block (b) were calculated from the proportions (mass%) of the respective components of the rubbery block copolymer, the amount of the styrene block of the rubbery block copolymer, and the proportions (mass%) of the respective components.

[0501] In addition, at least one block of the molecular terminal of the rubbery block copolymer (polymer 17) is the following block II.

[0502] Block II: a block having a content of 80 mass% or less of a vinyl aromatic monomer unit and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an a-olefin structure.

[0503] (Rubbery block copolymer (polymer 18))

[0504] The polymerization was started in the same manner as in Polymerization Example 13, and 258 g of styrene was added in the same manner, and the reaction was further performed. After reaching the peak of the reaction temperature, 1,3-dimethyl-2-imidazolidinone 1.40 g was added after 2 minutes, and a modification reaction was performed for 20 minutes. To the polymer solution, methanol 0.79 g was added as a reaction terminator, and a part of the solution of the rubbery block copolymer before hydrogenation was taken out for analysis, and was desolvated with a drier to obtain the rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0505] Thereafter, to the solution of the rubbery block copolymer before hydrogenation, the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added at 70 ppm based on Ti with respect to 100 parts by mass of the rubbery block copolymer before hydrogenation, and a hydrogenation reaction was performed for 50 minutes at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C to obtain a rubbery block copolymer (polymer 18). The iodine value of the obtained rubbery block copolymer (polymer 18) was 94.

[0506] To the obtained solution of the rubbery block copolymer (polymer 18), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid n-octadecyl ester 12.6 g and 4,6-bis(octylthiomethyl)-o-cresol 3.0 g as an antioxidant were added, and drying treatment was performed. The results of the analysis performed on the rubbery block copolymer (polymer 18) are shown in Table 2. The proportions of the polymer block (a) and the polymer block (b), and the proportions of the components (mass %) were calculated from the proportions of the components (mass %) of the rubbery block copolymer and the amount of the styrene block of the rubbery block copolymer.

[0507] In addition, at least one block of the molecular terminal of the rubbery block copolymer (polymer 18) is the following block II.

[0508] Block II: a block having a content of 80 mass % or less of a vinyl aromatic monomer unit and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an a-olefin structure.

[0509] (Rubbery block copolymer (polymer 19))

[0510] The amount of the addition of 1,3-dimethyl-2-imidazolidinone was changed to 2.11 g, and otherwise the same as in Polymerization Example 18 to obtain a polymer solution. To the polymer solution, methanol 0.79 g as a reaction terminator was added, and a part of the solution of the rubbery block copolymer before hydrogenation was taken out for analysis, and was desolvated with a drier to obtain the rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0511] Thereafter, to the solution of the rubbery block copolymer before hydrogenation, the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added at 70 ppm based on Ti with respect to 100 parts by mass of the rubbery block copolymer before hydrogenation, and hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain a rubbery block copolymer (polymer 19). The iodine value of the obtained rubbery block copolymer (polymer 18) was 94.

[0512] To the obtained solution of the rubbery block copolymer (polymer 19), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid n-octadecyl ester 12.6 g and 4,6-bis(octylthiomethyl)-o-cresol 3.0 g as an antioxidant were added, and drying treatment was performed. The results of the analysis performed on the rubbery block copolymer (polymer 19) are shown in Table 2. The proportions of the polymer block (a) and the polymer block (b), and the proportions of the components (mass %) were calculated from the proportions of the components (mass %) of the rubbery block copolymer and the amount of the styrene block of the rubbery block copolymer.

[0513] In addition, at least one block at the molecular terminal of the rubbery block copolymer (polymer 19) is the following block II.

[0514] Block II: a block having a content of 80 mass% or less of a vinyl aromatic monomer unit and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0515] (Rubbery block copolymer (polymer 20))

[0516] A high-pressure vessel having a content of 40 L, a stirrer, and a jacket capable of temperature control was used as a reactor, and 3677 g of 1,3-butadiene, 366 g of styrene, 25800 g of cyclohexane, 3.10 g of tetrahydrofuran (THF) as a polar substance, 3.29 g of 2,2-bis(2-tetrahydrofuryl)propane as a modifier of the polymerization initiation terminal, and 1.68 g of piperidine as a polymerization initiator were added to the reactor, and the temperature inside the reactor was maintained at 35°C. Further, 1.58 g of n-butyllithium as a polymerization initiator was supplied to the above reactor, and the polymerization reaction was initiated.

[0517] After the start of the polymerization reaction, the temperature inside the reactor started to rise due to the heat of polymerization, and after the monomer conversion rate in the reactor reached 99%, 258 g of styrene was added after 5 minutes, and the reaction was further carried out.

[0518] The temperature inside the reactor reached 85°C. After reaching the peak of the reaction temperature, 0.79 g of methanol as a reaction terminator was added after 2 minutes, and a part of the rubbery block copolymer solution before hydrogenation was extracted for analysis, and the solvent was removed with a drier to obtain the rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0519] Thereafter, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 with respect to 100 parts by mass of the rubbery block copolymer before hydrogenation based on Ti was added to the rubbery block copolymer solution before hydrogenation, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain a rubbery block copolymer (polymer 20). The iodine value of the obtained rubbery block copolymer (polymer 20) was 92.

[0520] To the obtained solution of the rubbery block copolymer (polymer 20), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and drying treatment was performed. The results of the analysis of the rubbery block copolymer (polymer 20) are shown in Table 2. The proportions of the polymer block (a) and the polymer block (b), and the proportions of the components (mass %) were calculated from the proportions of the components (mass %) of the rubbery block copolymer, and the amount of the styrene block of the rubbery block copolymer.

[0521] In addition, at least one block at the molecular terminal of the rubbery block copolymer (polymer 20) is the following block II.

[0522] Block II: a block having a content of 80 mass% or less of a vinyl aromatic monomer unit, and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0523] (Rubbery block copolymer (polymer 21))

[0524] Using the same method as in Polymerization Example 1, after the monomer conversion rate in the reactor reached 99% after the start of the polymerization reaction, 2.05 g of methanol was added to the polymer solution as a reaction terminator, and a rubbery block copolymer (polymer 21) before hydrogenation was obtained.

[0525] To the obtained solution of the rubbery block copolymer (polymer 21), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and drying treatment was performed. The iodine value of the obtained rubbery block copolymer (polymer 21) was 352. In addition, the molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method. The results of the analysis of the rubbery block copolymer (polymer 21) are shown in Table 3. The proportions of the polymer block (a) and the polymer block (b), and the proportions of the components (mass %) were calculated from the proportions of the components (mass %) of the rubbery block copolymer, and the amount of the styrene block of the rubbery block copolymer.

[0526] In addition, at least one block at the molecular terminal of the rubbery block copolymer (polymer 21) is the following block II.

[0527] Block II: a block having a content of 80 mass% or less of a vinyl aromatic monomer unit, and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0528] (Rubbery block copolymer (polymer 22))

[0529] A 40-L content, temperature-controllable autoclave equipped with a stirrer and a jacket was used as a reactor, and 2412 g of 1,3-butadiene, 1888 g of styrene, 25800 g of cyclohexane, and 3.10 g of tetrahydrofuran (THF) as a polar substance, from which impurities were previously removed, were charged into the reactor, and the temperature in the reactor was maintained at 45°C. Further, 3.29 g of n-butyllithium as a polymerization initiator was supplied to the reactor to initiate the polymerization.

[0530] After the initiation of the polymerization, the temperature in the reactor started to rise due to the heat of polymerization, and the temperature in the reactor finally reached 85°C.

[0531] After the monomer conversion in the reactor reached 99%, 1.6 g of methanol as a reaction terminator was added to the polymer solution, and a part of the rubbery block copolymer solution before hydrogenation was taken out for analysis, and was desolventized with a drier to obtain a rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0532] Thereafter, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added to the rubbery block copolymer solution before hydrogenation, based on 100 parts by mass of the rubbery block copolymer before hydrogenation, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain a rubbery block copolymer (polymer 22). The iodine value of the obtained rubbery block copolymer (polymer 22) was 49.

[0533] To the solution of the obtained rubbery block copolymer (polymer 22), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol as antioxidants were added, and drying treatment was performed. The results of the analysis of the rubbery block copolymer (polymer 22) are shown in Table 3. The proportions of the polymer block (a) and the polymer block (b), and the proportions of the components (mass %) were calculated from the proportions (mass %) of the respective components of the rubbery block copolymer and the amount of the styrene block of the rubbery block copolymer.

[0534] In addition, at least one block of the molecular terminal of the rubbery block copolymer (polymer 22) was the following block II.

[0535] Block II: a block in which the content of the vinyl aromatic monomer unit is 80 mass % or less and which contains a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0536] (Polymerization Example 23) Rubbery block copolymer (polymer 23)

[0537] Using the same method as in Polymerization Example 4, after the monomer conversion rate in the reactor reached 99% after the start of the polymerization reaction, 1.21 g of methanol as a reaction terminator was added to the polymer solution, to obtain a rubbery block copolymer (Polymer 23).

[0538] To the obtained solution of the rubbery block copolymer (Polymer 23), 12.6 g of n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol as antioxidants were added, and drying treatment was performed. The iodine value of the obtained rubbery block copolymer (Polymer 23) was 255. Further, the molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method. The results of the analysis of the rubbery block copolymer (Polymer 23) are shown in Table 3. From the proportion (mass%) of each component of the rubbery block copolymer, the proportion of the polymer block (a) and the polymer block (b), and the proportion (mass%) of each component were calculated.

[0539] Further, at least one block of the molecular terminal of the rubbery block copolymer (Polymer 23) was the following Block II.

[0540] Block II: a block having a content of 80 mass% or less of a vinyl aromatic monomer unit and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0541] (Polymerization Example 24) Rubbery Block Copolymer (Polymer 24)

[0542] A high-pressure vessel having a temperature-controllable agitator and jacket with a content volume of 40 L was used as a reactor, and 3096 g of 1,3-butadiene, 1204 g of styrene, 25800 g of cyclohexane, 3.10 g of tetrahydrofuran (THF) as a polar substance, and 12.64 g of 2,2-bis(2-tetrahydrofuryl)propane, from which impurities had been previously removed, were added to the reactor, and the temperature inside the reactor was maintained at 30°C. Further, 3.48 g of n-butyllithium as a polymerization initiator was supplied to the above reactor, and the polymerization reaction was initiated.

[0543] After the start of the polymerization reaction, the temperature inside the reactor started to rise due to the heat of polymerization, and the temperature inside the reactor eventually reached 83°C.

[0544] After the monomer conversion rate in the reactor reached 99%, 1.74 g of methanol was added to the polymer solution as a reaction terminator, and a portion of the rubbery block copolymer solution before hydrogenation was drawn out, desolventized with a drier, and a rubbery block copolymer before hydrogenation was obtained. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above method.

[0545] After that, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added to the rubbery block copolymer solution before hydrogenation, based on 100 parts by mass of the rubbery block copolymer before hydrogenation, and a hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 60 minutes, and a rubbery block copolymer (polymer 24) was obtained. The iodine value of the obtained rubbery block copolymer (polymer 14) was 101.

[0546] To the solution of the obtained rubbery block copolymer (polymer 24), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and drying treatment was performed. The results of the analysis of the rubbery block copolymer (polymer 24) are shown in Table 3. The proportions of the polymer block (a) and the polymer block (b) and the proportions of the components (mass%) were calculated from the proportions of the components (mass%) of the rubbery block copolymer and the amount of the styrene block of the rubbery block copolymer.

[0547] In addition, at least one block at the molecular terminal of the rubbery block copolymer (polymer 24) was the following block II.

[0548] Block II: a block in which the content of the vinyl aromatic monomer unit is 80 mass% or less and which contains a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0549] (Rubbery block copolymer (polymer 25))

[0550] Using the same method as in Polymerization Example 3, after the start of the polymerization reaction, after the monomer conversion rate in the reactor reached 99%, 11.2 g of 3-(4-methylpiperazin-1-yl)propyltriethoxysilane was added to the polymer solution, and a coupling reaction was performed for 20 minutes. To the polymer solution, 0.8 g of methanol was added as a reaction terminator, and a rubbery block copolymer (polymer 15) was obtained.

[0551] To the obtained solution of the rubbery block copolymer (polymer 25), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and a drying treatment was performed. The iodine value of the obtained rubbery block copolymer (polymer 25) was 352. Further, the molecular weight of the aromatic vinyl monomer (styrene) block was determined by the above-described method. The results of the analysis of the rubbery block copolymer (polymer 25) are shown in Table 3. The proportions of the polymer block (a) and the polymer block (b) and the proportions of the components (mass %) were calculated from the proportions (mass %) of the respective components of the rubbery block copolymer, and the amount of the styrene block of the rubbery block copolymer. The rubbery block copolymer (polymer 25) contained a nitrogen atom.

[0552] Further, at least one of the blocks at the molecular terminal of the rubbery block copolymer (polymer 25) was the following block II.

[0553] Block II: a block containing 80 mass% or less of a vinyl aromatic monomer unit, and an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0554] (Rubbery block copolymer (polymer 26))

[0555] A high-pressure vessel having a content volume of 40 L, a stirrer, and a jacket capable of temperature control was used as a reactor, and 3677 g of 1,3-butadiene, 624 g of styrene, 25800 g of cyclohexane, 3.10 g of tetrahydrofuran (THF) as a polar substance, and 3.29 g of 2,2-bis(2-tetrahydrofuryl)propane, from which impurities had been previously removed, were added to the reactor, and the temperature inside the reactor was maintained at 35°C. Further, 1.58 g of n-butyllithium as a polymerization initiator was supplied to the above-described reactor, and the polymerization reaction was initiated.

[0556] After the initiation of the polymerization reaction, the temperature inside the reactor started to rise due to the exothermic heat generated by the polymerization, and the temperature inside the reactor eventually reached 85°C. After reaching this reaction temperature peak, 2.25 g of 1,3-dimethyl-2-imidazolidinone was added after 2 minutes, and a modification reaction was performed for 20 minutes. Methanol 0.79 g as a reaction terminator was added to this polymer solution, and a part of the rubbery block copolymer solution before hydrogenation was withdrawn for analysis, and was desolvated with a drier to obtain a rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was determined by the above-described method.

[0557] Subsequently, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added to the rubbery block copolymer solution before hydrogenation, based on 100 parts by mass of the rubbery block copolymer before hydrogenation, and a hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain a rubbery block copolymer (polymer 26). The iodine value of the obtained rubbery block copolymer (polymer 26) was 81.

[0558] To the solution of the obtained rubbery block copolymer (polymer 26), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and drying treatment was performed. The results of the analysis of the rubbery block copolymer (polymer 26) are shown in Table 3. The proportions of the polymer block (a) and the polymer block (b) were calculated from the proportions (mass%) of the respective components of the rubbery block copolymer, and the styrene block amount of the rubbery block copolymer.

[0559] In addition, at least one block of the molecular terminal of the rubbery block copolymer (polymer 26) was the following block II.

[0560] Block II: a block having a content of 80 mass% or less of a vinyl aromatic monomer unit and containing a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0561] (Rubbery block copolymer (polymer 27))

[0562] A high-pressure vessel having a content volume of 40 L, a stirrer, and a jacket capable of temperature control was used as a reactor, and 3879 g of 1,3-butadiene, 335 g of styrene, 25800 g of cyclohexane, 3.10 g of tetrahydrofuran (THF) as a polar substance, and 3.29 g of 2,2-bis(2-tetrahydrofuryl)propane, from which impurities had been previously removed, were added to the reactor, and the temperature inside the reactor was maintained at 35°C. Further, 1.64 g of n-butyllithium as a polymerization initiator was supplied to the above reactor, and the polymerization reaction was initiated.

[0563] After the initiation of the polymerization reaction, the temperature inside the reactor started to rise due to the heat of polymerization, and after the monomer conversion rate in the reactor reached 99%, 86 g of styrene was added after 5 minutes, and the reaction was further performed.

[0564] The temperature in the final reactor reached 83°C. After reaching this reaction temperature peak, 0.82 g of methanol was added as a reaction terminator 2 minutes later, and a portion of the rubbery block copolymer solution before hydrogenation was drawn out and desolventized with a drier to obtain a rubbery block copolymer before hydrogenation. The molecular weight of the aromatic vinyl monomer (styrene) block was measured by the above-described method.

[0565] Thereafter, to the rubbery block copolymer solution before hydrogenation, 70 ppm of the hydrogenation catalyst (TC-1) prepared in Production Example 1 was added relative to 100 parts by mass of the rubbery block copolymer before hydrogenation on a Ti basis, and a hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and an average temperature of 85°C for 50 minutes to obtain a rubbery block copolymer (polymer 27). The iodine value of the obtained rubbery block copolymer (polymer 27) was 100.

[0566] To the solution of the obtained rubbery block copolymer (polymer 27), 12.6 g of n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.0 g of 4,6-bis(octylthiomethyl)-o-cresol were added as antioxidants, and a drying treatment was performed. The results of the analysis of the rubbery block copolymer (polymer 27) are shown in Table 3. The proportions of the polymer block (a) and the polymer block (b) and the proportions of the respective components (mass%) were calculated from the proportions (mass%) of the respective components of the rubbery block copolymer and the amount of the styrene block of the rubbery block copolymer.

[0567] In addition, at least one block of the molecular terminal of the rubbery block copolymer (polymer 27) was the following block II.

[0568] Block II: a block in which the content of the vinyl aromatic monomer unit is 80 mass% or less and which contains a vinyl aromatic monomer unit, an ethylene structure, a conjugated diene structure, and an α-olefin structure.

[0569] (Method for producing a briquette molded body of a rubbery block copolymer)

[0570] [Examples 1 to 20 and Comparative Examples 1 to 7]

[0571] Using the solution of each rubbery block copolymer (polymer 1 to 27) obtained by the method described in the above-described Polymerization Examples 1 to 27, a drying treatment and molding were performed by the following method to produce a briquette molded body.

[0572] First, for the solution of the rubbery block copolymer, a 15-L stirring tank with a stirrer (stirring blade rotation speed: 500 rpm) was used to remove the solvent by a stripping method at a water temperature of 90°C, to obtain a water-containing pellet of the rubbery block copolymer. The obtained water-containing pellet was subjected to a drying treatment in a vacuum drier at 80°C for 4 hours, to obtain a dried pellet. Thereafter, 1100 g of the obtained dried pellet was filled in a metal frame for molding having a size of 22 cm in length, 11 cm in short side, and 15 cm in depth, in a state of being heated to 80°C, and was compressed in a barrel at a pressure of 10 MPa for 2 minutes, to thereby obtain a briquette molded body of the rubbery block copolymer.

[0573] The residual solvent content and the moisture content in the obtained briquette molded body, and the cold flow resistance were measured by the above-described methods. The measurement results are shown in Tables 1 to 3.

[0574]

[0575]

[0576]

[0577] [Application Examples 1 to 12 and Comparative Examples 1 to 5]

[0578] (Preparation of Rubber Composition, Evaluation of Properties)

[0579] As the raw rubber components, the rubbery block copolymers (polymers 1 to 12, 21 to 25) obtained in the polymerization examples 1 to 12, 21 to 25 shown in Tables 1 to 3 and the briquetted polybutadiene rubber were mixed by the following method under the following mixing condition 1, to thereby obtain a rubber composition containing each of the raw rubber components. The properties of the obtained rubber composition were evaluated by the following method. The evaluation results are shown in Table 5.

[0580] (Mixing Condition 1)

[0581] The addition amount of each of the mixing agents is expressed in terms of a mass fraction with respect to 100 parts by mass of the rubber component not containing a rubber softening agent. The mixing ratio of each of the raw materials is shown in Table 4.

[0582] [Table 4]

[0583] Raw material Mass parts Rubber-like block copolymer 35 Polybutadiene rubber (*1) 65 Silica (*2) 30 Silane coupling agent (*3) 5 Zinc white 7.5 Stearic acid 2.0 Anti-aging agent (*4) 2.5 Sulfur 2 Vulcanization accelerator 1 (*5) 2 Vulcanization accelerator 2 (*6) 1.7

[0584] (*1) Manufactured by Ube Industries, Ltd., UBE POL 150

[0585] (*2) Manufactured by Degussa, ULTRASIL VN3

[0586] (*3) Silane coupling agent (trade name "Si69" manufactured by Evonik Degussa, bis(triethoxysilylpropyl) disulfide)

[0587] (*4) Anti-aging agent (N-(l,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine)

[0588] (*5) Vulcanization accelerator 1 (N-cyclohexyl-2-benzothiazylsulfenamide)

[0589] (*6) Vulcanization accelerator 2 (diphenyl guanidine)

[0590] (Mixing method)

[0591] The above materials were mixed by the following method to obtain a rubber composition. Using a closed mixer (content volume 0.3 L) equipped with a temperature control device, as a first stage of mixing, the rubbery block copolymer (polymer 1 to 15), polybutadiene rubber, filler (silica), silane coupling agent, zinc white, stearic acid were mixed under the conditions of a filling rate of 65% and a rotor rotation speed of 30 to 50 rpm to obtain each compound. At this time, the temperature of the closed mixer was controlled so that the discharge temperature was 155 to 160°C.

[0592] Next, as a second stage of mixing, the above obtained compound was cooled to room temperature, and the anti-aging agent was added, and mixing was performed again in order to improve the dispersion of the silica. In this case, the discharge temperature of the compound was also adjusted to 155 to 160°C by temperature control of the mixer. After cooling, as a third stage of mixing, sulfur, the vulcanization accelerators 1 and 2 were added and mixed in an open mill set to 70°C to obtain a rubber composition. Thereafter, the obtained rubber composition was molded, and vulcanized at 160°C for 20 minutes using a vulcanization press to obtain a vulcanized rubber composition.

[0593] (Evaluation method of properties of rubber composition)

[0594] The properties of the rubber composition before vulcanization and the rubber composition after vulcanization were evaluated. Specifically, the evaluation was performed by the following method.

[0595] (Evaluation 1) Processability (Mooney viscosity)

[0596] The above obtained rubber composition before vulcanization was used as a test sample, and the Mooney viscosity after rotating the rotor at 2 rotations per minute for 4 minutes was measured after preheating at 130°C for 1 minute according to JIS K6300-1. The results of the rubber composition using Comparative Example 1 were taken as 100, and each measured value was exponentiated. The larger the exponent, the better the processability, and when the exponent was 80 or more, it was evaluated that the processability was not a problem in practical use.

[0597] (2) Rigidity (viscoelastic parameters)

[0598] The vulcanized rubber composition obtained above was used as a test sample, and a viscoelastic tester "ARES" manufactured by Rheometric Scientific was used to measure viscoelastic parameters in a torsional vibration mode. The results obtained using the rubber composition of Comparative Example 1 were taken as 100, and each measured value was indexed.

[0599] The storage modulus (G') measured at 50°C at a frequency of 10 Hz and a strain of 3% was used as an index of rigidity. The greater the index, the better the rigidity.

[0600] (3) Breaking strength (tensile strength)

[0601] The vulcanized rubber composition obtained above was used as a test sample, and the tensile strength was measured according to the tensile test method of JIS K6251. The results obtained using the rubber composition of Comparative Example 1 were taken as 100, and each measured value was indexed. The greater the index, the better the tensile strength and the more excellent the breaking strength.

[0602] (4) Wear resistance

[0603] The vulcanized rubber composition obtained above was used as a test sample, and the wear resistance was measured by the DIN abrasion test method of JIS K6246-2 using a DIN abrasion tester (manufactured by Kamisawa Mfg. Co.). The results obtained using the rubber composition of Comparative Example 1 were taken as 100, and each measured value was indexed. The greater the index, the better the wear resistance.

[0604]

[0605] [Application Examples 13 and 14 and Application Comparative Example 6]

[0606] (Preparation of rubber composition, evaluation of properties)

[0607] The rubber-like block copolymer (polymer 5, 19, and 23) obtained in Polymerization Examples 5, 19, and 23 shown in Tables 1 to 3 was used as a raw rubber component, and each raw material was kneaded using the following method under Mixing Condition 2 shown below to obtain a rubber composition containing each raw rubber component. Regarding the properties of the obtained rubber composition, the results obtained using the rubber composition of Application Comparative Example 6 were taken as 100, and each measured value was indexed, and evaluation was performed by the same method as described above except for this. The evaluation results are shown in Table 7.

[0608] (Mixing Condition 2)

[0609] The amount of addition of each of the compounding agents is expressed in terms of parts by mass relative to 100 parts by mass of the rubber component not containing the softening agent for rubber. The compounding ratio of each of the raw materials is shown in Table 6.

[0610] [Table 6]

[0611] Raw material Mass parts Rubber-like block copolymer 100 Silica (*7) 75 Carbon black (*8) 5 Silane coupling agent (*9) 7.5 Process oil (*10) 37.5 Zinc white 2.5 Stearic acid 2 Anti-aging agent (*4) 2 Sulfur 1.7 Accelerator 1 (*5) 1.7 Accelerator 2 (*6) 1.5

[0612] (*7) Silica (trade name "Ultrasil 7000GR" manufactured by Evonik Degussa, nitrogen adsorption specific surface area 170 m 2 / g)

[0613] (*8) Carbon black (trade name "SEAST KH (N339)" manufactured by Tokai Carbon Co., Ltd.)

[0614] (*9) Silane coupling agent (trade name "Si75" manufactured by Evonik Degussa, bis(triethoxysilylpropyl) disulfide)

[0615] (*10) S-RAE oil (trade name "Process NC140" manufactured by JX Nippon Oil & Energy Corporation): 37.5 parts by mass

[0616] (*4) Anti-aging agent (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine)

[0617] (*5) Vulcanization accelerator 1 (N-cyclohexyl-2-benzothiazylsulfenamide)

[0618] (*6) Vulcanization accelerator 2 (diphenyl guanidine)

[0619] (Mixing method)

[0620] The above materials were mixed by the following method to obtain a rubber composition. Using a closed mixer (content volume 0.3 L) equipped with a temperature control device, as a first stage of mixing, the rubber-like block copolymer (polymer 5 or 13), the filler (silica and carbon black), the silane coupling agent, the process oil, the zinc white, and the stearic acid were mixed at a filling rate of 65% and a rotor rotation speed of 30 to 50 rpm to obtain each compounding material. At this time, the temperature of the closed mixer was controlled so that the discharge temperature was 155 to 160°C.

[0621] Next, as the second-stage mixing, after the above obtained mixture was cooled to room temperature, an anti-aging agent was added, and mixing was performed again in order to improve the dispersion of the silica. In this case, the discharge temperature of the mixture was adjusted to 155 to 160°C by temperature control of the mixer. After cooling, as the third-stage mixing, sulfur, vulcanization accelerators 1 and 2 were added to the roll mill set at 70°C, and mixing was performed to obtain a rubber composition. Thereafter, the obtained rubber composition was molded, and vulcanization was performed at 160°C for 20 minutes using a vulcanization press to obtain a vulcanized rubber composition.

[0622] [Table 7]

[0623]

[0624] [Application Examples 15 to 23 and Application Comparative Examples 7 to 9]

[0625] (Preparation of Rubber Composition, Evaluation of Properties)

[0626] As the raw rubber component, the rubbery block copolymer (polymer 4, 13 to 20) obtained in Polymerization Examples 4, 13 to 20 and the rubbery block copolymer (polymer 23, 26, 27) obtained in Polymerization Examples 23, 26, 27 shown in Tables 1 to 3 were used, and each raw material was mixed by the following method under the mixing condition 3 shown below to obtain a rubber composition containing each raw rubber component. As for the properties of the obtained rubber composition, the results of the rubber composition of Application Comparative Example 7 were taken as 100, and each measured value was index-numbered, and evaluation was performed using the same method as described above and the evaluation methods 5, 6 shown below. The evaluation results are shown in Table 9.

[0627] (Mixing Condition 3)

[0628] The addition amount of each mixing agent is expressed in parts by mass with respect to 100 parts by mass of the rubber component not containing a rubber softening agent. The mixing ratio of each raw material is shown in Table 8.

[0629] [Table 8]

[0630] Raw material Mass parts Rubber-like block copolymer 30 Natural rubber (*11) 40 Polybutadiene rubber (*1) 30 Carbon black (*12) 50 Process oil (*10) 10 Zinc white 3 Stearic acid 2 Wax (*13) 1.5 Anti-aging agent (*4) 3 Sulfur 1.5 Accelerator 1 (*15) 1.7

[0631] (*11) RSS No. 3 (Producer: UNIMAC RUBBER CO., LTD. (Thailand))

[0632] (*1) UBEPOL 150 manufactured by Ube Industries, Ltd.

[0633] (*12) Carbon black (trade name "SEAST SO (FEF)" manufactured by Tokai Carbon Co., Ltd.)

[0634] (*10) S-RAE oil (trade name "Process NC140" manufactured by JX Nippon Oil & Energy Corporation)

[0635] (*13) Wax (trade name "Sunnoc" manufactured by Otsu Shinsei Chemical Industry Co., Ltd.)

[0636] (*4) Anti-aging agent (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine)

[0637] (*15) Accelerator TBB S (N-tert-butylbenzothiazole-2-sulfenamide) (trade name "Sanceler NS-G" manufactured by Sanec Co., Ltd.)

[0638] (Mixing method)

[0639] The above-described materials were mixed by the following method to obtain a rubber composition. Using a closed mixer (content volume 0.3 L) equipped with a temperature control device, as a first-stage mixing, the rubber component (rubbery block copolymer, natural rubber, polybutadiene rubber), filler (carbon black), process oil, stearic acid, anti-aging agent, and wax were mixed at a filling rate of 65% and a rotor rotation speed of 50 to 90 rpm to obtain each compound. At this time, the temperature of the closed mixer was controlled so that the discharge temperature was 155 to 160°C.

[0640] Next, as a second-stage mixing, the above-obtained compound was cooled to room temperature, and mixing was performed again in order to improve the dispersion of the silica. In this case, the discharge temperature of the compound was adjusted to 155 to 160°C by temperature control of the mixer. After cooling, as a third-stage mixing, the rubber composition was obtained by mixing the zinc white, vulcanization accelerator, and sulfur in an open mill set to 70°C. Thereafter, the obtained rubber composition was molded, and vulcanized at 160°C for 20 minutes using a vulcanization press to obtain a vulcanized rubber composition.

[0641] (Evaluation 5) Fuel efficiency

[0642] The obtained vulcanized rubber composition was used as a test sample, and a viscoelastic tester "ARES" manufactured by Rheometric Scientific Co. was used to measure the viscoelastic parameters in a torsional vibration mode.

[0643] The tan δ measured at 50°C at a frequency of 10 Hz and a strain of 3% was used as an index of fuel efficiency.

[0644] Using each measured value, the results of the measurement were summarized. The results of the rubber composition of Comparative Example 7 were used as 100, and each measured value was exponentiated. The larger the exponent, the more excellent the fuel efficiency.

[0645] (6) Ozone resistance

[0646] Using the obtained vulcanized rubber composition, the ozone resistance was measured by the test method shown below.

[0647] <Assessment of ozone resistance>

[0648] Under the conditions of 160°C for 15 to 30 minutes, vulcanization press molding was performed using a prescribed mold (15 cm long x 15 cm wide x 2.0 mm thick), and a long strip-shaped sample (6 cm long x 1 cm wide x 2.0 mm thick) was punched out from the obtained vulcanized rubber sheet and placed in an ozone tank (50°C, 100 pphm) under a state of being stretched by 40%, and left standing for 48 hours. Thereafter, the long strip-shaped sample (vulcanized rubber sheet) was observed, and the number of cracks of 1 mm or more in length present on the surface was counted. Evaluation was performed by the following criteria. The results of the evaluation are shown in Table 9 (ozone resistance).

[0649] [Assessment criteria]

[0650] X: The vulcanized rubber sheet was broken

[0651] △: 21 or more of cracks of 1 mm or more in length

[0652] O: 10 or more but less than 20 of cracks of 1 mm or more in length

[0653] ◎: Less than 10 of cracks of 1 mm or more in length

[0654]

[0655] As shown in Tables 5, 7, and 9, it was confirmed that the balance of processability, rigidity, breaking strength, and wear resistance of the rubber compositions of the application examples 1 to 23 was excellent compared to the rubber compositions of the comparative examples 1 to 9.

[0656] This application is based on Japanese Patent Application (Japanese Patent Application No. 2020-161660) filed on September 28, 2020, the content of which is incorporated herein by reference in its entirety.

[0657] Industrial applicability

[0658] The briquetted molded body of the rubbery block copolymer of the present application can be used in the fields of automobile tire applications, footwear applications, vibration isolation rubber applications, and the like.

Claims

1. A compressed block copolymer, wherein, The rubber-like block copolymer is obtained by hydrogenation of a copolymer obtained by polymerizing at least a vinyl aromatic monomer and a conjugated diene monomer, and the rubber-like block copolymer satisfies the following conditions 1 to 8: Condition 1: The content of vinyl aromatic monomer units is more than 15% by mass and less than 50% by mass; Condition 2: The proportion of vinyl aromatic monomer blocks is more than 3% by mass and less than 30% by mass, wherein a vinyl aromatic monomer block refers to a block composed of more than 8 vinyl aromatic monomer units linked together. Condition 3: Iodine value is 3-250; Condition 4: The proportion of ethylene structure is more than 3% by mass and less than 70% by mass; Condition 5: Weight-average molecular weight is in the range of 80,000 to 1,000,000; Condition 6: At least one block at the end of the molecule is block I or block II as described below. Block I: A block composed of ethylene structure, conjugated diene structure and α-olefin structure; Block II: The content of vinyl aromatic monomer units is less than 80% by mass, and it includes blocks of vinyl aromatic monomer units, ethylene structure, conjugated diene structure and α-olefin structure; Condition 7: The content of α-olefin structure in the rubbery block copolymer is more than 10% by mass and less than 40% by mass; Condition 8: The weight-average molecular weight of the vinyl aromatic monomer blocks in the rubbery block copolymer is 10,000 or more.

2. A compressed block copolymer, wherein, The rubber-like block copolymer is obtained by hydrogenation of a copolymer obtained by polymerizing at least a vinyl aromatic monomer and a conjugated diene monomer, and the rubber-like block copolymer satisfies the following conditions 1 to 8: Condition 1: The content of vinyl aromatic monomer units is more than 9% by mass and less than 50% by mass; Condition 2: The proportion of vinyl aromatic monomer blocks is more than 3% by mass and less than 30% by mass, wherein a vinyl aromatic monomer block refers to a block composed of more than 8 vinyl aromatic monomer units linked together. Condition 3: Iodine value is 3-250; Condition 4: The proportion of ethylene structure is more than 3% by mass and less than 70% by mass; Condition 5: Weight-average molecular weight is in the range of 80,000 to 1,000,000; Condition 6: At least one block at the end of the molecule is block I or block II as described below. Block I: A block composed of ethylene structure, conjugated diene structure and α-olefin structure; Block II: The content of vinyl aromatic monomer units is less than 80% by mass, and it includes blocks of vinyl aromatic monomer units, ethylene structure, conjugated diene structure and α-olefin structure; Condition 7: The content of α-olefin structure in the rubbery block copolymer is more than 10% by mass and less than 40% by mass; Condition 8: In the gel permeation chromatography (GPC) curve of the rubber-like block copolymer, the number of peaks is more than two, and the peak area of ​​the peak with the smallest molecular weight is more than 5% and less than 95% of the total peak area.

3. The briquette molded body as described in claim 1 or 2, wherein, The number of vinyl aromatic monomer blocks in the rubbery block copolymer is one.

4. The briquette-formed body as described in claim 1 or 2, wherein, The rubbery block copolymer contains nitrogen atoms.

5. The briquette-formed body as described in claim 4, wherein, In the rubbery block copolymer, the modification rate determined by column adsorption GPC method is 40% by mass or more, where the modification rate represents the mass ratio of polymers with nitrogen-containing functional groups to the total amount of the rubbery block copolymer.

6. The briquette-formed body as described in claim 1, wherein, The gel permeation chromatography (GPC) curve of the rubbery block copolymer has one peak.

7. The briquette-formed body as described in claim 1, wherein, In the gel permeation chromatography (GPC) curve of the rubbery block copolymer, the number of peaks is more than two, and the peak area of ​​the peak with the smallest molecular weight is more than 5% and less than 95% of the total peak area.

8. The briquette-formed body as described in claim 1 or 2, wherein, The ratio of the proportion of vinyl aromatic monomer blocks to the content of vinyl aromatic monomer units in the rubbery block copolymer, i.e., the ratio of vinyl aromatic monomer blocks to the content of vinyl aromatic monomer units, is 0.28 to 1.

00.

9. The briquette-formed body as described in claim 2, wherein, The weight-average molecular weight of the vinyl aromatic monomer blocks in the rubbery block copolymer is above 10,000.

10. The compressed block copolymer of claim 1 or 2, wherein, The residual solvent content in the compressed block copolymer is less than 5000 ppm, and the moisture content is less than 0.05% to 1.5% by mass.

11. The briquette-formed body as described in claim 1 or 2, wherein, The iodine value of the rubbery block copolymer is 10 to 200.

12. The briquette-formed body as described in claim 1 or 2, wherein, The proportion of vinyl aromatic monomer blocks in the rubbery block copolymer is greater than 5% by mass and less than 25% by mass.

13. The briquette-formed body as described in claim 1 or 2, wherein, The content of polymer blocks other than vinyl aromatic monomer block a and polymer block b in the rubbery block copolymer is less than 30% by mass, where b represents a block composed of ethylene structure, conjugated diene structure and α-olefin structure, or a block composed of vinyl aromatic monomer unit less than 80% by mass and composed of vinyl aromatic monomer unit, ethylene structure, conjugated diene structure and α-olefin structure.

14. The briquette-formed body as described in claim 13, wherein, The content of ethylene structure in the polymer block b is more than 3% by mass and less than 70% by mass.

15. The briquette-formed body as described in claim 13, wherein, The content of ethylene structure in the polymer block b is more than 10% by mass and less than 60% by mass.

16. The briquette-formed body as described in claim 13, wherein, The content of polymer block b in the rubbery block copolymer is more than 50% by mass and less than 96% by mass.

17. The briquette-formed body as described in claim 1 or 2, wherein, The weight-average molecular weight of the rubbery block copolymer is between 100,000 and 700,000.

18. A method for manufacturing a briquette molded body according to any one of claims 1 to 17, comprising the following steps: The process of using an organolithium compound as a polymerization initiator to polymerize at least a vinyl aromatic monomer with a conjugated diene monomer to obtain a rubbery block copolymer. The process of hydrogenating the rubbery block copolymer to obtain a hydride of the rubbery block copolymer; and The process of molding the hydride of the rubber-like block copolymer to obtain a briquette-shaped body.

19. The method for manufacturing a briquette as described in claim 18, wherein, The process involves adding a vinyl aromatic monomer after copolymerization of the vinyl aromatic monomer and the conjugated diene monomer, or after polymerization of the conjugated diene monomer.

20. The method for manufacturing a briquette as claimed in claim 18 or 19, comprising a step of coupling the rubber-like block copolymer using a coupling agent.

21. The method for manufacturing a briquette as described in claim 18 or 19, wherein, Add less than 30% by weight of rubber softener.

22. The method for manufacturing a briquette as described in claim 20, wherein, The coupling agent contains tin atoms or nitrogen atoms.

23. A method for manufacturing a rubber composition, comprising the step of: mixing a rubber component of a briquette molded body comprising any one of claims 1 to 17 with a crosslinking agent of 0.1 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the rubber component.

24. The method for manufacturing the rubber composition according to claim 23, wherein, The crosslinking agent is selected from at least one of the group consisting of organic peroxides, azo compounds, and sulfur compounds.

25. The method for manufacturing the rubber composition according to claim 23 or 24, wherein, The filler is mixed in the mixing process of the crosslinking agent.

26. The method for manufacturing the rubber composition according to claim 23 or 24, wherein, The rubber component includes other rubber components besides rubber-like block copolymers.

27. The method for manufacturing the rubber composition according to claim 26, wherein, Other rubber components are selected from at least one of the groups consisting of polybutadiene rubber, natural rubber, and ethylene vinyl acetate copolymer.

28. The method for manufacturing the rubber composition according to claim 25, wherein, The amount of the filler mixed is 10 to 130 parts by mass relative to 100 parts by mass of the rubber component.

29. A method for manufacturing a shoe sole, comprising a step of molding a rubber composition obtained by any one of claims 23 to 28.

30. A method for manufacturing tire tread, comprising a step of molding a rubber composition obtained by any one of claims 23 to 28.

31. A method for manufacturing a tire sidewall, comprising a step of molding a rubber composition obtained by any one of claims 23 to 28.

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