Hydrogenated copolymers, resin compositions, molded articles and adhesive films

Abstract

A hydrogenated copolymer (X) comprising a hydrogenated copolymer (A) and a hydrogenated copolymer (B) satisfying the following (1) to (4): (1): The hydrogenated copolymer (A) has a random copolymer structure formed by a conjugated diene compound and a vinyl aromatic compound, wherein the content of the vinyl aromatic compound in (A) is 10 to 80% by mass. (2): The hydrogenated copolymer (B) has a random copolymer structure formed by a conjugated diene compound and a vinyl aromatic compound, wherein the content of the vinyl aromatic compound in (B) is 10 to 80% by mass. (3): The ratio of (Mn1) of the hydrogenated copolymer (A) to (Mn2) of the hydrogenated copolymer (B) (Mn1 / Mn2) is less than 0.25, and 1000 ≤ Mn1 ≤ 40000. (4): The mass ratio (A) / (B) of the content of the hydrogenated copolymer (A) to the content of the hydrogenated copolymer (B) is 5 / 95 to 50 / 50.

Description

Technical Field

[0001] This invention relates to hydrogenated copolymer and resin compositions, molded articles, and adhesive films. Background Technology

[0002] Hydrogenated copolymers of conjugated diene compounds and vinyl aromatic compounds exhibit the same elasticity as natural and synthetic rubber at room temperature and the same processability as thermoplastic resins at high temperatures, thus also possessing excellent weather resistance and heat resistance. Consequently, they have been widely used in plastic modifiers, automotive parts, medical molded products, asphalt modifiers, footwear, food containers and other molded products, packaging materials, adhesive sheets, and household / industrial components.

[0003] For example, Patent Document 1 discloses a hydrogenated copolymer and a resin composition comprising the hydrogenated copolymer, wherein the hydrogenated copolymer is a hydrogenated block copolymer having a random copolymer structure of a conjugated diene compound and a vinyl aromatic compound.

[0004] The resin composition has excellent mechanical properties and wear resistance, thus promoting its application in automotive interior materials and other applications.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2004 / 003027 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] However, the resin composition containing hydrogenated copolymer disclosed in Patent Document 1 has a high shear viscosity, which results in insufficient moldability for practical purposes.

[0010] In recent years, applications such as automotive interior materials have demanded improved design and more efficient molding processes. In such cases, injection molding is more suitable than traditional slush molding. However, compared to slush molding, injection molding suffers from poor moldability if the viscosity of the resin composition is not reduced, potentially leading to unsatisfactory appearance. Therefore, hydrogenated copolymers with sufficiently high wear resistance and sufficiently low shear viscosity are sought.

[0011] Therefore, in view of the problems of the prior art, the first object of the present invention is to provide a hydrogenated copolymer that has practically sufficient wear resistance and can produce a resin composition with low shear viscosity and excellent formability, and can produce a molded article with good appearance.

[0012] On the other hand, hydrogenated copolymers designed to reduce shear viscosity can also be expected to have improved adhesion. To obtain sufficient adhesive strength, adhesives are typically manufactured by mixing tackifiers into hydrogenated copolymers. However, by designing the adhesives to improve the adhesion of the hydrogenated copolymers themselves, the amount of tackifier added can be reduced or eliminated. In the manufacture of adhesives, it is expected that the cost of tackifiers can be reduced, or the process of mixing the tackifier with the hydrogenated copolymer can be omitted or shortened in the hydrogenation process.

[0013] Therefore, a second objective of the present invention is to provide a hydrogenated copolymer with high adhesion.

[0014] Methods for solving problems

[0015] In order to solve the problems of the prior art, the inventors have repeatedly conducted in-depth research and found that in a hydrogenated copolymer (X) comprising a hydrogenated copolymer (A) and a hydrogenated copolymer (B) having a random copolymer structure formed by a conjugated diene compound and a vinyl aromatic compound, the first and second objectives described above can be achieved by making the ratio of the number average molecular weights of the hydrogenated copolymer (A) and the hydrogenated copolymer (B) within a specific range, making the number average molecular weight of the hydrogenated copolymer (A) within a specific range, and making the mass ratio of the contents of the hydrogenated copolymer (A) and the hydrogenated copolymer (B) within a specific range, thereby completing the present invention.

[0016] That is, the present invention is as follows. [1]

[0018] A hydrogenated copolymer (X) comprising a hydrogenated copolymer (A) being a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene compound, and a hydrogenated copolymer (B) being a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene compound, satisfying the following conditions (1) to (4).

[0019] (1): The hydrogenated copolymer (A) has a random copolymer structure formed by conjugated diene compound and vinyl aromatic compound, wherein the content of vinyl aromatic compound in the hydrogenated copolymer (A) is more than 10% by mass and less than 80% by mass.

[0020] (2): The hydrogenated copolymer (B) has a random copolymer structure formed by a conjugated diene compound and a vinyl aromatic compound, and the content of the vinyl aromatic compound in the hydrogenated copolymer (B) is more than 10% by mass and less than 80% by mass.

[0021] (3): The ratio (Mn1 / Mn2) of the number-average molecular weight (Mn1) of the above-mentioned hydrogenated copolymer (A) to the number-average molecular weight (Mn2) of the above-mentioned hydrogenated copolymer (B) is less than 0.25.

[0022] And 1000≦Mn1≦40000.

[0023] (4): The mass ratio of the content of the above hydrogenated copolymer (A) to the content of the above hydrogenated copolymer (B) (A) / (B) is 5 / 95 to 50 / 50. [2]

[0025] The hydrogenated copolymer (X) described in [1] above, wherein the hydrogenated copolymer (B) has at least one polymer block mainly composed of a vinyl aromatic compound. [3]

[0027] The hydrogenated copolymer (X) as described in [1] or [2] above, wherein the hydrogenated copolymer (A) has at least one polymer block based on a vinyl aromatic compound. [4]

[0029] The hydrogenated copolymer (X) as described in any one of [1] to [3] above, wherein the number-average molecular weight (Mn2) of the hydrogenated copolymer (B) is 120,000 or more. [5]

[0031] The hydrogenated copolymer (X) as described in any one of [1] to [4] above, wherein the hydrogenation rate of the double bonds from the conjugated diene compound in the hydrogenated copolymer (A) and the hydrogenated copolymer (B) is 40% or more. [6]

[0033] The hydrogenated copolymer (X) as described in any one of [1] to [5] above, wherein, in the viscoelasticity determination (1Hz) spectrum, at least one tanδ peak exists in the range of -20°C to 40°C. [7]

[0035] The hydrogenated copolymer (X) as described in any one of [1] to [6] above, wherein the ratio (RS1 / RS2) of the mass fraction (RS1) of the vinyl aromatic compound in the random copolymer structure of the hydrogenated copolymer (A) to the mass fraction (RS2) of the vinyl aromatic compound in the random copolymer structure of the hydrogenated copolymer (B) above is 0.8 to 1.2. [8]

[0037] The hydrogenated copolymer (X) as described in any one of [1] to [7] above, wherein the ratio of the weight-average molecular weight (Mw2) to the number-average molecular weight (Mn2) of the hydrogenated copolymer (B) is less than 1.15 (Mw2 / Mn2). [9]

[0039] The hydrogenated copolymer (X) as described in any one of [1] to [8] above, wherein the ratio (Mn1 / Mn2) of the number-average molecular weight (Mn1) of the hydrogenated copolymer (A) to the number-average molecular weight (Mn2) of the hydrogenated copolymer (B) is less than 0.12.

[10]

[0041] The hydrogenated copolymer (X) as described in any one of [1] to [9] above, wherein the hydrogenated copolymer (A) has a polymer block mainly composed of vinyl aromatic compounds, and the ratio (MnS1 / MnS2) of the molecular weight (MnS1) of the polymer block mainly composed of vinyl aromatic compounds in the hydrogenated copolymer (A) to the molecular weight (MnS2) of the polymer block mainly composed of vinyl aromatic monomer units in the hydrogenated copolymer (B) is 0.9 or less.

[0042] (MnS1 and MnS2 are calculated using the following method.)

[0043] MnS1=Mn1×BS1

[0044] MnS2=Mn2×BS2÷f

[0045] BS1: via proton nuclear magnetic resonance (NMR) 1 The content of the polymer blocks mainly composed of vinyl aromatic compounds in the above-mentioned hydrogenated copolymer (A) was determined by H-NMR.

[0046] BS2: via proton nuclear magnetic resonance (NMR) 1 The content of the polymer blocks mainly composed of vinyl aromatic compounds in the above-mentioned hydrogenated copolymer (B) was determined by H-NMR.

[0047] f: Degree of branching of hydrogenated copolymer (B) determined by GPC-light scattering method with viscosity detector.

[0048] Mn1: Number average molecular weight of hydrogenated copolymer (A)

[0049] Mn2: Number average molecular weight of hydrogenated copolymer (B)

[11]

[0051] A resin composition comprising:

[0052] The hydrogenated copolymer (X) described in any one of [1] to

[10] above, wherein the content of vinyl aromatic compounds in the hydrogenated copolymers (A) and (B) is 30% by mass or more and 80% by mass or less; and

[0053] Thermoplastic resins other than the hydrogenated copolymer (X) mentioned above and / or rubber-like polymers other than the hydrogenated copolymer (X) mentioned above.

[12]

[0055] A molded body, which is a molded body of the resin composition described in

[11] above.

[13]

[0057] An adhesive film having a substrate layer and an adhesive layer on the substrate layer, wherein,

[0058] The adhesive layer described above contains the hydrogenated copolymer (X) described in any one of [1] to

[10] above.

[0059] The content of vinyl aromatic compounds in the hydrogenated copolymers (A) and (B) constituting the above-mentioned hydrogenated copolymer (X) is more than 10% by mass and less than 60% by mass.

[0060] The effects of the invention

[0061] According to the present invention, as a first effect, a hydrogenated copolymer can be provided, which yields a resin composition with excellent wear resistance and moldability, and a molded article with good appearance.

[0062] Furthermore, as a second effect of the present invention, a hydrogenated copolymer with high adhesion can be provided, which can be used as a material for adhesive films. Detailed Implementation

[0063] The following provides a detailed description of specific embodiments of the present invention (hereinafter referred to as "this embodiment"). It should be noted that the following embodiments are illustrative of the present invention and are not intended to limit the present invention to the following content. The present invention can be implemented in various modifications within the scope of its essential points.

[0064] [Hydrogenated copolymer (X)]

[0065] The hydrogenated copolymer (X) of this embodiment comprises:

[0066] Hydrogenated copolymer (A), which is a hydrogenated copolymer of a vinyl aromatic compound and a conjugated diene compound, and

[0067] Hydrogenated copolymer (B) is a hydrogenated copolymer of a vinyl aromatic compound and a conjugated diene compound, and the hydrogenated copolymer (X) satisfies the following conditions (1) to (4).

[0068] (1): The hydrogenated copolymer (A) has a random copolymer structure formed by conjugated diene compound and vinyl aromatic compound, wherein the content of vinyl aromatic compound in the hydrogenated copolymer (A) is more than 10% by mass and less than 80% by mass.

[0069] (2): The hydrogenated copolymer (B) has a random copolymer structure formed by conjugated diene compounds and vinyl aromatic compounds, wherein the content of vinyl aromatic compounds in the hydrogenated copolymer (B) is more than 10% by mass and less than 80% by mass.

[0070] (3): The ratio (Mn1 / Mn2) of the number-average molecular weight (Mn1) of the above-mentioned hydrogenated copolymer (A) to the number-average molecular weight (Mn2) of the above-mentioned hydrogenated copolymer (B) is less than 0.25.

[0071] And 1000≦Mn1≦40000.

[0072] (4): The mass ratio of the content of the above hydrogenated copolymer (A) to the content of the above hydrogenated copolymer (B) (A) / (B) is 5 / 95 to 50 / 50.

[0073] The hydrogenated copolymer (X) in this embodiment is essentially a mixture of the aforementioned hydrogenated copolymer (A) and hydrogenated copolymer (B). It should be noted that the term "mixture" refers not only to the mixing of multiple copolymers, but also to the mixing of multiple copolymers by producing multiple polymers using a single reactor. That is, it also includes the method of producing multiple copolymers through a single reaction.

[0074] The hydrogenated copolymer (X) of this embodiment, by having the above-described structure, has the following first effect: it yields a resin composition with excellent wear resistance and moldability, and a molded article with good appearance. As a second effect, it yields a hydrogenated copolymer with high adhesion, which can be used as a material for adhesive films.

[0075] (Hydrogenated copolymer (A))

[0076] The hydrogenated copolymer (X) of this embodiment contains hydrogenated copolymer (A).

[0077] Hydrogenated copolymer (A) is a hydrogenated copolymer of a copolymer of a vinyl aromatic compound and a conjugated diene compound, having a random copolymer structure formed by the vinyl aromatic compound and the conjugated diene compound.

[0078] In the hydrogenated copolymer (A), the content of vinyl aromatic compounds is more than 10% by mass and less than 80% by mass, and the number average molecular weight (Mn1) of the hydrogenated copolymer (A) is 1000 to 40000.

[0079] It should be noted that in the hydrogenated copolymer (X), hydrogenated copolymer (A), and hydrogenated copolymer (B) of this embodiment, when a vinyl aromatic compound is embedded in the polymer, although it is in the manner of constituting a monomer unit of the polymer, it is also referred to as "vinyl aromatic compound" in this specification.

[0080] Similarly, when a conjugated diene compound is embedded in a polymer, although it is in the manner of constituting a monomer unit of the polymer, it is also referred to as a "conjugated diene compound" in this specification.

[0081] Vinyl aromatic compounds

[0082] Examples of vinyl aromatic compounds constituting the hydrogenated copolymer (A) include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc.

[0083] Of these, styrene, α-methylstyrene, and 4-methylstyrene are preferred in terms of availability and productivity.

[0084] These compounds can be used in single-component or in combination of two or more.

[0085] <Conjugated diene compounds>

[0086] As the conjugated diene compound constituting the hydrogenated copolymer (A), any diene having a conjugated double bond can be used, and examples include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, farnesene, etc.

[0087] Among these, 1,3-butadiene and isoprene are preferred from the perspectives of availability and productivity. These compounds can be used alone or in combination of two or more.

[0088] The hydrogenated copolymer (A) has a random copolymer structure formed by vinyl aromatic compounds and conjugated diene compounds.

[0089] <Preferred method for using hydrogenated copolymer (A) in the case of using hydrogenated copolymer (X) of this embodiment as a resin composition>

[0090] When the hydrogenated copolymer (X) of this embodiment is used as a resin composition, the mass fraction (RS1) of the vinyl aromatic compound in the random copolymer structure of the hydrogenated copolymer (A) is preferably in the range of 30% to 80% by mass, more preferably in the range of 35% to 75% by mass, and even more preferably in the range of 40% to 70% by mass.

[0091] When the above (RS1) falls within the above range, the hydrogenated copolymer (X) of this embodiment tends to exhibit good wear resistance when used in a resin composition.

[0092] <Preferred embodiment of hydrogenated copolymer (A) when using the hydrogenated copolymer (X) of this embodiment as a material for an adhesive film>

[0093] When the hydrogenated copolymer (X) of this embodiment is used as the material of the adhesive film, the mass fraction (RS1) of the vinyl aromatic compound in the random copolymer structure of the hydrogenated copolymer (A) (hereinafter, when styrene is used, it is sometimes referred to as the styrene content in the random structure or the amount of random styrene) is preferably in the range of 10% to 60% by mass, more preferably in the range of 15% to 50% by mass, and even more preferably in the range of 20% to 45% by mass.

[0094] When the above-mentioned (RS1) falls within the above-mentioned range, the hydrogenated copolymer (X) of this embodiment is applied to the material of the adhesive film, and tends to exhibit a good balance between adhesion and delivery.

[0095] The content of vinyl aromatic compounds contained in the random copolymer structure of hydrogenated copolymer (A) can be determined by nuclear magnetic resonance (NMR). Specifically, it can be determined by the method described in the examples below.

[0096] The content of vinyl aromatic compounds in the random copolymer structure of hydrogenated copolymer (A) can be controlled within the above-mentioned range by adjusting the amount and timing of addition of vinyl aromatic compounds in the polymerization process.

[0097] <Preferred method for using hydrogenated copolymer (A) in the case of using hydrogenated copolymer (X) of this embodiment as a resin composition>

[0098] When the hydrogenated copolymer (X) of this embodiment is used as a resin composition, the content of vinyl aromatic compounds in the hydrogenated copolymer (A) is 10% to 80% by mass, preferably 30% to 80% by mass, more preferably 35% to 75% by mass, and even more preferably 40% to 70% by mass.

[0099] When the content of vinyl aromatic compounds in the hydrogenated copolymer (A) is 80% by mass or less, the hydrogenated copolymer (X) of this embodiment tends to have low hardness; when it is 10% by mass or more, it tends to exhibit excellent resistance to particle adhesion.

[0100] Furthermore, when the content of vinyl aromatic compounds in the hydrogenated copolymer (A) is in the range of 10% to 80% by mass, the hydrogenated copolymer (X) of this embodiment tends to exhibit good wear resistance when applied to the resin composition.

[0101] <Preferred embodiment of hydrogenated copolymer (A) when using the hydrogenated copolymer (X) of this embodiment as a material for an adhesive film>

[0102] When the hydrogenated copolymer (X) of this embodiment is used as the material of the adhesive film, the content of vinyl aromatic compounds in the hydrogenated copolymer (A) is 10% to 80% by mass, preferably 10% to 60% by mass, more preferably 20% to 55% by mass, and even more preferably 25% to 50% by mass.

[0103] When the content of vinyl aromatic compounds in the hydrogenated copolymer (A) is 80% by mass or less, the hydrogenated copolymer (X) of this embodiment tends to have improved adhesive strength, and when it is 10% by mass or more, it tends to exhibit excellent resistance to particle adhesion.

[0104] Furthermore, when the content of vinyl aromatic compounds in the hydrogenated copolymer (A) is in the range of 10% to 80% by mass, the hydrogenated copolymer (X) of this embodiment tends to exhibit a good balance between adhesion and delivery when applied to the material of the adhesive film.

[0105] The content of vinyl aromatic compounds in the hydrogenated copolymer (A) can be determined by proton nuclear magnetic resonance (NMR). 1 The determination is performed using ¹H-NMR. Specifically, the determination can be performed using the method described in the examples below.

[0106] The content of vinyl aromatic compounds in the hydrogenated copolymer (A) can be controlled within the above-mentioned range by adjusting the amount of vinyl aromatic compounds added during the polymerization process.

[0107] The number average molecular weight (Mn1) of the hydrogenated copolymer (A) is 1,000 to 40,000, preferably 10,000 to 40,000, and more preferably 10,000 to 30,000.

[0108] When the number average molecular weight of the hydrogenated copolymer (A) is 40,000 or less, the hydrogenated copolymer (X) of this embodiment tends to have low shear viscosity. When the hydrogenated copolymer (X) of this embodiment is used in a resin composition, it tends to suppress the generation of flow marks during injection molding.

[0109] From a productivity perspective, the number average molecular weight (Mn1) of the hydrogenated copolymer (A) is 1000 or more. When the number average molecular weight (Mn1) of the hydrogenated copolymer (X) of this embodiment is 1000 or more, it is less likely to cause gate breakage during injection molding and tends to have excellent mold release properties.

[0110] The number-average molecular weight (Mn1) of the hydrogenated copolymer (A) can be determined by gel permeation chromatography (hereinafter referred to as GPC) using a calibration curve prepared from standard polystyrene. Specifically, it can be determined by the method described in the examples below.

[0111] The number-average molecular weight (Mn1) of the hydrogenated copolymer (A) can be controlled within the above-mentioned range by adjusting conditions such as the amount of monomer added and the amount of polymerization initiator added in the polymerization process.

[0112] The hydrogenation rate (also known as hydrogenation rate) of the aliphatic double bond from the conjugated diene compound in the hydrogenated copolymer (A) is preferably 40% or more, more preferably 60% or more, and even more preferably 80% or more.

[0113] When the hydrogenation rate of the hydrogenated copolymer (A) is 40% or higher, the thermal degradation (oxidative degradation) of the hydrogenated copolymer (X) of this embodiment can be suppressed. In addition, it also tends to have good resistance to particle sticking.

[0114] The hydrogenation rate of the aliphatic double bond from the conjugated diene compound in the hydrogenated copolymer (A) can be controlled, for example, by adjusting the amount of catalyst during hydrogenation, and the hydrogenation rate can be controlled, for example, by adjusting the amount of catalyst, the amount of hydrogen fed, the pressure, and the temperature during hydrogenation.

[0115] The hydrogenation rate of the double bonds from the conjugated diene compounds in the hydrogenated copolymer (A) and the hydrogenated copolymer (B) described later can be determined by nuclear magnetic resonance (NMR).

[0116] The amount of unhydrogenated vinyl bonds in the conjugated diene compound of the hydrogenated copolymer (A) is preferably 5 mol% to 80 mol%, more preferably 7 mol% to 75 mol%, and even more preferably 10 mol% to 70 mol%.

[0117] When the amount of vinyl bonds in the hydrogenated copolymer (A) before hydrogenation is 5 mol% or more, the hydrogenated copolymer (X) of this embodiment tends to have low hardness. When the amount of vinyl bonds in the hydrogenated copolymer (A) before hydrogenation is 80 mol% or less, it tends to exhibit good resistance to particle adhesion.

[0118] It should be noted that, in this embodiment, the vinyl bond amount refers to the total content relative to the total 1,2-vinyl bond amount (conjugated dienes embedded in the polymer with 1,2-bonds) and the total 3,4-vinyl bond amount (conjugated dienes embedded in the polymer with 3,4-bonds) of all conjugated dienes (here, when 1,3-butadiene is used as the conjugated diene, it is the 1,2-vinyl bond content; when isoprene is used as the conjugated diene, it is the 3,4-vinyl bond content).

[0119] The amount of vinyl bonds can be determined using nuclear magnetic resonance (NMR). The microstructure (the ratio of cis, trans, and vinyl bonds) of the conjugated diene compound in the hydrogenated copolymer (A) can be arbitrarily altered by using polar compounds, etc., as described later.

[0120] The hydrogenated copolymer (A) is not limited as long as it contains a random copolymer structure, and preferably has a structure represented by the following general formula.

[0121] c

[0122] (ac) n

[0123] aca

[0124] bc

[0125] abc

[0126] acb

[0127] (c) m -Z

[0128] (ac) m -Z

[0129] (abc) m -Z

[0130] (acb) m -Z

[0131] In the above formula, a, b, and c represent polymer blocks (a), (b), and (c), respectively.

[0132] It should be noted that, from a productivity perspective, c or ac is preferred.

[0133] In addition, the hydrogenated copolymer (A) can be a mixture containing a plurality of the above structures in any proportion.

[0134] In the above general formulas representing hydrogenated copolymers (A), (a) is a polymer block mainly composed of vinyl aromatic compounds, (b) is a polymer block mainly composed of conjugated diene compounds, and (c) is a random copolymer block formed by vinyl aromatic compounds and conjugated diene compounds.

[0135] n is an integer of 1 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.

[0136] m is an integer of 2 or more, preferably an integer of 2 to 11, and more preferably an integer of 2 to 8.

[0137] Z represents a coupling agent residue. Here, a coupling agent residue refers to the bonded residue of the coupling agent used for bonding between polymer blocks (b) and between polymer blocks (c).

[0138] Examples of coupling agents include, but are not limited to, polyhalogenated compounds and esters, which will be described later.

[0139] The hydrogenated copolymer (A) preferably has polymer blocks mainly composed of vinyl aromatic compounds. By having the hydrogenated copolymer (A) have polymer blocks mainly composed of vinyl aromatic compounds, when the hydrogenated copolymer (X) of this embodiment is used as a resin composition, there is a tendency to improve abrasion resistance. In addition, when the hydrogenated copolymer (X) of this embodiment is used as a material for an adhesive film, there is a tendency to reduce adhesive residue and to obtain excellent adhesion.

[0140] It should be noted that, in this specification, "as the main body" means that the target monomer unit contains more than 70% by mass and less than 100% by mass in the target polymer block, and preferably more than 80% by mass and less than 100% by mass, more preferably more than 90% by mass and less than 100% by mass.

[0141] The vinyl aromatic compounds in polymer block (c) can be uniformly distributed or distributed in a gradient manner. Furthermore, there can be multiple portions of uniformly distributed vinyl aromatic compounds and / or portions of gradient distribution. Additionally, multiple portions of vinyl aromatic compounds with varying amounts can coexist in the polymer block (c).

[0142] (Hydrogenated copolymer (B))

[0143] The hydrogenated copolymer (X) in this embodiment contains hydrogenated copolymer (B).

[0144] Hydrogenated copolymer (B) is a hydrogenated copolymer of a copolymer of a vinyl aromatic compound and a conjugated diene compound, having a random copolymer structure formed by the vinyl aromatic compound and the conjugated diene compound.

[0145] In the hydrogenated copolymer (B), the content of vinyl aromatic compounds is more than 10% by mass and less than 80% by mass.

[0146] Vinyl aromatic compounds

[0147] Examples of vinyl aromatic compounds constituting the hydrogenated copolymer (B) include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc.

[0148] Of these, styrene, α-methylstyrene, and 4-methylstyrene are preferred in terms of availability and productivity.

[0149] These compounds can be used in single-component or in combination of two or more.

[0150] <Conjugated diene compounds>

[0151] As the conjugated diene compound constituting the hydrogenated copolymer (B), any diene having a conjugated double bond can be used, and examples include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, farnesene, etc.

[0152] Among these, 1,3-butadiene and isoprene are preferred from the perspectives of availability and productivity. These compounds can be used alone or in combination of two or more.

[0153] The hydrogenated copolymer (B) has a random copolymer structure formed by vinyl aromatic compounds and conjugated diene compounds.

[0154] <Preferred method for using hydrogenated copolymer (B) in the case of using hydrogenated copolymer (X) as a resin composition>

[0155] In the hydrogenated copolymer (B), the mass fraction (RS2) of the vinyl aromatic compound in the random copolymer structure is preferably in the range of 30% to 80% by mass, more preferably in the range of 35% to 75% by mass, and even more preferably in the range of 40% to 70% by mass.

[0156] When the above-mentioned (RS2) falls within the above-mentioned range, the hydrogenated copolymer (X) of this embodiment tends to exhibit good wear resistance when used in the resin composition.

[0157] <Preferred method of hydrogenated copolymer (B) when using hydrogenated copolymer (X) as a material for adhesive film>

[0158] In the hydrogenated copolymer (B), the mass fraction (RS2) of the vinyl aromatic compound in the random copolymer structure (hereinafter, when styrene is used, it is sometimes referred to as the styrene content in the random structure or the amount of random styrene) is preferably in the range of 10% to 60% by mass, more preferably in the range of 15% to 50% by mass, and even more preferably in the range of 20% to 45% by mass.

[0159] When (RS2) is within the above range, the hydrogenated copolymer (X) of this embodiment is used in the material of the adhesive film, and it tends to exhibit a good balance between adhesion and delivery.

[0160] The mass fraction of vinyl aromatic compounds in the random copolymer structure of the hydrogenated copolymer (B) can be determined by nuclear magnetic resonance (NMR). Specifically, it can be determined by the method described in the examples below. The mass fraction of vinyl aromatic compounds in the random copolymer structure of the hydrogenated copolymer (B) can be controlled within the above-mentioned range by adjusting the amount and timing of addition of vinyl aromatic compounds in the polymerization process.

[0161] <Preferred method for using hydrogenated copolymer (B) in the case of using hydrogenated copolymer (X) as a resin composition>

[0162] The content of vinyl aromatic compounds in the hydrogenated copolymer (B) is 10% to 80% by mass, preferably 30% to 80% by mass, more preferably 35% to 75% by mass, and even more preferably 40% to 70% by mass.

[0163] When the content of vinyl aromatic compounds in the hydrogenated copolymer (B) is 80% by mass or less, the hydrogenated copolymer (X) of this embodiment tends to have low hardness; when it is 10% by mass or more, it tends to exhibit excellent resistance to particle adhesion.

[0164] Furthermore, by keeping the content of vinyl aromatic compounds in the hydrogenated copolymer (B) in the range of 10% to 80% by mass, the hydrogenated copolymer (X) of this embodiment tends to exhibit good abrasion resistance when used in a resin composition.

[0165] <Preferred method of hydrogenated copolymer (B) when using hydrogenated copolymer (X) as a material for adhesive film>

[0166] The content of vinyl aromatic compounds in the hydrogenated copolymer (B) is 10% to 80% by mass, preferably 10% to 60% by mass, more preferably 20% to 55% by mass, and even more preferably 25% to 50% by mass.

[0167] When the content of vinyl aromatic compounds in the hydrogenated copolymer (B) is 80% by mass or less, the hydrogenated copolymer (X) of this embodiment tends to have improved adhesive strength, and when it is 10% by mass or more, it tends to exhibit excellent resistance to particle adhesion.

[0168] Furthermore, by keeping the content of vinyl aromatic compounds in the hydrogenated copolymer (B) in the range of 10% to 80% by mass, when the hydrogenated copolymer (X) of this embodiment is applied to the material of the adhesive film, it tends to exhibit a good balance between adhesion and delivery.

[0169] The content of vinyl aromatic compounds in the hydrogenated copolymer (B) can be determined by proton nuclear magnetic resonance (NMR) method (hereinafter referred to as...). 1 The determination is performed using ¹H-NMR. Specifically, the determination can be performed using the method described in the examples below.

[0170] The content of vinyl aromatic compounds in the hydrogenated copolymer (B) can be controlled within the above-mentioned range by adjusting the amount of vinyl aromatic compounds added during the polymerization process.

[0171] The hydrogenated copolymer (B) has a random copolymer structure formed by vinyl aromatic compounds and conjugated diene compounds.

[0172] In addition, the hydrogenated copolymer (B) preferably has at least one polymer block mainly composed of vinyl aromatic compounds.

[0173] The hydrogenated copolymer (B) preferably has, but is not limited to, a structure represented by the following general formula.

[0174] (de) o

[0175] ded

[0176] def

[0177] dfe

[0178] defd

[0179] defe

[0180] dfde

[0181] dfef

[0182] defed

[0183] dfefd

[0184] [(df) o ] p -Z

[0185] (def) p -Z

[0186] (dfe) p -Z

[0187] (defe) p -Z

[0188] (dfef) p -Z

[0189] In the above formula, d, e, and f represent polymer blocks (d), (e), and (f), respectively.

[0190] From the perspective of the mechanical strength of the hydrogenated copolymer (X) of this embodiment, the hydrogenated copolymer (B) is more preferably having two or more polymer blocks (d).

[0191] In addition, hydrogenated copolymer (B) can be a mixture of polymers containing a plurality of the above structures in any proportion.

[0192] In the above general formulas representing hydrogenated copolymers (B), (d) is a polymer block mainly composed of vinyl aromatic compounds, (e) is a polymer block mainly composed of conjugated diene compounds, and (f) is a random copolymer block formed by vinyl aromatic compounds and conjugated diene compounds.

[0193] o is an integer greater than or equal to 1, preferably an integer from 1 to 10, and more preferably an integer from 1 to 5.

[0194] p is an integer of 2 or more, preferably an integer of 2 to 11, and more preferably an integer of 2 to 8.

[0195] Z represents a coupling agent residue. Here, a coupling agent residue refers to the bonded residue of the coupling agent used for bonding between polymer blocks (e) and between polymer blocks (f).

[0196] Examples of coupling agents include, but are not limited to, polyhalogenated compounds and esters, which will be described later.

[0197] From a strength perspective, hydrogenated copolymer (B) is preferably polymerized by step-growth polymerization. "Polymerization by step-growth polymerization" means polymerizing from one end of the polymer structure as the final target to the opposite end, i.e., polymerizing without using a coupling reaction.

[0198] From a strength perspective, it is preferable that the hydrogenated copolymer (B) does not contain coupling agent residues. This prevents the incorporation of undesirable uncoupled polymers, etc.

[0199] The vinyl aromatic compounds in the polymer block (f) can be uniformly distributed or distributed in a gradient manner. Furthermore, the vinyl aromatic compounds can exist in multiple uniformly distributed portions and / or gradient-distributed portions. Additionally, multiple portions with varying amounts of vinyl aromatic compounds can coexist in the polymer block (f).

[0200] The lower limit of the number average molecular weight (Mn2) of the hydrogenated copolymer (B) is preferably 120,000 or more, more preferably 150,000 or more, and even more preferably 160,000 or more.

[0201] When the number average molecular weight (Mn2) of hydrogenated copolymer (B) is above 120,000, it tends to increase the entanglement between polymers and improve the mechanical strength, and also tends to exhibit good resistance to particle adhesion.

[0202] The upper limit of the number average molecular weight (Mn2) of the hydrogenated copolymer (B) is preferably 1 million or less, more preferably 800,000 or less, even more preferably 500,000 or less, and even more preferably 200,000 or less.

[0203] When the number average molecular weight (Mn2) of the hydrogenated copolymer (B) is less than 1 million, the hydrogenated copolymer (X) of this embodiment tends to have low shear viscosity and low hardness.

[0204] Furthermore, if the number average molecular weight (Mn2) of the hydrogenated copolymer (B) is less than 200,000, then when the hydrogenated copolymer (X) of this embodiment is made into a resin composition, it can be well mixed without affecting the viscosity of the thermoplastic resin other than the hydrogenated copolymer (X) and / or the rubbery polymer other than the hydrogenated copolymer (X) constituting the resin composition, and tends to have good wear resistance.

[0205] The number-average molecular weight (Mn2) of the hydrogenated copolymer (B) can be determined by GPC.

[0206] The number-average molecular weight (Mn2) of the hydrogenated copolymer (B) can be controlled within the above-mentioned range by adjusting conditions such as the amount of monomer added and the amount of polymerization initiator added in the polymerization process.

[0207] The ratio of the weight-average molecular weight (Mw2) to the number-average molecular weight (Mn2) of the hydrogenated copolymer (B) (Mw2 / Mn2) is preferably less than 1.15, more preferably less than 1.14, and even more preferably less than 1.13.

[0208] Polymers with a (Mw2 / Mn2) ratio less than 1.15 tend to have increased mechanical strength. Polymers with a (Mw2 / Mn2) ratio less than 1.15 tend to be readily manufactured through stepwise polymerization.

[0209] The hydrogenation rate (also known as hydrogenation rate) of the aliphatic double bond from the conjugated diene compound in the hydrogenated copolymer (B) is preferably 40% or more, more preferably 60% or more, and even more preferably 80% or more.

[0210] When the hydrogenation rate of the hydrogenated copolymer (B) is 40% or higher, it can suppress the thermal degradation (oxidative degradation) of the hydrogenated copolymer (X) of this embodiment. In addition, it also tends to have good resistance to particle sticking.

[0211] The hydrogenation rate can be controlled, for example, by the amount of catalyst during hydrogenation, and the hydrogenation speed can be controlled, for example, by the amount of catalyst, the amount of hydrogen fed, the pressure, and the temperature during hydrogenation.

[0212] It should be noted that the hydrogenation rate can be determined using NMR.

[0213] The amount of unhydrogenated vinyl bonds in the conjugated diene compound of the hydrogenated copolymer (B) is preferably 5 mol% to 80 mol%, more preferably 7 mol% to 75 mol%, and even more preferably 10 mol% to 70 mol%.

[0214] When the amount of vinyl bonds in the hydrogenated copolymer (B) before hydrogenation is 5 mol% or more, the hydrogenated copolymer (X) of this embodiment tends to have low hardness. When the amount of vinyl bonds in the hydrogenated copolymer (B) before hydrogenation is 80 mol% or less, it tends to exhibit good resistance to particle adhesion.

[0215] (The difference between hydrogenated copolymer (A) and hydrogenated copolymer (B))

[0216] The hydrogenated copolymer (X) in this embodiment comprises hydrogenated copolymer (A) and hydrogenated copolymer (B), and therefore has more than two peaks in the GPC spectrum. Hydrogenated copolymer (A) refers to all components with a number average molecular weight of 40,000 or less, or, if no components with a number average molecular weight of 40,000 or less exist, the component with the lowest molecular weight among the peaks in the GPC spectrum.

[0217] (Relationship between the number-average molecular weights of hydrogenated copolymers (A) and (B))

[0218] The ratio (Mn1 / Mn2) of the number-average molecular weight (Mn1) of the hydrogenated copolymer (A) to the number-average molecular weight (Mn2) of the hydrogenated copolymer (B) is less than 0.25, preferably less than 0.20, more preferably less than 0.17, and even more preferably less than 0.12.

[0219] When (Mn1 / Mn2) is less than 0.25, the hydrogenated copolymer (X) of this embodiment has good processability, tends to suppress the generation of flow marks during injection molding when applied to resin compositions, and tends to exhibit good wear resistance.

[0220] (Mass ratio of hydrogenated copolymer (A) to hydrogenated copolymer (B))

[0221] In the hydrogenated copolymer (X) of this embodiment, from the perspective of balancing shear viscosity and granule adhesion and abrasion resistance of the resin composition, the mass ratio (A) / (B) of the content of the above-mentioned hydrogenated copolymer (A) to hydrogenated copolymer (B) is 5 / 95 to 50 / 50, preferably 10 / 90 to 50 / 50, and more preferably 30 / 70 to 50 / 50.

[0222] By including 5% by mass or more of hydrogenated copolymer (A) in the hydrogenated copolymer (X) of this embodiment, the hydrogenated copolymer (X) tends to exhibit good processability and, when applied to a resin composition, tends to suppress the generation of flow marks during injection molding. By including 50% by mass or less of hydrogenated copolymer (A), when applied to a resin composition, it tends to suppress gate breakage during injection molding and tends to improve mold release properties.

[0223] In addition, the hydrogenated copolymer (A) alone will experience cold flow, making it difficult for the molded part to maintain its shape.

[0224] (tanδ peak in viscoelasticity determination of hydrogenated copolymer (X))

[0225] When the hydrogenated copolymer (X) of this embodiment is used as a resin composition, the hydrogenated copolymer (X) preferably has at least one tanδ peak in the viscoelasticity test (1 Hz) in the range of -20°C to 40°C, more preferably in the range of -10°C to 30°C, and even more preferably in the range of 0°C to 20°C.

[0226] By placing the tanδ peak of the hydrogenated copolymer (X) of this embodiment within the range of -20°C to 40°C, when the hydrogenated copolymer (X) of this embodiment is made into a resin composition, low hardness can be achieved, and it tends to improve wear resistance.

[0227] When the hydrogenated copolymer (X) of this embodiment is used as an adhesive film, the hydrogenated copolymer (X) preferably has at least one tanδ peak in the viscoelasticity test (1 Hz) in the range of -20°C to 40°C, more preferably in the range of -20°C to 25°C, and even more preferably in the range of -20°C to 10°C.

[0228] By placing the tanδ peak of the hydrogenated copolymer (X) of this embodiment in the range of -20°C to 40°C, low hardness can be achieved, and it tends to improve adhesion.

[0229] The tanδ peak temperature of the hydrogenated copolymer (X) can be controlled by adjusting the structure and content of the hydrogenated copolymers (A) and (B).

[0230] The greater the mass fraction (RS1) of vinyl aromatic compounds in the random copolymer structure of hydrogenated copolymer (A), the more it tends to increase the tanδ peak temperature of hydrogenated copolymer (X).

[0231] The greater the mass fraction (RS2) of vinyl aromatic compounds in the random copolymer structure of hydrogenated copolymer (B), the more it tends to have an increased tanδ peak temperature of hydrogenated copolymer (X).

[0232] Furthermore, when the tanδ peak temperature of hydrogenated copolymer (A) is lower than that of hydrogenated copolymer (B), the tanδ peak temperature of hydrogenated copolymer (X) tends to decrease as the content of hydrogenated copolymer (A) increases. Conversely, when the tanδ peak temperature of hydrogenated copolymer (A) is higher than that of hydrogenated copolymer (B), the tanδ peak temperature of hydrogenated copolymer (X) tends to increase as the content of hydrogenated copolymer (A) increases.

[0233] (Relationship between the content of vinyl aromatic compounds in the random copolymer structures of hydrogenated copolymers (A) and (B))

[0234] The ratio (RS1 / RS2) of the mass fraction (RS1) of the vinyl aromatic compound in the random copolymer structure of the hydrogenated copolymer (A) to the mass fraction (RS2) of the vinyl aromatic compound in the random copolymer structure of the hydrogenated copolymer (B) is preferably in the range of 0.80 to 1.20, more preferably in the range of 0.82 to 1.18, and even more preferably in the range of 0.85 to 1.15.

[0235] When (RS1 / RS2) is in the range of 0.80 to 1.20, hydrogenated copolymer (A) and hydrogenated copolymer (B) have high compatibility and tend to improve resistance to particle sticking.

[0236] It should be noted that the mass fraction of vinyl aromatic compounds in the random copolymer structures of hydrogenated copolymer (A) and hydrogenated copolymer (B) can be controlled within the above-mentioned range by adjusting the amount of vinyl aromatic compounds added during polymerization, and can be determined by NMR.

[0237] (Relationship of molecular weights of the vinyl aromatic-based blocks in hydrogenated copolymers (A) and (B))

[0238] When both hydrogenated copolymer (A) and hydrogenated copolymer (B) have polymer blocks mainly composed of vinyl aromatic compounds, the ratio (MnS1 / MnS2) of the molecular weight (MnS1) of the polymer block mainly composed of vinyl aromatic compounds in the hydrogenated copolymer (A) to the molecular weight (MnS2) of the polymer block mainly composed of vinyl aromatic compounds in the hydrogenated copolymer (B) is preferably 0.9 or less, more preferably 0.8 or less, and even more preferably 0.7 or less.

[0239] When (MnS1 / MnS2) is 0.9 or less, the hydrogenated copolymer (X) of this embodiment tends to have low hardness.

[0240] It should be noted that (MnS1) and (MnS2) can be adjusted by the amount of monomer added during polymerization.

[0241] MnS1 and MnS2 are calculated using the following method.

[0242] MnS1=Mn1×BS1

[0243] MnS2=Mn2×BS2÷f

[0244] ·BS1: via proton nuclear magnetic resonance (NMR) 1 The content of the polymer blocks mainly composed of vinyl aromatic compounds in the above-mentioned hydrogenated copolymer (A) was determined by H-NMR.

[0245] ·BS2: via proton nuclear magnetic resonance (NMR) 1 The content of the polymer blocks mainly composed of vinyl aromatic compounds in the above-mentioned hydrogenated copolymer (B) was determined by H-NMR.

[0246] • f: Degree of branching of the hydrogenated copolymer (B) determined by GPC-light scattering method with viscosity detector.

[0247] • Mn1: Number average molecular weight of hydrogenated copolymer (A)

[0248] • Mn2: Number average molecular weight of hydrogenated copolymer (B)

[0249] (Mn1) and (Mn2) can be determined by using GPC to create calibration curves from standard polystyrene.

[0250] (BS1) and (BS2) can be determined by NMR.

[0251] (f) It can be determined by the GPC-light scattering method with a viscosity detector.

[0252] It should be noted that the specific determination method is described below.

[0253] The method for determining the mass fraction (RS1) and (RS2) of vinyl aromatic compounds in random copolymer structures, and the content (BS1) and (BS2) of polymer blocks mainly composed of vinyl aromatic compounds, will be specifically explained using NMR, with styrene as the vinyl aromatic compound and 1,3-butadiene as the conjugated diene compound.

[0254] The samples were prepared by dissolving 30 mg of hydrogenated copolymer (A) and hydrogenated copolymer (B) in 1 g of deuterated chloroform, respectively. 1 The content (BS) of the block polymer structure (in this case, polystyrene block) mainly composed of vinyl aromatic compounds was determined by H-NMR determination based on the ratio of the integral value of the chemical shift 6.9ppm to 6.3ppm to the total integral value.

[0255] Block styrene strength (b-St strength) = (integral value from 6.9ppm to 6.3ppm) / 2

[0256] Random styrene strength (r-St strength) = (integral value from 7.5ppm to 6.9ppm) - 3 × (b-St)

[0257] Ethylene-butene strength (EB strength) = Total integral value - 3 × {(b-St strength) + (r-St strength)} / 8

[0258] Polystyrene block content (BS) = 104 × (b-St strength) / [104 × {(b-St strength) + (r-St strength)} + 56 × (EB strength)]

[0259] Styrene content (RS) in random copolymer structure = 104 × (r-St strength) / {104 × (r-St strength) + 56 × (EB strength)}

[0260] (Degree of branching (f) of hydrogenated copolymer (B))

[0261] The degree of branching (f) of the hydrogenated copolymer (B) can be determined by the GPC-light scattering method with a viscosity detector.

[0262] Hydrogenated copolymer (B) was used as a sample, and GPC-light scattering method with viscosity detector was performed to determine the absolute molecular weight (M) based on standard polystyrene, and intrinsic viscosity ([η]) was determined based on the results of light scattering detector and RI detector.

[0263] Next, the intrinsic viscosity ([η]0) used as a reference is calculated using the following formula.

[0264] [η]0=a×M b

[0265] a = -0.788 + 0.421 × (Vinyl Aromatic Compound Content of Hydrogenated Copolymer (B)) - 0.342 × (RS2) - 0.197 × (BS2)

[0266] b = 1.601 - 0.081 × (vinyl aromatic compound content of hydrogenated copolymer (B)) + 0.064 × (RS2) + 0.039 × (BS2)

[0267] RS2: Mass fraction of vinyl aromatic compounds in the random copolymer structure of hydrogenated copolymer (B)

[0268] BS2: via proton nuclear magnetic resonance (NMR) 1 The content of the polymer blocks mainly composed of vinyl aromatic compounds in the above-mentioned hydrogenated copolymer (B) was determined by H-NMR.

[0269] M: Absolute molecular weight of hydrogenated copolymer (B)

[0270] Next, the shrinkage factor g was calculated as the ratio of the intrinsic viscosity ([η]) of the hydrogenated copolymer (B) to the intrinsic viscosity ([η]0) used as a reference.

[0271] Contraction factor (g) = [η] / [η]0

[0272] Subsequently, the degree of branching (f), defined as g = f / {(f+1)(f+2)} (f≧2), was calculated using the obtained shrinkage factor (g).

[0273] (Methods for manufacturing hydrogenated copolymer (A) and hydrogenated copolymer (B))

[0274] Methods for manufacturing hydrogenated copolymer (A) and hydrogenated copolymer (B) can be exemplified, but are not limited to, those described in Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 48-4106, Japanese Patent Publication No. 51-49567, and Japanese Patent Application Publication No. 59-166518.

[0275] Copolymers before hydrogenation can be obtained by, but are not limited to, the following methods: using polymerization initiators such as organoalkali metal compounds in hydrocarbon solvents, or by living anionic polymerization using specified monomers; etc.

[0276] There are no particular limitations on what can be used as a hydrocarbon solvent. Examples include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cycloheptane, and methylcycloheptane; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

[0277] As polymerization initiators, organoalkali metal compounds known to have anionic polymerization activity for conjugated diene compounds and vinyl aromatic compounds can typically be used.

[0278] Examples include aliphatic hydrocarbon alkali metal compounds with 1 to 20 carbon atoms, aromatic hydrocarbon alkali metal compounds with 1 to 20 carbon atoms, and organic amino alkali metal compounds with 1 to 20 carbon atoms.

[0279] Examples of alkali metals included as polymerization initiators include, but are not limited to, lithium, sodium, and potassium.

[0280] It should be noted that an alkali metal can contain one or more types in a single molecule of an organoalkali metal compound.

[0281] Examples of polymerization initiators include, but are not limited to, reaction products of n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, diisopropenylbenzene and sec-butyllithium, and reaction products of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene.

[0282] Furthermore, alkyl lithium containing silaneoxy groups, such as 1-(tert-butoxy)propyllithium disclosed in U.S. Patent 5,708,092 and lithium compounds in which one to several molecules of isoprene monomer are inserted to improve their solubility, alkyl lithium containing silaneoxy groups, such as 1-(tert-butyldimethylsiloxy)hexyllithium disclosed in British Patent 2,241,239, and amino lithiums such as alkyl lithium containing amino groups, lithium diisopropylamine, and lithium hexamethyldisilazum disclosed in U.S. Patent 5,527,753, can also be used.

[0283] The amount of lithium compound used as a polymerization initiator depends on the molecular weight of the target copolymer, preferably 0.005 to 6.4 phm (relative to the mass parts per 100 parts by mass of monomer), more preferably 0.005 to 1.3 phr.

[0284] When using organoalkali metal compounds as polymerization initiators to copolymerize conjugated diene compounds with vinyl aromatic compounds, tertiary amine compounds or ether compounds can be added to adjust the content of vinyl bonds (1,2-bonds or 3,4-bonds) brought about by the conjugated diene compounds embedded in the copolymer, or to adjust the random copolymerization of the conjugated diene compounds and vinyl aromatic compounds.

[0285] There are no particular limitations on the tertiary amine compounds mentioned above; for example, compounds represented by the following formula can be cited.

[0286] R1R2R3N

[0287] (In the formula, R1, R2, and R3 are hydrocarbon groups or tertiary amino groups having 1 to 20 carbon atoms.)

[0288] Examples of such tertiary amine compounds include, but are not limited to, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinylethane, trimethylaminoethylpiperazine, N,N,N',N'',N''-pentamethylethylenetriamine, and N,N'-dioctyl-p-phenylenediamine. Among these, N,N,N',N'-tetramethylethylenediamine is preferred.

[0289] In addition, straight-chain ether compounds, cyclic ether compounds, etc., can be used as the above-mentioned ether compounds.

[0290] Examples of linear ether compounds include dialkyl ethers of ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; and dialkyl ethers of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.

[0291] In addition, examples of cyclic ether compounds include tetrahydrofuran, dioxane, 2,5-dimethyltetrahydrofuran, 2,2,5,5-tetramethyltetrahydrofuran, 2,2-bis(2-tetrahydrofuranyl)propane, and alkyl ethers of furfuryl alcohol.

[0292] The amount of tertiary amine compound or ether compound used relative to the polymerization initiator of the above-mentioned organoalkali metal compound is preferably 0.1 to 4 (moles / 1 mole of alkali metal), more preferably 0.2 to 3 (moles / 1 mole of alkali metal).

[0293] In the manufacturing process of hydrogenated copolymers (A) and (B), sodium alkoxide may coexist during the copolymerization of conjugated diene compounds and vinyl aromatic compounds.

[0294] Sodium alkoxides are, for example, but not limited to, compounds represented by the following formula. In particular, sodium alkoxides having alkyl groups having 3 to 6 carbon atoms are preferred, and sodium tert-butoxide and sodium tert-amyloxide are more preferred.

[0295] NaOR

[0296] (In the formula, R is an alkyl group with 2 to 12 carbon atoms.)

[0297] In the polymerization process of hydrogenated copolymers (A) and (B), the amount of sodium alkoxide used is preferably 0.01 or more and less than 0.1 (molar ratio) relative to the vinyl bonding amount adjuster (tertiary amine compound or ether compound), more preferably 0.01 or more and less than 0.08 (molar ratio), even more preferably 0.03 or more and less than 0.08 (molar ratio), and even more preferably 0.04 or more and less than 0.06 (molar ratio).

[0298] When the amount of sodium alkoxide is within this range, it has copolymer blocks containing conjugated diene compounds with high vinyl bonding content, and polymer blocks mainly composed of vinyl aromatic compounds with narrow molecular weight distribution, and tends to produce copolymers with narrow molecular weight distribution with high productivity.

[0299] There are no particular limitations on the method of copolymerizing conjugated dienes with vinyl aromatic compounds using organoalkali metal compounds as polymerization initiators; it can be batch polymerization, continuous polymerization, or a combination thereof.

[0300] There is no particular limitation on the polymerization temperature, which is usually 0 to 180°C, preferably 30 to 150°C.

[0301] The time required for polymerization varies depending on the conditions, but is usually within 48 hours, preferably 0.1 to 10 hours.

[0302] In addition, polymerization is preferably carried out in an inert gas atmosphere such as nitrogen.

[0303] Regarding polymerization pressure, polymerization can be carried out at a pressure sufficient to keep the monomer and solvent in the liquid phase within the above-mentioned polymerization temperature range, without any particular limitation.

[0304] In addition, at the end of the polymerization, a necessary amount of coupling agent with two or more functional groups can be added to carry out the coupling reaction.

[0305] There are no particular limitations on coupling agents with two or more functional groups; any known coupling agents may be used.

[0306] Examples of difunctional coupling agents include, but are not limited to, dihalides such as dimethyldichlorosilane and dimethyldibromosilane; and esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates.

[0307] Examples of multifunctional coupling agents with 3 or more functional groups include, but are not limited to, 1,1,1,2,2-pentachloroethane, perchloroethane, pentachlorobenzene, perchlorobenzene, octabromodiphenyl ether, decabromodiphenyl ether, polyols with 3 or more members, epoxidized soybean oil, diglycidyl bisphenol A and other polyepoxide compounds, 2- to 6-functional epoxy-containing compounds, carboxylic acid esters, divinylbenzene and other polyvinyl groups, and R1(4-n)SiX. n (Here, R1 represents a hydrocarbon group with 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 or 4) represents silicon halide compounds and tin halide compounds.

[0308] Examples of silicon halide compounds include, but are not limited to, methyltrichlorosilane, tert-butyltrichlorosilane, silicon tetrachloride, and their bromides.

[0309] Examples of tin halide compounds include, but are not limited to, methyltin trichloride, tert-butyltin trichloride, tin tetrachloride, and other multi-component halides. Dimethyl carbonate and diethyl carbonate can also be used.

[0310] Hydrogenated copolymers (A) and (B) can be obtained by adding a modifier that will generate functional groups to the active ends of the block copolymer obtained by the above method.

[0311] Examples of atomic groups containing functional groups include, but are not limited to, atomic groups containing at least one functional group selected from the group consisting of hydroxyl, carbonyl, thiocarbonyl, acyl halide, acid anhydride, carboxyl, thiocarboxylic acid, aldehyde, thioaldehyde, carboxylic acid ester, amide, sulfonic acid, sulfonate, phosphoric acid, phosphate ester, amino, imino, nitrile, pyridinyl, quinolinyl, epoxy, thioepoxy, thioether, isocyanate, isothiocyanate, silyl halide, silanol, alkoxysilyl, tin halide, alkoxytin, and phenyltin.

[0312] Examples of modifiers containing various functional groups include, but are not limited to, tetraglycidyl-m-phenylenediamine, tetraglycidyl-1,3-diaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxybenzophenone, γ-epoxypropoxyethyltrimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, γ-epoxypropoxypropyldimethylphenoxysilane, bis(γ-epoxypropoxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolinone, 1,3-diethyl-2-imidazolinone, N,N'-dimethylacrylurea, and N-methylpyrrolidone.

[0313] The amount of modifier added relative to 100 parts by weight of the copolymer before modification is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, and even more preferably 0.3 to 10 parts by weight.

[0314] The addition reaction temperature of the modifier is preferably 0 to 150°C, more preferably 20 to 120°C.

[0315] The time required for the modification reaction varies depending on the modification reaction conditions, preferably within 24 hours, and more preferably 0.1 to 10 hours.

[0316] The hydrogenated copolymers (A) and (B) constituting the hydrogenated copolymer (X) of this embodiment are manufactured by performing a hydrogenation process after the above-described polymerization process or after the above-described modification process.

[0317] There are no particular limitations on the hydrogenation catalyst used to manufacture hydrogenated copolymers (A) and (B). For example, hydrogenation catalysts described in Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, Japanese Patent Publication No. 1-53851, and Japanese Patent Publication No. 2-9041 can be used.

[0318] As preferred hydrogenation catalysts, mixtures of cyclopentadiene titanium compounds and / or reducing organometallic compounds can be cited.

[0319] There are no particular limitations on the cyclopentadiene titanium compound. For example, compounds described in Japanese Patent Application Publication No. 8-109219 can be cited. Specifically, compounds such as dicyclopentadiene titanium dichloride and monopentamethylcyclopentadiene titanium trichloride, which have at least one ligand with a (substituted) cyclopentadiene structure, an indene structure, or a fluorene structure, can be cited.

[0320] There are no particular limitations on reducing organometallic compounds; examples include organolithium and other organoalkali metal compounds, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

[0321] The reaction temperature for hydrogenation is typically 0–200°C, preferably 30–150°C.

[0322] The pressure of hydrogen used in the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and even more preferably 0.3 to 5 MPa.

[0323] The reaction time for hydrogenation is typically 3 minutes to 10 hours, preferably 10 minutes to 5 hours.

[0324] It should be noted that hydrogenation can be carried out using batch processes, continuous processes, or any combination thereof.

[0325] After the hydrogenation process, catalyst residue can be removed from the reaction solution as needed.

[0326] Methods for separating hydrogenated copolymers from solvents include, but are not limited to, the following: adding a polar solvent, such as acetone or alcohol, which is a poor solvent for the hydrogenated copolymer, to a solution of the hydrogenated copolymer to precipitate the copolymer and then recovering it; or immersing the solution of the hydrogenated copolymer in hot water under stirring to remove the solvent by stripping and then recovering it; or removing the solvent by directly heating the solution of the hydrogenated copolymer and then distilling it; and so on.

[0327] In the hydrogenated copolymer (X) of this embodiment, antioxidants such as those described below may be added during manufacturing to make the surface and / or interior contain antioxidants.

[0328] It should be noted that the antioxidants described below may also be added to the resin composition of this embodiment described later.

[0329] Examples of antioxidants include, but are not limited to, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and amine antioxidants.

[0330] Specifically, examples include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butyl-phenyl)propionate, tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 4,4'-butylenebis-(3-methyl-6-tert-butylphenol), and 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-di [Methylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)1,3,5-triazine, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylidene bis[3-(3,5-di-tert-butyl] [3,5-di-tert-butyl-4-hydroxybenzyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamonamide), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, a mixture of calcium bis(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate and polyethylene wax (50%), octyl diphenylamine, 2,4-bis[(octylthio)methyl]-o-cresol, isooctyl-3-(3,5-di-tert-butyl-4-hydroxybenzyl)propionate, N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, isooctyl-3-(3,5-di-tert-butyl-4-hydroxybenzyl)propionate, diethyl 3,5-di-tert-butyl-4-hydroxybenzyl)phosphon ... 3,3-bis(3-tert-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, and 2-[1-(2-hydroxy-3,5-ditert-pentylphenyl)-ethyl]-4,6-ditert-pentylphenyl acrylate, etc.

[0331] (Method for manufacturing hydrogenated copolymer (X))

[0332] There are no particular limitations on the manufacturing method of hydrogenated copolymer (X). Examples include: (1) mixing hydrogenated copolymer (A) and hydrogenated copolymer (B) separately before recovering them from the manufacturing solvent; (2) removing solvent and catalyst from hydrogenated copolymer (A) and hydrogenated copolymer (B) separately and then mixing them; (3) adding polymerization initiator in two stages during the polymerization reaction; (4) adding a modifier for the above-mentioned active ends or a protic agent such as an alcohol as a polymerization terminator during the polymerization reaction to stop the reaction of some active ends; (5) adding a modifier for the above-mentioned active ends or a protic agent such as an alcohol as a polymerization terminator after the polymerization reaction to stop the reaction of all active ends, and then adding polymerization initiator and monomer back into the solution to carry out polymerization; (6) adding liquid hydrogenated copolymer (A) to hydrogenated copolymer (B) during extrusion compounding; and so on.

[0333] The method described in (1) above can be implemented by either mixing the polymerization solutions of hydrogenated copolymer (A) and hydrogenated copolymer (B) before hydrogenation and then performing the hydrogenation reaction, or by performing hydrogenation reactions on hydrogenated copolymer (A) and hydrogenated copolymer (B) separately and then mixing their respective solutions. Furthermore, the mixing ratio of hydrogenated copolymer (A) and hydrogenated copolymer (B) can be controlled by adjusting the concentration of their respective polymerization solutions and the mixing volume of the solutions.

[0334] In the method described in (3) above, the mixing ratio of hydrogenated copolymer (A) and hydrogenated copolymer (B) can be arbitrarily controlled by adjusting the feeding rate of vinyl aromatic compound and conjugated diene compound, the amount of polymerization initiator added in the second stage, and the timing of the second stage addition of polymerization initiator.

[0335] In the method described in (4) above, the mixing ratio of hydrogenated copolymer (A) and hydrogenated copolymer (B) can be arbitrarily controlled by adjusting the feeding rate of vinyl aromatic compound and conjugated diene compound, the amount of modifier or polymerization terminator added midway, and the timing of addition.

[0336] The hydrogenated copolymer (A) is a low molecular weight polymer with minimal molecular entanglement. Therefore, when mixed before desolventizing as in methods (1), (3), (4), and (5), the desolventizing / finishing process can be performed at a high rate.

[0337] Methods (3), (4) and (5) can produce hydrogenated copolymer (A) and hydrogenated copolymer (B) simultaneously, which reduces production steps compared to producing hydrogenated copolymer (A) and hydrogenated copolymer (B) separately, thus improving production efficiency.

[0338] There are no particular limitations on what can be used as a polymerization terminator; examples include water; methanol, ethanol, isopropanol, 2-ethylhexanol, heptanol, mixtures thereof, and other alcohols; etc.

[0339] The hydrogenated copolymer (X) of this embodiment can be granulated.

[0340] Examples of granulation methods include: extruding hydrogenated copolymer (X) in a filament from a single-screw or twin-screw extruder and cutting it in water using rotating blades positioned in front of the die head; extruding hydrogenated copolymer in a filament from a single-screw or twin-screw extruder, and cutting it in water or air cooling using a filament pelletizer; melting and mixing the copolymer in an open mill or Banbury mixer, forming it into sheets using roll forming, cutting the sheets into strips, and then cutting them into cubic granules using a pelletizer; and so on.

[0341] It should be noted that there are no particular limitations on the size or shape of the hydrogenated copolymer (X) particles.

[0342] In hydrogenated copolymer (X), in order to prevent granules from sticking together, a granule anti-blocking agent can be mixed into the granules as needed.

[0343] Examples of anti-blocking agents for granules include, but are not limited to, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, ethylene bis-stearamide, talc, and amorphous silica.

[0344] The preferred mixing amount of the granule anti-blocking agent is 500 to 6000 ppm relative to the hydrogenated copolymer (X), and a more preferred amount is 1000 to 5000 ppm. The granule anti-blocking agent is preferably mixed in a state of adhering to the surface of the granules, but it may also be contained to some extent inside the granules.

[0345] (Molecular weight distribution of hydrogenated copolymers (A) and (B))

[0346] The molecular weight distribution (Mw / Mn) of the hydrogenated copolymer (A) is preferably 1.01 to 8.0, more preferably 1.01 to 6.0, and even more preferably 1.01 to 5.0. When the molecular weight distribution is within the above range, there is a tendency to obtain better molding and processability.

[0347] It should be noted that the shape of the molecular weight distribution of the hydrogenated copolymer (A) determined by GPC is not particularly limited. It can have a multi-peak molecular weight distribution with more than two peaks, or it can have a single-peak molecular weight distribution with only one peak.

[0348] It should be noted that the weight-average molecular weight (Mw) and molecular weight distribution [Mw / Mn; the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn)] of the hydrogenated copolymer (A) can be determined using a calibration curve (made using the peak molecular weight of standard polystyrene) derived from the determination of the peak molecular weight of commercially available standard polystyrene, based on the molecular weight of the peak in the chromatogram determined by GPC using the method described in the examples below.

[0349] The molecular weight distribution (Mw / Mn) of the hydrogenated copolymer (B) is preferably 1.01 to 8.0, more preferably 1.01 to 6.0, and even more preferably 1.01 to 5.0. When the molecular weight distribution is within the above range, there is a tendency to obtain better molding and processability.

[0350] It should be noted that the shape of the molecular weight distribution of the hydrogenated copolymer (B) determined by GPC is not particularly limited. It can have a multi-peak molecular weight distribution with more than two peaks, or it can have a single-peak molecular weight distribution with only one peak.

[0351] It should be noted that the weight-average molecular weight (Mw) and molecular weight distribution [Mw / Mn; the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn)] of the hydrogenated copolymer (B) can be determined using a calibration curve (made using the peak molecular weight of standard polystyrene) derived from the determination of the peak molecular weight of commercially available standard polystyrene, based on the molecular weight of the peak in the chromatogram determined by GPC using the method described in the examples below.

[0352] [Resin Composition]

[0353] In the resin composition of this embodiment, the content of vinyl aromatic compounds in hydrogenated copolymers (A) and (B) is more than 30% by mass and less than 80% by mass, and contains hydrogenated copolymer (X) of this embodiment and thermoplastic resins other than the above-mentioned hydrogenated copolymer (X) and / or rubbery polymers other than the above-mentioned hydrogenated copolymer (X).

[0354] By combining the hydrogenated copolymer (X) of this embodiment with thermoplastic resins other than the hydrogenated copolymer (X) and / or rubbery polymers other than the copolymers described above, resin compositions suitable for various molding materials can be obtained.

[0355] In this embodiment, the mixing ratio of hydrogenated copolymer (X) to thermoplastic resin and / or rubber-like polymer in the resin composition is preferably, by mass ratio, hydrogenated copolymer (X) / (thermoplastic resin and / or rubber-like polymer) = 1 / 99 to 99 / 1, more preferably 2 / 98 to 90 / 10, and even more preferably 5 / 95 to 80 / 20.

[0356] When the hydrogenated copolymer (X) of this embodiment is mixed with thermoplastic resins and / or rubbery polymers other than the hydrogenated copolymer (X), a resin composition with excellent impact resistance and molding processability can be obtained.

[0357] As a thermoplastic resin other than the hydrogenated polymer (X) of this embodiment used in the resin composition, examples include, but are not limited to, polymers of the vinyl aromatic compounds described above; copolymers of the vinyl aromatic compounds with other vinyl compounds (e.g., ethylene, propylene, butene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylates such as acrylic acid and methyl acrylate, methacrylates such as methacrylic acid and methyl methacrylate, acrylonitrile, methacrylonitrile, etc.); rubber-modified styrene resins (HIPS); acrylonitrile-butadiene-styrene. Copolymer resins (ABS); methacrylate-butadiene-styrene copolymer resin (MBS); polyethylene; ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, ethylene-vinyl acetate copolymers and their hydrolysates, etc., are copolymers formed from ethylene and other copolymerizable monomers, with an ethylene content of 50% by mass or more; ethylene-acrylic acid ionomers, chlorinated polyethylene and other polyethylene-based resins; polypropylene; propylene-ethylene copolymers, propylene-ethyl acrylate copolymers, chlorinated polypropylene and other polypropylene-based resins, ethylene-norbornene resins and other cyclic olefin-based resins. Polyesters, polybutene-based resins, polyvinyl chloride-based resins, polyvinyl acetate-based resins and their hydrolysates, etc., are copolymers formed from propylene and other copolymerizable monomers, with a propylene content of 50% by mass or more; polymers of acrylic acid and its esters or amides; polyacrylate-based resins; polymers of acrylonitrile and / or methacrylonitrile; copolymers formed from acrylonitrile monomers and other copolymerizable monomers, with an acrylonitrile monomer content of 50% by mass or more, i.e., nitrile resins; polyamide-based resins such as nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, nylon-6 and nylon-12 copolymers. Resins; polyester resins; thermoplastic polyurethane resins; polycarbonate polymers such as poly-4,4'-dioxydiphenyl-2,2'-propane carbonate; thermoplastic polysulfones such as polyethersulfone and polyallyl sulfone; polyoxymethylene resins; polyphenylene ether resins such as poly(2,6-dimethyl-1,4-phenylene) ether; polyphenylene sulfide resins such as polyphenylene sulfide and poly-4,4'-diphenylene sulfide; polyarylate resins; polyetherketone polymers or copolymers; polyketide resins; fluorinated resins; polyoxybenzoyl polymers; polyimide resins; polybutadiene resins such as 1,2-polybutadiene and trans-polybutadiene, etc.

[0358] These thermoplastic resins can be bonded with atomic groups containing polar groups such as hydroxyl, epoxy, amino, carboxylic acid, and anhydride groups.

[0359] The number-average molecular weight of the thermoplastic resin used in the resin composition of this embodiment is preferably 1,000 or more, more preferably 50 million to 5 million, and even more preferably 10,000 to 1 million.

[0360] It should be noted that the number-average molecular weight of the thermoplastic resin can be determined by GPC in the same manner as the molecular weight determination of the hydrogenated copolymer (X) in this embodiment.

[0361] Furthermore, from the perspectives of formability, lightweight, and wear resistance, polyolefin resins are preferred as the thermoplastic resins used in the resin composition of this embodiment, and polypropylene resins are more preferred.

[0362] The thermoplastic resin and rubbery polymer used in the resin composition of the above embodiment can be combined in two or more forms as needed.

[0363] When using two or more types together, two or more thermoplastic resins or two or more rubber-like polymers may be used, or thermoplastic resins and rubber-like polymers may be used together.

[0364] Specifically, rubber-like polymers may be used to improve the impact resistance of resinous compositions (i.e., compositions in which resin constitutes the majority) and achieve low hardness, or resins may be used to improve the strength and heat resistance of rubber-like compositions (i.e., compositions in which rubber-like polymer constitutes the majority).

[0365] In this embodiment, any additives may be mixed in the hydrogenated copolymer (X) and resin composition as needed.

[0366] There are no particular limitations on additives as long as they are commonly mixed in thermoplastic resins and rubber-like polymers. Examples include substances listed in publications such as "Gomu Plastic Mixed Drugs" (Japan RubberDigest).

[0367] Specifically, the following can be used: reinforcing fillers, inorganic fillers such as calcium sulfate and barium sulfate; pigments such as carbon black and iron oxide; lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylene bis-stearamide; anti-blocking agents such as stearamide, mustardamide, oleamide, glyceryl monostearate, stearyl alcohol, petroleum-based waxes (e.g., microcrystalline wax), and low molecular weight vinyl aromatic resins; release agents; plasticizers such as organopolysiloxanes and mineral oils; antioxidants such as hindered phenolic antioxidants and phosphorus-based heat stabilizers; hindered amine light stabilizers and benzotriazole ultraviolet absorbers; flame retardants; antistatic agents; reinforcing agents such as organic fibers, glass fibers, carbon fibers, and metal whiskers; colorants; and mixtures thereof.

[0368] (Method for manufacturing the resin composition)

[0369] The method for manufacturing the resin composition in this embodiment is not particularly limited, and existing known methods can be applied.

[0370] For example, the following methods can be used: melt mixing using common mixers such as pressure kneaders, Banbury mixers, internal mixers, torque rheometers, MIX-LABO mixing experimental devices, single-screw extruders, twin-screw extruders, worm kneaders, and multi-screw extruders; methods that dissolve or disperse the components and then heat to remove the solvent; and so on.

[0371] The shape of the resin composition in this embodiment is not particularly limited, and examples include granules, flakes, filaments, and chips.

[0372] Alternatively, the molten compound can be directly molded into a shaped part.

[0373] [Molded articles using resin compositions]

[0374] The molded body of this embodiment is the molded body of the resin composition of this embodiment described above.

[0375] The resin composition in this embodiment is not particularly limited, and can be processed into a practically useful molded body by, for example, extrusion molding, injection molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotational molding, powder slush molding, foaming molding, lamination molding, calendering, blow molding, etc.

[0376] There is no particular limitation on the molded body used in this embodiment. Examples of molded bodies include sheets, films, injection molded bodies of various shapes, hollow molded bodies, air-molded bodies, vacuum molded bodies, extruded bodies, foamed bodies, non-woven or fibrous molded bodies, synthetic leather, and many other types of molded bodies.

[0377] These molded parts can be used in automotive parts, food packaging materials, medical devices, home appliance parts, electronic device parts, building materials, industrial parts, household goods, toy materials, footwear materials, fiber materials, etc.

[0378] As automotive components, examples include, but are not limited to, side moldings, oil sealing rings, knobs, sealing strips, window frames and their sealing materials, armrests, assistant handles, door handles, door trim panels, handles, control boxes, headrests, dashboards, bumpers, spoilers, airbag covers, etc.

[0379] As medical devices, examples include, but are not limited to, medical tubes, medical tubing, infusion tubes, blood bags, infusion bags, platelet storage bags, and artificial dialysis bags.

[0380] Examples of building materials include, but are not limited to, wall materials and flooring materials.

[0381] In addition, examples, but not limited to, include various covering materials such as industrial hoses, food hoses, vacuum cleaner hoses, electric cooling seals, wires, handle covering materials, and soft dolls.

[0382] Examples of fiber materials include sound-absorbing materials, clothing components, non-woven fabrics for filtration, and hygiene products.

[0383] The molded body of this embodiment can be appropriately subjected to processes such as foaming, powdering, stretching, bonding, printing, coating, and plating.

[0384] In recent years, autonomous driving and mobility services have attracted attention as new directions for the automotive industry. Following this trend, the performance requirements for automotive interior materials have also changed.

[0385] For example, with the advent of autonomous driving, the meaning of cars as living spaces is expected to become stronger. Therefore, in order to create more comfortable living spaces for passengers, there is a push towards more sophisticated interior designs and greater diversity in interior decoration. Consequently, resin compositions used as automotive interior materials are required to have good processability, enabling more refined designs than ever before, as well as a good texture (low hardness) and appearance.

[0386] Furthermore, it is believed that from the perspective of travel services, the increasing penetration of car-sharing has led to a demand for longer vehicle lifespans and cleaner vehicles. Therefore, compared to the past, the frequency of cleaning car interior materials has increased, and the resin compositions used as materials for car interiors require higher wear resistance.

[0387] As mentioned above, due to the penetration of autonomous driving and mobility services, in recent years, hydrogenated copolymers used as materials in resin compositions have required good processability, good texture and appearance, and high wear resistance, which are superior to existing products.

[0388] However, processability and texture (low hardness) and abrasion resistance are usually physical properties that tend to be expressed through opposite polymer structures.

[0389] For example, by reducing the molecular weight of the polymer, hydrogenated copolymers tend to have improved flowability and processability, but on the other hand, wear resistance tends to decrease.

[0390] In addition, by reducing the content of vinyl aromatic compounds in the hydrogenated copolymer, there is a tendency to obtain a good texture (low hardness), but on the other hand, the wear resistance tends to decrease.

[0391] Considering the performance changes required for automotive interior materials and the issues of hydrogenated copolymers, the following issues were raised: (1) good processability and excellent appearance characteristics of the molded product; (2) good texture (low hardness) and high wear resistance. Thus, the resin composition containing hydrogenated copolymer (X) of this embodiment was conceived.

[0392] The resin composition containing the hydrogenated copolymer (X) in this embodiment has low shear viscosity, allowing for thin-wall molding and other processing, and the molded article does not exhibit appearance defects such as flow marks. Furthermore, although the resin composition has low hardness, it possesses high wear resistance, thus enabling it to withstand long-term use.

[0393] [Adhesive film]

[0394] The adhesive film of this embodiment comprises a substrate layer and an adhesive layer disposed on the substrate layer containing the hydrogenated copolymer (X) of this embodiment. From the perspective of balancing adhesion and delivery, the content of vinyl aromatic compounds in the hydrogenated copolymers (A) and (B) constituting the hydrogenated copolymer (X) in the adhesive layer is 10% by mass or more and 60% by mass or less. Preferably, it is 20% to 55% by mass, more preferably 25% to 50% by mass.

[0395] The adhesive layer of the adhesive film in this embodiment may contain an adhesive agent as needed.

[0396] As an adhesive, there is no particular limitation as long as it is a resin that can impart adhesiveness to the adhesive layer. Examples of known adhesive resins include hydrogenated terpene resins, rosin-based terpene resins, hydrogenated rosin terpene resins, aromatic modified hydrogenated terpene resins, benzofuran resins, phenolic resins, terpene phenolic resins, hydrogenated terpene phenolic resins, aromatic hydrocarbon resins, and aliphatic hydrocarbon resins.

[0397] Hydrogenated terpene resins, aromatic modified hydrogenated terpene resins, hydrogenated terpene phenol resins, and terpene phenol resins are particularly preferred.

[0398] A single adhesive can be used alone, or two or more can be used in combination.

[0399] As a specific example of an adhesive, substances described in "Rubber-Plastic Compound Chemicals" (published by Rubber Digest) can be used. By using an adhesive, the adhesive strength can be improved.

[0400] Regarding the content of the tackifier in the adhesive layer, it is preferable to contain 0 to 50% by mass, more preferably 0 to 20% by mass, and even more preferably 0 to 10% by mass, in order to effectively prevent over-adhesion and further reduce the amount of residue upon peeling. Furthermore, in order to obtain moderately low over-adhesion, moderately low residue, and stronger adhesive strength, it is more preferably 5 to 50% by mass, and even more preferably 10 to 30% by mass.

[0401] (Substrate layer)

[0402] There are no particular limitations on the materials used as the substrate layer; both non-polar and polar resins can be used.

[0403] From the perspectives of performance and price, polyethylene, homopolymer polypropylene, or block polypropylene are preferred non-polar resins. As polar resins, preferred options include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, ethylene-vinyl acetate copolymers, and their hydrolysates.

[0404] The thickness of the substrate layer is preferably less than 1 mm, more preferably less than 300 μm, and even more preferably 10 to 200 μm.

[0405] When the thickness of the substrate layer is 10μm or more, it can provide sufficient protection for the adhered object; when the thickness of the substrate layer is less than 1mm, it can achieve good elastic modulus in practical applications, good contour following ability, and effectively prevent arching or peeling.

[0406] (Adhesive layer)

[0407] The adhesive layer comprises the hydrogenated copolymer (X) of this embodiment. This adhesive layer may contain an adhesive agent as needed, or it may contain other hydrogenated copolymers besides the hydrogenated copolymer (X) of this embodiment.

[0408] The thickness of the adhesive layer is preferably 1 to 100 μm, more preferably 2 to 50 μm, and even more preferably 5 to 25 μm.

[0409] When the thickness of the adhesive layer is 1 μm or more, it can fully bond to the substrate. When the thickness of the adhesive layer is less than 100 μm, a film with less thickness unevenness can be obtained, which can effectively prevent excessive adhesion and obtain a good film with less adhesive residue when peeled off.

[0410] (Method for manufacturing the resin material constituting the adhesive layer of the adhesive film)

[0411] The resin material constituting the adhesive layer of the adhesive film in this embodiment can be manufactured, for example, by a method of dry mixing hydrogenated copolymer (X) and other components added as needed, or by a method of preparation using an apparatus typically used for mixing polymeric substances.

[0412] There are no particular limitations on the mixing device. Examples of mixing devices include Banbury mixers, torque rheometers, single-screw extruders, and twin-screw extruders. From the perspective of productivity and good mixing properties, it is preferable to manufacture it by using the melt mixing method of an extruder.

[0413] In addition, especially when the tackifier is mixed into the material constituting the adhesive layer, although the above-mentioned dry mixing method can be used, the tackifier has poor processability due to its strong stickiness and thin sheet-like form. Therefore, the tackifier can also be premixed into the above-mentioned hydrogenated copolymer (X) to form a masterbatch.

[0414] The melting temperature of the materials constituting the adhesive layer during mixing can be appropriately set, typically in the range of 130–300°C, preferably in the range of 150–250°C.

[0415] The adhesive layer comprising the hydrogenated copolymer (X) of this embodiment contains a low molecular weight hydrogenated copolymer (A), which effectively achieves high adhesion even without or with minimal tackifier. Therefore, especially when no tackifier is included, all the steps required in the case of containing the aforementioned tackifier are unnecessary. Furthermore, with minimal tackifier, the adhesive film can be produced simply by dry mixing during production, offering advantages such as simplified manufacturing processes and cost reduction.

[0416] In order to achieve the effects of lightweighting, softening and improved adhesion in the adhesive layer of the adhesive film constituting this embodiment, the resin material constituting the adhesive layer can be foamed.

[0417] Foaming methods include, but are not limited to, methods using chemical methods, physical methods, and thermally expandable microspheres. By adding various inorganic and organic foaming agents, chemical foaming agents, physical foaming agents, or thermally expandable microspheres, air bubbles can be distributed within the material. Additionally, adding hollow fillers (expanded microspheres) can achieve lightweighting, softening, and improved adhesion.

[0418] (Method for manufacturing adhesive films)

[0419] The adhesive film of this embodiment has an adhesive layer comprising a hydrogenated copolymer (X) on a substrate layer.

[0420] The method for manufacturing the adhesive film in this embodiment is not particularly limited. For example, methods such as coating a solution or melt of a resin material constituting the adhesive layer onto a specific film constituting the substrate layer; laminating the substrate layer and the adhesive layer using a film extruder; and so on.

[0421] Here, when using a solution or melt of the resin material constituting the adhesive layer, the solution or melt can be prepared after the resin composition is made, or a resin composition can be obtained by mixing a specific material with the solution or melt of the hydrogenated copolymer (X).

[0422] Methods for applying a solution of resin material constituting the adhesive layer include, but are not limited to, dissolving the resin material in a solvent in which it can be dissolved, applying it to a film constituting the substrate layer using a coating machine or the like, and then heating and drying the solvent.

[0423] As a method for melting and coating the resin material constituting the adhesive layer, examples include, but are not limited to, methods such as coating molten resin material onto a film constituting the substrate layer using a hot melt coating machine. In this case, it is preferable to use various films having a glass transition temperature, melting point, or softening point higher than the coating temperature as the substrate layer.

[0424] As a method for obtaining an adhesive film using a film extruder, examples, but not limited to, include the following: the components of an adhesive layer containing resin material and components such as thermoplastic resin that can constitute a substrate layer are formed into two fluids using a melt co-extrusion mechanism, that is, the fluid for forming the adhesive layer and the fluid for forming the substrate layer are merged in the die to form a single fluid for extrusion, thereby composited the adhesive layer and the substrate layer, and thus manufactured.

[0425] When an adhesive film is obtained using a film extruder, the resin material forming the adhesive layer can also be manufactured by pre-dry mixing the various components for the adhesive layer, making it a highly productive method. Furthermore, when the adhesive film is extruded using a film extruder, the resulting adhesive film tends to have particularly excellent adhesion and bonding strength.

[0426] The adhesive film of this embodiment can be temporarily bonded to the surface of optical system molded bodies such as light guide plates and prism sheets, synthetic resin boards, metal plates, decorative plywood, coated steel plates, various signs, etc., and used as a protective film to prevent scratches or dirt during the processing, transportation, and storage of these adhered items.

[0427] [Applications of hydrogenated copolymer (X), resin composition, and molded articles]

[0428] The hydrogenated copolymer (X) or resin composition of this embodiment can be used for various applications by mixing various additives as needed.

[0429] Examples of uses for the molded body in this embodiment include building materials, shock-absorbing / sound-damping materials, wire coating materials, high-frequency welding compositions, slush molding materials, adhesive compositions, asphalt compositions, automotive interior materials, automotive exterior materials, medical device materials, food packaging containers, and various containers, household appliances, industrial parts, toys, etc.

[0430] Example

[0431] The present invention is described in detail below with specific embodiments and comparative examples, but the present invention is not limited to the following embodiments.

[0432] First, the evaluation methods and property measurement methods applicable to the embodiments and comparative examples are as follows.

[0433] [Methods for determining the structure and measuring the physical properties of hydrogenated copolymers (A and B)]

[0434] ((1) The content of vinyl aromatic compounds (RS) and the content of polymer blocks dominated by vinyl aromatic compounds (BS) in the random copolymer structure of hydrogenated copolymer (A) and hydrogenated copolymer (B)

[0435] It should be noted that the definitions are as follows.

[0436] BS1: Content of vinyl aromatic polymer blocks in hydrogenated copolymer (A)

[0437] BS2: Content of vinyl aromatic polymer blocks in hydrogenated copolymer (B)

[0438] RS1: Mass fraction of vinyl aromatic compounds in the random copolymer structure of hydrogenated copolymer (A)

[0439] RS2: Mass fraction of vinyl aromatic compounds in the random copolymer structure of hydrogenated copolymer (B)

[0440] Hydrogenated block copolymer (A) and hydrogenated copolymer (B) were used as samples for analysis, and proton nuclear magnetic resonance (NMR) was used for the determination. 1 H-NMR and the ECS400 manufactured by JOEL RESONABCE distinguish the vinyl aromatic compounds contained therein from compounds from "polymer blocks mainly composed of vinyl aromatic compounds" and compounds from "random copolymer structures formed by vinyl aromatic compounds and conjugated diene compounds".

[0441] The solvent used was deuterated chloroform, the sample concentration was 50 mg / mL, the observation frequency was 400 MHz, the chemical shift standard was tetramethylsilane, and the determination was performed under the conditions of pulse delay of 2.904 seconds, 256 scans, and measurement temperature of 23 °C.

[0442] After calculating the styrene content of random and block copolymers from the integrated intensity of the signals belonging to the aromatic group and the integrated value of each 1H for each bonding mode, the total styrene content is calculated. The styrene content in the random copolymer structure (hereinafter referred to as random styrene content) (RS1)(RS2) and the styrene block content in the hydrogenated copolymer (BS1)(BS2) are also calculated. The calculation method is as follows.

[0443] Block styrene strength (b-St strength) = (integral value from 6.9ppm to 6.3ppm) / 2

[0444] Random styrene strength (r-St strength) = (integral value from 7.5ppm to 6.9ppm) - 3 × (b-St)

[0445] Ethylene-butene strength (EB strength) = Total integral value - 3 × {(b-St strength) + (r-St strength)} / 8

[0446] Polystyrene block content (BS) = 104 × (b-St strength) / [104 × {(b-St strength) + (r-St strength)} + 56 × (EB strength)]

[0447] Styrene content (RS) in random copolymer structure = 104 × (r-St strength) / {104 × (r-St strength) + 56 × (EB strength)}

[0448] ((2) Number-average molecular weight (Mn) of hydrogenated copolymer (A) and hydrogenated copolymer (B)

[0449] The measurements were performed using GPC [Apparatus: Tosoh HLC8220, TSKgel SuperH-RC column × 2].

[0450] The solvent used is tetrahydrofuran.

[0451] Regarding the measurement conditions, the measurement was conducted at 35°C. A calibration curve was prepared using commercially available standard polystyrene with a known weight-average molecular weight, and the converted number-average molecular weight of the polystyrene was determined using the obtained calibration curve.

[0452] Here, let the number average molecular weight of hydrogenated copolymer (A) be (Mn1), and let the number average molecular weight of hydrogenated copolymer (B) be (Mn2).

[0453] ((3) The content of hydrogenated copolymer (A) and hydrogenated copolymer (B) in hydrogenated copolymer (X)

[0454] The hydrogenated copolymer (X) was determined using a GPC [Apparatus: Tosoh HLC8220, TSKgel SuperH-RC column × 2]. Tetrahydrofuran was used as the solvent.

[0455] Regarding the measurement conditions, the measurement was conducted at a temperature of 35°C. The content of hydrogenated copolymer (A) and hydrogenated copolymer (B) contained in hydrogenated copolymer (X) was calculated based on the peak area ratio from hydrogenated copolymer (A) and hydrogenated copolymer (B).

[0456] It should be noted that the content of hydrogenated copolymer (B) is 100 - the content of hydrogenated copolymer (A).

[0457] ((4) Double bond hydrogenation rate of hydrogenated copolymer (A) and hydrogenated copolymer (B)

[0458] The hydrogenation rate of the hydrogenated copolymer was determined using a nuclear magnetic resonance apparatus (BRUKER DPX-400).

[0459] Using hydrogenated copolymers as hydrogenated copolymers, proton nuclear magnetic resonance (NMR) was employed. 1 The measurements were performed using H-NMR.

[0460] Specifically, the integral values ​​of the signals from the residual double bonds (4.5–5.5 ppm) and the signals from the hydrogenated conjugated diene were calculated, and their ratio was determined.

[0461] ((5) Degree of branching (f) of hydrogenated copolymer (B)

[0462] The degree of branching (f) of the hydrogenated copolymer (B) was determined by GPC-light scattering method with a viscosity detector.

[0463] Hydrogenated copolymer (B) was used as the sample. GPC (Malvern, GPCmax VE-2001, column: Tosoh, "TSKgel G4000HXL", "TSKgel G5000HXL", "TSKgel G6000HXL") was used. Three detectors, namely a light scattering detector, an RI detector, and a viscosity detector (trade name "TDA305" manufactured by Malvern), were connected in sequence. Based on standard polystyrene, the absolute molecular weight (M) was determined from the results of the light scattering detector and the RI detector, and the intrinsic viscosity ([η]) was determined from the results of the RI detector and the viscosity detector.

[0464] Next, the intrinsic viscosity ([η]0) used as a reference is calculated using the following formula.

[0465] [η]0=a×M b

[0466] a = -0.788 + 0.421 × (Vinyl Aromatic Compound Content of Hydrogenated Copolymer (B)) - 0.342 × (RS2) - 0.197 × (BS2)

[0467] b = 1.601 - 0.081 × (vinyl aromatic compound content of hydrogenated copolymer (B)) + 0.064 × (RS2) + 0.039 × (BS2)

[0468] RS2: Mass fraction of vinyl aromatic compounds in the random copolymer structure of hydrogenated copolymer (B)

[0469] BS2: via proton nuclear magnetic resonance (NMR) 1 The content of the polymer blocks mainly composed of vinyl aromatic compounds in the above-mentioned hydrogenated copolymer (B) was determined by H-NMR.

[0470] M: Absolute molecular weight of hydrogenated copolymer (B)

[0471] Next, the shrinkage factor g was calculated as the ratio of the intrinsic viscosity ([η]) of the hydrogenated copolymer (B) to the intrinsic viscosity ([η]0) used as a reference.

[0472] Contraction factor (g) = [η] / [η]0

[0473] Subsequently, the degree of branching (f), defined as g = f / {(f+1)(f+2)} (f≧2), was calculated using the obtained shrinkage factor (g).

[0474] The solvent used is tetrahydrofuran (hereinafter also referred to as "THF") with 5 mmol / L triethylamine added.

[0475] 100 μL of the test solution was injected into the GPC measuring device, and the measurement was performed at an oven temperature of 40 °C and a THF flow rate of 1 mL / min.

[0476] (Calculation of block styrene molecular weight (MnS) of hydrogenated copolymer (A) and hydrogenated copolymer (B))

[0477] Using the (Mn1), (Mn2), (BS1), (BS2), and (f) obtained in determinations (1), (2), and (5), the block styrene molecular weights (MnS1) and (MnS2) of hydrogenated copolymers (A) and (B) are calculated according to the following formula.

[0478] It should be noted that the calculation result is rounded to the tenth place, and values ​​below 500 are set to 0.

[0479] MnS1=Mn1×BS1

[0480] MnS2=Mn2×BS2÷f

[0481] (Separation of components (A) and (B) of the hydrogenated copolymer (X23) and hydrogenated copolymer (X31) described below)

[0482] Using a GPC [Apparatus: Waters ACQUITY UPLC H-Class; Columns: Waters ACQUITY APC XT900 (2.5μm, 4.6×150mm), Waters ACQUITY APC XT200 (2.5μm, 4.6×75mm), Waters ACQUITY APC XT125 (2.5mm, 4.6×75mm) in series], hydrogenated copolymers (X23) and (X31) were separated into low molecular weight components (A) and high molecular weight components (B).

[0483] Chloroform is used as the solvent.

[0484] Based on the GPC measurements of hydrogenated copolymers (X23) and (X31), the components were separated into low molecular weight peaks and high molecular weight peaks.

[0485] [Methods for determining the physical properties and characteristics of hydrogenated copolymer (X)]

[0486] ((1) Viscoelasticity determination of hydrogenated copolymer (X) (tanδ peak))

[0487] The peak temperature of the loss coefficient tanδ was obtained by measuring the dynamic viscoelastic spectrum using the following method (tanδ peak temperature).

[0488] First, the hydrogenated copolymer (X) was molded into a sheet with a thickness of 2 mm, and then cut into dimensions of 10 mm in width and 35 mm in length as samples for testing.

[0489] The test sample was placed in the torsion configuration of the ARES device (manufactured by TA Instruments Co., Ltd., trade name), and the measurement was performed under the following conditions: effective measurement length 25 mm, strain 0.5%, frequency 1 Hz, measurement range -100°C to 100°C, and heating rate 3°C / min.

[0490] ((2) Hardness of hydrogenated copolymer (X))

[0491] According to JIS K6253, the value after 10 seconds (10s hardness) is measured using a type A hardness tester.

[0492] The lower the hardness value, the better the feel of the molded object, as evaluated below.

[0493] ◎: A hardness value of less than 60 in 10s.

[0494] 〇: The 10s hardness value is 60 or higher and less than 70.

[0495] △: A 10s hardness value of 70 or higher but less than 80.

[0496] ×: A hardness value of 80 or higher in 10s.

[0497] (3) Shear viscosity of hydrogenated copolymer (X)

[0498] The shear viscosity of the hydrogenated copolymer (X) was determined by the following method.

[0499] 30g of hydrogenated copolymer granules were fed into the barrel of a Capillograph (Toyo Seiki Manufacturing Co., Ltd., Capillograph 1DPMD-C, barrel diameter = 9.55mm, barrel length = 350mm, orifice diameter = 1mm). The sample was heated at 180°C for 5 minutes, and the shear viscosity was measured at a measurement temperature of 180°C and a piston speed of 50mm / min.

[0500] From a processability perspective, a lower shear viscosity value is better, and the following criteria should be used for evaluation.

[0501] ◎: Shear viscosity less than 300 Pa·s

[0502] 〇: Shear viscosity above 300 Pa·s and below 450 Pa·s

[0503] △: Shear viscosity above 450 Pa·s and below 600 Pa·s

[0504] ×: Shear viscosity above 600 Pa·s

[0505] (4) Resistance to sticking of granules)

[0506] Anti-adhesion was determined by the following method.

[0507] 60g of sample granules of the same shape (approximately 3mm x 3mm in diameter) composed of hydrogenated copolymer (X) were placed in a 5cm diameter metal cylinder, and 1160g of weight was loaded on top of it.

[0508] After heating in a gear oven at 42°C for 20 hours under this condition, the adhesion of the granules in the cylinder was observed.

[0509] Specifically, since the granules removed from the cylinder disperse (but substances with poor adhesion remain in block form and do not disperse), the weight of the block consisting of 3 or more granules after dispersion is measured, and the ratio (%) of the weight of the granule block to the total weight of the granules (60g) is calculated.

[0510] Whether the anti-adhesion property is good or not is evaluated based on the following criteria.

[0511] It should be noted that calcium stearate equivalent to 2000 ppm was added to each sample granule before evaluation.

[0512] ◎: Particles with 3 or more connected pieces account for less than 5%

[0513] 〇: The percentage of pellets with three or more connected pieces is between 5% and 30%.

[0514] △: Particles with 3 or more connected pieces account for more than 30% but less than 60%.

[0515] ×: More than 60% of the pellets are three or more continuous.

[0516] [Manufacturing of hydrogenated copolymers]

[0517] (Preparation of hydrogenation catalyst)

[0518] The hydrogenation catalyst used in the hydrogenation reaction of the copolymer is prepared by the following method.

[0519] One liter of dried and purified cyclohexane was added to a reaction vessel that had been purged with nitrogen, along with 100 mmol of dicyclopentadienyl titanium dichloride. While stirring thoroughly, a solution of n-hexane containing 200 mmol of trimethylaluminum was added, and the reaction was carried out at room temperature for about 3 days to obtain the hydrogenation catalyst.

[0520] (Hydrogenated copolymer)

[0521] The hydrogenated copolymers (A1) to (A41) in Manufacturing Examples 1 to 41 (described later), the hydrogenated copolymers (B1) to (B22) in Manufacturing Examples 42 to 63, the hydrogenated copolymer (X23) in Manufacturing Example 64, the hydrogenated copolymer (X61) in Manufacturing Example 65, the hydrogenated copolymer (X31) in Manufacturing Example 66, the hydrogenated copolymers (A42) to (A43) in Manufacturing Examples 67 to 68, and the hydrogenated copolymers (B23) to (B25) in Manufacturing Examples 69 to 71 are manufactured as follows.

[0522] <Manufacturing Example 1: Hydrogenated Copolymer (A1)>

[0523] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0524] Add a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass).

[0525] Next, 0.534 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0526] Methanol was then added to stop the polymerization reaction.

[0527] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 15,000.

[0528] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0529] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0530] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A1).

[0531] <Manufacturing Example 2: Hydrogenated Copolymer (A2)>

[0532] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0533] Add a cyclohexane solution containing 35 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 65 parts by mass of butadiene (concentration 20% by mass).

[0534] Next, 0.306 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.4 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0535] Methanol was then added to stop the polymerization reaction.

[0536] The copolymer obtained above has a styrene content of 35% by mass, a random styrene content (RS1) of 35% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 30,000.

[0537] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0538] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0539] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A2).

[0540] <Manufacturing Example 3: Hydrogenated Copolymer (A3)>

[0541] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0542] Add a cyclohexane solution containing 40 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 60 parts by mass of butadiene (concentration 20% by mass).

[0543] Next, 0.299 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0544] Methanol was then added to stop the polymerization reaction.

[0545] The copolymer obtained above has a styrene content of 40% by mass, a random styrene content (RS1) of 40% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 30,000.

[0546] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0547] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0548] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A3).

[0549] <Manufacturing Example 4: Hydrogenated Copolymer (A4)>

[0550] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0551] Add a cyclohexane solution containing 50 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 50 parts by mass of butadiene (concentration 20% by mass).

[0552] Next, 0.282 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.6 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0553] Methanol was then added to stop the polymerization reaction.

[0554] The copolymer obtained above has a styrene content of 50% by mass, a random styrene content (RS1) of 50% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 30,000.

[0555] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0556] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0557] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A4).

[0558] <Manufacturing Example 5: Hydrogenated Copolymer (A5)>

[0559] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0560] Add a cyclohexane solution containing 70 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 30 parts by mass of butadiene (concentration 20% by mass).

[0561] Next, 0.251 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.8 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0562] Methanol was then added to stop the polymerization reaction.

[0563] The copolymer obtained above has a styrene content of 70% by mass, a random styrene content (RS1) of 70% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 30,000.

[0564] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0565] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0566] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A5).

[0567] <Manufacturing Example 6: Hydrogenated Copolymer (A6)>

[0568] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0569] Add a cyclohexane solution containing 77 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 23 parts by mass of butadiene (concentration 20% by mass).

[0570] Next, 0.240 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.9 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0571] Methanol was then added to stop the polymerization reaction.

[0572] The copolymer obtained above has a styrene content of 77% by mass, a random styrene content (RS1) of 77% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 30,000.

[0573] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0574] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0575] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A6).

[0576] <Manufacturing Example 7: Hydrogenated Copolymer (A7)>

[0577] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0578] Add a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass).

[0579] Next, 0.264 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0580] Methanol was then added to stop the polymerization reaction.

[0581] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 30,000.

[0582] The hydrogenation catalyst prepared above was further added to the obtained copolymer at a concentration of 100 ppm (based on Ti) per 100 parts by mass of the copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C. The reaction was then stopped when the hydrogenation rate reached 25%.

[0583] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A7).

[0584] <Manufacturing Example 8: Hydrogenated Copolymer (A8)>

[0585] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0586] Add a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass).

[0587] Next, 0.264 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0588] Methanol was then added to stop the polymerization reaction.

[0589] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 30,000.

[0590] The hydrogenation catalyst prepared above was further added to the obtained copolymer at a concentration of 100 ppm (based on Ti) per 100 parts by mass of the copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C. The reaction was then stopped when the hydrogenation rate reached 50%.

[0591] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A8).

[0592] <Manufacturing Example 9: Hydrogenated Copolymer (A9)>

[0593] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0594] Add a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass).

[0595] Next, 0.264 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0596] Methanol was then added to stop the polymerization reaction.

[0597] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 30,000.

[0598] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0599] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0600] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A9).

[0601] <Manufacturing Example 10: Hydrogenated Copolymer (A10)>

[0602] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0603] Add a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass).

[0604] Next, 0.232 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0605] Methanol was then added to stop the polymerization reaction.

[0606] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 34,000.

[0607] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0608] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0609] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A10).

[0610] <Manufacturing Example 11: Hydrogenated Copolymer (A11)>

[0611] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0612] Add a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass).

[0613] Next, 1.13 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0614] Methanol was then added to stop the polymerization reaction.

[0615] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 0.7 million.

[0616] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0617] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0618] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A11).

[0619] <Manufacturing Example 12: Hydrogenated Copolymer (A12)>

[0620] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0621] Add a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass).

[0622] Next, 0.608 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0623] Methanol was then added to stop the polymerization reaction.

[0624] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 13,000.

[0625] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0626] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0627] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A12).

[0628] <Manufacturing Example 13: Hydrogenated Copolymer (A13)>

[0629] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0630] Add a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass).

[0631] Next, 0.214 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0632] Methanol was then added to stop the polymerization reaction.

[0633] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 37,000.

[0634] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0635] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0636] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A13).

[0637] <Manufacturing Example 14: Hydrogenated Copolymer (A14)>

[0638] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0639] Add a cyclohexane solution containing 45 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 55 parts by mass of butadiene (concentration 20% by mass).

[0640] Next, 0.293 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0641] Methanol was then added to stop the polymerization reaction.

[0642] The copolymer obtained above has a styrene content of 45% by mass, a random styrene content (RS1) of 45% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 30,000.

[0643] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0644] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0645] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A14).

[0646] <Manufacturing Example 15: Hydrogenated Copolymer (A15)>

[0647] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0648] Add a cyclohexane solution containing 75 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 25 parts by mass of butadiene (concentration 20% by mass).

[0649] Next, 0.243 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.9 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0650] Methanol was then added to stop the polymerization reaction.

[0651] The copolymer obtained above has a styrene content of 75% by mass, a random styrene content (RS1) of 75% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 30,000.

[0652] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0653] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0654] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A15).

[0655] <Manufacturing Example 16: Hydrogenated Copolymer (A16)>

[0656] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0657] Add a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass).

[0658] Next, 1.581 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0659] Methanol was then added to stop the polymerization reaction.

[0660] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 0.5 million.

[0661] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0662] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0663] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A16).

[0664] <Manufacturing Example 17: Hydrogenated Copolymer (A17)>

[0665] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0666] Add cyclohexane (20% by mass) containing 40 parts by mass of styrene.

[0667] Next, 0.197 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 30 minutes.

[0668] Next, a cyclohexane solution containing 36 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 24 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out for 40 minutes.

[0669] Methanol was then added to stop the polymerization reaction.

[0670] The copolymer obtained above has a styrene content of 76% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 15,200, and a number-average molecular weight (Mn1) of 37,000.

[0671] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0672] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0673] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A17).

[0674] <Manufacturing Example 18: Hydrogenated Copolymer (A18)>

[0675] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0676] Add cyclohexane (20% by mass) containing 50 parts by mass of styrene.

[0677] Next, 0.192 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 30 minutes.

[0678] Next, a cyclohexane solution containing 30 parts by mass of styrene (20% by mass) and a cyclohexane solution containing 20 parts by mass of butadiene (20% by mass) were added, and polymerization was carried out for 40 minutes.

[0679] Methanol was then added to stop the polymerization reaction.

[0680] The copolymer obtained above has a styrene content of 80% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 19,600, and a number-average molecular weight (Mn1) of 37,000.

[0681] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0682] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0683] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A18).

[0684] <Manufacturing Example 19: Hydrogenated Copolymer (A19)>

[0685] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0686] Add a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass).

[0687] Next, 0.175 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0688] Methanol was then added to stop the polymerization reaction.

[0689] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 45,000.

[0690] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0691] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0692] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A19).

[0693] <Manufacturing Example 20: Hydrogenated Copolymer (A20)>

[0694] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0695] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 80 parts by mass of butadiene (concentration 20% by mass).

[0696] Next, 0.351 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.3 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0697] Methanol was then added to stop the polymerization reaction.

[0698] The copolymer obtained above has a styrene content of 20% by mass, a random styrene content (RS1) of 20% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 30,000.

[0699] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0700] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0701] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A20).

[0702] <Manufacturing Example 21: Hydrogenated Copolymer (A21)>

[0703] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0704] Add a cyclohexane solution containing 85 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 15 parts by mass of butadiene (concentration 20% by mass).

[0705] Next, 0.230 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.9 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0706] Methanol was then added to stop the polymerization reaction.

[0707] The copolymer obtained above has a styrene content of 85% by mass, a random styrene content (RS1) of 85% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 30,000.

[0708] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0709] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0710] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A21).

[0711] <Manufacturing Example 22: Hydrogenated Copolymer (A22)>

[0712] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0713] Add a cyclohexane solution containing 100 parts by mass of butadiene (concentration 20% by mass).

[0714] Next, 0.412 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0715] Methanol was then added to stop the polymerization reaction.

[0716] The polymer obtained above has a styrene content of 0% by mass, a random styrene content (RS1) of 0% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 30,000.

[0717] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0718] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0719] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A22).

[0720] <Manufacturing Example 23: Copolymer (A23)>

[0721] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0722] Add a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass).

[0723] Next, 0.232 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1 hour.

[0724] Methanol was then added to stop the polymerization reaction.

[0725] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 34,000.

[0726] Next, 0.3 parts by mass relative to 100 parts by mass of the copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A23).

[0727] It should be noted that in this manufacturing example 23, no hydrogenation reaction was carried out, but for ease of recording, (A23) is recorded in the hydrogenated copolymer (A) column of Table 3.

[0728] <Manufacturing Example 24: Hydrogenated Copolymer (A24)>

[0729] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0730] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[0731] Next, 0.508 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0732] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0733] Methanol was then added to stop the polymerization reaction.

[0734] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 3100, and a number-average molecular weight (Mn1) of 15,000.

[0735] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0736] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0737] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A24).

[0738] <Manufacturing Example 25: Hydrogenated Copolymer (A25)>

[0739] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0740] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[0741] Next, 0.285 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.4 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0742] Next, a cyclohexane solution containing 28 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 52 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0743] Methanol was then added to stop the polymerization reaction.

[0744] The copolymer obtained above has a styrene content of 48% by mass, a random styrene content (RS1) of 35% by mass, a block styrene molecular weight (MnS1) of 6100, and a number-average molecular weight (Mn1) of 30,000.

[0745] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0746] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0747] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A25).

[0748] <Manufacturing Example 26: Hydrogenated Copolymer (A26)>

[0749] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0750] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[0751] Next, 0.214 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0752] Next, a cyclohexane solution containing 32 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 48 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0753] Methanol was then added to stop the polymerization reaction.

[0754] The copolymer obtained above has a styrene content of 52% by mass, a random styrene content (RS1) of 40% by mass, a block styrene molecular weight (MnS1) of 6100, and a number-average molecular weight (Mn1) of 30,000.

[0755] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0756] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0757] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A26).

[0758] <Manufacturing Example 27: Hydrogenated Copolymer (A27)>

[0759] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0760] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[0761] Next, 0.278 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.6 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0762] Next, a cyclohexane solution containing 40 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0763] Methanol was then added to stop the polymerization reaction.

[0764] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS1) of 50% by mass, a block styrene molecular weight (MnS1) of 6100, and a number-average molecular weight (Mn1) of 30,000.

[0765] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0766] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0767] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A27).

[0768] <Manufacturing Example 28: Hydrogenated Copolymer (A28)>

[0769] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0770] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[0771] Next, 0.243 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.8 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0772] Next, a cyclohexane solution containing 56 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 24 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0773] Methanol was then added to stop the polymerization reaction.

[0774] The copolymer obtained above has a styrene content of 76% by mass, a random styrene content (RS1) of 70% by mass, a block styrene molecular weight (MnS1) of 6200, and a number-average molecular weight (Mn1) of 30,000.

[0775] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0776] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0777] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A28).

[0778] <Manufacturing Example 29: Hydrogenated Copolymer (A29)>

[0779] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0780] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[0781] Next, 0.254 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0782] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0783] Methanol was then added to stop the polymerization reaction.

[0784] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 6100, and a number-average molecular weight (Mn1) of 30,000.

[0785] The hydrogenation catalyst prepared above was further added to the obtained copolymer at a concentration of 100 ppm (based on Ti) per 100 parts by mass of the copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C. The reaction was then stopped when the hydrogenation rate reached 25%.

[0786] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A29).

[0787] <Manufacturing Example 30: Hydrogenated Copolymer (A30)>

[0788] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0789] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[0790] Next, 0.252 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0791] Next, a cyclohexane solution containing 48 parts by mass of styrene and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0792] Methanol was then added to stop the polymerization reaction.

[0793] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 6100, and a number-average molecular weight (Mn1) of 30,000.

[0794] The hydrogenation catalyst prepared above was further added to the obtained copolymer at a concentration of 100 ppm (based on Ti) per 100 parts by mass of the copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C. The reaction was then stopped when the hydrogenation rate reached 50%.

[0795] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A30).

[0796] <Manufacturing Example 31: Hydrogenated Copolymer (A31)>

[0797] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0798] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[0799] Next, 0.252 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0800] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0801] Methanol was then added to stop the polymerization reaction.

[0802] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 6100, and a number-average molecular weight (Mn1) of 30,000.

[0803] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0804] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0805] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A31).

[0806] <Manufacturing Example 32: Hydrogenated Copolymer (A32)>

[0807] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0808] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[0809] Next, 0.282 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0810] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0811] Methanol was then added to stop the polymerization reaction.

[0812] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 5500, and a number-average molecular weight (Mn1) of 27,000.

[0813] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0814] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0815] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A32).

[0816] <Manufacturing Example 33: Hydrogenated Copolymer (A33)>

[0817] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0818] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[0819] Next, 1.089 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0820] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0821] Methanol was then added to stop the polymerization reaction.

[0822] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 1400, and a number-average molecular weight (Mn1) of 0.7 million.

[0823] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0824] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0825] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A33).

[0826] <Manufacturing Example 34: Hydrogenated Copolymer (A34)>

[0827] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0828] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[0829] Next, 0.587 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0830] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0831] Methanol was then added to stop the polymerization reaction.

[0832] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 2700, and a number-average molecular weight (Mn1) of 13,000.

[0833] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0834] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0835] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A34).

[0836] <Manufacturing Example 35: Hydrogenated Copolymer (A35)>

[0837] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0838] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[0839] Next, 0.206 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0840] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added.

[0841] Methanol was then added to stop the polymerization reaction.

[0842] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 7700, and a number-average molecular weight (Mn1) of 37,000.

[0843] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0844] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0845] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A35).

[0846] <Manufacturing Example 36: Hydrogenated Copolymer (A36)>

[0847] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0848] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[0849] Next, 0.271 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0850] A cyclohexane solution containing 36 parts by mass of styrene (20% by mass) and a cyclohexane solution containing 44 parts by mass of butadiene (20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0851] Methanol was then added to stop the polymerization reaction.

[0852] The copolymer obtained above has a styrene content of 56% by mass, a random styrene content (RS1) of 45% by mass, a block styrene molecular weight (MnS1) of 6100, and a number-average molecular weight (Mn1) of 30,000.

[0853] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0854] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0855] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A36).

[0856] <Manufacturing Example 37: Hydrogenated Copolymer (A37)>

[0857] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0858] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 25 parts by mass of butadiene (concentration 20% by mass).

[0859] Next, 0.238 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.9 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0860] Next, a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 20 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0861] Methanol was then added to stop the polymerization reaction.

[0862] The copolymer obtained above has a styrene content of 80% by mass, a random styrene content (RS1) of 75% by mass, a block styrene molecular weight (MnS1) of 6200, and a number-average molecular weight (Mn1) of 30,000.

[0863] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0864] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0865] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A37).

[0866] <Manufacturing Example 38: Hydrogenated Copolymer (A38)>

[0867] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0868] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass).

[0869] Next, 1.525 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0870] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0871] Methanol was then added to stop the polymerization reaction.

[0872] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 1000, and a number-average molecular weight (Mn1) of 0.5 million.

[0873] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0874] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0875] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A38).

[0876] <Manufacturing Example 39: Hydrogenated Copolymer (A39)>

[0877] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0878] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[0879] Next, 0.381 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0880] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[0881] Methanol was then added to stop the polymerization reaction.

[0882] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 4100, and a number-average molecular weight (Mn1) of 20,000.

[0883] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0884] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0885] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A39).

[0886] <Manufacturing Example 40: Hydrogenated Copolymer (A40)>

[0887] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0888] Add a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass).

[0889] Next, 0.293 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 60 minutes.

[0890] Methanol was then added to stop the polymerization reaction.

[0891] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS1) of 60% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 27,000.

[0892] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0893] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0894] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A40).

[0895] <Manufacturing Example 41: Hydrogenated Copolymer (A41)>

[0896] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0897] Add a cyclohexane solution containing 100 parts by mass of butadiene (concentration 20% by mass).

[0898] Next, 1.76 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 60 minutes.

[0899] Methanol was then added to stop the polymerization reaction.

[0900] The polymer obtained above has a styrene content of 0% by mass, a random styrene content (RS1) of 0% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 0.7 million.

[0901] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0902] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0903] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A41).

[0904] <Manufacturing Example 42: Hydrogenated Copolymer (B1)>

[0905] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0906] Add a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass).

[0907] Next, 0.038 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[0908] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[0909] Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[0910] Methanol was then added to stop the polymerization reaction.

[0911] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS2) of 60% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 21,000, and a number-average molecular weight (Mn2) of 200,000.

[0912] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0913] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0914] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B1).

[0915] <Manufacturing Example 43: Hydrogenated Copolymer (B2)>

[0916] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0917] Add a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass).

[0918] Next, 0.047 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.3 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0919] Next, a cyclohexane solution containing 25 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 65 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[0920] Next, a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 15 minutes.

[0921] Methanol was then added to stop the polymerization reaction.

[0922] The copolymer obtained above has a styrene content of 35% by mass, a random styrene content (RS2) of 28% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 10,400, and a number-average molecular weight (Mn2) of 200,000.

[0923] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0924] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0925] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B2).

[0926] <Manufacturing Example 44: Hydrogenated Copolymer (B3)>

[0927] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0928] Add a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass).

[0929] Next, 0.044 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0930] Next, a cyclohexane solution containing 35 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 55 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[0931] Next, a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 15 minutes.

[0932] Methanol was then added to stop the polymerization reaction.

[0933] The copolymer obtained above has a styrene content of 45% by mass, a random styrene content (RS2) of 39% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 10,600, and a number-average molecular weight (Mn2) of 200,000.

[0934] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0935] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0936] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B3).

[0937] <Manufacturing Example 45: Hydrogenated Copolymer (B4)>

[0938] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0939] Add a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass).

[0940] Next, 0.041 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.6 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0941] Next, a cyclohexane solution containing 45 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 45 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[0942] Next, a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 15 minutes.

[0943] Methanol was then added to stop the polymerization reaction.

[0944] The copolymer obtained above has a styrene content of 55% by mass, a random styrene content (RS2) of 50% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 10,800, and a number-average molecular weight (Mn2) of 200,000.

[0945] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0946] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0947] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B4).

[0948] <Manufacturing Example 46: Hydrogenated Copolymer (B5)>

[0949] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0950] Add a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass).

[0951] Next, 0.038 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0952] Next, a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 30 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[0953] Next, a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 15 minutes.

[0954] Methanol was then added to stop the polymerization reaction.

[0955] The copolymer obtained above has a styrene content of 70% by mass, a random styrene content (RS2) of 67% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 11,000, and a number-average molecular weight (Mn2) of 200,000.

[0956] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0957] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0958] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B5).

[0959] <Manufacturing Example 47: Hydrogenated Copolymer (B6)>

[0960] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0961] Add a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass).

[0962] Next, 0.036 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.9 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0963] Next, a cyclohexane solution containing 69 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 21 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[0964] Next, a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 15 minutes.

[0965] Methanol was then added to stop the polymerization reaction.

[0966] The copolymer obtained above has a styrene content of 79% by mass, a random styrene content (RS2) of 77% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 11,300, and a number-average molecular weight (Mn2) of 200,000.

[0967] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0968] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[0969] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B6).

[0970] <Manufacturing Example 48: Hydrogenated Copolymer (B7)>

[0971] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0972] Add a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass).

[0973] Next, 0.038 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[0974] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[0975] Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[0976] Methanol was then added to stop the polymerization reaction.

[0977] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS2) of 60% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 21,000, and a number-average molecular weight (Mn2) of 200,000.

[0978] The hydrogenation catalyst prepared above was further added to the obtained copolymer at a concentration of 100 ppm (based on Ti) per 100 parts by mass of the copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C. The reaction was then stopped when the hydrogenation rate reached 25%.

[0979] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B7).

[0980] <Manufacturing Example 49: Hydrogenated Copolymer (B8)>

[0981] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0982] Add a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass).

[0983] Next, 0.038 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[0984] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[0985] Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[0986] Methanol was then added to stop the polymerization reaction.

[0987] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS2) of 60% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 21,000, and a number-average molecular weight (Mn2) of 200,000.

[0988] The hydrogenation catalyst prepared above was further added to the obtained copolymer at a concentration of 100 ppm (based on Ti) per 100 parts by mass of the copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C. The reaction was then stopped when the hydrogenation rate reached 50%.

[0989] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B8).

[0990] <Manufacturing Example 50: Hydrogenated Copolymer (B9)>

[0991] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0992] Add a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass).

[0993] Next, 0.055 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[0994] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[0995] Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[0996] Methanol was then added to stop the polymerization reaction.

[0997] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS2) of 60% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 14,700, and a number-average molecular weight (Mn2) of 140,000.

[0998] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0999] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1000] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B9).

[1001] <Manufacturing Example 51: Hydrogenated Copolymer (B10)>

[1002] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1003] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[1004] Next, 0.076 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 25 minutes.

[1005] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 1 hour.

[1006] Further, 0.25 moles of dimethoxydimethylsilane relative to 1 mole of n-butyllithium were added, and the reaction was carried out at 70°C for 30 minutes.

[1007] Methanol was then added to stop the polymerization reaction.

[1008] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS2) of 60% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 21,000, and a number-average molecular weight (Mn2) of 150,000.

[1009] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1010] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1011] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B10).

[1012] <Manufacturing Example 52: Hydrogenated Copolymer (B11)>

[1013] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1014] Add a cyclohexane solution containing 60 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass).

[1015] Next, 0.009 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 1.5 hours.

[1016] Methanol was then added to stop the polymerization reaction.

[1017] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS2) of 60% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 3800, and a number-average molecular weight (Mn2) of 900,000.

[1018] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1019] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1020] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B11).

[1021] <Manufacturing Example 53: Hydrogenated Copolymer (B12)>

[1022] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1023] Add a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass).

[1024] Next, 0.037 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[1025] Next, a cyclohexane solution containing 40 parts by mass of butadiene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 40 minutes.

[1026] Next, a cyclohexane solution containing 24 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 16 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 40 minutes.

[1027] Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[1028] Methanol was then added to stop the polymerization reaction.

[1029] The copolymer obtained above has a styrene content of 44% by mass, a random styrene content (RS2) of 60% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 24,100, and a number-average molecular weight (Mn2) of 240,000.

[1030] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1031] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1032] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B12).

[1033] <Manufacturing Example 54: Hydrogenated Copolymer (B13)>

[1034] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1035] Add a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass).

[1036] Next, 0.038 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[1037] Next, a cyclohexane solution containing 42 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 28 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[1038] Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[1039] Next, a cyclohexane solution containing 6 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 4 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 20 minutes.

[1040] Methanol was then added to stop the polymerization reaction.

[1041] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS2) of 60% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 21,000, and a number-average molecular weight (Mn2) of 200,000.

[1042] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1043] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1044] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B13).

[1045] <Manufacturing Example 55: Hydrogenated Copolymer (B14)>

[1046] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1047] Add a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass).

[1048] Next, 0.039 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[1049] Next, a cyclohexane solution containing 42 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 28 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[1050] Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[1051] Next, a cyclohexane solution containing 10 parts by mass of butadiene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[1052] Methanol was then added to stop the polymerization reaction.

[1053] The copolymer obtained above has a styrene content of 62% by mass, a random styrene content (RS2) of 60% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 20,800, and a number-average molecular weight (Mn2) of 200,000.

[1054] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1055] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1056] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B14).

[1057] <Manufacturing Example 56: Hydrogenated Copolymer (B15)>

[1058] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1059] Add a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass).

[1060] Next, 0.039 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[1061] Next, a cyclohexane solution containing 5 parts by mass of butadiene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 15 minutes.

[1062] Next, a cyclohexane solution containing 42 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 28 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[1063] Next, a cyclohexane solution containing 5 parts by mass of butadiene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 15 minutes.

[1064] Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[1065] Methanol was then added to stop the polymerization reaction.

[1066] The copolymer obtained above has a styrene content of 62% by mass, a random styrene content (RS2) of 60% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 20,800, and a number-average molecular weight (Mn2) of 200,000.

[1067] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1068] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1069] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B15).

[1070] <Manufacturing Example 57: Hydrogenated Copolymer (B16)>

[1071] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1072] Add a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass).

[1073] Next, 0.05 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.3 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[1074] Next, a cyclohexane solution containing 15 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 75 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 60 minutes.

[1075] Next, a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 15 minutes.

[1076] Methanol was then added to stop the polymerization reaction.

[1077] The copolymer obtained above has a styrene content of 25% by mass, a random styrene content (RS2) of 17% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 10200, and a number-average molecular weight (Mn2) of 200,000.

[1078] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1079] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1080] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B16).

[1081] <Manufacturing Example 58: Hydrogenated Copolymer (B17)>

[1082] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1083] Add a cyclohexane solution containing 15 parts by mass of styrene (concentration 20% by mass).

[1084] Next, 0.034 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.9 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 25 minutes.

[1085] Next, a cyclohexane solution containing 55 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 15 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 1 hour.

[1086] Next, a cyclohexane solution containing 15 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 25 minutes.

[1087] Methanol was then added to stop the polymerization reaction.

[1088] The copolymer obtained above has a styrene content of 85% by mass, a random styrene content (RS2) of 79% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 31,500, and a number-average molecular weight (Mn2) of 200,000.

[1089] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1090] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1091] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B17).

[1092] <Manufacturing Example 59: Hydrogenated Copolymer (B18)>

[1093] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1094] Add a cyclohexane solution containing 15 parts by mass of styrene (concentration 20% by mass).

[1095] Next, 0.048 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 25 minutes.

[1096] Next, a cyclohexane solution containing 70 parts by mass of butadiene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 60 minutes.

[1097] Next, a cyclohexane solution containing 15 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 25 minutes.

[1098] Methanol was then added to stop the polymerization reaction.

[1099] The copolymer obtained above has a styrene content of 30% by mass, a random styrene content (RS2) of 0% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 30,000, and a number-average molecular weight (Mn2) of 200,000.

[1100] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1101] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1102] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B18).

[1103] <Manufacturing Example 60: Copolymer (B19)>

[1104] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1105] Add a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass).

[1106] Next, 0.038 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[1107] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 60 minutes.

[1108] Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[1109] Methanol was then added to stop the polymerization reaction.

[1110] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS2) of 60% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 21,000, and a number-average molecular weight (Mn2) of 200,000.

[1111] Next, 0.3 parts by mass relative to 100 parts by mass of the copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain copolymer (B19).

[1112] It should be noted that no hydrogenation reaction was performed in this manufacturing example 60, but for convenience, (B19) is recorded in column (B) of the hydrogenated copolymer in Table 3.

[1113] <Manufacturing Example 61: Hydrogenated Copolymer (B20)>

[1114] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1115] Add a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass).

[1116] Next, 0.061 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[1117] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 60 minutes.

[1118] Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[1119] Methanol was then added to stop the polymerization reaction.

[1120] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS2) of 60% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 12,800, and a number-average molecular weight (Mn2) of 125,000.

[1121] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1122] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1123] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B20).

[1124] <Manufacturing Example 62: Hydrogenated Copolymer (B21)>

[1125] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1126] Add a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass).

[1127] Next, 0.070 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[1128] Next, a cyclohexane solution containing 80 parts by mass of butadiene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 60 minutes.

[1129] Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[1130] Methanol was then added to stop the polymerization reaction.

[1131] The copolymer obtained above has a styrene content of 20% by mass, a random styrene content (RS2) of 0% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 15,000, and a number-average molecular weight (Mn2) of 150,000.

[1132] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1133] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1134] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B21).

[1135] <Manufacturing Example 63: Hydrogenated Copolymer (B22)>

[1136] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1137] Add a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass).

[1138] Next, 0.070 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[1139] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[1140] Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[1141] Methanol was then added to stop the polymerization reaction.

[1142] The copolymer obtained above has a styrene content of 68% by mass, a random styrene content (RS2) of 60% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 11,500, and a number-average molecular weight (Mn2) of 110,000.

[1143] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1144] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1145] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B22).

[1146] <Manufacturing Example 64: Hydrogenated Copolymer (X23)>

[1147] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1148] Add a cyclohexane solution containing 6 parts by mass of styrene (concentration 20% by mass).

[1149] Next, 0.023 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[1150] Next, a cyclohexane solution containing 25 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 17 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 40 minutes.

[1151] Next, a cyclohexane solution containing 6 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[1152] Next, 0.158 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers were added, followed by the addition of a cyclohexane solution containing 28 parts by mass of styrene (20% by mass concentration) and a cyclohexane solution containing 18 parts by mass of butadiene (20% by mass concentration), and polymerization was carried out at 70°C for 30 minutes.

[1153] Methanol was then added to stop the polymerization reaction.

[1154] The copolymers obtained as described above were separated into low molecular weight components (hydrogenated copolymer (A)) and high molecular weight components (hydrogenated copolymer (B)) by chromatography. The components were analyzed separately. The results showed that in hydrogenated copolymer (A), the styrene content was 60% by mass, the random styrene content (RS1) was 60% by mass, the block styrene molecular weight (MnS1) was 100, and the number-average molecular weight (Mn2) was 20,000. In hydrogenated copolymer (B), the styrene content was 68% by mass, the random styrene content (RS1) was 60% by mass, the block styrene molecular weight (MnS1) was 21,000, and the number-average molecular weight (Mn2) was 200,000.

[1155] In addition, the ratio of the content of hydrogenated copolymer (A) to hydrogenated copolymer (B) is (A) / (B) = 40 / 60.

[1156] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1157] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1158] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (X23).

[1159] <Manufacturing Example 65: Hydrogenated Copolymer (X61)>

[1160] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1161] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[1162] Next, 0.085 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[1163] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 60 minutes.

[1164] Further addition of 0.08 moles of 1,3-bis{bis(3-trimethoxysilylpropyl)amino}propane relative to 1 mole of n-butyllithium, and reaction at 70°C for 30 minutes.

[1165] Methanol was then added to stop the polymerization reaction.

[1166] The copolymers obtained as described above were separated into low molecular weight components (hydrogenated copolymer (A)) and high molecular weight components (hydrogenated copolymer (B)) by chromatography. The components were analyzed separately. The results showed that in hydrogenated copolymer (A), the styrene content was 68% by mass, the random styrene content (RS1) was 60% by mass, the molecular weight of block styrene (MnS1) was 5100, and the number-average molecular weight (Mn2) was 25,000. In hydrogenated copolymer (B), the degree of branching (f) was 8, the styrene content was 68% by mass, the random styrene content (RS2) was 60% by mass, the molecular weight of block styrene (MnS2) was 5100, and the number-average molecular weight (Mn2) was 200,000.

[1167] In addition, the ratio of the content of hydrogenated copolymer (A) to hydrogenated copolymer (B) is (A) / (B) = 40 / 60.

[1168] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1169] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1170] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (X61).

[1171] <Manufacturing Example 66: Hydrogenated Copolymer (X31)>

[1172] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1173] Add a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass).

[1174] Next, 0.305 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.7 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[1175] Next, a cyclohexane solution containing 48 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 32 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 60 minutes.

[1176] Further addition of 0.20 moles of tetraethoxysilane relative to 1 mole of n-butyllithium was carried out, and the reaction was carried out at 70°C for 30 minutes.

[1177] Methanol was then added to stop the polymerization reaction.

[1178] The copolymers obtained as described above were separated into low molecular weight components (hydrogenated copolymer (A)) and high molecular weight components (hydrogenated copolymer (B)) by chromatography. The components were analyzed separately. The results showed that in hydrogenated copolymer (A), the styrene content was 68% by mass, the random styrene content (RS1) was 60% by mass, the molecular weight of block styrene (MnS1) was 19300, and the number-average molecular weight (Mn2) was 90,000. In hydrogenated copolymer (B), the degree of branching (f) was 3, the styrene content was 68% by mass, the random styrene content (RS2) was 60% by mass, the molecular weight of block styrene (MnS2) was 19300, and the number-average molecular weight (Mn2) was 270,000.

[1179] In addition, the ratio of the content of hydrogenated copolymer (A) to hydrogenated copolymer (B) is (A) / (B) = 50 / 50.

[1180] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1181] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1182] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (X31).

[1183] <Manufacturing Example 67: Hydrogenated Copolymer (A42)>

[1184] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1185] Add a cyclohexane solution containing 30 parts by mass of styrene (concentration 20% by mass).

[1186] Next, 0.493 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[1187] Next, a cyclohexane solution containing 30 parts by mass of styrene (20% by mass) and a cyclohexane solution containing 40 parts by mass of butadiene (20% by mass) were added, and polymerization was carried out at 70°C for 45 minutes.

[1188] Methanol was then added to stop the polymerization reaction.

[1189] The copolymer obtained above has a styrene content of 60% by mass, a random styrene content (RS1) of 43% by mass, a block styrene molecular weight (MnS1) of 4800, and a number-average molecular weight (Mn1) of 16,000.

[1190] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1191] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1192] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A42).

[1193] <Manufacturing Example 68: Hydrogenated Copolymer (A43)>

[1194] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1195] Add a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass).

[1196] Next, 0.375 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 10 minutes.

[1197] Next, a cyclohexane solution containing 70 parts by mass of butadiene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 60 minutes.

[1198] Next, a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 15 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 20 minutes.

[1199] Methanol was then added to stop the polymerization reaction.

[1200] The copolymer obtained above has a styrene content of 15% by mass, a random styrene content (RS1) of 25% by mass, a block styrene molecular weight (MnS1) of 0, and a number-average molecular weight (Mn1) of 30,000.

[1201] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1202] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1203] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (A43).

[1204] <Manufacturing Example 69: Hydrogenated Copolymer (B23)>

[1205] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1206] Add a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass).

[1207] Next, 0.052 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.3 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 10 minutes.

[1208] Next, a cyclohexane solution containing 10 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 80 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[1209] Next, a cyclohexane solution containing 5 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 10 minutes.

[1210] Methanol was then added to stop the polymerization reaction.

[1211] The copolymer obtained above has a styrene content of 20% by mass, a random styrene content (RS2) of 11% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 10,000, and a number-average molecular weight (Mn2) of 200,000.

[1212] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1213] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1214] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B23).

[1215] <Manufacturing Example 70: Hydrogenated Copolymer (B24)>

[1216] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1217] Add a cyclohexane solution containing 7.5 parts by mass of styrene (concentration 20% by mass).

[1218] Next, 0.063 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 1.3 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 30 minutes.

[1219] Next, a cyclohexane solution containing 20 parts by mass of styrene (concentration 20% by mass) and a cyclohexane solution containing 65 parts by mass of butadiene (concentration 20% by mass) were added, and polymerization was carried out at 70°C for 60 minutes.

[1220] Next, a cyclohexane solution containing 7.5 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 30 minutes.

[1221] Methanol was then added to stop the polymerization reaction.

[1222] The copolymer obtained above has a styrene content of 35% by mass, a random styrene content (RS2) of 24% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 11,300, and a number-average molecular weight (Mn2) of 150,000.

[1223] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1224] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1225] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B24).

[1226] <Manufacturing Example 71: Hydrogenated Copolymer (B25)>

[1227] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[1228] Add a cyclohexane solution containing 7.5 parts by mass of styrene (concentration 20% by mass).

[1229] Next, 0.057 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 moles of N,N,N',N'-tetramethylethylenediamine relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 10 minutes.

[1230] Next, a cyclohexane solution containing 35 parts by mass of styrene (20% by mass) and a cyclohexane solution containing 50 parts by mass of butadiene (20% by mass) were added, and polymerization was carried out at 70°C for 50 minutes.

[1231] Next, a cyclohexane solution containing 7.5 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 10 minutes.

[1232] Methanol was then added to stop the polymerization reaction.

[1233] The copolymer obtained above has a styrene content of 50% by mass, a random styrene content (RS2) of 41% by mass, a branching degree (f) of 2, a block styrene molecular weight (MnS2) of 11,300, and a number-average molecular weight (Mn2) of 150,000.

[1234] The hydrogenation catalyst prepared as described above was further added to the obtained copolymer at a concentration of 100 ppm based on Ti per 100 parts by mass of copolymer, and the hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[1235] The hydrogenation rate of the obtained hydrogenated copolymer was 98%.

[1236] Next, 0.3 parts by mass relative to 100 parts by mass of the hydrogenated copolymer were added as a stabilizer, namely octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, to obtain the hydrogenated copolymer (B25).

[1237] [Preparation of hydrogenated copolymer (X)]

[1238] Regarding the hydrogenated copolymers (X1)~(X22), (X24), (X26)~(X60), and (X62)~(X74), the hydrogenated copolymers (A1)~(A17) and (A19)~(A43) were mixed with the hydrogenated copolymers (B1)~(B25) in solution according to Tables 1 to 3, and then desolventized and refined into granules.

[1239] Regarding the hydrogenated copolymer (X25), the hydrogenated copolymer (A18) and hydrogenated copolymer (B13) were desolventized separately and then mixed using an extruder.

[1240] It should be noted that the hydrogenated copolymers (X23), (X31), and (X61) were manufactured according to the above-described [Manufacturing Example 64], [Manufacturing Example 66], and [Manufacturing Example 65].

[1241] It should be noted that the mixing amount (parts by mass) of hydrogenated copolymer (A) in Tables 1 to 3 is the value when the hydrogenated copolymer (X) is 100 parts by mass.

[1242] [Preparation of the polypropylene resin composition]

[1243] 80 parts by weight of hydrogenated copolymer (X) and 20 parts by weight of polypropylene were melt-blended using a twin-screw extruder ("TEX-30αII" manufactured by Nippon Steel, with a barrel diameter of 30 mm) at a set temperature of 220°C to obtain granules of polypropylene resin composition.

[1244] Molding was carried out at an injection molding temperature of 220℃ and a mold temperature of 40℃ to obtain a molded body of polypropylene resin composition (2.0 mm thick, with a textured surface).

[1245] PM801A (PP / SunAllomer; MFR=15) was used as the polypropylene resin.

[1246] The hydrogenated copolymers (X) described above, from (X1) to (X63), are used as hydrogenated copolymers (X).

[1247] [Methods for determining the physical properties of polypropylene resin compositions]

[1248] (1) Formability evaluation)

[1249] The polypropylene resin composition of hydrogenated copolymer (X) was molded into a flat plate (150 mm long, 100 mm wide, and 2 mm thick) at an injection molding temperature of 220 °C and a mold temperature of 40 °C. The moldability of the polypropylene resin composition was evaluated.

[1250] Regarding moldability, the demolding properties of the polypropylene resin composition of the hydrogenated copolymer (X) during injection molding, as well as the appearance characteristics of the injection-molded articles (presence or absence of shrinkage marks / flow marks / reflection), were evaluated. The evaluation criteria are as follows.

[1251] ○: There are no practical problems.

[1252] △: Slight shrinkage marks / flow marks / reflections may occur.

[1253] ×: Significantly poor release properties and / or significant problems with the appearance characteristics of the injection molded product.

[1254] (2) Abrasion resistance evaluation)

[1255] [Abrasion resistance (10,000 cycles)]

[1256] Using a vibration-type friction tester (manufactured by TESTER SANGYO Co., Ltd., AB-301 model), the surface of the molded body (textured surface) was rubbed with plain weave fine cotton cloth No. 3 under a load of 500g, and the mass reduction of the molded body was measured.

[1257] The smaller the mass reduction, the higher the abrasion resistance of the polypropylene resin composition is judged, and the following criteria are used for evaluation.

[1258] ◎: After 10,000 friction cycles, the mass reduction is less than 0.015g.

[1259] 〇: After 10,000 friction cycles, the mass reduction is greater than 0.015g and less than 0.03g.

[1260] △: After 10,000 friction cycles, the mass reduction is greater than 0.03g and less than 0.05g.

[1261] ×: After 10,000 friction cycles, the mass reduction is more than 0.05g.

[1262] [Abrasion resistance (fabric transfer after 2500 cycles)]

[1263] In addition, fabric transfer sometimes occurs between the molded body and the abrasion cloth during abrasion tests. The less fabric transfer occurs, the higher the abrasion resistance of the polypropylene resin composition is considered. Fabric transfer of the abrasion cloth relative to the contact surface of the molded body is evaluated according to the following criteria.

[1264] 〇: After 2500 friction cycles, the area where fabric transfer occurs is less than 10%.

[1265] △: After 2500 friction cycles, the area where fabric transfer occurs is more than 10% but less than 50%.

[1266] ×: After 2500 friction cycles, the area where fabric transfer occurs is over 50%.

[1267] [Abrasion resistance (change in gloss after 1000 cycles)]

[1268] In addition, the surface of the molded body may exhibit reflectivity or damage after the abrasion test. The less reflectivity or damage occurs, the higher the abrasion resistance of the polypropylene resin composition is considered. Changes in the surface of the molded body after the abrasion test are evaluated according to the following criteria.

[1269] ◎: No changes were observed on the surface of the molded body after 1000 rubbing cycles.

[1270] 〇: After 1000 rubbing cycles, slight wear marks (reflection) will appear on the surface of the molded body.

[1271] △: After 1000 rubbing cycles, significant wear marks (reflection) are produced on the surface of the molded body.

[1272] ×: After 1000 friction cycles, damage occurs on the surface of the molded body.

[1273] (3) Tensile strength)

[1274] According to JIS K6251, the test was conducted using a No. 3 dumbbell-shaped test piece at a crosshead speed of 500 mm / min.

[1275] Tensile strength is evaluated according to the following criteria.

[1276] ◎: The maximum tensile strength is above 18 MPa.

[1277] 〇: The maximum tensile strength is above 16 MPa and less than 18 MPa.

[1278] △: The maximum tensile strength is above 14 MPa and less than 16 MPa.

[1279] ×: The maximum tensile strength is less than 14 MPa.

[1280] [Evaluation results of hydrogenated copolymer (X)]

[1281] The evaluation results of Examples 1 to 51 (hydrogenated copolymers (X1) to (X62)) and Comparative Examples 1 to 4, Reference Example 5, and Comparative Examples 6 to 12 (hydrogenated copolymers (X28) to (X38), (X63)) are summarized in the table below.

[1282] It should be noted that the evaluation criteria are based on the methods for determining the physical properties and characteristics of hydrogenated copolymers and the methods for determining the characteristics of polypropylene resin compositions described above.

[1283] [Table 1]

[1284]

[1285] [Table 2]

[1286]

[1287] [Table 3]

[1288]

[1289]

[1290]

[1291]

[1292]

[1293]

[1294]

[1295]

[1296]

[1297] Examples 1 to 51 are evaluation results of hydrogenated copolymers (X) that satisfy the constituent elements of the present invention, while Comparative Examples 1 to 4 and 6 to 12 are evaluation results of hydrogenated copolymers (X) that do not satisfy the constituent elements of the present invention.

[1298] In the embodiment, none of the four evaluation items had an "X". On the other hand, in the comparative example, there was more than one "X". Therefore, the comparative example is inferior to the embodiment.

[1299] It should be noted that, in Reference Example 5, the styrene content in the hydrogenated copolymer (A) is low. This indicates that although the material used as an adhesive to form the adhesive film can perform well, its properties as a material for the molded body are poor.

[1300] [Manufacturing of adhesive films]

[1301] The dry mixtures of polyethylene (HDPE, manufactured by Asahi Kasei Chemicals Co., Ltd., trade name "Creolex T5070L", MFR (190°C, 2.16 kg load) = 7.0 g / 10 min), the hydrogenated copolymers (X64) to (X74), (X33), (B24), (B25) and (B24) constituting the substrate layer, and the tackifier were mixed and fed into the extruder according to the proportions shown in Examples 52 to 62 and Comparative Examples 13 to 18.

[1302] Using a multi-layer T-die extruder (manufactured by Plastics Engineering Research Institute Co., Ltd., PLABOR), two layers are co-extruded together at an extrusion temperature of 200°C and a die temperature of 220°C to produce an adhesive film with a substrate layer thickness of 40μm and an adhesive layer thickness of 10μm.

[1303] The dry blends mentioned above refer to blends that constitute the adhesive layer (hydrogenated copolymers, tackifiers).

[1304] YS Polyster-HU (hydrogenated terpene phenol resin / manufactured by YASUHARA CHEMICAL Co., Ltd.) was used as the above-mentioned adhesive.

[1305] To evaluate the performance of the adhesive films obtained in Examples 52-62 and Comparative Examples 13-18, initial adhesion, adhesion hyperactivity, and delivery were measured and evaluated.

[1306] The results are shown in Tables 12 to 14.

[1307] [Membrane adhesive properties]

[1308] The measuring apparatus used was a universal tensile and compression testing machine, "Technograph TGE-500N: manufactured by Minebea Co., Ltd."

[1309] (Evaluation of initial adhesion)

[1310] In Examples 52-62 and Comparative Examples 13-18, the prepared adhesive films were made into 25 mm wide sheets and then pasted onto PMMA boards (arithmetic mean surface roughness: 0.1 μm) and SUS304HL boards, respectively. The films were then rolled on a 2 kg rubber roller (10 cm in diameter) and left for 30 minutes at a temperature of 23°C and a relative humidity of 50%. After that, the peeling speed was 300 mm / min and the films were peeled at an angle of 180 degrees. The initial adhesion was measured according to test JIS K6854-2 and evaluated according to the following criteria.

[1311] PMMA board

[1312] Cases with a value of 250 (g / 25mm) or higher are marked with ◎.

[1313] Cases with values ​​above 150 (g / 25mm) but less than 250 (g / 25mm) are recorded as 0.

[1314] The case of 100 (g / 25mm) or more but less than 150 (g / 25mm) is denoted as △.

[1315] Cases less than 100 (g / 25mm) are marked as ×.

[1316] SUS board

[1317] Cases with a value of 150 (g / 25mm) or higher are marked with ◎.

[1318] Cases with a content of 70 (g / 25mm) or higher but less than 150 (g / 25mm) are recorded as 0.

[1319] The case of 35 (g / 25mm) or more but less than 70 (g / 25mm) is denoted as △.

[1320] Cases less than 35 (g / 25mm) are marked as ×.

[1321] (Evaluation of adhesive hyperactivity)

[1322] In Examples 52-62 and Comparative Examples 13-18, the prepared adhesive film was made into a 25mm wide sheet and pasted onto SUS304HL, and then further pasted by rolling a 2kg rubber roller (10cm in diameter).

[1323] Then, it was stored in an oven at 80°C for 1 hour, and then placed at 23°C and 50% relative humidity for 30 minutes. After that, the peeling speed was 300 mm / min and the peeling was performed at an angle of 180 degrees. The adhesive strength was determined according to test JISK6854-2.

[1324] The adhesion hyperactivity is evaluated according to the following formula.

[1325] Adhesive strength = (Adhesive force after heating at 80°C for 1 hour) / (Initial adhesive force)

[1326] The lower the value of adhesion hyperactivity, the better the assessment, which is evaluated according to the following criteria.

[1327] Values ​​below 1.5 are marked with ◎.

[1328] Values ​​greater than 1.5 and less than 2 are recorded as 0.

[1329] Values ​​greater than 2 and less than 3 are denoted as △.

[1330] A value greater than 3 is marked as ×.

[1331] [Submitted evaluation]

[1332] In Examples 52-62 and Comparative Examples 13-18, the prepared adhesive film was made into a 25mm wide sheet and pasted onto an HDPE board. A rubber roller with a weight of 2kg (diameter of 10cm) was used for pasting. The film was placed at a temperature of 23°C and a relative humidity of 50% for 30 minutes. Then, the peeling speed was set to 300mm / min and the film was peeled at 180 degrees. The initial adhesion was measured according to test JIS K6854-2 and evaluated according to the following criteria.

[1333] The smaller the output value, the better the evaluation, according to the following criteria.

[1334] The case with less than 12 (g / 25mm) is marked as ◎.

[1335] Cases with values ​​greater than 12 (g / 25mm) and less than 18 (g / 25mm) are recorded as 0.

[1336] The case of 18 (g / 25mm) or more but less than 26 (g / 25mm) is denoted as △.

[1337] Cases with a value of 26 (g / 25mm) or higher are marked as ×.

[1338] [Evaluation results of hydrogenated copolymer (X)]

[1339] The evaluation results of Examples 52-62 and Comparative Examples 13-18 are summarized in Tables 12-14 below.

[1340] It should be noted that the evaluation criteria are based on the aforementioned method for determining the properties of adhesive films.

[1341]

[1342]

[1343]

[1344] Examples 52-62 are evaluation results of hydrogenated copolymers (X) that satisfy the constituent elements of the present invention, while Comparative Examples 13-18 are evaluation results of hydrogenated copolymers that do not satisfy the constituent elements of the present invention.

[1345] In the embodiment, none of the four evaluation items had an "X". On the other hand, in the comparative example, there were more than one "X". Therefore, the comparative example is inferior to the embodiment.

[1346] This application is based on Japanese Patent Application No. 2020-107264, filed with the Japan Patent Office on June 22, 2020, the contents of which are incorporated herein by reference.

[1347] Industrial applicability

[1348] The hydrogenated copolymers and hydrogenated copolymer compositions of the present invention have industrial applicability in fields such as reinforcing filler compoundings, crosslinking products, foams, multilayer films and sheets, building materials, shock-absorbing / sound-damping materials, wire coating materials, high-frequency welding compositions, slush molding materials, adhesive compositions, asphalt compositions, automotive interior materials, automotive exterior materials, medical device materials, food packaging containers and other containers, household appliances, industrial parts, and toys.

Claims

1. A hydrogenated copolymer (X) comprising: Hydrogenated copolymer (A), which is a hydrogenated copolymer of a vinyl aromatic compound and a conjugated diene compound; and Hydrogenated copolymer (B) is a hydrogenated form of a copolymer of a vinyl aromatic compound and a conjugated diene compound. The hydrogenated copolymer (X) satisfies the following conditions (1) to (4) and satisfies the following conditions (5) or (6): (1): The hydrogenated copolymer (A) has a random copolymer structure formed by a conjugated diene compound and a vinyl aromatic compound, wherein the content of the vinyl aromatic compound in the hydrogenated copolymer (A) is more than 30% by mass and less than 80% by mass; (2): The hydrogenated copolymer (B) has a random copolymer structure formed by a conjugated diene compound and a vinyl aromatic compound, has at least one polymer block mainly composed of a vinyl aromatic compound, and the content of the vinyl aromatic compound in the hydrogenated copolymer (B) is more than 30% by mass and less than 80% by mass, wherein, The term "mainly composed of vinyl aromatic compounds" means that the vinyl aromatic compounds comprise more than 80% by mass and less than 100% by mass in the polymer blocks. (3): The number-average molecular weight Mn1 of the hydrogenated copolymer (A) is less than 0.25 relative to the number-average molecular weight Mn2 of the hydrogenated copolymer (B). And 1000≦Mn1≦40000; (4): The mass ratio (A) / (B) of the content of the hydrogenated copolymer (A) to the content of the hydrogenated copolymer (B) is 5 / 95 to 50 / 50; (5): The mass fraction RS1 of the vinyl aromatic compounds in the random copolymer structure of the hydrogenated copolymer (A) is 30% to 80% by mass. The mass fraction RS2 of vinyl aromatic compounds in the random copolymer structure of the hydrogenated copolymer (B) is 30% to 80% by mass. (6): The mass fraction RS1 of the vinyl aromatic compounds in the random copolymer structure of the hydrogenated copolymer (A) is 10% to 60% by mass. The mass fraction RS2 of the vinyl aromatic compounds in the random copolymer structure of the hydrogenated copolymer (B) is 10% to 60% by mass.

2. The hydrogenated copolymer (X) as claimed in claim 1, wherein, The hydrogenated copolymer (A) has at least one polymer block dominated by a vinyl aromatic compound, wherein being dominated by a vinyl aromatic compound means that the vinyl aromatic compound is present in the polymer block at a concentration greater than 80% by mass and less than 100% by mass.

3. The hydrogenated copolymer (X) as described in claim 1 or 2, wherein, The number-average molecular weight (Mn2) of the hydrogenated copolymer (B) is above 120,000.

4. The hydrogenated copolymer (X) as described in claim 1 or 2, wherein, The hydrogenation rate of the double bonds from the conjugated diene compound in the hydrogenated copolymer (A) and the hydrogenated copolymer (B) is more than 40%.

5. The hydrogenated copolymer (X) as described in claim 1 or 2, wherein, In the 1Hz viscoelasticity measurement spectrum, at least one tanδ peak is present in the range of -20℃ to 40℃.

6. The hydrogenated copolymer (X) as described in claim 1 or 2, wherein, The ratio of the mass fraction RS1 of the vinyl aromatic compounds in the random copolymer structure of the hydrogenated copolymer (A) to the mass fraction RS2 of the vinyl aromatic compounds in the random copolymer structure of the hydrogenated copolymer (B) is 0.8 to 1.

2.

7. The hydrogenated copolymer (X) as described in claim 1 or 2, wherein, The weight-average molecular weight Mw2 of the hydrogenated copolymer (B) is less than 1.15 relative to the number-average molecular weight Mn2.

8. The hydrogenated copolymer (X) as described in claim 1 or 2, wherein, The number-average molecular weight Mn1 of the hydrogenated copolymer (A) is less than 0.12 relative to the number-average molecular weight Mn2 of the hydrogenated copolymer (B).

9. The hydrogenated copolymer (X) as described in claim 1 or 2, wherein, The hydrogenated copolymer (A) has polymer blocks mainly composed of vinyl aromatic compounds, and the ratio of the molecular weight MnS1 of the polymer blocks mainly composed of vinyl aromatic compounds in the hydrogenated copolymer (A) to the molecular weight MnS2 of the polymer blocks mainly composed of vinyl aromatic monomer units in the hydrogenated copolymer (B), MnS1 / MnS2, is 0.9 or less. MnS1 and MnS2 are calculated using the following method: MnS1=Mn1×BS1 MnS2=Mn2×BS2÷f BS1: via proton nuclear magnetic resonance (NMR) 1 The content of the polymer blocks mainly composed of vinyl aromatic compounds in the hydrogenated copolymer (A) determined by H-NMR. BS2: via proton nuclear magnetic resonance (NMR) 1 The content of the polymer blocks mainly composed of vinyl aromatic compounds in the hydrogenated copolymer (B) determined by H-NMR. f: Degree of branching of hydrogenated copolymer (B) determined by GPC-light scattering method with viscosity detector. Mn1: Number average molecular weight of hydrogenated copolymer (A) Mn2: Number average molecular weight of hydrogenated copolymer (B).

10. The hydrogenated copolymer (X) as claimed in claim 1 or 2, wherein, The hydrogenated copolymer (B) is polymerized by stepwise polymerization.

11. The hydrogenated copolymer (X) as claimed in claim 3, wherein, The number-average molecular weight Mn2 of the hydrogenated copolymer (B) is between 120,000 and 1,000,000.

12. The hydrogenated copolymer (X) as described in claim 1 or 2, wherein, In condition (4), the mass ratio (A) / (B) of the content of the hydrogenated copolymer (A) to the content of the hydrogenated copolymer (B) is 10 / 90 to 50 / 50.

13. A resin composition comprising: The hydrogenated copolymer (X) according to any one of claims 1 to 12, wherein the content of vinyl aromatic compounds in the hydrogenated copolymers (A) and (B) is 30% by mass or more and 80% by mass or less; and Thermoplastic resins other than the hydrogenated copolymer (X) and / or rubbery polymers other than the hydrogenated copolymer (X).

14. The resin composition of claim 13, wherein, The mixing ratio of the hydrogenated copolymer (X) to the thermoplastic resin and / or the rubbery polymer, by mass, is hydrogenated copolymer (X) / (thermoplastic resin and / or rubbery polymer) = 1 / 99 to 99 / 1.

15. The resin composition of claim 13 or 14, wherein, The thermoplastic resin is a polyolefin resin.

16. A molded article, which is a molded article of the resin composition according to any one of claims 13 to 15.

17. An adhesive film having a substrate layer and an adhesive layer thereon on the substrate layer, wherein, The adhesive layer contains the hydrogenated copolymer (X) according to any one of claims 1 to 12. The content of vinyl aromatic compounds in the hydrogenated copolymers (A) and (B) constituting the hydrogenated copolymer (X) is more than 30% by mass and less than 60% by mass.

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