Modified conjugated diene polymer, modified conjugated diene polymer composition, multilayer body, method for producing multilayer body, and molded article

Abstract

To provide a modified conjugated diene polymer that has adhesiveness by thermal fusion to a polar resin, is excellent in fluidity during melting, and has excellent flexibility.SOLUTION: The modified conjugated diene polymer of the present invention has a polymer block mainly comprising conjugated diene monomer units, and satisfies the following conditions: (a) a vinyl bond content before hydrogenation in the polymer block mainly comprising conjugated diene monomer units is 60 mol% or more based on 100 mol% of total of the conjugated diene monomer units; (b) at least one or more conjugated diene monomer units in the polymer block mainly comprising conjugated diene monomer units are hydrogenated; (c) a content of a polymer block mainly comprising vinyl aromatic monomer units is 40 mass% or less; and (d) the modified conjugated diene polymer has a modifying group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a modified conjugated diene polymer, a modified conjugated diene polymer composition, a multilayer body, a method for producing a multilayer body, and a molded body.

Background Art

[0002] Conjugated diene-based (co)polymers exhibit various properties depending on the ratio of monomer units having side chains such as 1,2-bonds, the microstructure when copolymerized with other monomers (the ratio of block portions of block copolymers, the arrangement of block portions, and the structure of random copolymers, etc.), and the degree of hydrogenation. In recent years, for the purpose of imparting further performance, conjugated diene-based (co)polymers having a modifying group such as an affinity group capable of generating an intermolecular force with other materials or a reactive group capable of forming a chemical bond with other materials (hereinafter referred to as "modified conjugated diene polymers") have been proposed. For example, Patent Document 1 discloses an acid anhydride-modified conjugated diene polymer produced by reacting a conjugated diene block copolymer with an acid anhydride.

[0003] Modified conjugated diene polymers are excellent in adhesion to polar resins because they react with polar resins and / or generate intermolecular forces such as hydrogen bonds in the modifying groups. Therefore, modified conjugated diene polymer compositions in which a modified conjugated diene polymer is blended with polyolefin or the like as an adhesion-imparting agent for polar resins are widely used. For example, polyamide resin is one of the polar resins. Patent Document 2 discloses a technique related to the adhesion of polyamide resin using a modified conjugated diene polymer resin composition containing a modified block copolymer. Molded articles in which such a modified conjugated diene polymer resin composition and a polar resin are adhered are useful for various applications such as automotive parts, power tools, toys, electrical and electronic equipment parts, medical instruments, building materials and piping members, daily and cosmetic products, industrial parts, various hoses, various housings, various module cases, various power control unit parts, and medical instruments. Further, by forming the surface layer of the molded body using a flexible modified conjugated diene polymer resin composition, a flexible touch can be imparted to the molded article.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] Regardless of the type of polar resin, the type of polymer structure, and the presence or absence of a filler, it is desired to develop a modified conjugated diene polymer composition that is thermally fusible to a polar resin and exhibits excellent adhesiveness. Further, regardless of whether the molding method is injection molding (insert molding), two-color molding, coextrusion, multilayer blow molding, etc., it is desired to develop a modified conjugated diene polymer composition that is heat-sealed to a polar resin and exhibits excellent adhesiveness.

[0006] In addition, the modified conjugated diene polymer composition is required to have not only excellent adhesiveness but also high fluidity during melting so as to cope with the complication and thinning of the molded article, and high flexibility to obtain a good touch when the molded article comes into contact with the human body. However, in conventional modified conjugated diene polymer compositions including Patent Document 2, sufficient fluidity and flexibility have not yet been obtained.

[0007] Therefore, in view of the above problems, the present invention aims to provide a modified conjugated diene-based polymer having adhesiveness by heat fusion to a polar resin, excellent fluidity during melting, and excellent flexibility, a modified conjugated diene-based polymer composition, a multilayer body containing them, a method for producing the multilayer body, and a molded body. [Means for Solving the Problems]

[0008] As a result of intensive studies to solve the above problems of the prior art, the present inventors have found that a modified conjugated diene-based polymer having a modifying group and a specific polymer structure can solve the above problems, and have completed the present invention.

[0009] That is, the present invention is as follows. [1] A modified conjugated diene-based polymer having a polymer block mainly composed of conjugated diene monomer units and satisfying the following conditions (a), (b), (c) and (d). (a) In the polymer block mainly composed of the conjugated diene monomer units, the amount of vinyl bonds before hydrogenation is 60 mol% or more with respect to 100 mol% of the total amount of the conjugated diene monomer units. (b) At least a part of the conjugated diene monomer units in the polymer block mainly composed of the conjugated diene monomer units is hydrogenated. (c) The content of the polymer block mainly composed of vinyl aromatic monomer units in the modified conjugated diene-based polymer is 40% by mass or less with respect to the total amount of the modified conjugated diene-based polymer. (d) The modified conjugated diene-based polymer has a modifying group. [2] The modified conjugated diene-based polymer according to [1], wherein the amount of vinyl bonds before hydrogenation is 65 mol% or more with respect to 100 mol% of the total amount of the conjugated diene monomer units. [3] The modified conjugated diene-based polymer according to [1] or [2], wherein the amount of butylene and / or propylene in the polymer block mainly composed of the conjugated diene monomer units is 60 mol% or more with respect to 100 mol% of the total amount of the conjugated diene monomer units. [4] The modified conjugated diene polymer according to any one of [1] to [3], which has the modified group in a side chain. [5] The modified conjugated diene polymer according to any one of [1] to [4], wherein the content of the polymer block mainly composed of the vinyl aromatic monomer unit in the modified conjugated diene polymer is 20% by mass or less based on the total amount of the modified conjugated diene polymer. [6] The modified conjugated diene polymer according to any one of [1] to [5], wherein the modified group is at least one selected from the group consisting of an acid anhydride group, a carbonyl group, a carboxyl group, an amino group, an epoxy group, an alkoxysilane group, a hydroxyl group, an isocyanate group, and an ionic group. [7] A modified conjugated diene polymer composition comprising the modified conjugated diene polymer (A) according to any one of [1] to [6] and a polyolefin (B). [8] The modified conjugated diene polymer composition according to [7], wherein the polyolefin (B) is polypropylene. [9] The modified conjugated diene polymer composition according to [7] or [8], further comprising a conjugated diene polymer (C) having a weight average molecular weight of 150,000 or more.

[10] The modified conjugated diene polymer composition according to [9], wherein the conjugated diene polymer (C) includes at least a conjugated diene polymer having a random copolymer block of a conjugated diene monomer and a vinyl aromatic monomer.

[11] The modified conjugated diene polymer composition according to any one of [7] to

[10] , wherein the content of the modified conjugated diene polymer (A) is 5% by mass or more and 80% by mass or less.

[12] The modified conjugated diene polymer composition according to any one of [7] to

[11] , wherein the weight average molecular weight of the modified conjugated diene polymer (A) is 100,000 or more.

[13] The modified conjugated diene polymer composition according to any one of [7] to

[12] , further comprising a softening agent.

[14] The modified conjugated diene polymer composition according to any one of [7] to

[13] , having a melt flow rate at 230 °C and 2.16 kg of 10 g / 10 min or more.

[15] The modified conjugated diene polymer composition according to any one of [7] to

[14] , further comprising a filler.

[16] A multilayer body comprising a layer containing a polar resin and a layer containing the modified conjugated diene polymer composition according to any one of [7] to

[15] laminated on the layer.

[17] The multilayer body according to

[16] , wherein the layer containing the modified conjugated diene polymer composition is heat-sealed to the layer containing the polar resin.

[18] The polar resin is at least one selected from the group consisting of ABS, polymethyl methacrylate, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyphenylene sulfide. The multilayer body according to

[16] or

[17] .

[19] A method for producing the multilayer body according to any one of

[16] to

[18] , The method for production, wherein the multilayer body is molded by at least one method selected from the group consisting of an injection molding method, an insert molding method, an extrusion molding method, and a compression molding method.

[20] A molded body containing the multilayer body according to any one of

[16] to

[18] , The molded body, wherein the multilayer body constitutes at least one selected from the group consisting of a grip of a tool, an electric wire covering member, a connector housing, a grip of a handy electronic device, a grip of a toothbrush, a grip of a shaver, a grip of a cutlery, a grip of a writing instrument, a grip portion of a robot hand, and a grip portion of an automobile interior member. [Advantages of the Invention]

[0010] According to the present invention, there can be provided a modified conjugated diene-based polymer having adhesiveness by heat fusion to a polar resin, excellent fluidity during melting, and excellent flexibility, a modified conjugated diene-based polymer composition, a multilayer body containing them, a method for producing the multilayer body, and a molded body.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Figure 3

Figure 4

Embodiments for Carrying Out the Invention

[0012] Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as "the present embodiments") will be described in detail. The following present embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of its gist. In the present specification, the "polymer" shall include both a polymer composed of a single type of monomer unit and a copolymer having a plurality of types of monomer units. Also, in the present specification, unless otherwise specified, or unless clearly distinguished as described in parallel such as "conjugated diene-based polymer or modified conjugated diene-based polymer", the "conjugated diene-based polymer" includes an unmodified conjugated diene-based polymer and a modified conjugated diene-based polymer. In the case where it is described in parallel such as "conjugated diene-based polymer or modified conjugated diene-based polymer", the "conjugated diene-based polymer" means an unmodified conjugated diene-based polymer.

[0013] (Modified conjugated diene-based polymer (A)) The modified conjugated diene polymer (A) of the present embodiment has a polymer block mainly composed of conjugated diene monomer units and satisfies the following conditions (a), (b), (c), and (d). (a) In the polymer block mainly composed of conjugated diene monomer units, the amount of vinyl bonds before hydrogenation is 60 mol% or more with respect to a total of 100 mol% of the conjugated diene monomer units. (b) At least a part of the conjugated diene monomer units in the polymer block mainly composed of conjugated diene monomer units is hydrogenated. (c) The content of the polymer block mainly composed of vinyl aromatic monomer units in the modified conjugated diene polymer is 40% by mass or less with respect to the total amount of the modified conjugated diene polymer. (d) The modified conjugated diene polymer has a modifying group.

[0014] The conjugated diene monomer constituting the modified conjugated diene polymer is a diolefin having a pair of conjugated double bonds. Such diolefins include, but are not limited to, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-cyclopentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene, and farnesene. Among these, from the viewpoints of availability and productivity, 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is more preferable from the viewpoint of thermal stability. The conjugated diene monomer units contained in the modified conjugated diene polymer (A) may be only one kind or two or more kinds.

[0015] A polymer block mainly composed of a conjugated diene monomer unit means a polymer block in which the content of the conjugated diene monomer unit exceeds 70% by mass based on the entire polymer block. From the viewpoint of further improving the adhesiveness between the modified conjugated diene-based polymer composition and the polar resin, the content of the conjugated diene monomer unit contained in the polymer block mainly composed of the conjugated diene monomer unit described above is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. In addition, the content of the conjugated diene monomer unit in the polymer block mainly composed of the conjugated diene monomer unit may be 100% by mass or less, or may be 99% by mass or less.

[0016] The modifying group of the modified conjugated diene-based polymer is not particularly limited as long as it is an affinity group or a reactive group for the polar resin. For example, an acid anhydride group, a hydroxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, a carboxyl group, a thiocarboxyl group, an aldehyde group, a thioaldehyde group, a carboxylic acid ester group, an amide group, a sulfonic acid ester group, a phosphate ester group, an amino group, an imino group, a cyano group, a urethane group, a urea group, a pyridyl group, a quinoline group, an epoxy group, a thioepoxy group, a sulfide group, an isocyanate group, an isothiocyanate group, a silicon halide group, a silanol group, an alkoxysilane group, a tin halide group, an alkoxytin group, a phenyltin group, and an ionic group, etc. can be mentioned. The modified conjugated diene-based polymer has one of the above-mentioned modifying groups alone or in combination of two or more. Examples of the ionic group include a sulfonic acid group, a sulfonimide group, a sulfuric acid group, a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, and an ammonium group or a salt thereof. Among them, from the viewpoint of further improving the reactivity with the polar resin, as the modifying group of the modified conjugated diene-based polymer, an acid anhydride group, a carbonyl group, a carboxyl group, an amino group, an epoxy group, an alkoxysilane group, a hydroxyl group, an isocyanate group, and an ionic group are preferable. Furthermore, among them, from the viewpoint of further improving the reactivity with polyamide resin (hereinafter also simply referred to as "polyamide"), polyphenylene sulfide resin (hereinafter also simply referred to as "polyphenylene sulfide"), and polyester resin (hereinafter also simply referred to as "polyester"), which are the main structural materials of various molded products, the modifying group is more preferably an acid anhydride group, a carboxyl group, an amino group, an epoxy group, or a hydroxyl group. Also, from the viewpoints of high productivity and easy availability, the modifying group is more preferably an acid anhydride group or a carboxyl group, and among them, the acid anhydride group (particularly, maleic anhydride group and succinic anhydride group are preferable, and succinic anhydride group is more preferable) is particularly preferable. The maleic anhydride group and the succinic anhydride group mean groups obtained by removing one hydrogen atom from each C-H bond of maleic anhydride and succinic anhydride, respectively.

[0017] Polyamide resin is widely used as a molded body having a grip part such as a power tool or as a part of a molded body that requires strength and heat resistance. On the other hand, it has poor adhesiveness with conventional modified conjugated diene polymers. Among the above-mentioned modifying groups, the acid anhydride group is excellent in reactivity with the amino group, carboxyl group, and amide group of the polyamide resin. Therefore, the modified conjugated diene polymer used for adhering to the polyamide resin preferably contains an acid anhydride group. Among them, the modified conjugated diene polymer used for adhering to the polyamide resin preferably contains a maleic anhydride group or a succinic anhydride group from the viewpoints of high productivity and easy availability. The maleic anhydride group and the succinic anhydride group can firmly adhere the two by forming a chemical bond at the interface between the polyamide resin and the modified conjugated diene polymer in the modified conjugated diene polymer composition.

[0018] Preferred modified groups of the modified conjugated diene polymer used for adhesion to polyphenylene sulfide resin include acid anhydride group, carbonyl group, carboxyl group, amino group, epoxy group, alkoxysilane group, hydroxyl group, isocyanate group, and ionic group. The above-mentioned modified groups have even higher reactivity with carboxylic acid at the polymer chain end of polyphenylene sulfide.

[0019] Polyester resin has an ester structure in the main chain and a hydroxyl group or a carboxyl group at the end. Therefore, preferred modified groups of the modified conjugated diene polymer used for adhesion to polyester resin include acid anhydride group, carbonyl group, carboxyl group, amino group, epoxy group, alkoxysilane group, hydroxyl group, isocyanate group, and ionic group.

[0020] Polycarbonate resin (hereinafter also simply referred to as "polycarbonate") has a carbonate ester in the main chain and a hydroxyl group at the end. Therefore, preferred modified groups of the modified conjugated diene polymer in the modified conjugated diene polymer composition used for adhesion to polycarbonate resin include acid anhydride group, carbonyl group, carboxyl group, amino group, epoxy group, alkoxysilane group, hydroxyl group, isocyanate group, and ionic group.

[0021] Acrylonitrile-butadiene-styrene copolymer (ABS) resin (hereinafter also simply referred to as "ABS") has a nitrile group. Therefore, preferred modified groups of the modified conjugated diene polymer in the modified conjugated diene polymer composition used for adhesion to ABS resin include acid anhydride group, carboxyl group, amino group, and hydroxyl group.

[0022] (Meta)acrylic resin is a general term for polyacrylic acid, polyacrylate, polymethacrylic acid, and polymethacrylate, and has a carboxyl group and / or an ester group. Therefore, as the modified group of the modified conjugated diene polymer in the modified conjugated diene polymer composition used for adhering to the (meta)acrylic resin, an acid anhydride group, a carbonyl group, a carboxyl group, an amino group, an epoxy group, an alkoxysilane group, a hydroxyl group, an isocyanate group, and an ionic group are preferable.

[0023] Polyacetal resin (hereinafter, also simply referred to as "polyacetal") has an ether structure. Therefore, as the modified group of the modified conjugated diene polymer in the modified conjugated diene polymer composition used for adhering to the polyacetal resin, an acid anhydride group, a carbonyl group, a carboxyl group, an amino group, an epoxy group, an alkoxysilane group, a hydroxyl group, an isocyanate group, and an ionic group are preferable.

[0024] Note that polyamide resin, ABS resin, polyester resin, and polycarbonate resin are mainly used for tools, housings of electronic devices, and shavers. Polyamide resin, polyester resin, and polyphenylene sulfide resin are mainly used for connector housings. Polyamide resin and polyester resin are mainly used for wire members. Polyacetal resin is mainly used for toothbrushes and cutlery. Polycarbonate resin, ABS resin, and polyester resin are mainly used for writing utensils. Polyamide resin, ABS resin, polyester resin, and polycarbonate resin are mainly used for robot hands. Polyamide resin, ABS resin, polyester resin, polycarbonate resin, and (meta)acrylic resin are mainly used for automotive interior members. Polyamide resin, polyphenylene sulfide resin, and polyester resin are mainly used for automotive members and power modules that require heat resistance. Polyamide resin, polyphenylene sulfide resin, and polyester resin are mainly used for automotive members that require flexibility and chemical resistance. Note that the writing instrument includes not only a pen-like writing instrument that directly writes on an object by transferring a coloring material such as ink and graphite to the object, but also a writing instrument such as a touch pen and a stylus pen used to display corresponding characters or figures on the screen of an electronic terminal by tracing a part of the electronic terminal such as a tablet terminal.

[0025] When the modified conjugated diene polymer has a functional group that does not correspond to an affinity group capable of generating an intermolecular force with a polar resin or a functional group that does not correspond to a reactive group capable of forming a chemical bond, the adhesion of the modified conjugated diene polymer to the polar resin can be further improved by reacting the functional group with another compound capable of interacting with both the functional group and the polar resin. That is, the functional group of the modified conjugated diene polymer interacts with the other compound by an intermolecular force or a chemical bond, and the other compound interacting with the functional group further interacts with the polar resin by an intermolecular force or a chemical bond, so that the modified conjugated diene polymer and the polar resin can indirectly interact with each other.

[0026] Such other compounds include, but are not limited to, for example, carbodiimide compounds, amide condensing agents such as diphenylphosphoric acid azide, alkoxysilane compounds, amino compounds, hydroxy compounds, isocyanate compounds, and epoxy compounds. The other compounds are used alone or in combination of two or more. Examples of the carbodiimide compound include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide. Examples of the alkoxysilane compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane. Examples of the amine compound include diaminobutane, diaminopentane, diaminohexane, diaminoheptane, and diaminooctane. Examples of the hydroxy compound include dihydroxybutane, dihydroxypentane, dihydroxyhexane, dihydroxyheptane, and dihydroxyoctane. Examples of the isocyanate compound include hexamethylene diisocyanate, 1,4-phenylene diisocyanate, and dicyclohexylmethane 4,4'-diisocyanate. Examples of the epoxy compound include ethylene glycol diglycidyl ether and 1,4-butanediol diglycidyl ether. These compounds can also be used for a modified conjugated diene polymer having an affinity group capable of generating an intermolecular force with a polar resin or a reactive group capable of forming a chemical bond.

[0027] The content of the modifying group in the above-described modified conjugated diene polymer is not particularly limited, but from the viewpoint of further improving the adhesiveness to the polar resin, it is preferably 0.5 or more per chain. From the same viewpoint, it is more preferably 2.0 or more per chain, and still more preferably 4.0 or more per chain. When the content of the modifying group is 0.5 or more per chain, the modifying group can interact more sufficiently with the polar resin, and the heat fusion property is further improved. Further, from the viewpoint of further preventing problems such as gelation of the modified conjugated diene polymer composition, the content of the modifying groups is preferably 30 or less per chain. Here, the "chain" refers to one molecular chain in a polymer such as a modified conjugated diene polymer. For a polymer structure branched by chemical bonds, one branched chain is counted as one molecular chain.

[0028] When obtaining a modified conjugated diene polymer by reacting a conjugated diene polymer with a modifier, the content of the modifying groups may be controlled by adjusting the mass of the modifier to be reacted with the polymer. For example, when the modifier is an acid anhydride (e.g., maleic anhydride), the mass of the acid anhydride reacted (added) with the conjugated diene polymer may be 0.1 part by mass or more and 20 parts by mass or less, preferably 0.2 part by mass or more and 10 parts by mass or less, more preferably 0.3 part by mass or more and 5.0 parts by mass or less, still more preferably 0.3 part by mass or more and 2.0 parts by mass or less, even more preferably 0.3 part by mass or more and 1.3 parts by mass or less, and particularly preferably 0.7 part by mass or more and 1.3 parts by mass or less, based on 100 parts by mass of the modified conjugated diene polymer.

[0029] The position where the modifying groups are introduced in the conjugated diene polymer is not particularly limited. For example, the modifying groups may be bonded to the terminal of the conjugated diene polymer, may be bonded to a portion other than the terminal portion of the main chain of the conjugated diene polymer, and may be bonded to the side chain of the conjugated diene polymer in a block, random, or tapered manner. When the modified conjugated diene polymer and its composition adhere to a layer containing a polar resin, from the viewpoint of the modified conjugated diene polymer forming a physical crosslinking block and improving the adhesion strength by the anchor effect, it is preferable that the modifying groups are arranged on the side chain of the conjugated diene polymer, and more preferably arranged randomly on the side chain. Further, from the viewpoint of improving the adhesion strength without inhibiting the physical crosslinking by the polymer block mainly composed of the vinyl aromatic monomer unit of the modified conjugated diene polymer, it is even more preferable that the modifying groups are arranged in a part (especially the side chain) of the polymer block mainly composed of the conjugated diene monomer unit. From the viewpoint of increasing the number of modifying groups for the purpose of improving adhesion, it is also preferable that the modifying groups are located on the side chain. As a method for examining the position where the modified group is bonded, there is a method of analyzing the position where the modified group exists by observing the spatial distance between the modified group and the polymer block using a two-dimensional nuclear magnetic resonance apparatus (NMR). Specifically, by measuring two-dimensional NMR and observing which of the polymer block mainly composed of conjugated diene monomer units and the polymer block mainly composed of vinyl aromatic monomer units the modified group interacts with, it can be determined. Further, when the modified group is located on the side chain of the conjugated diene polymer block, there is a method of decomposing the remaining double bond of the polymer block mainly composed of conjugated diene monomer units by an appropriate method and detecting the modified group by matrix-assisted laser desorption ionization method or the like. In any method, by producing and analyzing samples having terminal modification and samples having side chain modification as references and comparing them with the modified conjugated diene polymer to be analyzed, it is possible to accurately examine where the modified group is located.

[0030] From the viewpoint of further improving the adhesiveness between the modified conjugated diene polymer in the modified conjugated diene polymer composition and the polar resin, in the polymer block mainly composed of conjugated diene monomer units, the amount of vinyl bonds before hydrogenation is 60 mol% or more with respect to 100 mol% in total of the conjugated diene monomer units. From the same viewpoint and the viewpoint of improving the fluidity of the modified conjugated diene polymer composition, the amount of the vinyl bonds is preferably 65 mol% or more, more preferably 70 mol% or more. In particular, when the modified conjugated diene polymer composition contains a polyolefin, and the polyolefin has an alkyl group in a side chain such as polypropylene, a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, and a random copolymer of propylene and an α-olefin having 4 to 20 carbon atoms, etc., it is presumed that when the amount of vinyl bonds before hydrogenation is 60 mol% or more, the compatibility between the modified conjugated diene polymer and the polyolefin is improved, and the adhesiveness and fluidity of the modified conjugated diene polymer composition are further improved. In the polymer block mainly composed of conjugated diene monomer units, the upper limit of the amount of vinyl bonds before hydrogenation is not particularly limited, and may be 100 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less with respect to 100 mol% in total of the conjugated diene monomer units.

[0031] The "vinyl bond amount before hydrogenation" refers to the ratio (mol ratio) of the amount of the conjugated diene monomer moiety incorporated into the polymer by 1,2-bonding (hereinafter referred to as the "1,2-bond moiety") to the total amount of the conjugated diene monomer moiety incorporated into the polymer by 1,4-bonding (including cis and trans) (hereinafter referred to as the "1,4-bond moiety") and the conjugated diene monomer moiety incorporated into the polymer by 1,2-bonding (hereinafter referred to as the "1,2-bond moiety") in the modified conjugated diene polymer before hydrogenation (also referred to as "hydrogenation" or "hydrogentation"). That is, it means the ratio of the monomer having undergone 1,2-addition among the conjugated diene monomers. However, when the conjugated diene monomer unit is incorporated into the polymer by 3,4-bonding, it refers to the ratio (mol ratio) of the total amount of the 1,2-bond moiety and the 3,4-bond moiety to the total amount of the 1,4-bond moiety, the 1,2-bond moiety, and the conjugated diene monomer moiety incorporated into the polymer by 3,4-bonding (hereinafter referred to as the "1,3-bond moiety"). The vinyl bond amount before hydrogenation of the modified conjugated diene polymer can be measured using methods such as a method using a nuclear magnetic resonance apparatus (NMR) and a method using an infrared spectrophotometer (Hampton method), and specifically, it can be measured by the method described in the examples below.

[0032] Note that the vinyl bond amount before hydrogenation can also be estimated by the proton nuclear magnetic resonance ( 1 1H-NMR) method using the modified conjugated diene polymer after hydrogenation as a sample. The method will be specifically described by taking as an example a conjugated diene polymer in which the vinyl aromatic monomer unit is styrene and the conjugated diene monomer unit is 1,3-butadiene. Using ECS400 (product name manufactured by JEOL) as the measuring instrument, deuterated chloroform as the solvent, and a sample concentration of 50 mg / mL, the measurement is carried out under the following conditions. (Measurement conditions) Observation frequency: 400 MHz Chemical shift standard: chloroform (7.26 ppm) Pulse delay: 3 seconds Number of scans: 256 times Pulse width: 45° Measurement temperature: 26 °C

[0033] The amount of vinyl bonds before hydrogenation can be determined using the area value of the signals in the chemical shift range of 10.0 ppm to 0.0 ppm in the obtained NMR spectrum. More specifically, it can be determined by the following formulas (1) to (6). [Number] However, the symbols X1, X2, X3, X4, X5, X6, and X7 in the above formulas (1) to (5) are defined as follows. X1: The area value of the range surrounded by the NMR spectrum and the line connecting the positions with the lowest signal intensity in each of the ranges of 7.26 ppm to 7.25 ppm and 7.27 ppm to 7.26 ppm centered at 7.26 ppm X2: The area value of the range surrounded by the NMR spectrum and the line connecting the signal positions at 8.0 ppm and 6.0 ppm X3: Among the area values of the range surrounded by the NMR spectrum and the line connecting the signal positions at 6.0 ppm and 4.0 ppm, the area value in the range from the chemical shift at the position with the lowest signal intensity between 5.2 ppm and 4.9 ppm to 4.0 ppm X4: Among the area values of the range surrounded by the NMR spectrum and the line connecting the signal positions at 6.0 ppm and 4.0 ppm, the area value in the range from the chemical shift at the position with the lowest signal intensity between 5.2 ppm and 4.9 ppm to 6.0 ppm X5: Among the area values of the range surrounded by the NMR spectrum and the line connecting the signal positions at 4.0 ppm and 0.3 ppm, the area value in the range from the chemical shift at the position with the lowest signal intensity in the valley of the NMR spectrum between 1.05 ppm and 0.85 ppm to 0.3 ppm (however, if there is no valley between 1.05 ppm and 0.85 ppm, it shall be the area value in the range from the chemical shift at the position with the lowest signal intensity between 1.05 ppm and 0.85 ppm among the area values of the range surrounded by the NMR spectrum and the line connecting the signal positions at 4.0 ppm and 0.3 ppm to 0.3 ppm). The area value of the range surrounded by the line connecting the signal positions of 4.0 ppm and 0.3 ppm in X6 and the NMR spectrum X7: In each of the ranges of 1.49 ppm to 1.50 ppm and 1.50 ppm to 1.51 ppm centered on 1.50 ppm, the area value of the range surrounded by the line connecting the positions with the lowest signal intensity and the NMR spectrum (however, if the line connecting the positions with the lowest signal intensity is above the NMR spectrum, it shall be 0). In addition, (1) to (5) in formulas (5) and (6) are the values obtained from the above formulas (1) to (5), respectively.

[0034] In addition, the above vinyl bond amount can be controlled within the above numerical range by adding a Lewis base, such as a compound such as ether or amine, as a vinyl bond amount regulator (hereinafter referred to as "vinylating agent") during the production of the modified conjugated diene polymer.

[0035] In the modified conjugated diene polymer of the present embodiment, at least a part of the conjugated diene monomer units in the polymer block mainly composed of conjugated diene monomer units is hydrogenated. From the viewpoint of further improving the adhesion between the modified conjugated diene polymer composition and the polar resin, the hydrogenation rate is preferably 50 mol% or more with respect to 100 mol% in total of the conjugated diene monomer units. From the viewpoint of further improving the compatibility between the modified conjugated diene polymer and the polyolefin resin, it is more preferably 80 mol% or more, and still more preferably 85 mol% or more. From the viewpoint of improving the thermal stability, the hydrogenation rate is still more preferably 90 mol% or more, and particularly preferably 95 mol% or more. The upper limit of the hydrogenation rate of the modified conjugated diene polymer is not particularly limited, and the hydrogenation rate may be 100 mol% or less, or 99 mol% or less with respect to 100 mol% in total of the conjugated diene monomer units. The hydrogenation rate of the modified conjugated diene polymer can be measured using a nuclear magnetic resonance apparatus (NMR) or the like, and specifically, it can be measured by the method described in the examples. Also, the hydrogenation rate can be controlled within the above numerical range, for example, by adjusting the supply amount of hydrogen during hydrogenation.

[0036] In the modified conjugated diene-based polymer of the present embodiment, the amount of butylene and / or propylene in the polymer block mainly composed of conjugated diene monomer units is preferably 50 mol% or more and 100 mol% or less, more preferably 60 mol% or more and 99 mol% or less, and still more preferably 65 mol% or more and 98 mol% or less, based on 100 mol% of the total conjugated diene monomer units. In the polymer block mainly composed of conjugated diene monomer units, the amount of butylene and / or propylene may be 90 mol% or less, or 80 mol% or less, based on 100 mol% of the total conjugated diene monomer units. The amount of butylene and / or propylene can be measured using a nuclear magnetic resonance apparatus (NMR) or the like, and specifically, it can be measured by the method described in the examples below.

[0037] Here, the "amount of butylene and / or propylene" means the ratio (mol ratio) of the portion of the conjugated diene monomer unit-derived portion in the modified conjugated diene-based polymer after hydrogenation that is incorporated into the polymer by 1,2-bonding and does not contain an unsaturated bond (i.e., is hydrogenated). Specifically, it refers to the ratio (mol ratio) of the amount of the portion of the 1,2-bonding portion that does not contain an unsaturated bond to the total amount of 100 mol% of the 1,4-bonding portion (including cis and trans) and the 1,2-bonding portion. However, when the conjugated diene monomer unit is incorporated into the polymer by 3,4-bonding, it refers to the ratio (mol ratio) of the total amount of the portion of the 1,2-bonding portion and the 3,4-bonding portion that does not contain an unsaturated bond to the total amount of 100 mol% of the 1,4-bonding portion, the 1,2-bonding portion, and the 3,4-bonding portion. The amount of butylene and / or propylene can be controlled by the amount of vinyl bonds before hydrogenation and the hydrogenation rate. For example, when the amount of vinyl bonds is 60 mol% and the hydrogenation rate is 100%, the amount of butylene and / or propylene is 60 mol%. When the amount of vinyl bonds is 75 mol% and the hydrogenation rate is 80%, the amount of butylene and / or propylene is 60 mol%. When the hydrogenation rate is 100%, the amount of butylene and / or propylene is 75 mol%. In addition, when the term "amount of butylene" is used alone rather than as "amount of butylene and / or propylene", it means the proportion (mol ratio) of the portion derived from 1,3-butadiene that is incorporated into the polymer by a 1,2-bond and does not contain an unsaturated bond (i.e., is hydrogenated).

[0038] From the perspective of further improving the adhesion between the modified conjugated diene-based polymer composition and the polar resin, in the modified conjugated diene-based polymer of the present embodiment, the content of the polymer block mainly composed of vinyl aromatic monomer units is 40% by mass or less based on the total amount of the modified conjugated diene-based polymer. From the same perspective and the perspective of further improving flexibility, the content is more preferably 3% by mass or more and 30% by mass or less, and even more preferably 5% by mass or more and 25% by mass or less. Also, from the perspective of further improving the fluidity and the resistance to deformation (mechanical properties) of the modified conjugated diene-based polymer composition, the content of the polymer block mainly composed of vinyl aromatic monomer units is even more preferably 10% by mass or more and 20% by mass or less. Incidentally, the content of the polymer block mainly composed of vinyl aromatic monomer units in the modified conjugated diene polymer can be calculated using the mass of the polymer block mainly composed of vinyl aromatic monomer units in the conjugated diene polymer before hydrogenation, which is obtained by the method of oxidative decomposition of the conjugated diene polymer before hydrogenation with t-butyl hydroperoxide under an osmium tetroxide catalyst (the method described in I.M. KOLTHOFF, et al., Polym. Sci., 1, 429 (1946)) (hereinafter referred to as the "osmium tetroxide decomposition method"). In the osmium tetroxide decomposition method, a polymer block mainly composed of vinyl aromatic monomer units with an average degree of polymerization of about 30 or more can be detected.

[0039] Also, the content of the polymer block mainly composed of vinyl aromatic monomer units in the modified conjugated diene polymer can be measured by a nuclear magnetic resonance apparatus (NMR) by the method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY, 54, 685 (1981) even using the conjugated diene polymer after hydrogenation. This method is hereinafter referred to as the NMR method. The NMR method will be specifically described by taking a conjugated diene polymer in which the vinyl aromatic monomer unit is styrene and the conjugated diene monomer unit is 1,3-butadiene as an example. Using a sample prepared by dissolving 30 mg of the conjugated diene polymer after hydrogenation in 1 g of deuterated chloroform, proton nuclear magnetic resonance ( 1 1H-NMR) is measured. In the obtained measurement result, the content (hereinafter referred to as the "Ns value") of the polymer block mainly composed of vinyl aromatic monomer units (in this case, a polystyrene block) can be determined by obtaining the ratio of the integral value in the range where the chemical shift is 6.9 ppm to 6.3 ppm to the total integral value. More specifically, it can be determined by the following formulas (7) to (10).

Equation

[0040] The polymer block mainly composed of vinyl aromatic monomer units means a polymer block in which the content of the vinyl aromatic monomer units exceeds 70% by mass based on the entire polymer block. From the viewpoint of further improving the adhesiveness between the modified conjugated diene polymer composition and the polar resin, the content of the vinyl aromatic monomer units in the polymer block mainly composed of vinyl aromatic monomer units is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. In addition, the content of the vinyl aromatic monomer units in the polymer block mainly composed of vinyl aromatic monomer units may be 100% by mass or less, or 99% by mass or less.

[0041] From the viewpoint of further improving the adhesiveness between the modified conjugated diene polymer composition and the polar resin, in the modified conjugated diene polymer of the present embodiment, the content of the vinyl aromatic monomer units is preferably 40% by mass or less based on the total amount of the modified conjugated diene polymer. From the same viewpoint and the viewpoint of further improving flexibility, the content is more preferably 3% by mass or more and 30% by mass or less, and still more preferably 5% by mass or more and 25% by mass or less. Further, from the viewpoint of further improving the fluidity and the resistance to deformation (mechanical properties) of the modified conjugated diene polymer composition, the content of the vinyl aromatic monomer units is still more preferably 10% by mass or more and 20% by mass or less. Incidentally, the content of the vinyl aromatic monomer unit in the modified conjugated diene polymer can be measured by a method using an ultraviolet spectrophotometer or a proton nuclear magnetic resonance ( 1 1H-NMR) method. For details, measurement may be performed by the method described in the examples.

[0042] Examples of the vinyl aromatic monomer include, but are not limited to, vinyl aromatic compounds such as styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene. Among these, from the viewpoints of availability and productivity, styrene, α-methylstyrene, and 4-methylstyrene are preferable, and styrene is more preferable. The polymer block mainly composed of the vinyl aromatic compound may be composed of one kind of vinyl aromatic monomer or may be composed of two or more kinds. Similarly, the modified conjugated diene polymer of the present embodiment may contain the above vinyl aromatic monomer alone or in combination of two or more kinds.

[0043] The modified conjugated diene polymer used in the resin composition of the present embodiment may further have a copolymer block of a conjugated diene monomer unit and a vinyl aromatic monomer unit. Such a copolymer block may be an alternating copolymer block or a random copolymer block.

[0044] Examples of the vinyl aromatic monomer and the conjugated diene monomer that can be included in the copolymer block of the conjugated diene compound and the vinyl aromatic compound are those exemplified as those that can be included in the block mainly composed of the above vinyl aromatic polymer and the block mainly composed of the conjugated diene monomer unit. The distribution state of vinyl aromatic monomer units in the random copolymer block is not particularly limited, and the vinyl aromatic monomer units may be uniformly distributed or tapered. Further, there may be a plurality of portions where the vinyl aromatic monomer units are uniformly distributed and / or a plurality of portions where the vinyl aromatic monomer units are tapered, and there may be a plurality of segments having different contents of vinyl aromatic monomer units.

[0045] In the modified conjugated diene polymer of the present embodiment, in addition to the conjugated diene monomer and the vinyl aromatic monomer, other monomers copolymerizable with the conjugated diene monomer and the vinyl aromatic monomer can also be used.

[0046] The structure of the modified conjugated diene polymer of the present embodiment is not particularly limited, and examples thereof include those having a structure represented by the following formula in part or having a structure represented by the following formula. In the following formula, the description of the modifying group may be omitted in some cases.

[0047] b, c, (b) m -X, (c) m -X, (b - c) n , c - (b - c) n , b - (c - b) n , (b - c) m -X, (c - b) m -X, [(b - c) n m -X, [(c - b) n m -X, [c - (b - c) n m -X, [b - (c - b) n m -X, [(b - c) n -b] m -X, [(c - b) n -c] m -X, (a - b) n , b - (a - b) n , a - (b - a) n , (a - b) m -X, (b - a)​​​​m -X, [(a - b) n m -X, [(b - a) n m -X, [b - (a - b) n m -X, [a - (b - a) n m -X, [(a - b) n -a] m -X, [(b - a) n -b] m -X, (a - c) n 、c - (a - c) n 、a - (c - a) n 、(a - c) m -X, (c - a) m -X, [(a - c) n m -X, [(c - a) n m -X, [c - (a - c) n m -X, [a - (c - a) n m -X, [(a - c) n -a] m -X, [(c - a) n -c] m -X, c - (b - a) n 、c - (a - b) n 、 c - (a - b - a) n 、c - (b - a - b) n 、 a - c - (b - a) n 、a - c - (a - b) n 、 a - c - (b - a) n -b, [(a - b - c) n m -X, [a - (b - c) n m -X, [(a - b) n -c] m -X, [(a - b - a) n -c] m -X, [(b - a - b) n ​​​​​​​​​​-c] m -X, [(c - b - a) n m -X, [c - (b - a)n] m -X, [c - (a - b - a) n m -X, [c - (b - a - b) n m -X, a - (b - c) n 、a - (c - b) n 、 a - (c - b - c) n 、a - (b - c - b) n 、 c - a - (b - c) n 、c - a - (c - b) n 、 c - a - (b - c) n -b, [(c - b - a) n m -X, [c - (b - a) n m -X, [(c - b) n -a] m -X, [(c - b - c) n -a] m -X, [(b - c - b) n -a] m -X, [(a - b - c) n m -X, [a - (b - c) n m -X, [a - (c - b - c) n m -X, [a - (b - c - b) n m -X, b - (a - c) n 、b - (c - a) n 、 b - (c - a - c) n 、b - (a - c - a) n 、 c - b - (a - c) n 、c - b - (c - a) n 、 c - b - (a - c) n ​​​​​​​​​-a, [(c - a - b) n m -X, [c - (a - b) n m -X, [(c - a) n -b] m -X, [(c - a - c) n -b] m -X, [(b - c - b) n -b] m -X, [(b - a - c) n m -X, [b - (a - c) n m -X, [b - (c - a - c) n m -X, [b - (a - c - a) n m -X, (b1 - b2) n -a, a - (b1 - b2) n -a, (b1 - b2 - b) n -a, (b1 - b2 - a) n 、 (b1 - b2 - a) n -b, (b1 - b2 - a - b) n 、 (b1 - b2 - a) m -X, (b1 - b2 - a - b) m -X。

[0048] ​​​​​​In the above formulas, a represents a vinyl aromatic polymer block mainly composed of vinyl aromatic monomer units, b represents a conjugated diene polymer block mainly composed of conjugated diene monomer units, b1 and b2 represent conjugated diene polymer blocks mainly composed of conjugated diene monomer units (however, the vinyl bond content in b1 is less than that in b2), and c represents a random copolymer block of a conjugated diene monomer and a vinyl aromatic monomer. n is an integer of 1 or more, preferably an integer of 1 to 5. m is an integer of 2 or more, preferably an integer of 2 to 11. X represents a residue of a coupling agent or a residue of a polyfunctional initiator.

[0049] From the viewpoint of improving flexibility, the modified conjugated diene-based polymer of this embodiment preferably mainly contains a structure having a b, b1 or b2 block. From the viewpoint of improving mechanical strength, a structure having an a block is preferable, and it is more preferably a polymer represented by at least one of the structural formulas of a-b, a-b-a, a-b-a-b, b1-b2-a, a-b1-b2-a, b1-b2-a-b, and b1-b2-b-a. From the viewpoint of improving low tackiness, a structure having two or more a blocks in the molecular chain is preferable, and it is also preferable that the b1 block has crystallinity, and it is more preferably a polymer represented by at least one of the structural formulas of a-b-a, a-b-a-b, b1-b2-a, a-b1-b2-a, b1-b2-a-b, and b1-b2-b-a. Also, from the viewpoint of improving the adhesion strength between the modified conjugated diene-based polymer and its composition and the layer containing the polar resin due to the anchor effect of the modified conjugated diene-based polymer, it is preferable that the modified conjugated diene-based polymer has a structure having at least two or more a blocks and / or crystalline b1 blocks in the molecular chain. By having two or more physical crosslinking blocks in the molecular chain, the modified conjugated diene-based polymer involved in adhesion is less likely to be pulled out from the layer of the modified conjugated diene-based polymer or its composition layer, and tends to contribute to the improvement of adhesion strength.

[0050] From the viewpoint of further improving the adhesiveness between the modified conjugated diene polymer composition and the polar resin and the fluidity of the modified conjugated diene polymer composition, the weight average molecular weight (Mw) of the modified conjugated diene polymer is preferably 80,000 or more and 600,000 or less, more preferably 100,000 or more and 400,000 or less, and still more preferably 120,000 or more and 300,000 or less.

[0051] The weight average molecular weight (Mw) of the modified conjugated diene polymer is the weight average molecular weight (Mw) determined based on the calibration curve obtained from the measurement of the molecular weight of the peak of the chromatogram obtained by measurement by gel permeation chromatography (GPC) using the calibration curve determined from the measurement of commercially available standard polystyrene. The calibration curve may be prepared using the peak molecular weight of the standard polystyrene. The molecular weight distribution of the conjugated diene polymer before modification can also be determined similarly from the measurement by GPC, and the molecular weight distribution can be determined from the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) (hereinafter, also simply referred to as "Mn").

[0052] The molecular weight distribution (Mw / Mn) of the single peak measured by GPC of the modified conjugated diene polymer is preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.0 or less, and even more preferably 2.5 or less. The molecular weight distribution may be 1.0 or more and 2.0 or less, or 1.1 or more and 1.5 or less within the above range.

[0053] In the modified conjugated diene polymer composition of the present embodiment, for each of the above-described parameters such as the vinyl bond amount, hydrogenation rate, content of the polymer block mainly composed of the conjugated diene monomer unit or vinyl aromatic monomer unit, content of the modifying group, butylene amount and / or propylene amount, and molecular weight, and the specific types of the conjugated diene monomer, vinyl aromatic monomer, and modifying group, etc., examples and preferred embodiments described separately can be arbitrarily selected and combined. In addition, in this specification, the numerical range of any parameter can be a numerical range obtained by arbitrarily combining the upper limit value and the lower limit value described as an example, a preferable range, or the like.

[0054] [Modified conjugated diene polymer composition] The modified conjugated diene polymer composition of this embodiment contains at least a modified conjugated diene polymer (A) which is the modified conjugated diene polymer of the above embodiment and a polyolefin (B). In this way, the modified conjugated diene polymer composition has the polyolefin (B), so that the fluidity during melting is improved and the adhesiveness to a polar resin is improved. Further, since the modified conjugated diene polymer (A) is hydrogenated, the modified conjugated diene polymer (A) is excellent in compatibility with the polyolefin (B). As a result, the modified conjugated diene polymer composition is excellent in mechanical strength, flexibility, and adhesiveness to a polar resin. By controlling the compatibility between the modified conjugated diene polymer (A) and the polyolefin (B), the balance of the mechanical strength, flexibility, and adhesiveness to a polar resin of the modified conjugated diene polymer composition can be improved.

[0055] (Polyolefin (B)) The modified conjugated diene polymer composition of this embodiment contains a polyolefin. As the polyolefin, any material belonging to the category called polyolefin may be used, but from the viewpoint of improving the mechanical strength of the modified conjugated diene polymer composition, a polypropylene-based resin and a polyethylene-based resin are preferable.

[0056] Examples of the polypropylene-based resin include homopolypropylene, random polypropylene, and block polypropylene. Here, "random" in random polypropylene means a copolymer of propylene and a monomer other than propylene, in which the monomer other than propylene is randomly incorporated into the propylene chain and the monomers other than propylene are not substantially linked. The random polypropylene is not particularly limited as long as the content of propylene units is less than 99% by mass.

[0057] Examples of the random polypropylene include random copolymers of propylene and α-olefins having 2 to 20 carbon atoms (excluding propylene). The α-olefins in the random copolymer of propylene and α-olefins having 2 to 20 carbon atoms are not limited to the following, but examples include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. The α-olefin is preferably an α-olefin having 2 to 8 carbon atoms (excluding propylene), and examples include ethylene, 1-butene, 3-methyl-1-butene, 1-hexene, and 4-methyl-1-pentene. These α-olefins can be used alone or in combination of two or more. Also, homopolypropylene, random polypropylene, and block polypropylene can be used alone or in combination of two or more.

[0058] Examples of the polyethylene-based resin include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and copolymers of ethylene and α-olefins having 3 to 8 carbon atoms. Examples of the α-olefins in the copolymer of ethylene and α-olefins having 3 to 8 carbon atoms include propylene, butene-1, isobutene, pentene-1, hexene-1, 4-methylpentene-1, and octene-1. In this case, the proportion of α-olefins in the copolymer is preferably 30% by mass or less.

[0059] From the viewpoint of further improving the moldability of the modified conjugated diene polymer composition, as the polyolefin (B), a polypropylene-based resin is preferable. From the viewpoint of further improving the compatibility with the modified conjugated diene polymer, the polyolefin (B) more preferably contains one or more selected from the group consisting of homopolypropylene and random polypropylene, or consists of homopolypropylene and / or random polypropylene.

[0060] The polyolefin (B) may have a modifying group, for example, an acid anhydride group, a hydroxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, a carboxyl group, a thiocarboxyl group, an aldehyde group, a thioaldehyde group, a carboxylic acid ester group, an amide group, a sulfonic acid ester group, a phosphate ester group, an amino group, an imino group, a cyano group, a urethane group, a urea group, a pyridyl group, a quinoline group, an epoxy group, a thioepoxy group, a sulfide group, an isocyanate group, an isothiocyanate group, a silicon halide group, a silanol group, an alkoxysilane group, a tin halide group, an alkoxytin group, a phenyltin group, and may have a functional group such as an ionic group. The polyolefin (B) may not have a modifying group.

[0061] (Conjugated diene polymer (C)) From the viewpoint of improving adhesiveness, the modified conjugated diene polymer composition of the present embodiment preferably contains a conjugated diene polymer (C) having a weight average molecular weight of 150,000 or more, separately from the above-mentioned modified conjugated diene polymer (A).

[0062] The conjugated diene polymer (C) preferably has two or more polymer blocks selected from the group consisting of the following polymer blocks (i) to (iii). (i) A vinyl aromatic polymer block having 80% by mass or more of vinyl aromatic monomer units (ii) A conjugated diene polymer block having 80% by mass or more of conjugated diene monomer units (iii) A random copolymer block of a conjugated diene monomer and a vinyl aromatic monomer The modified conjugated diene polymer composition of the present embodiment preferably contains, as the conjugated diene polymer (C), at least a conjugated diene polymer having the polymer block of (iii) above. The modified conjugated diene polymer composition of the present embodiment may contain, as the conjugated diene polymer (C), a conjugated diene polymer having the polymer block of (iii) above, a conjugated diene polymer having the polymer block of (i) above, and / or a conjugated diene polymer having the polymer block of (ii) above. The modified conjugated diene polymer composition of the present embodiment preferably contains, as the conjugated diene polymer (C), a conjugated diene polymer having the polymer block of (i) above and / or the polymer block of (ii) above. In this case, the modified conjugated diene polymer composition may contain a conjugated diene polymer having the polymer block of (i) above and the polymer block of (ii) above, or may contain a conjugated diene polymer having the polymer block of (i) above or the polymer block of (ii) above. In order to further improve the elongation at break, compression set, and / or low-temperature toughness, it is preferable to contain a conjugated diene polymer (C) having the polymer block of (i) above and the polymer block of (ii) above (which may be a polymer in which a part of the conjugated diene block, further hydrogenated, called SEBS). In order to further improve the adhesion to the polar resin, the peeling marks at the peeling interface with the polar resin, the vibration damping property, and / or the wear resistance, it is preferable to contain a conjugated diene polymer (C) having the polymer block of (i) above and the polymer block of (iii) above.

[0063] Examples of the vinyl aromatic monomer contained in the vinyl aromatic polymer block in which the vinyl aromatic monomer unit is 80% by mass or more include, but are not limited to, vinyl aromatic compounds such as styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene. Among these, from the viewpoints of availability and productivity, as the vinyl aromatic monomer, styrene, α-methylstyrene, and 4-methylstyrene are preferable, and styrene is more preferable. (i) The vinyl aromatic polymer block in which the vinyl aromatic monomer is 80% by mass or more may be composed of one kind of vinyl aromatic monomer unit or may be composed of two or more kinds of vinyl aromatic monomer units. From the viewpoint of improving the strength when the modified conjugated diene polymer composition is made into a molded article, the content of the vinyl aromatic monomer unit contained in the (i) vinyl aromatic polymer block is 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more.

[0064] (ii) The conjugated diene monomers contained in the conjugated diene polymer block in which the conjugated diene monomer unit amount is 80% by mass or more are not limited to the following, but include diolefins having a pair of conjugated double bonds. Such diolefins are not limited to the following, and examples include 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, and farnesene. Among these, from the viewpoints of availability and productivity, as the conjugated diene monomer, 1,3-butadiene and isoprene are preferably mentioned. From the viewpoint of thermal stability, among them, 1,3-butadiene is more preferable as the conjugated diene monomer. (ii) The conjugated diene polymer block in which the conjugated diene monomer unit is 80% by mass or more may be composed of one kind of conjugated diene monomer unit or may be composed of two or more kinds of conjugated diene monomer units. From the viewpoint of improving the impact resistance of the modified conjugated diene polymer composition, the content of the conjugated diene monomer unit contained in the (ii) conjugated diene polymer block is 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more.

[0065] (iii) Examples of the vinyl aromatic monomer and the conjugated diene monomer contained in the random copolymer block of the conjugated diene monomer and the vinyl aromatic monomer include those exemplified as those that may be contained in (i) the vinyl aromatic polymer block and (ii) the conjugated diene polymer block. (iii) The content of the vinyl aromatic monomer contained in the random copolymer block of the conjugated diene monomer and the vinyl aromatic monomer is preferably 30% by mass or more and less than 80% by mass based on the total mass of the random copolymer block. When the content of the vinyl aromatic monomer unit is 30% by mass or more, the modified conjugated diene-based polymer composition is excellent in abrasion resistance and scratch resistance, and furthermore, the surface energy difference from the polar resin becomes small and the adhesiveness tends to improve. When the content of the vinyl aromatic monomer unit is 80% by mass or less, the modified conjugated diene-based polymer composition tends to be excellent in flexibility and resilience. The content of the vinyl aromatic monomer unit in the random copolymer block is more preferably 40% by mass or more and 75% by mass or less, and even more preferably 45% by mass or more and 70% by mass or less. The content of the vinyl aromatic monomer unit in the random copolymer block can be calculated from the measured values by extracting the polymers before and after polymerizing the random copolymer block and performing the quantification of the content of the vinyl aromatic monomer unit by an ultraviolet spectrophotometer and the quantification of the vinyl aromatic polymer block component by the "osmium tetroxide decomposition method". The content of the vinyl aromatic monomer unit in the random copolymer block can be controlled within the above numerical range by adjusting the addition amount and addition timing of the vinyl aromatic monomer in the polymerization step. (iii) The distribution state of the vinyl aromatic monomer units in the random copolymer block is not particularly limited, and the vinyl aromatic monomer units may be uniformly distributed or may be distributed in a tapered shape. Further, there may be a plurality of portions where the vinyl aromatic monomer units are uniformly distributed and / or a plurality of portions where the vinyl aromatic monomer units are distributed in a tapered shape, and there may be a plurality of segments having different contents of the vinyl aromatic monomer units.

[0066] When the modified conjugated diene polymer composition of the present embodiment contains a conjugated diene polymer (C) including a random copolymer block of a conjugated diene monomer and a vinyl aromatic monomer, it is preferable to control the compatibility with a softening agent by adjusting the composition ratio of the conjugated diene monomer and the vinyl aromatic monomer contained in the random copolymer block. According to such an aspect, there is a tendency to provide a modified conjugated diene polymer composition that does not cause oil bleeding during normal use (low temperature state) and has excellent fluidity during molding processing (high temperature state).

[0067] In the conjugated diene polymer (C), in addition to the conjugated diene monomer and the vinyl aromatic monomer, other monomers copolymerizable with the conjugated diene monomer and the vinyl aromatic monomer can also be used.

[0068] The structure of the conjugated diene polymer (C) is not particularly limited, and examples thereof include those having a structure represented by the following formula in part or having a structure represented by the following formula. In the following formula, the description of the modifying group may be omitted in some cases.

[0069] b, c, (b) m -X, (c) m -X, (b - c) n , c - (b - c) n , b - (c - b) n , (b - c) m -X, (c - b) m -X, [(b - c) n m -X, [(c - b) n m -X, [c - (b - c) n m -X, [b - (c - b) n m -X, [(b - c) n -b] m -X, [(c - b) n -c] m -X, (a - b) n , b - (a - b)​​​​n 、a-(b - a) n 、(a - b) m -X、(b - a) m -X、[(a - b) n m -X、[(b - a) n m -X、[b-(a - b) n m -X、[a-(b - a) n m -X、[(a - b) n -a] m -X、[(b - a) n -b] m -X、 (a - c) n 、c-(a - c) n 、a-(c - a) n 、(a - c) m -X、(c - a) m -X、[(a - c) n m -X、[(c - a) n m -X、[c-(a - c) n m -X、[a-(c - a) n m -X、[(a - c) n -a] m -X、[(c - a) n -c] m -X、 c-(b - a) n 、c-(a - b) n 、 c-(a - b - a) n 、c-(b - a - b) n 、 a - c-(b - a) n 、a - c-(a - b) n 、 a - c-(b - a) n -b、[(a - b - c) n m -X、 [a-(b - c) n m -X、[(a - b) n -c] m -X、 [(a - b - a)​​​​​​​​​​n -c] m -X、 [(b - a - b) n -c] m -X、[(c - b - a) n m -X、 [c - (b - a)n] m -X、[c - (a - b - a) n m -X、[c - (b - a - b) n m -X、 a - (b - c) n 、a - (c - b) n 、 a - (c - b - c) n 、a - (b - c - b) n 、 c - a - (b - c) n 、c - a - (c - b) n 、 c - a - (b - c) n -b、[(c - b - a) n m -X、 [c - (b - a) n m -X、[(c - b) n -a] m -X、 [(c - b - c) n -a] m -X、 [(b - c - b) n -a] m -X、[(a - b - c) n m -X、 [a - (b - c) n m -X、[a - (c - b - c) n m -X、[a - (b - c - b) n m -X、 b - (a - c) n 、b - (c - a) n 、 b - (c - a - c) n 、b - (a - c - a) n 、 c - b - (a - c) n ​​​​​​​​​, c - b - (c - a) n , c - b - (a - c) n -a, [(c - a - b) n m -X, [c - (a - b) n m -X, [(c - a) n -b] m -X, [(c - a - c) n -b] m -X, [(b - c - b) n -b] m -X, [(b - a - c) n m -X, [b - (a - c) n m -X, [b - (c - a - c) n m -X, [b - (a - c - a) n m -X, (b1 - b2) n -a, a - (b1 - b2) n -a, (b1 - b2 - b) n -a, (b1 - b2 - a) n , (b1 - b2 - a) n -b, (b1 - b2 - a - b) n , (b1 - b2 - a) m -X, (b1 - b2 - a - b) m -X.

[0070] ​​​​​​In each of the above general formulas, a represents a vinyl aromatic polymer block in which the vinyl aromatic monomer unit is 80% by mass or more, b represents a conjugated diene polymer block in which the conjugated diene monomer unit is 80% by mass or more, b1 and b2 represent conjugated diene polymer blocks in which the conjugated diene monomer unit is 80% by mass or more (however, the vinyl bond amount in b1 is less than the vinyl bond amount in b2), and c represents a random copolymer block of a conjugated diene monomer and a vinyl aromatic monomer. n is an integer of 1 or more, preferably an integer of 1 to 5. m is an integer of 2 or more, preferably an integer of 2 to 11. X represents a residue of a coupling agent or a residue of a polyfunctional initiator.

[0071] From the viewpoint of improving flexibility, the conjugated diene polymer (C) preferably mainly contains a structure having a b, b1 or b2 block. From the viewpoint of improving mechanical strength, a structure having an a block is preferable, such as a-b, a-b-a, a-b-a-b, (a-b) m -X, b1-b2-a, a-(b1-b2) n -a, b1-b2-a-b, and it is preferably a polymer represented by at least one of the structural formulas of b1-b2-b-a. From the viewpoint of improving low tackiness, a structure having two or more a blocks in the molecular chain is preferable, and it is also preferable that the b1 block has crystallinity, such as a-b-a, a-b-a-b, (a-b) m -X, b1-b2-a, a-b1-b2-a, b1-b2-a-b, and it is more preferably a polymer represented by at least one of the structural formulas of b1-b2-b-a. Further, from the viewpoint of achieving a good balance of abrasion resistance, scratch resistance, and flexibility, a structure having a c block is preferable, such as (a-c) m -X, [a-(b-c) n m -X, [a-(c-b-c) n m -X, and [a-(b-c-b) n m -X, and it is preferably a polymer represented by at least one of the structural formulas.

[0072] ​​​Incidentally, in a multilayer body in which a layer containing a modified conjugated diene polymer composition and a layer containing a polar resin are laminated, or in a molded body containing such a multilayer body, as an index for determining the adhesive strength between the layer containing the modified conjugated diene polymer composition and the layer containing the polar resin, it may be necessary to check whether a peeling mark of the modified conjugated diene polymer composition remains on the peeling surface on the side of the layer containing the polar resin when the above two layers are peeled. That is, in order to examine the degree of adhesive strength between the above two layers, after laminating the above two layers, the adhesive layer (layer containing the modified conjugated diene polymer composition) is peeled from the base material (layer containing the polar resin), and a test to check whether a peeling mark remains may be used. When the conjugated diene polymer (C) has a c-block, in particular, (a-c) m -X, [a-(b-c) n m -X, [a-(c-b-c) n m -X, and [a-(b-c-b) n m -X, when it is a polymer represented by at least one of the structural formulas, there is a tendency for peeling marks to remain, that is, the adhesive strength between the layer containing the modified conjugated diene polymer composition and the layer containing the polar resin tends to be high. On the other hand, in a multilayer body or a molded body containing such a multilayer body, when each layer is separated and reused, etc., it is preferable to use a modified conjugated diene polymer composition in which no peeling mark remains in the above test. In such a case, it is conceivable to configure the conjugated diene polymer (C) to have no c-block.

[0073] The weight average molecular weight (Mw) of the conjugated diene polymer (C) is preferably 150,000 or more and 1,000,000 or less, more preferably 200,000 or more and 800,000 or less, and even more preferably 250,000 or more and 500,000 or less from the viewpoints of improving mechanical strength and wear resistance. When the weight average molecular weight (Mw) of the conjugated diene polymer (C) is 1,000,000 or less, the fluidity of the modified conjugated diene polymer composition is further improved. The weight average molecular weight of the conjugated diene polymer (C) may be 400,000 or less, 350,000 or less, or 300,000 or less.

[0074] ​​​The weight average molecular weight (Mw) of the conjugated diene polymer (C) is the weight average molecular weight (Mw) determined based on a calibration curve obtained from the measurement of the molecular weight of the peak in the chromatogram obtained by gel permeation chromatography (GPC), using a calibration curve determined from the measurement of commercially available standard polystyrene. The calibration curve may be created using the peak molecular weight of the standard polystyrene. The molecular weight distribution in the case where the conjugated diene polymer (C) is modified can also be determined similarly from measurements by GPC, and the molecular weight distribution can be determined from the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

[0075] The molecular weight distribution (Mw / Mn) of the single peak measured by GPC of the conjugated diene polymer (C) is preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.0 or less, and even more preferably 2.5 or less. The molecular weight distribution may be within the range of 1.0 or more and 2.0 or less, or 1.1 or more and 1.5 or less.

[0076] In the conjugated diene polymer (C), the vinyl aromatic monomer units in the vinyl aromatic polymer block are 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more, from the viewpoint of improving the mechanical strength and flexibility of the modified conjugated diene polymer composition.

[0077] In the conjugated diene polymer (C), from the viewpoint of improving the fluidity and flexibility of the modified conjugated diene polymer composition, the amount of vinyl bonds before hydrogenation is preferably more than 0 mol% with respect to a total of 100 mol% of the conjugated diene monomer units, more preferably 10 mol% or more and 90 mol% or less, still more preferably 15 mol% or more and 85 mol% or less, and even more preferably 18 mol% or more and 80 mol% or less. The amount of vinyl bonds in the conjugated diene polymer (C) may be 60 mol% or less, 50 mol% or less, 40 mol% or less, or 30 mol% or less with respect to a total of 100 mol% of the conjugated diene monomer units.

[0078] In the conjugated diene polymer (C), the hydrogenation rate of the remaining double bonds is 0 mol% or more and 100 mol% or less. From the viewpoint of improving heat resistance by hydrogenating thermally unstable 1,2-bond portions (however, in the case where 3,4-bonds are also incorporated into the polymer, 1,2-bond portions and 3,4-bond portions), the hydrogenation rate in the conjugated diene polymer (C) is preferably 20 mol% or more and 100 mol% or less, more preferably 40 mol% or more and 100 mol% or less, still more preferably 60 mol% or more and 100 mol% or less, and even more preferably 80 mol% or more and 100 mol% or less. When adhering to a polar resin, molding is often performed at a high temperature, and a modified conjugated diene polymer composition in which the hydrogenation rate of the conjugated diene polymer (C) is within the above range is preferable because heat resistance is improved.

[0079] The conjugated diene polymer (C) may be modified. When the conjugated diene polymer (C) is modified, a preferred embodiment of the modifying group is the same as the preferred embodiment of the modified conjugated diene polymer (A) described above, and more preferably, the modifying group is the same modifying group as that of the modified conjugated diene polymer (A).

[0080] In the modified conjugated diene polymer composition of the present embodiment, from the viewpoints of improving adhesiveness and suppressing stickiness, the content of the modified conjugated diene polymer (A) is preferably 5% by mass or more and 80% by mass or less with respect to the total amount of components excluding the filler of the modified conjugated diene polymer composition. The content is more preferably 10% by mass or more and 70% by mass or less, still more preferably 15% by mass or more and 60% by mass or less, even more preferably 20% by mass or more and 50% by mass or less, still even more preferably 23% by mass or more and 45% by mass or less, and particularly preferably 25% by mass or more and 40% by mass or less. The content of the modified conjugated diene polymer (A) may be 30% by mass or less within the above range.

[0081] In the modified conjugated diene polymer composition of the present embodiment, from the viewpoint of improving strength and fluidity, the content of the conjugated diene polymer (C) is preferably 0% by mass or more and 50% by mass or less with respect to the total amount of the components excluding the filler of the modified conjugated diene polymer composition. The content is more preferably 5% by mass or more and 40% by mass or less, still more preferably 10% by mass or more and 30% by mass or less, and even more preferably 15% by mass or more and 25% by mass or less. The content of the conjugated diene polymer (C) may be 20% by mass or more within the above range.

[0082] The content of the polyolefin (B) can be determined in consideration of the ratio with the content of the modified conjugated diene polymer (A) as described in [Production method of modified conjugated diene polymer composition] described later. The content of the polyolefin (B) is, for example, 3% by mass or more and 30% by mass or less, 5% by mass or more and 25% by mass or less, or 10% by mass or more and 20% by mass or less with respect to the total amount of the components excluding the filler of the modified conjugated diene polymer composition. The content of the polyolefin (B) may be 15% by mass or less within the above range.

[0083] The modified conjugated diene polymer composition of the present embodiment preferably contains a softening agent from the viewpoint of improving flexibility. Examples of the softening agent include paraffinic oil, naphthenic oil, aromatic oil, paraffin wax, liquid paraffin, white mineral oil, and vegetable softening agents. Among these, paraffinic oil, liquid paraffin, and white mineral oil are more preferable from the viewpoints of improving the low-temperature properties and bleed resistance of the modified conjugated diene polymer composition and its molded article.

[0084] The kinematic viscosity of the softening agent in the modified conjugated diene polymer composition at 40°C is preferably 500 mm 2 / s or less. The lower limit value of the kinematic viscosity of the softening agent at 40°C is not particularly limited, but it is preferably 10 mm 2 / s. When the kinematic viscosity of the softening agent at 40°C is 500 mm 2When it is less than or equal to [specific value] per second, the fluidity of the modified conjugated diene polymer composition tends to be further improved, and the moldability tends to be further improved. The kinematic viscosity of the softening agent can be measured by a method such as testing using a glass capillary viscometer.

[0085] In the modified conjugated diene polymer composition, the blending amount of the softening agent is preferably 0 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass in total of the modified conjugated diene polymer (A) and the conjugated diene polymer (C). From the viewpoints of improving flexibility and suppressing oil bleed, the blending amount of the softening agent is more preferably 5 parts by mass or more and 170 parts by mass or less, still more preferably 30 parts by mass or more and 150 parts by mass or less, even more preferably 40 parts by mass or more and 140 parts by mass or less, and particularly preferably 50 parts by mass or more and 130 parts by mass or less. The blending amount of the softening agent may be 100 parts by mass or less, or 90 parts by mass or less within the above range.

[0086] The fluidity of the modified conjugated diene polymer composition of the present embodiment is not particularly limited, but from the viewpoint of moldability, the melt flow rate (MFR) at 230 °C and 2.16 kg is preferably 10 g / 10 min or more. More preferably, from the viewpoint of improving adhesiveness, it is 15 g / 10 min or more, from the viewpoint of improving the appearance of the molded product, it is 20 g / 10 min or more, from the viewpoint of thinning the molded product, it is 25 g / 10 min or more or 30 g / 10 min or more, and from the viewpoint of low molding temperature, it is 50 g / 10 min or more, and more preferably 100 g / 10 min or more. The upper limit value of the melt flow rate is not particularly limited and may be, for example, 300 g / 10 min, 200 g / 10 min, or 150 g / 10 min.

[0087] The modified conjugated diene polymer composition of this embodiment preferably contains a filler from the viewpoints of cost reduction of the composition and improvement of flame retardancy and adhesiveness. The filler is not limited to the following. For example, talc, calcium carbonate, calcium oxide, zinc carbonate, wollastonite, zeolite, wollastonite, silica, alumina, clay, titanium oxide, magnesium hydroxide, magnesium oxide, sodium silicate, calcium silicate, magnesium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, zinc oxide, potassium titanate, hydrotalcite, barium sulfate, titanium black, and carbon black such as furnace black, thermal black, and acetylene black can be mentioned. These fillers may be used alone or in combination of two or more. Among these, talc, calcium carbonate, silica, and clay are preferable as the filler, and talc and calcium carbonate are more preferable.

[0088] In the modified conjugated diene polymer composition, the content of the filler is preferably 0% by mass or more and 50% by mass or less, more preferably 0% by mass or more and 40% by mass or less, based on the entire modified conjugated diene polymer composition. When the modified conjugated diene polymer composition contains a filler, mechanical properties such as the tensile elastic modulus and 100% modulus of the modified conjugated diene polymer composition tend to be further improved. The content of the filler may be 35% by mass or less or 30% by mass or less within the above range.

[0089] The modified conjugated diene polymer composition of this embodiment may contain additives other than the components described above. Such additives include, but are not limited to, for example, oil, filler, heat stabilizer, ultraviolet absorber, nucleating agent, antioxidant, weathering agent, light stabilizer, plasticizer, antistatic agent, flame retardant, slip agent, antiblocking agent, antifogging agent, lubricant, pigment, dye, dispersant, copper corrosion inhibitor, neutralizing agent, antifoaming agent, weld strength improver, natural oil, synthetic oil, and wax and other additives. Also, other elastomers and thermoplastic resins may be used as additives in any proportion. These may be used alone or in combination of two or more.

[0090] In the modified conjugated diene polymer composition of this embodiment, the examples and preferred embodiments of each component can be arbitrarily combined, and the content of each component can be independently selected except when specifically mentioned.

[0091] 〔Multilayer body〕 The modified conjugated diene polymer composition of this embodiment can form a multilayer body together with a polar resin. The multilayer body of this embodiment includes a layer containing a polar resin and a layer containing the above-described modified conjugated diene polymer composition laminated thereon. The polar resin is not particularly limited, and examples thereof include polyvinyl chloride, ABS, acrylonitrile-styrene copolymer, polyacrylic acid, polyacrylic acid esters such as methyl polyacrylate, polymethacrylic acid, polymethacrylic acid esters such as methyl polymethacrylate, polyvinyl alcohol, polyvinylidene chloride, polyethylene terephthalate, polyamide, polyacetal, polycarbonate, polybutylene terephthalate, polyvinylidene fluoride, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, polyamideimide, polyetherimide, polyether ketone, polyether ether ketone, polyimide, liquid crystal polymer, polytetrafluoroethylene, phenol resin, urea resin, melamine resin, unsaturated polyester, epoxy resin, and polyurethane. The polar resin is used alone or in combination of two or more kinds. Among these, as the polar resin, from the viewpoints of improving the mechanical strength, heat resistance, and chemical resistance of the multilayer body, ABS, methyl polymethacrylate, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyphenylene sulfide are preferable. From the viewpoint of improving the adhesiveness with the modified conjugated diene-based polymer composition, the polar resin is more preferably ABS, methyl polymethacrylate, polyamide, polycarbonate, and polyphenylene sulfide, and polyamide is even more preferable from the viewpoint of wear resistance.

[0092] Polyamides are identified by the number of carbon atoms in the diamine and dibasic acid that are the raw materials, or the number of carbon atoms in the lactam monomer. Examples of polyamides include polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide MXD6 (the diamine is metaxylenediamine), polyamide 46, polyamide 6T (T indicates that the dibasic acid is terephthalic acid), polyamide 9T, polyamide 10T, polyamide 11T, polyamide 6I, polyamide 6 / 66 (the / indicates a copolymer of polyamide 6 and polyamide 66. The same applies hereinafter), polyamide 6 / 6T, polyamide 66 / 6T, polyamide 66 / 6I, polyamide 66 / 6I / 6, polyamide 6T / 6I, nylon 6T / 11, polyamide 6T / 12, polyamide 66 / 6T / 6I, polyamide 6T / 5T, polyamide 6T / M5T, polyamide nylon 5T / 10T, polyamide 10T / 612, polyamide 10T / 66, and blends thereof. Typical polyamides include polyamide 6 and polyamide 66. The weight average molecular weight of these polyamides is preferably 5,000 or more and 200,000 or less, more preferably 10,000 or more and 150,000 or less, and even more preferably 20,000 or more and 100,000 or less from the viewpoints of improving heat resistance and moldability.

[0093] For the polyphenylene sulfide, any material may be used as long as it belongs to the category called polyphenylene sulfide. From the viewpoint of improving the heat resistance of the multilayer body, as its structural unit, those containing 70 mol% or more of p-phenylene sulfide units are preferred, and those containing 90 mol% or more are more preferred. Also, as other structural units, for example, o-phenylene sulfide units, m-phenylene sulfide units, phenylene sulfide ether units, phenylene sulfide sulfone units, phenylene sulfide ketone units, diphenylene sulfide units, substituent-containing phenylene sulfide units, and branched structure-containing phenylene sulfide units may be included. The polyphenylene sulfide resin may be linear, or may have a crosslinked or branched structure. In addition, the polyphenylene sulfide resin may have functional groups such as thiol groups and carboxyl groups at the terminals and / or in the main chain of the polymer structure.

[0094] The method for producing the polyphenylene sulfide resin is not particularly limited. For example, as a generally known production method, a production method in which an alkali metal sulfide and a dihaloaromatic compound are reacted in a polymerization solvent can be mentioned.

[0095] The layer containing the polar resin may contain a filler in addition to the polar resin. The filler in the layer containing the polar resin is not limited to the following, but for example, fibrous inorganic fillers such as glass fiber, glass sphere, glass hollow sphere, carbon fiber, cellulose nanofiber, wollastonite, potassium titanate whisker, calcium carbonate whisker, aluminum borate whisker, magnesium sulfate whisker, sepiolite, zonotrite, zinc oxide whisker, etc., talc, calcium carbonate, calcium oxide, zinc carbonate, wollastonite, zeolite, wollastonite, silica, alumina, clay, titanium oxide, magnesium hydroxide, magnesium oxide, sodium silicate, calcium silicate, magnesium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, zinc oxide, potassium titanate, hydrotalcite, barium sulfate, titanium black, and carbon black such as furnace black, thermal black, and acetylene black, etc. can be mentioned. Among these, fibrous fillers are preferable because they can easily enhance the strength, rigidity, and heat resistance of the multilayer body, and glass fiber, carbon fiber, cellulose nanofiber, and wollastonite are more preferable. The fibrous filler may be surface-treated with a compound having an affinity group or a reactive group for the polar resin. The fibrous filler may be used alone or in combination of two or more.

[0096] The multilayer body of this embodiment is not particularly limited in the number of laminated layers as long as it includes at least one layer each of a layer containing a modified conjugated diene polymer composition and a layer containing a polar resin. However, from the viewpoint of imparting flexibility and good texture, it is preferably included as one layer or two or more layers with the layer containing the modified conjugated diene polymer composition as the outermost layer.

[0097] The method for forming the layers of the multilayer body is not particularly limited, and conventionally known methods such as extrusion molding, injection molding (insert molding), two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotational molding, powder slush molding, foam molding, lamination molding, calender molding, and blow molding can be used. In the multilayer body of this embodiment, it is preferable that the layer containing the modified conjugated diene polymer composition is heat-sealed to the layer containing the polar resin. Details of the manufacturing method of the multilayer body will be described later.

[0098] 〔Molded article〕 The multilayer body of the modified conjugated diene polymer composition and the polar resin of this embodiment can be made into a molded article. That is, the molded article of this embodiment includes a multilayer body including a layer containing a modified conjugated diene polymer composition and a layer containing a polar resin.

[0099] The molded article of this embodiment can be made into a shape according to various applications such as automotive parts, tools, toys, electrical and electronic equipment parts, medical instruments, building materials and piping members, cutlery, daily and cosmetic products, industrial parts, various hoses, various housings, various module cases, various power control unit parts, writing utensils, robot hands, and medical instruments. Among these, those having a handle and those that require a gripping force and a good touch when touched by a person are preferable. Examples of such molded articles include tools, electric wires, connectors, handy electronic devices, toothbrushes, shavers, pens such as ballpoint pens, touch pens, and stylus pens, cutlery such as forks, knives, and spoons, and automotive interior members having a grip portion. Among them, power tools with a large load on the human body due to vibration during use are preferable.

[0100] From the viewpoint of effectively and surely achieving the effects of the present embodiment, it is preferable that the molded body of the present embodiment is constituted by a multilayer body of a modified conjugated diene polymer composition and a polar resin and forms a grip portion. More specifically, it is preferable that the multilayer body constitutes at least one selected from a grip of a tool, an electric wire covering member, a connector housing, a grip of a handy electronic device, a grip of a toothbrush, a grip of a shaver, a grip of a cutlery, a grip of a writing instrument, a grip portion of a robot hand, and a grip portion of an automotive interior member. Note that the "grip portion of a robot hand" means a portion in the robot hand that contacts an object to be grasped by the robot hand in order to grasp the object.

[0101] FIG. 1 shows an electric drill 10 which is an aspect of the molded body of the present embodiment. The electric drill 10 includes an electric drill housing 11 containing a polar resin and a grip portion 12 of the electric drill. By including a modified conjugated diene polymer composition in the grip portion 12 of the electric drill, the burden on the user's body when using the electric drill 10 can be reduced.

[0102] FIG. 2 shows a cutlery 20 which is an aspect of the molded body of the present embodiment. The cutlery 20 includes a main body 21 of the cutlery containing a polar resin and a grip portion 22 of the cutlery. By including a modified conjugated diene polymer composition in the grip portion 22 of the cutlery, the operation of the cutlery 20 becomes easy.

[0103] FIG. 3 shows a mobile phone housing 30 which is an aspect of the molded body of the present embodiment. The mobile phone housing 30 includes a main body 31 of the mobile phone housing containing a polar resin and a grip portion 32 of the mobile phone housing. By including a modified conjugated diene polymer composition in the grip portion 32 of the mobile phone housing, the mobile phone housing 30 gives a good touch feeling to the user.

[0104] FIG. 4 shows a cutter 40 which is one type of tool as an aspect of the molded article of the present embodiment. The tool (cutter) 40 includes a cutter housing 41 containing a polar resin and a grip portion 42 of the cutter. By including the grip portion 42 of the cutter with the modified conjugated diene polymer composition, the safety during the use of the cutter 40 is improved.

[0105] 〔Method for producing modified conjugated diene polymer〕 The method for producing the modified conjugated diene polymer of the present embodiment is not limited to the following, but for example, it may have a polymerization step, a modification step, and a hydrogenation step as described below. The polymerization step is not particularly limited. For example, in an organic solvent, using an organic alkali metal compound as a polymerization initiator, a conjugated diene compound is polymerized alone, or a conjugated diene compound and a vinyl aromatic compound are polymerized to obtain a homopolymer, a random copolymer, and / or a block copolymer. The hydrogenation step is not particularly limited. For example, it is a step of hydrogenating the conjugated diene polymer obtained by the polymerization step. The modification step is not particularly limited. For example, it is a step of performing a modification reaction by reacting the conjugated diene polymer hydrogenated by the hydrogenation step with a modifier to obtain a modified conjugated diene polymer. Alternatively, it may be a step of reacting the conjugated diene polymer before hydrogenation with a modifier. Note that the order of the hydrogenation step and the modification step is not particularly limited. That is, the order may be the polymerization step, the hydrogenation step, and the modification step, or the order may be the polymerization step, the modification step, and the hydrogenation step. From the viewpoint of more easily obtaining the above-described modified conjugated diene polymer, the order of the polymerization step, the hydrogenation step, and the modification step is preferable. Also, the modification step may be parallel to the polymerization step as described later.

[0106] (Polymerization step) The polymerization process is, for example, a process of obtaining a homopolymer, a random copolymer, and / or a block copolymer by polymerizing a conjugated diene compound alone or a conjugated diene compound and a vinyl aromatic compound using an organic alkali metal compound as a polymerization initiator in an organic solvent. The polymerization mode may be batch polymerization, continuous polymerization, or a combination thereof. From the viewpoint of making the size of the dispersed phase in the modified conjugated diene-based polymer composition that affects impact resistance and toughness constant, it is preferable to use a batch polymerization method with a narrow molecular weight distribution.

[0107] The reaction temperature in the polymerization process may be 0°C or higher and 180°C or lower. From the viewpoint of more easily obtaining the modified conjugated diene-based polymer of the present embodiment, the reaction temperature is preferably 20°C or higher and 160°C or lower, and more preferably 30°C or higher and 150°C or lower. The reaction time in the polymerization process varies depending on the target polymer, but may be within 48 hours. From the viewpoint of more easily obtaining the modified conjugated diene-based polymer of the present embodiment, the reaction time is preferably 0.1 hour or more and 10 hours or less. From the viewpoint of obtaining a modified conjugated diene-based polymer with a narrow molecular weight distribution and high strength, the reaction time is more preferably 0.5 hour or more and 5 hours or less. The atmosphere of the polymerization system in the polymerization process may be within a pressure range sufficient to maintain nitrogen and the solvent in the liquid phase, and is not particularly limited. It is preferable that impurities such as water, oxygen, and carbon dioxide gas that inactivate the polymerization initiator and the living polymer do not exist in the polymerization system.

[0108] Examples of the organic solvent include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cycloheptane, and methylcyclopentane; and aromatic hydrocarbons such as benzene, xylene, toluene, and ethylbenzene.

[0109] As the organic alkali metal compound which is a polymerization initiator, an organic lithium compound is preferable. Examples of the organic lithium compound include an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound. Examples of the organic lithium compound include, but are not limited to, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, hexamethylenedilithium, butadienyllithium, isopropenyldilithium, and lithium piperidide. When an organic lithium compound containing a nitrogen atom, such as lithium piperidide, is used as a polymerization initiator, a modified conjugated diene polymer having a nitrogen atom can be obtained. These polymerization initiators may be used alone or in combination of two or more. Among these, from the viewpoint of improving polymerization activity, n-butyllithium, sec-butyllithium, and lithium piperidide are preferable as the polymerization initiator.

[0110] The amount of the organic alkali metal compound used as the polymerization initiator depends on the molecular weight of the target modified conjugated diene polymer, but is typically preferably in the range of 0.01 phm or more and 1.5 phm or less (here, phm indicates parts by mass per 100 parts by mass of the monomer. The same applies hereinafter), more preferably in the range of 0.02 phm or more and 0.3 phm or less, and still more preferably in the range of 0.03 phm or more and 0.2 phm or less.

[0111] The vinyl bond amount of the modified conjugated diene polymer can be controlled by adding a Lewis base, such as a compound of ether and amine, as a vinylating agent. Also, the amount of the vinylating agent used can be adjusted according to the target vinyl bond amount.

[0112] Examples of the vinylating agent include, but are not limited to, an ether compound and a tertiary amine compound.

[0113] Examples of the ether compound include linear ether compounds and cyclic ether compounds. Examples of the linear ether compound include, but are not limited to, dimethyl ether, diethyl ether, diphenyl ether, dialkyl ether compounds of ethylene glycol such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether, and dialkyl ether compounds of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. Examples of the cyclic ether compound include, but are not limited to, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis(2-oxolanyl)propane, and alkyl ethers such as furfuryl alcohol.

[0114] Examples of the tertiary amine compound 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-dipiperidinoethane, trimethylaminoethylpiperazine, N,N,N’,N”,N”-pentamethylethylenetriamine, N,N’-dioctyl-p-phenylenediamine, pyridine, tetramethylpropanediamine, and bis[2-(N,N-dimethylamino)ethyl]ether. As the tertiary amine compound, a compound having two amines is preferable. Further, among them, as the tertiary amine compound, those having a symmetric structure in the molecule are more preferable, and N,N,N’,N’-tetramethylethylenediamine, bis[2-(N,N-dimethylamino)ethyl]ether, and 1,2-dipiperidinoethane are even more preferable. These vinylating agents may be used alone, or two or more of them may be used in combination.

[0115] In the polymerization step, in addition to the above-described vinylating agent and the organolithium compound, the conjugated diene monomer may be polymerized alone, or the conjugated diene monomer and the vinyl aromatic monomer may be polymerized in the presence of an alkali metal alkoxide. Here, the alkali metal alkoxide is a compound represented by the general formula MOR (wherein M represents an alkali metal and R represents an alkyl group). By allowing the alkali metal alkoxide to coexist in the polymerization step, it tends to be easier to control the vinyl bond amount, molecular weight distribution, polymerization rate, block ratio, and the like.

[0116] From the viewpoint of obtaining a high vinyl bond amount, a narrow molecular weight distribution, a high polymerization reaction rate, and a high block ratio, the alkali metal of the alkali metal alkoxide is preferably sodium or potassium. Examples of the alkali metal alkoxide include, but are not limited to, sodium alkoxides, lithium alkoxides, and potassium alkoxides having an alkyl group having 2 to 12 carbon atoms. Preferred alkali metal alkoxides are sodium alkoxides and potassium alkoxides having an alkyl group having 3 to 6 carbon atoms, and more preferred are sodium t-butoxide, sodium t-pentoxide, potassium t-butoxide, and potassium t-pentoxide. Among these, sodium t-butoxide and sodium t-pentoxide are more preferred.

[0117] (Hydrogenation step) The hydrogenation step is a step of hydrogenating a conjugated diene polymer or a modified conjugated diene polymer. The hydrogenation method in the hydrogenation step is not particularly limited. For example, a method of supplying hydrogen gas to the conjugated diene polymer obtained in the above polymerization step in the presence of a hydrogenation catalyst to perform hydrogenation can be mentioned. By having such a hydrogenation step in the production method of the modified conjugated diene polymer, the double bond residues in the conjugated diene monomer units are hydrogenated, and a more thermally stable hydrogenated conjugated diene polymer can be obtained. The hydrogenation rate can be controlled, for example, by the amount of catalyst during hydrogenation and the supply amount of hydrogen gas (hereinafter also referred to as "feed"). Further, the hydrogenation rate can be controlled, for example, by the amount of catalyst during hydrogenation, the supply amount of hydrogen gas, the pressure of hydrogen gas, and the reaction temperature. The hydrogenation step is preferably carried out at the timing after the production reaction of the conjugated diene polymer in the above polymerization step stops. After the hydrogenation reaction is completed, a stabilizer may be added. The stabilizer is not particularly limited, and for example, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate can be mentioned.

[0118] (Modification step) The modification step is not particularly limited as long as it is a step of obtaining a conjugated diene polymer having a modifying group. For example, it is a step of obtaining a modified conjugated diene polymer by reacting a conjugated diene polymer and / or a hydrogenated conjugated diene polymer with a modifier. Thereby, the obtained modified conjugated diene polymer has a modifying group.

[0119] The modification step may be carried out in parallel with the polymerization step described above. The modification reaction method is not particularly limited, and examples thereof include a method of using a polymerization initiator having an affinity group or a reactive group for a polar resin in the polymerization reaction in the polymerization step; and a method of using an unsaturated monomer having an affinity group or a reactive group for a polar resin in the polymerization reaction in the polymerization step. Further, as the modification reaction method, a method of adding a modifier that forms or contains an affinity group or a reactive group for a polar resin to the living end of the conjugated diene polymer obtained by the polymerization reaction in the polymerization step may also be used.

[0120] Examples of the "polymerization initiator having an affinity group or a reactive group for a polar resin" include, but are not limited to, 3-lithio-1-[N,N-bis(trimethylsilyl)]aminopropane, 2-lithio-1-[N,N-bis(trimethylsilyl)]aminoethane, 3-lithio-2,2-dimethyl-1-[N,N-bis(trimethylsilyl)]aminopropane, 2,2,5,5-tetramethyl-1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1-(3-lithio-2,2-dimethyl-propyl)-1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1-(2-lithioethyl)-1-aza-2,5-disilacyclopentane, 3-lithio-1-[N-(tert-butyl-dimethylsilyl)-N-trimethylsilyl]aminopropane, 3-lithio-1-(N-methyl-N-trimethylsilyl)aminopropane, 3-lithio-1-(N-thyl-N-trimethylsilyl)aminopropane, and lithium piperidide.

[0121] Examples of the "unsaturated monomer having an affinity group or reactive group for a polar resin" include, but are not limited to, p-[N,N-bis(trimethylsilyl)amino]styrene, p-[N,N-bis(trimethylsilyl)aminomethyl]styrene, p-{2-[N,N-bis(trimethylsilyl)amino]ethyl}styrene, m-[N,N-bis(trimethylsilyl)amino]styrene, p-(N-methyl-N-trimethylsilylamino)styrene, and p-(N-methyl-N-trimethylsilylaminomethyl)styrene.

[0122] Examples of the "modifying agent that forms or contains an affinity group or reactive group for a polar resin" include, but are not limited to, tetraglycidyl metaxylenediamine, tetraglycidyl-1,3-bis(aminomethyl)cyclohexane, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, and N-methylpyrrolidone.

[0123] Another method for introducing a modifying group includes, for example, reacting a conjugated diene polymer with an organic alkali metal compound such as an organolithium compound (metalation reaction) to obtain a polymer with an added organic alkali metal, and then adding a modifying agent having an affinity group or reactive group for a polar resin to the polymer with the added organic alkali metal.

[0124] Still another method for introducing a modifying group includes, for example, grafting an atomic group having an affinity group or reactive group for a polar resin onto a conjugated diene polymer. Such a method may be a method of directly grafting onto a conjugated diene polymer, or may be a method of reacting a conjugated diene polymer having a primary modifying group introduced therein with an atomic group having an affinity group or reactive group for a polar resin (secondary modification). Examples of the "atomic group having an affinity group or reactive group for a polar resin" include, but are not limited to, molecular units containing an α,β-unsaturated carboxylic acid or a derivative thereof. Examples of the α,β-unsaturated carboxylic acid or a derivative thereof include maleic acid, halogenated maleic acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid, etc., and anhydrides of these dicarboxylic acids; acrylic acid, methacrylic acid, crotonic acid, etc., and esters of these monocarboxylic acids (for example, 2-hydroxyethyl acrylate, methyl methacrylate, glycidyl methacrylate, and 3-(trimethoxysilyl)propyl methacrylate, etc.); and alkoxysilane compounds (for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltributoxysilane, vinyldimethoxymethylsilane, vinyldiethoxyethylsilane, vinyldipropoxypropylsilane, and vinyldibutoxybutylsilane, etc.). Among these, anhydrides are preferred, and maleic anhydride is more preferred from the viewpoint of improving reactivity.

[0125] The addition amount of the molecular unit containing an α,β-unsaturated carboxylic acid or a derivative thereof is preferably 0.1 part by mass or more and 20 parts by mass or less, more preferably 0.2 part by mass or more and 10 parts by mass or less, still more preferably 0.3 part by mass or more and 5.0 parts by mass or less, even more preferably 0.3 part by mass or more and 2.0 parts by mass or less, still even more preferably 0.3 part by mass or more and 1.3 parts by mass or less, and particularly preferably 0.7 part by mass or more and 1.3 parts by mass or less, based on 100 parts by mass of the modified conjugated diene polymer. From the viewpoint of improving compatibility with the polar resin composition, its addition amount is preferably 0.1 part by mass or more. On the other hand, from the viewpoint of improving the fluidity of the modified conjugated diene polymer composition, its addition amount is preferably 20 parts by mass or less. Further, although the modified conjugated diene polymer having a high vinyl bond amount before hydrogenation tends to have a low addition amount of molecular units containing an α,β-unsaturated carboxylic acid or its derivative, from the viewpoint of improving the adhesive strength, its addition amount may be high. In the production method of this embodiment, the addition amount may be increased by appropriately adjusting the modification method.

[0126] Examples of the graft addition method include, for example, a method of reacting a radical initiator, a conjugated diene polymer, and a compound containing an α,β-unsaturated carboxylic acid or its derivative group in a solution containing them; a method of reacting a radical initiator, a conjugated diene polymer, and a compound containing an α,β-unsaturated carboxylic acid or its derivative group under heating and melting or under non-heating and melting; a method of reacting a conjugated diene polymer and a compound containing an α,β-unsaturated carboxylic acid or its derivative group under heating and melting or under non-heating and melting; a method of reacting a compound that reacts with and forms a bond with any of a conjugated diene polymer and a compound containing an α,β-unsaturated carboxylic acid or its derivative group, a conjugated diene polymer, and a compound containing an α,β-unsaturated carboxylic acid or its derivative group in a solution containing them; a method of reacting a compound that reacts with and forms a bond with any of a conjugated diene polymer and a compound containing an α,β-unsaturated carboxylic acid or its derivative group, a conjugated diene polymer, and a compound containing an α,β-unsaturated carboxylic acid or its derivative group under heating and melting or under non-heating and melting. Preferably, it is a method of reacting a radical initiator, a conjugated diene polymer, and a compound containing an α,β-unsaturated carboxylic acid group or its derivative group under heating and melting or under non-heating and melting, and more preferably a method of reacting under heating and melting.

[0127] As a method for reacting a radical initiator, a conjugated diene polymer, and a compound containing an α,β-unsaturated carboxylic acid group or a derivative group thereof under heat melting, for example, a method of melt-kneading each component using a general kneader such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a conical twin-screw extruder, and a multi-screw extruder can be mentioned. Preferably, from the viewpoints of cost and production stability, a method using a single-screw, twin-screw or multi-screw extruder is used, and more preferably a method using a twin-screw extruder. The radical initiator, the conjugated diene polymer, and the compound containing an α,β-unsaturated carboxylic acid group or a derivative group thereof may be dry-blended and charged all at once, may be fed separately for each raw material, or the same raw material may be added in multiple portions. From the viewpoint of uniformly adding the compound containing an α,β-unsaturated carboxylic acid or a derivative group thereof into the conjugated diene polymer, the rotational speed of the screw is preferably 50 rpm or more and 400 rpm or less, and more preferably 100 rpm or more and 350 rpm or less. Also, from the viewpoints of suppressing the deterioration of the resin due to shear and uniformly adding the compound containing an α,β-unsaturated carboxylic acid or a derivative group thereof into the conjugated diene polymer, the rotational speed is preferably 150 rpm or more and 300 rpm or less. The kneading temperature is not particularly limited as long as it is a temperature at which the conjugated diene polymer melts and a temperature at which radicals are generated from the radical initiator, but it is preferably 100°C or more and 350°C or less. From the viewpoints of controlling the addition amount of the compound containing an α,β-unsaturated carboxylic acid or a derivative group thereof and suppressing the deterioration of the resin due to heat, the kneading temperature is more preferably 120°C or more and 300°C or less, and still more preferably 150°C or more and 250°C or less. In order to suppress the deactivation of radical active species by oxygen, melt-kneading may be performed under an inert gas atmosphere such as nitrogen.

[0128] Examples of radical initiators in graft addition include, but are not limited to, for example, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy esters, and peroxydicarbonates. Among them, preferably, the radical initiator has a half-life temperature of one and a half minutes within the kneading temperature range. More preferably, the radical initiator has a half-life temperature of 150 °C or higher and 250 °C or lower. Examples of such radical initiators include 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(4,4-di-(t-butylperoxy)cyclohexyl)propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylauric acid, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-di-(t-butylperoxy)butane, t-butylperoxybenzonate, n-butyl-4,4-di-(t-butylperoxy)valerate, di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-methane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide. From the viewpoint of improving compatibility with the conjugated diene polymer, di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 are preferred.Among them, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 are more preferred.

[0129] The molar equivalent of the compound containing an α,β-unsaturated carboxylic acid or its derivative group is preferably 300 molar equivalents or less, more preferably 200 molar equivalents or less, and even more preferably 100 molar equivalents or less, relative to the radical initiator. When the molar equivalent is within the above range, it is easier to add a compound containing an α,β-unsaturated carboxylic acid or its derivative group in an amount of more than 0 part by mass and up to about 20 parts by mass per 100 parts by mass of the conjugated diene polymer.

[0130] The reaction method when the conjugated diene polymer having a primary modified group is further secondarily modified with a group having an affinity group or a reactive group for a polar resin is not particularly limited, and known methods can be used. For example, after dry blending the primary modified conjugated diene polymer and a group having an affinity group or a reactive group for a polar resin, a method of melt-kneading each component using a general kneader such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a conical kneader, and a multi-screw extruder, and a method of dissolving or dispersing and mixing each component in a solvent and then heating and removing the solvent are mentioned. Among these, from the viewpoints of productivity and improvement of good kneadability, the melt-kneading method using an extruder is preferred.

[0131] The modified conjugated diene polymer of the present embodiment may be formed into an appropriate shape, and the shape is not particularly limited, but examples include pellet shape, crumb shape, powder shape, sheet shape, strand shape, and chip shape. Further, after melt-kneading, it may be formed directly into the shape of a molded article. Examples of the pelletization method include, for example, a method of extruding a modified conjugated diene polymer in a strand form from a single-screw or twin-screw extruder and cutting it underwater with a rotating blade installed in front of the die part (underwater cut); a method of extruding a modified conjugated diene polymer in a strand form from a single-screw or twin-screw extruder, cooling it with water or air, and then cutting it with a strand cutter; and a method of melt-mixing a modified conjugated diene polymer with an open roll or a Banbury mixer, molding it into a sheet form with a roll, further cutting the sheet into strips, and then cutting it into cubic pellets with a pelletizer. Note that the size and shape of the pellets are not particularly limited. However, from the viewpoint of suppressing adhesion between the pellets, pellets closer to a spherical shape are preferred because the adhesion surface between the pellets can be reduced more effectively than columnar pellets obtained by cutting a strand perpendicular to the long axis of the strand. General methods for producing pellets closer to a spherical shape include, for example, underwater cut and center hot cut.

[0132] The pellets of the modified conjugated diene polymer may contain an anti-blocking agent for the purpose of suppressing pellet blocking. Examples of the anti-blocking agent include, but are not limited to, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, ethylene bisstearylamide, talc, and amorphous silica. From the viewpoint of improving the transparency of the obtained modified conjugated diene polymer composition, multilayer body, and molded body containing the multilayer body, calcium stearate, polyethylene, polypropylene, and ethylene bisstearylamide are preferred as the anti-blocking agent. Further, from the viewpoint of improving the thermal fusion property between the modified conjugated diene polymer and the polar resin, calcium stearate, polyethylene, and polypropylene are preferred as the anti-blocking agent. The preferred amount of the anti-blocking agent used is 500 ppm or more and 8000 ppm or less based on the modified conjugated diene polymer. From the viewpoint of suppressing pellet blocking when the pellets of the modified conjugated diene polymer are stored for a long time and reducing the scattering of the anti-blocking agent when the pellets of the modified conjugated diene polymer are used, the amount of the anti-blocking agent used is more preferably 1000 ppm or more and 7000 ppm or less based on the modified conjugated diene polymer. The anti-blocking agent is preferably compounded in a state of adhering to the pellet surface, but may also be contained inside the pellet.

[0133] [Manufacturing method of modified conjugated diene polymer composition] The manufacturing method of the modified conjugated diene polymer composition of this embodiment is not particularly limited, and known methods can be used. For example, a method of melt-kneading each component such as the above-described modified conjugated diene polymer (A) and polyolefin (B) using a general mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a kneader, and a multi-screw extruder, and a method of dissolving or dispersing and mixing each component in a solvent and then heating and removing the solvent are exemplified. From the viewpoints of productivity and good kneading property, among these, the melt-kneading method using an extruder is preferable. In particular, by kneading with a multi-screw of two or more axes and sufficiently kneading, the compatible state of the modified conjugated diene polymer (A) and the polyolefin (B) becomes uniform as a whole, and a more uniform adhesive force can be obtained on the entire adhesive interface between the modified conjugated diene polymer composition and the polar resin. For this reason, in the molded body, the modified conjugated diene polymer composition can be preferably adhered to all parts of the surface of the layer containing the polar resin.

[0134] The maximum resin temperature during kneading may be a temperature at which the modified conjugated diene polymer (A), the polyolefin (B), and the conjugated diene polymer (C) melt, and is preferably 120°C or more and 350°C or less. From the viewpoint of suppressing the deterioration of these components due to heat such as shear heat generation during kneading, the maximum resin temperature is more preferably 180°C or more and 300°C or less.

[0135] In order to suppress the oxidation of the modified conjugated diene polymer (A), melt kneading may be carried out under an inert gas atmosphere such as nitrogen. When producing a modified conjugated diene polymer composition using an extruder, the positions and order of feeding the modified conjugated diene polymer (A), polyolefin (B), and other components are not particularly limited.

[0136] In the modified conjugated diene polymer composition of the present embodiment, the mass composition ratio of the modified conjugated diene polymer (A) to the polyolefin (B) is not particularly limited. From the viewpoint of suppressing the decrease in heat fusion properties due to the crystal domains of the polyolefin that do not have heat fusion properties with respect to the polar resin by the compatibility of the modified conjugated diene polymer (A) with the polyolefin (B), the modified conjugated diene polymer composition preferably contains more of the modified conjugated diene polymer (A) than the polyolefin (B). In the modified conjugated diene polymer composition, preferably, the content of the modified conjugated diene polymer (A) is 1.2 times or more the content of the polyolefin (B). From the viewpoint of improving the fluidity of the modified conjugated diene polymer composition, more preferably, the content of the modified conjugated diene polymer (A) is 1.5 times or more the content of the polyolefin (B). From the viewpoint of improving the flexibility of the modified conjugated diene polymer composition, more preferably, the content of the modified conjugated diene polymer (A) is 2 times or more the content of the polyolefin (B). Also, the content of the polyolefin (B) is preferably 1 / 5 times or more, more preferably 1 / 4 times or more, still more preferably 1 / 3 times or more, and particularly preferably 1 / 2.5 times or more with respect to the content of the modified conjugated diene polymer (A). In the modified conjugated diene polymer composition, when the content of the polyolefin (B) is within the above range, the mechanical properties such as the tensile modulus of elasticity and 100% modulus of the modified conjugated diene polymer composition tend to be further improved.

[0137] In the manufacturing process of the modified conjugated diene polymer composition of the present embodiment, the shape of the obtained modified conjugated diene polymer composition is not particularly limited, and it may be any of pellet shape, crumb shape, powder shape, sheet shape, strand shape, chip shape, etc. Further, after melt-kneading, it can also be made into a molded article having a desired shape.

[0138] The modified conjugated diene polymer composition of the present embodiment may be produced in a pelletized form. Examples of the pelletizing method include, for example, a method of extruding the modified conjugated diene polymer composition in a strand shape from a single-screw or twin-screw extruder and cutting it underwater by a rotating blade installed in front of the die part (underwater cut); a method of extruding the modified conjugated diene polymer composition in a strand shape from a single-screw or twin-screw extruder, cooling it with water or air, and then cutting it with a strand cutter; and a method of melt-mixing the modified conjugated diene polymer composition with an open roll or a Banbury mixer, molding it into a sheet shape with a roll, further cutting the sheet into strips, and then cutting it into cubic pellets with a pelletizer. Note that the size and shape of the pellets are not particularly limited, but from the viewpoint of suppressing adhesion between the pellets, pellets closer to a spherical shape are preferable because the adhesion surface between the pellets can be reduced compared to columnar pellets obtained by cutting a strand perpendicular to the long axis of the strand. An example of a general method for producing pellets closer to a spherical shape is underwater cut.

[0139] The pellets of the modified conjugated diene polymer composition may contain an antiblocking agent for the purpose of suppressing pellet blocking. Examples of the antiblocking agent include, but are not limited to, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, ethylene bisstearylamide, talc, and amorphous silica. From the viewpoint of improving the transparency of the resulting modified conjugated diene polymer composition, multilayer body, and molded article containing the multilayer body, calcium stearate, polyethylene, polypropylene, and ethylene bisstearylamide are preferable as antiblocking agents. Further, from the viewpoint of improving the heat fusion property between the modified conjugated diene polymer composition and the polar resin, calcium stearate, polyethylene, and polypropylene are preferable as antiblocking agents. The preferable amount of the antiblocking agent to be used is 500 ppm or more and 8000 ppm or less based on the modified conjugated diene polymer composition. From the viewpoints of suppressing pellet blocking when the pellets of the modified conjugated diene polymer composition are stored for a long period and reducing the scattering of the antiblocking agent when the pellets of the modified conjugated diene polymer composition are used, more preferably, it is 1000 ppm or more and 7000 ppm or less based on the modified conjugated diene polymer composition. The antiblocking agent is preferably blended in a state of adhering to the pellet surface, but may also be contained inside the pellet.

[0140] 〔Method for producing multilayer body and molded article〕 The modified conjugated diene polymer and the modified conjugated diene polymer composition of the present embodiment can be processed into a multilayer body or a practically useful molded article by a conventionally known method, for example, extrusion molding, injection molding, insert molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotational molding, powder slush molding, foam molding, lamination molding, calendar molding, and blow molding, etc. Further, if necessary, processing such as foaming, powdering, stretching, adhesion, printing, coating, and plating may be performed. By such a method, various molded articles such as sheets, films, multilayer bodies, injection molded articles of various shapes, hollow molded articles, pressure air molded articles, vacuum molded articles, extrusion molded articles, foam molded articles, non-woven fabrics and fibrous molded articles, and synthetic leather can be produced. These molded articles can be used for interior and exterior automotive materials, building materials, toys, home appliance parts, medical instruments, industrial parts, various hoses, various housings, various module cases, various power control unit parts, and other sundries.

[0141] In the method for manufacturing the multilayer body of the present embodiment, the multilayer body is formed by at least one method selected from the group consisting of injection molding, insert molding, extrusion molding, and compression molding. More specifically, the method for manufacturing the multilayer body of the present embodiment includes a step of forming a layer containing a modified conjugated diene polymer composition on a layer containing a polar resin that has already been formed, using at least one method selected from the group consisting of injection molding, insert molding, extrusion molding, and compression molding. The method for manufacturing the multilayer body of the present embodiment may include, before such a step, a step of forming a layer containing a polar resin (polar resin base material) by an arbitrary method, preferably at least one method selected from the group consisting of injection molding, insert molding, extrusion molding, and compression molding. Since the multilayer body of the present embodiment is manufactured using the modified conjugated diene polymer composition of the present embodiment, it can be suitably manufactured by various methods, particularly at least one method selected from the group consisting of injection molding, insert molding, extrusion molding, and compression molding.

[0142] The multilayer body of the present embodiment is not limited to the above manufacturing method, and can also be manufactured using conventionally known methods, such as extrusion molding, injection molding (insert molding), two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotational molding, powder slush molding, foam molding, lamination molding, calendar molding, and blow molding. By using such a method, a multilayer body in which at least one layer containing a modified conjugated diene polymer composition and at least one layer containing a polar resin are laminated can be obtained. More specifically, after forming a layer containing a polar resin, the modified conjugated diene polymer composition may be heat-sealed to the layer containing the polar resin to form a layer of the modified conjugated diene polymer composition. Immediately before thermally fusing a modified conjugated diene polymer composition to a layer containing a polar resin, the temperature of the modified conjugated diene polymer composition is preferably at or above the glass transition temperature of the polar resin, and more preferably at or above the melting point of the polar resin. By thermally fusing the modified conjugated diene polymer composition at the above temperature, the adhesion between the layer containing the polar resin and the layer of the modified conjugated diene polymer composition is further improved. Also, when thermally fusing the modified conjugated diene polymer composition in a mold at a temperature below the melting point of the polar resin, such as in injection molding (insert molding) or two-color injection molding, it is preferable to perform the thermal fusion at a temperature equal to or higher than the melting point of the modified conjugated diene polymer composition. When the temperature is at or above the melting point of the modified conjugated diene polymer composition, the molecular chains at the interface between the modified conjugated diene polymer composition and the polar resin become more likely to move. As a result, the intermolecular forces and / or chemical bonding points between the modifying group of the modified conjugated diene polymer and the polar resin increase, and thermal fusion is more likely to occur even if it is rapidly cooled in the mold. From the viewpoint of suppressing thermal degradation of the modified conjugated diene polymer composition, it is preferable to perform thermal fusion at 300 °C or lower.

[0143] The molded article of the present embodiment may be formed into a molded article by hot pressing, thermal fusion, cutting, etc. after forming a multilayer body once, or may have the shape of a molded article when forming the multilayer body. The molded article may have a shape suitable for various applications such as automotive parts, tools, toys, electrical and electronic equipment parts, medical instruments, building materials and piping members, cutlery, writing instruments, robot hands, daily and cosmetic products, industrial parts, various hoses, various housings, various module cases, various power control unit parts, and medical instruments. Among these, those having a handle and those that require a gripping force and a good touch feeling when touched by a person are preferable. Examples of such molded articles include tools, electric wires, connectors, handy electronic devices, toothbrushes, shavers, and pens such as ballpoint pens, touch pens, and stylus pens, and cutlery such as forks, knives, and spoons, and automotive interior members having a grip portion. Among them, it is suitable for power tools and the like that impose a large load on the human body due to vibration during use.

Examples

[0144] Hereinafter, the present embodiment will be described in detail with specific examples and comparative examples, but the present embodiment is not limited in any way by the following examples and comparative examples.

[0145] The structures of the modified conjugated diene polymers, as well as the measurement methods and evaluation methods for the physical properties of the modified conjugated diene polymer compositions, the multilayers of the modified conjugated diene polymer compositions and the polar resins, and the molded articles in the examples and comparative examples are shown below.

[0146] 〔Measurement and Evaluation of the Structures of Conjugated Diene Polymers and Modified Conjugated Diene Polymers, and the Physical Properties of Conjugated Diene Polymer Compositions and Modified Conjugated Diene Polymer Compositions〕 Hereinafter, the modified conjugated diene polymer and the unmodified conjugated diene polymer are collectively referred to as a conjugated diene polymer.

[0147] (1) Content of each monomer unit in the conjugated diene polymer Using the following formula, the content of each monomer unit in the unmodified conjugated diene polymer before hydrogenation was calculated, and the content of each polymer block in the conjugated diene polymer was calculated. Content of each monomer unit in the unmodified conjugated diene polymer before hydrogenation = 〔(Total amount of each monomer fed in each step) / (Total monomer amount)〕×100 (mass%) However, in the following manner, for each step of each polymerization process of the conjugated diene polymer, it was confirmed that the polymerization rates of the butadiene monomer and the styrene monomer were 100%. The polymer solution sampled at each step of the polymerization process was injected into a 100 mL bottle containing 0.50 mL of n-propylbenzene used as an internal standard and about 20 mL of toluene to prepare a sample. Each sample was measured using gas chromatography (manufactured by Shimadzu Corporation, GC-14B (product name)) equipped with a back column carrying apiezon grease. The amount of residual monomer in the polymer solution was determined from the calibration curves of the butadiene monomer and the styrene monomer obtained in advance, and it was confirmed that no residual monomer was present. In addition, as the temperature conditions in the measurement by gas chromatography, the polymerization rate of butadiene was kept constant at 90°C, and the polymerization rate of styrene was set under the conditions of 90°C (10-minute hold) to a temperature increase of 150°C (10°C / min).

[0148] (2) Vinyl bond amount of the conjugated diene polymer before hydrogenation The vinyl bond amount of the conjugated diene polymer before hydrogenation was measured by proton nuclear magnetic resonance ( 1 H-NMR) using the polymer solution sampled at each step of the polymerization process of the conjugated diene polymer. Using ECS400 (product name manufactured by JEOL) as the measuring instrument, deuterated chloroform as the solvent, and a sample concentration of 50 mg / mL, the measurement was carried out under the following conditions. The vinyl bond amount was calculated from the signal ratio of the 1,4-bond part and the 1,2-bond part after obtaining the integral values of the signals attributed to the 1,4-bond part and the 1,2-bond part in the conjugated diene monomer unit. (Measurement conditions) Observation frequency: 400 MHz Chemical shift standard: Tetramethylsilane Pulse delay: 2.904 seconds Number of scans: 64 times Pulse width: 45° Measurement temperature: 26°C

[0149] (3) Hydrogenation rate of the conjugated diene polymer The hydrogenation rate of the unsaturated bonds based on the conjugated diene monomer units of the conjugated diene polymer was measured by proton nuclear magnetic resonance ( 1 H-NMR) using the unmodified conjugated diene polymer before and after hydrogenation. The measurement conditions and the method for processing the measurement data were the same as those in (2) above. In addition, the hydrogenation rate was calculated from the signal ratio after obtaining the integral values of the signals derived from the double bonds at 4.5 - 5.5 ppm and the signals derived from the hydrogenated conjugated diene.

[0150] (4) Butylene amount of the conjugated diene polymer In the conjugated diene polymer, the amount of butylene relative to a total of 100 mol% of the conjugated diene monomer units was measured by proton nuclear magnetic resonance ( 1 1H-NMR) using the non-modified conjugated diene polymer after hydrogenation. The measurement conditions and the method for processing the measurement data were the same as those in (2) and (3) above. Note that the amount of butylene relative to a total of 100 mol% of the conjugated diene monomer units was calculated from the signal ratio obtained by determining the integral values of the signals derived from all the conjugated diene monomer units in the non-modified conjugated diene polymer after hydrogenation and the signals derived from the butylene part (hydrogenated 1,2-bond part) in the spectrum at 0 to 2.0 ppm.

[0151] (5) Styrene content of the conjugated diene polymer The styrene content of the modified conjugated diene polymer was calculated by measuring the absorption intensity at 262 nm using an ultraviolet spectrophotometer (UV-2450 (product name) manufactured by Shimadzu Corporation) with the conjugated diene polymer before hydrogenation as a sample. In the conjugated diene polymer, it is known that the content of the vinyl aromatic monomer units hardly changes before and after hydrogenation. Therefore, the styrene content of the conjugated diene polymer before hydrogenation was taken as the styrene content of the modified conjugated diene polymer. Note that the styrene content indicates the content of styrene units, which are vinyl aromatic monomers, in the modified conjugated diene polymer.

[0152] (6) Content of the polymer block mainly composed of styrene units in the conjugated diene polymer (Os value) Using the non-modified conjugated diene polymer before hydrogenation, the content of the polymer block mainly composed of styrene units in the conjugated diene polymer (hereinafter also referred to as the "Os value") was measured by the osmium tetroxide decomposition method described in I.M. KOLTHOFF, et al., J. Polym. Soi., 1, 429 (1946). For the decomposition of the non-modified conjugated diene polymer before hydrogenation, a 0.1 g / 125 mL tertiary butanol solution of osmium acid was used.

[0153] (7) Weight-average molecular weight and molecular weight distribution of the conjugated diene polymer Using the unmodified conjugated diene polymer after hydrogenation, the weight-average molecular weight and molecular weight distribution of the conjugated diene polymer were measured by GPC [GPC apparatus: HLC8220 (product name manufactured by Tosoh Corporation), column: TSKgel SUPER-HZM-N (product name manufactured by Sigma-Aldrich Corporation) with a size of 4.6 mm × 30 cm]. Tetrahydrofuran was used as the solvent. The weight-average molecular weight was determined based on the calibration curve obtained using commercially available standard polystyrene from the peak of the chromatogram. In addition, when there are multiple peaks in the chromatogram, the molecular weight was determined as the weight-average molecular weight from the molecular weight of each peak and the composition ratio of each peak (determined by the area ratio of each peak in the chromatogram). The molecular weight distribution was calculated from the ratio (Mw / Mn) of the obtained weight-average molecular weight (Mw) to the number-average molecular weight (Mn).

[0154] (8) Amount of acid anhydride added to the modified conjugated diene polymer The amount of acid anhydride added to the modified conjugated diene polymer was calculated by dissolving the modified conjugated diene polymer after modification with the acid anhydride in toluene and titrating it with a methanol solution of sodium methoxide with a factor of 1 ± 0.05.

[0155] (9) Fluidity of the conjugated diene polymer and the conjugated diene polymer composition The fluidity of the conjugated diene polymer and the conjugated diene polymer composition was measured in accordance with ISO 1133. Specifically, the melt flow rate (MFR) value at 230°C and a load of 2.16 kg was measured and evaluated according to the following evaluation criteria. Note that a high MFR value means that the polymer or composition has excellent fluidity. (Evaluation criteria) 5: 100 g / 10 min or more 4: 50 g / 10 min or more and less than 100 g / 10 min 3: 30 g / 10 min or more and less than 50 g / 10 min 2: More than 10 g / 10 min and less than 30 g / 10 min 1: Less than 10 g / 10 min

[0156] (10) Flexibility of conjugated diene polymers and conjugated diene polymer compositions The flexibility of the conjugated diene polymers and conjugated diene polymer compositions was measured in accordance with JIS K6253. The Shore A hardness was measured at a measurement temperature of 23°C and a measurement time of 10 seconds, and evaluated according to the following evaluation criteria. Note that a lower Shore A hardness means that the polymer or composition has excellent flexibility. (Evaluation criteria) 3: Less than 50 2: 50 or more and less than 60 1: 60 or more

[0157] (11) Tensile modulus, 100% modulus, 300% modulus, tensile strength, and elongation at break of conjugated diene polymer compositions The tensile modulus, 100% modulus, 300% modulus, tensile strength, and elongation at break of the conjugated diene polymer compositions were measured in accordance with JIS K6251 under the conditions of a No. 3 dumbbell and a crosshead speed of 500 mm / min. The test was carried out using three or more test pieces for each composition, and the average value (arithmetic mean) was taken as the physical property value. Note that the 100% modulus and 300% modulus mean the stress required to stretch the test piece before stretching by 100% and 300% respectively (i.e., 2-fold and 4-fold stretching). The tensile modulus was determined from the slope of the stress-strain curve (SS curve) in the region where the stress and strain are in a proportional relationship immediately after measurement. In practical applications, since it is required that the material is difficult to deform in the region of small deformation amount, the larger the tensile modulus and 100% modulus, the more preferable the tendency.

[0158] (12) Interfacial peel strength of a multilayer body of a conjugated diene polymer composition and a polar resin The interfacial peel strength of the multilayer body of the conjugated diene polymer composition and the polar resin was measured by a 180-degree peel test using the multilayer body obtained by heat-fusing the conjugated diene polymer composition to the polar resin. Specifically, a flat plate made of various polar resins with a thickness of 2 mm was fixed to an injection molding die (mold temperature 40 °C) with a depth of 3 mm, and the conjugated diene polymer composition was poured into this die by injection molding to produce a multilayer body composed of a 2-mm-thick polar resin and a 1-mm-thick conjugated diene polymer composition. A cut with a width of 10 mm was made on the surface of the obtained multilayer body on the polymer composition side, and the end of the layer made of the polymer composition was peeled off by several centimeters. In the peeled portion, the layer made of the polymer composition and the layer made of the polar resin were separately fixed to the chucks of a tensile testing machine [manufactured by Minebea Mitsumi Inc., TGE-500N (product name)]. The layer made of the polymer composition and the layer made of the polar resin were peeled by pulling at 300 mm / min in the 180 °C direction, and the tensile force applied during peeling was defined as the interfacial peel strength (N / cm) of the multilayer body of the conjugated diene polymer composition and the polar resin, and evaluated according to the following evaluation criteria. (Evaluation Criteria) 4: 10 N / cm or more 3: 5 N / cm or more and less than 10 N / cm 2: 1 N / cm or more and less than 5 N / cm 1: Less than 1 N / cm

[0159] (13) Interfacial peel marks of the multilayer body of the conjugated diene polymer composition and the polar resin After the peel test of the multilayer body of the conjugated diene polymer composition and the polar resin performed in the above "(12) Interfacial peel strength of the multilayer body of the conjugated diene polymer composition and the polar resin", the peeled polar resin substrate was visually observed. The peel marks of the modified conjugated diene polymer composition remaining on the polar resin substrate side were evaluated according to the following evaluation criteria. (Evaluation Criteria) 4: Peel marks remained on 90% or more of the peeled surface 3: Peel marks remained on 50% or more and less than 90% of the peeled surface 2: Peel marks remained on 1% or more and less than 50% of the peeled surface 1: No peel marks

[0160] [Production of Conjugated Diene Block Copolymer] (Preparation of Hydrogenation Catalyst) The hydrogenation catalyst used in the hydrogenation reaction of the conjugated diene polymer was prepared by the following method. 1 L of dried and purified cyclohexane was placed in a reaction vessel purged with nitrogen, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added, and while stirring thoroughly, an n-hexane solution containing 200 mmol of trimethylaluminum was added. After that, the reaction was carried out at room temperature for about 3 days to obtain a hydrogenation catalyst.

[0161] [Production Example 1] (Production of Conjugated Diene Block Copolymer (a-1)) <Step 1>[ Batch polymerization was carried out using a stirred apparatus with an internal volume of 10 L and a jacketed tank reactor. 1 L of cyclohexane was placed in the reactor, n-butyllithium was added so as to be 0.13 parts by mass with respect to 100 parts by mass of all monomers, and further 0.3 mol of N,N,N',N'-tetramethylethylenediamine (TMEDA) was added per 1 mol of n-butyllithium. Next, a cyclohexane solution containing 16 parts by mass of styrene (with respect to 100 parts by mass of all monomers; the same applies in the following paragraph) (styrene concentration: 20% by mass) was charged into the reactor and polymerized at 70°C for 45 minutes. Next, a cyclohexane solution containing 68 parts by mass of butadiene (butadiene concentration: 20% by mass) was added and polymerized at 70°C for 1.5 hours. Finally, a cyclohexane solution containing 16 parts by mass of styrene (styrene concentration: 20% by mass) was charged and polymerized at 70°C for 45 minutes. After completion of the reaction, methanol was added to obtain a conjugated diene block copolymer as Step 1. The obtained conjugated diene block copolymer had a styrene content of 32% by mass, an Os value of 32% by mass, and a vinyl bond content of 36 mol%.

[0162] <Step 2>[ To the obtained conjugated diene-based block copolymer, the above-described hydrogenation catalyst was added so that the titanium conversion concentration was 100 ppm per 100 parts by mass of the conjugated diene-based block copolymer, and a hydrogenation reaction (synonymous with hydrogenation reaction and hydrogen addition reaction; the same shall apply hereinafter) was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 °C. After completion of the hydrogenation reaction, next, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 part by mass with respect to 100 parts by mass of the conjugated diene-based block copolymer to produce a hydrogenated conjugated diene-based block copolymer. The obtained hydrogenated conjugated diene-based block copolymer (a-1) had a styrene content of 32% by mass, an Os value of 32% by mass, a butylene amount of 36 mol%, a weight average molecular weight of 82,000, a molecular weight distribution of 1.2, and a hydrogen addition rate of 99 mol%.

[0163] [Production Example 2] (Production of conjugated diene-based block copolymer (a-2)) <Step 1> Batch polymerization was carried out using a stirring device with an internal volume of 10 L and a jacketed tank reactor. 1 L of cyclohexane was placed in the reactor, n-butyllithium was added so as to be 0.12 part by mass with respect to 100 parts by mass of all monomers, and further, N,N,N’,N’-tetramethylethylenediamine (TMEDA) was added in an amount of 0.3 mol per 1 mol of n-butyllithium. Next, a cyclohexane solution containing 9.5 parts by mass of styrene (with respect to 100 parts by mass of all monomers; the same shall apply in this paragraph hereinafter) (styrene concentration: 20% by mass) was charged into the reactor and polymerized at 70 °C for 45 minutes. Next, a cyclohexane solution containing 81 parts by mass of butadiene (butadiene concentration: 20% by mass) was added and polymerized at 70 °C for 1.5 hours. Finally, a cyclohexane solution containing 9.5 parts by mass of styrene (styrene concentration: 20% by mass) was charged and polymerized at 70 °C for 45 minutes. After completion of the reaction, methanol was added to obtain a conjugated diene-based block copolymer in Step 1. The obtained conjugated diene-based block copolymer had a styrene content of 19% by mass, an Os value of 19% by mass, and a vinyl bond amount of 36 mol%.

[0164] <Engineering 2> To the obtained conjugated diene-based block copolymer, the above-described hydrogenation catalyst was added such that the titanium conversion concentration was 100 ppm per 100 parts by mass of the conjugated diene-based block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70°C. After completion of the hydrogenation reaction, next, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 part by mass per 100 parts by mass of the conjugated diene-based block copolymer to produce a hydrogenated conjugated diene-based block copolymer. The obtained hydrogenated conjugated diene-based block copolymer (a-2) had a styrene content of 19% by mass, an Os value of 19% by mass, a butylene amount of 36 mol%, a weight average molecular weight of 95,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.

[0165] [Production Example 3] (Production of conjugated diene-based block copolymer (a-3)) <Process 1> Batch polymerization was carried out using a stirrer with an internal volume of 10 L and a jacketed tank reactor. 1 L of cyclohexane was placed in the reactor, n-butyllithium was added such that the amount was 0.08 part by mass per 100 parts by mass of all monomers, and further, TMEDA (tetramethylethylenediamine) was added in an amount of 0.5 mol per 1 mol of n-butyllithium. Next, a cyclohexane solution containing 6.5 parts by mass of styrene (based on 100 parts by mass of all monomers; the same applies in the following paragraph) (styrene concentration: 20% by mass) was charged into the reactor and polymerized at 70°C for 45 minutes. Next, a cyclohexane solution containing 87 parts by mass of butadiene (butadiene concentration: 20% by mass) was added and polymerized at 50°C for 80 minutes. Next, a cyclohexane solution containing 6.5 parts by mass of styrene (styrene concentration: 20% by mass) was charged and polymerized at 70°C for 45 minutes. After completion of the reaction, methanol was added to obtain a conjugated diene-based block copolymer. The obtained conjugated diene-based block copolymer had a styrene content of 13% by mass, an Os value of 13% by mass, and a vinyl bond amount of 45 mol%. <Process 2> To the obtained conjugated diene block copolymer, the above-described hydrogenation catalyst was added so that the titanium conversion concentration was 100 ppm per 100 parts by mass of the conjugated diene block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 °C. After completion of the hydrogenation reaction, next, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass with respect to 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer. The obtained hydrogenated conjugated diene block copolymer (a-3) had a styrene content of 13% by mass, an Os value of 13% by mass, a butylene amount of 45 mol%, a weight average molecular weight of 80,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.

[0166] [Production Example 4] (Production of conjugated diene block copolymer (a-4)) <Step 1> Batch polymerization was carried out using a stirrer with an internal volume of 10 L and a jacketed tank reactor. 1 L of cyclohexane was placed in the reactor, n-butyllithium was added so as to be 0.11 parts by mass per 100 parts by mass of all monomers, and further, TMEDA (tetramethylethylenediamine) was added in an amount of 1.5 mol per 1 mol of n-butyllithium, and sodium t-pentoxide was added in an amount of 0.05 mol per 1 mol of n-butyllithium. Next, a cyclohexane solution containing 5 parts by mass of butadiene (based on 100 parts by mass of all monomers; the same applies in the following paragraph) (butadiene concentration: 20% by mass) was added and polymerized at 70 °C for 20 minutes. Next, a cyclohexane solution containing 9 parts by mass of styrene (styrene concentration: 20% by mass) was added and polymerized at 70 °C for 45 minutes. Next, a cyclohexane solution containing 77 parts by mass of butadiene (butadiene concentration: 20% by mass) was added and polymerized at 50 °C for 80 minutes. Next, a cyclohexane solution containing 9 parts by mass of styrene (styrene concentration: 20% by mass) was added and polymerized at 70 °C for 45 minutes. After completion of the reaction, methanol was added to obtain a conjugated diene block copolymer. The obtained conjugated diene-based block copolymer had a styrene content of 18% by mass, an Os value of 18% by mass, and a vinyl bond content of 73 mol%.

[0167] <Step 2> To the obtained conjugated diene-based block copolymer, the above-described hydrogenation catalyst was added so that the titanium conversion concentration was 100 ppm per 100 parts by mass of the conjugated diene-based block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 °C. After completion of the hydrogenation reaction, next, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 part by mass with respect to 100 parts by mass of the conjugated diene-based block copolymer to produce an unmodified hydrogenated conjugated diene-based block copolymer (a-4). The obtained hydrogenated conjugated diene-based block copolymer (a-4) had a styrene content of 18% by mass, an Os value of 18% by mass, a butylene amount of 73 mol%, a weight average molecular weight of 107,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.

[0168] [Production Example 5] (Production of conjugated diene-based block copolymer (a-5)) <Step 1> Batch polymerization was carried out using a stirrer with an internal volume of 10 L and a jacketed tank reactor. 1 L of cyclohexane was placed in the reactor, and n-butyllithium was added so as to be 0.07 part by mass per 100 parts by mass of all monomers. Further, TMEDA (tetramethylethylenediamine) was added in an amount of 1.8 moles per 1 mole of n-butyllithium, and sodium t-pentoxide was added in an amount of 0.05 mole per 1 mole of n-butyllithium. Next, a cyclohexane solution containing 5 parts by mass of butadiene (based on 100 parts by mass of all monomers; the same applies in the following paragraph) (butadiene concentration: 20% by mass) was added, and polymerization was carried out at 70 °C for 20 minutes. Next, a cyclohexane solution containing 7 parts by mass of styrene (styrene concentration: 20% by mass) was introduced, and polymerization was carried out at 70 °C for 45 minutes. Next, a cyclohexane solution containing 82 parts by mass of butadiene (butadiene concentration: 20% by mass) was added, and polymerization was carried out at 50 °C for 80 minutes. Next, a cyclohexane solution containing 6 parts by mass of styrene (styrene concentration: 20% by mass) was introduced, and polymerization was carried out at 70 °C for 45 minutes. After completion of the reaction, methanol was added to obtain a conjugated diene-based block copolymer. The obtained conjugated diene-based block copolymer had a styrene content of 13% by mass, an Os value of 13% by mass, and a vinyl bond amount of 78 mol%.

[0169] <Step 2> To the obtained conjugated diene-based block copolymer, the above-described hydrogenation catalyst was added so that the titanium conversion concentration was 100 ppm per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 °C. After completion of the hydrogenation reaction, next, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass per 100 parts by mass of the conjugated diene-based block copolymer to produce a hydrogenated conjugated diene-based block copolymer (a-5). The obtained hydrogenated conjugated diene-based block copolymer (a-5) had a styrene content of 13% by mass, an Os value of 13% by mass, a butylene amount of 78 mol%, a weight average molecular weight of 160,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.

[0170] [Production Example 6] (Production of conjugated diene-based block copolymer (a-6)) <Step 1> Batch polymerization was carried out using a stirring device with an internal volume of 10 L and a jacketed tank reactor. 1 L of cyclohexane was placed in the reactor, and n-butyllithium was added so that the amount was 0.07 parts by mass per 100 parts by mass of all monomers. Further, TMEDA (tetramethylethylenediamine) was added in an amount of 1.8 moles per 1 mole of n-butyllithium, and sodium t-pentoxide was added in an amount of 0.05 moles per 1 mole of n-butyllithium. Next, a cyclohexane solution containing 6.5 parts by mass of styrene (based on 100 parts by mass of all monomers; the same applies in the following paragraph) (styrene concentration: 20% by mass) was charged and polymerized at 70 °C for 45 minutes. Next, a cyclohexane solution containing 87 parts by mass of butadiene (butadiene concentration: 20% by mass) was added and polymerized at 50 °C for 80 minutes. Next, a cyclohexane solution containing 6.5 parts by mass of styrene (styrene concentration: 20% by mass) was charged and polymerized at 70 °C for 45 minutes. After completion of the reaction, methanol was added to obtain a conjugated diene block copolymer. The obtained conjugated diene block copolymer had a styrene content of 13% by mass, an Os value of 13% by mass, and a vinyl bond content of 78 mol%.

[0171] <Step 2> To the obtained conjugated diene block copolymer, the above-described hydrogenation catalyst was added so that the titanium conversion concentration was 100 ppm per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 °C. After completion of the hydrogenation reaction, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass per 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer (a-6). The obtained hydrogenated conjugated diene block copolymer (a-6) had a styrene content of 13% by mass, an Os value of 13% by mass, a butylene content of 78 mol%, a weight average molecular weight of 160,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.

[0172] [Production Example 7] (Production of conjugated diene-based block copolymer (a-7)) <Step 1> Batch polymerization was carried out using a stirring device with an internal volume of 10 L and a jacketed tank reactor. 1 L of cyclohexane was placed in the reactor, and n-butyllithium was added so that the amount was 0.05 parts by mass based on 100 parts by mass of all monomers. Further, TMEDA (tetramethylethylenediamine) was added in an amount of 0.05 mol per 1 mol of n-butyllithium. Next, a cyclohexane solution containing 10 parts by mass of butadiene (based on 100 parts by mass of all monomers; the same applies in the following paragraph) (butadiene concentration: 20% by mass) was added and polymerized at 65 °C for 20 minutes. Next, after adding TMEDA in an amount of 1.50 mol per 1 mol of n-butyllithium and sodium t-pentoxide in an amount of 0.05 mol per 1 mol of n-butyllithium, a cyclohexane solution containing 85 parts by mass of butadiene (butadiene concentration: 20% by mass) was added and polymerized at 60 °C for 70 minutes. Next, a cyclohexane solution containing 5 parts by mass of styrene (styrene concentration: 20% by mass) was added and polymerized at 65 °C for 15 minutes. After completion of the reaction, methanol was added to obtain a conjugated diene-based block copolymer. The obtained conjugated diene-based block copolymer had a styrene content of 5% by mass, an Os value of 5% by mass, and a vinyl bond content of 78 mol%.

[0173] <Step 2> To the obtained conjugated diene-based block copolymer, the above-described hydrogenation catalyst was added so that the titanium conversion concentration was 100 ppm per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 °C. After completion of the hydrogenation reaction, next, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 parts by mass per 100 parts by mass of the conjugated diene-based block copolymer to produce a hydrogenated conjugated diene-based block copolymer (a-7). The obtained hydrogenated conjugated diene block copolymer (a-7) had a styrene content of 5% by mass, an Os value of 5% by mass, a butylene amount of 78 mol%, a weight average molecular weight of 249,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.

[0174] [Production Example 8] (Production of conjugated diene block copolymer (a-8)) <Step 1> Batch polymerization was carried out using a stirrer with an internal volume of 10 L and a jacketed tank reactor. 1 L of cyclohexane was placed in the reactor, and n-butyllithium was added so that the amount was 0.10 parts by mass per 100 parts by mass of all monomers. Further, TMEDA (tetramethylethylenediamine) was added in an amount of 1.8 moles per 1 mole of n-butyllithium, and sodium t-pentoxide was added in an amount of 0.05 moles per 1 mole of n-butyllithium. Next, a cyclohexane solution containing 5 parts by mass of butadiene (based on 100 parts by mass of all monomers; the same applies in this paragraph hereinafter) (butadiene concentration: 20% by mass) was added and polymerized at 70 °C for 20 minutes. Next, a cyclohexane solution containing 21.5 parts by mass of styrene (styrene concentration: 20% by mass) was introduced and polymerized at 70 °C for 45 minutes. Next, a cyclohexane solution containing 52 parts by mass of butadiene (butadiene concentration: 20% by mass) was added and polymerized at 50 °C for 80 minutes. Next, a cyclohexane solution containing 21.5 parts by mass of styrene (styrene concentration: 20% by mass) was introduced and polymerized at 70 °C for 45 minutes. After the reaction was completed, methanol was added to obtain a conjugated diene block copolymer. The obtained conjugated diene block copolymer had a styrene content of 43% by mass, an Os value of 43% by mass, and a vinyl bond amount of 78 mol%.

[0175] <Step 2> To the obtained block copolymer, the above-described hydrogenation catalyst was added so that the titanium conversion concentration was 100 ppm per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 °C. After the hydrogenation reaction was completed, 0.3 parts by mass of octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the conjugated diene-based block copolymer to produce a hydrogenated conjugated diene-based block copolymer (a-8). The obtained hydrogenated conjugated diene-based block copolymer (a-8) had a styrene content of 43% by mass, an Os value of 43% by mass, a butylene content of 78 mol%, a weight average molecular weight of 103,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.

[0176] [Production Example 9] (Production of conjugated diene-based block copolymer (c-2)) <Step 1> Batch polymerization was carried out using a stirred apparatus with an internal volume of 10 L and a jacketed tank reactor. 1 L of cyclohexane was placed in the reactor, and n-butyllithium was added in an amount of 0.085 parts by mass based on 100 parts by mass of all monomers. Further, 0.8 mol of N,N,N',N'-tetramethylethylenediamine (TMEDA) was added per 1 mol of n-butyllithium. Next, a cyclohexane solution containing 20 parts by mass of styrene (based on 100 parts by mass of all monomers; the same applies in the following paragraph) (styrene concentration: 20% by mass) was introduced and polymerized at 70°C for 20 minutes. Next, a cyclohexane solution containing 3 parts by mass of butadiene (butadiene concentration: 20% by mass) was added and polymerized at 70°C for 5 minutes. Next, a cyclohexane solution containing 27 parts by mass of butadiene and 47 parts by mass of styrene (monomer concentration: 20% by mass) was supplied so that the reaction temperature was constant, and polymerization was carried out at 70°C for 45 minutes. Next, a cyclohexane solution containing 3 parts by mass of butadiene (butadiene concentration: 20% by mass) was added and polymerized at 70°C for 5 minutes. Finally, 0.2 mol of tetraethoxysilane was added per 1 mol of n-butyllithium, and the reaction was carried out at 70°C for 30 minutes. After the reaction was completed, methanol was added to obtain a conjugated diene-based block copolymer in Step 1. The obtained conjugated diene-based block copolymer had a styrene content of 67% by mass, an Os value of 20% by mass, a styrene content in the random block of 63.4% by mass, and a vinyl bond content of 20 mol%.

[0177] <Engineering 2> To the obtained conjugated diene block copolymer, the above-described hydrogenation catalyst was added so that the titanium conversion concentration was 100 ppm per 100 parts by mass of the conjugated diene block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 °C. After completion of the hydrogenation reaction, next, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 part by mass with respect to 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer. The obtained hydrogenated conjugated diene block copolymer (c-2) had a styrene content of 67% by mass, an Os value of 20% by mass, a styrene content in the random block of 63.4% by mass, a butylene amount of 20 mol%, a weight average molecular weight of 291,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.

[0178] [Production Example 10] (Production of conjugated diene block copolymer (d)) <Process 1> Batch polymerization was carried out using a stirring device with an internal volume of 10 L and a jacketed tank reactor. 1 L of cyclohexane was placed in the reactor, and n-butyllithium was added so as to be 0.084 part by mass per 100 parts by mass of all monomers. Further, N,N,N',N'-tetramethylethylenediamine (TMEDA) was added in an amount of 1.8 mol per 1 mol of n-butyllithium and sodium t-pentoxide was added in an amount of 0.05 mol per 1 mol of n-butyllithium. Next, a cyclohexane solution containing 9 parts by mass of styrene (relative to 100 parts by mass of all monomers; the same applies in the following paragraph) with a styrene concentration of 20% by mass was introduced and polymerized at 70 °C for 20 minutes. Next, a cyclohexane solution containing 21 parts by mass of butadiene and 25 parts by mass of styrene (monomer concentration: 20% by mass) was supplied so that the reaction temperature became constant, and polymerized at 70 °C for 45 minutes. Next, a cyclohexane solution containing 45 parts by mass of butadiene (butadiene concentration: 20% by mass) was added and polymerized at 60 °C for 1 hour. After completion of the reaction, methanol was added, and a conjugated diene block copolymer was obtained in Step 1. The obtained conjugated diene block copolymer had a styrene content of 34% by mass, an Os value of 9% by mass, a styrene content in the random block of 54.3% by mass, and a vinyl bond content of 77 mol%.

[0179] <Step 2> To the obtained conjugated diene block copolymer, the above-described hydrogenation catalyst was added so that the titanium conversion concentration was 100 ppm per 100 parts by mass of the conjugated diene block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 °C. After completion of the hydrogenation reaction, next, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer in an amount of 0.3 part by mass per 100 parts by mass of the conjugated diene block copolymer to produce a hydrogenated conjugated diene block copolymer. The obtained hydrogenated conjugated diene block copolymer (d) had a styrene content of 34% by mass, an Os value of 9% by mass, a styrene content in the random block of 54.3% by mass, a butylene content of 77 mol%, a weight average molecular weight of 148,000, a molecular weight distribution of 1.2, and a hydrogenation rate of 99 mol%.

[0180] 〔Production of modified conjugated diene block copolymer〕 Using the following materials, a modified conjugated diene polymer (modified conjugated diene block copolymer) was produced. Maleic anhydride (manufactured by Fuso Chemical Industry Co., Ltd.) Radical initiator: Perhexa 25B (manufactured by NOF Corporation)

[0181] [Production Example 11 (Comparative Example 1)] (Production of Modified Conjugated Diene Block Copolymer (aa-1)) <Step 3> 100 parts by mass of the hydrogenated conjugated diene block copolymer (a-1) in pellet form, 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B were dry blended. These were melt kneaded in a twin screw extruder TEX30 (manufactured by Japan Steel Works, Ltd.) at a cylinder set temperature of 210°C, a screw rotation speed of 253 rpm, and a discharge rate of 5 kg / hour to produce a maleic anhydride modified conjugated diene polymer (aa-1).

[0182] [Production Example 12 (Comparative Example 2)] (Production of Modified Conjugated Diene Block Copolymer (aa-2)) <Step 3> A modified conjugated diene polymer (aa-2) was produced in the same manner as in Production Example 11, except that 100 parts by mass of the hydrogenated conjugated diene block copolymer (a-2) in pellet form, 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B were dry blended.

[0183] [Production Example 13 (Comparative Example 3)] (Production of Modified Conjugated Diene Block Copolymer (aa-3)) <Step 3> A maleic anhydride modified conjugated diene polymer (aa-3) was produced in the same manner as in Production Example 11, except that the components at the time of dry blending were changed to 100 parts by mass of the hydrogenated conjugated diene block copolymer (a-3) in pellet form, 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B.

[0184] [Production Example 14 (Example 1)] (Production of Modified Conjugated Diene Block Copolymer (aa-4)) <Step 3> Except for changing each component during dry blending to 100 parts by mass of the hydrogenated conjugated diene block copolymer (a-4) in pellet form, 1.4 parts by mass of maleic anhydride, and 0.08 parts by mass of Perhexa 25B, an anhydride-modified conjugated diene polymer (aa-4) was produced in the same manner as in Production Example 11.

[0185] [Production Example 15 (Example 2)] (Production of Modified Conjugated Diene Block Copolymer (aa-5)) <Step 3> Except for changing each component during dry blending to 100 parts by mass of the hydrogenated conjugated diene block copolymer (a-5) in pellet form, 1.4 parts by mass of maleic anhydride, and 0.08 parts by mass of Perhexa 25B, an anhydride-modified conjugated diene polymer (aa-5) was produced in the same manner as in Production Example 11.

[0186] [Production Example 16 (Example 3)] (Production of Modified Conjugated Diene Block Copolymer (aa-6)) <Step 3> Except for changing each component during dry blending to 100 parts by mass of the hydrogenated conjugated diene block copolymer (a-6) in pellet form, 1.4 parts by mass of maleic anhydride, and 0.08 parts by mass of Perhexa 25B, an anhydride-modified conjugated diene polymer (aa-6) was produced in the same manner as in Production Example 11.

[0187] [Production Example 17 (Example 4)] (Production of Modified Conjugated Diene Block Copolymer (aa-7)) <Step 3> Except for changing each component during dry blending to 100 parts by mass of the hydrogenated conjugated diene block copolymer (a-7) in pellet form, 1.4 parts by mass of maleic anhydride, and 0.08 parts by mass of Perhexa 25B, an anhydride-modified conjugated diene polymer (aa-7) was produced in the same manner as in Production Example 11.

[0188] [Production Example 18 (Comparative Example 4)] (Production of Modified Conjugated Diene Block Copolymer (aa-8)) <Step 3> A maleic anhydride-modified conjugated diene polymer (aa-8) was produced in the same manner as in Production Example 11, except that each component in the dry blend was changed to 100 parts by mass of the hydrogenated conjugated diene block copolymer (a-8) in pellet form, 2.1 parts by mass of maleic anhydride, and 0.12 parts by mass of Perhexa 25B. [Production Example 19 (Example 26)] (Production of Modified Conjugated Diene Block Copolymer (aa-9)) <Step 3> A maleic anhydride-modified conjugated diene polymer (aa-9) was produced in the same manner as in Production Example 11, except that each component in the dry blend was changed to 100 parts by mass of the hydrogenated conjugated diene block copolymer (a-5) in pellet form, 3.0 parts by mass of maleic anhydride, and 0.17 parts by mass of Perhexa 25B.

[0189] Table 1 shows the measurement results of the structures and physical properties of the modified conjugated diene polymers obtained in Examples 1 to 4, 26 and Comparative Examples 1 to 4.

[0190]

Table 1

[0191] [Production of Conjugated Diene Polymer Composition and Molding of Multilayer Body] Based on the compounding amounts (unit: "parts by mass") of [Examples 5 to 25, 27 to 38] and [Comparative Examples 5 to 18] described in Tables 2 to 6 below, a conjugated diene polymer resin composition was produced using the following materials, and further a multilayer test piece with each base material was prepared. Conjugated diene block copolymers (a-1), (a-5), and (d): Conjugated diene block copolymers produced by the above method Modified conjugated diene block copolymers (aa-1) to (aa-9): Modified conjugated diene block copolymers produced by the above method Polyolefin resin (b-1): Polypropylene PL500A (product name manufactured by Sun Allomer Co., Ltd.) Polyolefin resin (b-2): Polypropylene PM900C (product name manufactured by San Allomer Co., Ltd.) Polyolefin resin (b-3): Polypropylene S13B (product name manufactured by Prime Polymer Co., Ltd.) Polyolefin resin (b-4): Polypropylene PC630S (product name manufactured by San Allomer Co., Ltd.) Conjugated diene block copolymer (number average molecular weight of 150,000 or more) (c-1): Styrenic thermoplastic elastomer Tough Tech N504 (styrene content 32% by mass, product name manufactured by Asahi Kasei Corporation) Conjugated diene block copolymer (number average molecular weight of 150,000 or more) (c-2): Conjugated diene block copolymer produced by the above method Softening agent (e): Paraffin oil PW-90 (product name manufactured by Idemitsu Kosan Co., Ltd.) Stabilizer (f): Irgafos 168 (product name manufactured by BASF Japan Ltd.) Filler (g): Calcium carbonate Whiton SB (product name manufactured by Shiraishi Calcium Co., Ltd.) Polyamide resin: Nylon 66 Leona 1300S (product name manufactured by Asahi Kasei Corporation), Glass fiber reinforced nylon 66 Leona 1300G (product name manufactured by Asahi Kasei Corporation), Nylon 6 UBE Nylon 1015B (product name manufactured by Ube Industries, Ltd.), Glass fiber reinforced nylon 6 Zytel 73G30L (product name manufactured by DuPont (Japan) Co., Ltd.) Polyphenylene sulfide resin: Polyphenylene sulfide Trellina M2888 (product name manufactured by Toray Industries, Inc.), Glass fiber reinforced polyphenylene sulfide Trellina A604 (product name manufactured by Toray Industries, Inc.) Polycarbonate resin: Polycarbonate resin sheet PC1600 (product name manufactured by Takiron Seia Co., Ltd.) ABS resin: ABS Tough Ace R EAR-003 (product name manufactured by Sumitomo Bakelite Co., Ltd.) Polymethyl methacrylate resin: Polymethyl methacrylate Delpet 80N (product name manufactured by Asahi Kasei Corporation)

[0192] As the adherend (polar resin substrate) of the multilayer test piece, a substrate made of various polar resins was produced by injection molding using a mold of 150 mm × 100 mm × 2 mm (length × width × thickness).

[0193] 〔Examples 5 to 7〕 A modified conjugated diene-based block copolymer (aa-4), a polyolefin resin (b-1), a conjugated diene-based block copolymer (c-1) previously containing a softening agent (e), and a stabilizer (f) were dry-blended. These were melt-kneaded using a twin-screw extruder TEX-30αII (product name manufactured by Nippon Steel Works, Ltd., cylinder diameter 30 mm) at a cylinder set temperature of 220°C, a screw rotation speed of 253 rpm, and a discharge rate of 5 kg / hour to obtain a modified conjugated diene-based block copolymer composition. Thereafter, a substrate made of various polar resins with a thickness of 2 mm was fixed in a mold of 150 mm × 100 mm × 3 mm (length × width × thickness). At a cylinder set temperature of 280°C and a mold set temperature of 40°C, the modified conjugated diene-based block copolymer composition was poured into the mold by injection molding to obtain a multilayer body composed of a 2-mm-thick layer of polar resin and a 1-mm-thick layer of the modified conjugated diene-based block copolymer composition.

[0194] 〔Example 8〕 A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 5, except that the modified conjugated diene-based block copolymer (aa-5) was used as the modified conjugated diene-based block copolymer.

[0195] 〔Example 9〕 A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 8, except that the cylinder set temperature of the injection molding machine during multilayer body production was set to 270°C.

[0196] 〔Example 10〕 A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 8, except that the cylinder set temperature of the injection molding machine during multilayer body production was set to 260°C.

[0197] 〔Example 11〕 A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 6, except that the modified conjugated diene-based block copolymer (aa-5) was used as the modified conjugated diene-based block copolymer.

[0198] 〔Example 12〕 A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 7, except that the modified conjugated diene-based block copolymer (aa-5) was used as the modified conjugated diene-based block copolymer.

[0199] 〔Example 13〕 A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 5, except that the modified conjugated diene-based block copolymer (aa-6) was used as the modified conjugated diene-based block copolymer.

[0200] 〔Example 14〕 A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 5, except that the modified conjugated diene-based block copolymer (aa-7) was used as the modified conjugated diene-based block copolymer.

[0201] 〔Example 15〕 The modified conjugated diene-based block copolymer (aa-5), the polyolefin resin (b-1), the conjugated diene-based block copolymers (c-1) and (c-2) previously containing the softening agent (e), and the stabilizer (f) were dry-blended. These were melt-kneaded using a twin-screw extruder TEX-30αII (product name manufactured by Nippon Steel & Sumitomo Metal Corporation, cylinder diameter 30 mm) at a cylinder set temperature of 220°C, a screw rotation speed of 253 rpm, and a discharge rate of 5 kg / hour to obtain a modified conjugated diene-based block copolymer composition. Thereafter, a base material made of various polar resins with a thickness of 2 mm was fixed in a mold of 150 mm × 100 mm × 3 mm (length × width × thickness). By pouring the modified conjugated diene-based block copolymer composition into the mold by injection molding at a cylinder set temperature of 280°C and a mold set temperature of 40°C, a multilayer body composed of a 2-mm-thick layer of polar resin and a 1-mm-thick layer of the modified conjugated diene-based block copolymer composition was obtained.

[0202] 〔Example 16〕 A modified conjugated diene-based block copolymer (aa-5), a polyolefin resin (b-1), conjugated diene-based block copolymers (c-1) and (c-2) previously containing a softening agent (e), a conjugated diene-based block copolymer (d), and a stabilizer (f) were dry-blended. These were melt-kneaded using a twin-screw extruder TEX-30αII (product name manufactured by Japan Steel Works, Ltd., cylinder diameter 30 mm) at a cylinder set temperature of 220°C, a screw rotation speed of 253 rpm, and a discharge rate of 5 kg / hour to obtain a modified conjugated diene-based block copolymer composition. Thereafter, a base material made of various polar resins with a thickness of 2 mm was fixed in a mold of 150 mm × 100 mm × 3 mm (length × width × thickness). By pouring the modified conjugated diene-based block copolymer composition into the mold by injection molding at a cylinder set temperature of 280°C and a mold set temperature of 40°C, a multilayer body composed of a 2-mm-thick layer of polar resin and a 1-mm-thick layer of the modified conjugated diene-based block copolymer composition was obtained.

[0203] 〔Example 17〕 A modified conjugated diene-based block copolymer (aa-5), a polyolefin resin (b-1), a conjugated diene-based block copolymer (c-1) previously containing a softening agent (e), a stabilizer (f), and a filler (g) were dry-blended. These were melt-kneaded using a twin-screw extruder TEX-30αII (product name manufactured by Japan Steel Works, Ltd., cylinder diameter 30 mm) at a cylinder set temperature of 220°C, a screw rotation speed of 253 rpm, and a discharge rate of 5 kg / hour to obtain a modified conjugated diene-based block copolymer composition. Subsequently, a base material made of various polar resins with a thickness of 2 mm was fixed in a mold of 150 mm × 100 mm × 3 mm (length × width × thickness). By injecting the modified conjugated diene-based block copolymer composition into the mold at a cylinder set temperature of 280°C and a mold set temperature of 40°C, a multilayer body composed of a 2-mm-thick layer of polar resin and a 1-mm-thick layer of the modified conjugated diene-based block copolymer composition was obtained.

[0204] [Example 18] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 5, except that polyolefin resin (b-2) was used as the polyolefin resin.

[0205] [Example 19] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 5, except that polyolefin resin (b-3) was used as the polyolefin resin.

[0206] [Example 20] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 17, except that polyolefin resin (b-3) was used as the polyolefin resin.

[0207] [Example 21] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 19, except that the blending amounts of the conjugated diene-based block copolymer (c-1) and the softening agent (e) were changed.

[0208] [Example 22] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 8, except that polyolefin resin (b-4) was used as the polyolefin resin.

[0209] [Example 23] In the same manner as in Example 8, a modified conjugated diene-based block copolymer composition was obtained. Thereafter, when obtaining a multilayer body composed of a layer of a polar resin and a layer of the modified conjugated diene-based block copolymer composition, a multilayer body was obtained in the same manner as in Example 8, except that the polar resin described in Table 6 was used. In Table 6, "PPS" means polyphenylene sulfide resin, "PC" means polycarbonate resin, "ABS" means ABS resin, and "PMMA" means polymethyl methacrylate resin, respectively.

[0210] [Example 24] In the same manner as in Example 22, a modified conjugated diene-based block copolymer composition was obtained. Thereafter, when obtaining a multilayer body composed of a layer of a polar resin and a layer of the modified conjugated diene-based block copolymer composition, a multilayer body was obtained in the same manner as in Example 22, except that the polar resin described in Table 6 was used.

[0211] [Example 25] A modified conjugated diene-based block copolymer (aa-5) and a polyolefin resin (b-2) were dry blended. These were melt kneaded using a twin-screw extruder TEX-30αII (product name manufactured by Japan Steel Works, Ltd., cylinder diameter 30 mm) at a cylinder set temperature of 220°C, a screw rotation speed of 253 rpm, and a discharge rate of 5 kg / hour to obtain a modified conjugated diene-based block copolymer composition. Thereafter, a substrate made of various polar resins with a thickness of 2 mm was fixed in a mold of 150 mm × 100 mm × 3 mm (length × width × thickness). At a cylinder set temperature of 280°C and a mold set temperature of 40°C, the modified conjugated diene-based block copolymer composition was poured into the mold by injection molding to obtain a multilayer body composed of a 2-mm-thick layer of a polar resin and a 1-mm-thick layer of the modified conjugated diene-based block copolymer composition.

[0212] [Example 27] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 5, except that the modified conjugated diene-based block copolymer (aa-9) was used as the modified conjugated diene-based block copolymer.

[0213] [Example 28] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 7, except that the modified conjugated diene-based block copolymer (aa-9) was used as the modified conjugated diene-based block copolymer.

[0214] [Example 29] A modified conjugated diene-based block copolymer (aa-5), a conjugated diene-based block copolymer (a-5), a polyolefin resin (b-1), a conjugated diene-based block copolymer (c-1) previously containing a softening agent (e), and a stabilizer (f) were dry blended. These were melt-kneaded using a twin-screw extruder TEX-30αII (product name manufactured by Japan Steel Works, Ltd., cylinder diameter 30 mm) at a cylinder set temperature of 220°C, a screw rotation speed of 253 rpm, and a discharge rate of 5 kg / hour to obtain a modified conjugated diene-based block copolymer composition. Thereafter, a base material made of various polar resins with a thickness of 2 mm was fixed in a mold of 150 mm × 100 mm × 3 mm (length × width × thickness). The modified conjugated diene-based block copolymer composition was poured into the mold by injection molding at a cylinder set temperature of 280°C and a mold set temperature of 40°C to obtain a multilayer body composed of a 2-mm-thick layer of polar resin and a 1-mm-thick layer of the modified conjugated diene-based block copolymer composition.

[0215] [Example 30] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 15, except that the blending amounts of the respective components were changed.

[0216] [Example 31] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 15, except that the blending amounts of the respective components were changed.

[0217] [Example 32] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 15, except that the blending amounts of the respective components were changed.

[0218] [Example 33] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 15, except that the compounding amounts of the respective components were changed.

[0219] [Example 34] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 5, except that the modified conjugated diene-based block copolymer (aa-5) was used as the modified conjugated diene-based block copolymer and the conjugated diene-based block copolymer (c-2) was used as the conjugated diene-based block copolymer.

[0220] [Example 35] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 8, except that the compounding amount of the softening agent (e) was changed.

[0221] [Example 36] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 15, except that the compounding amounts of the respective components were changed.

[0222] [Example 37] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 15, except that the compounding amounts of the respective components were changed.

[0223] [Example 38] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 34, except that the compounding amount of the softening agent (e) was changed.

[0224] [Comparative Example 5] A polyolefin resin (b-1), a conjugated diene-based block copolymer (c-1) previously containing a softening agent (e), and a stabilizer (f) were dry-blended. These were melt-kneaded using a twin-screw extruder TEX-30αII (product name manufactured by Japan Steel Works, Ltd., cylinder diameter 30 mm) at a cylinder set temperature of 220°C, a screw rotation speed of 253 rpm, and a discharge rate of 5 kg / hour to obtain a modified conjugated diene-based block copolymer composition. Subsequently, a base material made of various polar resins with a thickness of 2 mm was fixed in a mold of 150 mm × 100 mm × 3 mm (length × width × thickness). By pouring the modified conjugated diene-based block copolymer composition into the mold by injection molding at a cylinder set temperature of 280°C and a mold set temperature of 40°C, a multilayer body composed of a 2-mm-thick layer of polar resin and a 1-mm-thick layer of modified conjugated diene-based block copolymer composition was produced.

[0225] [Comparative Example 6] A conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 5, except that the conjugated diene-based block copolymer (a-1) was used instead of the modified conjugated diene-based block copolymer (aa-4).

[0226] 〔Comparative Example 7〕 A conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 17, except that the conjugated diene-based block copolymer (a-1) was used instead of the modified conjugated diene-based block copolymer (aa-5).

[0227] 〔Comparative Example 8〕 A conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 5, except that the conjugated diene-based block copolymer (a-5) was used instead of the modified conjugated diene-based block copolymer (aa-4).

[0228] 〔Comparative Example 9〕 A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 5, except that the modified conjugated diene-based block copolymer (aa-1) was used as the modified conjugated diene-based block copolymer.

[0229] 〔Comparative Example 10〕 A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 17, except that the modified conjugated diene-based block copolymer (aa-1) was used as the modified conjugated diene-based block copolymer.

[0230] 〔Comparative Example 11〕 A modified conjugated diene block copolymer composition and a multilayer body were obtained in the same manner as in Example 19, except that the modified conjugated diene block copolymer (aa-1) was used as the modified conjugated diene block copolymer.

[0231] [Comparative Example 12] A modified conjugated diene block copolymer composition and a multilayer body were obtained in the same manner as in Example 20, except that the modified conjugated diene block copolymer (aa-1) was used as the modified conjugated diene block copolymer.

[0232] [Comparative Example 13] A modified conjugated diene block copolymer composition and a multilayer body were obtained in the same manner as in Example 5, except that the modified conjugated diene block copolymer (aa-2) was used as the modified conjugated diene block copolymer.

[0233] [Comparative Example 14] A modified conjugated diene block copolymer composition and a multilayer body were obtained in the same manner as in Example 5, except that the modified conjugated diene block copolymer (aa-11) was used as the modified conjugated diene block copolymer.

[0234] [Comparative Example 15] A modified conjugated diene block copolymer composition and a multilayer body were obtained in the same manner as in Example 5, except that the modified conjugated diene block copolymer (aa-8) was used as the modified conjugated diene block copolymer.

[0235] [Comparative Example 16] A modified conjugated diene block copolymer composition was obtained in the same manner as in Comparative Example 9. Thereafter, when obtaining a multilayer body composed of a layer of a polar resin and a layer of the modified conjugated diene block copolymer composition, a multilayer body was obtained in the same manner as in Comparative Example 9, except that the polar resin described in Table 6 was used.

[0236] [Comparative Example 17] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 25, except that the modified conjugated diene-based block copolymer (aa-1) was used as the modified conjugated diene-based block copolymer.

[0237] [Comparative Example 18] A modified conjugated diene-based block copolymer composition and a multilayer body were obtained in the same manner as in Example 34, except that the modified conjugated diene-based block copolymer (aa-1) was used as the modified conjugated diene-based block copolymer.

[0238] The structures and physical properties of the conjugated diene-based polymer compositions obtained in Examples 5 to 25, 27 to 38 and Comparative Examples 5 to 18, and the measured values and evaluation results of the physical properties of the multilayer bodies obtained in Examples 5 to 25, 27 to 38 and Comparative Examples 5 to 18 are shown in Tables 2 to 6.

[0239] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6]

[0240] From the results in Table 1, it was found that Examples 1 to 4 and 26 are modified grades excellent in fluidity and flexibility. From Tables 2 to 6, it was found that Examples 5 to 25 and 27 to 38 were excellent in fluidity, flexibility, mechanical properties, and adhesion to polar resins. Also, in Examples 32, 33, 34, and 38, it was confirmed that peeling marks of the modified conjugated diene-based polymer composition remained on the polar resin substrate side after the peeling test. For example, when comparing Examples 30 to 34, etc., it was found that by controlling the composition of each component in the modified conjugated diene-based polymer composition, it was possible to increase the adhesive strength between the layer containing the modified conjugated diene-based polymer composition and the layer containing the polar resin to the extent that peeling marks remained. It is presumed that whether peeling marks remain is also affected by the sample shape and the molding conditions of the multilayer body. This suggests that for the modified conjugated diene-based polymer compositions where peeling marks were not confirmed this time, there is a possibility that peeling marks may be confirmed by changing the sample shape, the molding conditions of the multilayer body, etc. Also, in Comparative Examples 5 to 18, even though they were excellent in the evaluation of fluidity and hardness, there were some cases where the evaluation of the peel strength was "1" depending on the substrate, indicating that the adhesion to the polar resin was insufficient.

Industrial Applicability

[0241] The modified conjugated diene-based block copolymer and the modified conjugated diene-based block copolymer resin composition of the present invention are excellent in fluidity, flexibility, and adhesion to polar resins. Therefore, they have industrial applicability for various uses such as automotive parts, power tools, toys, electrical and electronic equipment parts, medical instruments, building materials and piping members, cutlery, daily and cosmetic products, industrial parts, various hoses, various housings, various module cases, various power control unit parts, writing instruments, robot hands, and medical instruments.

Explanation of Symbols

[0242] 10... Electric drill, 11... Electric drill housing, 12, 22, 32, 42... Grip part, 20... Cutlery, 21... Main body of cutlery, 30... Mobile phone housing, 31... Main body of mobile phone housing, 40... Cutter, 41... Cutter housing.

Claims

Claim 1: A modified conjugated diene polymer composition comprising a modified conjugated diene polymer (A), a polyolefin (B), and a conjugated diene polymer (C) having a weight average molecular weight of 150,000 or more (excluding those corresponding to the modified conjugated diene polymer (A)). The modified conjugated diene polymer (A) is a polymer block mainly composed of conjugated diene monomer units, and in the polymer block, the content of conjugated diene monomer units exceeds 70% by mass based on the entire polymer block, and has a modified conjugated diene polymer satisfying the following conditions (a), (b), (c), and (d). Modified conjugated diene polymer composition (a) In the polymer block mainly composed of the conjugated diene monomer units, the amount of vinyl bonds before hydrogenation is 60 mol% or more based on 100 mol% of the total conjugated diene monomer units. (b) At least a part of the conjugated diene monomer units in the polymer block mainly composed of the conjugated diene monomer units is hydrogenated. (c) The content of the polymer block mainly composed of vinyl aromatic monomer units in the modified conjugated diene polymer, wherein the content of vinyl aromatic monomer units in the polymer block exceeds 70% by mass based on the entire polymer block, is 3% by mass or more and 40% by mass or less based on the total amount of the modified conjugated diene polymer. (d) The modified conjugated diene polymer has a modifying group, and the modifying group is at least one selected from the group consisting of an acid anhydride group, a carbonyl group, a carboxyl group, an amino group, an epoxy group, an alkoxysilane group, a hydroxyl group, an isocyanate group, and an ionic group. Claim 2: The modified conjugated diene polymer composition according to Claim 1, wherein the amount of vinyl bonds before hydrogenation of the modified conjugated diene polymer (A) is 65 mol% or more based on 100 mol% of the total conjugated diene monomer units. Claim 3: The modified conjugated diene polymer composition according to Claim 1 or 2, wherein after hydrogenation, the proportion of the conjugated diene monomer portion incorporated into the modified conjugated diene polymer by 1,2-bonding and containing no unsaturated bond in the entire portion derived from the conjugated diene monomer units is 60 mol% or more based on 100 mol% of the total conjugated diene monomer units.

4. The modified conjugated diene polymer composition according to any one of claims 1 to 3, wherein the modified conjugated diene polymer (A) has the modifying group in a side chain.

5. The modified conjugated diene polymer composition according to any one of claims 1 to 4, wherein the content of the polymer block mainly composed of the vinyl aromatic monomer unit in the modified conjugated diene polymer in the modified conjugated diene polymer (A) is 3% by mass or more and 20% by mass or less based on the total amount of the modified conjugated diene polymer.

6. The modified conjugated diene polymer composition according to any one of claims 1 to 5, wherein the polyolefin (B) is polypropylene.

7. The modified conjugated diene polymer composition according to any one of claims 1 to 6, wherein the conjugated diene polymer (C) includes at least a conjugated diene polymer having a random copolymer block of a conjugated diene monomer and a vinyl aromatic monomer.

8. The modified conjugated diene polymer composition according to any one of claims 1 to 7, wherein the content of the modified conjugated diene polymer (A) is 5% by mass or more and 80% by mass or less.

9. The modified conjugated diene polymer composition according to any one of claims 1 to 8, wherein the weight average molecular weight of the modified conjugated diene polymer (A) is 100,000 or more.

10. The modified conjugated diene polymer composition according to any one of claims 1 to 9, further comprising a softening agent.

11. The modified conjugated diene polymer composition according to any one of claims 1 to 10, having a melt flow rate of 10 g / 10 min or more at 230 °C and 2.16 kg.

12. The modified conjugated diene polymer composition according to any one of claims 1 to 11, further comprising a filler.

13. A multilayer body including a layer containing a polar resin and a layer containing the modified conjugated diene polymer composition according to any one of claims 1 to 12 laminated on the layer.

14. The multilayer body according to claim 13, wherein the layer containing the modified conjugated diene polymer composition is heat-sealed to the layer containing the polar resin.

15. The multilayer body according to claim 13 or 14, wherein the polar resin is at least one selected from the group consisting of ABS, polymethyl methacrylate, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyphenylene sulfide.

16. A method for manufacturing a multilayer body according to any one of claims 13 to 15, wherein the multilayer body is formed by at least one method selected from the group consisting of an injection molding method, an insert molding method, an extrusion molding method, and a compression molding method. **Claim 17** A molded body including the multilayer body according to any one of claims 13 to 15, wherein the multilayer body constitutes at least one selected from a grip of a tool, an electric wire covering member, a connector housing, a grip of a handy electronic device, a grip of a toothbrush, a grip of a shaver, a grip of a cutlery, a grip of a writing instrument, a grip portion of a robot hand, and a grip portion of an automobile interior member.

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