Resin composition, foaming composition, and crosslinked foam

Abstract

This resin composition contains, as component (x), a hydrogenated product (X) of a block copolymer having a polymeric block (A-1) derived from an aromatic vinyl compound and having a polymeric block (B-1) derived from a conjugated diene compound, and, as component (y), a block copolymer (Y0) having a polymeric block (A-2) derived from an aromatic vinyl compound and having a polymeric block (B-2) derived from a conjugated diene compound, or a hydrogenated product (Y) of the block copolymer (Y0), and satisfies conditions [1]-[4]. [1] The glass transition temperature of component (x) is at least -40°C. [2] The glass transition temperature of component (y) is at most -50°C. [3] A ratio Mx / My of the mass Mx of component (x) with respect to the mass My of component (y) in the resin composition is 1 / 99 to 99 / 1. [4] The polymeric block (B-2) includes a structural unit derived from β-farnesene.

Description

Technical Field

[0001] The present invention relates to a resin composition, a foaming composition, and a crosslinked foam.

Background Art

[0002] Hydrogenated products of block copolymers containing a polymer block (A) composed of structural units derived from an aromatic vinyl compound and a polymer block (B) composed of structural units derived from a conjugated diene compound, such as hydrogenated styrene-based elastomers (hereinafter sometimes referred to as "hydrogenated block copolymers" or "hydrogenated products") are known. Hydrogenated block copolymers have vibration damping properties and are widely used in various fields as vibration damping materials.

[0003] For example, in order to improve mechanical properties such as vibration damping properties, flexibility, heat resistance, tensile strength, and impact resistance, hydrogenated block copolymers of styrene-based compounds and conjugated diene compounds such as isoprene and butadiene, in which the peak temperature of the loss tangent (tanδ) and the vinyl bond content are specified, are disclosed (see, for example, Patent Document 1).

[0004] Also, as hydrogenated block copolymers, hydrogenated block copolymers containing monomer units derived from farnesene are known (see, for example, Patent Document 2). In Patent Document 2, it is said that the molding processability and flexibility are improved by the above hydrogenated block copolymer.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in various applications, improvement of the properties of hydrogenated block copolymers is required, and there is a demand for further enhancing moldability and exhibiting flexibility at low temperatures while maintaining vibration damping performance. For this reason, there is still room for improvement even in the hydrogenated block copolymers described in Patent Documents 1 and 2.

[0007] Therefore, an object of the present invention is to provide a resin composition, a foaming composition, and a crosslinked foam that can exhibit at least one of good moldability and flexibility at low temperatures while maintaining vibration damping properties near room temperature.

Means for Solving the Problems

[0008] The present inventors have found that the resin composition can solve the above problems by using, as component (x), a hydrogenated product (X) of a block copolymer having a polymer block (A-1) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B-1) containing a structural unit derived from a conjugated diene compound, and, as component (y), a block copolymer (Y0) having a polymer block (A-2) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B-2) containing a structural unit derived from a conjugated diene compound or a hydrogenated product (Y) thereof, specifying the glass transition temperatures of the above component (x) and component (y), and using a specific component for the polymer block (B-2), and thus have completed the present invention.

[0009] The present invention relates to the following <1> to <20>. <1> As component (x), a hydrogenated product (X) of a block copolymer having a polymer block (A-1) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B-1) containing a structural unit derived from a conjugated diene compound, and As component (y), it contains a polymer block (A-2) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B-2) containing a structural unit derived from a conjugated diene compound, or a hydrogenated product (Y) thereof, and is a resin composition satisfying the following conditions [1] to [4]. [1] The glass transition temperature of component (x) is -40°C or higher. [2] The glass transition temperature of component (y) is -50°C or lower. [3] In the resin composition, the ratio Mx / My of the mass Mx of component (x) to the mass My of component (y) is 1 / 99 to 99 / 1. [4] The polymer block (B-2) contains a structural unit derived from β-farnesene. <2> The resin composition according to <1> above, wherein the content of the polymer block (A-1) in component (x) is 23% by mass or less. <3> The resin composition according to <1> or <2> above, wherein the hydrogenation rate of component (x) is 85 mol% or more. <4> The resin composition according to any one of <1> to <3> above, wherein the weight average molecular weight of component (x) is 100,000 to 250,000. <5> The resin composition according to any one of <1> to <4> above, wherein the melt flow rate of component (x) at 230°C and a load of 2.16 kg, measured in accordance with JIS K 7210:2014, is 20 g / 10 min or less. <6> The resin composition according to any one of <1> to <5> above, wherein the polymer block (B-1) contains a structural unit derived from isoprene. <7> The resin composition according to any one of <1> to <6> above, wherein the vinyl bond content of the polymer block (B-1) is 50 mol% or more. <8> The resin composition according to any one of <1> to <7> above, wherein the content of the polymer block (A-2) in component (y) is 35% by mass or less. <9> The resin composition according to any one of <1> to <8> above, wherein component (y) is a hydrogenated product (Y) of a block copolymer, and the hydrogenation rate of the hydrogenated product (Y) of the block copolymer is 85 mol% or more. The resin composition according to any one of <1> to <9> above, wherein the weight average molecular weight of component (y) is 40,000 to 400,000. The resin composition according to any one of <1> to <10> above, wherein the melt flow rate of component (y) at 230 °C and a load of 2.16 kg measured in accordance with JIS K 7210:2014 is 10 g / 10 min or more. The resin composition according to any one of <1> to <11> above, wherein Mx / My is 45 / 55 to 80 / 20. The resin composition according to any one of <1> to <11> above, wherein Mx / My is 20 / 80 to 37 / 63. The resin composition according to any one of <1> to <13> above, wherein the bio-based degree of the resin composition measured in accordance with ASTM D6866-20 is 1 to 80 mass%. The resin composition according to any one of <1> to <14> above, wherein the melt flow rate of the resin composition at 230 °C and a load of 2.16 kg measured in accordance with JIS K 7210:2014 is 100 g / 10 min or less. The resin composition according to any one of <1> to <15> above, wherein the peak top strength of tanδ measured under the conditions of a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of -30 to +50 °C, a heating rate of 3 °C / min, and a shear mode in accordance with JIS K7244-10:2005 is 0.4 or more. The resin composition according to any one of <1> to <16> above, wherein the content of the structural unit derived from β-farnesene in component (x) is smaller than the content of the structural unit derived from β-farnesene in component (y). In the resin composition according to any one of <1> to <17> above, one of component (x) and component (y) is used as a matrix, and a domain in which the other of component (x) and component (y) is dispersed is formed in the matrix, and the average aspect ratio of the domain is 1.0 to 3.0. The resin composition (i) according to any one of <1> to <18> above, and At least one olefin polymer (ii) selected from the group consisting of ethylene-propylene-diene copolymer rubber, ethylene-vinyl acetate copolymer, and polyethylene-based resin, a crosslinking agent (iii), a foaming agent (iv), and a foaming composition containing the same. <20> The crosslinked foam of the foaming composition according to <19> above.

Advantages of the Invention

[0010] According to the present invention, it is possible to provide a resin composition, a foaming composition, and a crosslinked foam that can exhibit at least one of good moldability and flexibility at low temperature while maintaining vibration damping properties near room temperature.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0012] Hereinafter, embodiments of the present invention will be described. Aspects arbitrarily selected from the matters described in this specification or aspects arbitrarily combined are also included in the present invention. In this specification, the provisions defined as preferable can be arbitrarily selected, and combinations of the provisions defined as preferable can be said to be more preferable. In this specification, the description of "XX to YY" means "XX or more and YY or less". In this specification, for preferred numerical ranges (for example, ranges such as content), the lower limit value and the upper limit value described step by step can be combined independently. For example, from the description "preferably 10 to 90, more preferably 30 to 60", it is also possible to combine the "preferred lower limit value (10)" and the "more preferred upper limit value (60)" to obtain "10 to 60".

[0013] [Resin composition] The resin composition according to an embodiment of the present invention includes, as component (x), a hydrogenated product (X) of a block copolymer having a polymer block (A-1) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B-1) containing a structural unit derived from a conjugated diene compound, and, as component (y), a block copolymer (Y0) having a polymer block (A-2) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B-2) containing a structural unit derived from a conjugated diene compound or a hydrogenated product (Y) thereof, and satisfies the following conditions [1] to [4]. [1] The glass transition temperature of component (x) is -40°C or higher. [2] The glass transition temperature of component (y) is -50°C or lower. [3] The ratio Mx / My of the mass Mx of component (x) to the mass My of component (y) in the resin composition is 1 / 99 to 99 / 1. [4] The block copolymer (Y0) or its hydrogenated product (Y) contains at least one structural unit derived from β-farnesene as the polymer block (B-2).

[0014] By the resin composition satisfying the conditions [1] to [4], it is possible to exhibit at least one of good moldability and flexibility at low temperature while maintaining the vibration damping property near room temperature. More specifically, the resin composition has a high loss tangent (tanδ) near room temperature and at least one of good moldability and flexibility at low temperature. According to the studies of the present inventors, by adding component (y), which is a block copolymer or a hydrogenated block copolymer with a low glass transition temperature (Tg) and contains structural units derived from β-farnesene, to component (x), which is a hydrogenated block copolymer with a high glass transition temperature (Tg), when the ratio Mx / My of the mass Mx of component (x) to the mass My of component (y) in the resin composition is in the range of 45 / 55 to 99 / 1, good moldability is exhibited while maintaining vibration damping properties. Further, when the Mx / My is in the range of 1 / 99 to 44 / 56, it has been found that flexibility is exhibited at low temperatures without significantly reducing the vibration damping properties. The reason for this is, but not limited to this, firstly, since component (y), which is a component with a low Tg, contains structural units derived from β-farnesene, the compatibility with component (x) is increased, and as a result, it becomes difficult for component (x) or component (y) to generate structural anisotropy in the resin component, and it is considered that a decrease in the peak top intensity of tanδ of the entire resin composition is suppressed. In addition to this, it is considered that the moldability and low-temperature flexibility of component (y) contribute to the expression of moldability and flexibility at low temperatures while maintaining the vibration damping properties.

[0015] <Glass transition temperature (Tg) of component (x) and component (y)> The above-mentioned component (x) is a hydrogenated product (X) of a block copolymer having a polymer block (A-1) containing structural units derived from an aromatic vinyl compound and a polymer block (B-1) containing structural units derived from a conjugated diene compound, and satisfies the above condition [1]. The above-mentioned component (y) is a block copolymer (Y0) having a polymer block (A-2) containing structural units derived from an aromatic vinyl compound and a polymer block (B-2) containing structural units derived from a conjugated diene compound or its hydrogenated product (Y), and satisfies the above condition [2]. By component (x) satisfying condition [1], the tanδ of the resin composition near room temperature can be increased. Further, by component (y) satisfying condition [2], the moldability and flexibility at low temperatures of the resin composition can be ensured. In this specification, the Tg of component (x) and the Tg of component (y) are measured using a differential scanning calorimeter (DSC). Specifically, in the DSC curve created using DSC, the temperature at which a baseline shift occurs is defined as the Tg. The Tg of component (x) and the Tg of component (y) are more specifically measured according to the method described in the examples.

[0016] From the viewpoint of increasing tanδ near room temperature, the Tg of component (x) is preferably -30°C or higher, more preferably -20°C or higher, still more preferably -10°C or higher, and particularly preferably 0°C or higher. There is no particular upper limit, but from the viewpoint of ease of manufacture, it is preferably +40°C or lower, more preferably +35°C or lower, and still more preferably +30°C or lower. In other words, the Tg of component (x) is preferably -40 to +40°C.

[0017] From the viewpoint of flexibility at low temperatures, the Tg of component (y) is preferably -51°C or lower, more preferably -52°C or lower. Also, there is no particular lower limit, but from the viewpoint of ease of manufacture, it is preferably -65°C or higher, more preferably -60°C or higher, and still more preferably -55°C. In other words, the Tg of component (y) is preferably -65 to -50°C. From the viewpoint of facilitating the securing of moldability, the difference between the Tg of component (x) and the Tg of component (y) is at least 10°C or higher, preferably 20°C or higher, more preferably 30°C or higher, and still more preferably 40°C or higher. Also, from the viewpoint of facilitating the increase of tanδ near room temperature, it is preferably 100°C or lower, more preferably 90°C or lower, and still more preferably 80°C or lower. In other words, the difference between the Tg of component (x) and the Tg of component (y) is preferably 10 to 100°C.

[0018] <Content ratio of component (x) and component (y)> As defined in the above condition [3], the ratio Mx / My of the mass Mx of component (x) to the mass My of component (y) in the above resin composition is 1 / 99 to 99 / 1. When the mass ratio Mx / My is within the above range, a high tanδ can be obtained mainly due to the presence of component (x) near room temperature, and excellent moldability can be obtained mainly due to the presence of (y). From the viewpoint of facilitating the improvement of the moldability of the resin composition and the vibration damping property near room temperature, the above mass ratio Mx / My is preferably 45 / 55 to 95 / 5, more preferably 45 / 55 to 90 / 10, still more preferably 45 / 55 to 85 / 15, even more preferably 45 / 55 to 80 / 20, even more preferably 50 / 50 to 80 / 20, even more preferably 55 / 45 to 80 / 20, even more preferably 60 / 40 to 80 / 20, even more preferably 65 / 35 to 80 / 20, particularly preferably 65 / 35 to 75 / 25. Also, from the viewpoint of facilitating the improvement of flexibility at low temperatures, it is preferably 5 / 95 to 44 / 56, more preferably 10 / 90 to 43 / 57, still more preferably 15 / 85 to 40 / 60, even more preferably 20 / 80 to 37 / 63, even more preferably 21 / 79 to 37 / 63, particularly preferably 25 / 75 to 35 / 65.

[0019] <Component (x)> The above component (x) is a hydrogenated product (X) of a block copolymer having a polymer block (A-1) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B-1) containing a structural unit derived from a conjugated diene compound, and satisfies the above conditions [1] and [3]. In order for component (x) to satisfy condition [1], for example, by controlling the vinyl bond amount of the conjugated diene compound of the polymer block (B-1) constituting the hydrogenated product (X) of the block copolymer to an appropriate value, the Tg of component (x) can be set within the above range.

[0020] Component (x) may contain a hydrogenated product (X) of a block copolymer alone or in combination of two or more. When component (x) contains a hydrogenated product (X) of a block copolymer alone, the production is easy, and when it contains two or more, it is easy to widen the temperature range in which the resin composition exhibits a high tanδ.

[0021] The content of the polymer block (A-1) in the component (x) (when there are a plurality of polymer blocks (A-1), the total content thereof) is preferably 23% by mass or less, more preferably 21% by mass or less, still more preferably 18% by mass or less, and even more preferably 15% by mass or less from the viewpoint of vibration damping property. Also, from the viewpoint of mechanical properties, it is preferably 5% by mass or more, more preferably 8% by mass or more, and still more preferably 10% by mass or more. In other words, the content of the polymer block (A-1) in the hydrogenated product (X) of the block copolymer which is the component (x) is preferably 5 to 23% by mass. Incidentally, the content of the polymer block (A-1) in the above component (x) 1 is a value determined by H-NMR measurement, and more specifically, it is a value measured according to the method described in the examples. The same applies to the content of the polymer block (A-2) in the component (y) described later.

[0022] The weight average molecular weight of the component (x) is preferably 60,000 to 400,000, more preferably 80,000 to 300,000, still more preferably 100,000 to 250,000, and even more preferably 130,000 to 200,000 from the viewpoints of heat resistance and moldability. All of the "weight average molecular weight" described in this specification and the claims is the weight average molecular weight in terms of standard polystyrene determined by gel permeation chromatography (GPC) measurement, and the detailed measurement method can follow the method described in the examples. The weight average molecular weight of the hydrogenated product (X) of the block copolymer as the component (x) can be within the above range, for example, by adjusting the monomer amount with respect to the polymerization initiator.

[0023] The content of the structural unit derived from β-farnesene in the component (x) is preferably smaller than the content of the structural unit derived from β-farnesene in the component (y) from the viewpoint of vibration damping property near room temperature, more preferably 10% by mass or less, still more preferably 5% by mass or less, even more preferably 2% by mass or less, and particularly preferably 0% by mass (that is, does not contain the structural unit derived from β-farnesene).

[0024] <Component (y)> The above-mentioned component (y) is a block copolymer (Y0) having a polymer block (A-2) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B-2) containing a structural unit derived from a conjugated diene compound, or a hydrogenated product (Y) thereof, and satisfies the above conditions [2] to [4]. In order to make component (y) satisfy condition [2], for example, by controlling the vinyl bond amount of the conjugated diene compound in the polymer block (B-2) constituting the block copolymer (Y0) or its hydrogenated product (Y) to an appropriate value, the Tg of component (y) can be set within the above range. Further, in order to make component (y) satisfy condition [4], β-farnesene is used as the conjugated diene compound used in the synthesis of the polymer block (B-2). By making component (y) satisfy condition [4], the temperature characteristics of tanδ of the resin composition near room temperature can be made close to the characteristics before the addition of component (y).

[0025] From the viewpoint of the vibration damping property of the resin composition near room temperature, the content of the polymer block (A-2) in component (y) is preferably 35% by mass or less, more preferably 28% by mass or less, still more preferably 23% by mass or less. From the viewpoint of mechanical properties, it is preferably 10% by mass or more, more preferably 14% by mass or more, still more preferably 17% by mass or more. In other words, the content of the polymer block (A-2) in the block copolymer (Y0) or its hydrogenated product (Y) which is component (y) is preferably 10 to 35% by mass.

[0026] From the viewpoints of heat resistance and moldability, the weight average molecular weight of component (y) is preferably 40,000 to 400,000, more preferably 40,000 to 300,000, still more preferably 40,000 to 250,000, even more preferably 60,000 to 250,000, particularly preferably 80,000 to 250,000, and most preferably 90,000 to 200,000. The weight-average molecular weight of the block copolymer (Y0) and the hydrogenated product (Y) of the block copolymer as component (y) can be within the above range, for example, by adjusting the amount of monomer relative to the polymerization initiator.

[0027] Component (y) may contain only one of the hydrogenated product (Y) of the block copolymer and the block copolymer (Y0), or may contain both. The hydrogenated product (Y) of the block copolymer contained in component (y) may be of one type or two or more types. The block copolymer (Y0) contained in component (y) may be of one type or two or more types. When component (y) contains two or more types of the block copolymer (Y0) or its hydrogenated product (Y), it becomes easier to increase tanδ of the resin composition near room temperature.

[0028] Hereinafter, the common configurations, physical properties of components (x) and (y), other components constituting the resin composition, and physical properties of the resin composition will be described. First, the block copolymers (X0), (Y0) used to obtain components (x) and (y) will be described.

[0029] <Block copolymers (X0), (Y0)> The block copolymer (X0) before hydrogenation for obtaining the hydrogenated product (X) of the block copolymer as component (x) contained in the resin composition according to an embodiment of the present invention includes a polymer block (A-1) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B-1) containing a structural unit derived from a conjugated diene compound. Further, the block copolymer (Y0) before hydrogenation as component (y) contained in the resin composition according to an embodiment of the present invention includes a polymer block (A-2) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B-2) containing a structural unit derived from a conjugated diene compound. Similarly, the block copolymer (Y0) for obtaining the hydrogenated product (Y) of the block copolymer as component (y) contained in the resin composition according to an embodiment of the present invention also includes the polymer block (A-2) and the polymer block (B-2). Note that the block copolymer (X0) and the block copolymer (Y0) may be collectively referred to simply as the block copolymer. Also, the hydrogenated product (X) of the block copolymer and the hydrogenated product (Y) of the block copolymer may be collectively referred to simply as the hydrogenated product of the block copolymer. The polymer block (A-1), the polymer block (A-2), the polymer block (B-1), and the polymer block (B-2) may each independently be contained only one in the resin composition, or two or more may be contained. When two or more of the polymer block (A-1), the polymer block (A-2), the polymer block (B-1), and the polymer block (B-2) are contained, the two or more polymer blocks may be the same as each other or different from each other.

[0030] The total content of the polymer block (A-1) and the polymer block (B-1) in the block copolymer (X0) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 100% by mass. That is, the total content of the polymer block (A-1) and the polymer block (B-1) in the block copolymer (X0) is, for example, 80 to 100% by mass. Also, the total content of the polymer block (A-2) and the polymer block (B-2) in the block copolymer (Y0) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 100% by mass. That is, the total content of the polymer block (A-2) and the polymer block (B-2) in the block copolymer (Y0) is, for example, 80 to 100% by mass.

[0031] Hereinafter, the polymer block (A-1) and the polymer block (A-2) are collectively referred to as the polymer block (A). Also, the polymer block (B-1) and the polymer block (B-2) are collectively referred to as the polymer block (B). And for the block copolymer related to the component (x) (block copolymer (X0)) and the block copolymer related to the component (y) (block copolymer (Y0)), the common parts are described collectively, and the block copolymers (X0) and (Y0) may be simply referred to as the "block copolymer".

[0032] (Polymer block (A)) The polymer block (A) contains a structural unit derived from an aromatic vinyl compound (hereinafter, may be abbreviated as "aromatic vinyl compound unit"). From the viewpoint of mechanical properties, it is preferably more than 70 mol%, more preferably 80 mol% or more, still more preferably 85 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more, and may be substantially 100 mol%. The upper limit of the content of the structural unit derived from the aromatic vinyl compound in the polymer block (A) may be 100 mol%, 99 mol%, or 98 mol%.

[0033] Examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-t-butylstyrene, m-t-butylstyrene, p-t-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, styrene derivatives substituted with silyl groups, indene, vinylnaphthalene, and the like. These aromatic vinyl compounds may be used alone or in combination of two or more. Among them, from the viewpoints of production cost and physical property balance, styrene, α-methylstyrene, p-methylstyrene, and mixtures thereof are preferred, and styrene is more preferred.

[0034] However, as long as it does not interfere with the object and effect of the present invention, the polymer block (A) may contain structural units derived from unsaturated monomers other than aromatic vinyl compounds (hereinafter may be abbreviated as "other unsaturated monomer units") in a proportion of less than 30 mol%. Examples of the other unsaturated monomers include at least one selected from the group consisting of butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, methyl vinyl ether, N-vinylcarbazole, β-pinene, 8,9-p-menthene, dipentene, methylene norbornene, 2-methylene tetrahydrofuran, and the like. When the polymer block (A) contains the other unsaturated monomer units, the bonding form is not particularly limited and may be either random or tapered. The content of the structural units derived from the other unsaturated monomers in the polymer block (A) is preferably 10 mol% or less, more preferably 5 mol% or less, and still more preferably 0 mol%.

[0035] The block copolymer may have at least one polymer block (A). When the block copolymer has two or more polymer blocks (A), these polymer blocks (A) may be the same or different. In the present specification, "the polymer blocks are different" means that at least one of the monomer units constituting the polymer blocks, the weight average molecular weight, the stereoregularity, and when having a plurality of monomer units, the ratio of each monomer unit and the copolymerization form (random, gradient, block) is different. The block copolymer preferably has two polymer blocks (A).

[0036] The weight average molecular weight (Mw) of the polymer block (A) is not particularly limited. However, among the polymer blocks (A) of the block copolymer, the weight average molecular weight of at least one polymer block (A) is preferably 3,000 to 60,000, more preferably 4,000 to 50,000. By having at least one polymer block (A) with a weight average molecular weight within the above range in the block copolymer, the mechanical strength is further improved, and the fluidity and film formability are also excellent.

[0037] In addition, the weight average molecular weight of each polymer block of the block copolymer can be determined by measuring the sampled liquid each time the polymerization of each polymer block is completed in the production process. Also, for example, when two types of polymer blocks (A) are represented as "A1" and "A2", and one type of polymer block (B) is represented as "B", in the case of a triblock copolymer having a structure of A1-B-A2, the weight average molecular weights of the polymer block "A1" and the polymer block "B" are determined by the above method, and by subtracting them from the weight average molecular weight of the block copolymer, the weight average molecular weight of the polymer block "A2" can be determined. Also, as another method, in the case of a triblock copolymer having the above A1-B-A2 structure, the total weight average molecular weight of the polymer blocks "A1" and "A2" is calculated from the total content of the polymer blocks "A1" and "A2" confirmed by 1H-NMR measurement, and the weight average molecular weight of the deactivated first polymer block "A1" is calculated by GPC measurement, and by subtracting this, the weight average molecular weight of the polymer block "A2" can also be determined. 1 The weight average molecular weight of the polymer block "A2" can also be determined by calculating from the total content of the polymer blocks "A1" and "A2" confirmed by 1H-NMR measurement, calculating the weight average molecular weight of the deactivated first polymer block "A1" by GPC measurement, and subtracting this.

[0038] (Polymer block (B)) The polymer block (B) contains a structural unit derived from a conjugated diene compound (hereinafter, may be abbreviated as "conjugated diene compound unit"). The conjugated diene compound may be used alone or in combination of two or more.

[0039] Examples of the conjugated diene that constitutes the conjugated diene compound unit contained in the polymer block (B-1) include isoprene and butadiene. The polymer block (B-1) preferably contains a structural unit derived from isoprene. When producing the polymer block (B-1), for example, isoprene can be used alone or isoprene and butadiene can be used as the conjugated diene compound. In the polymer block (B-1), the content of the structural unit derived from β-farnesene is preferably low. Specifically, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0% by mass (i.e., not contained). The polymer block (B-2) contains a structural unit derived from β-farnesene (hereinafter sometimes referred to as “β-farnesene unit”). The polymer block (B-2) may contain the β-farnesene unit alone or may contain a structural unit derived from β-farnesene and other conjugated diene compounds. Since β-farnesene has a bulky side chain, it has a high effect of making it difficult to crystallize the polymer block (B-2). In addition, when β-farnesene is hydrogenated, its Tg is as low as about -60°C, so it is easy to enhance the flexibility of the resin composition at low temperatures. Examples of the conjugated diene compound that can be used together with β-farnesene when obtaining the polymer block (B-2) include butadiene, myrcene, isoprene, etc. Such a conjugated diene compound may be used alone or in combination of two or more together with β-farnesene. When the polymer block (B-2) contains a structural unit derived from β-farnesene and other conjugated diene compounds, the moldability and flexibility at low temperatures of the resin composition can be enhanced.

[0040] The content of β-farnesene units in the total amount of polymer block (B-2) is preferably 55% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, from the viewpoint of ensuring good moldability. There is no particular limitation on the upper limit, and it can be 100% by mass, and it may be 99% by mass or 98% by mass. In other words, the content of β-farnesene units in the total amount of polymer block (B-2) is preferably 55 to 100% by mass. In addition, the content of β-farnesene units in the total amount of polymer block (B-2) is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 65 mol% or more, even more preferably 80 mol% or more, particularly preferably 90 mol% or more, most preferably substantially 100 mol% in terms of molar amount. The upper limit may be 99 mol% or 98 mol%. In other words, the content of β-farnesene units in the total amount of polymer block (B-2) is preferably 30 to 100 mol%.

[0041] The total content of conjugated diene compound units in the total amount of polymer block (B) is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, from the viewpoints of flexibility and rubber elasticity. There is no particular limitation on the upper limit, and it can be 100% by mass, and it may be 99% by mass or 98% by mass. In other words, the total content of structural units derived from conjugated diene compounds in the total amount of polymer block (B) is preferably 60 to 100% by mass. In addition, the total content of the above conjugated diene compound units in the total amount of the polymer block (B) is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 65 mol% or more, even more preferably 80 mol% or more, particularly preferably 90 mol% or more, and most preferably substantially 100 mol% in terms of molar amount. The upper limit may be 99 mol% or 98 mol%. In other words, the total content of the structural units derived from the conjugated diene compound in the total amount of the polymer block (B) is preferably 30 to 100 mol%.

[0042] In the polymer block (B-1), when isoprene and another conjugated diene compound are used, the content ratio of the two [another conjugated diene compound / isoprene] (mass ratio) is not particularly limited as long as the effects of the present invention are not impaired, but is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10, still more preferably 15 / 85 to 50 / 50, and particularly preferably 18 / 82 to 48 / 52. In addition, in the polymer block (B-1), when butadiene is used as the above another conjugated diene compound, the content ratio of the two [butadiene / isoprene] expressed as a molar ratio is preferably 6 / 94 to 96 / 4, more preferably 12 / 88 to 92 / 8, still more preferably 18 / 82 to 55 / 45, and particularly preferably 22 / 78 to 54 / 46.

[0043] In the polymer block (B-2), when β-farnesene and another conjugated diene compound are used, the content ratio of the two [another conjugated diene compound / β-farnesene] (mass ratio) is not particularly limited as long as the effects of the present invention are not impaired, but is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10, still more preferably 15 / 85 to 50 / 50, and particularly preferably 18 / 82 to 45 / 55. In the polymer block (B-2), when butadiene is used as the other conjugated diene compound, the content ratio [butadiene / β-farnesene] of the two, expressed as a molar ratio, is preferably 16 / 84 to 99 / 1, more preferably 30 / 70 to 97 / 3, still more preferably 40 / 60 to 80 / 20, and particularly preferably 45 / 55 to 78 / 22.

[0044] Further, as long as it does not prevent the object and effect of the present invention, the polymer block (B) may contain structural units derived from other polymerizable monomers other than the conjugated diene compound. In this case, in the polymer block (B), the content of the structural units derived from other polymerizable monomers other than the conjugated diene compound is preferably 70 mol% or less, more preferably 50 mol% or less, still more preferably 35 mol% or less, and particularly preferably 20 mol% or less. There is no particular limitation on the lower limit value of the content of the structural units derived from other polymerizable monomers other than the conjugated diene compound, and it may be 0 mol%, 5 mol%, or 10 mol%. In other words, the content of the structural units derived from other polymerizable monomers other than the conjugated diene compound in the polymer block (B) is preferably 0 to 70 mol%.

[0045] Examples of the other polymerizable monomers include at least one compound selected from the group consisting of aromatic vinyl compounds such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, and vinylanthracene, and methyl methacrylate, methyl vinyl ether, N-vinylcarbazole, β-pinene, 8,9-p-menthene, dipentene, methylene norbornene, 2-methylene tetrahydrofuran, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, etc. Among them, styrene, α-methylstyrene, and p-methylstyrene are more preferable, and styrene is still more preferable.

[0046] When the polymer block (B) contains a structural unit derived from a polymerizable monomer other than a conjugated diene compound, its bonding form is not particularly limited and may be either random or tapered, but a random form is preferred.

[0047] Also, the block copolymer (X0) only needs to have at least one polymer block (B-1), and the block copolymer (Y0) only needs to have at least one polymer block (B-2). When the block copolymers (X0) and (Y0) have two or more polymer blocks (B), these polymer blocks (B) may be the same or different. When the polymer block (B) has two or more types of structural units, their bonding forms may consist of random, tapered, completely alternating, partially blocky, block, or a combination of two or more of these.

[0048] As long as the object and effect of the present invention are not impaired, there is no particular limitation on the bonding form of the conjugated diene compound. For example, when the structural unit constituting the polymer block (B-1) is a mixture unit of butadiene and isoprene, the bonding forms of butadiene and isoprene can be 1,2-bonding and 1,4-bonding for butadiene, and 1,2-bonding, 3,4-bonding, and 1,4-bonding for isoprene. Also, when the structural unit constituting the polymer block (B-2) is a mixture unit of butadiene and β-farnesene, the bonding forms of butadiene and β-farnesene can be 1,2-bonding and 1,4-bonding for butadiene, and 1,2-bonding, 1,13-bonding, and 3,13-bonding for β-farnesene. Only one of these bonding forms may be present, or two or more may be present. Note that the carbon position numbers of β-farnesene are assigned in the following order.

[0049]

Chemical formula

[0050] (Vinyl bond amount of polymer block (B)) When the structural unit constituting the polymer block (B-1) is a butadiene unit or a mixture unit of butadiene and isoprene, the 1,2-bond of butadiene, the 1,2-bond and 3,4-bond of isoprene are regarded as vinyl bonds, and the content of the vinyl bond unit is defined as the vinyl bond amount. Also, when the structural unit constituting the polymer block (B-2) is a β-farnesene unit or a mixture unit of butadiene and β-farnesene, the 1,2-bond of butadiene, the 1,2-bond and 3,13-bond of β-farnesene are regarded as vinyl bonds, and the content of the vinyl bond unit is defined as the vinyl bond amount.

[0051] In the above component (x), from the viewpoint of increasing Tg, the vinyl bond amount in the polymer block (B-1) is preferably 50 mol% or more, more preferably 57 mol% or more, still more preferably 65 mol% or more, even more preferably 70 mol% or more, and particularly preferably 75 mol% or more. Also, although not particularly limited, the upper limit value of the vinyl bond amount in the polymer block (B-1) may be 95 mol% or less, or 90 mol% or less, from the viewpoint of ease of production. In other words, the vinyl bond amount in the polymer block (B-1) is preferably 50 to 95 mol%.

[0052] In the above component (y), from the viewpoint of flexibility at low temperatures, the vinyl bond amount in the polymer block (B-2) is preferably 1 to 50 mol%, more preferably 3 to 30 mol%, and still more preferably 5 to 20 mol%. The vinyl bond amount is a value calculated by 1 1H-NMR measurement according to the method described in the examples.

[0053] The weight-average molecular weight of the polymer block (B) is preferably from 15,000 to 800,000, more preferably from 20,000 to 600,000, still more preferably from 30,000 to 400,000, particularly preferably from 50,000 to 250,000, and most preferably from 70,000 to 200,000 in the state before hydrogenation, from the viewpoint of vibration damping properties and the like. When the block copolymers (X0) and (Y0) each contain a plurality of polymer blocks (B), the weight-average molecular weight (Mw) of the above polymer block (B) is the total weight-average molecular weight (Mw) of the plurality of polymer blocks (B).

[0054] The block copolymers (X0) and (Y0) only need to have at least one of the above polymer blocks (B). When the block copolymers (X0) and (Y0) have two or more polymer blocks (B), these polymer blocks (B) may be the same or different.

[0055] In the above components (x) and (y), it is preferable that the content of the structural unit derived from the aromatic vinyl compound in the polymer block (B) is small, and it is desirable that the structural unit is not contained. When the polymer block (B) contains a structural unit derived from an aromatic vinyl compound, the vibration damping property may be reduced. From the above viewpoints, the content of the structural unit derived from the aromatic vinyl compound in the polymer block (B) is preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0% by mass.

[0056] (Bonding mode of polymer block (A) and polymer block (B)) As long as the polymer block (A) and the polymer block (B) are bonded, the bonding form thereof is not limited, and any of a linear form, a branched form, a radial form, or a combination of two or more of these forms may be used. Among them, the bonding form of the polymer block (A) and the polymer block (B) is preferably linear. For example, when the polymer block (A) is represented by "A" and the polymer block (B) is represented by "B", a diblock copolymer represented by A-B, a triblock copolymer represented by A-B-A or B-A-B, a tetrablock copolymer represented by A-B-A-B, a pentablock copolymer represented by A-B-A-B-A or B-A-B-A-B, a (A-B)nX type copolymer (X represents a coupling agent residue, and n represents an integer of 3 or more), etc. can be mentioned. Among them, a linear triblock copolymer or a diblock copolymer is preferable, and an A-B-A type triblock copolymer is preferably used from the viewpoints of flexibility, ease of production, etc. Here, in this specification, when the same kind of polymer blocks are linearly bonded via a bifunctional coupling agent or the like, the entire bonded polymer blocks are treated as one polymer block. Accordingly, including the above examples, the polymer blocks that should originally be strictly represented as Y-X-Y (X represents a coupling residue) are represented as Y as a whole, except when it is necessary to particularly distinguish them from the single polymer block Y. In this specification, since this type of polymer block containing a coupling agent residue is treated as described above, for example, a block copolymer that contains a coupling agent residue and should originally be strictly represented as A-B-X-B-A (X represents a coupling agent residue) is represented as A-B-A and is treated as an example of a triblock copolymer.

[0057] As long as the object and effect of the present invention are not impaired, the above block copolymer may have one or two or more functional groups such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain and / or at the molecular end, or may have no functional group.

[0058] (Polymer block composed of other monomers) In addition to the polymer blocks (A) and (B), the block copolymers (X0) and (Y0) may contain polymer blocks composed of other monomers as long as the effects of the present invention are not inhibited. Examples of such other monomers include unsaturated hydrocarbon compounds such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene; functional group-containing unsaturated compounds such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, maleic acid, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethane sulfonic acid, 2-methacryloylethane sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamido-2-methylpropane sulfonic acid, vinyl sulfonic acid, vinyl acetate, methyl vinyl ether, etc. These may be used alone or in combination of two or more. When the block copolymers (X0) and (Y0) have other polymer blocks, the content thereof is preferably 10% by mass or less, more preferably 5% by mass or less.

[0059] <Hydrogenated product of block copolymer> The hydrogenated product of the block copolymer is obtained by hydrogenating the block copolymer. In this specification, the hydrogenated product of the block copolymer may also be referred to as "hydrogenated block copolymer". The block copolymer (X0) for obtaining the hydrogenated product (X) of the block copolymer and the block copolymer (Y0) for obtaining the hydrogenated product (Y) of the block copolymer both have structural units derived from the polymer block (A) and structural units derived from the polymer block (B), and there is no change in their main skeletons even after hydrogenation. Therefore, the descriptions of the constituent components, their usage ratios, and properties, etc. of the above-mentioned block copolymer (X0) and block copolymer (Y0) are common to the hydrogenated product (X) of the block copolymer and the hydrogenated product (Y) of the block copolymer unless otherwise specified.

[0060] The hydrogenation rate of the polymer block (B) is preferably 85 mol% or more. That is, it is preferable that 85 mol% or more of the carbon-carbon double bonds possessed by the polymer block (B) are hydrogenated. When the hydrogenation rate of the polymer block (B) is high, it is excellent in vibration damping properties, heat resistance, and weather resistance at a wide range of temperatures. From the same viewpoint, the hydrogenation rate of the polymer block (B) is more preferably 86 mol% or more, still more preferably 87 mol% or more, and even more preferably 88 mol% or more. There is no particular limitation on the upper limit value of the hydrogenation rate, but the upper limit value may be 99 mol% or 98 mol%. In other words, the hydrogenation rate of the polymer block (B) is preferably 85 to 99 mol%.

[0061] From the same viewpoint, the hydrogenation rate of the component (x) is preferably 85 mol% or more, more preferably 86 mol% or more, still more preferably 87 mol% or more, and even more preferably 88 mol% or more, and the upper limit value may be, for example, 99 mol% or less, or 98 mol% or less. In other words, the hydrogenation rate of the component (x) is preferably 85 to 99 mol%.

[0062] Also, from the same perspective, when component (y) is a hydrogenated product (Y) of a block copolymer, the hydrogenation rate of component (y) which is the hydrogenated product is preferably 85 mol% or more, more preferably 87 mol% or more, still more preferably 88 mol% or more, even more preferably 89 mol% or more, and the upper limit is, for example, 99 mol% or less, and may be 98 mol% or less. In other words, when component (y) is a hydrogenated product (Y) of a block copolymer, the hydrogenation rate is preferably 85 to 99 mol%.

[0063] Note that the above hydrogenation rate is a value obtained by measuring the content of carbon-carbon double bonds in the structural units derived from the conjugated diene compound in the polymer block (B) by 1 1H-NMR measurement, and more specifically, it is a value measured according to the method described in the examples.

[0064] As long as the object and effect of the present invention are not impaired, the above hydrogenated block copolymer may have one or more functional groups such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain and / or at the molecular terminal, or may have no functional group.

[0065] (Physical properties of block copolymer and hydrogenated block copolymer) Based on JIS K7244-10:2005, the peak top intensity of the loss tangent tanδ of the block copolymer (X0) or the hydrogenated product (X) of the block copolymer measured under the conditions of a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of -30 to +50°C, a heating rate of 3°C / min, and a shear mode indicates that the larger the numerical value, the better the physical properties such as vibration damping property at that temperature. If it is 1.0 or more, sufficient vibration damping property can be obtained in the actual use environment. The peak top intensity of the above tanδ is preferably 1.0 or more, more preferably 1.3 or more, still more preferably 1.5 or more, and even more preferably 1.9 or more. In addition, when the resin composition obtained by mixing component (x) and component (y) exhibits the desired physical properties, the peak top intensity of tanδ of at least the block copolymer (X0) or its hydrogenated product (X) may be outside the above range. The peak top intensity of the loss tangent tanδ of the block copolymer (Y0) or the hydrogenated product (Y) of the block copolymer measured by the above procedure indicates that the larger the numerical value, the better the physical properties such as vibration damping properties at that temperature. If it is 0.5 or more, sufficient vibration damping properties can be obtained in the actual use environment. The peak top intensity of the above tanδ is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.2 or more, even more preferably 1.5 or more, and particularly preferably 1.9 or more. In addition, when the resin composition obtained by mixing component (x) and component (y) exhibits the desired physical properties, the peak top intensity of tanδ of at least the block copolymer (Y0) or its hydrogenated product (Y) may be outside the above range.

[0066] Also, in accordance with JIS K7244-10:2005, the peak top temperature of the loss tangent tanδ of the hydrogenated product (X) of the block copolymer, measured under the conditions of a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of -30 to +50°C, a heating rate of 3°C / min, and a shear mode, is preferably +45°C or less, more preferably +40°C or less, still more preferably +35°C or less, from the viewpoint of ease of manufacture. Also, from the viewpoint of vibration damping properties near room temperature, it is preferably -30°C or more, more preferably -20°C or more, still more preferably -10°C or more, and particularly preferably 0°C or more. In other words, the peak top temperature of tanδ of the hydrogenated product (X) of the block copolymer is preferably -30 to +45°C. The peak top temperature of the loss tangent tanδ of the block copolymer (Y0) or its hydrogenated product (Y) measured by the above procedure is preferably -30°C or lower, more preferably -40°C or lower, still more preferably -45°C or lower, from the viewpoint of flexibility at low temperatures. There is no particular limitation on the lower limit of the peak top temperature of tanδ of the block copolymer (Y0) or its hydrogenated product (Y), but from the viewpoint of ease of production, it is, for example, -70°C or higher. In other words, the peak top temperature of tanδ of the block copolymer (Y0) or its hydrogenated product (Y) is preferably -70 to -30°C.

[0067] Note that the peak top intensity of tanδ is the value of tanδ when the peak of tanδ is at its maximum. Also, the peak top temperature of tanδ is the temperature when the peak of tanδ is at its maximum. The peak top temperature and peak top intensity of tanδ of the hydrogenated block copolymer are specifically measured by the method described in the examples. In order to make these values within the above ranges, for example, the type and ratio of the conjugated diene compound which is the monomer for forming the polymer block (B) can be adjusted, or the amount of vinyl bonds in the polymer block (B) can be adjusted.

[0068] The melt flow rate of the hydrogenated product (X) of the block copolymer as the component (x) at 230°C and a load of 2.16 kg measured in accordance with JIS K 7210:2014 is preferably 25 g / 10 min or lower, more preferably 20 g / 10 min or lower, still more preferably 15 g / 10 min or lower, even more preferably 10 g / 10 min or lower, even more preferably 7 g / 10 min or lower, particularly preferably 5 g / 10 min or lower, from the viewpoint of ease of production, and preferably 0.5 g / 10 min or higher, more preferably 0.7 g / 10 min or higher, still more preferably 0.9 g / 10 min or higher, from the viewpoint of the moldability of the resin composition. In other words, the above melt flow rate of the hydrogenated product (X) of the block copolymer is preferably 0.5 to 25 g / 10 min. The melt flow rate of the block copolymer (Y0) or its hydrogenated product (Y), which is component (y), measured at 230 °C and a load of 2.16 kg in accordance with JIS K 7210:2014, is preferably 0 g / 10 min or more, more preferably 3 g / 10 min or more, still more preferably 5 g / 10 min or more, even more preferably 10 g / 10 min or more, particularly preferably 30 g / 10 min or more, and most preferably 40 g / 10 min or more, from the viewpoint of the moldability of the resin composition. Also, from the viewpoint of ease of production, it is preferably 300 g / 10 min or less, more preferably 90 g / 10 min or less, still more preferably 80 g / 10 min or less, and even more preferably 70 g / 10 min or less. In other words, the melt flow rate of the block copolymer (Y0) or its hydrogenated product (Y) is preferably 0 to 300 g / 10 min.

[0069] (Other resin components) The resin composition according to an embodiment of the present invention may contain, as the other resin component (z1), one or more selected from the group consisting of styrene resins, polyphenylene ethers, polyester resins, polycarbonates, polyacetals, polyamides, polyarylene sulfides, polyarylates, polyimides, polyether ether ketones, and liquid crystal polyesters.

[0070] The above resin composition may contain, as resin components other than the above components (x), (y), and (z1), hydrogenated resins such as hydrogenated coumarone-indene resins, hydrogenated rosin-based resins, hydrogenated terpene resins, and alicyclic hydrogenated petroleum resins; tackifying resins such as aliphatic resins composed of olefin and diolefin polymers; and other polymers such as hydrogenated polyisoprene, hydrogenated polybutadiene, butyl rubber, polyisobutylene, and polybutene, as long as the effects of the present invention are not impaired. When the above resin composition contains resin components other than component (x), component (y) and component (z1), although it is not particularly limited, the content of components other than component (x), component (y) and component (z1) in the composition is preferably 50% by mass or less. And in this case, the total content of component (x) and component (y) in the composition is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, most preferably 95% by mass or more from the viewpoint of vibration damping performance.

[0071] (Additive) Examples of the component (component (z2)) other than the above resin components that can be contained in the above resin composition include additives such as antioxidants, ultraviolet absorbers, light stabilizers, heat shielding materials, antiblocking agents, pigments, dyes, softeners, crosslinking agents, crosslinking aids, crosslinking accelerators, fillers, reinforcing materials, lubricants, antistatic agents, flame retardants, foaming agents, water repellents, waterproof agents, conductivity imparting agents, heat conductivity imparting agents, electromagnetic wave shielding property imparting agents, fluorescent agents, antibacterial agents, etc., but are not particularly limited thereto. These can be used alone or in combination of two or more.

[0072] Examples of the antioxidant include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, etc. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, etc. In addition, triazine-based compounds, benzophenone-based compounds, malonic ester compounds, oxalic anilide compounds, etc. can also be used. Examples of the light stabilizer include hindered amine-based light stabilizers, etc. Examples of the heat shielding material include materials containing heat shielding particles having a heat ray shielding function in a resin or glass, materials containing an organic dye compound having a heat ray shielding function, and the like. Examples of the particles having a heat ray shielding function include particles of oxides such as tin-doped indium oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, tin-doped zinc oxide, and silicon-doped zinc oxide, and particles of inorganic materials having a heat ray shielding function such as LaB6 (lanthanum hexaboride) particles. Examples of the organic dye compound having a heat ray shielding function include diimonium dyes, ammonium dyes, phthalocyanine dyes, anthraquinone dyes, polymethine dyes, benzenedithiol type ammonium compounds, thiourea derivatives, and thiol metal complexes. Examples of the antiblocking agent include inorganic particles and organic particles. Examples of the inorganic particles include oxides, hydroxides, sulfides, nitrides, halides, carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylates, silicates, titanates, borates, and hydrates thereof of elements of Group IA, Group IIA, Group IVA, Group VIA, Group VIIA, Group VIIIA, Group IB, Group IIB, Group IIIB, and Group IVB, and composite compounds and natural mineral particles centered thereon. Examples of the organic particles include fluororesins, melamine resins, styrene-divinylbenzene copolymers, acrylic resins, silicones, and crosslinked products thereof. Examples of the pigment include organic pigments and inorganic pigments. Examples of the organic pigments include azo pigments, quinacridone pigments, phthalocyanine pigments, and the like. Examples of the inorganic pigments include titanium oxide, zinc sulfide, carbon black, lead pigments, cadmium pigments, cobalt pigments, iron pigments, chromium pigments, ultramarine, and indigo. Examples of the dye include dyes such as azo dyes, anthraquinone dyes, phthalocyanine dyes, quinacridone dyes, perylene dyes, dioxazine dyes, indolinone dyes, isoindolinone dyes, quinoneimine dyes, triphenylmethane dyes, thiazole dyes, nitro dyes, and nitroso dyes. As the softening agent, known softening agents such as paraffinic hydrocarbon oils such as paraffin oil, naphthenic hydrocarbon oils, aromatic hydrocarbon oils, etc.; vegetable oils such as peanut oil, rosin, etc.; phosphate esters; low molecular weight polyethylene glycols; liquid paraffin; hydrocarbon synthetic oils such as low molecular weight polyethylene, ethylene-α-olefin copolymer oligomers, liquid polybutene, liquid polyisoprene or its hydrogenated product, liquid polybutadiene or its hydrogenated product, etc. can be used. These may be used alone or in combination of two or more.

[0073] Examples of the crosslinking agent include radical generators, sulfur and sulfur compounds. Examples of the radical generator include dialkyl monoperoxides such as dicumyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide; diperoxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, bis(t-butyldioxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(t-butylperoxy)valerate; benzoyl group-containing peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide; monoacylalkyl peroxides such as t-butylperoxybenzoate; percarbonates such as t-butylperoxyisopropyl carbonate; organic peroxides such as diacetyl peroxide, lauroyl peroxide, etc. These may be used alone or in combination of two or more. Among them, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and dicumyl peroxide are preferable from the viewpoint of reactivity. Examples of the sulfur compound include sulfur monochloride, sulfur dichloride, etc. As crosslinking agents, in addition, phenolic resins such as alkylphenol resins and brominated alkylphenol resins; combinations such as p - quinonedioxime and lead dioxide, p,p’ - dibenzoylquinonedioxime and lead sesquioxide can also be used.

[0074] As crosslinking aids, known crosslinking aids can be used. For example, polyfunctional monomers such as trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, triallyl trimellitate, triallyl 1,2,4 - benzenetricarboxylate, triallyl isocyanurate, 1,6 - hexanediol dimethacrylate, 1,9 - nonanediol dimethacrylate, 1,10 - decanediol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, divinylbenzene, glycerol dimethacrylate, 2 - hydroxy - 3 - acryloyloxypropyl methacrylate; stannous chloride, ferric chloride, organic sulfonic acids, polychloroprene, chlorosulfonated polyethylene, etc. The crosslinking aids may be used alone or in combination of two or more.

[0075] As crosslinking accelerators, for example, thiazoles such as N,N - diisopropyl - 2 - benzothiazole - sulfenamide, 2 - mercaptobenzothiazole, 2 - (4 - morpholinodithio)benzothiazole; guanidines such as diphenylguanidine, triphenylguanidine; aldehyde - amine - based reactants or aldehyde - ammonia - based reactants such as butyraldehyde - aniline reactant, hexamethylenetetramine - acetaldehyde reactant; imidazolines such as 2 - mercaptoimidazoline; thiocarbanilide, diethyl ThioThioureas such as urea, dibutylthiourea, trimethylthiourea, and diorthotolylthiourea; dibenzothiazyl disulfide; thiuram monosulfides or thiuram polysulfides such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, and pentamethylenethiuram tetrasulfide; thiocarbamates such as zinc dimethyldithiocarbamate, zinc ethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium diethyldithiocarbamate; xanthates such as zinc dibutylxanthate; zinc white, etc. The crosslinking accelerator may be used alone or in combination of two or more.

[0076] Examples of the filler and / or reinforcing material include inorganic fillers such as talc, clay, mica, calcium silicate, glass, glass hollow spheres, glass fibers, calcium carbonate, magnesium carbonate, basic magnesium carbonate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc borate, dawsonite, ammonium polyphosphate, calcium aluminate, hydrotalcite, silica, diatomaceous earth, alumina, titanium oxide, iron oxide, magnesium oxide, tin oxide, antimony oxide, barium ferrite, strontium ferrite, carbon fiber, activated carbon, carbon hollow spheres, calcium titanate, lead zirconate titanate, silicon carbide; organic fillers such as wood powder and starch; conductive fillers such as carbon black, graphite, and carbon nanotubes; and metal fillers such as silver powder, copper powder, nickel powder, tin powder, copper fiber, stainless steel fiber, aluminum fiber, and iron fiber.

[0077] There is no particular limitation on the content of the additive contained in the above resin composition, and it can be appropriately adjusted according to the type of the additive and the like. When the above resin composition contains the above additive, the content of the above additive may be, for example, 50% by mass or less, 45% by mass or less, 30% by mass or less, or 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, based on the total mass of the resin composition. In other words, the content of the above additive is, for example, 0.01 to 50% by mass based on the total mass of the resin composition. The component (z1) which is the above other resin component and the above component (z2) may be used in combination. For example, a polyolefin such as polypropylene and paraffin oil can be used in combination. In this case, since it becomes easier to widen the temperature range of tanδ showing a predetermined strength, the resin composition is more suitable for a wider range of applications.

[0078] <Physical properties of the resin composition> Various physical properties of the resin composition according to the embodiment of the present invention will be described.

[0079] (Peak top strength and temperature of tanδ) From the viewpoint of easily ensuring the vibration damping property near room temperature, the peak top strength of tanδ measured for the above resin composition under the conditions of a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of -30 to +50°C, a heating rate of 3°C / min, and a shear mode in accordance with JIS K7244-10:2005 is preferably 0.4 or more, more preferably 0.6 or more, still more preferably 0.8 or more, even more preferably 1.0 or more, and particularly preferably 1.3 or more. There is no particular limitation on the upper limit, but from the viewpoint of ease of manufacture, it is, for example, 3.0 or less. In other words, the peak top strength of tanδ measured for the above resin composition by the above procedure is preferably 0.4 to 3.0. Also, from the viewpoint of ease of production, the peak top temperature of tanδ of the above resin composition is preferably +45°C or lower, more preferably +40°C or lower, still more preferably +35°C or lower. Also, from the viewpoint of vibration damping properties near room temperature, it is preferably -30°C or higher, more preferably -20°C or higher, still more preferably -10°C or higher, even more preferably 0°C or higher, and particularly preferably 10°C or higher. In other words, The above resin composition the peak top temperature of tanδ of is preferably -30 to +45°C. The peak top strength and temperature of tanδ of the resin composition are specifically measured by the procedure described in the examples.

[0080] (Melt Flow Rate (MFR)) From the viewpoint of ease of production, the melt flow rate of the above resin composition measured at 230°C and a load of 2.16 kg in accordance with JIS K 7210:2014 is preferably 100 g / 10 min or lower, more preferably 70 g / 10 min or lower, still more preferably 50 g / 10 min or lower. Also, from the viewpoint of moldability, it is preferably 1 g / 10 min or higher, more preferably 3 g / 10 min or higher, still more preferably 5 g / 10 min or higher. In other words, the melt flow rate of the above resin composition is preferably 1 to 100 g / 10 min. The melt flow rate of the resin composition is specifically measured by the procedure described in the examples.

[0081] (Bio-based content) From the viewpoints of effective utilization of depleted resources, CO2 reduction, and ensuring vibration damping properties and moldability, the bio-based content of the above resin composition measured in accordance with ASTM D6866-20 is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, still more preferably 10 to 65% by mass, even more preferably 20 to 60% by mass, and particularly preferably 30 to 55% by mass. In the case of the crosslinked foam described later, the above bio-based content is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, still more preferably 10 to 65% by mass, even more preferably 20 to 60% by mass, and particularly preferably 30 to 55% by mass. The bio-based content is specifically measured by the procedure described in the examples.

[0082] (Shear storage modulus G’ at -20°C) The shear storage modulus G’ at -20°C, which is measured by performing a complex shear viscosity test on the resin composition under the condition of a frequency of 1 Hz in accordance with JIS K7244-10:2005, is preferably 300 MPa or less, more preferably 200 MPa or less, still more preferably 100 MPa or less, even more preferably 50 MPa or less, particularly preferably 30 MPa or less, and most preferably 20 MPa or less from the viewpoint of flexibility at low temperatures. There is no particular limitation on the lower limit of the shear storage modulus G’, but from the viewpoint of mechanical strength, it is, for example, 0.1 MPa. In other words, the shear storage modulus G’ at -20°C of the resin composition is preferably 0.1 to 300 MPa. Note that the shear storage modulus G’ is more specifically measured according to the method described in the examples.

[0083] (Morphology of the resin composition) In one aspect of the resin composition, a dispersion structure (morphology) is formed in which one of component (x) and component (y) serves as a matrix and domains in which the other of component (x) and component (y) is dispersed are formed in the matrix. Figure 1 is an example of the morphology of the resin composition and is an example of an atomic force microscope (AFM) image of the cross-section of the resin composition. In the AFM image shown in Figure 1, the dark part indicates component (x) and the bright part indicates component (y), and component (y) is dispersed as domains in the matrix of component (x). The closer the shape of the domain approaches a sphere, the greater the contribution of the matrix component to the viscoelasticity of the resin composition. For this reason, it becomes difficult for the peak top strength of tanδ to decrease due to the addition of component (y).

[0084] The average aspect ratio of the domain is preferably 1.0 to 3.0, more preferably 1.1 to 2.5, and still more preferably 1.2 to 2.0 from the viewpoint of dispersibility. In the present specification, the above average aspect ratio is a value obtained by examining the aspect ratio (length of the major axis / length of the minor axis) for 100 domains by AFM observation and calculating the average value thereof. Specifically, it is measured by the method described in the examples.

[0085] <Method for producing block copolymer> The method for producing a block copolymer (block copolymers (X0) and (Y0)) used to obtain the resin composition according to an embodiment of the present invention uses at least an aromatic vinyl compound and a conjugated diene compound as monomers and performs a polymerization reaction to obtain a polymer block (A) containing a structural unit derived from the aromatic vinyl compound and a polymer block (B) containing a structural unit derived from the conjugated diene compound. It has a first step of obtaining a block copolymer containing the same.

[0086] In the above first step, the block copolymer can be produced, for example, by a solution polymerization method, an emulsion polymerization method, a solid phase polymerization method, or the like. Among them, the solution polymerization method is preferable. For example, known methods such as anionic polymerization, cationic polymerization, and other ionic polymerization methods, and radical polymerization methods can be applied. Among them, the anionic polymerization method is preferable. In the anionic polymerization method, an aromatic vinyl compound and a conjugated diene compound are sequentially added in the presence of a solvent, an anionic polymerization initiator, and, if necessary, a Lewis base to obtain a block copolymer, and a coupling agent is added and reacted if necessary. Here, when producing the block copolymer (Y0), at least β-farnesene is used as the conjugated diene compound.

[0087] Examples of the organolithium compound that can be used as the polymerization initiator for anionic polymerization include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, and the like. Examples of the dilithium compound that can be used as the polymerization initiator include naphthalenedilithium, dilithiohexylbenzene, and the like.

[0088] Examples of the coupling agent include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, phenyl benzoate, methyldimethoxysilane, trimethoxysilane, tetramethoxysilane, methyltrimethoxysilane, isobutyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and the like. The amounts of these polymerization initiators and coupling agents used are appropriately determined according to the desired weight average molecular weight of the target block copolymer. Usually, initiators such as alkyllithium compounds and dilithium compounds are preferably used in a proportion of 0.01 to 0.2 parts by mass per 100 parts by mass in total of monomers such as aromatic vinyl compounds and conjugated diene compounds used for polymerization. When a coupling agent is used, it is preferably used in a proportion of 0.001 to 0.8 parts by mass per 100 parts by mass in total of the above monomers.

[0089] The solvent is not particularly limited as long as it does not adversely affect the anionic polymerization reaction. Examples thereof include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane; and aromatic hydrocarbons such as benzene, toluene, and xylene. The polymerization reaction is usually carried out at a temperature of 0 to 100°C, preferably 10 to 70°C, for 0.5 to 50 hours, preferably 1 to 30 hours.

[0090] In addition, by adding a Lewis base as a cocatalyst (vinylating agent) during the polymerization, the contents of 3,4-bonds, 1,2-bonds, and 3,13-bonds (vinyl bond amount) in the polymer block (B) can be increased. Examples of the Lewis base include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane (DTHFP); glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; amines such as triethylamine, N,N,N’,N’-tetramethylenediamine, N,N,N’,N’-tetramethylethylenediamine (TMEDA), N-methylmorpholine; metal salts such as sodium or potassium salts of aliphatic alcohols such as sodium t-butyrate, sodium t-amylate or sodium isopentylate, or sodium or potassium salts of alicyclic alcohols such as dialkylsodium cyclohexanolate, for example, sodium mentholate; and the like. Among the above Lewis bases, from the viewpoints of vibration damping properties and thermal stability, it is preferable to use tetrahydrofuran and DTHFP. Further, since a high vinyl bond content can be obtained, a high hydrogenation rate can be easily achieved without using an excessive amount of hydrogenation catalyst, and better vibration damping properties and thermal stability can be realized simultaneously, it is more preferable to use DTHFP. These Lewis bases can be used alone or in combination of two or more.

[0091] The addition amount of the Lewis base is determined by how much the vinyl bond content of the conjugated diene compound unit constituting the polymer block (B) is controlled. Therefore, although there is no strict limitation on the addition amount of the Lewis base, it is preferably used in the range of usually 0.1 to 1,000 moles, preferably 1 to 100 moles, per gram atom of lithium contained in the alkyllithium compound or dilithium compound used as the polymerization initiator. Of course, it is also possible to carry out the above polymerization reaction without adding a Lewis base. In particular, from the viewpoint of easily lowering the glass transition temperature of the hydrogenated product of the block copolymer, it is preferable not to add a Lewis base in the first step.

[0092] In the above first step, after polymerization, active hydrogen compounds such as alcohols, carboxylic acids, and water are added to terminate the polymerization reaction.

[0093] <Process for producing hydrogenated block copolymer> The method for producing the hydrogenated block copolymers (X) and (Y) according to the embodiment of the present invention includes the above first step and a second step of hydrogenating the block copolymer (X0) or (Y0).

[0094] In the above second step, for example, a hydrogenated copolymer is obtained by performing a hydrogenation reaction (hydrogenation reaction) in the presence of a hydrogenation catalyst in an inert organic solvent. The hydrogenation reaction can be carried out with a hydrogen pressure of 0.1 to 20 MPa, preferably 0.5 to 15 MPa, more preferably 0.5 to 5 MPa, a reaction temperature of 20 to 250 °C, preferably 50 to 180 °C, more preferably 70 to 180 °C, and a reaction time of usually 0.1 to 100 hours, preferably 1 to 50 hours. As the hydrogenation catalyst, from the viewpoint of performing the hydrogenation reaction of the polymer block (B) while suppressing the nuclear hydrogenation of the above aromatic vinyl compound, for example, Raney nickel; a Ziegler catalyst composed of a combination of a transition metal compound and an alkylaluminum compound, an alkyllithium compound, etc.; a metallocene catalyst, etc. can be mentioned. From the same viewpoint as above, among them, a Ziegler catalyst is preferable, a Ziegler catalyst composed of a combination of a transition metal compound and an alkylaluminum compound is more preferable, and a Ziegler catalyst composed of a combination of a nickel compound and an alkylaluminum compound (Al / Ni-based Ziegler catalyst) is even more preferable.

[0095] In particular, as described above, when DTHFP is used as a Lewis base in the first step, it is easy to obtain a hydrogenated block copolymer having a high Tg as the hydrogenated block copolymer obtained through the second step. Therefore, a hydrogenated block copolymer (X) having a high Tg suitable for component (x) can be obtained.

[0096] The hydrogenated block copolymer thus obtained can be obtained by pouring the polymerization reaction solution into methanol or the like, filtering it after stirring, and drying it by heating or under reduced pressure, or by pouring the polymerization reaction solution into hot water together with steam, subjecting it to so-called steam stripping to azeotropically remove the solvent, and then drying it by heating or under reduced pressure.

[0097] [Method for producing resin composition] There are no particular restrictions on the method for producing the above resin composition, and known methods can be employed. For example, the hydrogenated product (X) of the above block copolymer which is component (x) and the above block copolymer Body( Y0) or its hydrogenated product (Y) are mixed using a mixer such as a Henschel mixer, V blender, ribbon blender, tumbler blender, or conical blender, or after the mixing, they are melt-kneaded using a single-screw extruder, twin-screw extruder, kneader, etc. to produce the resin composition. Even when the above resin composition contains additives etc. as described above in addition to component (x) and component (y), the above resin composition can be produced by mixing the above additives etc. with component (x) and component (y) using the above mixer or by melt-kneading with the above apparatus after mixing.

[0098] [Foamable composition and crosslinked foam] The foamable composition according to an embodiment of the present invention contains the above component (x) and component (y), a resin composition (i) that satisfies the above conditions [1] to [4], at least one olefin-based polymer (ii) selected from the group consisting of ethylene-propylene-diene copolymer rubber, ethylene-vinyl acetate copolymer, and polyethylene-based resin, a crosslinking agent (iii), and a foaming agent (iv). Further, the crosslinked foam according to an embodiment of the present invention is a crosslinked foam of the above foamable composition.

[0099] Examples of the above olefin polymer (ii) include at least one olefin polymer selected from the group consisting of ethylene-propylene-diene copolymer (hereinafter sometimes abbreviated as "EPDM") rubber, ethylene-vinyl acetate copolymer (hereinafter sometimes abbreviated as "EVA"), and polyethylene-based resin. As the ethylene-propylene-diene copolymer rubber, usable dienes include chain non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,6-heptadiene, and 7-methyl-1,6-octadiene; cyclohexadiene, di Cyclo cyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, and other cyclic non-conjugated dienes; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 1,3,7-octatriene, 1,4,9-decatriene, and other trienes.

[0100] The ethylene-vinyl acetate copolymer (EVA) is not particularly limited, but the content of vinyl acetate is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass based on the total mass of EVA. When the content of vinyl acetate in EVA is low, the product tends to be hard. When the content of vinyl acetate in EVA is high, it is not sufficiently crosslinked, and the mechanical strength of the crosslinked foam tends to be insufficient. If the content of vinyl acetate in EVA is 5 to 45% by mass, the crosslinked foam obtained from the foaming composition containing the above resin composition (i) and the olefin polymer has appropriate flexibility, good vibration damping property, sound insulation property, gas permeability, adhesiveness to other members such as panels, can achieve weight reduction, and can maintain mechanical properties such as breaking strength. Also, the melt flow rate (MFR) measured in accordance with JIS K7210:2014 for EVA is preferably 0.3 g / 10 min or more, more preferably 0.5 to 80.0 g / 10 min, still more preferably 1.0 to 50.0 g / 10 min, and particularly preferably 1.2 to 30.0 g / 10 min. The MFR is measured under the conditions of 190°C and a load of 21.18 N. When the melt flow rate of EVA is within the above range, the moldability becomes good.

[0101] In this specification, the polyethylene-based resin means a polyethylene-based resin excluding those containing an ethylene-vinyl acetate copolymer. Examples of the polyethylene-based resin include homopolymers of ethylene such as high-density polyethylene, medium-density polyethylene, and low-density polyethylene; ethylene-based copolymers such as ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / hexene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, ethylene / 4-methylpentene-1 copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ethylene / methacrylic acid copolymer, and ethylene / methacrylic acid ester copolymer. From the viewpoint of appropriate flexibility of the crosslinked foam obtained from the above resin composition (i) and the foaming composition containing an olefin-based polymer, the content of the structural unit derived from ethylene in the polyethylene-based resin is preferably 30 to 100 mol%, more preferably 40 to 95 mol%, still more preferably 50 to 90 mol% based on all the structural units of the polyethylene-based resin.

[0102] The content ratio of the olefin polymer (ii) to the resin composition (i) in the above-mentioned foaming composition [olefin polymer (ii) / resin composition (i)] is preferably 1 / 99 to 99 / 1 by mass ratio. The mass ratio [olefin resin (ii) / resin composition (i)] is more preferably 5 / 95 to 95 / 5, still more preferably 10 / 90 to 80 / 20, even more preferably 10 / 90 to 60 / 40, and particularly preferably 10 / 90 to 45 / 55. Within this range, the cross-linked foam obtained from the foaming composition containing the resin composition (i) and the olefin polymer (ii) has good vibration damping properties, sound insulation properties, gas permeability, adhesiveness to other members such as panels, can achieve weight reduction, and can maintain mechanical properties such as breaking strength. In the above-mentioned foaming composition (100% by mass), the total content of the resin composition (i) and the olefin polymer (ii) is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0103] (Cross-linking agent) Examples of the cross-linking agent (iii) for obtaining the cross-linked foam include radical generators, sulfur and sulfur compounds. Examples of radical initiators include dialkyl monoperoxides such as dicumyl peroxide, di-t-butyl peroxide, and t-butyl cumyl peroxide; diperoxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, bis(t-butyl-dioxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, and n-butyl-4,4-bis(t-butylperoxy)valerate; diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, and 2,4-dichlorobenzoyl peroxide; monoacyl alkyl peroxides such as t-butyl peroxybenzoate; percarbonates such as t-butyl peroxyisopropyl carbonate; and organic peroxides such as diacetyl peroxide and lauroyl peroxide. These may be used alone or in combination of two or more. Among them, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and dicumyl peroxide are preferred from the viewpoint of reactivity. When using a radical initiator, its content is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, still more preferably 0.1 to 5 parts by mass, and particularly preferably 0.1 to 3 parts by mass, based on 100 parts by mass in total of the above resin composition (i) and the olefin polymer (ii).

[0104] Examples of sulfur compounds include sulfur monochloride and sulfur dichloride. When containing sulfur or a sulfur compound, its content is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 1 to 10 parts by mass, based on 100 parts by mass in total of the above resin composition (i) and the olefin polymer (ii).

[0105] As other crosslinking agents (iii) for obtaining the crosslinked foam, phenolic resins such as alkylphenol resins and brominated alkylphenol resins; combinations of p - quinonedioxime and lead dioxide, p,p’ - dibenzoylquinonedioxime and lead sesquioxide, etc. can also be used.

[0106] In addition to the crosslinking agent (iii), the above - mentioned foaming composition may contain a crosslinking aid and a crosslinking accelerator. As the crosslinking aid, known crosslinking aids can be used. For example, polyfunctional monomers such as trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, triallyl trimellitate, triallyl 1,2,4 - benzenetricarboxylate, triallyl isocyanurate, 1,6 - hexanediol dimethacrylate, 1,9 - nonanediol dimethacrylate, 1,10 - decanediol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, divinylbenzene, glycerol dimethacrylate, 2 - hydroxy - 3 - acryloyloxypropyl methacrylate; stannous chloride, ferric chloride, organic sulfonic acids, polychloroprene, chlorosulfonated polyethylene, etc. Among them, triallyl isocyanurate is preferable. The crosslinking aid may be used alone or in combination of two or more. When containing the crosslinking aid, its content is preferably 0.1 - 40 parts by mass, more preferably 0.5 - 20 parts by mass, and still more preferably 2 - 20 parts by mass with respect to 100 parts by mass in total of the above - mentioned resin composition (i) and the olefin - based polymer (ii).

[0107] Examples of the crosslinking accelerator include thiazoles such as N,N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, 2-(4-morpholinodithio)benzothiazole; guanidines such as diphenylguanidine, triphenylguanidine; aldehyde-amine reaction products or aldehyde-ammonia reaction products such as butyraldehyde-aniline reaction product, hexamethylenetetramine-acetaldehyde reaction product; imidazolines such as 2-mercaptoimidazoline; thiocarbanilide, diethyl Thio thioureas such as urea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; dibenzothiazyl disulfide; thiuram monosulfides or thiuram polysulfides such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, pentamethylenethiuram tetrasulfide; thiocarbamates such as zinc dimethyldithiocarbamate, zinc ethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium diethyldithiocarbamate; xanthates such as zinc dibutylxanthate; zinc white, etc. The crosslinking accelerator may be used alone or in combination of two or more kinds.

[0108] (Blowing agent) Examples of the foaming agent (iv) include inorganic foaming agents such as ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, sodium borohydride, and azides; N-nitroso compounds such as N,N'-dinitrosopentamethylenetetramine and N,N'-dimethyl-N,N'-dinitrosoterephthalamide; azo compounds such as azobisisobutyronitrile, azodicarbonamide, and barium azodicarboxylate; halogenated alkanes such as trichloromonofluoromethane and dichloromonofluoromethane; sulfonylhydrazide compounds such as paratoluenesulfonylhydrazide, diphenylsulfone-3,3'-disulfonylhydrazide, 4,4'-oxybis(benzenesulfonylhydrazide), and allylbis(sulfonylhydrazide); sulfonyl semicarbazide compounds such as p-toluenesulfonyl semicarbazide and 4,4'-oxybis(benzenesulfonyl semicarbazide); triazole compounds such as 5-morpholyl-1,2,3,4-thiatriazole; and organic foaming agents such as heat-expandable compounds such as isobutane and pentane, and heat-expandable fine particles encapsulated in microcapsules made of thermoplastic resins such as vinylidene chloride, acrylonitrile, acrylate esters, and methacrylate esters. These may be used alone or in combination of two or more.

[0109] The content of the foaming agent (iv) is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 25 parts by mass, still more preferably 0.5 to 20 parts by mass, and particularly preferably 0.5 to 10 parts by mass with respect to 100 parts by mass in total of the above resin composition (i) and the olefin polymer (ii).

[0110] Examples of the foaming aid include stearic acid and its salts; zinc compounds such as zinc oxide and zinc acetate; and urea compounds. When the foaming aid is contained, its content is preferably 0.01 to 10 equivalents, more preferably 0.05 to 5 equivalents, still more preferably 0.1 to 2 equivalents, and particularly preferably 0.3 to 1.8 equivalents in terms of the mass ratio to the foaming agent (iv).

[0111] (Other components) The above foaming composition may further contain other thermoplastic polymers. Examples of other thermoplastic polymers include polyphenylene ether-based resins; polyamide-based resins such as polyamide 6, polyamide 6.6, polyamide 6.10, polyamide 11, polyamide 12, polyamide 6.12, polyhexamethylenediamine terephthalamide, polyhexamethylenediamine isophthalamide, and xylene group-containing polyamides; polyester-based resins such as polyethylene terephthalate and polybutylene terephthalate; acrylic-based resins such as polymethyl acrylate and polymethyl methacrylate; polyoxymethylene-based resins such as polyoxymethylene homopolymers and polyoxymethylene copolymers; styrene-based resins such as styrene homopolymers, acrylonitrile-styrene resins, and acrylonitrile-butadiene-styrene resins; polycarbonate resins; styrene-based elastomers such as styrene / butadiene copolymer rubbers and styrene / isoprene copolymer rubbers, and their hydrogenated products or modified products; natural rubber; chloroprene rubber; acrylic rubber; acrylonitrile-butadiene rubber; epichlorohydrin rubber; silicone rubber; chlorosulfonated polyethylene; urethane rubber; polyurethane-based elastomers; polyamide-based elastomers; polyester-based elastomers; and soft vinyl chloride resins.

[0112] The above foaming composition may further contain various additives as long as the effects of the present invention are not impaired. Examples of such additives include processing aids, reinforcing materials, fillers, plasticizers, cell formers, heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, lubricants, antistatic agents, antibacterial agents, antifungal agents, dispersants, and colorants.

[0113] The above foaming composition may contain a processing aid as needed. The processing aid exhibits effects such as improving processability and promoting the dispersion of fillers. Examples of the processing aid include fatty acid amides. When a processing aid is contained, the content of the processing aid in the above foaming composition is usually 0.1 to 5 parts by mass, preferably 0.5 to 4 parts by mass, based on 100 parts by mass in total of the above resin composition (i) and the olefin polymer (ii).

[0114] Examples of the reinforcing material and / or filler include those exemplified as the additives that can be added to the above resin composition (i). When a reinforcing material and / or filler is contained, the content of the reinforcing material and / or filler in the above foaming composition is usually 10 to 200 parts by mass, preferably 20 to 180 parts by mass, more preferably 30 to 160 parts by mass, based on 100 parts by mass in total of the above resin composition (i) and the olefin polymer (ii). When the content of the reinforcing material and / or filler is within the above range, the moldability is good, and the mechanical properties such as the breaking strength of the crosslinked foam obtained from the above foaming composition can be maintained.

[0115] Examples of the plasticizer include petroleum-based process oils such as paraffinic process oil and naphthenic process oil; aromatic process oil; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; ester-based plasticizers such as di-2-ethylhexyl phthalate, dihexyl phthalate, dinonyl phthalate, di-2-ethylhexyl adipate, dioctyl adipate, and dinonyl adipate; white oil; mineral oil; vegetable oil-based plasticizers such as peanut oil and rosin; liquid paraffin; and synthetic plasticizers such as liquid co-oligomers of ethylene and α-olefin. When a plasticizer is contained, its content is preferably 0.5 to 200 parts by mass, more preferably 0.5 to 100 parts by mass, still more preferably 1 to 50 parts by mass, particularly preferably 1.5 to 25 parts by mass, and most preferably 1.5 to 10 parts by mass, based on 100 parts by mass of the total amount of the above foaming composition.

[0116] Examples of the light stabilizer, ultraviolet absorber, and antioxidant include those exemplified as the additives that can be added to the above resin composition (i).

[0117] When containing any one or two or more of a light stabilizer, an ultraviolet absorber, and an antioxidant, the content is usually 0.01 to 10.0 parts by mass, preferably 0.3 to 7.0 parts by mass, more preferably 0.5 to 5.0 parts by mass with respect to a total of 100 parts by mass of the above resin composition (i) and the olefin polymer (ii). When the total content of the light stabilizer, the ultraviolet absorber, and the antioxidant is within the above range, it is preferable because no precipitate (bloom) is generated on the surface of the obtained crosslinked foam and no vulcanization inhibition occurs.

[0118] [Crosslinking method] In the above foaming composition, it is preferable that the resin compositions (i) with each other, the resin composition (i) and the olefin polymer (ii), or the olefin polymers (ii) with each other are crosslinked. Examples of the crosslinking method include a method of appropriately adding a crosslinking agent, a crosslinking aid, and a crosslinking accelerator to the resin composition (i) and the olefin polymer (ii) and kneading them (crosslinking method 1), a resin crosslinking method (crosslinking method 2), a quinoid crosslinking method (crosslinking method 3), a method using active energy rays (crosslinking method 4), and the like.

[0119] <Regarding crosslinking method 1> In the above foaming composition for obtaining the crosslinked foam of the present invention, by appropriately adding a crosslinking agent, a crosslinking aid, and a crosslinking accelerator to the resin composition (i) and the olefin polymer (ii) and kneading them, the polymer block (B) of the resin composition (i) and the olefin polymer (ii) can be crosslinked. For example, together with a crosslinking agent such as the radical generator, if necessary, a crosslinking aid such as the polyfunctional monomer and a crosslinking accelerator such as dibenzothiazyl disulfide and tetramethylthiuram disulfide (so-called disulfide-based compounds) may be used. When crosslinking is carried out by such a method, for example, there is a method of melt-kneading the above-mentioned foaming composition containing a radical generator and, if necessary, another thermoplastic polymer under heating. The heating temperature is preferably 100 to 230°C. The melt-kneading can be carried out batchwise or continuously using devices such as an extruder, a kneader, a roll, or a plastograph. The crosslinking reaction may proceed through such a melt-kneading step. Also, when producing a crosslinked foam, for example, the foaming reaction and the crosslinking reaction may proceed simultaneously. In that case, the heating temperature during the above-mentioned melt-kneading can be set at a temperature lower than the decomposition temperature of the foaming agent.

[0120] When sulfur or a sulfur compound is used as the crosslinking agent, it is extremely preferable to use a crosslinking accelerator such as thiazoles, guanidines, butyraldehyde-aniline reactants, hexamethylenetetramine-acetaldehyde reactants, aldehyde-amine reactants, thiurams, or dithiocarbamate salts in combination. When crosslinking is carried out by such a method, the crosslinking agent, crosslinking accelerator, etc. are kneaded using mixers such as rolls or Banbury mixers, preferably at 50 to 250°C (more preferably 80 to 200°C), and then preferably maintained at 60°C or higher (more preferably 90 to 250°C) for usually 1 minute to 2 hours (more preferably 5 minutes to 1 hour) to form crosslinks.

[0121] <Regarding Crosslinking Method 2> In the crosslinking method by the resin crosslinking method, phenolic resins such as alkylphenol resins and brominated alkylphenol resins are used as the crosslinking agent, and stannous chloride, ferric chloride, organic sulfonic acids, polychloroprene, or chlorosulfonated polyethylene are used as the crosslinking aid. When crosslinking is carried out by such a method, the crosslinking temperature is preferably 100 to 250°C, more preferably 130 to 220°C. When resin crosslinking is carried out, it is extremely preferable to use a crosslinking accelerator in combination.

[0122] <Regarding Crosslinking Method 3> In the crosslinking method by the quinoid crosslinking method, combinations such as p - quinone dioxime and lead dioxide, p,p'-dibenzoyl quinone dioxime and lead sesquioxide are used as crosslinking agents. When crosslinking is carried out by such a method, the crosslinking temperature is preferably 90 - 250 °C, more preferably 110 - 220 °C. When carrying out quinoid crosslinking, it is preferable to use a crosslinking accelerator in combination.

[0123] <Regarding Crosslinking Method 4> Examples of the active energy rays that can be used in the crosslinking method by active energy rays include particle rays, electromagnetic waves, and combinations thereof. Examples of particle rays include electron beams (EB), α rays, etc., and examples of electromagnetic waves include ultraviolet rays (UV), visible light, infrared rays, γ rays, X rays, etc. Among these, electron beams (EB) or ultraviolet rays (UV) are preferred. There are no particular restrictions on the irradiation time and irradiation dose, and they can be arbitrarily selected according to the degree of crosslinking.

[0124] <Manufacturing Method of Foaming Composition and Crosslinked Foam> There are no particular restrictions on the manufacturing method of the above-mentioned foaming composition. The above-mentioned resin composition (i), olefin-based polymer (ii), crosslinking agent (iii), foaming agent (iv), and other components blended as required are mixed using a mixer such as a Henschel mixer, V blender, ribbon blender, tumbler blender, conical blender, etc., or after the mixing, they can be manufactured by melt-kneading using a single-screw extruder, twin-screw extruder, kneader, roll kneader, etc. The temperature during melt-kneading can be set appropriately, but usually, it is preferably 80 - 300 °C, more preferably 100 - 250 °C.

[0125] The crosslinked foam according to this embodiment is obtained by foam molding the above foaming composition. In the present invention, as the foaming method, a chemical method of foaming by decomposition or reaction of a foaming agent, a physical method such as supercritical foaming or water foaming can be adopted, and these methods may be used in combination. Further, there is no particular limitation on the method for producing the crosslinked foam, and methods usually used for foam molding, such as injection foam molding, extrusion foam molding, and press foam molding, can be adopted. The above crosslinked foam can be obtained, for example, by injection foam molding into a mold having a cavity of a desired shape a dry blend of the above resin composition (i), olefin polymer (ii), crosslinking agent (iii), and foaming agent (iv). Alternatively, the mixture can be extrusion foam molded into an arbitrary shape such as a columnar shape, and the molded product can be cut into a predetermined size to obtain a crosslinked foam of a desired shape. Further, foam molding can also be performed using a melt-kneaded product of each component and a foaming agent when producing the above foaming composition. In this case, the kneading temperature is preferably below the decomposition temperature of the foaming agent.

[0126] There is no particular limitation on the method for producing the crosslinked foam. Examples of the method for producing the crosslinked foam include a melt foaming method and a solid phase foaming method. The melt foaming method is a method of generating bubbles in the above foaming composition heated and melted. After kneading the above foaming composition, there are methods of molding while foaming the foaming agent in the above foaming composition (two-step method), methods of continuously molding while blowing gas into an extruder (one-step method), etc. Specifically, injection foaming method, extrusion foaming method, etc. can be mentioned. The solid phase foaming method is a method of melting the above foaming composition, then solidifying it, and then generating bubbles in the solidified foaming composition. Specifically, bead foaming, press foaming, etc. can be mentioned.

[0127] The above foaming composition may be foamed after crosslinking, may be crosslinked by irradiating with an electron beam or the like after foaming, or may be crosslinked while foaming. As the cell structure of the crosslinked foam, it may be a closed-cell type in which the cells do not contact each other, or an open-cell type in which the cells partially contact each other. In this specification, an open cell refers to a cell that is connected to other cells or the outside and is continuous with each other. The closed-cell type crosslinked foam is preferable in that it is difficult for moisture to penetrate, and it has excellent mechanical properties such as waterproofness, dustproofness, and breaking strength. When the open-cell type crosslinked foam is adhered to other members using an adhesive or the like, the permeability of the adhesive is good. In particular, when the adhesive is a moisture-curing type adhesive, it is preferable because moisture can be absorbed through the open cells and firmly adhered. Also, when the open-cell type crosslinked foam is used for a dam rubber or the like that prevents the adhesive from spreading to parts other than the adhesion area, it can absorb into the open cells of the crosslinked foam and reliably prevent the unnecessary spread of the adhesive. When using a moisture-curing type adhesive or the like, it is preferable because moisture in the air can be supplied through the open cells and gas such as carbon dioxide can be released to the outside through the open cells.

[0128] <Physical properties of the crosslinked foam> The apparent density (specific gravity) of the crosslinked foam is preferably 20 to 500 kg / m 3 If the apparent density of the crosslinked foam is within this range, it can exhibit excellent vibration damping and sound insulation properties while being lightweight, and can also maintain mechanical properties such as breaking strength. Moldability and workability can also be maintained. The apparent density of the crosslinked foam is more preferably 30 to 400 kg / m 3 Even more preferably 70 to 300 kg / m 3 Even more preferably 110 to 280 kg / m 3 Particularly preferably 120 to 270 kg / m 3 It is also possible to appropriately set the apparent density according to the target frequency range and the like.

[0129] The expansion ratio of the crosslinked foam is not particularly limited, and the expansion ratio of the crosslinked foam is preferably 1.3 to 30 times. When the expansion ratio of the crosslinked foam is 1.3 to 3.0 times, it can be suitably used as exterior members such as moldings, weather strip sponges, and glass run channels for transportation equipment such as automobiles, ships, railway vehicles, and airplanes. When the expansion ratio of the crosslinked body exceeds 3.0 times and is 30 times or less, it can be suitably used as a dam rubber for transportation equipment, a dam rubber for buildings, and a heat insulating sponge.

[0130] From the viewpoint of easily ensuring the vibration damping property near room temperature, the peak top strength of tanδ of the above crosslinked foam at a measurement temperature of -30 to +50°C is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, even more preferably 0.4 or more, and particularly preferably 0.5 or more. There is no particular limitation on the upper limit, but from the viewpoint of ease of manufacture, it is, for example, 3.0 or less. The peak top strength of tanδ of the above crosslinked foam is a value measured by vibrating at a frequency of 10 Hz with a strain amount of 1% and raising the temperature at a constant speed of 2°C / min from -30°C to +50°C in accordance with JIS K6394:2007. From the viewpoint of flexibility at low temperatures, the compression storage elastic modulus E' of the above crosslinked foam at -20°C measured in accordance with JIS K6394:2007 at a frequency of 10 Hz and a strain amount of 1% is preferably 100 MPa or less, more preferably 70 MPa or less, still more preferably 50 MPa or less, and particularly preferably 40 MPa or less. There is no particular limitation on the lower limit of the compression storage elastic modulus E', but from the viewpoint of mechanical strength, it is, for example, 0.1 MPa. In other words, the compression storage elastic modulus E' of the crosslinked foam at -20°C is preferably 0.1 to 100 MPa. The compression storage elastic modulus E' is more specifically measured according to the method described in the examples.

[0131] The rebound resilience of the crosslinked foam measured in accordance with JIS K6400:2011 is preferably 30% or less, more preferably 25% or less, still more preferably 20% or less, and even more preferably 15% or less at 0°C, and preferably 30% or less, more preferably 25% or less, still more preferably 20% or less, and even more preferably 16% or less at 20°C from the viewpoint of impact absorbency.

[0132] The hardness (type C) of the crosslinked foam measured in accordance with JIS K7312:1996 is preferably 1 to 80, more preferably 3 to 70, still more preferably 5 to 60 at 0°C, and preferably 1 to 80, more preferably 3 to 70, still more preferably 5 to 60 at 20°C from the viewpoints of flexibility and mechanical strength.

Examples

[0133] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples at all.

[0134] <Measurement and Evaluation of Physical Properties of Hydrogenated Block Copolymers and Resin Compositions> The measurement of various physical properties of the hydrogenated block copolymers TPE-1 to TPE-7 obtained in the following production examples and the measurement and evaluation of various physical properties of the resin compositions obtained in the following examples and comparative examples were carried out according to the following procedures.

[0135] (Content of Polymer Block (A)) The hydrogenated block copolymer was dissolved in CDCl3 1 1H-NMR measurement [Apparatus: " AV ANCE III 400 Nano B bay" (manufactured by Bruker), measurement temperature: 30°C] was performed, and the content of the polymer block (A) was calculated from the ratio of the peak area derived from styrene to the peak area derived from conjugated diene. Also, the same measurement was performed on the samples after polymerization of each block during the production of the hydrogenated block copolymer to measure the content of aromatic vinyl compound units in the polymer block (A).

[0136] (Vinyl bond content of polymer block (B)) The block copolymer before hydrogenation was dissolved in CDCl3 1 1H-NMR measurement [Apparatus: " AV ANCE III 400 Nano B bay" (manufactured by Bruker), measurement temperature: 30 °C] was performed. From the ratio of the peak areas corresponding to the 3,4-bond units and 1,2-bond units in the isoprene structural units, the 3,13-bond units and 1,2-bond units in β-farnesene, and the 1,2-bond units in the butadiene structural units to the total peak areas of the structural units (TPE-1) derived from isoprene and butadiene, the structural units (TPE-2, TPE-3, TPE-6, TPE-7) derived from isoprene, the structural unit (TPE-4) derived from β-farnesene, or the structural units (TPE-5) derived from butadiene and β-farnesene, the vinyl bond content was calculated.

[0137] (Hydrogenation rate of polymer block (B)) The hydrogenated block copolymer was dissolved in CDCl3 1 1H-NMR measurement [Apparatus: " AV ANCE III 400 Nano B bay" (manufactured by Bruker), measurement temperature: 30 °C] was performed, and the hydrogenation rate was calculated from the ratio of the peak area derived from the residual olefin of β-farnesene, isoprene or butadiene to the peak area derived from the hydrogenated β-farnesene, hydrogenated isoprene, or hydrogenated butadiene.

[0138] (Weight average molecular weight (Mw)) The weight average molecular weight (Mw) in terms of polystyrene of the hydrogenated block copolymer was determined by gel permeation chromatography (GPC) measurement under the following conditions. Also, Mw was measured for only the polymer block (A) before adding the conjugated diene compound in the same procedure. <<GPC measurement apparatus and measurement conditions>> · Apparatus: GPC apparatus "HLC-8020" (manufactured by Tosoh Corporation) · Separation column: Two "TSKgel G4000HX" columns manufactured by Tosoh Corporation were connected in series. · Eluent: Tetrahydrofuran · Eluent flow rate: 0.7 mL / min · Sample concentration: 5 mg / 10 mL · Column temperature: 40 °C · Detector: Differential refractive index (RI) detector · Calibration curve: Prepared using standard polystyrene

[0139] (Tan δ and shear storage modulus G' of the hydrogenated block copolymer and resin composition) For the following measurements, the hydrogenated block copolymer obtained in the production example and the resin compositions obtained in the examples and comparative examples were pressurized at a temperature of 230 °C and a pressure of 10 MPa for 3 minutes to prepare a single-layer sheet with a thickness of 1.0 mm. The single-layer sheet was cut into a disc shape and used as the test sheet. For the measurement, based on JIS K7244-10:2005, a strain-controlled dynamic viscoelasticity apparatus "ARES-G2" (manufactured by TA Instruments) with a disc diameter of 8 mm was used as a parallel plate vibration rheometer. The gap between the two plates was completely filled with the above test sheet, and the sample was vibrated at a frequency of 1 Hz in shear mode with a strain of 0.1%, and the temperature was increased at a constant rate of 3 °C / min from -80 °C to +100 °C to obtain the maximum value of the peak intensity (peak top intensity) of tan δ of the hydrogenated block copolymer or resin composition and the temperature (peak top temperature) at which the maximum value was obtained at the measurement temperature of -30 to +50 °C. Also, in the same procedure, the tan δ of the resin composition at 0 °C, 20 °C, and 40 °C and the shear storage modulus (G') at -20 °C were determined.

[0140] (Glass transition temperature (Tg)) The Tg of the hydrogenated block copolymer was measured by heating from -100°C to +80°C at a rate of 10°C / min using a DSC250 manufactured by TA Instruments, and the shift position of the baseline of the DSC curve (specifically, the intersection of the line at the midpoint between the baselines before and after the specific heat change and the DSC curve) was defined as the Tg.

[0141] (Melt Flow Rate (MFR)) For the hydrogenated product of the block copolymer obtained in the production example and the resin compositions obtained in the examples and comparative examples, in accordance with JIS K 7210:2014, using a melt indexer, the efflux rate (g / 10 min) of the sample was measured under the conditions of a temperature of 230°C and a load of 2160 g.

[0142] (Bio-based content) For the resin compositions of the examples and comparative examples, and the crosslinked foams obtained in the examples and comparative examples, the bio-based content was measured in accordance with ASTM D6866-20. Specifically, the resin composition or crosslinked foam was burned, and the CO2 generated by the combustion of the resin composition was quantified. For the quantified CO2, using an accelerator mass spectrometer (AMS), 14 the concentration of 14 C was measured. Then, the bio-based content was calculated by comparing the concentration of 14 C in the CO2 in the atmosphere with the measured concentration of

[0143] (Average aspect ratio of domains in the resin composition) Cross-sections were prepared from the resin compositions obtained in Example 2 and Comparative Example 1 using a cryo-ultramicrotome (EM UC7, EM FC7 manufactured by Leica Microsystems GmbH), and the surface of the cross-section was observed in the tapping mode of an atomic force microscope (AFM) to obtain a phase difference image. From the above phase difference image, the aspect ratio (length of the major axis / length of the minor axis) was examined for 100 domains, and the average value was calculated to determine the average aspect ratio of the domains.

[0144] (Foaming ratio of the crosslinked foam) From the compositions before and after foaming of the examples and comparative examples, test pieces without a molded skin having a length of 25 mm × width of 25 mm × thickness of 2 mm were cut out, and the expansion ratio of the crosslinked foam was calculated from the weights per unit volume before and after foaming.

[0145] (Specific gravity of crosslinked foam) The specific gravities of the crosslinked foams obtained in the examples and comparative examples were measured in accordance with JIS K7222:2005.

[0146] (tanδ and compression storage modulus E' of crosslinked foam) For the following measurements, test pieces without a molded skin having a diameter of 8 mm and a thickness of 5 mm were cut out from the foams obtained in the examples and comparative examples. For the measurement, a dynamic viscoelasticity apparatus "EPLEXOR 500N" (manufactured by NETZSCH) was used based on JIS K6394:2007. The above test pieces were vibrated at a frequency of 10 Hz in the compression mode with a strain amount of 1%, and the temperature was raised at a constant rate of 2 °C / min from -30 °C to +50 °C, and the tanδ at 0 °C, 20 °C, and 40 °C of the crosslinked foams obtained in the examples and comparative examples was measured. Also, in the same procedure, the compression storage modulus E' at -20 °C was measured.

[0147] (Rebound resilience of crosslinked foam) Three sheets without a molded skin having a length of 50 mm × width of 50 mm × thickness of 20 mm were cut out from the crosslinked foams obtained in the examples and comparative examples, and a laminate having a length of 50 mm × width of 50 mm × thickness of 60 mm formed by laminating them was used as a test piece. This test piece was subjected to a rebound resilience test at 0 °C and 20 °C by a method conforming to JIS K6400-3:2011, and the rebound resilience was measured.

[0148] (Hardness of crosslinked foam) In accordance with JIS K7312:1996, the hardness (type C) of the crosslinked foams obtained in the examples and comparative examples at 0 °C and 20 °C was measured using a type C durometer (manufactured by Kobunshi Keiki Co., Ltd.).

[0149] [Production Example 1] <Production of Hydrogenated Block Copolymer TPE-1> 50 kg of cyclohexane as a solvent and 57 g of a cyclohexane solution of sec-butyllithium with a concentration of 10.5% by mass as an anionic polymerization initiator (substantial addition amount of sec-butyllithium: 6.0 g) were charged into a pressure-resistant container that had been purged with nitrogen and dried. After the temperature inside the pressure-resistant container was raised to 50°C, 0.8 kg of styrene (1) was added and polymerized for 1 hour. At a container internal temperature of 50°C, 42 g of 2,2-bis(2-tetrahydrofuryl)propane (DTHFP) as a Lewis base was added, and a mixed solution of 6.1 kg of isoprene and 4.9 kg of butadiene was added and polymerized for 2 hours. Further, 0.8 kg of styrene (2) was added and polymerized for 1 hour to obtain a reaction solution containing a polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer. To the reaction solution, a Ziegler-type hydrogenation catalyst formed from nickel octylate and trimethylaluminum was added under a hydrogen atmosphere, and the reaction was carried out at a hydrogen pressure of 1 MPa and 80°C for 5 hours. After the reaction solution was allowed to cool and depressurized, the above catalyst was removed by washing with water and vacuum dried to obtain a hydrogenated product TPE-1 of a polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer.

[0150] [Production Examples 2 to 5] <Production of Hydrogenated Block Copolymers TPE-2 to TPE-5> Hydrogenated block copolymers TPE-2 to TPE-5 were produced in the same procedure as in Production Example 1 except that the raw materials and their usage amounts were as shown in Table 1.

[0151] [Production Example 6] <Production of Hydrogenated Block Copolymer TPE-6> 50 kg of cyclohexane as a solvent, 227 g of a cyclohexane solution of sec-butyllithium with a concentration of 10.5% by mass as an anionic polymerization initiator (substantial addition amount of sec-butyllithium: 23.9 g), and 100 g of tetrahydrofuran as a Lewis base were charged into a pressure-resistant container that had been purged with nitrogen and dried. After heating the inside of the pressure vessel to 50 °C, 7.4 kg of β-farnesene was added and polymerization was carried out for 2 hours. Subsequently, 3.0 kg of styrene (1) was added and polymerized for 1 hour, and further 4.6 kg of butadiene was added and polymerization was carried out for 1 hour. Subsequently, 100 g of phenyl benzoate as a coupling agent was added to this polymerization reaction solution and reacted for 1 hour to obtain a reaction solution containing poly(β-farnesene)-polystyrene-polybutadiene-polystyrene-poly(β-farnesene) pentablock copolymer. A Ziegler-type hydrogenation catalyst formed from nickel octylate and trimethylaluminum was added to the reaction solution under a hydrogen atmosphere, and the reaction was carried out at a hydrogen pressure of 1 MPa and 80 °C for 5 hours. After allowing the reaction solution to cool and releasing the pressure, the catalyst was removed by washing with water and vacuum drying was carried out to obtain a hydrogenated product TPE-6 of poly(β-farnesene)-polystyrene-polybutadiene-polystyrene-poly(β-farnesene) pentablock copolymer.

[0152] [Comparative Production Examples 1-2] <Production of Hydrogenated Products TPE-7 to TPE-8 of Block Copolymers> Hydrogenated block copolymers TPE-7 to TPE-8 were produced in the same procedure as in Production Example 1, except that the raw materials and their usage amounts were as shown in Table 1.

[0153]

Table 1

[0154] For the hydrogenated products of each block copolymer, various physical properties were measured according to the above-described measurement procedure. The measurement results are shown in Table 2 together with their compositions.

[0155]

Table 2

[0156] As shown in Table 2, the hydrogenated block copolymers TPE-1 to TPE-4 satisfy the above-mentioned condition [1], and the hydrogenated block copolymers TPE-5 and TPE-6 satisfy the above-mentioned conditions [2] and [4]. And, the peak top intensity of tanδ of the hydrogenated block copolymers TPE-1 to TPE-4 shows a value of 1.0 or more. The peak top temperature of tanδ of the hydrogenated block copolymers TPE-1 to TPE-4 is in the range of -20 to +45°C, and the peak top temperature of tanδ of the hydrogenated block copolymers TPE-5 to TPE-6 is in the range of -70 to -30°C. On the other hand, TPE-7 and TPE-8 of the comparative production examples satisfy the above-mentioned condition [2], but do not contain β-farnesene and do not satisfy the above-mentioned condition [4].

[0157] [Example 1] 90 parts by mass of the hydrogenated block copolymer TPE-1 and 10 parts by mass of the hydrogenated block copolymer TPE-6 were used, and a resin composition was produced by melt-kneading using a twin-screw extruder ("ZSK26Mc" manufactured by Coperion) under the conditions of a cylinder temperature of 230°C and a screw rotation speed of 300 rpm.

[0158] [Examples 2 to 4, Comparative Examples 1 to 2] A resin composition was produced in the same procedure as in Example 1 except that the resin composition was as shown in Table 3.

[0159] For each resin composition, various physical properties were measured according to the above-mentioned measurement procedure. The measurement results are shown in Table 3 together with the composition. Also, the AFM image of the resin composition of Example 2 is shown in FIG. 1, and the AFM image of the resin composition of Comparative Example 1 is shown in FIG. 2.

[0160]

Table 3

[0161] As shown in Table 3, the resin composition of Example 1 contains component (x) and component (y) at a mass ratio of 90 / 10, the resin composition of Example 2 contains component (x) and component (y) at a mass ratio of 70 / 30, and the resin composition of Example 3 contains component (x) and component (y) at a mass ratio of 50 / 50. And all of them have a peak of tanδ near 10°C, the peak top intensity is high, and the value of tanδ is large near room temperature. The resin composition of Example 4 contains component (x) and component (y) at a mass ratio of 70 / 30, has a peak of tanδ near 30°C, and the peak top intensity is high. Also, the melt flow rate of any resin composition shows a value of 3 g / 10 min or more, and particularly the resin compositions of Example 3 and Example 4 have significantly large melt flow rate values. In addition, as shown in Fig. 1, in the resin composition of Example 2, the domains are dispersed in the matrix in a state where the aspect ratio is relatively small, and the average aspect ratio was 1.3. That is, it can be understood that the resin compositions of Examples 1 to 4 satisfy the above-described conditions [1] to [4], can exhibit high vibration damping performance near room temperature, and have good moldability.

[0162] On the other hand, the resin composition of Comparative Example 1 that does not contain component (y) has a lower peak top intensity of tanδ, a smaller value of tanδ at 20°C, and inferior vibration damping performance near room temperature compared to the resin composition of Example 2 that contains component (x) at the same ratio. Also, it can be seen that the value of the melt flow rate is smaller than that of the resin composition of Example 2, and the moldability is inferior to that of the resin composition of Example 2. In addition, the resin composition of Comparative Example 2 has a very small melt flow rate value and inferior moldability compared to the resin composition of Example 3 that contains component (x) at the same ratio. Also, it can be seen that the value of tanδ at 20°C is smaller than that of the resin composition of Example 3, and the vibration damping performance near room temperature is inferior to that of Example 3. Also, as shown in Fig. 2, the resin composition of Comparative Example 1 had a larger domain size than that of the resin composition of Example 2, and the average aspect ratio of the domain was 5. Further, it can be seen from Fig. 2 that other resin components are present in a streak-like manner in the matrix of component (x), indicating the presence of structural anisotropy.

[0163] [Example 5] 30 parts by mass of a hydrogenated block copolymer TPE-1 and 70 parts by mass of a hydrogenated block copolymer TPE-6 were used, and a resin composition was produced by melt-kneading using a twin-screw extruder ("ZSK26Mc" manufactured by Coperion) under the conditions of a cylinder temperature of 230°C and a screw rotation speed of 300 rpm.

[0164] [Examples 6 to 8, Comparative Examples 3 to 4] A resin composition was produced in the same procedure as in Example 5, except that the resin composition was as shown in Table 4.

[0165] For each resin composition, various physical properties were measured according to the above-described measurement procedures. The measurement results are shown in Table 4 together with their compositions.

[0166]

Table 4

[0167] As shown in Table 4, the resin compositions of Examples 5 to 7 contained component (x) and component (y) at a mass ratio of 30 / 70, and the resin composition of Example 8 contained component (x) and component (y) at a mass ratio of 20 / 80. And all of them showed a high peak intensity of tanδ and a low G' value at -20°C, and were excellent in flexibility at low temperatures. That is, it can be seen that the resin compositions of Examples 5 to 8 satisfy the above-described conditions [1] to [4], can exhibit high vibration damping properties near room temperature, and are excellent in flexibility at low temperatures. Also, it can be seen that the resin compositions of Examples 5 and 6 have very large melt flow rate values, and by selecting the type of component (y), in addition to the vibration damping properties near room temperature and the flexibility at low temperatures, the moldability can also be improved.

[0168] On the other hand, in the resin composition of Comparative Example 3 that does not contain component (y), the peak top temperature of tanδ is shifted to a higher temperature range than that of the resin composition of the Example, and the peak top intensity of tanδ is lower than that of the resin composition of the Example. And, compared with Examples 5 and 7 that contain TPE-1 as component (x) at the same ratio, the value of tanδ at 20°C is small, and it can be seen that the vibration damping property near room temperature is inferior to that of the resin compositions of Examples 5 and 7. Furthermore, compared with the resin composition of Example 5 that contains component (x) at the same ratio, the value of the melt flow rate is small, and it can be seen that the moldability is inferior to that of Example 5. The resin composition of Comparative Example 4 that does not contain component (y) and consists only of component (x) has a very large value of G’ at -20°C, indicating poor flexibility at low temperatures.

[0169] [Examples 9, Comparative Examples 5 to 6] Using component (x), component (y), ethylene-vinyl acetate resin, foaming aid, filler, and crosslinking aid at the ratio of the compounding composition shown in Table 5 below, a masterbatch was obtained by melt mixing at a temperature of 120°C using a kneader. Next, a crosslinking agent and a foaming agent were added to the obtained masterbatch at the ratio of the compounding composition shown in Table 5, and roll kneading was performed at a roll temperature of 110°C to obtain a foamable composition. The obtained foamable composition was press-treated at 165°C and 10 MPa for 20 minutes using a mold with a thickness of 10 mm to obtain a crosslinked foam. The measurement and evaluation of the physical properties of the crosslinked foam thus obtained were carried out according to the above-described procedure.

[0170] The components used for producing each crosslinked foam are as follows. (Component (x)) ·TPE-1 (Component (y)) ·TPE-5 ·TPE-6 (Ethylene-vinyl acetate resin) ·EVA-1: "EVAFLEX EV40LX" manufactured by Mitsui Dow Polychemical Co., Ltd. ·EVA-2: "EVAFLEX EV460" manufactured by Mitsui Dow Polychemical Co., Ltd. (Filler) ·Calcium carbonate (Crosslinking agent) ·DCP-40: "Parkmill D-40" manufactured by NOF Corporation (Crosslinking aid) ·TAIC-60: "Taike M-60" manufactured by Mitsubishi Chemical Corporation (Blowing agent) ·ADCA: Azocompound blowing agent "Cellmic CE" manufactured by Sankyo Kasei Co., Ltd. (Blowing aid) ·Stearic acid ·Zinc oxide

[0171] For each crosslinked foam, various physical properties were measured according to the above-described measurement procedures. The measurement results are shown in Table 5 together with their compositions.

[0172]

Table 5

[0173] As shown in Table 5, the crosslinked foam of Example 9 contains component (x) and component (y) at a mass ratio of 30 / 40. And it shows a high peak intensity of tanδ, a low value of E' at -20°C, small rebound resilience ratios at 0°C and 20°C, and a small hardness at 0°C. That is, it can be seen that the crosslinked foam of Example 9 satisfies the above-described conditions [1] to [4], can exhibit high vibration damping performance near room temperature, and is excellent in flexibility at low temperatures. On the other hand, the crosslinked foam of Comparative Example 5 that does not contain component (y) and contains the same amount of component (x) as the total of component (x) and component (y) in Example 9 has a smaller value of tanδ at 0°C than the crosslinked foam of Example 9, and it can be seen that its vibration damping performance at low temperatures is inferior. Also, the value of E' at -20°C is very large, and the hardness at 0°C is very high, and it can be seen that its flexibility at low temperatures is inferior compared to the crosslinked foam of Example 9. In addition, the crosslinked foams of Comparative Examples 6 and 7 that do not contain component (x) have smaller tanδ values at 0 to 40°C than the crosslinked foam of Example 9, indicating that their vibration damping performance is inferior in the low temperature to near room temperature range. Also, the resilience modulus values at 0°C and 20°C are large, indicating that their flexibility at low temperatures is inferior compared to the crosslinked foam of Example 9.

Industrial Applicability

[0174] The resin composition of the present invention can be used for sole members such as insoles, sock liners, midsoles, and outsoles, as well as for automotive casings, various parts mounted on automobiles and their housings. It can also be used for various electrical products in the home appliance field, such as televisions, Blu-ray recorders, HDD recorders and other recorders, projectors, game machines, digital cameras, home videos, antennas, speakers, electronic dictionaries, IC recorders, FAX machines, copiers, telephones, door phones, rice cookers, microwave ovens, oven ranges, refrigerators, dishwashers, dish dryers, IH cooking heaters, hot plates, vacuum cleaners, washing machines, chargers, sewing machines, irons, dryers, electric bicycles, air purifiers, water purifiers, electric toothbrushes, lighting fixtures, air conditioners, outdoor units of air conditioners, dehumidifiers, humidifiers, etc.

Claims

1. As component (x), a hydrogenated product (X) of a block copolymer having a polymer block (A-1) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B-1) containing a structural unit derived from a conjugated diene compound, As component (y), a block copolymer (Y0) having a polymer block (A-2) containing a structural unit derived from an aromatic vinyl compound and a polymer block (B-2) containing a structural unit derived from a conjugated diene compound or a hydrogenated product (Y) thereof, and including, When the polymer block (A-1) and the polymer block (A-2) are represented by "A", and the polymer block (B-1) and the polymer block (B-2) are represented by "B", the hydrogenated product (X) of the block copolymer is a triblock copolymer represented by A-B-A, and the block copolymer (Y0) and its hydrogenated product (Y) are a triblock copolymer represented by A-B-A or a pentablock copolymer represented by B-A-B-A-B, The vinyl bond amount of the polymer block (B-1) is 70 mol% or more, A resin composition satisfying the following conditions [1] to [4]. [1] The glass transition temperature of component (x) is -40°C or higher. [2] The glass transition temperature of component (y) is -50°C or lower. [3] The ratio Mx / My of the mass Mx of component (x) to the mass My of component (y) in the resin composition is 1 / 99 to 99 / 1. [4] The polymer block (B-2) contains a structural unit derived from β-farnesene.

2. The resin composition according to claim 1, wherein the content of the polymer block (A-1) in component (x) is 23% by mass or less.

3. The resin composition according to claim 1 or 2, wherein the hydrogenation rate of component (x) is 85 mol% or more.

4. The resin composition according to claim 1 or 2, wherein the weight average molecular weight of component (x) is 100,000 to 250,000.

5. The resin composition according to claim 1 or 2, wherein the melt flow rate of component (x) at 230°C and a load of 2.16 kg measured in accordance with JIS K 7210:2014 is 20 g / 10 min or less.

6. The resin composition according to claim 1 or 2, wherein the polymer block (B-1) contains a structural unit derived from isoprene.

7. The resin composition according to claim 1 or 2, wherein the vinyl bond amount of the polymer block (B-1) is 75 mol% or more.

8. The resin composition according to claim 1 or 2, wherein the content of the polymer block (A-2) in the component (y) is 35% by mass or less.

9. The resin composition according to claim 1 or 2, wherein the component (y) is a hydrogenated product (Y) of a block copolymer, and the hydrogenation rate of the hydrogenated product (Y) of the block copolymer is 85 mol% or more.

10. The resin composition according to claim 1 or 2, wherein the weight average molecular weight of the component (y) is 40,000 to 400,000.

11. The resin composition according to claim 1 or 2, wherein the melt flow rate of the component (y) measured at 230 ° C. and a load of 2.16 kg in accordance with JIS K 7210:2014 is 10 g / 10 min or more.

12. The resin composition according to claim 1 or 2, wherein Mx / My is 45 / 55 to 80 / 20.

13. The resin composition according to claim 1 or 2, wherein Mx / My is 20 / 80 to 37 / 63.

14. The resin composition according to claim 1 or 2, wherein the bio-based degree of the resin composition measured in accordance with ASTM D6866-20 is 1 to 80% by mass.

15. The resin composition according to claim 1 or 2, wherein the melt flow rate of the resin composition measured at 230 ° C. and a load of 2.16 kg in accordance with JIS K 7210:2014 is 100 g / 10 min or less.

16. The resin composition according to claim 1 or 2, wherein the peak top strength of tan δ measured under the conditions of a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of -30 to +50 ° C., a heating rate of 3 ° C. / min, and a shear mode in accordance with JIS K7244-10:2005 is 0.4 or more.

17. The resin composition according to claim 1 or 2, wherein the content of the structural unit derived from β-farnesene in the component (x) is smaller than the content of the structural unit derived from β-farnesene in the component (y).

18. In the resin composition, one of the component (x) and the component (y) is used as a matrix, and the other of the component (x) and the component (y) forms a domain dispersed in the matrix, and the average aspect ratio of the domain is 1.0 to 3.

0. The resin composition according to claim 1 or 2.

19. The resin composition (i) according to claim 1 or 2, and At least one olefin polymer (ii) selected from the group consisting of ethylene-propylene-diene copolymer rubber, ethylene-vinyl acetate copolymer, and polyethylene-based resin, a crosslinking agent (iii), a foaming agent (iv), and a foaming composition containing the same.

20. The crosslinked foam of the foaming composition according to Claim 19.

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