Resin composition, adhesive, and compatibilizer

Abstract

A resin composition comprising: a modified hydrogenated product (A) of a block copolymer including a polymeric block (A-1) that has a structural unit derived from an aromatic vinyl compound and a polymeric block (A-2) that has a structural unit derived form a conjugated diene compound; and a polyolefin-based resin (B), wherein the modified hydrogenated product (A) has one or more functional groups selected from alkoxysilyl groups, carboxy group, amino group, hydroxy group, epoxy group, and groups derived from acid anhydrides, and the vinyl bonding amount of the polymeric block (A-2) is 50-99 mol%. A resin composition additionally comprising a polar resin (C).

Description

[Technical field]

[0001] The present invention relates to a resin composition, an adhesive, and a compatibilizer. [Background technology]

[0002] It is known that some block copolymers having a polymer block containing a structural unit derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from a conjugated diene compound and their hydrogenated products have vibration-damping properties and have been used as vibration-damping materials. It is also known that the block copolymers or their hydrogenated products modified to introduce reactive functional groups can be used as compatibilizers for compatibilizing polar resins and non-polar resins.

[0003] For example, Patent Documents 1 to 4 disclose that a modified olefin elastomer or styrene elastomer is used as the compatibilizer in a resin composition containing a polyolefin resin, a polyamide resin, and a compatibilizer. Among these, Patent Documents 1, 2, and 4 disclose that the styrene elastomer includes a block copolymer of an aromatic vinyl compound and a conjugated diene compound, and a hydrogenated product thereof. Furthermore, Patent Document 5 describes a blow molding composition containing a mixture of a polyamide resin and a polyolefin resin containing a modified polyolefin, and also describes that the polyolefin resin may contain a polyolefin resin and a modified polyolefin. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2017 / 169814 [Patent Document 2] JP 2013-147645 A [Patent Document 3] JP 2013-147648 A [Patent Document 4] International Publication No. 2017 / 094738 [Patent Document 5] Japanese Patent Application Publication No. 6-234897 Summary of the Invention [Problem to be solved by the invention]

[0005] However, as the use of the above-mentioned block copolymer or modified products of its hydrogenated product becomes widespread, there is a demand for compatibilizers that can better compatibilize polar and non-polar resins and have properties that show good compatibility even in small amounts so as to be suitable for various applications. On the other hand, for example, when it is assumed to be used for in-vehicle parts, adhesion to metals such as aluminum may be required, but the reality is that resin compositions containing modified block copolymers or hydrogenated products thereof have not been sufficiently studied from the viewpoint of adhesion to metals.

[0006] Therefore, an object of the present invention is to provide a resin composition and an adhesive that have high adhesion to metals. Another object of the present invention is to provide a resin composition in which one of a polar resin and a polyolefin resin is well dispersed in the other. A further object of the present invention is to provide a compatibilizer that exhibits good compatibility between polar resins and non-polar resins. [Means for solving the problem]

[0007] As a result of intensive research aimed at solving the above problems, the present inventors have conceived the following invention and found that the problems can be solved. That is, the present invention is as follows.

[0008] [1] A modified hydrogenated product (A) of a block copolymer including a polymer block (A-1) having a structural unit derived from an aromatic vinyl compound and a polymer block (A-2) having a structural unit derived from a conjugated diene compound, and a polyolefin resin (B), The modified hydrogenated product (A) has one or more functional groups selected from an alkoxysilyl group, a carboxy group, an amino group, a hydroxyl group, an epoxy group, and a group derived from an acid anhydride, A resin composition, wherein the vinyl bond content in the polymer block (A-2) is 50 to 99 mol %. [2] The resin composition according to the above [1], wherein the modified hydrogenated product (A) has a glass transition temperature of -30 to +30°C. [3] The resin composition according to [1] or [2] above, wherein the polyolefin resin (B) is at least one resin selected from the group consisting of polypropylene, polyethylene, polymethylpentene, ethylene-vinyl acetate copolymer, homopolymers or copolymers of α-olefins, and copolymers of propylene and / or ethylene with α-olefins. [4] The resin composition according to any one of the above [1] to [3], wherein the content of the polymer block (A-1) in the modified hydrogenated product (A) is 4 to 50 mass %. [5] The resin composition according to any one of the above [1] to [4], wherein the average molecular weight of the modified hydrogenated product (A) is 50,000 to 400,000. [6] The resin composition according to any one of the above [1] to [5], wherein the hydrogenation rate of the polymer block (A-2) is 50 to 99 mol %. [7] The resin composition according to any one of the above [1] to [6], wherein the content of the functional group in the modified hydrogenated product (A) is 0.1 to 5.0 phr relative to the modified hydrogenated product (A). [8] The resin composition according to any one of [1] to [7] above, having a melt flow rate of 1 to 30 g / 10 min, measured in accordance with JIS K7210 (2014) at a temperature of 230°C and a load of 21 N. [9] The resin composition according to any one of the above [1] to [8], wherein Aa / Ba is 95 / 5 to 5 / 95, where Aa is the mass of the modified hydrogenated product (A) and Ba is the mass of the polyolefin resin (B).

[10] An adhesive comprising the resin composition according to any one of [1] to [9] above.

[11] The resin composition according to any one of the above [1] to [8], further comprising a polar resin (C).

[12] The resin composition according to the above

[11] , comprising 10 to 90 mass % of a polar resin (C) based on the total mass of the resin composition.

[13] The resin composition according to

[11] or

[12] above, wherein domains containing the other of the polyolefin resin (B) and the polar resin (C) and having an average diameter of 500 nm or less are dispersed in a matrix of one of the polyolefin resin (B) and the polar resin (C).

[14] The resin composition according to any one of the above

[11] to

[13] , wherein the polar resin (C) is at least one resin selected from the group consisting of polyamide resins, polyvinyl alcohol-based resins, polyester-based resins, and polycarbonate resins.

[15] The resin composition according to any one of the above

[11] to

[14] , wherein the loss tangent (tan δ) measured in accordance with JIS K7244-10 (2005) under conditions of a distortion of 0.1%, a frequency of 10 Hz, a measurement temperature of -100 to +150°C, and a heating rate of 3°C / min has a peak intensity of 0.1 to 2.0 at 0 to 50°C.

[16] The resin composition according to any one of the above

[11] to

[15] , wherein, in the resin composition, the mass of the modified hydrogenated product (A) is Ab and the mass of the polyolefin resin (B) is Bb, Ab / Bb is 30 / 70 to 1 / 99.

[17] The resin composition according to any one of the above

[11] to

[16] , wherein, in the resin composition, the mass of the polyolefin resin (B) is Bb and the mass of the polar resin (C) is C, the ratio Bb / C is 90 / 10 to 10 / 90.

[18] A compatibilizer for compatibilizing a polar resin and a non-polar resin, comprising: The present invention comprises a modified hydrogenated product (A) of a block copolymer including a polymer block (A-1) having a structural unit derived from an aromatic vinyl compound and a polymer block (A-2) having a structural unit derived from a conjugated diene compound, The modified hydrogenated product (A) has one or more functional groups selected from an alkoxysilyl group, a carboxy group, an amino group, a hydroxyl group, an epoxy group, and a group derived from an acid anhydride, A compatibilizer, in which the vinyl bond content in the polymer block (A-2) is 50 to 99 mol %. Effect of the Invention

[0009] According to the present invention, it is possible to provide a resin composition and an adhesive having high adhesion to metals. Furthermore, according to the present invention, it is possible to provide a resin composition in which one of the polar resin and the polyolefin resin is well dispersed in the other. Furthermore, according to the present invention, it is possible to provide a compatibilizer that exhibits good compatibility between a polar resin and a non-polar resin. [Brief description of the drawings]

[0010] [Figure 1] 3 is an enlarged cross-sectional photograph showing an example of the morphology of a first resin composition (D1) and a comparative resin composition. [Diagram 2] FIG. 2 is a schematic cross-sectional view showing an example of an island structure. [Diagram 3] 4 is an enlarged cross-sectional photograph showing an example of the morphology of the second resin composition (D2) and a comparative resin composition. [Figure 4] 4 is an enlarged cross-sectional photograph showing an example of the morphology of the second resin composition (D2) and a comparative resin composition. [Diagram 5] FIG. 4 is a diagram showing an example of the viscoelastic properties of a second resin composition (D2). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] In this specification, preferred definitions may be selected arbitrarily, and combinations of preferred definitions may be considered more preferred. In this specification, the expression "XX to YY" means "at least XX and at most YY." In this specification, the lower limit and upper limit described in stages for the preferred numerical range (e.g., range of content, etc.) can be independently combined. For example, the description "preferably 10 to 90, more preferably 30 to 60" can be combined with the "preferable lower limit (10)" and the "more preferable upper limit (60)" to form "10 to 60." In this specification, the term "unit" (where "" indicates a monomer) means "a structural unit derived from", for example, "propylene unit" means "a structural unit derived from propylene". In this specification, for example, "(meth)acrylic acid" refers to both "acrylic acid" and "methacrylic acid", and similar terms. In this specification, the weight average molecular weight is a weight average molecular weight calculated in terms of standard polystyrene, determined by gel permeation chromatography (GPC). In this specification, the term "BB mainly composed of AA" means that the BB contains at least more than 50 mass % AA.

[0012] [First resin composition (D1)] The first resin composition according to an embodiment of the present invention comprises a modified hydrogenated product (A) of a block copolymer including a polymer block (A-1) having a structural unit derived from an aromatic vinyl compound and a polymer block (A-2) having a structural unit derived from a conjugated diene compound, and a polyolefin resin (B); The modified hydrogenated product (A) has one or more functional groups selected from an alkoxysilyl group, a carboxy group, an amino group, a hydroxyl group, an epoxy group, and a group derived from an acid anhydride, The vinyl bond amount of the polymer block (A-2) is 50 to 99 mol %. In this specification, the first resin composition (D1) may be referred to as "resin composition (D1)".

[0013] When the vinyl bond amount in the polymer block (A-2), i.e., the total content of 3,4-bond units and 1,2-bond units in the polymer block (A-2), is within the above range, the resin composition (D1) is likely to exhibit excellent vibration damping properties, and in addition, the resin composition (D1) exhibits high adhesion to various materials, particularly to metals. Here, the vinyl bond amount is measured according to the method described in the Examples. 1 This value was calculated by H-NMR measurement. When the polymer block (A-2) is composed only of butadiene, the above-mentioned "content of 3,4-bond units and 1,2-bond units" is to be read as "content of 1,2-bond units".

[0014] The resin composition (D1) has high adhesion to various materials, particularly to metals. The reason why the resin composition (D1) has excellent adhesion is presumed to be as follows, although not limited thereto. In the resin composition (D1), the vinyl bond amount of the polymer block (A-2) constituting the modified hydrogenated product (A) is set within a predetermined range, so that the solubility parameter (SP value) of the modified hydrogenated product (A) approaches the SP value of the polyolefin resin (B), and the modified hydrogenated product (A) and the polyolefin resin (B) show good compatibility, forming a fine co-continuous structure. This ensures flexibility of the entire composition, and the modified hydrogenated product (A) is uniformly dispersed in the resin composition (D1), making it easier for a sufficient amount of the modified hydrogenated product (A) to exist even near the surface of the composition. For this reason, it is presumed that the functional group of the modified hydrogenated product (A) introduced by modification is more likely to come into contact with the adherend, resulting in high adhesion to metals and various other materials.

[0015] <Morphology of Resin Composition (D1)> A preferred embodiment of the resin composition (D1) has a co-continuous structure in which the modified hydrogenated product (A) and the polyolefin resin (B) extend alternately adjacent to each other. Fig. 1(a) is an enlarged cross-sectional photograph taken with an atomic force microscope (AFM) showing an example of the morphology of resin composition (D1). In Fig. 1(a), a bicontinuous structure extending in the direction from the upper left to the lower right is formed. As described above, the modified hydrogenated product (A) exhibits good compatibility with the polyolefin resin (B). Therefore, the co-continuous structure formed in the resin composition (D1) or a molded article thereof is very fine, with a maximum value of, for example, about 10 to 500 nm in the length direction.

[0016] <Modified hydrogenated product (A)> The modified hydrogenated product (A) contained in the resin composition (D1) is a modified hydrogenated product of a block copolymer including a polymer block (A-1) having a structural unit derived from an aromatic vinyl compound and a polymer block (A-2) having a structural unit derived from a conjugated diene compound. The modified hydrogenated product (A) has one or more functional groups selected from an alkoxysilyl group, a carboxy group, an amino group, a hydroxyl group, an epoxy group, and a group derived from an acid anhydride. Furthermore, the vinyl bond amount of the polymer block (A-2) is 50 to 99 mol%. In this specification, a group derived from an acid anhydride means a group having a structure obtained by dehydration condensation of two carboxylic acid groups contained in an acid anhydride. When the acid anhydride is maleic anhydride, for example, the group has the structure shown below.

[0017] [ka] Hereinafter, the above block copolymer may be represented by the symbol (A0), and the hydrogenated product of the block copolymer (A0) may be represented by the symbol (A1). Also, the hydrogenated product of the block copolymer (A0) may be referred to as "hydrogenated block copolymer (A1)".

[0018] The modified hydrogenated product (A) is a modified product of the hydrogenated product (A1) of the block copolymer (A0), or a hydrogenated product of the modified product of the block copolymer (A0). By using the block copolymer (A0) as a raw material for the modified hydrogenated product (A), mechanical properties such as vibration damping and impact resistance can be imparted to the resin composition (D1). In addition, by hydrogenating the block copolymer (A0), the thermal stability can be easily improved. Furthermore, the amount of vinyl bonds in the polymer block (A-2) (i.e., the content of 3,4-bond units and 1,2-bond units in the polymer block (A-2)) is 50 to 99 mol%, which enhances vibration damping properties and facilitates the formation of a bicontinuous structure in which the modified hydrogenated product (A) and the polyolefin resin (B) are alternately arranged in a narrow width. As a result, the properties of the modified hydrogenated product (A), such as vibration damping properties and impact resistance, are easily exhibited in the resin composition (D1). In addition, because a specific functional group is introduced by modification, coupled with the above-mentioned fine cocontinuous structure, the resin composition (D1) has high adhesiveness to metals and various other materials.

[0019] Next, the components of the block copolymer (A0) or its hydrogenated product (A1) for obtaining the modified hydrogenated product (A), their usage ratios, and characteristics will be described. Although these are substances before modification, the modified hydrogenated product (A) also has the polymer block (A-1) and polymer block (A-2) that the block copolymer (A0) and the hydrogenated block copolymer (A1) have, and their main skeletons do not change even after modification. Therefore, the following description of the polymer block (A-1) and polymer block (A-2) also applies to the modified hydrogenated product (A).

[0020] (Block copolymer (A0)) The block copolymer (A0) has a polymer block (A-1) containing a structural unit derived from an aromatic vinyl compound and a polymer block (A-2) containing a structural unit derived from a conjugated diene compound. The polymer block (A-1) and the polymer block (A-2) are described below.

[0021] (Configuration of polymer block (A-1)) From the viewpoint of mechanical properties such as vibration damping and impact resistance, the polymer block (A-1) constituting the block copolymer (A0) preferably has a structural unit derived from an aromatic vinyl compound used as a monomer. The polymer block (A-1) preferably contains structural units derived from aromatic vinyl compounds (hereinafter sometimes abbreviated as "aromatic vinyl compound units") in the polymer block (A-1) at more than 70% by mass, and from the viewpoint of mechanical properties such as impact resistance, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably substantially 100% by mass. In other words, the content of aromatic vinyl compound units in the polymer block (A-1) is preferably more than 70% by mass and 100% by mass or less. From the viewpoint of mechanical properties, the block copolymer (A0) preferably contains structural units derived from aromatic vinyl compounds only in the polymer block (A-1). From the viewpoint of flexibility, the content of structural units derived from aromatic vinyl compounds in the block copolymer (A0) is preferably 4 to 50 mass%, more preferably 5 to 30 mass%, and even more preferably 6 to 16 mass%, and it is even more preferable that all structural units derived from aromatic vinyl compounds in the block copolymer (A0) are contained in the polymer block (A-1).

[0022] 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 Examples of the aromatic vinyl compounds include -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, ot-butylstyrene, mt-butylstyrene, pt-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 N-vinylcarbazole. These aromatic vinyl compounds may be used alone or in combination of two or more. Among these, from the viewpoint of the balance between production costs and physical properties, styrene, α-methylstyrene, p-methylstyrene, and mixtures thereof are preferred, and styrene is more preferred.

[0023] As long as it does not interfere with the object and effect of the present invention, the polymer block (A-1) may contain structural units derived from other unsaturated monomers other than aromatic vinyl compounds (hereinafter, sometimes abbreviated as "other unsaturated monomer units"), but the content of the other unsaturated monomer units in the polymer block (A-1) is preferably 30 mol% or less, more preferably less than 20 mol%, even more preferably less than 15 mol%, still more preferably less than 10 mol%, still more preferably less than 5 mol%, and particularly preferably 0 mol%. In other words, the content of the other unsaturated monomer units in the polymer block (A-1) is preferably 0 to 30 mol%. Examples of the other unsaturated monomer include at least one selected from the group consisting of butadiene, isoprene, β-farnesene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, methyl vinyl ether, β-pinene, 8,9-p-menthene, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran, etc. When the polymer block (A-1) contains the other unsaturated monomer unit, the bonding form is not particularly limited and may be either random or tapered.

[0024] The block copolymer (A0) may have at least one polymer block (A-1). When the block copolymer (A0) has two or more polymer blocks (A-1), the polymer blocks (A-1) may be the same or different. In this specification, "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 a plurality of monomer units are present, the ratio of each monomer unit and the form of copolymerization (random, gradient, block) is different.

[0025] (Weight average molecular weight of polymer block (A-1)) The weight average molecular weight (Mw) of the polymer block (A-1) is not particularly limited, but among the polymer blocks (A-1) contained in the block copolymer (A0), at least one polymer block (A-1) preferably has a weight average molecular weight of 3,000 to 60,000, more preferably 4,000 to 50,000. When the block copolymer (A0) has at least one polymer block (A-1) having a weight average molecular weight within the above range, this can contribute to further improvement of vibration damping properties. The weight average molecular weight is a weight average molecular weight calculated using standard polystyrene standards and determined by gel permeation chromatography (GPC).

[0026] (Content of polymer block (A-1)) The content of the polymer block (A-1) in the block copolymer (A0) is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 16% by mass or less, and particularly preferably 14% by mass or less. If it is 50% by mass or less, the block copolymer (A0) or hydrogenated block copolymer (A1) can have moderate flexibility and excellent vibration damping properties without decreasing the peak top intensity of tan δ (hereinafter, sometimes referred to as peak intensity). The lower limit is preferably 4% by mass or more, more preferably 5% by mass or more, and even more preferably 6% by mass or more. If it is 4% by mass or more, the block copolymer (A0) or hydrogenated block copolymer (A1) can have mechanical properties such as impact resistance, and handleability such as moldability and coatability suitable for various applications of the resin composition (D1) and the resin composition (D2) described later. In other words, the content of the polymer block (A-1) in the block copolymer (A0) or hydrogenated block copolymer (A1) is preferably 4 to 50% by mass. The content of the polymer block (A-1) in the block copolymer (A0) is 1 The value was determined by H-NMR measurement, and more specifically, the value was measured according to the method described in the Examples. In the present invention, the content of the polymer block (A-1) in the block copolymer (A0) is defined as the content of the polymer block (A-1) in the modified hydrogenated product (A).

[0027] (Configuration of polymer block (A-2)) The polymer block (A-2) constituting the block copolymer (A0) has a structural unit derived from a conjugated diene compound (hereinafter sometimes referred to as a "conjugated diene compound unit") from the viewpoints of vibration damping properties, thermal stability, and the like. The polymer block (A-2) preferably contains 30 mol% or more of the conjugated diene compound unit. From the viewpoint of vibration damping property and thermal stability, the polymer block (A-2) preferably contains 50 mol% or more of the conjugated diene compound unit, more preferably 65 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably substantially 100 mol%. In other words, the content of the conjugated diene compound unit in the polymer block (A-2) is preferably 30 mol% or more and 100 mol% or less. The above-mentioned "conjugated diene compound unit" may be a structural unit derived from one type of conjugated diene compound, or may be a structural unit derived from two or more types of conjugated diene compounds.

[0028] From the viewpoint of achieving both excellent vibration-damping properties and thermal stability, the conjugated diene compound preferably contains isoprene, or isoprene and butadiene. In addition, the conjugated diene compound may contain a conjugated diene compound other than isoprene and butadiene, as described later. On the other hand, from the viewpoint of easily achieving excellent vibration-damping properties and thermal stability, the content of isoprene in the conjugated diene compound is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, even more preferably 55% by mass or more, even more preferably 75% by mass or more, and particularly preferably 100% by mass, that is, it is particularly preferable to use isoprene as the conjugated diene compound. In other words, the content of isoprene in the conjugated diene compound is preferably 20% by mass or more and 100% by mass or less.

[0029] When the conjugated diene compound is a mixture of butadiene and isoprene, the mixing ratio [isoprene / butadiene] (mass ratio) is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10, even more preferably 40 / 60 to 70 / 30, and particularly preferably 45 / 55 to 65 / 35. The mixing ratio [isoprene / butadiene] is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10, even more preferably 40 / 60 to 70 / 30, and particularly preferably 45 / 55 to 55 / 45 in molar ratio.

[0030] Examples of the conjugated diene compound include, in addition to the above-mentioned isoprene and butadiene, β-farnesene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, myrcene, etc. The conjugated diene compound may be used alone or in combination of two or more kinds.

[0031] In addition, the polymer block (A-2) may contain a structural unit derived from a polymerizable monomer other than the conjugated diene compound, as long as it does not interfere with the object and effect of the present invention. In this case, the content of the structural unit derived from the polymerizable monomer other than the conjugated diene compound in the polymer block (A-2) is preferably less than 70 mol%, more preferably less than 50 mol%, even more preferably less than 35 mol%, and particularly preferably less than 20 mol%. There is no particular restriction on the lower limit of the content of the structural unit derived from the polymerizable monomer other than the conjugated diene compound, but it may be 0 mol%, 5 mol%, or 10 mol%.

[0032] As the other polymerizable monomer, for example, aromatic vinyl compounds such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, vinylnaphthalene and vinylanthracene, as well as at least one compound selected from the group consisting of methyl methacrylate, methyl vinyl ether, N-vinylcarbazole, β-pinene, 8,9-p-menthene, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, etc. are preferred. Among them, styrene, α-methylstyrene and p-methylstyrene are more preferred, and styrene is even more preferred.

[0033] The block copolymer (A0) may have at least one polymer block (A-2). When the block copolymer (A0) has two or more polymer blocks (A-2), the polymer blocks (A-2) may be the same or different. When the polymer block (A-2) has two or more types of structural units, the bonding form thereof may be random, tapered, completely alternating, partially block-like, block, or a combination of two or more of them.

[0034] There is no particular restriction on the bond form of the conjugated diene compound as long as it does not impair the object and effect of the present invention. For example, when the structural unit constituting the polymer block (A-2) is either an isoprene unit or a mixed unit of isoprene and butadiene, the bond form of each of isoprene and butadiene can be 1,2-bond or 1,4-bond in the case of butadiene, and 1,2-bond, 3,4-bond or 1,4-bond in the case of isoprene. Only one type of these bond forms may be present, or two or more types may be present.

[0035] In the block copolymer (A0), the total content of 3,4-bond units and 1,2-bond units (i.e., vinyl bond amount) in the polymer block (A-2) is 50 mol% or more, preferably 55 mol% or more, more preferably 60 mol% or more, even more preferably 65 mol% or more, even more preferably 70 mol% or more, and even more preferably 75 mol% or more. If the vinyl bond amount in the polymer block (A-2) is 50 mol% or more, good vibration damping properties are ensured, and the vibration damping properties tend to improve as the vinyl bond amount increases. The amount of vinyl bonds in the polymer block (A-2) is 99 mol % or less, may be 95 mol % or less, may be 92 mol % or less, or may be 90 mol % or less. In other words, the vinyl bond content of the polymer block (A-2) is 50 to 99 mol%, preferably 55 to 99 mol%, more preferably 60 to 99 mol%, even more preferably 65 to 99 mol%, still more preferably 70 to 99 mol%, and particularly preferably 75 to 99 mol%. Here, the vinyl bond amount is measured according to the method described in the Examples. 1 This value is calculated by H-NMR measurement.

[0036] The polymer block (A-2) may have a structural unit derived from a conjugated diene compound and containing one or more alicyclic skeletons (X) represented by the following formula (X) in the main chain.

[0037] [ka]

[0038] In the above formula (X), R 1 ~R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, 1 ~R 3may be the same or different. The number of carbon atoms in the hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 (i.e., a methyl group). The hydrocarbon group may be a straight chain or branched chain, and may be a saturated or unsaturated hydrocarbon group. From the viewpoint of physical properties and the formation of an alicyclic skeleton (X), R 1 ~R 3 It is particularly preferable that each independently represents a hydrogen atom or a methyl group. When the block copolymer (A0) is hydrogenated, the vinyl group in the above formula (X) can be hydrogenated to give a hydrogenated product. Therefore, the meaning of the alicyclic skeleton (X) in the hydrogenated product also includes a skeleton in which the vinyl group in the above formula (X) is hydrogenated.

[0039] The polymer block (A-2) contains an alicyclic skeleton (X) in an amount of preferably 1 mol% or more, more preferably 1.1 mol% or more, even more preferably 1.4 mol% or more, still more preferably 1.8 mol% or more, still more preferably 4 mol% or more, still more preferably 10 mol% or more, and particularly preferably 13 mol% or more. The upper limit of the content of the alicyclic skeleton (X) in the polymer block (A-2) is not particularly limited as long as it is within a range that does not impair the effects of the present invention, but from the viewpoint of productivity, it is preferably 40 mol% or less, may be 30 mol% or less, may be 20 mol% or less, or may be 18 mol% or less. The content of the alicyclic skeleton (X) in the block copolymer (A0) or the hydrogenated block copolymer (A1) is 13 This value was determined from the integral value derived from the alicyclic skeleton (X) in the polymer block (A-2) by C-NMR measurement.

[0040] (Amount of vinyl bonds in polymer block (A-2)) When the structural unit constituting the polymer block (A-2) is any one of an isoprene unit, a butadiene unit, and a mixed unit of isoprene and butadiene, the respective bonding forms of isoprene and butadiene other than the bonding form forming the alicyclic skeleton (X) can be 1,2-bonds and 1,4-bonds in the case of butadiene, and 1,2-bonds, 3,4-bonds and 1,4-bonds in the case of isoprene.

[0041] In the block copolymer (A0) and the hydrogenated block copolymer (A1), the total content of 3,4-bond units and 1,2-bond units in the polymer block (A-2) (hereinafter, sometimes simply referred to as "vinyl bond content") is 50 to 99 mol%, preferably 55 to 95 mol%, more preferably 63 to 95 mol%, and even more preferably 70 to 95 mol%. Within the above range, compatibility with non-polar resins, particularly with the polyolefin resin (B), can be improved, which in turn leads to high adhesion to metals and other materials, and also makes it easier to develop excellent vibration damping properties.

[0042] (Weight average molecular weight of polymer block (A-2)) The weight average molecular weight (Mw) of the polymer block (A-2) is not particularly limited, but the total weight average molecular weight of the polymer blocks (A-2) in the block copolymer (A0) before hydrogenation is preferably 15,000 to 400,000, more preferably 20,000 to 300,000, even more preferably 30,000 to 250,000, still more preferably 30,000 to 200,000, and even more preferably 30,000 to 150,000. If the total weight average molecular weight of the polymer blocks (A-2) is within the above range, it is easy to exhibit better vibration damping properties.

[0043] (Content of polymer block (A-2)) The content of the polymer block (A-2) in the block copolymer (A0) is preferably 99% by mass or less, more preferably 97% by mass or less, still more preferably 94% by mass or less. If the content of the polymer block (A-2) is 99% by mass or less, it becomes easy to obtain a modified hydrogenated product (A) having vibration damping properties and suitable mechanical properties, mechanical physical properties, and moldability for various applications, or a resin composition (D1) containing the same. Further, the content of the polymer block (A-2) in the block copolymer (A0) is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 60% by mass or more, even more preferably 75% by mass or more, even more preferably 80% by mass or more, and even more preferably 85% by mass or more. If the content of the polymer block (A-2) is 30% by mass or more, a modified hydrogenated product (A) having more excellent vibration damping properties or a resin composition (D1) containing the same can be obtained.

[0044] (Other structural units in the polymer block (A-2)) The polymer block (A-2) may contain structural units derived from other polymerizable monomers other than the conjugated diene compound as long as it does not interfere with the object and effect of the present invention. In this case, in the polymer block (A-2), the content of the structural units derived from other polymerizable monomers other than the conjugated diene compound is preferably less than 50 mol%, more preferably less than 30 mol%, still more preferably less than 20 mol%, even more preferably less than 10 mol%, and particularly preferably 0 mol%. In other words, in the polymer block (A-2), the content of the structural units derived from other polymerizable monomers other than the conjugated diene compound is preferably 0 mol% or more and less than 50 mol%. Preferred examples of the other polymerizable monomer include aromatic vinyl compounds such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, N-vinylcarbazole, vinylnaphthalene, and vinylanthracene, as well as at least one compound selected from the group consisting of methyl methacrylate, methyl vinyl ether, β-pinene, 8,9-p-menthene, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, and 1,3-cyclooctadiene. The block copolymer (A0) may have at least one of the polymer blocks (A-2). When the block copolymer (A0) has two or more polymer blocks (A-2), the polymer blocks (A-2) may be the same or different.

[0045] (Bonding Mode Between Polymer Block (A-1) and Polymer Block (A-2)) The block copolymer (A0) is not limited in the bonding form as long as the polymer block (A-1) and the polymer block (A-2) are bonded, and may be any of linear, branched, radial, or a combination of two or more of these. Among them, the bonding form between the polymer block (A-1) and the polymer block (A-2) is preferably linear, and examples thereof include a diblock copolymer represented by AB, a triblock copolymer represented by ABA or BAB, a tetrablock copolymer represented by ABAB, a pentablock copolymer represented by ABABA or BABAB, and an (AB)nZ type copolymer (Z represents a coupling agent residue, and n represents an integer of 3 or more), when the polymer block (A-1) is represented by A and the polymer block (A-2) is represented by B. Among them, a linear triblock copolymer or a diblock copolymer is preferred, and an ABA type triblock copolymer is preferably used from the viewpoints of flexibility, ease of production, and the like. A specific example of the ABA triblock copolymer is a styrene-hydrogenated butadiene / isoprene-styrene copolymer. That is, the block copolymer preferably contains at least a styrene-hydrogenated butadiene / isoprene-styrene copolymer.

[0046] Here, in this specification, when the same type of polymer blocks are linearly bonded via a bifunctional coupling agent or the like, the entirety of the bonded polymer blocks is treated as one polymer block. Accordingly, including the above examples, polymer blocks that should strictly be expressed as YZY (Z represents a coupling residue) are expressed as Y as a whole, except when it is necessary to distinguish them from a single polymer block Y. In this specification, since this type of polymer block containing a coupling agent residue is treated as above, for example, a block copolymer containing a coupling agent residue and that should strictly be expressed as ABZBA (Z represents a coupling agent residue) is expressed as ABA and is treated as an example of a triblock copolymer.

[0047] (Content of polymer blocks (A-1) and (A-2)) In the block copolymer (A0), polymer blocks other than the polymer blocks (A-1) and (A-2) may be contained as long as the object and effect of the present invention are not hindered, but the total content of the polymer blocks (A-1) and (A-2) is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably substantially 100% by mass. If it is 90% by mass or more, it is easy to obtain a resin composition that is likely to exhibit better vibration damping properties. In other words, the total content of the polymer blocks (A-1) and (A-2) in the block copolymer (A0) is preferably 90 to 100% by mass.

[0048] (Weight average molecular weight of block copolymer (A0) and hydrogenated block copolymer (A1)) The weight average molecular weight (Mw) determined by gel permeation chromatography in terms of standard polystyrene of the block copolymer (A0) and the hydrogenated block copolymer (A1) is preferably from 50,000 to 400,000, more preferably from 60,000 to 300,000, still more preferably from 70,000 to 250,000, even more preferably from 80,000 to 200,000, and particularly preferably from 90,000 to 180,000. When the weight average molecular weight of the block copolymer (A0) or the hydrogenated block copolymer (A1) is 50,000 or more, the heat resistance is high, and when it is 400,000 or less, the handleability of the resulting resin composition is good.

[0049] (Hydrogenation rate) In the case of the modified hydrogenated product (A) or the hydrogenated block copolymer (A1) which is an unmodified hydrogenated block copolymer, the hydrogenation rate of the polymer block (A-2) is more than 0 mol%. That is, at least a part of the carbon-carbon double bonds possessed by the polymer block (A-2) is hydrogenated. From the viewpoint of ensuring the vibration damping property and the thermal stability at a wide range of temperatures, the above hydrogenation rate is preferably 50 mol% or more. Further, from the viewpoint of the flexibility and mechanical properties of the resin composition (D1) containing the modified hydrogenated product (A), the above hydrogenation rate is more preferably 60 mol% or more, still more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 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 98.5 mol%. In other words, the above hydrogenation rate is preferably from 50 to 99 mol%. Incidentally, 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 (A-2) by 1 1H-NMR measurement, and more specifically, it is a value measured according to the method described in the examples.

[0050] (Functional group) The modified hydrogenated product (A) can be produced, for example, by reacting a compound having one or more functional groups selected from an alkoxysilyl group, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, and a group derived from an acid anhydride with the hydrogenated block copolymer (A1) obtained by hydrogenating the block copolymer (A0) to introduce functional groups, thereby modifying the hydrogenated block copolymer (A1). The functional groups are preferably one or more functional groups selected from an alkoxysilyl group and a group derived from an acid anhydride. The method for producing the modified hydrogenated product (A) will be described later. By introducing the above-mentioned functional group into the hydrogenated block copolymer (A1), the resin composition (D1) containing the modified hydrogenated product (A) can be provided with high adhesion to metals and other materials. The modified hydrogenated product (A) preferably has the above-mentioned functional group in the side chain, which increases the difference in molecular mobility between the main chain and the side chain, and the glass transition temperature can be controlled to provide excellent vibration damping properties over a wide range of temperatures.

[0051] The content of the functional group in the modified hydrogenated product (A) is preferably 0.1 phr or more, more preferably 0.15 phr or more, even more preferably 0.2 phr or more, and even more preferably 0.25 phr or more. The content of the functional group in the modified hydrogenated product (A) is preferably 5.0 phr or less, more preferably 4.0 phr or less, even more preferably 3.0 phr or less, even more preferably 2.0 phr or less, and even more preferably 0.95 phr or less. In other words, the content of the functional group in the modified hydrogenated product (A) is preferably 0.1 to 5.0 phr. The content of the functional group in the modified hydrogenated product (A) is preferably 0.1 mol% or more, more preferably 0.15 mol% or more, even more preferably 0.2 mol% or more, and even more preferably 0.25 mol% or more. The content of the functional group in the modified hydrogenated product (A) is preferably 5.0 mol% or less, more preferably 4.0 mol% or less, even more preferably 3.0 mol% or less, even more preferably 2.0 mol% or less, and even more preferably 0.95 mol% or less. In other words, the content of the functional group in the modified hydrogenated product (A) is preferably 0.1 to 5.0 mol%. If the content of the functional group in the modified hydrogenated product (A) is within the above range, the adhesiveness of the resin composition (D1) containing the modified hydrogenated product (A) can be excellent. The content (phr) of the functional group means the parts by mass of the functional group relative to 100 parts by mass of the modified hydrogenated product (A), and the content of the functional group in the modified hydrogenated product (A) can be determined by titration or the like. 1 It can be calculated by H-NMR measurement or infrared spectroscopy (IR measurement). The degree of modification in the modified hydrogenated product (A) can be adjusted by adjusting the proportion or type of the modifier used.

[0052] (Characteristics of modified hydrogenated product (A)) The weight average molecular weight of the modified hydrogenated product (A) is preferably 50,000 to 400,000, more preferably 60,000 to 300,000, still more preferably 70,000 to 250,000, particularly preferably 80,000 to 200,000, and most preferably 90,000 to 180,000. The weight average molecular weight of the modified hydrogenated product (A) can be adjusted, for example, by the amount of polymerization initiator used during polymerization.

[0053] The glass transition temperature of the modified hydrogenated product (A) is preferably from -30 to +30°C, more preferably from -15 to +30°C, and even more preferably from -10 to +25°C, from the viewpoint of improving vibration damping properties. In addition, in this specification, the glass transition temperature is a value measured using a differential scanning calorimeter (DSC) measuring device, and specifically, it is measured by the method described in the examples. The glass transition temperature of the modified hydrogenated product (A) can be adjusted, for example, by the content of the 3,4-bond and 1,2-bond of the conjugated diene.

[0054] The melt flow rate of the modified hydrogenated product (A) measured according to JIS K7210 (2014) under the conditions of a temperature of 230 °C and a load of 21 N is preferably 1 to 30 g / 10 min, more preferably 3 to 25 g / 10 min, and even more preferably 5 to 20 g / 10 min from the viewpoint of moldability.

[0055] The tanδ (loss tangent) of the modified hydrogenated product (A) is the ratio of the loss modulus to the storage modulus at a frequency of 1 Hz in dynamic viscoelastic measurement. The peak top temperature and intensity of tanδ greatly contribute to the damping property and other physical properties. Here, the peak top intensity of tanδ is the value of tanδ when the peak of tanδ is maximum. Also, the peak top temperature of tanδ is the temperature when the peak of tanδ is maximum. In this specification, the peak top temperature and intensity of tanδ of the block copolymer (A0) or the hydrogenated block copolymer (A1) are measured by preparing a single-layer sheet with a thickness of 1.0 mm by pressurizing the block copolymer (A0) or the hydrogenated block copolymer (A1) at a temperature of 230 °C and a pressure of 10 MPa for 3 minutes, cutting out the single-layer sheet into a disc shape, and using this as a test piece. The measurement conditions are in accordance with JIS K 7244-10 (2005), with a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of -70 to +100 °C, and a heating rate of 3 °C / min. Note that the peak top temperature of tanδ and the peak top intensity of tanδ of the block copolymer (A0) or the hydrogenated block copolymer (A1) are values measured more specifically according to the method described in the examples.

[0056] The modified hydrogenated product (A) can have a peak top intensity of tan δ of 1.0 or more by the above measurement. In some cases, it can be as high as 1.5 or more, or even 1.9 or more. The higher the peak top intensity of tan δ, the better the physical properties such as vibration damping at that temperature. If it is 1.0 or more, sufficient vibration damping can be obtained in the actual usage environment. The modified hydrogenated product (A) has a peak top temperature of tan δ of preferably -50°C or higher, more preferably -40°C or higher, even more preferably -30°C or higher, and even more preferably -25°C or higher, and may be 0°C or higher. The upper limit of the peak top temperature of tan δ may be within a range that does not impair the effects of the present invention, and may be +50°C or lower, +40°C or lower, or +35°C or lower. The range of the peak top temperature of tan δ is, for example, preferably -50 to +50°C, more preferably -40 to +40°C, even more preferably -30 to +30°C, and even more preferably -25 to +25°C. If the peak top temperature of tan δ is -50°C or higher or +50°C or lower, sufficient vibration damping properties can be obtained in an actual use environment.

[0057] <Method for producing modified hydrogenated product (A)> The modified hydrogenated product (A) can be produced by using at least an aromatic vinyl compound and a conjugated diene compound as monomers, polymerizing them to form a block copolymer (A0), and then subjecting this block copolymer (A0) to a modification reaction using a modifying agent before or after hydrogenation.

[0058] (Preparation of Block Copolymer (A0)) The block copolymer (A0) can be obtained by carrying out a polymerization reaction using at least an aromatic vinyl compound and a conjugated diene compound as monomers, as a block copolymer having a polymer block (A-1) containing a structural unit derived from the aromatic vinyl compound and a polymer block (A-2) containing a structural unit derived from the conjugated diene compound. The aromatic vinyl compound, the conjugated diene compound, the polymer block (A-1) and the polymer block (A-2) have the same meanings as those described above in the explanation of the modified hydrogenated product (A).

[0059] The polymerization reaction can be carried out, for example, by a solution polymerization method, an emulsion polymerization method, or a solid-phase polymerization method. Among these, the solution polymerization method is preferred, and known methods such as an ionic polymerization method such as anionic polymerization or cationic polymerization, or a radical polymerization method can be applied. Among these, the anionic polymerization method is preferred. In the anionic polymerization method, an aromatic vinyl compound and a conjugated diene compound are successively 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 if necessary to cause a reaction.

[0060] In the above-mentioned method, examples of organolithium compounds that can be used as a polymerization initiator for anionic polymerization include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, etc. Examples of dilithium compounds that can be used as a polymerization initiator include naphthalenedilithium, dilithiohexylbenzene, etc. Examples of the coupling agent include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, and phenyl benzoate. The amount of these polymerization initiators and coupling agents used is appropriately determined depending on the desired weight average molecular weight of the block copolymer (A0) or hydrogenated block copolymer (A1). Usually, initiators such as alkyllithium compounds and dilithium compounds are preferably used in an amount of 0.01 to 0.2 parts by mass per 100 parts by mass of the total of the monomers of the polymer block (A-1) and the monomers such as the conjugated diene compound used in the polymerization, and when a coupling agent is used, it is preferably used in an amount of 0.001 to 0.8 parts by mass per 100 parts by mass of the total of the monomers.

[0061] The solvent is not particularly limited as long as it does not adversely affect the anionic polymerization reaction, and examples thereof include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, n-pentane, etc., and aromatic hydrocarbons such as benzene, toluene, xylene, etc. 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.

[0062] Furthermore, by adding a Lewis base as a co-catalyst during polymerization of the conjugated diene compound, the content of the alicyclic skeleton (X) and the contents of 3,4-bonds and 1,2-bonds in the polymer block (A-2) can be increased. Examples of the Lewis base that can be used include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and 2,2-di(2-tetrahydrofuryl)propane (DTHFP); glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether; amines such as triethylamine, N,N,N',N'-tetramethylenediamine, N,N,N',N'-tetramethylethylenediamine (TMEDA), and N-methylmorpholine; and metal salts such as sodium or potassium salts of aliphatic alcohols such as sodium t-butylate, sodium t-amylate, and sodium isopentylate, or sodium or potassium salts of alicyclic alcohols such as dialkyl sodium cyclohexanolate, for example, sodium mentholate. Among the above Lewis bases, from the viewpoint of vibration-damping property and thermal stability, it is preferable to use tetrahydrofuran and DTHFP.Moreover, it is more preferable to use DTHFP, since it can have a high vinyl bond amount, it is easy to achieve a high hydrogenation rate without using an excessive amount of hydrogenation catalyst, and it can realize both of better vibration-damping property and thermal stability. These Lewis bases can be used alone or in combination of two or more.

[0063] The amount of Lewis base added is determined by the extent to which the vinyl bond amount of the isoprene unit and / or butadiene unit constituting the polymer block (A-2) is controlled when the polymer block (A-2) contains a structural unit derived from isoprene and / or butadiene. Therefore, the amount of Lewis base added is not strictly limited, but is preferably used within the range of usually 0.1 to 1,000 mol, preferably 1 to 100 mol per gram atom of lithium contained in the alkyllithium compound or dilithium compound used as a polymerization initiator. After polymerization has been carried out by the above-mentioned method, an active hydrogen compound such as an alcohol, a carboxylic acid, or water is added to terminate the polymerization reaction, thereby obtaining a block copolymer.

[0064] (Hydrogenation reaction) The block copolymer (A0) obtained by the above-mentioned production method can be subjected to a hydrogenation reaction (hydrogenation reaction) in an inert organic solvent in the presence of a hydrogenation catalyst to produce a hydrogenated block copolymer (A1). The hydrogenation reaction hydrogenates the carbon-carbon double bonds derived from the conjugated diene compound in the polymer block (A-2) in the block copolymer (A0), producing a hydrogenated product of the block copolymer (A0), i.e., a hydrogenated block copolymer (A1). The block copolymer (A0) may be modified by the method described below and then hydrogenated. The hydrogenation reaction can be carried out at a hydrogen pressure of about 0.1 to 20 MPa, preferably 0.5 to 15 MPa, and more preferably 0.5 to 5 MPa, at a reaction temperature of about 20 to 250° C., preferably 50 to 180° C., and more preferably 70 to 180° C., for a reaction time of usually about 0.1 to 100 hours, and preferably 1 to 50 hours. Examples of the hydrogenation catalyst include Raney nickel; heterogeneous catalysts in which a metal such as Pt, Pd, Ru, Rh, or Ni is supported on a carrier such as carbon, alumina, or diatomaceous earth; Ziegler catalysts consisting of a combination of a transition metal compound with an alkylaluminum compound, an alkyllithium compound, or the like; and metallocene catalysts.

[0065] The hydrogenated block copolymer (A1) (or modified hydrogenated product (A)) thus obtained can be obtained by pouring the polymerization reaction liquid into methanol or the like, stirring, filtering, and then heating or drying under reduced pressure, or by pouring the polymerization reaction liquid together with steam into hot water to remove the solvent by azeotropy (so-called steam stripping), followed by heating or drying under reduced pressure.

[0066] The hydrogenation rate of the carbon-carbon double bonds in the polymer block (A-2) when the hydrogenated product is obtained can be determined depending on the desired performance in various applications of the resin composition (D1) and the resin composition (D2) described later. The higher the hydrogenation rate of the hydrogenated product, the more improved the heat resistance and weather resistance of the hydrogenated product can be. In the modified hydrogenated product (A) used in the resin composition (D1), the hydrogenation rate of the polymer block (A-2) is preferably 50 to 99 mol %, as described above.

[0067] (Degeneration reaction) The modified hydrogenated product (A) can be produced by hydrogenating the block copolymer (A0) and then introducing the functional group described above, or by introducing the functional group before hydrogenating the block copolymer (A0) and then hydrogenating the block copolymer (A0). In the case of modification by radical reaction, from the viewpoint of reaction control, it is preferable to produce the hydrogenated block copolymer (A1) by hydrogenating the block copolymer (A0) and then introducing a specific functional group.

[0068] The reaction for modifying the hydrogenated block copolymer (A1) by introducing the above-mentioned functional group (hereinafter, sometimes referred to as "modification reaction") can be carried out by a known method. The above modification reaction can be carried out, for example, by dissolving the hydrogenated block copolymer (A1) in an organic solvent, adding various modifiers capable of adding the above-mentioned functional groups thereto, and reacting at about 50 to 300° C. for about 0.5 to 10 hours. The modification reaction can be carried out, for example, by melting the hydrogenated block copolymer (A1) using an extruder or the like without using a solvent, and adding various modifiers. In this case, the temperature of the modification reaction is usually from the melting point of the hydrogenated block copolymer (A1) to 400°C, preferably 90 to 350°C, more preferably 100 to 300°C, and the reaction time is usually about 0.5 to 10 minutes. In addition, when the above-mentioned modification reaction is carried out in a molten state, it is preferable to add a radical initiator, and from the viewpoint of suppressing side reactions, an antioxidant may be added.

[0069] In the method for producing the modified hydrogenated product (A), the modification reaction is preferably carried out by the latter method of modification in a molten state, from the viewpoint of improving workability, vibration damping properties and thermal stability. That is, a preferred embodiment of the method for producing the modified hydrogenated product (A) further comprises a step of hydrogenating the block copolymer (A0) to obtain the hydrogenated block copolymer (A1), and then introducing one or more functional groups selected from an alkoxysilyl group, a carboxy group, an amino group, a hydroxyl group, an epoxy group, and a group derived from an acid anhydride into the molten hydrogenated block copolymer (A1) using a radical initiator.

[0070] Examples of the modifying agent capable of adding the functional group include dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, hydroxymethyltriethoxysilane, vinylbenzyldiethylamine, vinylbenzyldimethylamine, 1-glycidyl-4-(2-pyridyl)piperazine, 1-glycidyl-4-phenylpiperazine, 1-glycidyl-4-methylpiperazine, 1-glycidyl-4-methylhomopiperazine, 1-glycidylhexamethyleneimine, and tetraglycidyl-1,3-bisaminomethylcyclohexane. In addition, as the modifying agent, unsaturated carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, and itaconic anhydride can also be used. Furthermore, the modifying agent capable of adding the functional group may be selected from the modifying agents described in JP-A-2011-132298. The above-mentioned modifying agents can be used alone or in combination of two or more.

[0071] The amount of the modifier to be added may be appropriately determined so as to obtain a desired content of the functional groups according to the content of the functional groups in the modified hydrogenated product (A) described above. The amount of the modifier to be added is usually about 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, and even more preferably 0.05 to 2 parts by mass, per 100 parts by mass of the hydrogenated block copolymer (A1) or block copolymer (A0).

[0072] As the radical initiator, organic peroxides or organic peresters such as dialkyl peroxides, diacyl peroxides, peroxy esters, peroxy ketals, and hydroperoxides can be used, and azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate can also be used. Among the above radical initiators, organic peroxides are preferred, and dialkyl peroxides are more preferred. The amount of the radical initiator to be added may be appropriately determined depending on the combination of the hydrogenated block copolymer (A1) or block copolymer (A0) and the modifier. The amount of the radical initiator to be added is usually about 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, and even more preferably 0.05 to 2 parts by mass, per 100 parts by mass of the hydrogenated block copolymer (A1) or block copolymer (A0).

[0073] <Polyolefin resin (B)> Examples of the polyolefin resin (B) contained in the resin composition (D1) include polypropylene, polyethylene, polymethylpentene, ethylene-vinyl acetate copolymer, and combinations of two or more of these resins. Examples of the polypropylene include homopolypropylene, block polypropylene which is a block copolymer with an α-olefin such as ethylene, and random polypropylene which is a random copolymer with an α-olefin such as ethylene. Examples of the polyethylene include high density polyethylene, medium density polyethylene, low density polyethylene, and linear low density polyethylene. Examples of the polymethylpentene include a homopolymer of 4-methyl-1-pentene and a copolymer having a structural unit derived from 4-methyl-1-pentene and a structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene). The ethylene-vinyl acetate copolymer is not particularly limited as long as it is a resin in which ethylene is copolymerized with acetic acid as a comonomer, and those having various vinyl acetate group contents (VA contents) can be used. Furthermore, homopolymers or copolymers of α-olefins, copolymers of propylene and / or ethylene with α-olefins, etc. can also be used as the polyolefin resin (B). Examples of the α-olefin include α-olefins having 20 or less carbon atoms, such as 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, and one or more of these may be used. In one embodiment, the polyolefin resin (B) is at least one resin selected from the group consisting of polypropylene, polyethylene, polymethylpentene, ethylene-vinyl acetate copolymer, and homopolymers or copolymers of α-olefins, and copolymers of propylene and / or ethylene with α-olefins.

[0074] <Additives> The resin composition (D1) may contain various additives within the range that does not impair the effects of the present invention. Examples of additives include inorganic fillers such as talc, clay, mica, calcium silicate, glass, hollow glass 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, zinc oxide, magnesium oxide, tin oxide, antimony oxide, barium ferrite, strontium ferrite, carbon black, graphite, carbon fibers, activated carbon, hollow carbon spheres, calcium titanate, lead zirconate titanate, and silicon carbide; organic fillers such as wood flour and starch, cellulose fibers, cellulose nanofibers, carbon fibers, and carbon nanofibers. Further examples of the additives include tackifier resins, plasticizers, fillers, crosslinkers (isocyanate-based crosslinkers, epoxy-based crosslinkers, metal chelate-based crosslinkers, aziridine-based crosslinkers, amine resins, etc.), heat stabilizers, light stabilizers, ultraviolet absorbers, infrared absorbers, antioxidants, lubricants, colorants, antistatic agents, flame retardants, water repellents, waterproofing agents, hydrophilicity-imparting agents, electrical conductivity-imparting agents, thermal conductivity-imparting agents, electromagnetic wave shielding agents, light transmittance adjusting agents, fluorescent agents, sliding properties-imparting agents, transparency-imparting agents, antiblocking agents, metal deactivators, antibacterial agents, crystal nucleating agents, crack prevention agents, ozone degradation inhibitors, rodent repellents, dispersants, thickeners, light resistance agents, weather resistance agents, copper damage inhibitors, reinforcing agents, antifungal agents, and macrocyclic molecules (cyclodextrin, calixarene, cucurbituril, etc.). The above additives may be used alone or in combination of two or more. The content of the additive in the resin composition (D1) is not limited, and can be appropriately adjusted depending on the type of the additive and the use of the resin composition (D1). When the resin composition (D1) contains the additive, the content of the additive may be, for example, 50 mass% or less, 45 mass% or less, 30 mass% or less, 20 mass% or less, or 10 mass% or less, or 0.01 mass% or more, 0.1 mass% or more, 1 mass% or more, or 5 mass% or more, based on the total mass of the resin composition (D1). In other words, the content of the additive in the resin composition (D1) is preferably 0.01 to 50 mass%.

[0075] <Proportion of each component in resin composition (D1)> In the first resin composition (D1), when the mass of the modified hydrogenated product (A) is Aa and the mass of the polyolefin resin (B) is Ba, from the viewpoint of adhesion, Aa / Ba is preferably 95 / 5 to 5 / 95, more preferably 80 / 20 to 10 / 90, and even more preferably 70 / 30 to 10 / 90.

[0076] In addition, the total mass of the modified hydrogenated product (A) and the polyolefin resin (B) contained in the first resin composition (D1) is preferably 50% by mass or more, more preferably 65% ​​by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, from the viewpoint of fully expressing adhesiveness. There is no particular upper limit to the total mass, and it may be 100% by mass, 99.9% by mass, or 99.5% by mass. In other words, the total mass of the modified hydrogenated product (A) and the polyolefin resin (B) contained in the first resin composition (D1) is preferably 50 to 100% by mass.

[0077] <Characteristics of resin composition (D1)> (Adhesive strength to metal) The adhesive strength of the resin composition (D1) to an aluminum alloy plate (A5052P) is preferably 2.5 N / mm 2 More preferably, 3.0N / mm 2More preferably, 3.5N / mm 2 More preferably, 4.0N / mm 2 That's all. In addition, the adhesive strength of the resin composition (D1) to a stainless steel plate (SUS304) is preferably 3.5 N / mm 2 More preferably, 4.0N / mm 2 More preferably, 4.5N / mm 2 More preferably, 5.0 N / mm 2 More preferably, 5.5 N / mm 2 That's all. In either case, there is no upper limit to the adhesive strength, but as a guideline for the adhesive strength that can be actually measured, 30N / mm 2 may be also possible.

[0078] The adhesive strength of the resin composition (D1) when a metal plate is used as an adherend is measured by placing a test piece of 34 mm long x 10 mm wide x 0.05 cm thick between a pair of metal plates, pressurizing and heating the test piece, and pulling the non-adhered ends of the two adherends in opposite directions at a tensile speed of 5 mm / min using a shear peel tester Instron 3345 (manufactured by Instron Corporation) to shear peel the test piece. In detail, the test piece is measured by the method described in the Examples.

[0079] (Melt Flow Rate (MFR)) From the viewpoint of ensuring the fluidity during preparation of the resin composition (D1), the MFR of the resin composition (D1) is preferably 5 to 30 g / 10 min, more preferably 10 to 25 g / 10 min, and further preferably 15 to 25 g / 10 min. The MFR is measured in accordance with JIS K7210 (2014) at a temperature of 230°C and a load of 21N using a melt indexer (MELT INDEXER L241 manufactured by Tateyama Scientific High-Technologies Corporation).

[0080] (tensile modulus) From the viewpoint of achieving both flexibility and mechanical strength, the tensile modulus of the resin composition (D1) is preferably 10 to 400 MPa, more preferably 20 to 350 MPa, and even more preferably 25 to 300 MPa. There is no particular upper or lower limit to the tensile modulus, and it can be appropriately specified depending on the application. The tensile modulus can be measured in accordance with JIS K6251 (2017) using a No. 3 dumbbell as the test piece at a tensile speed of 500 mm / min.

[0081] (Breaking Stress) From the viewpoint of mechanical strength, the breaking stress of the resin composition (D1) is preferably 10 to 35 MPa, more preferably 15 to 30 MPa, and further preferably 20 to 30 MPa. There is no particular upper limit to the breaking stress, and it can be appropriately specified depending on the application. The breaking stress can be measured in accordance with JIS K6251 (2017) using a No. 3 dumbbell as the test piece at a tensile speed of 500 mm / min.

[0082] (Elongation at break) In addition, from the viewpoint of mechanical strength, the resin composition (D1) has a breaking elongation measured in accordance with JIS K6251 (2017) using a dumbbell No. 3 test piece at a tensile speed of 500 mm / min of preferably 200% or more, more preferably 300% or more, and even more preferably 600% or more.

[0083] (hardness) From the viewpoint of flexibility, the resin composition (D1) has a type D durometer hardness at an ambient temperature of 23° C., measured in accordance with JIS K6253-3 (2012), of preferably 20 to 70, more preferably 25 to 65, and even more preferably 30 to 60.

[0084] <Method for producing resin composition (D1)> The resin composition (D1) can be produced by mixing the modified hydrogenated product (A), the polyolefin resin (B), and, if necessary, various additives, using a mixer such as a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or a conical blender, or by subsequently melt-kneading the mixture at about 80 to 350°C using a kneader such as a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or a roll. Alternatively, the resin composition can be prepared by dissolving and mixing at least the modified hydrogenated product (A) and the polyolefin resin (B) in a solvent in which they are soluble, and then removing the solvent. The resin composition can be in any shape such as veil, crumb, pellet, etc. The resin composition can be molded into various molded products by a melt kneading molding machine, or by using the veil, crumb, pellet, etc. of the resin composition as a raw material, by injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, etc.

[0085] <Uses of resin composition (D1)> The resin composition (D1) has adhesive properties to various materials, and particularly has high adhesive properties to metals, and therefore can be suitably used as a sealant for joints between glass and aluminum sashes or metal openings in windows of automobiles or buildings, and joints between glass and metal frames in solar cell modules, etc. In addition, it is useful in a wide range of applications as molded articles or structures bonded to glass, such as window moldings and gaskets for automobiles or buildings, glass sealants, and anticorrosive materials. Furthermore, it can be used as an adhesive or coating agent for separators of secondary batteries used in various information terminal devices such as notebook computers, mobile phones, and video cameras, hybrid automobiles, fuel cell automobiles, etc.

[0086] [glue] The adhesive according to an embodiment of the present invention contains a resin composition (D1). The adhesive contains the resin composition (D1) and thereby exhibits adhesiveness to various materials such as metals, glass, and resins, and can bond, for example, metal and resin, glass and resin, metal and glass, polar resin and non-polar resin, non-polar resin and non-polar resin, polar resin and polar resin, etc. The adhesive has particularly high adhesiveness to metals.

[0087] There are no particular limitations on the metal to be bonded by the adhesive, and examples thereof include aluminum, aluminum alloys, stainless steel, copper, magnesium alloys, etc. In particular, the adhesive exhibits high adhesion to aluminum, aluminum alloys, and stainless steel, and is therefore preferably applied to these metals.

[0088] The adhesive may be entirely made of the resin composition (D1), or may contain the resin composition (D1) and other additives.

[0089] Additives that can be included in the adhesive include those similar to those mentioned above.

[0090] The total amount of the modified hydrogenated product (A) and the polyolefin resin (B) contained in the adhesive is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, from the viewpoint of ensuring adhesion to the adherend. In other words, the total amount of the modified hydrogenated product (A) and the polyolefin resin (B) contained in the adhesive is preferably 70 to 100% by mass.

[0091] The properties of the adhesive, such as adhesive strength to the adherend, hardness, tensile modulus, breaking stress, and breaking elongation, are the same as those described for the resin composition (D1).

[0092] When the adhesive is bonded to a metal, the adhesive can be placed on the metal to be bonded and heated, or the adhesive that has been heated and melted can be supplied onto the metal to be bonded. Furthermore, when using the above adhesive to bond metals together, the adhesive can be placed on one of the metals to be bonded, and the other metal placed on top of it and then heated and pressurized, or the adhesive that has been heated and melted can be supplied onto one of the metals to be bonded, and the other metal placed on top of it and then pressed.

[0093] [Compatibilizer] The compatibilizer according to an embodiment of the present invention is a compatibilizer for compatibilizing a polar resin and a non-polar resin, The present invention comprises a modified hydrogenated product (A) of a block copolymer including a polymer block (A-1) having a structural unit derived from an aromatic vinyl compound and a polymer block (A-2) having a structural unit derived from a conjugated diene compound, The modified hydrogenated product (A) has one or more functional groups selected from an alkoxysilyl group, a carboxy group, an amino group, a hydroxyl group, an epoxy group, and a group derived from an acid anhydride, The vinyl bond amount of the polymer block (A-2) is 50 to 99 mol %.

[0094] The compatibilizer may consist of the modified hydrogenated product (A) alone, or may contain components other than the modified hydrogenated product (A). Examples of such components include processing aids, reinforcing agents, fillers, plasticizers, interconnecting cell agents, heat stabilizers, light stabilizers, ultraviolet absorbers, antioxidants, lubricants, antistatic agents, antibacterial agents, antifungal agents, dispersants, colorants, foaming agents, foaming assistants, flame retardants, water repellents, waterproofing agents, electrical conductivity imparting agents, thermal conductivity imparting agents, electromagnetic wave shielding agents, fluorescent agents, and crystal nucleating agents. The content of the modified hydrogen additive (A) in the compatibilizer is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total mass of the compatibilizer, from the viewpoint of ensuring sufficient compatibility. There is no particular limit to the upper limit, and it may be 100% by mass, but from the viewpoint of ensuring good productivity, it can be, for example, 99.8% by mass or less. In other words, the content of the modified hydrogen additive (A) in the compatibilizer is preferably 80 to 100% by mass.

[0095] The polar resin to be compatibilized by the compatibilizer is the same as the polar resin (C) described below. The non-polar resin to be compatibilized by the compatibilizer is, for example, the resin listed as the polyolefin resin (B) above, and other examples include styrene resins.

[0096] The above compatibilizer may be mixed together with the polar resin (C) and the polyolefin resin (B), or may be mixed with the polar resin (C) and then the polyolefin resin (B) is added, or may be mixed with the polyolefin resin (B) and then the polar resin (C) is added.

[0097] [Second resin composition (D2)] The second resin composition (D2) according to the embodiment of the present invention includes the first resin composition (D1) and a polar resin (C). Hereinafter, the second resin composition (D2) may be referred to as "resin composition (D2)".

[0098] The modified hydrogenated product (A) contained in the first resin composition (D1) has a specific functional group introduced by modification and has a polymer block (A-2) with a high vinyl bond content. Therefore, when the resin composition (D1) and the polar resin (C) are melt-kneaded, for example, the modified hydrogenated product (A) promotes the compatibility of the polyolefin resin (B) and the polar resin (C), and a second resin composition (D2) is obtained in which one of the polyolefin resin (B) and the polar resin (C) is well dispersed in the other of the polyolefin resin (B) and the polar resin (C). Therefore, the resin composition (D2) has excellent processability and moldability compared to the polyolefin resin (B) alone. In addition, the amount of the modified hydrogenated product (A) can be reduced. In addition, since one of the polar resin (C) and the polyolefin resin (B) is easily dispersed in the other of the polar resin (C) and the polyolefin resin (B), the resin composition (D2) or a molded article thereof has a good appearance. In addition, the characteristics due to the block copolymer (A0) used as a raw material are easily exhibited in the resin composition (D2) or a molded article thereof. Since the resin composition (D2) uses a modified hydrogenated product (A) obtained from a block copolymer (A0) having a high vinyl bond amount in the polymer block (A-2), the vibration damping property of the resin composition (D2) or a molded article thereof can be improved. In addition, by appropriately selecting the type of the polar resin (C) or the polyolefin resin (B), the resin composition (D2) or a molded article thereof can have excellent physical properties such as tensile strength and elongation property.

[0099] <Morphology of Resin Composition (D2)> A preferred embodiment of the resin composition (D2) has a sea-island structure in which domains containing the polar resin (C) are dispersed in the form of islands in a matrix of the polyolefin resin (B), and more preferably has a structure in which a component mainly composed of the modified hydrogenated product (A) is present along the periphery of a domain mainly composed of the polar resin (C). Fig. 2 is a cross-sectional schematic diagram showing an example of an island-in-sea structure in resin composition (D2). As shown in Fig. 2, in resin composition (D2) or a molded product thereof, a plurality of domains 10 are present in a matrix 20 made of polyolefin resin (B). The domains 10 include a core portion 10a mainly made of polar resin (C) and a shell portion 10b mainly made of modified hydrogenated product (A).

[0100] Fig. 3(a) is an enlarged cross-sectional photograph taken with a scanning electron microscope (SEM) showing an example of the morphology of the resin composition (D2). Fig. 3(a) corresponds to Example 8 described later, and shows that domains containing a polar resin (C) are dispersed in the form of islands in a matrix of a polyolefin resin (B). Another preferred embodiment of the resin composition (D2) has a sea-island structure in which domains containing the polyolefin resin (B) are dispersed in the form of islands in a matrix of the polar resin (C), and more preferably has a structure in which a component mainly composed of the modified hydrogenated product (A) is present along the periphery of a domain mainly composed of the polyolefin resin (B).

[0101] As described above, the modified hydrogenated product (A) having the polymer block (A-2) with a high vinyl bond content promotes the compatibilization of the polyolefin resin (B) and the polar resin (C). Therefore, the size of the domains mainly composed of the polar resin (C) and the domains mainly composed of the polyolefin resin (B) formed in the resin composition (D2) or a molded article thereof can be made fine, for example, with an average diameter of 500 nm or less.

[0102] The dispersion diameter of the domains mainly made of polar resin (C) or the domains mainly made of polyolefin resin (B) is preferably 0.01 to 8 μm, more preferably 0.02 to 6 μm, and even more preferably 0.03 to 4 μm. Here, the dispersion diameter is the volume average dispersion diameter of the major axis of the core-shell structure. Specifically, a test piece having a thickness of 1 mm obtained by the sheet preparation method described later was cross-sectioned using an ultramicrotome, stained with a 0.5% aqueous solution of ruthenium tetroxide, and vapor-deposited with platinum. The cross-section thus treated was then observed by SEM, and the average value of the major axes of 50 pieces was taken as the volume average dispersion diameter. The average diameter, which is the average value of the dispersed diameters, is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. There is no particular lower limit to the average diameter of the domains, but it is, for example, 100 nm or more. When the volume average dispersed diameter or average diameter of the domains is within the above numerical range, the dispersibility of the polar resin (C) in the polyolefin resin (B) or the dispersibility of the polar resin (C) in the polyolefin resin (B) can be improved, and the mechanical properties of the resin composition (D2) or a molded article of the resin composition (D2) can be improved.

[0103] The domain mainly made of the polar resin (C) may contain one or more subdomains made of a component different from the polar resin (C). Examples of the subdomain include domains made of the polyolefin resin (B), the modified hydrogenated product (A), a polymer before modification, a hydrogenated product, etc. In this way, when a core-shell structure including a domain made of a component different from the polar resin (C) exists, impact resistance is easily improved. In addition, the domain mainly made of the polyolefin resin (B) may contain one or more subdomains made of a component different from the polyolefin resin (B). Examples of the subdomain include domains made of the polar resin (C), the modified hydrogenated product (A), a polymer before modification, a hydrogenated product, etc. In this way, when a core-shell structure including a domain made of a component different from the polyolefin resin (B) exists, impact resistance is easily improved.

[0104] <Polar resin (C)> The polar resin (C) contained in the resin composition (D2) refers to a resin having a polar group such as a carboxy group, a sulfonic acid group, a hydroxyl group, or a cyano group; a resin having an ether bond, an ester bond, an amide bond, a sulfide bond, or the like in the resin; or a resin containing at least one of oxygen, nitrogen, sulfur, and a halogen in the molecule, and is a resin in which electronic polarization occurs within the molecule and which has thermoplasticity. The polar resin (C) is preferably a resin having a polar group such as a sulfonic acid group or a cyano group, a resin having an ether bond, an ester bond, an amide bond, a sulfide bond, or the like in the resin, a resin containing at least one of oxygen, nitrogen, sulfur, and a halogen in the molecule, or the like, and more preferably a resin having at least one of an ether bond, an ester bond, and an amide bond in the resin. The preferred polar resin is at least one selected from the group consisting of polyamide resins such as nylon 6, nylon 66, nylon 610, nylon 9, nylon 6 / 66, nylon 66 / 610, nylon 6 / 11, nylon 6 / 12, nylon 12, nylon 46, and amorphous nylon; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polylactic acid; polyacetal resins such as polyoxymethylene homopolymers and polyoxymethylene copolymers; polyphenylene sulfide (PPS) resins, polyphenylene ether resins, polyarylate resins, polyethersulfone resins, polyurethane resins, polyvinyl alcohol-based resins, polycarbonate resins, ethylene-vinyl acetate copolymers, ethylene-methacrylic acid copolymers, polyether ketones, polyether ether ketones, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, vinylon, triacetyl cellulose, ABS resins, AS resins, ACS resins, xylene resins, acrylic resins, and polyester-based thermoplastic elastomers. More preferably, the resin is at least one selected from polyamide resin, polyester resin, polyacetal resin, polyphenylene sulfide resin, polyurethane resin, polyvinyl alcohol-based resin, polycarbonate resin, and polyester-based thermoplastic elastomer, and even more preferably, the resin is at least one selected from polyamide resin, polyvinyl alcohol-based resin, polyester-based resin, and polycarbonate resin.

[0105] The polyester-based thermoplastic elastomer used as the polar resin (C) can be obtained, for example, by subjecting (i) an aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, (ii) an aromatic dicarboxylic acid or an alkyl ester thereof, and (iii) a polyalkylene ether glycol as raw materials to an esterification reaction or a transesterification reaction to obtain an oligomer, and then subjecting the oligomer to a polycondensation reaction. An example of a commercially available polyester-based thermoplastic elastomer is Hytrel 3046 (registered trademark) manufactured by DuPont-Toray Co., Ltd.

[0106] <Additives> The resin composition (D2) may contain various additives within the range that does not impair the effects of the present invention. Examples of such additives include those similar to those described for the resin composition (D1).

[0107] The content of the additives in the resin composition (D2) is not limited, and can be appropriately adjusted depending on the type of the additives and the use of the resin composition (D2). When the resin composition (D2) contains the additives, the content of the additives may be, for example, 50 mass% or less, 45 mass% or less, 30 mass% or less, 20 mass% or less, or 10 mass% or less, or 0.01 mass% or more, 0.1 mass% or more, 1 mass% or more, or 5 mass% or more, based on the total mass of the resin composition (D2). In other words, the content of the additives in the resin composition (D2) is preferably 0.01 to 50 mass%.

[0108] <Proportion of each component in resin composition (D2)> The proportion of the polar resin (C) in the resin composition (D2) is preferably 10 to 90% by mass, based on the total mass of the resin composition (D2). From the viewpoint of flexibility of the composition, it is more preferably 10 to 50% by mass, even more preferably 10 to 45% by mass, and even more preferably 10 to 40% by mass. Also, from the viewpoint of mechanical strength, it is more preferably 50 to 90% by mass, even more preferably 50 to 85% by mass, and even more preferably 50 to 80% by mass, based on the total mass of the resin composition (D2). In addition, when the mass of the polyolefin resin (B) in the resin composition (D2) is Bb and the mass of the polar resin (C) is C, from the viewpoint of flexibility of the composition, Bb / C is preferably 90 / 10 to 50 / 50, more preferably 90 / 10 to 55 / 45, even more preferably 90 / 10 to 60 / 40, still more preferably 90 / 10 to 70 / 30, and particularly preferably 90 / 10 to 75 / 25. In addition, from the viewpoint of mechanical strength, Bb / C is preferably 50 / 50 to 10 / 90, more preferably 50 / 50 to 15 / 85, even more preferably 50 / 50 to 20 / 80, still more preferably 50 / 50 to 25 / 75, and particularly preferably 50 / 50 to 30 / 70. When Bb / C is within the above range, it is possible to improve physical properties such as vibration damping properties while suppressing a significant decrease in the mechanical properties of the polyolefin resin (B).

[0109] In the resin composition (D2), the mass of the modified hydrogenated product (A) is Ab and the mass of the polyolefin resin (B) is Bb. From the viewpoint of making it easier for the modified hydrogenated product (A) to exhibit its properties such as vibration damping, Ab / Bb is preferably 30 / 70 to 1 / 99, more preferably 25 / 75 to 3 / 98, and even more preferably 20 / 80 to 5 / 95.

[0110] In addition to the resin composition (D1) and the polar resin (C), the resin composition (D2) may further contain a block copolymer (A0) and its hydrogenated product (A1). From the viewpoint of mechanical properties, the total content of the block copolymer (A0) and its hydrogenated product (A1) is preferably 1 to 20 mass%, more preferably 1 to 10 mass%, and even more preferably 1 to 5 mass%, based on the total mass of the resin composition (D2).

[0111] The resin composition (D2) may contain resin components other than the modified hydrogenated product (A), the polyolefin resin (B), the block copolymer (A0), and the hydrogenated block copolymer (A1). For example, the resin composition (D2) may contain a non-polar resin other than the polyolefin resin (B). A preferred embodiment of the resin composition (D2) is one in which the non-polar resin is only the polyolefin resin (B). From the viewpoint of ensuring the vibration damping properties and mechanical properties of the resin composition (D2), the content of resin components contained in the resin composition (D2) other than the modified hydrogenated product (A), the polyolefin resin (B), the block copolymer (A0), and the hydrogenated block copolymer (A1) is preferably 0 to 50 mass%, more preferably 0 to 30 mass%, even more preferably 0 to 20 mass%, still more preferably 0 to 10 mass%, and most preferably 0 to 5 mass%.

[0112] <Characteristics of resin composition (D2)> (loss tangent (tanδ)) From the viewpoint of exhibiting good vibration damping properties over a wide temperature range, the resin composition (D2) preferably has a peak intensity of 0.1 to 2.0, more preferably 0.1 to 1.0, and even more preferably 0.1 to 0.5 of loss tangent (tan δ) at 0 to 50°C, measured in accordance with JIS K7244-10 (2005) under conditions of a strain of 0.1%, a frequency of 10 Hz, a measurement temperature of -100 to +150°C, and a heating rate of 3°C / min. The good vibration damping properties of the resin composition (D2) over a wide temperature range can be achieved by controlling the type of block copolymer (A0), the type and content ratio of the monomers used in the modified hydrogenated product (A), the balance between the vinyl bond amount and the hydrogenation rate, selection of the production method for the modified hydrogenated product (A), control of other components of the modified hydrogenated product (A), or adjustment of the combination of the polar resin (C) and the polyolefin resin (B) used in the resin composition (D2) and their content ratios, etc.

[0113] (tensile breaking strain) Furthermore, the resin composition (D2) has a tensile breaking strain measured in accordance with JIS K7161-1 (2014) using a multipurpose test specimen A1 type test specimen at a tensile speed of 50 mm / min, which is, from the viewpoint of mechanical strength, preferably 25% or more, more preferably 30% or more, even more preferably 50% or more, still more preferably 75% or more, still more preferably 100% or more, still more preferably 150%, still more preferably 200% or more, still more preferably 250% or more, and still more preferably 300% or more.

[0114] (hardness) The resin composition (D2) has a type D durometer hardness at an ambient temperature of 23° C., measured in accordance with JIS K6253-3 (2012), of preferably 20 to 90, more preferably 25 to 85, and even more preferably 30 to 80, from the viewpoint of flexibility.

[0115] <Method for producing resin composition (D2)> The resin composition (D2) can be produced by mixing the polar resin (C) and the resin composition (D1), and, if necessary, various additives, using a mixer such as a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or a conical blender, or by subsequently melt-kneading the mixture at about 80 to 350°C using a kneader such as a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or a roll. Alternatively, the resin composition can be prepared by dissolving and mixing at least the polar resin (C) and the resin composition (D1) in a solvent in which they are soluble, and then removing the solvent. In addition, when producing the resin composition (D2), it is sufficient that the polar resin (C) and the resin composition (D1) are mixed as a result, and there is no particular restriction on the mixing order of the individual components constituting them. For example, the modified hydrogenated product (A) and the polyolefin resin (B) constituting the resin composition (D1) may be added and mixed individually and sequentially to the polar resin (C), or the modified hydrogenated product (A) and the polyolefin resin (B) may be mixed and then added and mixed to the polar resin (C), or the polar resin (C), the modified hydrogenated product (A), and the polyolefin resin (B) may be mixed all at once. As described above, there is no restriction on the addition order, but from the viewpoint of further improving the dispersibility and the physical properties of the resulting resin composition (D2), it is preferable to add the modified hydrogenated product (A) and the polar resin (C) and then add the polyolefin resin (B). The resin composition (D2) can be in any shape such as veil, crumb, pellet, etc. The resin composition (D2) can be molded into various molded products by a melt kneading molding machine or by using the veil, crumb, pellet, etc. of the resin composition as a raw material through injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, etc.

[0116] <Uses of resin composition (D2)> The resin composition (D2) can be used for various applications. The resin composition (D2) of the present embodiment has excellent vibration-damping properties and high elongation properties, and can be used in various applications. Therefore, the present invention also provides vibration-damping materials, films, sheets, and the like, which use the resin composition (D2). It is also possible to provide a laminate having an X layer containing the resin composition (D2) and a Y layer laminated on at least one surface of the X layer. For example, a laminated glass is suitable as the laminate, and by forming the laminated glass with the X layer as an interlayer film for laminated glass and the Y layer as glass, not only excellent vibration damping properties but also excellent sound insulation properties can be expected.

[0117] Other applications include pellets, bales, sound absorbing materials, sound insulating materials, dam rubber, shoe sole materials, flooring materials, weather strips, floor mats, dash insulators, roof linings, door panels, engine head covers, door hole seals, fender liners, etc., and the material is also useful for these applications. The resin composition (D2) can be used in a wide variety of automotive components in the automotive field, for example: cooling parts such as thermostat housings, radiator tanks, radiator hoses, water outlets, water pump housings, and rear joints; intake and exhaust system parts such as intercooler tanks, intercooler cases, turbo duct pipes, EGR cooler cases, resonators, throttle bodies, intake manifolds, and tail pipes; fuel system parts such as fuel delivery pipes, gasoline tanks, quick connectors, canisters, pump modules, fuel piping, oil strainers, lock nuts, and seals; structural parts such as mount brackets, torque rods, and cylinder head covers; drive system parts such as bearing retainers, gear tensioners, headlamp actuator gears, HVAC gears, sliding door rollers, and clutch peripheral parts; air brakes, etc. It can also be used for brake system parts such as brake tubes; automotive electrical parts such as wire harness connectors in the engine bay, motor parts, sensors, ABS bobbins, combination switches, on-board switches, electronic control unit (ECU) boxes, etc.; interior and exterior parts such as sliding door dampers, door mirror stays, door mirror brackets, inner mirror stays, roof rails, engine mount brackets, air cleaner inlet pipes, door checkers, plastic chains, emblems, clips, breaker covers, cup holders, airbags, fenders, spoilers, radiator supports, radiator grilles, louvers, air scoops, hood bulges, back doors, fuel sender modules, floor mats, instrument panels, dashboards, dash insulators, dam rubber, weather strips, and tires.

[0118] In addition, it can be used in the field of home appliances, such as televisions, various recorders such as Blu-ray recorders and HDD recorders, projectors, game machines, digital cameras, home videos, antennas, speakers, electronic dictionaries, IC recorders, FAX machines, copy machines, 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 equipment, air conditioners, outdoor units of air conditioners, dehumidifiers, humidifiers, and other electrical products, as sealing materials, adhesives, pressure sensitive adhesives, packing, O-rings, belts, soundproofing materials, etc. It can also be used as a fiber. EXAMPLES

[0119] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these.

[0120] 1. Modified hydrogenated products (A) [Measurement methods for each physical property] The methods for evaluating the physical properties of the hydrogenated block copolymer (A1) and the modified hydrogenated product (A) obtained in the Production Examples described later are shown below. (1) Content of polymer block (A-1) The block copolymer before hydrogenation was dissolved in CDCl 3 Dissolve in 1 H-NMR measurement [apparatus: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30°C] was performed, and the content of polymer block (A-1) was calculated from the ratio of the peak intensity derived from styrene to the peak intensity derived from diene.

[0121] (2) Weight average molecular weight (Mw) The weight average molecular weight (Mw) of the polymer block (A-1), the polymer block (A-2), the hydrogenated product of the block copolymer, and the modified hydrogenated product was determined in terms of polystyrene by gel permeation chromatography (GPC) measurement under the following conditions. (GPC measurement equipment and measurement conditions) · Apparatus: GPC apparatus "HLC-8020" (manufactured by Tosoh Corporation) Separation columns: "TSKgel GMHXL", "G4000HXL" and "G5000HXL" manufactured by Tosoh Corporation were connected in series. Eluent: Tetrahydrofuran ·Eluent flow rate: 0.7mL / min Sample concentration: 5mg / 10mL Column temperature: 40℃ Detector: Refractive index (RI) detector Calibration curve: Created using standard polystyrene

[0122] (3) Hydrogenation rate in polymer block (A-2) 1 It was calculated from the ratio of the peak area derived from the residual olefins of isoprene and / or butadiene to the peak area derived from ethylene, propylene and / or butylene by H-NMR measurement. Equipment: Nuclear magnetic resonance equipment "ADVANCE 400 Nano bay" (Bruker) Solvent: CDCl 3

[0123] (4) Amount of vinyl bonds in polymer block (A-2) The block copolymer before hydrogenation was dissolved in CDCl 3 Dissolve in 1 H-NMR measurement was performed [apparatus: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30°C]. The vinyl bond amount (total content of 3,4-bond units and 1,2-bond units) was calculated from the ratio of the total peak area of ​​structural units derived from isoprene and / or butadiene to the peak area corresponding to the 3,4-bond units and 1,2-bond units in the isoprene structural unit, the 1,2-bond units in the butadiene structural unit, or, in the case of structural units derived from a mixture of isoprene and butadiene, the vinyl bond amount (total content of 3,4-bond units and 1,2-bond units) was calculated from the ratio of the peak area corresponding to each of the above bond units.

[0124] (5) Amount of modification of modified hydrogenated product (A) (phr) The amount of modification with maleic anhydride in the modified hydrogenated product (A) was measured by the following procedure: 5 g of the modified hydrogenated product (A) was dissolved in 180 ml of toluene, 20 ml of ethanol was added, and the solution was titrated with a 0.1 mol / L potassium hydroxide solution to calculate the amount of modification using the following formula. Maleic anhydride modification amount (phr) = titration amount x 5.611 / sample amount x 98 x 100 / 56.11 x 1000

[0125] (6) Amount of modification of modified hydrogenated product (A) (mol %) The modification amount (mol%) was calculated from the maleic anhydride modification amount (phr) calculated above using the following formula. Amount of maleic anhydride modification (mol%)={amount of maleic anhydride modification (phr) / molecular weight of maleic anhydride} / {amount of maleic anhydride modification (phr) / molecular weight of maleic anhydride+content of polymer block (A) (mass%) / molecular weight of structural unit of polymer block (A)+content of polymer block (B) (mass%) / molecular weight of structural unit of polymer block (B)}×100

[0126] (7) Glass transition temperature of modified hydrogenated product (A) The glass transition temperatures of the modified hydrogenated products (Y-2) to (Y-7) described below, which are the modified hydrogenated product (A), were measured using a DSC measurement device (DSC250 manufactured by TA Instruments, Inc.) Specifically, using the above device, measurements were performed under conditions of a temperature range of -120°C to +350°C and a heating rate of 10°C / min, and the inflection point temperature of the baseline shift due to the glass transition was determined as the glass transition temperature. The glass transition temperature of the hydrogenated block copolymer (Y-1) was also measured in the same manner.

[0127] (8) Peak top temperature and peak top intensity of tan δ The peak top temperature and strength of tan δ of modified hydrogenated products (Y-2) to (Y-7) described later, which are modified hydrogenated products (A), were measured by pressurizing the modified hydrogenated product (A) at a temperature of 230°C and a pressure of 10 MPa for 3 minutes to produce a single-layer sheet with a thickness of 1.0 mm, which was then cut into a disk shape to serve as a test piece. For the measurement, a distortion-controlled dynamic viscoelasticity device "ARES-G2" (manufactured by TA Instruments Co., Ltd.) with a disk diameter of 8 mm was used as a parallel plate vibration rheometer based on JIS K 7244-10 (2005). The gap between the two flat plates was completely filled with the test sheet, and the test sheet was subjected to vibration at a frequency of 1 Hz with a distortion of 0.1%. The temperature was raised from -70°C to 200°C at a constant rate of 3°C / min, and the maximum value of the peak intensity of tan δ (peak top intensity) and the temperature at which this maximum value was obtained (peak top temperature) were determined.

[0128] [Production Example 1] (Production of hydrogenated block copolymer (Y-1)) A nitrogen-purged, dried pressure vessel was charged with 50 kg of cyclohexane as a solvent and 87 g of a 10.5 mass % cyclohexane solution of sec-butyllithium as an anionic polymerization initiator (effective amount of sec-butyllithium added: 9.14 g). After the temperature inside the pressure vessel was raised to 50°C, 1.0 kg of styrene (1) was added and polymerized for 1 hour. At a vessel temperature of 50°C, 33 g of 2,2-di(2-tetrahydrofuryl)propane (DTHFP) was added as a Lewis base, and a mixed liquid of 8.16 kg of isoprene and 6.48 kg of butadiene was added over 5 hours and polymerized for 2 hours. Further, 1.0 kg of styrene (2) was added and polymerized for 1 hour, thereby obtaining a reaction liquid containing a polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer. A Ziegler-based hydrogenation catalyst formed from nickel octylate and trimethylaluminum was added to the reaction solution under a hydrogen atmosphere, and the reaction was carried out for 5 hours under conditions of a hydrogen pressure of 1 MPa and 80° C. After the reaction solution was allowed to cool and the pressure was released, the catalyst was removed by washing with water, and the mixture was dried in a vacuum to obtain a hydrogenated product of polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer (hereinafter referred to as Y-1). The raw materials and their amounts used are shown in Table 1, and the results of the physical property evaluation are shown in Table 2.

[0129] [Production Example 2] (Production of modified hydrogenated product (Y-2)) A twin-screw extruder "ZSK26mc" (26 mmφ, L / D=56) manufactured by Coperion was used under the following extrusion conditions. 10 kg of the hydrogenated block copolymer Y-1 obtained above was blended and melted, and 0.05 kg of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Perhexa 25B-40, manufactured by Nippon Oil & Fats Co., Ltd.) was blended as a radical initiator and 0.15 kg of maleic anhydride as a modifier, and a modification reaction was carried out to obtain a modified hydrogenated product (Y-2). The raw materials and their amounts used are shown in Table 1, and the results of the physical property evaluation are shown in Table 2.

[0130] [Production Example 3] (Production of modified hydrogenated product (Y-3)) A hydrogenated block copolymer was produced in the same manner as in Production Example 1, except that 73.4 g of a cyclohexane solution of sec-butyllithium with a concentration of 10.5 mass% (effective amount of sec-butyllithium added: 7.71 g) was used as the anionic polymerization initiator. Furthermore, this hydrogenated product was modified with maleic acid in the same manner as in Production Example 2, to prepare a modified hydrogenated product (Y-3). The raw materials and their amounts used are shown in Table 1, and the results of the physical property evaluation are shown in Table 2.

[0131] [Production Example 4] (Production of modified hydrogenated product (Y-4)) A hydrogenated block copolymer was produced in the same manner as in Production Example 1, except that the amounts of isoprene and catalyst were changed to those shown in Table 1 and that butadiene was not used. Furthermore, this hydrogenated product was modified with maleic acid in the same manner as in Production Example 2, except that the amounts of maleic anhydride and radical initiator were changed to those shown in Table 1, to prepare a modified hydrogenated product (Y-4). The raw materials and their amounts used are shown in Table 1, and the results of the physical property evaluation are shown in Table 2.

[0132] [Production Example 5] (Production of modified hydrogenated product (Y-5)) A hydrogenated block copolymer was produced in the same manner as in Production Example 1, except that the amounts of styrene (1), styrene (2), butadiene, and catalyst were changed to those shown in Table 1, isoprene was not used, and the Lewis base was changed to 110 g of tetrahydrofuran. Furthermore, this hydrogenated product was modified with maleic acid in the same manner as in Production Example 2, except that the amounts of maleic anhydride and radical initiator were changed to those shown in Table 1, to prepare a modified hydrogenated product (Y-5). The raw materials and their amounts used are shown in Table 1, and the results of the physical property evaluation are shown in Table 2.

[0133] [Production Example 6] (Production of modified hydrogenated product (Y-6)) A hydrogenated block copolymer was produced in the same manner as in Production Example 1, except that the amounts of styrene (1), styrene (2), butadiene, and catalyst were changed to those shown in Table 1, isoprene was not used, and the Lewis base was changed to 110 g of tetrahydrofuran. Furthermore, this hydrogenated product was modified with maleic acid in the same manner as in Production Example 2, except that the amounts of maleic anhydride and radical initiator were changed to those shown in Table 1, to prepare a modified hydrogenated product (Y-6). The raw materials and their amounts used are shown in Table 1, and the results of the physical property evaluation are shown in Table 2.

[0134] [Production Example 7] (Production of modified hydrogenated product (Y-7)) A hydrogenated block copolymer was produced in the same manner as in Production Example 1, except that the amounts of styrene (1), styrene (2), isoprene, butadiene, and catalyst were changed to those shown in Table 1, and the Lewis base was changed to 310 g of tetrahydrofuran. Furthermore, this hydrogenated product was modified with maleic acid in the same manner as in Production Example 2, to prepare a modified hydrogenated product (Y-7). The raw materials and their amounts used are shown in Table 1, and the results of the physical property evaluation are shown in Table 2.

[0135] [Table 1]

[0136] [Table 2]

[0137] As shown in Table 2, the hydrogenated product (Y-1) of the block copolymer of Production Example 1 was not modified. The vinyl bond amounts of the polymer blocks (A-2) of the modified hydrogenated products (Y-2) to (Y-4) of Production Examples 2 to 4 were 82, 78, and 83 mol%, respectively, whereas the vinyl bond amounts of the polymer blocks (A-2) of the modified hydrogenated products (Y-5) and (Y-6) of Production Examples 5 and 6 were 40 mol%, and the vinyl bond amount of the polymer block (A-2) of the modified hydrogenated product (Y-7) of Production Example 7 was 60 mol%. In addition, as shown in Table 2, the hydrogenated block copolymer (Y-1) and the modified hydrogenated block copolymers (Y-2) to (Y-4) show a peak top intensity of tan δ of 1.0 or more, and the peak top temperature of tan δ is higher than that of the modified hydrogenated block copolymers (Y-5) and (Y-6). Therefore, it can be said that the hydrogenated block copolymers (Y-1) and the modified hydrogenated block copolymers (Y-2) to (Y-4) have suitable properties as a vibration-damping material at temperatures closer to room temperature than that of the modified hydrogenated block copolymers (Y-5) and (Y-6). The modified hydrogenated block copolymer (Y-7) also shows a peak top intensity of tan δ of 1.0 or more, and the peak top temperature of tan δ is higher than that of the modified hydrogenated block copolymers (Y-5) and (Y-6). Therefore, the modified hydrogenated block copolymer (Y-7) has suitable properties as a vibration-damping material at higher temperatures than that of the modified hydrogenated block copolymers (Y-5) and (Y-6).

[0138] 2. Resin composition (D1) and resin composition (D2) [Measurement methods for each physical property] The methods for measuring the various physical properties of the resin compositions obtained in the respective Examples and Comparative Examples described later are shown below.

[0139] (1) Preparation of test specimen sheets and test specimens The resin compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 8 described below were each preheated at 230°C for 1 minute using a press molding machine "NF-50H" (manufactured by Shinto Metal Industry Co., Ltd.), and then pressed at the same temperature for 3 minutes at a pressure of 10 MPa through a spacer of a specified thickness to produce a sheet, which was then cut to a specified size to prepare a test piece. In Examples 1 to 7 and Comparative Examples 1 to 3, the test pieces or sheets for obtaining test pieces for the "tensile test", "hardness measurement", and "morphology observation" described below were 15 cm long x 15 cm wide x 0.1 cm thick, and the sheets for obtaining test pieces for the "shear peel test" were 15 cm long x 15 cm wide x 0.05 cm thick. The sheets for obtaining test pieces for the "impact resistance" measurement were 15 cm long x 15 cm wide x 0.4 cm thick. The test pieces for the "dynamic viscoelasticity measurement" were 2 cm long x 0.5 cm wide x 0.1 cm thick. For Examples 8 to 12 and Comparative Examples 4 to 8, the test pieces or sheets for obtaining the test pieces for the "tensile test," "hardness measurement," and "impact resistance" described below were 15 cm long x 15 cm wide x 0.4 cm thick, and the test pieces for the "dynamic viscoelasticity measurement" were 2 cm long x 0.5 cm wide x 0.1 cm thick. For Examples 13 to 18 and Comparative Examples 9 to 15, multipurpose test pieces A1 type were prepared using an injection molding machine (C75SX manufactured by Toshiba Machine Co., Ltd.) at the temperatures shown in Table 5 below, and used as test pieces for each test item. For the test pieces for "dynamic viscoelasticity measurement", sheets were prepared in the same manner as in Examples 1 to 12 and Comparative Examples 1 to 8, and had dimensions of 2 cm in length × 0.5 cm in width × 0.1 cm in thickness.

[0140] (2) Shear peel test For Examples 1 to 7 and Comparative Examples 1 to 3, the above-mentioned sheets having a thickness of 0.05 cm were cut into pieces having a length of 34 mm and a width of 10 mm to prepare test pieces for the "shear peel test." A test piece was inserted between the upper surface of one end of a pair of metal plates serving as the adherends and the lower surface of the other end, and together with a 2.5 mm thick spacer, the two adherends were bonded together by pressing them for 2 minutes using the above-mentioned press molding device at a press temperature of 200°C and a press pressure of 0 MPa. Then, using a shear peel tester Instron 3345 (manufactured by Instron Corporation), the non-bonded ends of the two adherends were pulled in opposite directions at a tensile speed of 5 mm / min to shear peel the adhesive strength. The adherends used were a stainless steel plate (SUS304) and an aluminum alloy plate (A5052P) each measuring 120 mm in length, 35 mm in width, and 1 mm in thickness.

[0141] (3) Tensile test For Examples 1 to 7 and Comparative Examples 1 to 3, dumbbell No. 3 test pieces were prepared by cutting out the above-mentioned sheets. Using the above test pieces, in accordance with JIS K6251 (2017), with an Instron 3345 (manufactured by Instron Corporation), at a tensile speed of 500 mm / min, the tensile modulus (MPa), breaking stress (MPa), and elongation at break (%) were measured. For Examples 8 to 12 and Comparative Examples 4 to 8, by cutting out the above sheet, a multi-purpose test piece A1 type was produced. For Examples 13 to 18 and Comparative Examples 9 to 15, using the multi-purpose test piece A1 type produced by the above injection molding machine, in accordance with JIS K7161-1 (2014), with an Instron 3345 (manufactured by Instron Corporation), at a tensile speed of 50 mm / min, the tensile modulus (MPa), tensile strength (MPa), and tensile fracture strain (%) were measured.

[0142] (4) Measurement of hardness In accordance with JIS K6253-3 (2012), the hardness was measured using a type D durometer (manufactured by Kobunshi Keiki Co., Ltd.).

[0143] (5) Measurement of melt flow rate (MFR) In accordance with JIS K7210 (2014), under the conditions of a temperature of 230 °C and a load of 21 N, using a melt indexer (MELT INDEXER L241 manufactured by Tatsuyama Kagaku Kogyo Co., Ltd.), the MFR of each resin composition was measured.

[0144] (6) Observation of morphology 1 Using the resin compositions obtained in Example 4, Comparative Examples 2 and 3, sheets were produced by the above procedure to obtain test pieces. Then, the morphology of the cross-section of the test pieces was observed using an atomic force microscope (AFM). In the observation, the cross-section of the test piece was prepared using an ultramicrotome (Leica EM FC7 manufactured by Leica Microsystems). Then, the cross-section of the above test piece was observed using an AFM (SPM scanning probe microscope SPM-0700 manufactured by Shimadzu Corporation).

[0145] (7) Observation of morphology 2 Test pieces were prepared by producing sheets according to the above procedure using the resin compositions obtained in Example 8 and Comparative Examples 4 to 6. The morphology of the cross section of the test pieces was then observed with a scanning electron microscope (SEM). For the observation, the cross section of the test piece was cut using an ultramicrotome (Leica EM FC7 manufactured by Leica Microsystems), stained with a 0.5% aqueous solution of ruthenium tetroxide, and evaporated with platinum. The cross section thus treated was then observed using a SEM (JSM-6510 manufactured by JEOL Ltd.).

[0146] (8) Morphological Observation 3 Test pieces were prepared by the above-mentioned procedure using the resin compositions obtained in Examples 8 and 11 and Comparative Examples 4 and 5. The morphology of the cross section of the test pieces was observed with a scanning electron microscope (TEM). For the observation, the test pieces were cut into thin films using an ultramicrotome (Leica EM FC7 manufactured by Leica Microsystems) and stained with a 0.5% aqueous solution of ruthenium tetroxide. The stained cross sections were then observed using a TEM (HT7700 manufactured by Hitachi High-Technologies Corporation).

[0147] (9) Impact resistance For Examples 8 to 12 and Comparative Examples 4 to 8, test pieces (thickness 4 mm, length 80 mm, width 10 mm (remaining width after notch processing 8 mm)) were prepared by cutting out a sheet of the above-mentioned resin composition. For Examples 13 to 18 and Comparative Examples 9 to 15, both ends of the multipurpose test piece A1 type were cut to prepare test pieces (thickness 4 mm, length 80 mm, width 10 mm (remaining width after notch processing 8 mm)). Then, in accordance with JIS K7111-1:2012, a digital impact tester IT type (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used to measure the Charpy impact value at 23°C with a hammer load of 2 J to determine the impact resistance (kJ / m 2 ) was evaluated.

[0148] (10) Dynamic viscoelasticity measurement Measurements were performed according to JIS K 7244-4 (1999). Specifically, for Examples 8 to 18 and Comparative Examples 4 to 15, the test pieces were used and the temperature was raised from -100°C to +150°C at a rate of 3°C / min using "DMA242" (manufactured by NETZSCH) at a frequency of 10Hz, to measure the peak temperature and peak strength of tan δ at 0 to 50°C. A higher value of the peak strength of tan δ indicates better vibration damping properties.

[0149] [Examples 1 to 7] [Comparative Examples 1 to 3] The resin compositions of Examples 1 to 7 were prepared as the first resin composition (D1) by melt-kneading the formulations shown in Table 3 for 3 minutes under conditions of a temperature of 230°C and a screw rotation speed of 100 rpm using a small torque detection motor unit equipped with a Brabender mixer (Brabender's "Plastograph (registered trademark) EC"). In addition, the resin compositions of Comparative Examples 1 to 3 were prepared by the same procedure. The types and amounts of each component used to prepare each resin composition and the measurement results are shown in Table 3. In addition, the AFM phase contrast image of the composition of Example 4 is shown in Figure 1(a), and the AFM phase contrast images of Comparative Examples 2 and 3 are shown in Figures 1(b) and 1(c), respectively.

[0150] The components used in preparing each resin composition are as follows: (Modified hydrogenated product (A)) Modified hydrogenated products Y-2, Y-3, Y-4, Y-5, Y-6 (Hydrogenated block copolymer) Hydrogenated Y-1 (Polyolefin resin (B)) Random polypropylene (Prime Polypro J226T, manufactured by Prime Polymer Co., Ltd., melt index (MI) = 20) (Antioxidants) Phenolic antioxidant Adeka STAB AO-60 (made by ADEKA Corporation)

[0151] [Table 3]

[0152] As is clear from Table 3, the resin compositions of Examples 1 to 7 exhibit high adhesion to aluminum and stainless steel. In addition, when Example 4 is compared with Comparative Examples 2 and 3, first, as is clear from Table 3, it is found that the resin composition of Example 4 has a large MFR and high fluidity. Then, as is clear from Figures 1(a) to 1(c), the resin composition of Example 4 has a fine co-continuous structure with a width of about several nm, whereas the resin compositions of Comparative Examples 2 and 3 have a co-continuous structure with a width of about 1 µm to several µm, which is coarser than the co-continuous structure of the resin composition of Example 4. These results show that by using a modified hydrogenated product (A) in which the polymer block (A-2) has a vinyl bond content within a specific range, a fine bicontinuous structure is formed in the resin composition (D1), reducing the tensile modulus of elasticity and softening the polyolefin resin (B), and that high fluidity is imparted to the resin composition (D1), resulting in high adhesion to the metal substrate.

[0153] [Examples 8 to 12] [Comparative Examples 4 to 8] The resin compositions of Examples 8 to 12 were prepared as the second resin composition (D2) by melt-kneading for 3 minutes using a small torque detection motor unit ("Plastograph (registered trademark) EC" manufactured by Brabender) equipped with a mixer manufactured by Brabender in the formulation shown in Table 4 at a temperature of 230°C and a screw rotation speed of 100 rpm. The resin compositions of Comparative Examples 4 to 8 were also prepared by the same procedure. The types and amounts of each component used to prepare each resin composition, and the measurement results are shown in Table 4 below. The results of the viscoelasticity measurement are shown in FIG. 5. An enlarged cross-sectional SEM photograph of Example 8 is shown in FIG. 3(a), and enlarged cross-sectional SEM photographs of Comparative Examples 4 to 6 are shown in FIG. 3(b) to FIG. 3(d), respectively. Enlarged cross-sectional TEM photographs of Examples 8 and 11 are shown in FIG. 4(a) and FIG. 4(b), respectively, and enlarged cross-sectional TEM photographs of Comparative Examples 4 and 5 are shown in FIG. 4(c) and FIG. 4(d), respectively.

[0154] The components used in preparing each of the resin compositions are as follows: (Modified hydrogenated product (A)) Modified hydrogenated products Y-2, Y-3, Y-4, Y-5, Y-6 (Polyolefin resin (B)) Random polypropylene (Prime Polypro F327, MI=7, manufactured by Prime Polymer Co., Ltd.) (Polar resin (C)) Polyamide 6 (UBE Nylon 1013B manufactured by Ube Industries, Ltd.) (Maleic anhydride modified polypropylene) -Mitsui Chemicals ADMER QE840 (Maleic anhydride modified ethylene alpha-olefin copolymer) Mitsui Chemicals Tafmer MH5020 (Antioxidants) Phenolic antioxidant Adeka STAB AO-60 (made by ADEKA Corporation)

[0155] [Table 4]

[0156] As shown in Table 4, the resin compositions of Examples 8 to 12 all have a larger tensile break strain than the comparative examples, and in particular, the tensile break strain of the resin compositions of Examples 8 to 11 is much larger than that of the comparative examples. In addition, when the resin compositions of Examples 8 and 11 are compared with Comparative Example 4, which is a resin composition that does not contain a modified hydrogen additive, and Comparative Example 5, which is a resin composition that contains a modified hydrogen compound with a small vinyl bond amount, the Charpy impact value of the former is greater than or equal to the Charpy impact value of the latter, so that it is understood that the resin compositions of the Examples are easy to improve impact resistance. Furthermore, as is clear from FIG. 3(a), in the resin composition of Example 8, it is understood that the polyamide resin, which is the polar resin (C), is dispersed in the random polypropylene, which is the polyolefin resin (B), with a fine diameter of about tens to hundreds of nm. In addition, as is clear from FIG. 4(a) and FIG. 4(b), it is understood that the domains of the resin composition of Example 11 also have a sea-island structure similar to that of Example 8. From these, it can be understood that in the resin compositions of Examples 8 to 12, the polar resin (C) is well compatible with the polyolefin resin (B). Furthermore, as is clear from Table 4 and FIG. 5, the resin compositions of Examples 8 to 10 have high tan δ peak strengths in the temperature range of 0 to 50° C., and it can be seen that they exhibit good vibration damping properties in this temperature range.

[0157] In contrast, in the resin compositions of Comparative Examples 4 to 6, it can be seen that there is a bias in the dispersion of the polar resin (C), and its dispersion diameter is also very large compared to Examples 6 to 8 (see FIGS. 3(b) to 3(d)). And as shown in FIG. 4(c), in the resin composition of Comparative Example 4, reflecting the difference in the shrinkage rate during molding between the polyolefin resin (B) and the polyamide resin which is a polar resin, voids are formed around the domain, and it can be seen that cracks have occurred in the matrix of the polyolefin resin (B) starting from the domain. Further, as shown in FIG. 4(d), in the resin composition of Comparative Example 5, it can be seen that a large number of dispersoids have aggregated to form large aggregates. Also, as shown in Table 4, in the resin compositions of Comparative Examples 4 to 8, it can be seen that the tensile fracture strain is lower than that of the resin compositions of Examples 8 to 12. In particular, in Comparative Example 4 which does not use a modified hydrogenated additive, the tensile fracture strain is extremely low, indicating that the compatibility between the polar resin (C) and the polyolefin resin (B) is poor. Also, Examples 8 to 10 have a higher tensile strength than Comparative Examples 5 and 6. This is presumably because the compatibility of the resin components contained in the resin compositions of Examples 8 to 10 is good, improving the interfacial strength between polypropylene and polyamide.

[0158] [Examples 13 to 18][Comparative Examples 9 to 15] With the formulations shown in Table 5, using a twin-screw extruder (ZSK-26mc manufactured by Coperion), at the temperatures shown in Table 5, under the condition of a screw rotation speed of 300 rpm, melt-kneading was performed and discharged at a rate of 10 kg / h to produce the resin compositions of Examples 13 to 18 as the second resin composition (D2). Also, in the same procedure, the resin compositions of Comparative Examples 9 to 15 were produced. The types and amounts of use of the respective components used to produce each resin composition and the measurement results are shown in Table 5 below.

[0159] The components used to produce each of the resin compositions are as follows. (Modified hydrogenated additive (A)) · Modified hydrogenated additives Y-3, Y-6, Y-7 (Polyolefin resin (B)) Random polypropylene (Prime Polypro F327, MI=7, manufactured by Prime Polymer Co., Ltd.) Homopolypropylene (Prime Polypro J106G, MI=15, manufactured by Prime Polymer Co., Ltd.) (Polar resin (C)) Polyamide 6 (UBE Nylon 1013B manufactured by Ube Industries, Ltd.) Polybutylene terephthalate (Toray Industries, Inc., Toraycon 1401) Polycarbonate (Iupilon S3000 manufactured by Mitsubishi Engineering Plastics Corporation) Polylactic acid (NatureWorks Ingeo 3001D) (Maleic anhydride modified polypropylene) · Mitsui Chemicals, Inc. ADMER QE840 (Antioxidants) Phenolic antioxidant Adeka STAB AO-60 (made by ADEKA Corporation)

[0160] [Table 5]

[0161] As shown in Table 5, the resin compositions of Examples 13 to 18 have larger peak intensities of tan δ and are superior in vibration damping properties compared to the resin compositions of Comparative Examples 9 to 15 which do not use modified hydrogenated products in which the vinyl bond content in the polymer block (A-2) is 50 to 99 mol %. Furthermore, as shown in Table 5, the resin compositions of Examples 14 to 17 have a higher tensile modulus and better mechanical strength than the resin compositions of Examples 13 and 18. In particular, the resin compositions of Examples 14, 15, and 17 have a particularly high tensile modulus and a high tensile strength, and therefore are found to have superior mechanical strength. It is also found that the resin compositions of Examples 13, 16, and 18 have larger tensile break strains and superior elongation properties than the resin compositions of Examples 14, 15, and 17. It is also found that the resin composition of Example 17 has a significantly larger Charpy impact value and particularly superior impact resistance than the resin compositions of Comparative Examples 9 to 15 and the resin compositions of Examples 13 to 16 and 18. [Industrial Applicability]

[0162] The first resin composition and adhesive of the present invention exhibit good adhesion to various materials and can be used in a wide range of fields such as automobiles, electrical products, building materials, etc. The second resin composition of the present invention has good mechanical properties such as high vibration damping over a wide temperature range and has high elongation properties, and can be used in pellets, veils, vibration damping materials, sound insulation materials, shoe sole materials, flooring materials, adhesives, pressure sensitive adhesives, laminates, fibers, and automobile parts, etc. Furthermore, since the compatibilizer of the present invention has high compatibilizing performance, it can be used in fields such as the recycling of food packaging containers. [Explanation of symbols]

[0163] 10: Domain 10a: Core part 10b: Shell part 20: Matrix

Claims

1. The present invention relates to a modified hydrogenated block copolymer (A) that includes a polymer block (A-1) having a structural unit derived from an aromatic vinyl compound and a polymer block (A-2) having a structural unit derived from a conjugated diene compound, and a polyolefin resin (B), The modified hydrogenated product (A) has one or more functional groups selected from an alkoxysilyl group, a carboxy group, an amino group, a hydroxyl group, an epoxy group, and a group derived from an acid anhydride, the vinyl bond content of the polymer block (A-2) is 50 to 99 mol %, the peak intensity of the loss tangent (tan δ) of the modified hydrogenated product (A) is 1.0 or more, as measured in accordance with JIS K7244-10 (2005) under conditions of a strain of 0.1%, a frequency of 1 Hz, a measurement temperature of −70 to +100° C., and a heating rate of 3° C. / min; The hydrogenation rate of the polymer block (A-2) is 50 to 99 mol %. Resin composition.

2. The resin composition described in claim 1, wherein the glass transition temperature of the modified hydrogenated product (A) is -30 to +30°C.

3. The resin composition described in claim 1 or 2, wherein the polyolefin resin (B) is at least one resin selected from the group consisting of polypropylene, polyethylene, polymethylpentene, ethylene-vinyl acetate copolymer, and homopolymers or copolymers of α-olefins, and copolymers of propylene and / or ethylene with α-olefins.

4. A resin composition described in any one of claims 1 to 3, wherein the content of the polymer block (A-1) in the modified hydrogenated product (A) is 4 to 50 mass%.

5. A resin composition described in any one of claims 1 to 4, wherein the weight average molecular weight of the modified hydrogenated product (A) is 50,000 to 400,000.

6. The resin composition according to any one of claims 1 to 5, wherein the hydrogenation rate of the polymer block (A-2) is 60 to 99 mol %.

7. A resin composition described in any one of claims 1 to 6, wherein the content of the functional group in the modified hydrogenated product (A) is 0.1 to 5.0 phr relative to the modified hydrogenated product (A).

8. The modified hydrogenated product (A) has a melt flow rate of 1 to 30 g / 10 min, measured according to JIS K7210 (2014) at a temperature of 230 ° C. and a load of 21 N. The resin composition according to any one of claims 1 to 7.

9. A resin composition described in any one of claims 1 to 8, wherein Aa / Ba is 95 / 5 to 5 / 95, where Aa is the mass of the modified hydrogenated product (A) and Ba is the mass of the polyolefin resin (B).

10. The resin composition according to any one of claims 1 to 9, further comprising a polar resin (C).

11. The resin composition according to claim 10, wherein the polar resin (C) is contained in an amount of 10 to 90% by mass based on the total mass of the resin composition.

12. A resin composition described in claim 10 or 11, wherein domains containing the other of the polyolefin resin (B) and the polar resin (C), having an average diameter of 500 nm or less, are dispersed in a matrix of one of the polyolefin resin (B) and the polar resin (C).

13. A resin composition described in any one of claims 10 to 12, wherein the polar resin (C) is at least one resin selected from the group consisting of polyamide resins, polyvinyl alcohol-based resins, polyester-based resins, and polycarbonate resins.

14. The resin composition according to any one of claims 10 to 13, wherein the loss tangent (tan δ) measured in accordance with JIS K7244-10 (2005) under the conditions of a distortion of 0.1%, a frequency of 10 Hz, a measurement temperature of -100 to +150 ° C., and a heating rate of 3 ° C. / min has a peak intensity of 0.1 to 2.0 at 0 to 50 ° C.

15. The resin composition according to any one of claims 10 to 14, wherein Ab / Bb is 30 / 70 to 1 / 99, where Ab is the mass of the modified hydrogenated product (A) and Bb is the mass of the polyolefin resin (B) in the resin composition.

16. The resin composition according to any one of claims 10 to 15, wherein the mass of the polyolefin resin (B) in the resin composition is Bb and the mass of the polar resin (C) is C, and Bb / C is 90 / 10 to 10 / 90.

17. An adhesive comprising the resin composition according to any one of claims 1 to 16.

18. A compatibilizer for compatibilizing a polar resin and a non-polar resin, The present invention comprises a modified hydrogenated product (A) of a block copolymer including a polymer block (A-1) having a structural unit derived from an aromatic vinyl compound and a polymer block (A-2) having a structural unit derived from a conjugated diene compound, The modified hydrogenated product (A) has one or more functional groups selected from an alkoxysilyl group, a carboxy group, an amino group, a hydroxyl group, an epoxy group, and a group derived from an acid anhydride, A compatibilizer in which the vinyl bond content of the polymer block (A-2) is 50 to 99 mol %.

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